JPH09211809A - Developing solution for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress silver stain in a developing tank, etc., and to facilitate maintenance without deteriorating photographic characteristics and the stability of a developing soln. by incorporating a mercaptopyrazine compd. and/or a mercaptopyridazine compd. SOLUTION: This developing soln. contains a mercaptopyrazine compd. and/or a mercaptopyridazine compd., preferably a mercaptopyrazine compd. represented by formula I and/or a mercaptopyrazine compd. represented by formula II. In the formula I, each of R11 -R14 is H, an aliphatic hydrocarbon, etc., and at least one of them is mercapto. In the formula II, each of R21 -R24 is H, an aliphatic hydrocarbon, etc., and at least one of them is mercapto.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing method used for processing a silver halide photographic material (hereinafter, also referred to as a "photosensitive material"). More specifically, in the processing of black-and-white photographic light-sensitive materials for general use, black-and-white photographic light-sensitive materials for printing, and X-ray photographic light-sensitive materials for medical and industrial use, they adhere to the light-sensitive materials, developing tanks, developing racks and rollers of automatic developing machines Or precipitated silver stain (also called silver sludge)
And a method for facilitating the maintenance of daily instruments and machines.

[0002]

2. Description of the Related Art Generally, in the development processing of a silver halide photosensitive material, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used from the viewpoints of speed, simplicity and handling. When using an automatic developing machine, usually, development-fixing-
There is a process of washing and drying. In recent years, there has been an increasing demand for faster development processing. For rapid processing, increasing the activity of the developing solution is one means. For rapid processing of black-and-white photosensitive materials, the activity can be increased by increasing the concentration of the developing agent or the pH of the developing solution, but the deterioration of the developing solution due to air oxidation is remarkable and it is difficult to maintain the activity. In addition, approaches from photosensitive materials have been actively studied for rapid processing. Reducing the film thickness (for example, protective layer) of the photosensitive material is effective for rapid processing.

The use of sulfites to prevent the deterioration of the developer has been known for a long time. However, since a compound having a silver halide dissolving action, such as a sulfite, is added to the developer, the use of a sulfite is difficult. Silver elutes from the photosensitive material as a silver sulfite complex. As the silver complex is reduced in the developing solution, silver gradually adheres and accumulates on the developing tank and the developing roller. This is called silver dirt or silver sludge, which adheres to the photosensitive material to be processed and contaminates the image, so that it is necessary to periodically clean and maintain the equipment. When the amount of sulfite added is increased, the amount of silver sulfite complex eluted increases, and as a result, the degree of silver contamination is further increased, and there is a disadvantage that the advantage of rapid processing cannot be fully utilized.

On the other hand, as a method for reducing the silver contamination, a compound which reduces the amount of silver ions eluted in a developer and / or suppresses the reduction of silver ions to silver as disclosed in JP-A-56-24347. Is known. However, this method has the drawback that the action of suppressing development itself is inevitable and the sensitivity is reduced. Light-sensitive materials that are going to be used with a high sensitivity
As a development processing system, a decrease in sensitivity is a serious drawback. Although reducing the thickness of the photosensitive material (eg, protective layer) is extremely effective for rapid processing, running such a photosensitive material on a self-developing machine increases the amount of silver ions eluted into the developer. Silver contamination will worsen. Various compounds have been disclosed so far as compounds for reducing silver dust, but mercaptopyridazines and mercaptopyrazines have not been disclosed. Japanese Patent Sho 60
No. 24464 discloses a method for processing a silver halide color photographic light-sensitive material using a mercaptopyridazine compound and a bleach-fixing solution containing a mercaptopyrazine compound. These compounds are added to the bleach-fixing solution, not to the developing solution. Further, these compounds are bleaching accelerators, and there is no mention of silver sludge, which is the main object of the present invention.

[0005]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is, firstly, when processing a silver halide light-sensitive material capable of rapid processing, first of all, silver stains generated in a developing tank and / or developing racks and rollers. The second, the maintenance of the developing machine and the developing equipment is easy, the third is the reduction of silver stain without affecting the photographic characteristics at all, and the fourth is the stability of the developer. It is to reduce silver dust without damaging it.

[0006]

The above object was achieved by a developer for a silver halide photographic light-sensitive material, which contains at least one mercaptopyrazine compound and / or a mercaptopyridazine compound.
The object of the present invention is to provide at least one compound represented by the following general formula (I) among mercaptopyrazine compounds.
Can be achieved by a developer for a silver halide photographic light-sensitive material characterized by containing a seed,
It could be achieved by a developer for silver halide photographic light-sensitive material, which is characterized by containing at least one compound represented by the following general formula (II) among mercaptopyridazine compounds. General formula (I)

[0007]

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In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group,
Halogen atom, cyano group, nitro group, sulfo group, sulfino group, carboxy group, phosphono group, amino group, ammonio group, phosphonio group, hydroxy group, mercapto group,
It represents an oxy group, a thio group, an acyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a urethane group, and a ureido group. However, R ₁₁ , R ₁₂ ,
At least one of R ₁₃ and R ₁₄ represents a mercapto group. General formula (II)

[0009]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group,
Halogen atom, cyano group, nitro group, sulfo group, sulfino group, carboxy group, phosphono group, amino group, ammonio group, phosphonio group, hydroxy group, mercapto group,
It represents an oxy group, a thio group, an acyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a urethane group, and a ureido group. However, R ₂₁ , R ₂₂ ,
At least one of R ₂₃ and R ₂₄ represents a mercapto group.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (I) will be described in detail below. In the general formula (I), R ₁₁ , R ₁₂ , R ₁₃ and R
_The aliphatic hydrocarbon group represented by ₁₄ is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, particularly a straight chain, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 8 carbon atoms. Is. Here, the branched ones may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-octyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and examples of the alkenyl group include an allyl group and 2-butenyl group. Base, 3
-Pentenyl group may be mentioned, the alkynyl group may, for example, be a propargyl group or a 3-pentynyl group, and the aralkyl group may, for example, be a benzyl group.

In the general formula (I), R ₁₁ , R ₁₂ , R ₁₃ ,
The aromatic hydrocarbon group represented by R ₁₄ is preferably an aromatic hydrocarbon group having 5 to 15 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group. Etc.

In the general formula (I), R ₁₁ , R ₁₂ , R ₁₃ ,
The heterocyclic group represented by R ₁₄ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, for example, pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group,
Examples thereof include a thienyl group, a furyl group and a benzothiazolyl group.

In the general formula (I), R ₁₁ , R ₁₂ ,
Examples of the halogen atom represented by R ₁₃ and R ₁₄ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (I), R ₁₁ , R ₁₂ ,
Examples of the amino group represented by R ₁₃ and R ₁₄ include unsubstituted amino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, anilino group, o-toluidino group, and 2,4-xylidino group. Examples of the ammonio group include, for example, a trimethylammonio group, a triethylammonio group, and an unsubstituted ammonio group.Examples of the phosphonio group include a trimethylphosphonio group.
Examples thereof include a triethylphosphonio group.

In the general formula (I), R ₁₁ , R ₁₂ ,
Examples of the oxy group represented by R ₁₃ and R ₁₄ include an alkoxy group (methoxy group, ethoxy group, isopropoxy group, n-butoxy group, cyclohexyloxy group, etc.), aryloxy group (phenoxy group, p-methyl group). Phenoxy group, etc.), an oxy group in which an oxygen atom is bonded to a heterocycle (2-
Pyridyloxy group, 2-imidazolyloxy group, etc.), allyloxy group, benzyloxy group and the like.

In the general formula (I), the thio groups represented by R ₁₁ and R ₁₂ include, for example, alkylthio groups (methylthio group, ethylthio group, isopropylthio group, n-butylthio group, cyclohexylthio group, etc.), Examples thereof include an arylthio group (phenylthio group, p-methylphenylthio group, etc.), a thio group having a sulfur atom bonded to a heterocycle (2-pyridylthio group, 2-imidazolylthio group, etc.), an allylthio group, a benzylthio group, and the like.

In formula (I), examples of the acyl group represented by R ₁₁ and R ₁₂ include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, pivaloyl group, octanoyl group, acryloyl group and pyruvoyl group. Group, benzoyl group, 1-naphthoyl group, m-toluoyl group, cinnamoyl group, and the like. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an N, N-dimethyl group. Examples thereof include a carbamoyl group, an N, N-diethylcarbamoyl group and an N-phenylcarbamoyl group. Examples of the acylamino group include an acetylamino group, a benzamide group, a propionylamino group, a pivaloylamino group and the like. For example, an unsubstituted sulfamoyl group, Examples thereof include a methylsulfamoyl group, an ethylsulfamoyl group, a dimethylsulfamoyl group, a diethylsulfamoyl group, and a phenylsulfamoyl group. Examples of the sulfonamide group include a benzenesulfonamide group and a methylsulfonylamino group. Examples of the sulfonyl group include a mesyl group, tosyl group, tauryl group, and the like, and examples of the sulfinyl group include a methylsulfinyl group, a phenylsulfinyl group, and the like.

In the general formula (I), R ₁₁ , R ₁₂ ,
Examples of the oxycarbonyl group represented by R ₁₃ and R ₁₄ include an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, naphthyloxycarbonyl group, etc.) Is mentioned.

In the general formula (I), R ₁₁ , R ₁₂ ,
Examples of the ureido group represented by R ₁₃ and R ₁₄ include N'-
Methylureido group, N ', N'-dimethylureido group, N,
Examples thereof include N ', N'-trimethylureido group, N'-ethylureido group, N'-phenylureido group and the like, and examples of the urethane group include methoxycarbonylamino group, phenoxycarbonylamino group and the like.

In the general formula (I), R ₁₁ ,
Each group represented by R ₁₂ , R ₁₃ and R ₁₄ may be substituted. Examples of the substituent include the following.

Halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, Cyclohexyl group), alkenyl group (for example, allyl group, 2-butenyl group, 3-pentenyl group), alkynyl group (for example, propargyl group, 3-pentynyl group), aralkyl group (for example, benzyl group, phenethyl group), aryl Group (for example, phenyl group, naphthyl group, 4-methylphenyl group), heterocyclic group (for example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group), alkoxy group (for example, methoxy group, ethoxy group, Butoxy group), aryloxy group (eg, phenoxy group, 2-
Naphthyloxy group), amino group (for example, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group), ureido group (for example, unsubstituted ureido group, N-methylureido group, N-phenylureido group), Urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group), sulfonyl group (eg, mesyl group, tosyl group), sulfinyl group (eg, methylsulfinyl group, phenylsulfinyl group), alkyloxycarbonyl group (eg, methoxy group) Carbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (eg, phenoxycarbonyl group), acyl group (eg,
Acetyl group, benzoyl group, formyl group, pivaloyl group), acyloxy group (eg acetoxy group, benzoyloxy group), phosphoric acid amide group (eg, N, N-diethyl phosphoric acid amide group), alkylthio group (eg, methylthio) Group, ethylthio group), arylthio group (eg phenylthio group), cyano group, hydroxy group, mercapto group, phosphono group, nitro group, carboxy group, sulfo group, sulfino group, ammonio group (eg trimethylammonio group), phosphonio Group, silyl group (eg, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group) and the like.
These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), preferably R ₁₁ ,
R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a sulfo group, a carboxy group,
It represents an amino group, a hydroxy group, a mercapto group, an oxy group, a thio group, an acylamino group, and a sulfonamide group. However, at least one of R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ represents a mercapto group.

More preferably in the general formula (I),
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom, an aliphatic hydrocarbon group, a heterocyclic group, a sulfo group, a carboxy group, an amino group, a hydroxy group, a mercapto group, an oxy group and an acylamino group. However, at least two of R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ represent a mercapto group.

Most preferably, R in the general formula (I)
₁₁ , R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom, an aliphatic hydrocarbon group, a sulfo group, a carboxy group, an amino group, a hydroxy group, a mercapto group and an oxy group. Where R ₁₁ and R
_At least two of ₁₂ , R ₁₃ and R ₁₄ represent a mercapto group, and at least one represents a hydroxy group.

Next, the general formula (II) will be described in detail. An aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an amino group, an ammonio group, a phosphonio group, which is represented by R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ in the general formula (II). An oxy group, a thio group, an acyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a urethane group, and a ureido group are each represented by R ₁₁ and R in the general formula (I). _An aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an amino group, an ammonio group, a phosphonio group, an oxy group, a thio group, an acyl group, or carbamoyl represented by ₁₂ , R ₁₃ and R _14. Group, acylamino group, sulfamoyl group, sulfonamide group, sulfonyl group, sulfinyl group, oxycarbonyl group, urethane group, and ureido group Is the significance.

In the general formula (II), preferably
R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a sulfo group, a carboxy group, an amino group, a hydroxy group, a mercapto group, an oxy group, It represents a thio group, an acylamino group or a sulfonamide group. However, at least one of R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ represents a mercapto group.

More preferably, in the general formula (II), R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each a hydrogen atom, an aliphatic hydrocarbon group, a heterocyclic group, a sulfo group, a carboxy group, an amino group or a hydroxy group. , A mercapto group, an oxy group, and an acylamino group. However, at least two of R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ represent a mercapto group.

Most preferably in the general formula (II)
R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ represent a hydrogen atom, an aliphatic hydrocarbon group, a sulfo group, a carboxy group, an amino group, a hydroxy group, a mercapto group, or an oxy group. However, R ₂₁ , R
_At least two of ₂₂ , R ₂₃ and R ₂₄ represent a mercapto group, and at least one represents a hydroxy group.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0031]

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[0032]

[Chemical 6]

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The compounds represented by the general formulas (I) and (II) are known in the following literature, G. B. Perlin, The Pyrazins (The Chemistry of Heterocyclic Compounds Series, published by Intersunence Publishers), Raymond N.P. It can be synthesized according to the method described in Pyridazins by The Castle (The Chemistry of Heterocyclic Compounds Series, published by Intersunence Publishers).

The amount of the mercaptopyrazine compound or the mercaptopyridazine compound of the present invention added to the developer is preferably 0.01 to 10 mmol, and particularly preferably 0.1 to 5 mmol per liter of the developer.

The processing agents and processing methods such as the developing solution and the fixing solution in the present invention will be described below, but needless to say, the present invention is not limited to the following description and specific examples.

Any known method can be used for the developing treatment of the present invention, and a known developing treatment solution can be used. There are no particular restrictions on the developing agents used in the developer used in the present invention (hereinafter, both the development start solution and the development replenisher are collectively referred to as a developer), but dihydroxybenzenes, ascorbic acid derivatives, hydroquinone It preferably contains a monosulfonate, and may be used alone or in combination. Furthermore, in terms of developing ability, it is 1 with dihydroxybenzenes and ascorbic acid derivatives.
-A combination of phenyl-3-pyrazolidones, or dihydroxybenzenes and ascorbic acid derivatives and p-
A combination of aminophenols is preferred. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferable from the viewpoint of material cost.

It is preferred to use an auxiliary developing agent in the present invention. Examples of auxiliary developing agents for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl. −
4-hydroxymethyl-3-pyrazolidone and the like.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based auxiliary developing agent used in the present invention Among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene type developing agent is usually used preferably in an amount of 0.05 mol / liter to 0.8 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l. It is preferable to use 0.5 to 0.5 mol / l and the latter in an amount of 0.06 mol / l or less, preferably 0.03 to 0.003 mol / l.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / liter to 0.5 mol / liter, and preferably 0.05 mol / liter to
0.3 mol / l is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or less.
It is preferable to use 0.5 mol / l, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / l to 0.2 mol / l.

The developing solution for processing the light-sensitive material in the present invention may contain additives which are usually used (for example, developing agents, alkaline agents, pH buffer agents, preservatives, chelating agents, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of the buffer, especially carbonate, used is preferably 0.5 mol / liter or more, particularly 0.5 to 1.5 mol / liter.

Examples of the preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is more than 0.2 mol / l, especially 0.3
It is used in an amount of at least mol / l, but if it is added in too large an amount, it causes silver contamination in the developing solution.
Desirably, it is mol / liter. Particularly preferably,
It is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite.
Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide,
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3-
(5-Mercaptotetrazol-1-yl) benzenesulfonate sodium salt, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A No. 62-212651 may be added as a physical development unevenness preventing agent. Further, a mercapto compound, an indazole compound, a benzotriazole compound, and a benzimidazole compound may be contained as an antifoggant or a black pepper inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole,
5-nitrobenzimidazole, 2-isopropyl-5
-Nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-thiadiazole- 2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these additives is usually 0.01 to 10 mmol per liter of the developing solution,
More preferably, it is 0.1 to 2 mmol.

Further, in the developer of the present invention, various organic compounds,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of aminopolycarboxylic acids include:
Aspartic acid diacetic acid, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediamine tetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropane tetraacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine Hexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, etc. JP-A-52-25632, 55-67747, 57-10
2624, and the compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene described in US Pat.
Diphosphonic Acid and Research Disclosure No. 181
Vol., Item 18170 (May 1979 issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to the above, Research Disclosure 18170 and JP-A-57-20855.
4, ibid 54-61125, ibid 55-29883, ibid 56
-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, 54-112127, 55-4024 and 55-40.
25, 55-126241, 55-65955, 55-69556 and the above-mentioned Research Disclosure 18170.

These organic and / or inorganic chelating agents are not limited to those mentioned above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol, per liter of the developing solution.

The compound of the present invention may be used alone as a silver stain preventing agent, and for example, JP-A-56-2434.
7, JP-B-56-46585, JP-B-62-2849,
In addition to the compounds described in JP-A-4-362942, polyoxyalkylphosphonates described in US Pat. No. 5457011 may be used in combination. The amount of the silver stain inhibitor added is preferably 0.05 to 10 mmol, and more preferably 0.1 to 5 mmol, per liter of the developing solution.

Further, as a dissolution aid, JP-A-61-267
The compound described in 759 can be used. Further, if necessary, a color toning agent, a surfactant, a defoaming agent, a hardener and the like may be contained.

The preferred pH of the developer is 9.0 to 12.0.
And particularly preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

The replenishment amount of the developing solution is 3 per 1 m ² of the light-sensitive material.
It is 90 ml or less, preferably 325 to 30 ml, and most preferably 180 to 120 ml. The development replenisher has the same composition and //
Alternatively, it may have a concentration, or may have a composition and / or concentration different from that of the starting solution.

Ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used as the fixing agent of the fixing processing agent in the present invention. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt which acts as a hardening agent, and the water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as the aluminum ion concentration in the used liquid.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

Preservatives (for example, sulfite, bisulfite, metabisulfite, etc., 0.0
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), a compound having an aluminum stabilizing ability or a water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides,
0.001 mol / liter to 0.5 mol / boric acid
Liter, preferably 0.005 mol / l to 0.
3 mol / l).

In addition, the compounds described in JP-A-62-78551, pH adjusting agents (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be used, and known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-B-58-122535, and JP-B-58-1.
22536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.
739, ibid. 1-159645 and ibid. 3-101728.
And the mesoionic compound and thiocyanate described in 4-1-170539.

The pH of the fixing solution in the present invention is 4.0 or higher, preferably 4.5 to 6.0.

The replenishing amount of the fixing solution is 5 per 1 m ² of the light-sensitive material.
The amount is 00 ml or less, preferably 390 ml or less, and more preferably 320 to 80 ml. The replenishing solution may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration as the starting solution.

The fixing solution can be recycled and used by a known fixing solution recycling method such as electrolytic silver recovery. Examples of the reproducing device include Reclaim R-60 manufactured by Fuji Hunt.

When the developing and fixing processing agents used in the present invention are stored in a liquid form, for example, JP-A-61-731.
47, it is preferable to store in a packaging material having low oxygen permeability. Furthermore, when these liquids are supplied as a concentrated liquid, they are diluted with water to a predetermined concentration at the time of use, and are diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated liquid.

Even if the developing treatment agent and the fixing treatment agent in the present invention are solid, the same result as the liquid agent can be obtained. However, the solid treatment agent will be described below.

The solid processing agent used in the present invention may have a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, crushed product, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or coating film to separate components that react with each other upon contact,
A plurality of layers may be formed to separate the components that react with each other, or these may be used in combination.

As the coating, known ones can be used, such as polyvinylpyrrolidone, polyethylene glycol,
Polystyrene sulfonic acid and vinyl compounds are preferred. In addition, gelatin, pectin, polyacrylic acid,
Polyvinyl alcohol, vinyl acetate copolymer, polyethylene oxide, carboxymethyl cellulose sodium, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid, xanthanic acid gum, gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, Polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene ethyl ether, polyoxyethylene alkylphenol ether such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, or a water-soluble binder described in Japanese Patent Application No. 2-203165. It can be used alone or in combination of two or more. That. These can also be used as granulation aids.

In the case of forming a plurality of layers, components that do not react even if they come into contact with each other may be sandwiched between components that react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. Examples of these methods include, for example, JP-A-61-25992.
1, JP-A-4-15641, JP-A-4-16841, and JP-A-4-15641
32837, 4-78848, 5-93991 and the like.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferred, especially tablets are 1.0-5.0 g / cm ³
Is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, as a packaging method, Japanese Patent Application Laid-Open Nos. 61-259921 and 4-1
6841 and 4-78848 can be used. As a method of solidification, JP-A No. 4-8
5533, 4-85534, 4-85535, 5
-134362, 5-197070, 5-2040
98, 5-224361, 6-138604, 6
138605, Japanese Patent Application No. 7-89123, and the like.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The particle size and shape of the granulated product suitable for the present invention vary depending on the desired characteristics, but generally, the solubility desired for the photographic processing agent and the residual powder amount or transportation in the waste packaging material after preparation are required. Considering the durability against breakage of the granulated product due to vibration at the time, in the case of granular form, the sphere-converted particle size is 0.5 to 5
The shape is about 0 mm, preferably about 1 to 15 mm, and the shape is cylindrical, spherical, cubic, rectangular, or the like, and more preferably spherical or cylindrical. The roller-compacted product may be crushed and further sieved to a diameter of about 2 mm to 1 cm. Similarly, in the case of briquettes and tablets, the particle size and shape differ depending on the desired characteristics, but a diameter of about 2 mm to 5 cm is preferable, and the shape is cylindrical, spherical, cubic, rectangular parallelepiped, etc., more preferably spherical or cylindrical. Is. When it is desired to improve the solubility, a plate-shaped material having a reduced thickness, a material having a further reduced central portion thickness, and a hollow donut shape are also useful. Conversely, the diameter and thickness may be further increased for the purpose of slowly dissolving, and can be arbitrarily adjusted. Further, the surface state (smooth, porous, etc.) may be changed in order to control the solubility. Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid processing agent is preferably a material having low oxygen and water permeability, and the packaging material may have a known shape such as a bag, a cylinder or a box. Also,
JP-A-6-242585, 6-242588, 6-
247432, 6-247448, and Japanese Patent Application No. 5-306.
64, JP-A-7-5664, and 7-5666 to 7-5.
The foldable shape as disclosed in 669 is also preferable in order to reduce the storage space of the waste packaging material. These packaging materials may be provided with a screw cap, a pull-top, an aluminum seal at the processing agent outlet, or the packaging material may be heat-sealed, but other known packaging materials may be used and are not limited to these. I don't. In addition, recycling or reusing the waste packaging material is preferable in terms of environmental conservation.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in Japanese Patent Application No. 7-235499. Dissolve in
Method of replenishing from stock section, JP-A-5-11945
No. 4, 6-19102, and No. 7-261357, a method of adding a processing agent to the circulation system of an automatic developing machine to dissolve and replenish it, and processing a photosensitive material with an automatic developing machine having a dissolution tank. Depending on the method, a treatment agent may be added and dissolved, and any other known method may be used. In addition, the processing agent may be manually opened and charged, or may be automatically opened and automatically loaded by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferable from the viewpoint of the working environment. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting, a method of pushing off, and
102, 6-95331, and the like.

The light-sensitive material that has been developed and fixed is then washed or stabilized (hereinafter, referred to as washing including stabilizing treatment, unless otherwise specified. The liquid used for these is water or washing water). That.). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. If washing with a low replenishment volume,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A Nos. 63-18350 and 62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishment amount of water washing, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time, and the replenishment amount of water washing is 200 to 50 per 1 m ² of the light-sensitive material.
Milliliters are preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, the method of the present invention may be provided with a scale preventing means in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example,
-Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, Japanese Patent Application Laid-Open Nos.
7, 4-16280, 4-18980 and the like.

In addition to the above, known water-soluble surfactants and antifoaming agents may be added in order to prevent unevenness of water bubbles and transfer of stains. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

A part or all of the overflow liquid from the washing step can be mixed and used in a processing liquid having fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

There is also a case where a stabilizing treatment is carried out after the water washing treatment, and examples thereof include JP-A-2-201357 and JP-A-2-201357.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents. Agents can also be added.

Additives such as antifungal agents and stabilizers to be added to the washing and stabilizing baths may be solid agents like the above-mentioned developing and fixing processing agents.

The waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is preferably incinerated. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5439560 or the like before disposing.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of the liquid and the oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. further,
A rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, 2 to Dry to Dry is used.
5 to 160 seconds is preferable, development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each liquid is 25 to 50 seconds.
C. is preferable, and 30 to 40.degree. C. is preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C,
The drying time can be changed depending on the surrounding conditions. Any known method can be used as the drying method, and the drying method is not particularly limited. However, warm air drying, JP-A-4-15534 and JP-A-52-152
There are heat roller drying and drying by far-infrared rays as disclosed in JP-A Nos. 256 and 5-289294, and a plurality of methods may be used in combination.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as a silver halide, a conventional halogenated silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide or the like. Any silver halide emulsion may be used, preferably silver chloride, silver chlorobromide or silver chloroiodobromide or positive silver halide containing 60 mol% or more of silver chloride as a negative silver halide emulsion. Silver chlorobromide, silver bromide, and silver iodobromide containing 60 mol% or more of silver bromide as silver halide. The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method. The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. The particles may be particles formed mainly in the particles or particles mainly formed inside the particles. Further, it may be particles whose surface is previously covered. The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, and the like, The Journal of Photographic Science (J. Photogr. Sci.) 21 ~
39 (1973) and the like.
Particles having a shape of a tetrahedron, a tetrahedron, a dodecahedron or the like can be prepared and used. Further, particles having a twin plane may be used. As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed. In the present invention, a monodisperse emulsion is preferred. The monodisperse silver halide grains in the monodisperse emulsion have an average grain size γ of ± 10%.
The weight of silver halide contained in the grain size range is preferably 60% or more of the total weight of silver halide grains. The halogen composition of the silver halide emulsion used in the present invention is not particularly limited. In order to achieve the object of the present invention more effectively, silver chloride, silver chlorobromide and silver chloroiodobromide having a silver chloride content of 50 mol% or more are preferred. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, a light-sensitive material suitable for high-illuminance exposure such as scanner exposure and a light-sensitive material for line drawing are
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograph by P. Glafkides.
ique (published by Paul Montel, 1967), by GFDufin
Photographic Emulsion Chemistry (The Focal Press
, 1966), by VL Zelikman et al Making and
Coating Photographic Emulsion (The Focal Press,
1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions.

The grain shape of the silver halide used in the present invention is not particularly limited, and it may be cubic, octahedral, spherical, or
Research Disclosure 22534 (January 1983)
Any of the tabular silver halide grains having a high aspect ratio described in 1) can be used.

In order to make the particle size uniform,
British Patent No. 1,535,016, Japanese Patent Publication No. 48-3689
0, 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
5, it is preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-55-158124 to grow the growth rapidly within a range not exceeding the critical saturation.
The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 20%.
It is particularly preferably 15% or less. The average grain size of grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.1 μm to 0.4 μm.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the sulfur sensitizer, various sulfur compounds, such as thiosulfates, thioureas, thiazoles and rhodanins, can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat. No. 1,574,94.
4, Same 2,278,947, Same 2,410,689, Same 2,728,668, Same 3,501,313, Same 3,6
56,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Moisar, K
lein Gelationc. Proc. Symp. 2nd. 301-309
The method of combining polyvinylpyrrolidone and thiosulfate as reported by (1970) et al. Also gives good results.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240 and JP-A-4-324855 can be used. In particular, JP-A-4-32485
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in 5.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in 313284. Specifically, US Patent Nos. 1,623,499 and 3,3
20,069, 3,772,031, UK Patent No. 2
35, 211, first 1,121,496, first 1,29
No. 5,462, No. 1,396,696, and Canadian Patent No. 8
00,958, JP-A-4-204640 and 4-271.
341, 4-333043, 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.)
635 (1980), ibid 1102 (1979), ib
id 645 (1979), Journal of Chemical Society Perkin Transactions (J.Ch
em.Soc.Perkin.Trans.) 1, 191 (1980), S.
The Chemistry of Organic Serenium and Telluniu, edited by S. Patai
m Compounds), Vol 1 (1986), Vol 2 (19)
The compounds described in 87) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in JP-A-5-313284.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

In the present invention, a silver halide emulsion particularly suitable as a reversing light-sensitive material is a silver halide containing 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. 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 used in the light-returning light-sensitive material of the present invention preferably contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
r, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenoate ligand Cyanate, tellurocyanate, acid and aquo ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salts, sodium salts, potassium salts, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl ₅ ] ^-2 6 [Re (NO) CN ₅ ] ^-2 7 [Re (NO) ClCN ₄ ] ^-2 8 [Rh (NO) ₂ Cl ₄ ] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-3 15 [Re (NO) Cl ₅ ] ^-1 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The spectral sensitizing dye used in the present invention is not particularly limited. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but it is used in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount range of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain. , Especially 6.5 × 10 ^{−7 to} 2.0 ×
The addition amount range of 10 ⁻⁶ mol is preferable.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
Item 1X (p.437, August 1978), US-4425
425 and 4425426. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
62247, JP-A-2-48653, US Pat. No. 2,16
1,331, West German Patent 936,071, JP-A-5-11
389, simple merocyanines, B) helium
Japanese Patent Application Laid-Open No. 50-6242 discloses a neon laser light source
5, trinuclear cyanine dyes shown in Nos. 54-18726 and 59-102229, C) LED light source and red semiconductor laser, Japanese Patent Publication No. 48-42172, No. 51.
-9609, 55-39818, JP-A-62-284.
343, thiacarbocyanines described in JP-A-2-105135, and D) tricarbocyanines described in JP-A-59-191032 and JP-A-60-80841 for infrared semiconductor laser light sources. Kaisho 59-192
242, dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIa) and the general formula (IIIb) of JP-A-3-67242 are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (published December 1978), page 23, IV-J.

For an argon light source, Japanese Patent Application No. 7-37
S1-1 to S1-13 described in 811 can be preferably used.

For the helium-neon light source, the sensitizing dye represented by formula (I) described in Japanese Patent Application No. 6-75322, page 7, column 11, line 42 to page 8 is particularly preferable. . Specifically, the compounds I-1 to I-35 in the same specification are preferable. In addition to these, all of those described in the general formula (I) of JP-A-6-75322 and I-1 to I-34 of the general formula (I) of Japanese Patent Application No. 6-103272 are preferably used.

Regarding the LED light source and the infrared semiconductor laser, S3-1 to S3 described in Japanese Patent Application No. 7-37811.
A dye of -8 is particularly preferably used.

For the infrared semiconductor laser light source, S4-1 to S4-9 described in Japanese Patent Application No. 7-37811 are also available.
Are preferably used.

For white light sources such as those photographed by a camera, the sensitizing dyes of the general formula (IV) described in JP-A-6-313937 are preferable, and specifically, IV-1 to IV-20 in the specification are preferred. It is preferably used. In addition, general formulas (III) and (IV) described in JP-A-4-19647 are preferable, and specifically, III-1 to III-20 and IV-1 to IV-1 in the specification.
1 is preferably used.

In the case of an X-ray sensitive material, it is preferable to use a tabular silver halide emulsion. In this case, silver bromide or silver iodobromide is preferred.
-5 mol% is preferred, and a highly sensitive one is obtained, and it is suitable for rapid processing.

A preferred grain form of the tabular silver halide emulsion is an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Furthermore, the particle thickness is 0.3μ
The following is preferable, and 0.2 μ or less is particularly preferable. Here, the aspect ratio of the tabular silver halide emulsion is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain. . The tabular grains are preferably 80% by weight of all grains in the tabular silver halide emulsion, more preferably 90% by weight.
Preferably, it is present in an amount of at least% by weight. By using a tabular silver halide emulsion, the photographic stability during running processing according to the present invention can be further enhanced. Also, since the amount of coated silver can be reduced,
Especially, the load of the fixing process and the drying process is reduced, and the rapid processing is possible also from this point.

The tabular silver halide emulsion is a knuck (Cug
nac) and Chateau "Evolution of Morphology of Silver Bromide Crystals during Physical Ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Ripping)" Science・ E-Industrie Photography, 33
Vol. 2, No. 2 (1962), pp. 121-125, Duffin, "Photographic emulsion chemistry," Focal Press, New York, 196.
6 years, p. 66 to p. 72, APH Tribelli (Tribvll
i), WF Smith Photographic Journal, 80, 285 (194)
No. 58,127,92.
1, JP-A-58-113,927, JP-A-58-11
It can be easily prepared by referring to the method described in 3,928. In addition, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed in an atmosphere having a pBr value of 1.3 or less and a pBr value is kept at the same level, and silver and a halogen solution are added at the same time. Obtained by growing crystals. It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process. The size of the tabular silver halide grains can be adjusted by controlling the temperature,
It can be adjusted by selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth. In the present invention, a tetrazolium compound, a hydrazine compound and a nucleation accelerator may be added.

The hydrazine derivative used in the present invention is described in JP-A-7-287335 (corresponding EP670516).
Preference is given to using the compounds of the general formula (I) described under A). Specifically, I-1 to I-53 described in the same specification
The compound represented by

The following hydrazine derivatives are also preferably used. The compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically the compounds described on pages 3 and 4 of the publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication; Compounds represented by the general formula (4), the general formula (5) and the general formula (6) described in JP-A-6-230497, specifically, Compound 4-1 described on pages 25 and 26 of the same publication. -Compound 4-10, Compounds 5-1 to 5-42 described on pages 28 to 36, and Compound 6-1 to Compound 6-7 described on pages 39 and 40. JP-A-6-28
9520 are compounds represented by the general formula (1) and the general formula (2), specifically, compounds 1-1) to 1-17) and 2-1 described on pages 5 to 7 of the publication. ). JP 6
The compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in -313936, specifically, the compounds described on pages 6 to 19 of the same publication; The compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically the compounds described on pages 3 to 5 of the same. Compounds represented by the general formula (I) described in JP-A-7-5610, specifically compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication. Compounds represented by formula (H) and formula (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the publication. Japanese Patent Application No. 7-
General formula (1), (A), (B),
Compounds represented by (C), specifically compounds N-1 to N-30 and D-1 to D-55 described in the same publication. Regarding the addition method, addition layer, and addition amount of the hydrazine derivative, the above-mentioned JP-A-7-287335 (corresponding EP670516) is also used.
The description in A) may be referred to.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of a silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, Nitrobenzotriazoles, etc .; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added. Of these, benzotriazole (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole) are preferable. Further, these compounds may be contained in the treatment liquid. Further, a compound capable of releasing an inhibitor during the development described in JP-A-62-30243 may be contained for the purpose of stabilizing or preventing black spots.

Further, a technique of incorporating a polymer latex into a silver halide emulsion layer or a backing layer to improve dimensional stability can also be used. These techniques are disclosed in, for example, Japanese Examined Patent Publication Nos. 39-4272, 39-17702 and 43
-13482, etc. For the purpose of dimensional stability, a dispersion of a water-insoluble or sparingly soluble synthetic polymer may be included. For example, use of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, or the like. You can

The emulsion layer of the photographic light-sensitive material of the present invention may contain a polymer such as an alkyl acrylate latex, an emulsion, and a plasticizer such as a polyol such as trimethylolpropane in order to improve pressure characteristics.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material prepared by using the present invention may be coated with a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amino oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings.

The silver halide photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer on a support, and in the case of a direct medical X-ray sensitive material, it is disclosed in JP-A-58-58. 127921, 59-90841, 58-
As described in JP-A-111934 and 61-201235, those having at least one silver halide emulsion layer on each side of the support are preferred. The photographic material of the present invention may further have an intermediate layer, a filter layer, an antihalation layer, and the like, if necessary.

The silver amount of the light-sensitive material used in the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 1 g / m ^{2 to} 4 g / m ² (on one side). Is. Preferably, the suitability for rapid processing does not exceed 5 g / m ² . Further, in order to obtain a constant image density and a constant contrast, 0.5 g / m ² or more is preferable.

Gelatin is used as the binder of the light-sensitive material used in the present invention. Gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or co-polymers. A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as coalesced can also be used in combination.

As the binder or protective colloid for the photographic emulsion, 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, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

It is particularly preferable for the X-ray sensitive material to contain an organic substance which flows out in the development processing step in the emulsion layer or in the hydrophilic colloid layer. When the substance to be washed away is gelatin, gelatin species that are not involved in the crosslinking reaction of gelatin with a hardening agent are preferable, and examples thereof include acetylated gelatin and phthalated gelatin, and those having a small molecular weight are preferable. On the other hand, as a polymer substance other than gelatin, US Pat. No. 3,271,1
58, or hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be effectively used, and saccharides such as dextran, saccharose and pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less,
More preferably, it is 10,000 or less. The amount of effluent in the process is 1 of the total weight of the applied organic substances other than silver halide grains.
0% or more and 50% or less is effective, and preferably 15% or more and 30% or less disappears. The layer containing the organic substance flowing out in the treatment of the present invention may be either an emulsion layer or a surface protective layer.However, when the total amount of the organic substance applied is the same, the layer containing the organic substance is more effective than the layer containing only the emulsion layer. It is preferable that the compound is contained in the emulsion layer, and it is more preferable that the compound is contained only in the surface protective layer. In the case of a light-sensitive material having a multi-layered emulsion layer, when the total amount of the organic substance applied is the same, it is preferable to include a large amount in the emulsion layer closer to the surface protective layer.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 4,142,89 are used.
4, homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid, organic compounds such as starch,
Fine particles of an inorganic compound such as silica, titanium dioxide, or strontium barium sulfate can be used. The particle size is preferably 1.0 to 10 μm, and particularly preferably 2 to 5 μm.

The silver halide photographic light-sensitive material of the present invention has the purpose of absorbing light in a specific wavelength range, that is, halation and irradiation, and a spectral composition of light to be incident on a photographic emulsion layer provided with a filter layer. The photographic emulsion layer or other layers may be dyed for control purposes. In a double-sided film such as a direct medical x-ray film, a layer for crossover cut may be provided below the emulsion layer. Such dyes include oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus, hemioxonol dyes, azo dyes, azomethine dyes, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, cyanine dyes, etc. Is mentioned. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in German Patent 616,00.
7, British Patents 584,609, 1,117,429,
Japanese Patent Publications 26-7777, 39-22069, 54-
38129, JP-A-48-85130, and JP-A-49-996.
20, the same 49-114420, the same 49-129537,
It is described in PB Report 74175 and Photographic Abstr. 128 ('21). In particular, it is preferable to use these dyes in a bright room reversal light-sensitive material. In addition, Japanese Patent Application No. 5-2
Solid fine particle dispersions of dyes described on pages 23 to 30 of 44717 may be used. In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

When using these dyes, it is an effective technique to mordante an anionic dye into a specific layer in a light-sensitive material using a polymer having a cation site. In this case, it is preferable to use a dye which irreversibly decolorizes during the development-fixing-washing step. The layer in which the dye is mordanted by using a polymer having a cation site may be the emulsion layer, the surface protective layer may be on the side opposite to the emulsion layer and the support, but preferably between the emulsion layer and the support. For the purpose of crossover cutting of medical X-ray double-sided films, it is ideal to mordant into the undercoat layer.

As a coating aid for the undercoat layer, a polyethylene oxide nonionic surfactant can be preferably used in combination with a polymer having a cation site. As the polymer providing the cation site, an anion conversion polymer is preferable. Various known quaternary ammonium salt (or phosphonium salt) polymers can be used as the anion conversion polymer. Quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers in the publications listed below. JP-A-59-166940, U.S. Pat. No. 3,958,99
5, JP-A-55-142339, JP-A-54-126,
027, JP-A-54-155835, JP-A-53-3
0328, water-dispersed latex described in JP-A-54-92274; polyvinylpyridinium salts described in U.S. Pat. Nos. 2,548,564, 3,148,061, 3,756,814; U.S. Pat. , 709, 69
Water-soluble quaternary ammonium salt polymer described in US Pat. No. 3,898,088; and the like. Further, since it moves from a desired layer to another layer or into a processing solution and does not adversely affect photographically, a monomer having at least two (preferably 2 to 4) ethylenically unsaturated groups is copolymerized. It is particularly preferable to use it as a crosslinked aqueous polymer latex.

As a method for immobilizing a dye, JP-A-55-1 is used.
The solid dispersion method described in 55350, WO88 / 04794 or the like is also effective.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

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, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-). Hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), etc. They can be used alone or in combination.

The photographic light-sensitive material of the present invention contains a hydroquinone derivative (so-called DIR-hydroquinone) which releases a development inhibitor in a photographic emulsion layer or other hydrophilic colloid layer corresponding to the density of an image at the time of development. May be. Specific examples thereof are U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, U.S. Pat. No. 4,377,63.
4, U.S. Pat. No. 4,332,878, JP-A-49-12
9,536, JP-A-54-67,419, JP-A-56-
153, 336, JP-A-56-153, 342, JP-A-59-278, 853, 59-90435, 59-.
The compounds described in 90436, 59-138808 and the like can be mentioned.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid,
A polymer or copolymer having an acid monomer such as maleic acid or phthalic acid as a repeating unit can be given. These compounds are disclosed in JP-A-61-2238.
34, 61-228437, 62-25745, and 62-55642. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and a high molecular compound composed of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

The silver halide emulsion thus produced is applied to a support such as a cellulose acetate film or a polyethylene terephthalate film by a dip method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method or the like and dried. It

The present invention can also be applied to a color light-sensitive material. In this case, various color couplers can be used. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17
643 (December 1978) Item VII-D and 187
17 (November 1979).

In addition, various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following sections can be preferably used. Item This section 1) Nucleation accelerator A compound represented by formula (I), (II), (III), (IV), (V) or (VI) described in JP-A-6-82943. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 from general formulas (II-m) to (II-p) and compound examples II-1 to II-22, The compounds described in JP-A-1-179939. 2) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to right lower column, line 4; JP-A 2-103536, page 16, lower right column, line 3 to page 17, lower left column The 20th line, and further, the spectral sensitizing dyes described in JP-A Nos. 1-112235, 2-124560, 3-79928 and 5-11389, and Japanese Patent Application No. 3-411064. 3) Surfactants JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, lower right column 18th line. 4) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and further JP-A-1-237538. The thiosulfinic acid compound described. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 of the same. 9) Dyes The dyes described in JP-A-2-103536, page 17, lower right column, lines 1 to 18 and solid dyes described in JP-A 2-294638 and 5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 12) Redox compound A compound represented by the general formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), a general formula (R -1), (R-2), (R-3), Compound Examples 1 to 75, further compounds described in 5-257239 and 4-278939. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 14) Dihydroxybenzes Compounds described in JP-A-3-39948, page 11, upper left column to type 1, pages 2, left lower column, and EP452772A.

[0133]

EXAMPLES The composition of the developing solution (1) per liter of the used solution is shown below. Potassium hydroxide 35.0 g Diethylenetriamine / pentaacetic acid 2.0 g Potassium carbonate 40.0 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 Compound shown in Table 1 Amount shown in Table 1 Sodium erythorbate 3.0 g Diethylene glycol 20.0 g pH 10.5

The composition of the developer (2) is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (bulk powder) 63.0 g Sodium sulfite (bulk powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g Diethylenetriamine to be briquetted together -Pentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g Compound shown in Table 1 Amount shown in Table 1 3- (5-mercaptotetrazole -1-yl) Sodium benzenesulfonate 0.1 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve this in water to make 1 liter. pH 10.65

Here, in the raw material form, the bulk powder was used as a general industrial product, and the beads of the alkali metal salt were commercial products. When the raw material form is briquette, it is compressed and compressed using a briquetting machine to give an irregular length of 4 to 6
A rugby ball shape having a size of about mm was prepared, crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treatment agent was filled in a foldable container made of high-density polyethylene,
The outlet was sealed with an aluminum seal. For dissolution and replenishment, Japanese Patent Application No. 7-235499 and Japanese Patent Application No. 7-235498
The lysis replenisher with automatic opening mechanism disclosed in US Pat.

The formulation of the fixing solution (1) per liter of the working solution is shown below. Ammonium thiosulfate 120 g Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.03 g Sodium thiosulfate / 5-hydrate 11.0 g Sodium metasulfite 19.0 g Sodium hydroxide 12.4 g Acetic acid (100%) 30.0 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g pH 4.8

The composition of the fixing agent (2) is shown below. Agent A (solid) Ammonium thiosulfate (Compact) 125.0 g Anhydrous sodium thiosulfate (bulk powder) 19.0 g Sodium metabisulfite (bulk powder) 18.0 g Anhydrous sodium acetate (bulk powder) 42.0 g Agent B (liquid) Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.03 g Anhydrous citric acid 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 ml. Agents A and B were dissolved in water to make 1 liter. pH 4.8

Ammonium thiosulfate (compact) was prepared by spray-drying a flake product which was compressed under pressure with a roller compactor and crushed into irregularly shaped chips of about 4 to 6 mm, which were then blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. Patent application Hei 7 for dissolution and replenishment
No. 235499, Japanese Patent Application No. 7-235498, and a dissolution replenishing apparatus having an automatic opening mechanism was used.

Photosensitive materials (1) to (1) used in Examples are described below.
The production method of (4) will be described. Manufacturing method of the light-sensitive material (1) The method of manufacturing the emulsion-A will be described. While stirring 2nd and 3rd liquids in 1st liquid of Table 1 kept at 38 ° C and pH 4.5, 2 at the same time
Added over 4 minutes to form 0.18 μm particles. Subsequently, the liquids 4 and 5 in Table 1 were added over 8 minutes,
Grain formation was completed by adding 0.15 g of potassium iodide. After that, it was washed with water by the flocculation method according to a conventional method, and after adding gelatin, the pH was adjusted to 5.2 and pAg.
Adjusted to 7.5, added sodium thiosulfate 4 mg, N, N-dimethylselenourea 2 mg, chloroauric acid 10 mg, sodium benzenethiosulfonate 4 mg and sodium benzenethiosulfinate 1 mg, and optimum sensitivity at 55 ° C. Chemically sensitized so that Further, 50 mg of 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was used as a stabilizer, and phenoxyethanol was used as a preservative in an amount of 10 mg.
It was added so as to be 0 ppm, and finally silver iodochlorobromide cubic particles having an average particle size of 0.20 μm and containing 80 mol% of silver chloride were obtained. (Variation coefficient 9%)

<1 solution> Water 1.0 liter Gelatin 20 g Sodium chloride 2 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenethiosulfonate 3 mg <2 solution> Water 600 ml Silver nitrate 150 g <3 solution > Water 600 ml Sodium chloride 45 g Potassium bromide 21 g Potassium hexachloroiridium (III) (0.001% aqueous solution) 15 ml Ammonium hexabromorhodium (III) (0.001% aqueous solution) 1.5 ml <4 solutions> Water 200 ml Silver nitrate 50 g <5 liquid> Water 200 ml Sodium chloride 15 g Potassium bromide 7 g K ₄ Fe (CN) ₆ 30 mg

<Preparation of silver halide photographic light-sensitive material> A layer structure of a UL layer, an EM layer, a PC layer and an OC layer is formed in this order from the support side on a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride. Was applied to prepare a sample. The preparation method and coating amount of each layer are shown below.

(UL layer) To a gelatin aqueous solution, a dispersion of 30 wt% of polyethyl acrylate with respect to gelatin was added and coated to give gelatin of 0.5 g / m ² .

(EM Layer) The following compound (S-1) as a sensitizing dye was added to the above emulsion A at 2.5 × 10 ⁻⁴ per mol of silver.
3 × 10 ⁻⁴ mol of mercapto compound represented by the following (a), which is added per mol of silver: KBr 3.0 × 1
0 ^-3 mol, of 4-hydroxy-6-methyl-l, 3,3
a, 7-Tetrazaindene 7.0 × 10 ⁻⁴ , 4 × 10 ⁻⁴
Molar mercapto compound represented by (b), 4 × 10 ⁻⁴
Mol of the triazine compound represented by (c), 2 × 10 ⁻³
Mol of 5-chloro-8-hydroxyquinoline, nucleating agent (HZ-1) (hydrazine derivative) 7.0 × 10 ⁻⁵ mol, nucleation accelerator (AC-1) 4.2 × 10 ⁻⁴ mol, p-
9 × 10 ⁻³ mol of sodium dodecylbenzenesulfonate and 3 × 10 ⁻² mol of hydroquinone were added. Furthermore,
A dispersion of polyethyl acrylate is 200 mg / m ² , a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 8
8: 5: 7) to 200 mg / m ^2, colloidal silica having an average particle size of 0.02μm 200mg / m ^2, as a further hardening agent (d) is added 200 mg / m ^2. The amount of silver coated on them 3.
It was applied so as to be 5 g / m ² . The pH of the finished liquid is 5.
It was 7.

(PC layer) A dispersion of 50% by weight of ethyl acrylate in gelatin aqueous solution, and
The following surfactant (e) was added at 5 mg / m ² and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² so that gelatin was 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 40 having an average particle size of about 3.5 μm
mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , silicone oil 20 mg / m ^2, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (f) as a coating aid. 100 mg / m ^{2 of} sodium dodecylbenzenesulfonate and 20 mg / m ² of the following structural formula (g) were applied.

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant p-sodium dodecylbenzenesulfonate 40 mg / m ² Hardener Hardeners (d) 200 mg / m ² SnO ₂ / Sb ( Weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² dye [b] 70 mg / m ² dye [C] 90 mg / m ²

[Back protective layer] Gelatin 0.8 mg / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid sodium salt 15 mg / M ² Sodium acetate 40mg / m ²

The swelling ratio ((swelled film thickness / dry film thickness) × 100) on the side having the emulsion layer was 100.

Preparation of Photosensitive Material (2) Emulsion B The same preparation as Emulsion A was carried out except that 2 mg of sodium thiosulfate was added per 1 mol of silver and no selenium sensitizer was used.

The sensitizing dye of the light-sensitive material (1) was replaced with the following S-2 (5 ×
10 ⁻⁴ mol / mol Ag) and S-3 (5 × 10 ⁻⁴ mol / mol Ag), Emulsion B as emulsion for EM layer
A sample was prepared in the same manner as in the light-sensitive material (1) except that was used.

The swelling ratio on the side having the emulsion layer was the same as that of the light-sensitive material (1).

Preparation of Photosensitive Material (3) Emulsion C 3 per mol of sodium chloride and silver kept at 40 ° C.
× 10 ^-5 mol sodium benzenesulfonate, 5 × 1
0 ^-3 mole of 4-hydroxy-6-methyl-l, 3,3
a, 1.5 containing pH = 2.0 containing 7-tetrazaindene
% Gelatin aqueous solution and sodium chloride aqueous solution containing 2.0 × 10 ⁻⁶ mol of K ₂ Ru (NO) Cl ₅ per 1 mol of silver by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds to half the amount of silver in the final grains. Is added at the same time, and the particles of the core are 0.12
μm was prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 6.0 × 10 ⁻⁶ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes, and chloride having an average particle size of 0.15 μm was added. Silver cubic particles were prepared (coefficient of variation 12%). Then, after washing with water by a flocculation method well known in the art to remove soluble salts, gelatin is added, and compound-A and phenoxyethanol as preservatives are added at 60 mg each per 1 mol of silver, and then pH is adjusted to 5.
7, pAg = 7.5, and per mol of silver,
4 × 10 ^-5 mol of chloroauric acid, 4 × 10 ^-5 mol of compound-
After Z is added, 1 × 10 ^-5 mol of sodium thiosulfate and 1 × 10 ^-5 mol of potassium selenocyanide are added, and 6
After heating for 60 minutes at 0 ° C. and chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer was added.
Tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver (as final particles, pH = 5.7, pAg = 7.
5, Ru = 4.0 × 10 ⁻⁶ mol / Ag mol).

EM, PC and OC were applied in this order on the following support. (EM) The following compounds were added to the above emulsion C, and a silver halide emulsion layer was coated so that the gelatin coating amount was 0.9 g / m ² and the coating silver amount was 2.7 g / m ² . 1-phenyl-5-mercapto-tetrazole 1 mg / m ² nucleation accelerator (AC-2) 3.6 × 10 ⁻³ mol / mol Ag N-oleyl-N-methyltaurine sodium salt 10 mg / m ² compound-B 10 mg / m ² compound-C 10 mg / m ² compound-D 10 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 760 mg / m ² compound-E (hardening film Agent) 105 mg / m ² Sodium polystyrene sulfonate 57 mg / m ² Nucleating agent (HZ-3) 1.2 × 10 ⁻³ mol / mol Ag

The following compounds were added to the (PC) gelatin aqueous solution, and the gelatin coating amount was 0.6 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.6 g / m ² p-sodium dodecylbenzene sulfonate 10 mg / m ² sodium polystyrene sulfonate 6 mg / m ² compound-A 1 mg / m ² compound-F 14 mg / m ² n- Butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 250 mg / m ²

The following compounds were added to the (OC) gelatin aqueous solution and coated so that the gelatin coating amount was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.45g / m ² Amorphous silica matting agent 40mg / m ² (Average particle size 3.5μ, Pore diameter 25Å, Surface area 700m ² / g) Amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² p-sodium dodecylbenzenesulfonate 30 mg / m ² compound- A 1 mg / m ² Liquid paraffin 40 mg / m ² Solid disperse dye-G ₁ 30 mg / m ² Solid disperse dye-G ₂ 150 mg / m ² Sodium polystyrene sulfonate 4 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 Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² p-sodium dodecylbenzenesulfonate 13 mg / m ² dihexyl-α- Sulfosuccinate sodium 12 mg / m ² Polystyrene sodium sulfonate 10 mg / m ² Compound-A 1 mg / m ²

<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 would be 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 3.4μ) 15mg / m ² Compound -H 140 mg / m ² Compound -I 140 mg / m ² Compound -J 30 mg / m ² compound-K 40 mg / m ² p-sodium dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-L 5 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine Potassium 5 mg / m ² Sodium sulfate 150 mg / m ² Sodium acetate 40 mg / m ² Compound-E (hardener) 105 mg / m ²

(Support, Undercoat Layer) 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 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g Colloidal silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. The dry film thickness was 0.
It was applied so as to be 9μ.

<Undercoat Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-N 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-A 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm. A sample was prepared in this way. The swelling ratio on the side having the emulsion layer was 100.

Preparation of Photosensitive Material (4) Emulsion D 250 cc of silver nitrate aqueous solution in which 64 g of silver nitrate was dissolved, and K ₂ R corresponding to 1 × 10 ^-7 mol per 1 mol of silver in the whole emulsion
h (H ₂ O) Cl ₅ and K ₃ corresponding to 2 × 10 ⁻⁷ mol
250 cc of an aqueous solution of a halogen salt in which 20 g of potassium bromide containing IrCl ₆ and 14 g of sodium chloride were dissolved, sodium chloride (0.3%), 1,3-dimethyl-2-imidazolithione (0.002%) and citric acid ( 0.05%)
Nucleation was carried out by adding to a 2% gelatin aqueous solution containing 2% by stirring with a double jet method at 38 ° C. for 12 minutes to obtain silver chlorobromide grains having an average grain size of 0.16 μm and a silver chloride content of 55 mol%. It was Then, silver nitrate 10
300 cc of an aqueous solution of silver nitrate in which 6 g was dissolved and 300 cc of an aqueous solution of halogen salt in which 28 g of potassium bromide and 26 g of sodium chloride were dissolved were added by the double jet method over 20 minutes to form particles.

Then, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, and the product was washed with water by a flocculation method according to a conventional method. Then, 40 g of gelatin was added per 1 mol of silver, pH was 5.9, pAg was
After adjusting to 7.5, 3 mg of sodium benzenethiosulfonate, 1 mg of sodium benzenesulfinate, 2 mg of sodium thiosulfate, 2 mg of the compound represented by the following structural formula (h) and 8 mg of chloroauric acid were added per mol of silver. , 60
Chemical sensitization was performed by heating at 70 ° C. for 70 minutes. Then, 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer
-After adding 150 mg of tetrazaindene and 100 mg of proxel as a preservative, 400 mg of the dye represented by the following structural formula (i) was added, and the temperature was lowered after 10 minutes. The obtained grains were cubic silver iodochlorobromide grains having an average grain size of 0.22 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10
%)

(Preparation of Emulsion Layer Coating Solution) To this emulsion, silver 1
2 × 10 ⁻⁴ mol per mol of a short-wave cyanine dye represented by the following structural formula (j), 5 × 10 ⁻³ mol of potassium bromide,
2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 2 × 10 ⁻⁴ mol of the mercapto compound represented by the following structural formula (k), 3 × 10 ⁻⁴ mol of the following structural formula (l)
And a nucleation accelerator (AC-1) represented by
6 × 10 ^-4 mol, nucleating (HZ-2) was added 2 × 10 ^-4 mol, further, hydroquinone 100 mg / m ^2, sodium p- dodecylbenzenesulfonate 10 mg / m ^2, colloidal silica (Nissan Chemical Made Snowtex C) 150mg
/ M ² , polyethyl acrylate dispersion 500 mg / m ² ,
1,2-bis (vinylsulfonylacetamido) ethane was added so as to be coated at 80 mg / m ² to prepare an emulsion layer coating solution. The pH of the coating solution was adjusted to 5.6.

(Preparation of PC and OC coating liquid) In a gelatin solution containing proxel as an antiseptic, 10 mg / m ^{2 of} the compound represented by (n) and 10 mg of the compound represented by (o) were added.
0 mg / m ² , 300 mg of polyethyl acrylate dispersion
/ M ² was added so as to be applied to prepare a PC solution. Further, a gelatin solution containing proxel as a preservative was added to an amorphous SiO ₂ matting agent 5 having an average particle size of about 3.5μ.
0 mg / m ² , colloidal silica (Snowtex C manufactured by Nissan Kagaku) 100 mg / m ² , liquid paraffin 30 mg / m ² , and a fluorosurfactant 5 mg / m ² represented by the following structural formula (p) as a coating aid. An OC solution was prepared by adding 30 mg / m ^{2 of} p-dodecylbenzenesulfonic acid sodium salt so as to be applied.

These coating solutions were applied to a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides, and an emulsion layer (silver content 3.0 g / m ² , gelatin 1.
5 g / m ² ) as the bottom layer, PC (gelatin 0.5 g / m ² ),
OC (gelatin 0.4 g / m ² ) was applied. The pH of the emulsion surface of the obtained sample was 5.8.

The back layer was coated according to the following formulation. (Back layer) Gelatin 1.5 g / m ² Surfactant P-dodecylbenzenesulfonic acid sodium salt 30 mg / m ² Gelatin hardening agent 1,2-bis (vinylsulfonylacetamide) ethane 100 mg / m ² Dye The following dye (q), Mixture of (r), (s) and (t) Dye (q) 50 mg / m ² Dye (r) 100 mg / m ² Dye (s) 30 mg / m ² Dye (t) 50 mg / m ² Proxel 1 mg / m ²

The swelling ratio on the side having the emulsion layer was 15
It was 0.

The structures of various additives used in the light-sensitive materials (1) to (4) are shown below.

[0168]

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[0169]

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[0171]

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[0172]

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[0173]

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[0175]

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[0176]

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[Chemical 21]

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Example 1 250 ml of the developing solution was heated to 38 ° C. and 16 sheets of contact film RU-100 (3.6 cm × 12 cm) manufactured by Fuji Photo Film Co., Ltd. were soaked for 20 seconds while stirring with nitrogen bubbling. The silver concentration inside was measured. The results for the developer (1) are shown in Table 1, and the results for the developer (2) are shown in Table 2. The compound of the present invention showed an excellent ability to suppress silver elution.

Example 2 The developing solution and the fixing solution were observed in the automatic developing machine FG-460A manufactured by Fuji Photo Film Co., Ltd., and the light-sensitive materials (1) to (4) and the output light-sensitive material LS-5500 manufactured by the same company, and the duplication paper feeling were detected. Material DU-150WP was subjected to sensitometry. The developer (1) was used in combination with the fixer (1), and the developer (2) was used in combination with the fixer (2). The exposure and processing conditions were as follows. Light-sensitive material (1) Through a 633 nm interference filter, exposed through a step wedge with xenon flash light with a light emission time of 10 ^-6 seconds Light-sensitive material (2) Through an interference filter having a peak at 488 nm, a light emission time of 10 ^-5 through a step wedge Exposure with xenon flash light for 2 seconds Sensitive material (3) Exposure through step wedge with Dainippon Screen P-627FM printer Sensitive material (4) 3200 ° K through step wedge
Exposure with tungsten light of LS-5500 Through an interference filter having a peak at 488 nm, exposure with xenon flash light with emission time of 10 ^-4 seconds through step wedge DU-150WP Step wedge with P-627FM printer manufactured by Dainippon Screen Co., Ltd. Exposure processing conditions The photosensitive materials (1), (2) and (4) were processed by setting the developing temperature to 35 ° C, the fixing temperature to 34 ° C and the developing time to 30 seconds. Other sensitive materials are developing temperature 38 ℃, fixing temperature 37 ℃,
Processing was performed by setting the developing time to 20 seconds. Tables 1 and 2 show the difference between the minimum density (Dmin) and the sensitivity (S3.0) at a density of 3.0 with respect to the blank. It is understood that the smaller the difference is, the more the photographically has no effect, and the compound of the present invention has less influence on the photographic property. Especially, even in a large amount of addition, Dmin of the duplication sensitive material is not affected and it is excellent. In addition, the Dmin difference is within 0.03, and the S1.5 difference is within ± 0.02, which are practically permissible ranges.

Example 3 In Example 2, unexposed contact film RU-100 manufactured by the same company was treated with 100 m ² a day for 5 days, and then,
Unexposed contact paper sensitive material KU-150W
P (4 pieces) was processed, and the degree of stain attachment was observed. The replenishment of the developing solution (1) was 320 ml / m ² , the replenishment of the developing solution (2) was 160 ml / m ² , and the replenishment of the fixing solution was 260 ml / m ^{2 in} all cases.
The results are shown in Tables 1 and 2. A level of 4 or more is a level at which there is no practical problem.

[0182]

[Table 1]

[0183]

[Table 2]

Here, comparative compound C- in Table 1 and Table 2
The structures of 1, C-2 and C-3 are shown below.

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[0186]

By using the compound of the present invention, it is possible to obtain an excellent effect of preventing silver stain without affecting the photographic performance.

Claims (5)

[Claims] 1. A developer for a silver halide photographic light-sensitive material, comprising at least one mercaptopyrazine compound and / or mercaptopyridazine compound. 2. A developer for a silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a sulfo group, a sulfino group, Carboxy group, phosphono group, amino group, ammonio group, phosphonio group, hydroxy group, mercapto group, oxy group,
Thio group, acyl group, carbamoyl group, acylamino group,
Sulfamoyl group, sulfonamide group, sulfonyl group,
It represents a sulfinyl group, an oxycarbonyl group, a urethane group, and a ureido group. However, R ₁₁ , R ₁₂ , R ₁₃ ,
At least one of R ₁₄ represents a mercapto group. 3. A developer for a silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula (II). Formula (II) In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom,
Cyano group, nitro group, sulfo group, sulfino group, carboxy group, phosphono group, amino group, ammonio group, phosphonio group, hydroxy group, mercapto group, oxy group, thio group, acyl group, carbamoyl group, acylamino group, sulfamoyl group , A sulfonamide group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a urethane group, and a ureido group. However, at least one of R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ represents a mercapto group. 4. A method for developing a black-and-white silver halide photographic light-sensitive material, which comprises subjecting the black-and-white silver halide photographic light-sensitive material to image exposure and then treating it with the developer according to claim 1, 2 or 3. 5. A black-and-white silver halide photographic light-sensitive material containing a hydrazine derivative is further exposed to 0.3 mol / min after image exposure.
4. The method according to claim 1, 2 or 3 containing liter or more of sulfite.
The method for developing a black-and-white silver halide photographic light-sensitive material, which comprises processing with a developing solution of