JP2000155397A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for processing the silver halide photographic sensitive material free from occurrence of stains on a drying roller and small in occurrence of residual dye stains and high in disinfection effect and free of occurrence of fur and deposition of compounds and the like in a rinsing bath by adopting a multistage countercurrent rinsing system in the rinsing bath of a automatic developing machine and incorporating a specified compound in a fixing solution and a stabilizing solution. SOLUTION: The rinsing bath of the automatic developing machine adopts the multistage coutercurrent system and the fixing solution and the stabilizing solution contains the compound represented by the formula in which each of R1-R4 is an H atom or a 1-3C alkyl group; R5 is a hydroxyl or amino or 1-3C alkyl group; each of R6 and R7 is an H atom or 1-5C alkyl or <=18C acyl or -COOM0 group; M0 is an H atom or 1-4C alkyl group or the like; each of R1 and R2, and R6 and R7 is not an H atom at the same time; M1 is an alkali metal atom or an ammonium group; and k1 is 0, 1, or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic material, and more particularly to a method for processing a black-and-white silver halide photographic material.

[0002]

2. Description of the Related Art A black-and-white silver halide photographic light-sensitive material is subjected to development, fixing, washing with water or stabilization after exposure to obtain an image. At that time, the fixing is usually performed with a fixing solution containing thiosulfate as a fixing agent. Further, a water-soluble aluminum compound is added to a fixing solution to harden the silver halide photographic light-sensitive material in the fixing step, to reduce the load in the subsequent stabilization and washing steps and the drying step, and to improve transportability. This is also well known and widely practiced. Generally, it is processed by an automatic developing machine having a developing section, a fixing section, a washing section or a stabilizing bath section and a drying section.

Conventionally, in a processing method of a silver halide photographic light-sensitive material, a multi-stage countercurrent system using a rinsing liquid can reduce washing water. However, when the washing water is reduced, silver is liable to precipitate in the washing tank. Therefore, a silver sludge inhibitor has been conventionally added. Conventionally, silver sludge inhibitors which have been studied cannot be added because they are precipitated together with silver and deteriorate. Also, from the start of running to the time when the equilibrium state is reached, the mixing ratio with the fixing solution containing the developing solution changes, so that silver tends to precipitate, and furthermore, when a concentration kit is used, the preservability deteriorates. Therefore, there is a problem that the disinfectant is decomposed and deteriorates with time to lose the disinfecting effect.

In addition, problems such as contamination of the drying roller have occurred. Furthermore, there is a serious problem that the obtained image of the silver halide photographic light-sensitive material has a residual color, and scales and precipitation of compounds occur in a washing tank, and a solution has been strongly demanded.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a dry roller free from dirt and having good residual color.
It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material having a high sterilizing effect and free from deposits of scale and compounds in a washing tank.

[0006]

The above object of the present invention is achieved by the following constitution.

(1) A silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support is prepared by using an automatic developing machine having a developing tank, a fixing tank and at least two washing tanks. In the processing method of a silver halide photographic light-sensitive material which is subjected to development, fixing, washing or stabilizing processing, the washing tank of the automatic developing machine is a multi-stage countercurrent system, and the fixing solution and the stabilizing solution are represented by the following general formula (1) A method for processing a silver halide photographic light-sensitive material, comprising a compound represented by the formula:

[0008]

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[In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ₁ and R ₂ are not simultaneously hydrogen atoms. R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₅ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₆ and R ₇
Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 or less carbon atoms, or a -COOM ⁰ group, respectively. Here, M ⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom or an aryl group, but R ₆ and R ₇ are not simultaneously hydrogen atoms. M ¹ represents an alkali metal atom or an ammonium group. k ₁ is 0, 1 or 2. (2) The method for processing a silver halide photographic material as described in (1) above, wherein the amount of silver contained in the fixing solution is 10 g / L or more.

(3) A silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support is prepared by using an automatic developing machine having a developing tank, a fixing tank and at least two washing tanks. Developing, fixing, washing or stabilizing the silver halide photographic light-sensitive material, the washing tank of the automatic developing machine is a multi-stage countercurrent system, and the developer contains substantially a dihydroxybenzene compound. Without containing a compound represented by the following general formula (A),
A method for processing a silver halide photographic material, wherein the developer and the stabilizing solution contain the compound represented by the above general formula (1).

[0011]

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[Wherein, R ₈ and R ₉ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group;
These may have a substituent and may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₃ and M ₄ each represent a hydrogen atom or an alkali metal. (4) The above-mentioned 1 to 3, wherein the stabilizing solution is used after being diluted 1.5 to 30 times when used.
A method for processing a silver halide photographic material according to any one of the above.

(5) The silver halide photographic light-sensitive material according to any one of the above items 1 to 4, wherein a silver halide photographic light-sensitive material containing a compound represented by the following general formula [H] is processed. Material treatment method.

[0014]

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Wherein A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom;
Is-(CO) _n -group, sulfonyl group, sulfoxy group,-
A P (ＯO) R ₂₂ — group or an iminomethylene group;
n represents an integer of 1 or 2; A ₁ and A _{2 each} represent a hydrogen atom or one of a hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group; Represents an atom, each substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, and amino group. (6) The method for processing a silver halide photographic material as described in any one of (1) to (5) above, wherein at least one of the developer and the fixing agent is a solid processing agent.

Hereinafter, the present invention will be described in detail. In the compound represented by the general formula (1) of the present invention, the alkyl group having 1 to 3 carbon atoms represented by R ₁ or R ₂ represents a methyl group, an ethyl group or a propyl group. Preferably, there is. The alkyl group having 1 to 3 carbon atoms represented by R ₃ and R ₄ represents a methyl group, an ethyl group or a propyl group.
The hydroxyl group represented by R ₅ also includes a metal salt, and the alkyl group having 1 to 3 carbon atoms represents a methyl group, an ethyl group or a propyl group. The alkyl group having 1 to 5 carbon atoms represented by R ₆ or R ₇ represents a methyl group, an ethyl group or a propyl group, and the acyl group having 18 or less carbon atoms is preferably an acyl group having 2 to 18 carbon atoms. , An acetyl group, a propionyl group and the like are more preferred.

Specific examples of the compound represented by the formula (1) are shown below.

[0018]

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In the compound represented by the general formula (A) of the present invention, a compound represented by the following general formula (Aa) wherein R ₈ and R ₉ are bonded to each other to form a ring is preferred.

[0020]

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In the formula, R ₁₀ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group, or a sulfonamide group, and Y ₁ represents O or S is represented, and Y ₂ represents O, S or NR ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group or aryl group. M ₃ and M ₄ each represent a hydrogen atom or an alkali metal.

The alkyl group in the general formula (A) or the general formula (Aa) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group or An amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Examples of the group which can be substituted include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or (Aa) are shown below, but are not limited thereto.

[0024]

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[0025]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by known synthesis methods.

In combination with the above developing agents of ascorbic acid or erythorbic acid, 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (eg, o-aminophenol, p-aminophenol, N
It is preferable to use an auxiliary developer such as -methyl-o-aminophenol, N-methyl-p-aminophenol, and 2,4-diaminophenol. In this case, 3-
The developing agents such as pyrazolidones and aminophenols are preferably used in an amount of 0.001 to 1.4 mol per liter of the developing solution. The amount of ascorbic acid or erythorbic acid used is about 0.05 to 1 mol per liter of developer.

In the present invention, dihydroxybenzenes such as hydroquinone and methylhydroquinone are preferably not substantially used from the viewpoint of environment and performance.

Among the compounds represented by the general formula [H] of the present invention, more preferred are the compounds represented by the following general formula [Ha].

[0030]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, chenyl group, Furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The ballast group is preferably a ballast group commonly used in immobile photographic additives such as couplers, and is relatively inert to photographic properties having 8 or more carbon atoms, for example, an alkyl group, an alkenyl group, and an alkynyl. Groups, alkoxy groups, phenyl groups, phenoxy groups, alkylphenoxy groups and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and preferably both are hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵⁾ groups (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ⁵ is alkenyl A alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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Specific examples of other preferable hydrazine derivatives are described in US Pat. No. 5,229,248, columns 4 to 60, (1) to (252).
Is mentioned.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization, the type of the inhibitor, etc., it is generally 10 ^-6 to 10 ^-1 per mol of silver halide.
Molar range, preferably from 10 ^-5 to 10 ^-2 mol. The hydrazine derivative used in the present invention is preferably added to a silver halide emulsion layer or a layer adjacent thereto.

The fixing solution and the stabilizing solution used in the method for processing a silver halide photographic light-sensitive material of the present invention contain the compound represented by the general formula (1) of the present invention. In the method for processing a silver halide photographic light-sensitive material of the present invention, the developer contains substantially no dihydroxybenzene-based compound and contains the compound represented by the general formula (A) of the present invention. And the stabilizing solution contains the compound represented by the general formula (1).
Particularly, in the method for processing a silver halide photographic light-sensitive material of the present invention, processing of a silver halide photographic light-sensitive material containing the compound represented by the general formula [H] of the present invention is preferable.

In the method for processing a silver halide photographic light-sensitive material of the present invention, development, fixing, washing or stabilizing treatment is carried out using an automatic developing machine having a developing tank, a fixing tank and at least two washing tanks. The washing tank of the automatic developing machine is of a multi-stage countercurrent type.

The compound represented by the general formula (1) of the present invention is used by adding about 0.1 to 100 g / L to a fixing solution and a stabilizing solution, preferably 0.5 to 60 g / L, and more preferably 0.5 to 60 g / L. Is 1 to 30 g / L.

As the fixing solution containing the compound represented by the general formula (1) of the present invention, a fixing solution having a pH of about 3 to 8 of a generally used composition can be employed.

The fixing agent can form thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate; and soluble stable silver complex salts. Organic sulfur compounds known as fixing agents can be used.

The fixing solution contains a water-soluble aluminum salt (aluminum chloride, aluminum sulfate, potassium alum, etc.), an aldehyde compound (glutaraldehyde or glutaraldehyde sulfite adduct) which acts as a hardener, a preservative (sulfurous acid). Salt, bisulfite, etc.), a pH buffer (acetic acid, citric acid, etc.), a pH adjuster (sulfuric acid, etc.), a chelating agent capable of softening water, and the like.

The concentration of ammonium ion in the fixing solution is 0.1.
It is preferably at most 1 mol / l, more preferably 0 to 0.05 mol / l. Further, the acetate ion concentration is preferably less than 0.33 mol / l, more preferably 0.22 mol / l or less,
Further, at 0.13 mol / L or less, the amount of acetic acid gas generated can be greatly reduced. However, it is most preferable that acetic acid ions are not substantially contained.

In the present invention, the silver halide photographic light-sensitive material is processed by an automatic developing machine having a developing section, a fixing section, a washing section or a stabilizing section and a drying section, and the replenishing amount of the fixing replenisher is adjusted. The effect is reduced to 300 ml or less per 1 m ^2, and the effect is exhibited without regret.

As the developing agent used in the developing solution, known compounds such as dihydroxybenzenes, 3-pyrazolidones, aminophenols, ascorbic acids and metal complex salts can be used. Among them, the compounds represented by the general formula (A) of the present invention can be used. A developer containing the compound to be prepared and its derivative is preferred.

An alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are preferably added to the developer. Preferably, if necessary, dissolution aids (polyethylene glycols and their esters, alkanolamines, etc.), sensitizers (polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoamers, fog Inhibitors (sodium bromide, nitrobenzimidazole, benzotriazole, thiazoles, etc.),
Chelating agents (such as ethylenediaminetetraacetic acid and polyphosphate), hardening agents (such as glutaraldehyde) and the like can be added.

The pH of the developer is about 7.5 to 10.5, preferably 8.5 to 10.4.

After the fixing process, a washing or stabilizing process is performed. The stabilizing bath contains an acid or alkali agent and a salt thereof (borate, metaborate, borax, phosphate, carbonate, hydroxide) for adjusting the film surface pH of the processed image to 3 to 8. Potassium, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid,
Malic acid, acetic acid, etc.), aldehydes (formalin, glyoxal, glutaraldehyde, etc.), chelating agents (ethylenediamine tetraacetic acid, nitrilo triacetate, polyphosphate, etc.), fungicides (phenol, 4-chlorophenol, cresol, etc.) o-phenylphenol, chlorophen, dichlorophen, formaldehyde, p-hydroxybenzoate, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-
Benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4
4'-trichloro-2'-hydroxydiphenyl ether, etc.), a color tone adjuster, and a residual color improver (such as a nitrogen-containing heterocyclic compound having a mercapto group). It is particularly preferable to add a fungicide.

In the present invention, in order to reduce the amount of waste liquid, the amount of replenishment to the fixing section is 300 per 1 m ² of the photosensitive material.
Although a sufficient effect can be obtained with an amount of 30 ml or less, the amount is more preferably 30 to 250 ml per m ^{2 of the} light-sensitive material.

[0061] Further, it is preferable that the replenishing amount of the developing unit is not more than the light-sensitive material 1 m ² per 250 ml, more preferably photosensitive material 1 m ² per 30 to 200 ml.

In the present invention, the replenishing amount refers to the replenishing amount when the same solution as the developing mother liquor and the fixing mother liquor is replenished. When the developing concentrated solution and the fixing concentrated solution are replenished with a solution diluted with water, respectively. It refers to the total amount of the concentrated solution and water, and when replenished with a solution prepared by dissolving the solid developing agent and the solid fixing agent in water, it refers to the total amount of each solid processing agent volume and water volume. For example, when the solid processing agent is directly charged into the processing tank of the automatic developing machine, the amount is the sum of the volume of the solid processing agent and the volume of replenishment water to be added separately.

The temperature of each processing section is preferably 10 to 45 ° C., and the temperature may be adjusted for each processing section.

The processing of the present invention is performed using an automatic developing machine. The total processing time (Dry t) from the insertion of the leading end of the photosensitive material into the automatic developing machine until it comes out of the drying zone is obtained.
odry) is preferably from 10 to 60 seconds, more preferably from 15 to 50 seconds. To stably process a large amount of photosensitive material of 100 m ² or more,
The development time is preferably 2 to 18 seconds. The automatic developing machine of the present invention has a developing tank, a fixing tank, and at least two or more washing tanks, and the washing tank is a multistage countercurrent system.
If this multi-stage countercurrent method is used, the photosensitive material after fixing is gradually contacted and processed in a clean direction, that is, a processing solution that is not stained with the fixing solution, so that more efficient water washing is performed.

As the automatic developing machine, a heat transfer material of 60 ° C. or more (heat roller of 60 ° C. to 130 ° C.) or 150 ° C.
The above radiating objects (tungsten, carbon, nichrome, zirconium oxide, yttrium oxide, a mixture of thorium oxide, silicon carbide, etc.) are directly heated to radiate heat, and heat energy from a resistance heating body is made of copper, stainless steel, nickel, various ceramics, etc. (Which emit infrared rays by transmitting to a radiator) and have a drying zone.

As the automatic developing machine, those employing the following methods or functions can be preferably used.

Deodorizing device: JP-A-64-37560, page 544 (2), upper left column to page 545 (3), upper left column Washing water regeneration purifying agent and device: JP-A-6-25035
No. 2, page (3) paragraph “0011” to page (8) paragraph “0”
058 ”Waste liquid treatment method: JP-A-2-64638, No. 388
(2) Bottom left column to page 391 (5) Bottom left column Rinse bath between developing bath and fixing bath: JP-A-4-313
No. 749, page (18), paragraph "0054" to page (21), paragraph "0065" Replenishing water replenishment method: JP-A-1-281446, No. 25
0 (2) lower left column to lower right column Detect dry air temperature and humidity to control drying air: JP-A-1-315745, page 496 (2), lower right column to 50th
1 (7) lower right column and JP-A-2-108051-58
8 (2) lower left column to 589 (3) lower left column Silver recovery from fixing waste solution: JP-A-6-27623, page (4), paragraph "0012" to page (7), paragraph "007"
1 ".

The replenishing amount of the silver halide in the silver halide photographic light-sensitive material subjected to the processing of the present invention is preferably silver chloride, silver chlorobromide or silver chloroiodobromide having a silver chloride content of 60 mol% or more. Good for reduction and rapid processing.

The average particle size of the silver halide grains is preferably 1.2 μm or less, particularly preferably 0.1 to 0.8 μm. Further, it is preferable that the particle size distribution is narrow, and it is preferable to use a so-called monodispersed emulsion. Further, an emulsion composed of tabular grains having a (100) plane as a main plane is preferable, and such an emulsion is disclosed in US Pat.
264,337, 5,314,798, 5,3
20, 958.
Further, in order to obtain high illuminance characteristics, iridium is doped in a range of 10 ^-9 to 10 ^-3 mol per 1 mol of silver halide, and at least one selected from rhodium, ruthenium, osmium and rhenium in order to harden the emulsion. 1
It is preferred to dope the seed in the range of 10 ^-9 to 10 ^-3 mole per mole of silver halide.

The silver halide emulsion can be subjected to known chemical sensitization such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization.

The following techniques are preferably employed for the silver halide photographic light-sensitive material to be processed in the present invention.

1) Solid dispersed fine particles of a dye:
No. 5629, page (3), paragraph "0017" to page (16), paragraph "0042" 2) Compound having an acid group: JP-A-62-237445.
No. 292 (8), lower left column, 11th line to 309 (25)
3rd line, lower right column of the page 3) Acidic polymer: JP-A-6-186659, (1)
0) page paragraph “0036” to page (17) page “006”
2) 4) Sensitizing dye Paragraph "0017" on page (3) of JP-A-5-224330
To page (13), paragraph “0040” JP-A-6-194777, page (11), paragraph “004”
2 "to page (22), paragraph" 0094 "JP-A-6-242533, page (2), paragraph" 0015 "
To page (8), paragraph “0034” JP-A-6-337492, page (3), paragraph “0012”
To page (34), paragraph “0056” JP-A-6-337494, page (4), paragraph “0013”
To page (14), paragraph "0039" 5) Supersensitizer JP-A-6-347938, page (3), paragraph "0011"
To page (16), paragraph "0066" 6) Nucleation accelerator JP-A-7-114126, page (32), paragraph "015"
8 ”to (36), paragraph“ 0169 ”7) Tetrazolium compound JP-A-6-208188, page (8), paragraph“ 0059 ”
To page (10), paragraph "0067" 8) Pyridinium compound JP-A-7-110556, page (5), paragraph "0028"
To page (29), paragraph "0068" 9) Redox compounds JP-A-4-245243, 235 (7) to 250
(22) 10) Syndiotactic polystyrene support JP-A-3-131843, pages 324 (2) to 327
(5) Page About other additives, for example, Research Disclosure No. No. 17643 (December 1978); No. 18716 (November 1979) and the same No. 3
08119 (December, 1989).

Next, the solid processing agent will be described. The solid processing agent of the present invention refers to a solid formed of two or more components constituting the processing liquid, and a single solid containing all of the processing liquid components, or a solid having two or more solid components. It may be one that can constitute a component. In the solid processing agent, at least one solid in which at least two or more compounds are formed may be used, and a single substance other than the formed solid may be used.

As a method of preparing a solid processing agent, a method of adding water, granulating and then drying to obtain granules, and a method of forming granules by adding a small amount of water, or performing granulation by adding a small amount of water, There is a method in which molding is performed directly without a drying step without the addition of a polymer. The amount of water added is preferably 0% or more and 2% or less based on the total amount of the raw materials.

A briquetting machine is an example of a system in which raw materials are directly compression-molded without granulation to form a granular solid processing agent.

As a means for granulating, there is a method using a commonly used stirring granulator or Henschel mixer.

The granulation principle of the briquetting machine is a method in which a raw material is supplied between two rotating rolls and compression granulation is performed in a concave portion on the roll surface. Briquetting machines are supplied not only vertically but also horizontally.

The purpose of briquetting is to prevent the generation of dust, reduce the volume to rationalize the transportation of packaging, reduce the surface area to control the reaction with gas or liquid, dissolve or disperse in liquid. To improve handling properties, prevent caking in a packaging container, and facilitate handling.

The Henschel mixer is a batch type stirring granulator having a cylindrical container and a shaft seal portion set at the lower part of the container. The shape and quantity of the stirring blades can be selected according to the purpose. Usually, two stages of upper and lower stirring blades are mounted and rotated at high speed. When a liquid binder is used, the peripheral speed of the stirring blade is about 5 to 10 m / s. In addition, the peripheral speed for raising the temperature by the frictional heat generated by the rotation of the stirring blade to form granules is 20 to 30 m / s or 40 m / s. By providing a jacket on the side wall of the cylindrical container and controlling the temperature of the heating medium, multiple processes such as reducing the heating time and performing cooling after granulation can be performed by one unit. .

In order to perform granulation without performing the drying step, it is necessary to previously reduce the amount of water added during granulation. The amount of water to be added is preferably such that the water content of all the materials of the treating agent is 3% or less. More preferably, the water content is 0.0
Between 1 and 2.0%, more preferably 0.05%
To 1.5% of the treating agent used in the present invention may be supplied in any form such as a powder, a paste, a granule, a tablet, a concentrate, and a use solution.
It is preferably supplied in the form of a tablet or a concentrate. When used as starting solutions, they are prepared by dissolving them in water as specified. When used as a replenisher, it may be used by mixing and dissolving it with water in advance, or may be used by directly charging it into an automatic developing machine.

The developing waste liquid can be regenerated by energizing. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer,
For example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor and the like which can be added to the developer can be added. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

As a special type of development processing, a developing agent is contained in a light-sensitive material, for example, in an emulsion layer or in an adjacent layer, and is used in an activator processing solution for processing the light-sensitive material in an alkaline aqueous solution to perform development. Is also good. Further, a light-sensitive material containing a developing agent in a light-sensitive material, for example, in an emulsion layer or in a layer adjacent thereto, may be processed with a developer. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.

The fixing starting solution may be used by diluting a commonly used concentrated liquid kit with water, or by dissolving a single or mixture of solid processing agents formed from two or more compounds in water. May be used. As for the replenisher, it is preferable to use a solid processing agent formed from two or more compounds alone or as a mixture dissolved in water.

In the treatment method of the present invention, the stabilizing solution used in the stabilizing tank preferably contains a chelating agent.

Examples of the chelating agent include ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid. , Hydroxyethyl iminodiacetic acid, 1,3-diaminopropanol tetraacetic acid, triethylenetetramine hexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, Nitrilotrimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphospho Ethane-2-carboxylic acid, 2-
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, hexametaphosphoric acid Sodium and the like; particularly preferably, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, and 2-phosphonobutane-1,2,4-
Tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1 -Diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

[0086]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) An average thickness of 70 mol% of silver chloride and the balance of silver bromide was 0.05 by a double jet method.
Silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. When mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 per mole of silver.
× 10 ^-8 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a silver / chloroiodobromide (90 mol% of silver chloride, having a core / shell type monodispersion (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. Silver iodobromide
2 mol%, the balance being silver bromide).

This emulsion was cooled to 40 ° C. and modified with a phenylcarbamoyl group as an aggregating polymer (substitution rate: 90%).
Modified gelatin 13.8% by weight aqueous solution 1800m
was added and stirred for 3 minutes. Thereafter, an aqueous solution of 56% by weight of acetic acid was added to adjust the pH of the emulsion to 4.6, and the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.

Thereafter, 9.0 L of distilled water at 40 ° C. was added, the supernatant was drained after stirring and standing, and 11.25 L of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% by weight aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 pAg at 8.06 at 40 ° C. After desalting, the EAg of this emulsion was 50 ° C.
At 190 mV.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5%. .6, adjust to EAg123mV,
After adding 1 × 10 ⁻³ mol of sodium p-toluenethiosulfonate, 350 mg of chloramine T per mol of silver was added.
0.6 mg of inorganic sulfur (S8) and 6 mg of trichloroaurate were added and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene per mol of silver was 2 × 10 ⁻³ mol, 1-phenyl-5-mercaptotetrazole was 3 × 10 ⁻⁴ mol, and potassium iodide was 300 mg.
Was added.

(Preparation of Silver Halide Emulsion B) An average thickness of 0.05 μm and an average diameter of 0.1% comprising silver chloride of 60 mol%, silver iodide of 2.5 mol% and the remainder of silver bromide were obtained by a double jet method.
5 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ RhBr ₅ (H ₂ O) was added in an amount of 2 × 10
^-8 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion had an average thickness of 0.
10 μm core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (average diameter: 0.42 μm) (silver chloride: 90 mol%,
(I.e., 0.5 mol% of silver iodobromide, the balance being silver bromide). Then, a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, JP-A-2-28001)
Desalting was carried out using Compound No. 39, page 287 (3), exemplified compound G-8). The EAg after desalting was 190 mV at 50 ° C.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and 2 × 10 ⁻⁵ mol of chloroauric acid was added.
N'-trimethyl-N'-heptafluoroselenourea was added in an amount of 3 × 10 ^-5 mol and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol, and gelatin.

On one subbing layer of a polyethylene terephthalate support, a gelatin subbing layer of the following formula 1 was coated thereon such that the amount of gelatin was 0.5 g / m ^2, and the silver halide emulsion of the formula 2 was Layer 1 was coated with a coating solution having the following formulation 3 as an intermediate protective layer so that the amount of silver was 1.5 g / m ² and the amount of gelatin was 0.5 g / m ² .
So that 3 g / m ^2, as further silver amount 1.4 g / m ² of silver halide emulsion layers 2 formulations 4 thereon, the amount of gelatin is 0.4 g / m ^2, further following formulation 5 Was applied simultaneously so that the amount of gelatin became 0.6 g / m ² . On the other side of the undercoat layer, a backing layer having the following formulation 6 was prepared so that the gelatin amount was 0.6 g / m ² .
A hydrophobic polymer layer of the following formula 7 is further formed thereon, and a backing protective layer of the following formula 8 is further formed thereon.
A sample was obtained by simultaneous multi-layer coating with the emulsion layer side so as to be 4 g / m ² .

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Solid dispersed fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound S- 1 0.4 mg / m ² Prescription 2 (Silver halide emulsion layer 1 composition) Silver halide emulsion A (silver content) 1.5 g / m ² Solid dispersed fine particles of dye a (average particle size 0.1 μ) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² hydrazine derivative (types are described in Tables 1, 2 and 3) 20 mg / m ² nucleation promoter AM-1 40 mg / m ² Redox compound RE-1 20 mg / m ² Compound e 100 mg / m ² Latex polymer f 0.5 g / m ² Hardener g 5 mg / m ² Compound S- 1 0.7mg / M ² 2-mercapto-6-hydroxypurine 5 mg / m ² Ethylenediaminetetraacetic acid 30 mg / m ² Colloidal silica (average particle size 0.05 μ) 10 mg / m ² Prescription 3 (intermediate layer composition) Gelatin 0.3 g / m ² Compound S-1 2 mg / m ² Formula 4 (Silver halide emulsion layer 2 composition) Silver halide emulsion B (silver content) 1.4 g / m ² sensitizing dye d-1 3 mg / m ² sensitizing dye d-2 3 mg / m ² hydrazine derivative (types are described in Tables 1, 2 and 3) 20 mg / m ² nucleation promoting agent AM-1 40 mg / m ² Redox compound RE-1 20 mg / m ² 2-mercapto-6 hydroxypurine 5 mg / m ² ethylenediaminetetraacetic acid 20 mg / m ² latex polymer f 0.5 g / m ² compound S-1 1.7mg / m ² formulation 5 (emulsion protective layer composition) gelatin 0.6 g / m ² dye Of the solid dispersion (average particle size 0.1μ) 40mg / m ² Compound S-1 12mg / m ² Matting agent: average particle size monodispersed silica 25 mg / m ² 1,3-vinylsulfonyl of 3.5 [mu]-2- Propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (mean particle size 0.05 μ) 10 mg / m ² Hardener j 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 mg / m ² compound S-1 5 mg / m ² latex polymer f 0.3 g / m ² colloidal silica (mean particle size 0.05 μ) 70 mg / m ² sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 7 (hydrophobic polymer Layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant h 1 mg / m ² dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener j 20 mg / m ²

[0096]

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[0097]

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[0098]

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[0099]

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<Preparation of solid developer kit (10 L of working solution)
Min)> ・ Pretreatment of the material Sodium erythorbate was added to Hosokawa Micron M
IKRO-PULVERIZER AP-B crusher,
And crushed at a mesh of 8 mm and a rotation speed of 25 Hz. In the case of the comparative example, hydroquinone (also referred to as HQ) was used instead of sodium erythorbate.

8-Mercaptoadenine was pulverized with the same pulverizer at a mesh of 8 mm and a rotation speed of 50 Hz.

[0102] KBr is crushed by the above-mentioned pulverizer at a mesh of 8 m.
and crushed at 50 Hz.

Mixing of Materials Using a commercially available V-type mixer (capacity 200 L), the following formulation was mixed for 10 minutes.

Sodium erythorbate (the above-mentioned pulverized material) 163 kg (in the case of the comparative example: hydroquinone (the above-mentioned pulverized substance) 65 kg) Dimezone S 3.5 kg 8-mercaptoadenine (the above-mentioned pulverized substance) 0.3 kg DTPA. 5H 11 kg KBr (the above pulverized material) 6.5 kg sorbitol 5 kg The compound represented by the general formula (1) (the type is described in Table 1) 50 g Sampling is performed by sampling 50 g at an arbitrary point (5 places) of the obtained mixture. As a result of the analysis, the concentration of each component was within ± 5% of the above prescribed value, and the components were sufficiently uniformly mixed.

Molding: The above mixture was subjected to a compression granulator Briquetta BS manufactured by Shinto Kogyo Co., Ltd.
Using S-IV type, pocket shape 5.0mmΦ ×
1.2mm (Depth), roller rotation speed 20rpm
m, at a feeder rotation speed of 50 rpm. The obtained plate-like molded product was crushed by a classifier, and was 2.4 to 7.0 mm.
And fine powder having a size of 2.4 mm or less (fractions having a size of 7.0 mm or more were crushed). Further, fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to the compression molding machine to be molded again. Thus, about 95 kg of granules DA was obtained.

Preparation of Raw Materials The following raw materials were prepared and pretreated.

Mixture of sodium sulfite / 1-phenyl-5-mercaptotetrazole / benzotriazole 18 g of 1-phenyl-5-mercaptotetrazole and benzotriazole 78 in 400 ml of ethyl alcohol
g was dissolved. The resulting solution was added dropwise in small amounts to 20 kg of sodium sulfite being rotated by a mixer, and the rotation was continued until the solution was sufficiently dried. The obtained mixture was sampled at 10 g points from arbitrary points (five places) and analyzed. As a result, 1-phenyl-5mercaptotetrazole and benzotriazole were sufficiently homogeneously mixed. Let the obtained mixture be M-1.

Mixing of potassium carbonate / sodium carbonate / anhydrous / lithium hydroxide / 1H ₂ O Using a commercially available V-type mixer (capacity: 200 L), 56 kg of potassium carbonate, 42 kg of sodium carbonate, lithium hydroxide / 1H ₂ O were used. 2 kg (22 kg in the case of using the comparative example HQ)
kg) for 10 minutes. Let the obtained mixture be M-2.

Packaging (10 L kit for use solution) A raw material mixture and a molded product were filled in a standing pouch in the following order and sealed with a heat sealer.

Mixture M-2 600 g (bottom layer) Mixture M-1 663.2 g (middle layer) Granules DA 399 g (top layer) This kit was finished and the pH after dissolving in 10 L was 9.8. In the case of using HQ of the comparative example, the pH was 10.70.

<Preparation of a solid fixing agent kit (100
L)> Pretreatment of Material The sodium 1-octanesulfonate was pulverized with a MIKRO-PULVERIZER AP-B pulverizer manufactured by Hosokawa Micron Corporation at a mesh of 4 mm and a rotation speed of 60 Hz.

Mixing of Materials Using a commercially available V-type mixer (capacity 200 L), the following formulation was mixed for 10 minutes.

Sodium thiosulfate 15 kg Sodium sulfite 2.2 kg Compound represented by general formula (1) Type and amount described in Table 1 1 kg of sodium 1-octanesulfonate (the above ground product) was added to the obtained mixture. And mixed for an additional 5 minutes.

Molding: The above mixture was subjected to a compression granulator Briquetta BS manufactured by Shinto Kogyo Co., Ltd.
Using S-IV type, pocket shape 5.0mmΦ × 1.
Molding was performed at 2 mm (Depth), a roller rotation speed of 30 rpm, and a feeder rotation speed of 67 rpm. The obtained plate-like molded product was pulverized with a classifier, and divided into 2.4 to 7.0 mm granules and 2.4 mm or less fine powder (fractions of 7.0 mm or more were pulverized). Further, fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to the compression molding machine to be molded again.
Thus, granule FA was obtained.

Mixing of Materials Using a commercially available V-type mixer (capacity 200 L), the following formulation was mixed for 10 minutes.

Trisodium citrate dihydrate 2.94 kg Sodium gluconate 0.5 kg Succinic acid 1.2 kg Molding The above mixture was compressed granulator Briquetta BS manufactured by Shinto Kogyo Co., Ltd.
Using S-IV type, pocket shape 5.0mmΦ ×
1.2mm (Depth), roller rotation speed 30rpm
m, at a feeder rotation speed of 67 rpm. The obtained plate-like molded product was crushed by a classifier, and was 2.4 to 7.0 mm.
And fine powder having a size of 2.4 mm or less (fractions having a size of 7.0 mm or more were crushed). The fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to the compression molding machine to be molded. Thus, granules FB were obtained.

Packaging A molded product was filled in the form of a standing pouch in the following order.

Granule FB (bottom layer) Granule FA (top layer) 100 L of this was packaged in a 10 L kit, and finished 10
The pH after dissolution in L was 5.4.

<Preparation of Stabilizing Solution (for 1 L)> Common use of starting solution and replenishing solution DTPA-5Na 1.0 g / L 5-chloro-2-methyl-4isothiazoline-3one 0.1 g / L dipropylene glycol 3 g / L NaCl 5.85 g / L Compound represented by the general formula (1) Type and amount are described in Table 1. The above materials were dissolved in pure water to prepare 100 L.

The silver halide photographic light-sensitive material prepared according to the above-mentioned formula was exposed so as to have a blackening ratio of 10%, and a washing tank of an automatic developing machine GR-26SR manufactured by Konica Corp. A silver halide photographic light-sensitive material was prepared by installing a mixer SM-10 manufactured by Konica Co., Ltd., which was modified so as to be capable of charging granules, using a developer, a fixing agent and a stabilizing solution having the above formulation. 1m ² per developer replenisher 130ml
/ M ² , fixer replenisher 130 ml / m ² , stabilizing solution 130 m
l / L was replenished, and 500 sheets were treated per day for 20 days. The resulting solution was used as a running solution, and the following evaluation was performed.
Shows the results.

<Processing Conditions> Temperature Time Developing 35 ° C. 10 seconds Fixing 35 ° C. 7 seconds Stabilization 1 Room temperature 5 seconds Stabilization 2 Room temperature 5 seconds Drying 48 ° C. 8 seconds <Dry roller dirt> Dirt generated on the dry roller after running The degree was visually evaluated on a five-point scale as described below.

A: There is no stain B: There is almost no stain, but a little stain is seen at the end C: There is a little stain, but there is no problem with the film D: The stain is entirely generated on the roller In some cases, the film adhered to the film. E: C or higher, at which dirt accumulated on the roller as a whole and the treated film was at an unusable level, was judged to be practical.

<Residual Color> 8 to 10 sheets of the above-described photographic light-sensitive material which had been subjected to development processing in an unexposed state were overlaid. The residual color was visually observed.
It was evaluated on a scale. 5 is a good level and 1 is a poor level.

<Bactericidal Effect> After the above-mentioned running sample was immersed in a bio-checker TTC manufactured by San-ai Oil Co., Ltd. for 1 minute, the lid was closed and stored at 30 ° C. for 3 days. It was measured.

When the number of detected bacteria is 1 × 10 ³ or more, the level is unacceptable. When the number of spots that appear is 10 or less, the level is acceptable. No detection is the most preferred level.

Precipitation / scale in the washing tank The degree of precipitation generated in the washing tank after running was visually evaluated in five steps as follows.

A: No precipitation, no precipitation / scale, and the solution is clear B: No precipitation / precipitation, and almost no scale C: No precipitation, but a small amount of scale on the inner wall of the washing tank Adhesion. P: Practical possible D: Slight precipitation occurs and scale is partially generated E: Precipitation accumulates at the bottom and scale is generated as a whole.

The general formula (1) of the present invention as shown in Table 1
A developer, a fixer and a stabilizing solution prepared from a developer and a fixer, respectively, and a silver halide photographic light-sensitive material in which the hydrazine derivative of Formula 2 and Formula 4 were changed were used. The processing of 1-1 to 1-12 was performed.
Table 1 shows the results.

[0129]

[Table 1]

From Table 1, it is considered that in the comparative example, the processed photosensitive material is adversely affected. On the other hand, in the present invention, a good result was obtained, and it was sufficiently practical.

Example 2 An experiment and evaluation were conducted in the same manner as in Example 1 except that the developer and the fixing agent were changed from granules to tablets as shown below.

<Preparation of Developer> Preparation of Developer A Part (for 1 L of used solution) 8-mercaptoadenine 0.09 g Dimezone S 1.3 g 5-methylbenzotriazole 0.26 g Sodium sulfite 7.1 g Sodium erythorbate 60 g (instead of hydroquinone 24 g in the case of the comparative example) D-sorbitol 5.0 g The compound represented by the general formula (1) The type and amount are described in Table 2.-Preparation of replenishment developer B part.・ 5Na 4.35 g Sodium carbonate 28.77 g Potassium carbonate 37.5 g Potassium bromide 2.0 g Sodium sulfite 49.5 g liOH · H ₂ O 2.2 g (8.8 g for comparative example (using HQ)) D- Mannitol (trade name: Kao) 11.7 g D-sorbitol 5 g Compound represented by the general formula (1) The type and amount are described in Table 2. <Preparation of Fixing Agent>-Preparation of Fixing Agent A Part (for 1 L of liquid used) Sodium thiosulfate 150 g Sodium sulfite 2 g Trisodium citrate dihydrate 19.4 g Pine flow (trade name: (Matsutani Chemical) 9 g Compound represented by general formula (1) Type and amount are described in Table 2. Preparation of fixing agent B part (for 1 L of used solution) Sodium gluconate 5 g Succinic acid 11.9 g Trisodium citrate 2 water Salt 10 g D-mannitol 2.5 g D-sorbit 1.2 g Macrogol PEG # 4000 0.75 g Each material of the developer and the fixing agent was added to each part by adding 0.5 wt% of water with a commercially available Henschel mixer. 10 at room temperature
Granulation was performed for minutes to obtain each granulated material.

Sodium 1-octanesulfonate was added in an amount of 2% by weight to each of the developed granulated product parts A and B, and the fixed granulated product parts A and B, and each A.B. The B-part was thoroughly mixed, and the resulting mixture was compression-compressed at 1.5 ton / m ² using a Massina UD / DFE30 / 40 tableting machine manufactured by Masina Co., Ltd. to a tablet having a diameter of 30 mm, a thickness of 10 mm and a weight of 10 g. Tablets were obtained.

The above-prepared developing agent and fixing agent were each placed in an aluminum foil bag in an amount of 4 L and stored at 50 ° C. and 70% for 2 weeks.

When using the above tablets, Konica Corporation was added to water.
It melt | dissolved using the mixer SM-10 made, and finished it to 4L.

The pH when the developer was dissolved was 9.8.
0 (pH when HQ of Comparative Example was used was 10.70), and pH when the fixing agent was dissolved was 5.4.

The general formula (1) of the present invention as shown in Table 2
A developer, a fixer and a stabilizing solution prepared from a developer and a fixer, respectively, and a silver halide photographic light-sensitive material in which the hydrazine derivative of Formula 2 and Formula 4 were changed were used. The processes of 2-1 to 2-12 were performed.
Table 2 shows the results.

[0138]

[Table 2]

The results were the same as those in Table 1 of Example 1. That is, in the comparative example, it is considered that the processed photosensitive material is adversely affected. On the other hand, in the present invention, a good result was obtained, and it was sufficiently practical.

Example 3 An experiment and evaluation were conducted in the same manner as in Example 1 except that the developer and the fixing agent were changed from granules to liquid as shown below.

<Developing solution formulation (per 1 L)> Sodium sulfite 50.0 g Developing agent hydroquinone 20.0 g or sodium erythorbate 60. 0 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g disodium ethylenediaminetetraacetate 2.0 g potassium carbonate 12.0 g potassium bromide 0.3 g 5-methylbenzotriazole 0.3 g diethylene glycol 25 0.0g Compound represented by general formula (1) Type and amount are described in Table 3. Water is added to make the total amount 1 L, and pH is adjusted to 10.3 with KOH.

<Fixing solution formulation (per liter)> Ammonium thiosulfate (72.5% w / v aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Sulfuric acid (50% w / v aqueous solution) 2.0 g Compound represented by general formula (1) Type and amount are described in Table 3. This was adjusted to 1 liter with pure water. The pH is 5.
Adjusted to zero.

The general formula (1) of the present invention as shown in Table 3
A developer, a fixer and a stabilizing solution prepared from a developer and a fixer, respectively, and a silver halide photographic light-sensitive material in which the hydrazine derivative of Formula 2 and Formula 4 were changed were used. The processing of 3-1 to 3-12 was performed.
Table 3 shows the results.

[0144]

[Table 3]

The results were the same as those in Table 1 of Example 1. That is, in the comparative example, it is considered that the processed photosensitive material is adversely affected. On the other hand, in the present invention, a good result was obtained, and it was sufficiently practical.

[0146]

According to the present invention, there is provided a method for processing a silver halide photographic light-sensitive material which is free from stains on a drying roller, has excellent residual color properties, has a high sterilizing effect, and has no scum or compounds deposited in a washing tank. Could be provided.

Claims (6)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support is prepared by using an automatic developing machine having a developing tank, a fixing tank and at least two washing tanks. In a processing method of a silver halide photographic light-sensitive material to be subjected to development, fixing, washing or stabilizing processing, a washing tank of the automatic developing machine is a multistage countercurrent system, and a fixing solution and a stabilizing solution are represented by the following general formula (1). A method for processing a silver halide photographic material, comprising a compound represented by the formula: Embedded image [In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ₁ and R ₂ are not simultaneously hydrogen atoms. R ₃ and R ₄ each represent a hydrogen atom or a group having 1 to 3 carbon atoms.
R ₅ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₆ and R ₇ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 or less carbon atoms, or a —COOM ⁰ group. Here, M ⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom or an aryl group, but R ₆ and R ₇ are not simultaneously hydrogen atoms. M ¹ represents an alkali metal atom or an ammonium group. k ₁ is 0, 1 or 2. ] 2. The amount of silver contained in the fixing solution is 10 g.
2. The method for processing a silver halide photographic material according to claim 1, wherein the ratio is not less than / L. 3. A silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support is prepared by using an automatic developing machine having a developing tank, a fixing tank and at least two washing tanks. In a processing method of a silver halide photographic light-sensitive material to be subjected to development, fixing, washing or stabilizing processing, a washing tank of the automatic developing machine is a multi-stage countercurrent system, and a dihydroxybenzene compound is substantially contained in a developer. A method for processing a silver halide photographic light-sensitive material, characterized by comprising a compound represented by the following general formula (A) and a developing solution and a stabilizing solution containing a compound represented by the above general formula (1). . Embedded image Wherein R ₈ and R ₉ are an alkyl group, an amino group,
Represents an alkoxy group or an alkylthio group, which may have a substituent and may combine with each other to form a ring;
k represents 0 or 1, and when k = 1, X represents -CO- or-
Represents CS-. M ₃ and M ₄ each represent a hydrogen atom or an alkali metal. ] 4. The method according to claim 1, wherein the stabilizing solution is 1.5 times or more when used.
The method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein the method is used after being diluted to 0 or less. 5. The silver halide photographic light-sensitive material according to claim 1, wherein a silver halide photographic light-sensitive material containing a compound represented by the following general formula [H] is processed. Material treatment method. Embedded image [In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-(CO)
_n -group, sulfonyl group, sulfoxy group, -P (= O) R
_A represents a ₂₂ -group or an iminomethylene group; n represents an integer of 1 or 2; A ₁ and A ₂ are each a hydrogen atom or one of a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group; Represents an unsubstituted acyl group, R is a hydrogen atom, each substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group,
Represents an amino group, a carbamoyl group, or an oxycarbonyl group. R ₂₂ is a substituted or unsubstituted alkyl group,
Represents an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or an amino group. ] 6. The method for processing a silver halide photographic material according to claim 1, wherein at least one of the developer and the fixing agent is a solid processing agent.