JPH09197632A - Method for processing halogenated silver photographic material and fixer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the residual silver and the residue of color by including the specified compound, and to improve the environment fitness and using efficiency by worker. SOLUTION: The fixer includes one kind of the compound expressed with a formula. In the formula, Q means a non-metal group to be required for cooperating with carbon atom and nitrogen atom so as to from a nitrogen included heterocycle, L means divalent group, (n) means a numeric among 0-2. M<1> means hydrogen atom, ammonium ion or metal ion. R<1> , R<2> mean hydrogen atom, alkyl group, ammonium ion or metal ion, and they can be the same one or they can be different from each other. R<1> , R<2> can be connected to each other so as to from a ring formed of five or six members. Each group and each ring can have a substituent group. Residual silver and the residue of color is thereby improved. Furthermore, environment fitness and using efficiency can be improved by using the solid processing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide photographic light-sensitive material and a fixing agent, and more particularly, to processing of a silver halide photographic light-sensitive material having improved residual silver and residual color and good environmental suitability. A method and a fixing agent.

[0002]

BACKGROUND OF THE INVENTION In recent medical fields, reduction of the amount of waste liquid is required from the viewpoint of speeding up and environmental protection. Further, ascorbic acid has been attracting attention in place of hydroquinone (HQ) which has been conventionally used as a main agent of a developing solution for environmental protection. However, the rapid low replenishment process increases the concentration of silver ions and halogen ions and deteriorates the residual silver and residual color of the photographic light-sensitive material. This also applies to a system using ascorbic acid as a developing agent.

By the way, since the liquid agent contains water, it is heavy in weight, and a strong packaging material is required for the risk of liquid leakage from the packaging material, and a large amount of waste is generated, which is bad for the environment. Further, in many cases, since it is sold as a concentrated liquid, it has to be diluted at the time of use, and there is an increasing demand for improvement in the working efficiency of workers.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing method and a fixing agent for a silver halide photographic light-sensitive material which has improved residual silver and residual color and improved environmental suitability and efficiency of use by workers. Is to provide.

[0005]

[Means for Solving the Problems]

1. At least one of the compounds represented by the following general formula (1)
A fixing agent comprising a seed.

[0006]

Embedded image In the formula, Q represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle with carbon atoms and nitrogen atoms.

L represents a divalent group, and n represents an integer of 0-2.

M ¹ represents a hydrogen atom, an ammonium ion or a metal ion.

R ¹ and R ² represent a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ¹ and R ² are bonded to each other to form a 5- or 6-membered group. You may form a ring. Each of these groups and rings may have a substituent. 2. 2. The fixing agent as described in 1 above, which is a solid processing agent. 3. After processing the silver halide photographic light-sensitive material with a developer,
A method of processing a silver halide photographic light-sensitive material, which comprises processing with a fixing solution containing at least one compound represented by the following general formula (1).

[0010]

Embedded image In the formula, Q represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle with carbon atoms and nitrogen atoms.

L represents a divalent group, and n represents an integer of 0-2.

M ¹ represents a hydrogen atom, an ammonium ion or a metal ion.

R ¹ and R ² represent a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ¹ and R ² are bonded to each other to form a 5- or 6-membered group. You may form a ring. Each of these groups and rings may have a substituent. 4. 4. The method for processing a silver halide photographic light-sensitive material as described in 3 above, wherein the developer contains a compound represented by the following general formula (2).

[0014]

[Chemical 6] In the formula, R ³ and R ⁴ are each a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, an alkylthio group, and X represents R ³ ,
It represents an atomic group necessary for forming a 5- or 6-membered ring in cooperation with two vinyl carbon atoms substituted by R ⁴ and a carbonyl carbon atom. Each of these groups and rings may have a substituent.

[0015]

With the present invention, residual silver and residual color are improved. Furthermore, by using a solid processing agent, environmental suitability and use efficiency were also improved.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (1) of the present invention has a boron atom bonded to at least two oxygen atoms, and is known as, for example, an organic boronic acid compound or an organic boric acid compound. The compound represented by the general formula (1) is preferable in order to more effectively achieve the object of the present invention.

[0017]

Embedded image

In the formula, Q represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle with carbon atoms and nitrogen atoms. L represents a divalent group, and n represents an integer of 0-2. M ¹ represents a hydrogen atom, an ammonium ion, or a metal ion. R ¹ and R ² represent a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ¹ and R ² are bonded to each other to form a 5- or 6-membered ring. You may. Each of these groups and rings may have a substituent.

Next, the compound represented by the general formula (1) will be described in more detail. Q represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle containing a monocycle or a condensed ring together with a carbon atom and a nitrogen atom, and these nitrogen-containing heterocycles are preferably 5- or 6-membered rings. Preferred heterocycles are imidazole ring, pyrazole ring, triazole ring,
Tetrazole ring, oxazole ring, thiazole ring, selenazole ring, tellurazole ring, oxadiazole ring, thiadiazole ring, pyridine ring, pyrimidine ring and benzimidazole ring, benzoxazole ring, benzothiazole ring in which these rings are condensed with benzene ring Is preferred. Another preferred example includes azaindenes such as 1,3,3a, 7-tetrazaindene.

L represents a divalent group. Examples of L include an optionally substituted alkylene group, an optionally substituted arylene group, and an optionally substituted heterocycle and a divalent group in which an arylene group is bonded. Ether bond (-O-), thioether bond (-S-), urethane bond (-NRCOO-), urea bond (-NRCON)
R-), ester bond (-COO-), amide bond (-
-CONR-), sulfonamide linkage _(-SO 2 NR
-), A thiourea bond (-NRCSNR-), a carbonic acid ester bond (-OCOO-) and other divalent groups may be combined.

N represents an integer of 0 to 2, and when n = 0, Q
Represents that the boron atom is directly bonded to the heterocycle formed by.

M ¹ represents a hydrogen atom or a cation such as an ammonium ion or a metal ion, and a hydrogen atom is preferable. Examples of ammonium ions include NH ₄ ⁺ , H
Examples thereof include N (C ₂ H ₅ ) ₃ ⁺ , N (C ₂ H ₅ ) ₄ ^{+ and the} like. As metal ions, Na ⁺ , K ⁺ , Ag ⁺ , L
Examples thereof include i ⁺ , Ca ⁺⁺ , Zn ^{++, and the} like.

R ¹ and R ² represent a hydrogen atom, an alkyl group which may be substituted, or a cation such as an ammonium ion or a metal ion, and preferred as R ¹ and R ² are a hydrogen atom, an ammonium ion and a metal. It is a cation such as an ion. The alkyl group preferably has 5 or less carbon atoms,
Examples thereof include a methyl group, an ethyl group, a propyl group, and a methoxyethyl group, and R ¹ and R ² may be bonded to each other to be a 1,2-ethylene group, a 1,3-propylene group, or the like. Examples of ammonium ions and metal ions are the same as those described for M ¹ .

A heterocycle containing Q or 2 corresponding to L
The valent group may have a substituent, and examples of these substituents include those shown below. When these substituents have carbon, those having 10 or less carbon atoms are preferable.

Hydrogen atom, nitro group, nitroso group, cyano group, carboxy group, sulfo group, mercapto group, hydroxy group, halogen atom (eg, fluorine atom, chlorine atom,
Bromine atom, iodine atom, etc.), alkyl group, aralkyl group (optionally substituted alkyl group, aralkyl group, for example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl) Group, aminomethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, n-
(Propyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-undecyl group, etc.)

Alkenyl group (Alkenyl group which may be substituted, such as vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexene-
1-yl group etc.)

Alkynyl group (alkynyl group which may be substituted, for example, ethynyl group, 1-provinyl group, 2-ethoxycarbonylethynyl group, etc.)

Aryl group (aryl group which may be substituted, for example, phenyl group, naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group , 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc.)

Heterocyclic group (heterocyclic group which may be substituted, for example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 5-nitro-2-pyridyl group, 3-pyridyl group,
3,5-Dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazoline-2- (Ile group, morpholino group, etc.)

Acyl group (acyl group which may be substituted, for example, acetyl group, propionyl group, iso-butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3-acetylamino -4-Methoxybenzoyl group, 4-methylbenzoyl group, etc.)

Sulfonyl group (a sulfonyl group which may be substituted, for example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group,
(Benzenesulfonyl group, 4-toluenesulfonyl group, etc.)

Amino group (optionally substituted amino group, for example, amino group, methylamino group, dimethylamino group,
(Ethylamino group, ethyl-3-carboxypropylamino group, ethyl-2-sulfoethylamino group, phenylamino group, methylphenylamino group, methyloctylamino group, etc.)

Alkoxy group (alkoxy group which may be substituted, for example, methoxy group, ethoxy group, n-propyloxy group, cyclohexylmethoxy group, etc.)

Aryloxy group, heteroaryloxy group (optionally substituted aryloxy group, heteroaryl group)
Ruoxy group, for example, phenoxy group, naphthyloxy group, 4-acetylaminophenoxy group, pyrimidine-2
-Yloxy group, 2-pyridyloxy group, etc.)

Alkylthio group (optionally substituted alkylthio group, for example, methylthio group, ethylthio group, n-
Butylthio group, n-octylthio group, t-octylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-hydroxyethylthio group, etc.)

Arylthio group, heteroarylthio group (optionally substituted arylthio group, heteroarylthio group, for example, phenylthio group, 4-chlorophenylthio group, 2-n-butoxy-5-t-octylphenylthio group, 4-nitrophenylthio group, 2-nitrophenylthio group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-yl group, etc.)

Ammonio group (ammonio group which may be substituted, for example, ammonio group, trimethylammonio group, phenyldimethylammonio group, dimethylbenzylammonio group, etc.)

Carbamoyl group (optionally substituted carbamoyl group, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, cyclohexylcarbamoyl group, etc.)

Sulfamoyl group (sulfamoyl group which may be substituted, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, bis- (2
-Methoxyethyl) sulfamoyl group, di-n-butylsulfamoyl group, etc.)

Acylamino group (acylamino group which may be substituted, for example, acetylamino group, 2-carboxybenzoylamino group, 3-nitrobenzoylamino group,
3-diethylaminopropanoylamino group, acryloylamino group, etc.)

Acyloxy group (acyloxy group which may be substituted, for example, acetoxy group, benzoyloxy group, 2-butenoyloxy group, 2-methylpropanoyloxy group, etc.)

Sulfonylamino group (optionally substituted sulfonylamino group, for example, methanesulfonylamino group, benzenesulfonylamino group, 2-methoxy-5-
n-methylbenzenesulfonylamino group, etc.)

Alkoxycarbonylamino group (alkoxycarbonylamino group which may be substituted, for example, methoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group,
Benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.)

Aryloxycarbonylamino group (aryloxycarbonylamino group which may be substituted, for example, phenoxycarbonylamino group, 2,4-nitrophenoxycarbonyl group, etc.)

Alkoxycarbonyloxy group (alkoxycarbonyloxy group which may be substituted, for example, methoxycarbonyloxy group, t-butoxycarbonyloxy group, 2-benzenesulfonylethoxycarbonyloxy group, benzylcarbonyloxy group, etc.)

Aryloxycarbonyloxy group (optionally substituted aryloxycarbonyloxy group, for example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group, 4-t-butoxycarbonylamino group Phenoxycarbonyloxy group, etc.)

Aminocarbonylamino group (optionally substituted aminocarbonylamino group, for example, methylaminocarbonylamino group, morpholinocarbonylamino group,
N-ethyl-N-phenylaminocarbonylamino group,
4-methanesulfonylaminocarbonylamino group etc.)

[0048]

Aminocarbonyloxy group (optionally substituted aminocarbonyloxy group, for example, dimethylaminocarbonyloxy group, pyrrolidinocarbonyloxy group, 4-dipropylaminophenylaminocarbonyloxy group, etc.)

Aminosulfonylamino group (optionally substituted aminosulfonylamino group, for example, diethylaminosulfonylamino group, di-n-butylaminosulfonylamino group, phenylaminosulfonylamino group, etc.)

Sulfonyloxy group (optionally substituted sulfonyloxy group, for example, phenylsulfonyloxy group, methanesulfonyloxy group, chloromethanesulfonyloxy group, 4-chlorophenylsulfonyloxy group, etc.)

Alkoxy or aryloxycarbonyl group (optionally substituted alkoxy or aryloxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, 2-methoxyethoxycarbonyl group, etc.) Although the compound represented by the general formula (1) is specifically shown, the present invention is not limited to these specific examples.

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

(Synthesis Example of Exemplified Compound 1) 0.72 g (5 mmol) of 3-aminophenylboronic acid is dissolved in an aqueous solution of 0.2 g (5 mmol) of sodium hydroxide and 3 ml of water and cooled with ice. When the liquid temperature is 5 ° C or lower, thiophosgene
Add 38 ml (5 mmol) and stir. After 10 minutes, the precipitated yellow substance is taken out. The yellow substance taken out is added to an aqueous solution of 1.3 g (20 mmol) of sodium azide in 5 ml of water, and the mixture is refluxed for 5 hours. After cooling, concentrated sulfuric acid was added to the filtrate from which insoluble substances were removed by filtration, and a white precipitate was formed when the solution was acidified. Therefore, the precipitate was taken out by filtration, and 3- (5-mercaptotetrazol-1-yl) was obtained.
0.53 g of phenylboronic acid was obtained. Recrystallization is carried out with a mixed solvent of ethanol / water to give 0.14 g of colorless needle crystals.
Obtained. Melting point (mp)> 270 ° C., negative ion FAB-MS
(Matrix: glycerin) m / e 193 (M + Gl
y-2H ₂ O)

Other exemplified compounds can be similarly synthesized. The compound represented by the general formula (1) is contained in the fixing agent. When it is contained in the fixing solution as a working solution, its content is preferably 1 × 10 ^{−5 to} 1 g / liter, more preferably 5 × 10 ^{−5 to} 5 × 10 ⁻² g / liter.
As a method of adding to the fixing agent or the fixing solution, an ordinary adding method can be applied.

The developer used in the processing method of the present invention preferably contains the compound represented by the general formula (2). Furthermore, it is preferable that hydroquinones are not contained.

[0066]

Embedded image

In the formula, R ³ and R ⁴ represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group and an alkylthio group, respectively, and X represents R ³ , Two vinyl carbon atoms substituted by R ⁴ and a carbonyl carbon atom together form a 5- or 6-membered ring. Hereinafter, the general formula (2) will be described in detail. In the formula, R ³ and R ⁴ each have a hydroxy group, an amino group (as a substituent, an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group, etc., as a substituent). ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), It represents an alkoxycarbonylamino group (such as a methoxycarbonylamino group), a mercapto group, and an alkylthio group (such as a methylthio group and an ethylthio group). R ³ , R
Preferred examples of ⁴ include a hydroxy group, an amino group,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group. X jointly forms a 5- to 6-membered ring with two vinyl carbon atoms substituted by R ³ and R ⁴ and a carbonyl carbon atom. The 5- or 6-membered ring may be a carbon ring alone or a heterocycle containing an oxygen atom or a nitrogen atom in addition to the carbon atom. As a specific example of the atomic group of X, -O-,

[0068]

Embedded image

-C (R ⁷ ) =, -C (= O)-, -N
(R ⁸ )-, -N =, are combined. However, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen atoms and have 1 to 10 carbon atoms.
An optionally substituted alkyl group (as the substituent, a hydroxy group, a carboxy group and a sulfo group can be mentioned), and an optionally substituted aryl group having 6 to 15 carbon atoms (the substituents are an alkyl group and a halogen). Atom, hydroxy group, carboxy group, sulfo group).
Represents a hydroxy group and a carboxy group. Furthermore, this 5-6
A saturated or unsaturated condensed ring may be formed in the member ring. As an example of this 5- or 6-membered ring, a dihydrofuranone ring,
Dihydropyrone ring, pyranone ring, cyclopentenone ring,
Cyclohexenone ring, pyrrolinone ring, pyrazolinone ring,
Examples thereof include a pyridone ring, an azacyclohexenone ring, and a uracil ring, and examples of preferred 5- or 6-membered rings include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring. be able to. Specific compounds are shown below.

[0070]

Embedded image

[0071]

[Chemical 21]

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as tablets, pills, granules, etc., which have been subjected to moisture-proof processing as required.

The powder used in the present invention refers to an aggregate of fine crystal grains. The granules in the present invention are obtained by adding a granulating step to a powder, and refer to granules having a particle size of 50 to 5000 μm. The tablet referred to in the present invention refers to a tablet obtained by compression-molding powder or granules into a given shape.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. Arbitrary means such as forming a coating layer by spraying (see JP-A-4-29136 and 4-8)
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

A preferable tablet manufacturing method is a method in which a powdery solid processing agent is granulated and then a tableting step is performed to form the tablet. Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. You can
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a pre-ketting machine can be used. The solid processing agent obtained by compression under pressure can take any shape, but from the viewpoint of productivity, handleability or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing the tablet treating agent is described in, for example, JP-A Nos.
-88025, British Patent 1,213,808, etc., and can be produced by a general method.
109043, 3-39735 and 3-397.
It can be manufactured by a general method described in the specification such as No. 39. Furthermore, powder processing agents are described, for example, in JP-A-54-13.
No. 3332, British Patent Nos. 725,892 and 729,8
No. 62 and German Patent 3,733,861, etc., it can be produced by a general method.

[0082] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g ^/ cm ³ ~2.5g ^/ cm 3 is preferably 1. 0
g / cm ³ , in terms of the strength of the solid obtained,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

When the developer is solidified, all of the alkali agent and the reducing agent are made into solid processing agents, and in the case of tablets, at least 3 tablets and most preferably 1 tablet is used. It is a preferred embodiment of the agent. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

As the package of the solid processing agent of the present invention, the material described in Japanese Patent Application No. 6-273959 can be used.

The solid processing agent used in the present invention includes, as a binder, saccharides (monosaccharides, polysaccharides in which a plurality of monosaccharides are glucosidic-bonded to each other) described in Japanese Patent Application No. 6-91987 (pages 23 to 30). Decomposition products) are preferred, and those selected from dextrins and sugar alcohols are particularly preferably used. There is little change in shape during long-term storage, troubles occur during addition, and usability is improved.

In the solid processing agent used in the present invention, it is preferable to use acylated amino acids described in Japanese Patent Application No. 5-186254 (pages 9 to 15) as lubricants.
The solid processing agent can be manufactured stably without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved.

As an explanation of the present invention, an automatic developing machine having a substantially three-tank structure having a developing tank, a fixing tank and a stabilizing tank will be described below.

FIG. 2 is a schematic view of the developing tank 1A which is a processing tank in the I-I cross section of the automatic developing machine A of FIG. Since the fixing tank has the same configuration as the developing tank 1A, hereinafter, when the processing tank is described, both the developing tank 1A and the fixing tank 1B are referred to. It should be noted that, in the figure, a conveying means for conveying the photosensitive material is omitted for easy understanding of the configuration. In this example, a case where a tablet is used as a solid processing agent will be described.

The processing tank of the present invention has a processing section for processing a photosensitive material and a processing agent kit dissolving section called a chemical mixer tank (hereinafter referred to as CM tank) which is connected to the processing section by a pump and a pipe.

The cylindrical filter is replaceably provided below the CM tank near the pipe that goes to the processing tank, and has a function of removing insoluble matter in the processing liquid, such as paper waste.

The circulation system is composed of a circulation pipe forming a liquid circulation passage, a circulation pump, a processing tank and the like. The other end of the circulation pipe communicating with the discharge side of the circulation pump penetrates the lower wall of the CM tank and communicates with the CM tank. With such a configuration, when the circulation pump operates, the processing liquid is sucked from the CM tank and discharged to the processing unit. The replenishment amount can be adjusted by the discharge amount of the processing liquid from the circulation pump. The preferred replenishment rate is 300 ml /
m ² or less, preferably 250 ml / m ² or less.

The rod-shaped heater is arranged so as to be immersed in the CM tank. This heater is for heating the CM tank to facilitate dissolution of the tablets.

The processing amount information detecting means 8 is provided at the entrance of the developing machine and is used for detecting the processing amount of the photosensitive material to be processed. The processing amount information detecting means 8 includes a plurality of detecting members arranged in the left-right direction, and functions as an element for detecting the width of the photosensitive material and counting the detected time. Since the conveying speed of the photosensitive material is mechanically set in advance, the processing area of the photosensitive material can be calculated from the width information and the time information. The processing amount information detecting means may be any means that can detect the width and the transport time of the photosensitive material, such as an infrared sensor, a microswitch, and an ultrasonic sensor.

Further, the information to be detected is not limited to the above in the above description, but is processed.
The value may be a value proportional to the processed amount of the photosensitive material that has been processed or is being processed, and may be the concentration of the processing solution contained in the processing tank or a change in the concentration. Further, it is not necessary to provide the processing amount information detecting means 8 for each processing tank, developing tank, fixing tank, and water washing tank, and it is preferable to provide one for each automatic developing machine.

The treating agent supplying means is the filtering means 14 described later.
And a pushing member configured to extrude one or a plurality of tablets. The processing agent supply unit is controlled by a processing agent supply control unit 9 described later, and pushes out the waiting tablet with an extruding member in conjunction with a supply signal issued from the processing agent supply control unit 9 to convert the tablet into a CM. It is supplied to the filtration section in the tank. In the present invention, the solid processing agent is supplied to the filtration unit in the solid processing agent receiving unit. However, the solid processing agent may be supplied anywhere as long as it is in the CM tank. It is necessary that the solid processing agent can be dissolved in such a manner that the components corresponding to the processing amount information of the photosensitive material are reliably supplied, and that the processing characteristics of the processing liquid in the processing tank 1 are kept constant.

The filtering means is immersed in the treatment liquid in the CM tank, and is insoluble in the tablets supplied by the treatment agent kit supply unit, for example, insoluble components mixed in the tablets,
It removes things that cause scratches on the finished image and insufficient processing of the attached parts, such as clumps of tablets resulting from the disintegration of tablets, when attached to not only tablets but also photosensitive materials derived from solid processing agents. is there. This filtering means is processed with resin. It is not essential that the filtration means be provided in the CM tank, so that the tablets supplied by the processing agent kit supply unit are not mixed into the photosensitive material transport path shown in FIG. 1 or the processing liquid in the processing tank. It is good to do.

The processing agent supply control means controls the processing agent supply means, and processing amount information (processing area in this embodiment) of the photosensitive material detected by the processing amount information detecting means.
When the value reaches a predetermined constant value, a processing agent supply signal is issued to the processing agent supply means. The treatment agent supply control means may control the treatment agent supply means so as to supply a necessary treatment agent amount to the CM tank according to the treatment amount information.

Next, the operation of the present invention will be described with reference to FIG. Processing amount information of the exposed photosensitive material is detected by the processing amount information detecting means 8 at the entrance of the automatic developing machine A.
When the cumulative area of the photosensitive material to be processed reaches a predetermined area according to the processing amount information detected by the processing amount information detecting unit 8, the processing agent supply unit 9 controls the processing agent supply unit 9.
Issue a supply signal. Upon receiving the supply signal, the processing agent supply unit 9 pushes out the tablets of the cartridge 15 by the pushing member 10 and supplies the tablets to the filtering unit 14 in the CM tank 11. The supplied tablets are dissolved by the processing liquid in the CM tank 11, but are supplied from the CM tank to the circulation pump 5 to the processing tank by the circulation means. On the other hand, the detected photosensitive material is in the developing tank 1
A, the fixing tank 1B, and the washing tank are sequentially conveyed by roller conveying means (see automatic developing machine A in FIG. 1). The developing tank 1A and the fixing tank 1B, which are processing tanks, respectively, may be provided with a processing agent supply means 9 and may simultaneously supply them. Further, a stirring blade may be inserted into the filtering means to dissolve the tablets.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method.

Examples of silver halide emulsions that are preferably used include internal high iodine type monodisperse grains. The crystal habit is cubic, tetrahedral, octahedral and intermediate (11
The 1) plane and the (100) plane may be arbitrarily mixed.

The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. A preferred embodiment of the emulsion is a core / shell type monodisperse emulsion having a two-layer structure comprising a low iodine shell layer on a high iodine core portion. The silver iodide content of the high iodine part is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Another silver halide emulsion preferably used in the present invention is a tabular grain having an average aspect ratio of more than 1. The advantages of such tabular grains are that spectral sensitization efficiency is improved, image graininess and sharpness are improved.

Still another preferred silver halide emulsion used in the present invention is silver chlorobromide or silver chloride having a silver chloride content of 50% or more.

The above-mentioned emulsion is either a surface latent image type emulsion forming a latent image on the grain surface, an internal latent image type emulsion forming a latent image inside the grain, or a type emulsion forming 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, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron 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 noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or an aggregating polymer agent exemplified by G3 and G8 described in JP-A-63-158644 may be used. The method used is a particularly preferred desalting method. The chemical ripening method of the emulsion used in the light-sensitive material of the present invention is preferably gold sensitization, sulfur sensitization, reduction sensitization, increase with a chalcogen compound, or a combination thereof.

The emulsion of the light-sensitive material used in the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. A hydrazine compound can also be added, and a compound of Japanese Patent Application No. 5-134743 is preferable, and particularly a compound of the general formula (5) and a compound of the general formula (7) or (8) as a nucleation accelerator is preferable. 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 No. 17
No. 643 (December 1978); 18716 (1
No. 997) and the same No. 308119 (1989
(December, 2000). The types of compounds and the locations described in these three research disclosures 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 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 III Hardener 26 X 651 Left 1004-5 X Surfactant Agents 26-27 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 003~4 IX support 28 XVII 1009 XVII

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643-2.
8 and RD-308119, page 1009.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge or ultraviolet irradiation in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

Emulsion layers may be present on both sides of the support,
Only one side may be used. In the case of both sides, both sides may have the same performance or different performances.

In the present invention, the processing time of the silver halide photographic light-sensitive material is preferably dry to dry 90 seconds or less, more preferably 45 seconds or less, and further preferably 30 seconds or less. The preferred replenishment rate is 350 ml / m ^2.
Hereafter, it is more preferably 250 ml / m ² or less.

[0111]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 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. A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-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 potassium bromide 841 g water 2825 ml D1 1.75N potassium bromide aqueous solution The following silver potential control amount at 42 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828.
The solution B1 was added to the solution A1 by using the mixing stirrer shown in
Then, 464.3 ml of each of Solution C1 and Solution C1 were added by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of the solution B1 and the solution C1, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B1 and solution C1 were added by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 42 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mV each using the solution D1. 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 diameter ( It was confirmed with an electron microscope that the circle diameter conversion) was 0.595 μm.
The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%. <Preparation of Em-1> Tabular silver halide emulsion Em-1 was prepared using seed emulsion-1 and the following four solutions. A2 ossein gelatin 34.03g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25ml Seed emulsion-1 1.218mol equivalent Water to make 3150ml B2 Potassium bromide 1734g Water to 3644ml Finishing C2 Silver nitrate 2478 g Finishing to 4165 ml with water D2 Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) Equivalent to 0.080 mol * 0.06 mol potassium iodide To 6.64 liters of a 5.0% by weight gelatin aqueous solution containing 1 mol., 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 6.0.

Solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of solution B2, a part of solution C2 and half of 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 remaining whole amount of the solution D2 are added over 15 minutes, and finally, Solution B2 and solution C2 with the remaining total amount of 33
Added over minutes. During this time, the pH was 5.8 and pAg
Kept 8.8 at all times. Here, the solution B2 and the solution C2
The addition rate was varied as a function of time to match the critical growth rate.

Further, the above solution D2 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol% equivalent.

After the addition was completed, this emulsion was cooled to 40 ° C., and 1800 ml of a 13.8% (weight) aqueous solution of modified gelatin modified with phenylcarbamoyl groups (substitution rate 90%) was added as an aggregating polymer agent, and the mixture was added for 3 minutes. It was stirred. Thereafter, a 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.
After stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 4
9.0 liters of distilled water at 0 ° C. was added, the supernatant was drained after stirring and standing, and 11.25 liters of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, a gelatin aqueous solution and a 10% (by weight) aqueous solution of sodium carbonate are added, and p
H was adjusted to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.8 at 40 ° C.
0, pAg was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio of about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average distance between twin planes is 0.020 μm, and 97% (number) of all tabular silver halide grains have a ratio of twin plane distance to thickness of 5 or more. 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 solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and thiosulfuric acid were added. Add a mixed aqueous solution of sodium and a dispersion of triphenylphosphine selenide,
After a further 60 minutes, a silver iodide fine grain emulsion was added and ripening was effected for a total of 2 hours. After completion of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above-mentioned additive and its addition amount (AgX1
(Per mole) is shown below.

5,5′-Dichloro-9-ethyl-3,3′-di- (sulfopropyl) -oxacarbaocyanine 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 Iodine Silver halide 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.
Prepared by a method according to the method described in No. 37. That is, it was obtained by adding a predetermined amount of the spectral sensitizing dye to water whose temperature had been adjusted to 27 ° C. in advance and stirring the mixture with a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 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., stirred and completely dissolved. On the other hand, 3.8Kg of photographic gelatin
Was dissolved in pure water, and 93 g of a 25 wt% sodium dodecylbenzenesulfonate 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. Thereafter, ethyl acetate was removed while stirring under reduced pressure immediately until the residual concentration of ethyl acetate became 0.3 wt% or less.
Thereafter, the dispersion was diluted with pure water to finish up to 80 kg.
A part of the dispersion thus obtained was fractionated and used in the above experiment.

The average iodine content of the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) by the addition of the above silver iodide fine particles 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 coating solution for the protective layer was prepared.

Next, for X-rays colored blue with a density of 0.15
Polyethylene terephthalate film base (with thickness
175 μm) on both sides of which the following transverse light-shielding layer was previously applied.
On both sides of the support, protect the emulsion layer coating solution from above from the bottom.
Simultaneous multi-layer coating of layer coating solution to the prescribed coating amount below
Cloth and dry. First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m² Gelatin 0.2g / m² Sodium dodecylbenzene sulfonate 5mg / m² Compound (I) 5 mg / m² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m² Colloidal silica (average particle size 0.014 μm) 10 mg / m²  Second layer (emulsion layer) Each of the emulsions obtained above has the following various additions.
Compound (G) with additives 0.5 mg / m² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m² t-butyl-catechol 130 mg / m² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m² Styrene-maleic anhydride copolymer 80 mg / m² Sodium polystyrene sulfonate 80mg / m² Trimethylol propane 350mg / m² Diethylene glycol 50 mg / m² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m² 1,3-Dihydroxybenzene-4-sulfonic acid ammonium salt 500 mg / m² 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 5 mg / m² Compound (H) 0.5 mg / m² n-C₄H₉OCH₂CH (OH) CH₂N (CH₂COOH)₂ 350 mg / m² Compound (M) 5 mg / m² Compound (N) 5 mg / m² Colloidal silica 0.5g / m² Latex (L) 0.2 g / m² Dextrin (average molecular weight 1000) 0.2 g / m²  However, as gelatin, 1.0 g / m²To be
It was adjusted. Third layer (protective layer) Gelatin 0.8 g / m² Matting agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 50 mg / m² Formaldehyde 20mg / m² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m² Bis-vinylsulfonyl methyl ether 36mg / m² Latex (L) 0.2 g / m² Polyacrylamide (average molecular weight 10,000) 0.1 g / m² Sodium polyacrylate 30mg / m² Polysiloxane (SI) 20mg / m² Compound (I) 12 mg / m² Compound (J) 2 mg / m² Compound (S-1) 7 mg / m² Compound (K) 15 mg / m² Compound (O) 50 mg / m² Compound (S-2) 5 mg / m² C₉F₁₉-O- (CH₂CH₂O)₁₁-H 3 mg / m² C₈F₁₇SO₂N (C₃H₇) [(CH₂CH₂O)_FifteenH] 2 mg / m² C₈F₁₇SO₂N (C₃H₇) [(CH₂CH₂O)₄-(CH₂)₄SO ₃ Na] 1 mg / m²  The amount of the material is for one side, and the amount of silver applied is
1.6 g / m²I adjusted it to be.

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

When a liquid agent is used, the automatic processor is SRX-5.
03 (manufactured by Konica Corp.) and the solid processing agent was used, the above-mentioned automatic processor A was used. The amount of replenishment was the amount described in Table 1.

[0129]

Developer [Developer] Potassium carbonate 40 g Compound of general formula (2) Amount shown in Table 1 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10 g Diethylenetriamine pentaacetic acid-5Na (DTPA) ) 1 g 5-methylbenzotriazole 0.1 g 1-phenyl-5-mercaptotetrazole 0.03 g 2-mercaptohypoxanthine 0.05 g sodium sulfite 30.00 g potassium sulfite 25 g KOH 2 g glutaraldehyde 5 g diethylene glycol 50 g N-acetyl-D, L-penicillamine 0.1 g These were dissolved in 300 ml of water, and finally 400 m with pure water.
finished to 1. This concentrate was diluted with water to 1 liter to prepare a replenisher. The pH of this replenisher was 10.60. This is designated as Liquid I. A liquid II is prepared by using hydroquinone in the amount shown in Table 1 in place of the general formula (2).

Fixing Solution [Fixing Agent] Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g Glacial acetic acid 17.3 g Sodium acetate 12.7 g Tartaric acid 2. 0 g Aluminum sulphate 3.0 g Compound of general formula (1) Amount described in Table 1 These are dissolved in 400 ml of water and finally 500 m with pure water.
finished to 1. This concentrate was diluted with water to 1 liter to prepare a replenisher. The pH of this replenisher was 4.50.

Tablets for development replenishment were prepared according to the following procedures (A) and (B). Operation (A) The compound of the general formula (2) is pulverized in a commercially available bandam mill to an average particle size of 10 μm. 3000 g of sodium sulfite and 2 parts of potassium sulfite were added to the fine powder.
000 g and Dimezone S1000 g were added and mixed in a mill for 30 minutes, and then in a commercially available stirring granulator at room temperature for about 10 minutes,
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material. 100 g of polyethylene glycol 6000 was added to the thus-prepared granules for 2 hours.
After uniformly mixing for 10 minutes in a room controlled at 5 ° C. and 40% RH or less, the resulting mixture was mixed with a tabletting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compressing tableting was carried out with the filling amount per tablet being 3.84 g to prepare 2,500 development-supplementing tablet A agents.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 3 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, N-acetyl-D, L-.
Penicillamine, glutaraldehyde bisulfite Na 50
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture thus obtained was compressed into tablets with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.73 g, and 2,500 developing replenishers were replenished. Tablet B formulation was prepared.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
Granulate with l. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was tough press collect 1 manufactured by Kikusui Seisakusho KK
Using a tableting machine modified from 527HU, the filling amount per tablet was 6.202 g, and compression tableting was performed to prepare 2500 fixing replenishing tablet C agents.

Operation (D) 1000 g of boric acid, 150 parts of aluminum sulfate and 18 hydrates
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g, the compound of the general formula (1) is used in the amount described in Table 1 (A)
Pulverize and granulate as in The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. In this manner, 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes, and then the obtained mixture was used per tablet by a tablet machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. Was compressed to 4.562 g to prepare 1250 fixing replenishment tablets D agent. Developer starter Glacial acetic acid 2.98 g KBr 4.0 g Pure water was added to the above compound to make 1 liter.

2 parts of this starter per liter of replenisher solution
0 ml was added. The pH of the developer to which the starter was added was 10.45 for each of the liquid agents I and II and the tablet formulation. The following evaluations were carried out using the treating agent thus obtained.

Evaluation Method of Residual Solution The unexposed sample subjected to the development treatment was treated with 2.6 × of sodium sulfide.
A 10 ^-3 mol / l aqueous solution was dropped as a residual silver evaluation liquid,
After standing for 3 minutes, the solution was wiped well and dried, and then the concentration of the produced silver sulfide was measured with a photographic densitometer PDA-65 (manufactured by Konica Corp.) using an interference filter of spectral filter 436 ± 10 nm. In the table, the difference in blue light transmission density between the portion below the residual silver evaluation droplet and the portion not dropped is noted. That is, the larger this difference is, the higher the residual silver concentration in the processed film is. If this value is 0.04 or more, discoloration occurs during long-term storage. Evaluation of residual color property After developing the unexposed sample, it was visually evaluated.

A: No residual color contamination B: There is a residual color, but practical use is possible.

[0139]

[Table 1]

[0140]

According to the present invention, it is possible to provide a processing method and a fixing agent for a silver halide photographic light-sensitive material which has improved residual silver and residual color and good environmental suitability.

[Brief description of drawings]

FIG. 1 is a schematic vertical sectional view showing an example of an automatic processor which is preferably used in a processing method of the present invention.

FIG. 2 is a schematic vertical cross-sectional view showing an example of a processing tank preferably used in the processing method of the present invention, for example, a developing tank.

Claims (4)

[Claims] 1. A fixing agent containing at least one compound represented by the following general formula (1). Embedded image In the formula, Q represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle with carbon atoms and nitrogen atoms. L represents a divalent group, and n represents an integer of 0-2. M ¹ represents a hydrogen atom, an ammonium ion or a metal ion. R ¹ ,
R ² represents a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ¹ and R ² may be bonded to each other to form a 5- or 6-membered ring. Good. Each of these groups and rings may have a substituent. 2. The fixing agent according to claim 1, which is a solid processing agent. 3. A silver halide photographic light-sensitive material, which comprises treating a silver halide photographic light-sensitive material with a developing solution and then processing it with a fixing solution containing at least one compound represented by the following general formula (1). Material processing method. Embedded image In the formula, Q represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle with carbon atoms and nitrogen atoms. L represents a divalent group, and n represents an integer of 0-2. M ¹ represents a hydrogen atom, an ammonium ion or a metal ion. R ¹ ,
R ² represents a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ¹ and R ² may be bonded to each other to form a 5- or 6-membered ring. Good. Each of these groups and rings may have a substituent. 4. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the developing solution contains a compound represented by the following general formula (2). Embedded image In the formula, R ³ and R ⁴ are each a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, an alkylthio group, and X represents R ³ ,
It represents an atomic group necessary for forming a 5- or 6-membered ring in cooperation with two vinyl carbon atoms substituted by R ⁴ and a carbonyl carbon atom. Each of these groups and rings may have a substituent.