JPH08262651A - Processing solution for silver halide photographic material, and processing method of silver halide photographic material using this processing solution - Google Patents

Abstract

PURPOSE: To provide a processing solution for silver halide photographic material and a processing method using this processing solution in which precipitation of reductones can be prevented, and sufficient photographic performance can be provided by containing a specified compound in the thickened solution of a developer kit. CONSTITUTION: A compound represented by the formula is contained in at least one thickened solution of a developer kit. In this silver halide photographic material processing solution, at least 0.01 mole/l of a compound having an acid dissociation constant of 7-9 is contained in the thickened solution containing this compound. In the formula, R1 , R2 each independently represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group. X represents an atomic group necessary for forming a 5 to 6 membered ring together with two vinyl carbon atom and carbonyl carbon atom replaced by R1 , R2 .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material processing solution and a method for processing a silver halide photographic light-sensitive material using the processing solution. The present invention provides a processing solution for a silver halide photographic light-sensitive material capable of obtaining stable photographic performance with little hydrolysis deterioration of a concentrated processing solution, and a silver halide photographic light-sensitive material using the processing solution. Is provided.

[0002]

2. Description of the Related Art A developer kit is made up of a plurality of developer concentrates. In this case, the treatment liquid is usually stored as a concentrated liquid and diluted with water at the time of use.

On the other hand, adding reductones to the developing solution is described in British Patent 956368, British Patent 1030495,
It is known from British Patent 1380309, US Patent 3821000, US Patent 2688549, JP-A-59-191035, JP-B-36-17599 and the like. It is known that reductones are hydrolyzed by alkali when stored in a highly concentrated alkali solution, resulting in deterioration of photographic performance over time.

Therefore, in order to prevent hydrolysis, pH 7
Although it may be possible to store at about -9, it was discovered that when stored in a concentrated solution having a pH of 7-9, precipitation occurs particularly at high temperature, resulting in deterioration of photographic performance. . When the concentrated liquid of pH 7 to 9 is stored with time, the pH after storage is lower than that of the highly alkaline concentrated liquid,
Therefore, it is considered that the solubility deteriorates and precipitation occurs.
Further, when the developing kit solution was a concentrated solution having a pH of 7 to 9 alone, sufficient sensitivity was not obtained in use after dilution.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above problems and uses a processing solution for a silver halide photographic light-sensitive material and a processing solution capable of preventing the deposition of reductones and obtaining a sufficient photographic performance. Another object of the present invention is to provide a method for processing a silver halide photographic light sensitive material.

[0006]

The above object of the present invention is to provide a processing solution for a silver halide photographic light-sensitive material containing a developing solution kit composed of a plurality of developing solution concentrated solutions in at least one developing solution kit. To the concentrated liquid containing the compound represented by the general formula (1) (detailed later) and having a compound having an acid dissociation constant of 7 to 9 in a concentrated liquid containing the compound represented by the general formula (1). It was achieved by a processing solution of a silver halide photographic light-sensitive material characterized by containing 0.011 mol / liter or more, and a processing method of a silver halide photographic light-sensitive material which is processed using this processing solution.

Further, the silver halide photographic light-sensitive material processing solution in which the pH of the concentrated solution containing the compound represented by the general formula (1) is 7 to 9, and the halogenation in which the processing is performed using this processing solution. It was achieved by the processing method of silver photographic light-sensitive material.

It has been found that the constitution of the present invention makes it possible to obtain a developing concentrate which is less likely to deteriorate due to hydrolysis of the concentrate over time and has improved precipitation due to a decrease in solubility. The inclusion of reductones in the concentrated liquid is disclosed in JP-A-5-165161 and JP-A-6-222517, but there is no description about the effect of precipitation.

Further, the developing solution kit is not limited to a concentrated solution having a pH of 7 to 9 as in the present invention, but is composed of a plurality of concentrated solutions as described above, and other than the developing solution kit composed of a concentrated solution. For at least one of the developing kit solutions mentioned above, for example, a constitution for raising the pH can be adopted, and by doing so, it has been solved that sufficient performance could not be obtained conventionally.

The compound represented by the following general formula (1) of the present invention may be an acid or a salt. A specific example will be shown later. Particularly preferred compounds are ascorbic acid, erythorbic acid (stereoisomer) (1) and salts thereof. Addition amount is developer 1
The amount is preferably 0.005 to 0.500 mol, and particularly preferably 0.01 to 0.30 mol per liter.

[0011]

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Next, the general formula (1) will be described in detail. In the formula, R ₁ and R ₂ are each independently a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group,
Represents an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, an alkylthio group, X is a ring-forming atomic group, preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and R ₁ and R ₂ are substituted. Two vinyl carbons and a carbonyl carbon jointly form a 5- or 6-membered ring. More specifically, R ₁ and R ₂ are each independently a hydroxy group or an amino group (having 1 to 1 carbon atoms as a substituent).
Including those having 10 alkyl groups such as methyl group, ethyl group, n-butyl group and hydroxyethyl group as a substituent. ), An acylamino group (acetylamino group,
Benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto Group, alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group,
An arylsulfonylamino group can be mentioned. X
Is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and two vinyl carbons substituted by R ₁ and R ₂ and a carbonyl carbon together form a 5- or 6-membered ring. Examples of X, -O -, - C ( R 3)
_{(R 4) -, - C} (R 5) =, - C (= O) -, - N
(R ₆₎ -, - formed by combining the N =. However, R ₃ , R ₄ , R ₅ , and R ₆ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, or a sulfo group can be mentioned as the substituent). An optionally substituted aryl group having 6 to 15 carbon atoms (as a substituent, an alkyl group, a halogen atom, a hydroxy group, a carboxy group, a sulfo group can be mentioned),
It represents a hydroxy group or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring.
Examples of the 5- or 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Examples of the preferred 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring. Specific examples of the compound represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0013]

[Chemical 4]

[0014]

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[0015]

[Chemical 6]

[0016]

[Chemical 7]

Examples of the compound having an acid dissociation constant of 7 to 9 used in the present invention include the compounds described in Kagaku Binran (Maruzen). Preferred are sodium borate, potassium borate, sodium tetraborate, orthoboric acid (boric acid), potassium tetraborate, trisodium phosphate, tripotassium phosphate, tripotassium phosphate, and dipotassium phosphate. The addition amount is 0.01 mol / liter or more, preferably 0.01 mol / liter to 1 mol / liter, and more preferably 0.01 mol / liter to 0.5 mol / liter.

Also, two or more of each may be used together.

The developing solution used in the present invention may or may not contain dihydroxybenzenes. As dihydroxybenzenes, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,
There are 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, and hydroquinone is particularly preferable. The addition amount is preferably 0 to 0.4 mol / liter,
More preferably, it is 0 to 0.1 mol / liter.

The developing solution may contain sulfite. Examples of sulfites include sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The preferred content of sulfite is 1-1.
The amount is 2 mol / liter, more preferably 0 to 0.5 mol / liter, and further preferably 0 to 0.1 mol / liter.

The developing kit solution which does not contain the compound represented by the general formula (1) (sometimes referred to as the compound (1)) contains potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate as an alkali agent. Is preferably used.

The pH of the developing solution when a plurality of developing kit solutions is diluted into a use solution state is generally preferably 9 to 1.
2, and more preferably pH 9-11.

In carrying out the present invention, the treatment temperature is from 10 ° C to
The temperature is preferably 45 ° C, more preferably 25 ° C to 38 ° C.

The concentration rate of the developer kit of the present invention is preferably 2.5 times or more that of the used solution.

The pH of the alkaline solution used in the present invention may be in any range as long as it is alkaline, but preferably 8 to 1
2, more preferably 9-11.

When an alkaline solution is used in the present invention, it is preferable to use a buffering agent, and as the buffering agent, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The pH of the aqueous solution containing the compound represented by the general formula (1) used in the present invention is preferably 7 or less.

In the developing solution obtained by mixing and diluting a plurality of developing kit solutions of the present invention, as a development accelerator, Japanese Patent Publication No.
7-16088, 37-5987, 38-78
No. 26, No. 44-12380, No. 45-9019 and U.S. Pat. No. 3,813,247, thioether compounds, JP-A Nos. 52-49829 and 51-
No. 15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, JP-A-56-156826 and JP-A-52-43.
429 and the like, quaternary ammonium salts, p-aminophenols described in US Pat. Nos. 2,610,122 and 4,119,462, and US Pat. No. 2,494,90.
No. 3, No. 3,128,182, No. 4,230,796
No. 32-53919, Japanese Patent Publication No. 41-11431
No. 2,482,546 and 2,596,9
26 and 3,582,346, amine compounds described in JP-B-37-16088 and JP-B-42-25201.
No. 3, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-11
431, 42-23883 and U.S. Pat. No. 3,53
No. 2,501 and other polyalkylene oxides,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as necessary.

As the antifoggant, an alkali metal halide such as potassium iodide or an organic antifoggant can be used. As the organic antifoggant, for example,
Benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-
Nitrogen-containing heteronitride compounds such as benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmerti-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned, and 1-phenyl-5-mercaptotetrazole is a typical example. Can be mentioned.

Further, the general formula (1) used in the present invention is
In the developing kit solution containing the compound represented by the following, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, other compounds described in JP-B-47-33378 and 44-9509. Can be used as an organic solvent.

Furthermore, other various additives such as stain inhibitors and layering effect accelerators can be used.

The 1-phenyl-3-pyrazolidones which can be used in the developing solution include 1-phenyl-3-
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4
-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like. As p-aminophenols, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p, benzylaminophenol, etc., but especially N-methyl-
P-aminophenol is preferred. The addition amount is preferably 0.01 mol to 0.05 mol per liter of the developing solution.

As the chelating agent which can be used in the developing solution, the following compounds can be mentioned. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminoprobantetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2
Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopyropan-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, 2-phosphonobutane-1,2,4.
-Tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, ditrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-
Examples thereof include diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and salts thereof.

In the present invention, as a silver stain preventing agent in a developing solution, JP-B-56-46585 and JP-B-62-4702 are used.
Japanese Patent Publication No. 62-4703, US Pat. No. 4,254,
215, 3,318,701, JP-A-58-20.
No. 3439, No. 62-56959, No. 62-1782.
47, Japanese Patent Application Laid-Open No. 1-20249, Japanese Patent Application No. 3-949.
The compounds described in No. 55, No. 3-112275 and No. 3-233718 can be used.

In addition, the developing solution used in the practice of the present invention may contain a dialdehyde hardener or its bisulfite adduct. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-
Isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butyl maleic dialdehyde,
Or these bisulfite addition products etc. are available. The dialdehyde compound is preferably used in such an amount that the sensitivity of the photographic layer to be processed cannot be suppressed and that the drying time is not significantly lengthened. Of these, glutaraldehyde or its bisulfite adduct is most commonly used.

Of course, when a bisulfite adduct of a dialdehyde hardener is used, the bisulfite of this adduct is also calculated as the phosphite in the developer. Besides this,
L. F. A. Mason, "Photographic Processing Chemistry," published by Focal Press (19
66), pages 226-229, US Pat. No. 2,193,
015, 2,592,364 and JP-A-48-6.
You may use the additive as described in No. 4933.

The fixing agent used in the practice of the present invention preferably contains thiosulfate. Thiosulfate is generally supplied as a solid, specifically lithium,
Often supplied as salts of potassium, sodium, ammonium, preferably sodium thiosulfate,
It is supplied as ammonium thiosulfate and dissolved before use. More preferably, a fixing solution having a high fixing rate can be obtained by supplying and dissolving it as an ammonium salt, but a sodium salt is preferable from the viewpoint of retention.

The concentration of thiosulfate is preferably 0.1-5.
It is mol / liter, more preferably 0.5 to 2 mol / liter, and further preferably 0.7 to 1.8 mol / liter. Other fixing agents such as iodide salts and thiocyanates can also be used.

The fixing agent generally contains a sulfite, and the concentration of the sulfite is preferably 0.2 mol / liter or less when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent. As the sulfite, solid lithium, potassium, sodium, ammonium salt and the like are used, and it is usually used by dissolving with the solid thiosulfate.

Further, the fixer may contain citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid, β-alanine or optical isomers thereof.

Examples of these salts include potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium tartrate. Preferred examples include lithium, potassium, sodium and ammonium salts represented by potassium, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate and the like.

Of the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The above-mentioned citric acid, tartaric acid, malic acid, succinic acid, β-alanine and the like are generally supplied as a solid and used by dissolving them in an aqueous solvent. The preferred content in the fixing solution after dissolution is 0.05 mol / liter or more, and the most preferred content is 0.2 to 0.6 mol / liter.

The content of the aluminum-based hardener in the fixing solution used in the practice of the present invention is preferably 0 to 2 × 10.
-It is ¹ mol / liter (aluminum equivalent). The aluminum-based hardener is a compound that is soluble in the fixer and releases aluminum ions or aluminum double salt ions in the fixer, and is preferably added to the fixer in the form of alum of aluminum sulfate.

Acids that can be used as the fixing agent include
Examples thereof include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, boric acid, and organic acids such as formic acid, propionic acid, oxalic acid, and malic acid, with boric acid and aminopolycarboxylic acids being preferred. Acids and their salts. The preferable addition amount is 0.5 to 20 g / liter.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

As the surfactant, for example, anionic surfactants such as sulfate ester compounds and sulfonate compounds, nonionic surfactants such as polyethylene glycol and ester compounds, and amphoteric surfactants described in JP-A-57-6840. And so on.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include, for example, JP-A-45-
No. 35754, Japanese Patent Publication No. 58-122535, No. 58-
122536, thiourea derivative, alcohol having triple bond in the molecule, US Pat. No. 4,126,459
And the thioethers described in No.

The fixer preferably has a pH of 3.8 or higher, more preferably 4.2 to 5.5.

As the emulsion used in the light-sensitive material to be processed of the present invention, grains having an average grain size or a thickness of 0.3 μm or less are preferably used. The thickness of the silver halide grain here is defined as the minimum distance between the two parallel principal planes constituting the tabular grain. The thickness of the tabular silver halide grains is calculated by depositing a metal from a diagonal direction of the grain together with a comparative latex, measuring the shadow length on an electron microscope, and referring to the shadow length of the latex.
Alternatively, it can be determined from an electron micrograph of a sample slice obtained by coating and drying a silver halide emulsion on a support.

As the silver halide emulsion, those having monodispersion are preferably used, and those having an average grain size of 50% by weight or more of silver halide grains contained in a grain size range of ± 20% at the center are particularly preferably used. To be The silver halide emulsion may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but from the viewpoint of high sensitivity silver bromide or silver iodobromide. The average silver iodide content is preferably 0.
To 5.0 mol%, particularly preferably 0.1 to 3.
It is 0 mol%.

The use of a tabular silver halide emulsion is one preferred embodiment, and the method for producing such an emulsion is described in JP-A Nos. 58-113926 and 58-113927.
It is also possible to refer to JP-A-58-113934, JP-A-62-1855, European Patents 219,849, 219,850 and the like. Further, as a method for producing a monodisperse tabular silver halide emulsion, JP-A-61-6643 can be referred to.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

The size of the tabular silver halide grains can be controlled by the temperature at the time of grain formation and the addition rate of the silver salt and halide aqueous solution.

The aspect ratio can be controlled by the method of preparing the seed crystal, the thickness and pAg during growth, pH, the halogen composition, the aging time and the temperature.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

When producing tabular silver halide grains, a silver halide solvent such as ammonia, thioether or thiourea can be used if necessary.

The grains may be grown by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions.
It may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution and a silver ion-containing solution can be supplied.

As the silver halide emulsion, core / shell type or double structure type grains having a silver halide composition whose surface is different from the grain interior are also preferably used. A method for obtaining a core / shell type emulsion will be described in detail in, for example, U.S. Pat. Nos. 3,505,068, 4,444,877, British Patent 1,027,146, and JP-A-60-14331. Has been. In the core / shell type grains of the silver halide emulsion, the silver iodide content of the outermost shell layer of the grains is less than 5 mol%, preferably less than 3 mol%.

The silver iodide content of the outermost shell layer of silver halide grains can be detected by various surface elemental analysis means. X
PS (X-ray Photoelectron Sp
electron spectroscopy), Auger electron spectroscopy, ISS
It is useful to use a method such as. XPS is one of the simplest and highly accurate means. For example, the silver iodide content of the outermost shell layer of silver halide grains can be defined by the value measured by this method.

The depth analyzed by the XPS surface analysis method is said to be about 10Å. For the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, refer to Junichi Aihara's "Electron spectroscopy" (Kyoritsu Library 16, published by Kyoritsu Publishing, 1978). You can

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the surface of the grain, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. May be. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, a ruthenium salt, an osmium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof at the stage of physical ripening or grain preparation.

The emulsion may be subjected to a water washing method such as a Nudel water washing method or a full curation precipitation method in order to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-5-16086, or JP-A-63-
The method of using G3, G8, etc. exemplified by the aggregation polymer agent described in No. 158644 is mentioned as a particularly preferable desalting method.

As the sensitizing means for chemically sensitizing the emulsion, so-called sulfur sensitization, sensitization with Se compound, Te
Sensitization with a compound, sensitization with gold, sensitization with a noble metal of Group VIII of the periodic table (for example, Pd, Pt, Id, etc.), and a combination of these can be used.
Above all, combining gold sensitization and sulfur sensitization, gold sensitization and S
A combination of sensitization with the e compound is preferable. Further, it is also preferable to use it in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of chemical sensitization, from the viewpoints of sensitivity and dye adsorption. A method of adding in the form of fine grains of silver iodide is particularly preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferred compounds are azoles, cyazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having these mercapto groups and compounds having a benzene ring.

When a reduction treatment, so-called reduction sensitization, is used, a method of adding a reducing compound, p called silver ripening is used.
This can be applied to the silver halide emulsion by a method of passing a silver ion excess state of Ag = 1 to 7 or a method of passing a high pH state of pH = 8 to 11 called high pH ripening. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted.

The reducing compound may be either an inorganic compound or an organic compound, such as thiourea dioxide, stannous salt,
Examples include amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfites, and the like, with thiourea dioxide, stannous chloride and dimethylamineborane being particularly preferred. . The addition amount of these reducing compounds varies depending on the reducing property of the compound and the type of silver halide and the emulsion production conditions such as dissolution conditions, but it is 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver halide. The range is appropriate. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

It is also preferable to subject any portion and / or shell layer other than the outermost shell layer of the silver halide grain to a reduction treatment and further grow the grain as it is. From the viewpoint of effect control, the surface of the inner shell layer to be laminated in multiple stages is preferable. For example, it is preferably applied to the surface of the seed emulsion grains or the surface of the shell layer at the time of growth suspension.

The reduction treatment is described in JP-A-2-135439,
It may be carried out in the presence of a thiosulfonic acid compound as disclosed in JP-A-2-136852.

The silver halide photographic light-sensitive material may be spectrally sensitized with a methine dye or other spectral sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobola cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes can be applied to any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
Oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc., and nuclei in which aliphatic hydrocarbon rings are fused to these nuclei, namely indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei , Naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus,
Benzimidazole nucleus, quinoline nucleus, etc. can be applied.
These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethine structure, a pyrazolin-5-one nucleus, a thiobitantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazoline-2,4-dione nucleus are used. , Rhodanine nucleus, thioparbituric acid nucleus, etc. 5-6
Member heterocyclic nuclei can be applied.

These techniques are described, for example, in German Patent No. 92
9,080, U.S. Patents 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329. ,
No. 3,655,394, No. 3,656,959
No. 3,672,897, No. 3,649,21
7, British Patent No. 1,242,588, Japanese Patent Publication No. 44-
No. 14030.

These sensitizing dyes may be used alone or in combination. Sensitizing dyes are often used in combination. Typical examples thereof include U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,299, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
617,293, 3,628,964, 3,666,480, 3,679,428, 3,703,377, 3,837,862,
British Patent No. 1,344,281, Japanese Patent Publication No. 43-493
No. 6 and the like.

The sensitizing dye may be added at any time during grain formation, before and after chemical sensitization, during the sensitization, and before coating, but it is preferably added at several points.

The light-sensitive material may be provided with a crossover cut layer between the support and the emulsion layer. This layer may be an undercoat layer provided between the support and the hydrophilic colloid layer,
A dye layer may be provided between the undercoat layer and the emulsion layer. Examples of the dye used in the undercoat layer include an oxonol dye having a pyrazolone nucleus and a barbituric acid nucleus, an azo dye, an azomethine dye, an anthraquinone dye, an arylidene dye, a styryl dye, a triarylmethane dye, a merocyanine dye, and a cyanine dye. To be The dye used in the dye layer may be dispersed in the form of fine particles. Specific examples of the dye include pages 6 to 12 of JP-A-2-264272.
Exemplified Compounds (I-2, 4, 6, 8, 9, 1, 1)
0, 11, 12, 13-27, II-2, 5, 6, II
I-3, 4, 6, 8, 9, 10, 11, 12, 14-2
8, IV-3, 5, 6, 8, 10-16, V-3, 5,
6, 7) and the like can be mentioned and used.

Further, these compounds are disclosed in International Patent Publication 8
8/04794, European Patent 0274723A1
No. 276, 566, 299, 435, JP-A Nos. 52-92716, 55-155350, 55-.
No. 155351, No. 61-205934, No. 48-6.
8623, U.S. Pat. Nos. 2,527,583 and 3,
No. 486,897, No. 3,746,539, No. 3,9
33,798, 4,130,429, 4,04
It can be easily synthesized according to the method described in No. 0,841.

Various photographic additives can be used in the emulsion in the steps before and after physical ripening or chemical ripening. It is also possible to add a hydrazine compound.
The compound of −134743 is preferable, and the general formula (5) and the general formulas (7) and (8) are particularly preferable as the nucleation accelerator. A tetrazolium salt may be added, and those described in JP-A-2-250050 are particularly preferable. Other known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978)
No.), the same No. 18716 (November 1979) and No. The compound described in 308119 (December 1989) is mentioned. The types of compounds shown in these three Research Disclosures and their locations are listed below. Additive RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog control agent / stable 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant 26 to 7 XI 650 right 1005-6 XI antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII slippery agent 27 II matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 support 8 XVII 1009 XVII

Examples of the support that can be used in the light-sensitive material include the above-mentioned RD-17643, page 2 and RD-.
18716, page 1009. Further, polyethylene-2,6-naphthalate may be used as the support. A suitable support is a plastic film or the like, and an undercoat layer may be provided on the surface of these supports in order to improve adhesion of the coating layer, corona discharge, ultraviolet irradiation or the like may be applied.

[0082]

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

Example 1 In this example, the processing method of the present invention was applied to a silver halide photographic light-sensitive material which can be used as, for example, an X-ray light-sensitive material. Here, first, a photosensitive material for evaluation was prepared as follows. (Preparation of Photosensitive Material) Preparation of Seed Emulsion-1 Seed emulsion-1 was prepared as follows using the following solutions A1 to D1.
1 was prepared. A1 ossein gelatin 24.2 g water 9675 ml polypropylene oxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 odor Potassium bromide 841 g Water 2825 ml D1 1.75N potassium bromide aqueous solution Silver potential control amount below

Japanese Patent Publication No. 58-58288 and No. 5 at 42 ° C.
Solution A using the mixing stirrer shown in No. 8-58289.
464.3 ml of each of solution B1 and solution C1 was added to 1 by the simultaneous mixing method over 1.5 minutes to perform nucleation. After stopping the addition of solution B1 and solution C1,
The temperature of the solution Al was raised to 60 ° C. over 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and the solution B1 and the solution C1 were mixed again by the simultaneous mixing method to obtain 55.4 ml each. / Min for 42 minutes. This 42
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at the time of temperature increase from 60 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was made + using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.064 μm and an average grain size of 0.064 μm. Diameter (circle diameter conversion)
Was confirmed to be 0.595 μm with an electron microscope. The variation coefficient of thickness was 40%, and the variation coefficient of distance between twin planes was 42%.

Preparation of Emulsion Em-1 Using seed emulsion-1 and the following four solutions A2 to D2,
A tabular silver halide emulsion Em-1 was prepared. A2 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml seed emulsion-1 1.218 mol equivalent Water to make 3150 ml B2 potassium bromide 1734 g 3644 ml with water C2 Silver nitrate 2478 g Finish to 4165 ml with water D2 Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05μ) Equivalent to 1.080 mol (* 0.06 mol of iodide) 5.0 wt% gelatin aqueous solution containing potassium 6.64 liters)

Above, 7.06 moles of silver nitrate and 7.0
2 liters of an aqueous solution each containing 6 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by the simultaneous mixing method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 is continuously added over 37 minutes, and then a part of the solution B2, a part of the solution C2 and the entire remaining amount of the solution D2 are added over 15 minutes. The remaining total amount of the solution B2 and the solution C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and pAG was
I kept it at 8.8 from beginning to end. Here, the addition rates of the solution B2 and the solution C2 were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate.

Further, the above solution D2 was added in an amount corresponding to 0.15 mol% with respect to the total amount of silver for halogen substitution.

After the addition is complete, the emulsion is cooled to 40.degree.
As an aggregating polymer agent, 1800 ml of a 13.8% (weight) modified gelatin aqueous solution modified with a phenylcarbamoyl group (substitution rate 90%) was added, and the mixture was stirred for 3 minutes.
After that, a 56% (weight) aqueous solution of acetic acid was added to add p
After adjusting H to 4.6 and stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, 9.01 of distilled water at 40 ° C. was added, and the mixture was left to stir, and the supernatant was drained. Further, 11.25 liters of distilled water was added, and after standing to stir, the supernatant was drained. Subsequently, a gelatin aqueous solution and a sodium carbonate 10% (weight) aqueous solution are added to adjust the pH to 5.80, and the pH is adjusted to 30 at 50 ° C.
It was stirred for a minute and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μ and the average thickness was 0.25.
μ, average aspect ratio about 4.5, width of particle size distribution 18.
It was 1% of tabular silver halide grains. Further, the average distance between twin planes is 0.020 μm, and grains having a ratio of distance between twin planes to a thickness of 5 or more are 9% of all tabular silver halide grains.
7% (number), particles of 10 or more accounted for 49%, and particles of 15 or more accounted for 17%.

Next, after the above emulsion Em-1 was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a dispersion in the form of solid fine particles, and then adenine, ammonium thiocyanate,
A mixed aqueous solution of chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and after 60 minutes, a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours. 4-hydroxy- as a stabilizer at the end of aging
6-methyl-1,3,3a, 7-tetrazaindene (T
A predetermined amount of AI) was added.

The above-mentioned additives and their addition amounts (per mol of silver halide AgX) are shown below. 5,5'-Dichloro-9-ethyl-3,3'-di- (sulfobropyr) -oxacarbocyanine sodium salt anhydrous 2.0 mg 5,5'-di- (butoxycarbonyl) -3,3'-di -(4-Sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydrate 120 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-994.
It was prepared by a method similar to that described in No. 37. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C., and the mixture was mixed with a high-speed stirrer (dissolver) at 500 rpm for 3
Obtained by stirring for 0-120 minutes.

The above selenium sensitizer dispersion was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C. and stirred to completely dissolve it. On the other hand 3.8 kg of photographic gelatin
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% sodium dodecylbenzene sulfonate aqueous solution was added thereto. Next, these two liquids were mixed and dispersed at a peripheral speed of the dispersing blade of 40 m / sec for 30 minutes at 50 ° C. by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Immediately after that, the residual concentration of ethyl acetate was reduced to 0.3 under reduced pressure.
Ethyl acetate was removed while stirring until the content became not more than wt%. Then, dilute this dispersion with pure water to obtain 80 kg.
Finished. A part of the thus obtained dispersion was collected and used as above.

By the addition of the above silver iodide fine particles, the average iodine content of the outermost surface of the silver halide grains contained in the silver halide emulsion Em-1 was about 4 mol%.

Next, the following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared.

Next, a blue-colored polyethylene terephthalate film base for X-ray having a density of 0.15 (thickness: 1
75 μm) on both sides of a support having the following transverse light-shielding layer pre-coated on both sides, and the above emulsion layer coating solution and protective layer coating solution are simultaneously layered from the bottom to the following prescribed coating amounts. Coated and dried. First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro -6-Hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² second layer (emulsion layer) Each of the emulsions obtained above has the following various types. Additives were added. Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCHN _{2 CH (OH) CH 2 N (} CH 2 C OH) ^₂ 350mg / m ₂ Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 mg / m ² Latex (L) 0.2mg / m ² Dextrin (average molecular weight 1000) 0.2 mg / m ^2, however, as the gelatin was adjusted to 1.0 g / m ^2. Third layer (protective layer) Gelatin 0.8 g / m ² poly Merrill meth consisting Kure rate matting agent 50 mg / m ² (area average particle 7.0 .mu.m) Formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy - 1,3,5-Triazine sodium salt 10 mg / m ² bisvinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 mg / m ² polyacrylamide (average molecular weight 10000) 0.1 mg / m ² sodium polyacrylate 30 mg / M ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ —O— (CH ₂ CH ₂ O) ₁₁ —H 3 mg / m ² The amount of material applied was for one side, and the amount of coated silver was adjusted to be 1.6 g / m ² for one side.

[0098]

Embedded image

[0099]

[Chemical 9]

[0100]

[Chemical 10]

[0101]

[Chemical 11]

[0102]

[Chemical 12]

The compositions of the developing replenisher and fixing solution used in this example are shown below. Part-A (for finishing 18 liters) Potassium hydroxide 900 g Potassium sulfite (50% solution) 3258 g Diethylenetetraamine pentaacetic acid 144 g Sodium bicarbonate 360 g Boric acid 360 g 5-Methylbenzotriazole 1.8 g 1-Phenyl-5-mercapto Tetrazole 3.6 g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 300 g Hydroquinone 540 g Add water to finish to 7500 ml Part-B (for 18 liter finish) Glacial acetic acid 360 g Triethylene glycol 486 g 1-phenyl -5-pyrazolidone 23.4 g n-acetyl-D, L-benicillamine 3.6 g

The developer was prepared by adding Part to about 8 liters of water.
A and Part B were added at the same time, water was added while stirring and dissolving to make 18 liter, and the pH was adjusted to 10.60 with KOH. 2.4 liters of glacial acetic acid is added to 1 liter of this developer.
/ L, and potassium bromide (7.9 g / L) were added, and the pH was adjusted to 10.45 with KOH to prepare a developing solution.

Next, the development prescription will be described. The development recipe is as follows.

Development Formulation (per liter) A-1 Part Potassium hydroxide 25 g Sodium carbonate monohydrate 10 g Diethylenetriaminepentaacetic acid 2 g 1-Phenyl-4-methyl-4′-hydroxymethyl-3-pyrazolidone 4 g 5-Methylbenz Triazole 0.2 g 1-Phenyl-5-mercaptotetrazole 0.02 g Diethylene glycol 50 g Finally 150 ml with water The pH was adjusted to 11.0.

Part A-2 Part A-1 is charged with Exemplified Compound (1) which is a compound represented by the general formula (1), and the pH is adjusted to 1 with potassium hydroxide.
It was the same as A-1 except that it was 2.0 (see Table 1).

A-3 part Potassium hydroxide 15 g Sodium carbonate, monohydrate 5 g Diethylenetriaminepentaacetic acid 2 g 1-Phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone 4 g 5-Methylbenztriazole 0.2 g 1- Phenyl-5-mercaptotetrazole 0.02 g Diethylene glycol 50 g Boric acid Amount shown in Table 1 Compound represented by general formula (1) Type and amount shown in Table 1 Water and finally 150 ml pH is potassium hydroxide and boron Adjusted to 9.0 with acid.

A-4 Part Boric Acid Amount Listed in Table 1 Sodium Phosphate Amount Listed in Table 1 Compound Represented by General Formula (1) Amount Listed in Table 1 Water Lastly 200 mL pH Hydroxylated Adjusted to 8.0 with potassium and boric acid.

The solutions used were the combinations shown in Table 1 and used as a developing solution by mixing the respective solutions into a developing kit.

The fixing formulation was as follows. Fixing formulation (for 1 liter finish) Pure 130 g Sodium bisulfite 25 g Boric acid 5 g β-alanine 90 g Acetic acid (90%) 25 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 1 g Ammonium thiosulfate (70 wt / vol) %) 250 g

In this example, the developing process was carried out as follows.

Sample film intensifying screen SRO-
250 (Konica Co., Ltd.) was sandwiched and exposed by X-ray by the distance method. Development at the temperature of each processing solution of 30 ° C. for 20 seconds,
Fixing was carried out for 15 seconds and washing with water was carried out for 15 seconds.
Incidentally, the development treatment was carried out on the day of preparation of the developing kit solution by using the working solution and by treating the kit solution for 30 days in a thermostat at 40 ° C. and then using the working solution.

The sensitivity was determined as the reciprocal of the X-ray dose required to obtain the density of fog +1.0 on the sample film. The results are sample No. The value was expressed as a relative value when the value of the sample film developed with the kit solution immediately after the preparation of No. 1 was 100.

The precipitation property was evaluated as follows and is shown in Table 1. Put the development kit solution in a plastic container and stopper tightly at 40 ° C.
I saved it on a thermo machine. It was taken out on the 10th and 30th days and visually evaluated. 1 Nothing is deposited. 2 There is a slight precipitate on the bottom of the plastic container. 3 There is a deposit on the entire bottom of the plastic container.

As can be seen from Table 1, according to the comparative treatments other than the present invention, the variation with time of photosensitivity is large (Sample N).
o. 1) to 3) and when it is composed of a plurality of developers, there is a problem in the depositability.

On the other hand, according to the processing of the present invention using a plurality of developing solutions, a stable image can be obtained with a small change in sensitization with time, there is no problem in the depositability, and these effects are added. It has the advantage that it can be obtained regardless of the type and type of thing.

[0118]

[Table 1]

[0119]

As described above, according to the processing solution for a silver halide photographic light-sensitive material of the present invention and the method for processing a silver halide photographic light-sensitive material using the processing solution, a stable and stable image can be obtained. Also, there is an effect that there is no problem with the depositability.

Claims (4)

[Claims] 1. A processing solution for a silver halide photographic light-sensitive material, comprising a developer kit composed of a plurality of developer concentrates, wherein at least one concentrate of the developer kit is represented by the general formula (1). The acid dissociation constant is 7 to 9 in the concentrated liquid containing the compound represented by the general formula (1).
A silver halide photographic light-sensitive material processing solution containing at least 0.01 mol / liter or more of the compound (1). Embedded image In formula (1), R ₁ and R ₂ each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. X represents an atomic group necessary for forming a 5- or 6-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbonyl carbon atom. 2. The silver halide photographic light-sensitive material processing solution according to claim 1, wherein the concentrated solution containing the compound represented by the general formula (1) has a pH of 7-9. 3. A developer kit comprising a plurality of developer concentrates, wherein at least one concentrate contains a compound represented by the formula (1) and is represented by the formula (1). Halogenation, characterized in that processing is carried out using a silver halide photographic light-sensitive material processing solution containing at least 0.01 mol / liter or more of a compound having an acid dissociation constant of 7 to 9 in a concentrated solution containing the compound Processing method of silver photographic light-sensitive material. Embedded image In formula (1), R ₁ and R ₂ each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. X represents an atomic group necessary for forming a 5- or 6-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbonyl carbon atom. 4. The method of processing a silver halide photographic light-sensitive material according to claim 3, wherein the concentrated liquid containing the compound represented by the general formula (1) has a pH of 7-9.