JP2001324782A - Developer and processing method for black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer and a processing method for a black-and-white silver halide photographic sensitive material which do not cause change in sensitivity and the lowering of contrast in running processing and take the environment into consideration. SOLUTION: The developer for a black-and-white silver halide photographic sensitive material does not substantially contain hydroquinone and contains a compound of formula (1), a compound of one of formulae (2)-(6) and a compound having an acid dissociation constant pk1 of <=9.80 at 20 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a running processing system for continuously developing a photosensitive material with a developer containing a hydroquinone developing agent while replenishing a fixed amount with an automatic developing machine has been known and generally used.

[0003] In recent years, there has been an increasing interest in the safety of processing solutions along with increasing interest in the environment. In a developing solution, a method using ascorbic acids as described in US Pat. No. 5,326,816 as a developing agent having higher safety is known. However,
There is a drawback that the sensitivity is easily changed and the contrast is lowered in the running process.

[0004] Further, from the viewpoint of environmental protection, it is strongly desired to reduce the processing waste liquid, and in order to achieve this, it is desired to realize a stable treatment with a replenishment amount as small as possible. The reduction in the replenishment amount causes a fluctuation in sensitivity in order to prolong the residence time of the processing solution in the processing tank of the developing machine, and at present, stable processing cannot be performed.
Most replenishers are provided to users in concentrated form,
Decomposition and reaction of the components in the concentrated solution occur, so that the photographic performance tends to fluctuate during running, and the fluctuation increases as the replenishment progresses. Therefore, it is conceivable to provide the treatment agent to the user in a solid state and prepare the solution before use to obtain a use solution, but it has not been sufficient for stabilization.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a black-and-white halogen lamp that does not cause a change in sensitivity or a decrease in contrast during running processing and is environmentally friendly. An object of the present invention is to provide a developer for a silver halide photographic material and a processing method.

[0006]

The object of the present invention is to provide a compound represented by the general formula (1), which is substantially free of hydroquinone, and a compound represented by the general formula (2) to (6). A developer for a black-and-white silver halide photographic light-sensitive material containing the compound represented by formula (1) and a compound having an acid dissociation constant pk1 at 20 ° C. of 9.80 or less, containing substantially no hydroquinone and represented by the general formula (1) A black-and-white silver halide photographic material developer comprising a compound represented by the general formula selected from the above (7) to (9) and a compound having an acid dissociation constant pk1 at 20 ° C. of 9.80 or less; , Pk
The compound in which 1 is 9.80 or less is a polyhydroxybenzene, is a solid, a processing method of a black-and-white silver halide photographic material which is developed using the above-mentioned developer, and a replenishing amount of a developing replenisher. Is 22
0 ml / m ² or less, substantially free of hydroquinone, a compound represented by the general formula (1), a compound represented by the general formula selected from the above (2) to (6), and 20 A developer for a black-and-white silver halide photographic light-sensitive material containing a compound having a half-wave potential E _1/2 at 130 ° C. and a pH of 10 or more, a compound substantially free of hydroquinone and represented by the general formula (1), A developer for a black-and-white silver halide photographic light-sensitive material containing a compound represented by the general formula selected from the above (7) to (9) and a compound having a half-wave potential E _{1/2 at} 20 ° C. and pH 10 of 130 mV or more. in ,,, the compound E _1/2 is more than 130mV is polyhydroxy benzenes, be a solid, a method of processing black-and-white silver halide photographic light-sensitive material to developing treatment with a developing agent, present The replenishment rate of the replenisher 2
20 ml / m ² or less, substantially free of hydroquinone, a compound represented by the general formula (1), a compound represented by a general formula selected from the above (2) to (6), and solubility A developer for a black-and-white silver halide photographic material containing a compound having a product logP of 0.75 or less; a compound substantially free of hydroquinone and represented by the general formula (1); ), And a developer for a black-and-white silver halide photographic material containing a compound having a solubility product log P of 0.75 or less, wherein log P is 0.7
Wherein the compound which is 5 or less is a polyhydroxybenzene, is a solid, a processing method of a black-and-white silver halide photographic material which is developed using a developer, and a replenishing amount of a developing replenisher is 2
At least 20 ml / m ² .

Hereinafter, the present invention will be described in detail. In the compound represented by the general formula (1), a compound represented by the following general formula (1-a) in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0008]

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In the general formula (1-a), R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, Represents a sulfo group, a carboxyl group, an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents —O—, —S— or —N (R ₄ )
Represents-. R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the formula (1) or (1-a) 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. Alternatively, 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. Preferred examples of the substituent 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 (1) or (1-a) are shown below, but the present invention is not limited thereto.

[0012]

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[0013]

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These compounds are typically ascorbic acid or erythorbic acid or a derivative derived from them, and are commercially available or can be easily synthesized by a known synthesis method.

In the general formulas (2) and (3), R ₂₁ ,
The R _22, R _23, an alkyl group having 1 to 3 carbon atoms represented by R ₂₄ and R _25, a methyl group, an ethyl group, a propyl group and the like, carbon atoms represented by R ₂₆ and R ₂₇ 1 Examples of the alkyl group of (5) to (5) include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group, and examples of the acyl group having 18 or less carbon atoms include an acetyl group and a benzoyl group. The alkyl group having 1 to 4 carbon atoms represented by M _22, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group as the aryl group, a naphthyl group and the like, aralkyl group having 15 or less carbon atoms Is a benzyl group or a phenethyl group.

Various methods for synthesizing the compound represented by the general formula (2) or (3) are known. For example, a Strecker amino acid synthesis method known as an amino acid synthesis method may be used. Is performed by alternately adding an alkali and acetic anhydride in an aqueous solution.

Next, specific examples of the compound represented by the general formula (2) or (3) are shown, but the present invention is not limited only to these.

[0018]

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[0019]

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[0020]

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Next, specific examples of the compound represented by the general formula (4) will be shown, but it should not be construed that the invention is limited thereto.

[0022]

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In the general formula (5), substituents represented by R _{51 to} R ₅₅ include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an amino group, a sulfonyl group, a carboxyl group and a hydroxyl group. An acylamino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a ureido group, a sulfamoylamino group, a sulfonamide group, an imide group, an amide group, an alkylamide group,
Examples include an alkoxycarbonylamino group, an aryloxycarbonylamino group, an ammonium group, an aminoalkyl group, a phosphonyl group, a mercapto group, and the like.These substituents further include an alkyl group, an aryl group, a carboxyl group, a sulfonyl group, a hydroxyl group, and an alkyl group. Carboxyl group, alkylsulfonyl group, alkylhydroxyl group,
It may be substituted with an arylcarboxyl group, an arylsulfonyl group, an arylhydroxyl group or the like. Also, R
_{51 to} R ₅₅ may combine with each other to form a condensed ring with a hydrocarbon ring, a hetero ring or an aromatic ring.

Examples of the compound represented by formula (5) are shown below, but are not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The compound represented by the general formula (6) is a tricarboxylic acid having a sulfide group in the molecule or an alkali metal salt thereof. Examples of the alkylene group represented by R ₆₀ include a methylene group, an ethylene group, a propylene group, a trimethylene group, a 1,4-butylene group, a 1,2-butylene group,
1,6-hexylene group, 1,8-octylene group, 1,1
Examples thereof include a 0-decylene group and the like, preferably a methylene group or an ethylene group. M ₆₁ , M ₆₂ and M ₆₃ each represent a hydrogen atom or an alkali metal, but may be any of an unneutralized product, a partially neutralized product and a completely neutralized product.

The compound represented by the general formula (6) is
B. Zienty, Journalof Organi
c Chemistry, 27, 3140, 19
It can be synthesized with reference to the method shown in 1962. Hereinafter, specific examples thereof will be described, but the present invention is not limited thereto.

[0035] The amount of the compounds represented by the general formulas (2) to (6) is not particularly limited, but the concentration of the developer in the working solution is 0.00
It is preferably from 0.1 to 0.1% by mass.

The acid dissociation constant p at 20 ° C. according to the present invention
k1 can be obtained by a conventional method.

In the present invention, a compound having an acid dissociation constant pk1 at 20 ° C. of 9.80 or less is used.
Is preferably 5.00 to 9.80. The compound may have any structure, but is preferably a polyhydroxybenzene. Polyhydroxybenzenes refer to compounds in which a benzene ring contains two or more hydroxy groups.

The acid dissociation constant p at 20 ° C. according to the present invention
The amount of the compound having k1 of 9.80 or less is preferably from 0.01 mol to 0.5 mol, and more preferably from 0.02 mol to 0.3 mol, per liter of the developing solution. preferable.

Specific examples of compounds having an acid dissociation constant pk1 at 20 ° C. of 9.80 or less are shown below, but the present invention is not limited thereto.

[0040]

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Preferred specific examples of the compounds represented by formulas (7) to (9) are shown below, but the present invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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The amount of the compounds represented by formulas (7) to (9) is not particularly limited, but the concentration of the developer in the working solution is preferably 0.0001 to 0.1% by mass.

The half-wave potential E _{1/2 at} 20 ° C. and pH 10 according to the present invention can be obtained by a conventional method using a standard hydrogen electrode.

In the present invention, a compound having a half-wave potential E _{1/2 of} not less than 130 mV at 20 ° C. and pH 10 is used, and it is preferable that E _1/2 is not less than 130 mV and not more than 300 mV. The compound may have any structure, but is preferably a polyhydroxybenzene.
Polyhydroxybenzenes refer to compounds in which a benzene ring contains two or more hydroxy groups.

The amount of the compound according to the present invention having a half-wave potential E _1/2 of 130 mV or more at 20 ° C. and pH 10 is preferably 0.01 mol to 0.5 mol per liter of a developing solution. And more preferably 0.02 mol to 0.3 mol.

Specific examples of compounds having a half-wave potential E _1/2 of 130 mV or more at 20 ° C. and pH 10 are shown below, but the present invention is not limited thereto.

[0064]

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The solubility product logP according to the present invention is a solubility product in water at 20 ° C. and can be obtained by a conventional method.

In the present invention, a compound having a solubility product logP of 0.75 or less is used.
It is preferably from 0 to 0.75. The compound may have any structure, but is preferably a polyhydroxybenzene. Polyhydroxybenzenes refer to compounds in which a benzene ring contains two or more hydroxy groups.

The solubility product logP according to the present invention is 0.75
The following compounds are used in an amount of 0.
It is preferably from 0.01 mol to 0.5 mol, and more preferably from 0.02 mol to 0.3 mol.

Specific examples of compounds having a solubility product logP of 0.75 or less are shown below, but the present invention is not limited to these.

[0069]

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In the present invention, the black-and-white silver halide photographic material is preferably subjected to photographic processing after exposure by an automatic developing machine having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

In the present invention, “contains substantially no hydroquinone” means an amount of less than 0.01 mol per liter of a developing solution.

In the present invention, 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 (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-
p-aminophenol, 2,4-diaminophenol, etc.). The developing agents for 3-pyrazolidones and aminophenols are usually
It is preferably used in an amount of 0.01 to 1.4 mol per L.

The developer used in the processing method of the present invention includes:
Although it may be supplied in any form such as powder, paste, granules, tablets, concentrated liquid, and used liquid, it is preferably supplied as granules, tablets, and concentrated liquid. When used as a starting liquid, they are used by adjusting them 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 development starting solution may be used by diluting a commonly used concentrated solution 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. Regarding the replenisher, it is preferable to use a solid processing agent formed from two or more compounds alone or as a mixture by dissolving in water.

In the developing solution, a preservative (sodium sulfite,
Potassium sulfite, ammonium sulfite, sulfites such as sodium metabisulfite, metabisulfite), alkaline agents (sodium hydroxide, potassium hydroxide, etc.) and pH buffering agents (for example, carbonate, phosphate, borate, boric acid, Acetic acid, citric acid, alkanolamine, etc.) are preferably added. Sulfite is 0.25 mol / L or more, preferably 0.1 mol / L or more.
Used at 4 mol / L or more. As the pH buffer, a carbonate is preferable, and the amount of the carbonate added is 0.5 mol / L to 2 mol / L.
5 mol is preferred, and more preferably 0.75 mol
The range is 1.5 moles. If necessary, a silver sludge inhibitor (a compound containing a mercapto group, etc.), a dissolution aid (a polyethylene glycol, an ester thereof, an alkanolamine, etc.), a sensitizer (a nonionic surfactant containing a polyoxyethylene, etc.) Quaternary ammonium compounds), surfactants, defoamers, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole,
Benzothiazoles, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetates, polyphosphates, etc.),
A development accelerator (a compound described in U.S. Pat. No. 2,304,025, Japanese Patent Publication No. 47-45541, etc.), a hardening agent (glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent Can be added. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5.
More preferably, the pH is 8.5 or more and 9.4 or less.

The waste developing solution 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 process according to the present invention can be performed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, p
An H buffer, a sensitizer, an antifoggant, a silver sludge inhibitor, and the like can be additionally added. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. At this time, an additive which can be added to the developing solution as described above can be added.

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. Regarding the replenisher, it is preferable to use a solid processing agent formed from two or more compounds alone or as a mixture by dissolving in water.

The fixing solution is an aqueous solution containing a thiosulfate, and the pH of the fixing initiating solution is 4.0 or more, preferably 4.2 to 7.0.
0, and more preferably 4.2 to 5.5. As fixing agents, sodium thiosulfate and ammonium thiosulfate can be used, and thiosulfate ions are an essential component. Sodium thiosulfate is particularly preferred for the purpose of preventing generation of odor. The amount of the fixing agent to be used can be appropriately changed, and is generally 0.1 to about 6 mol / L. Further, it is preferable not to contain a water-soluble aluminum salt in an amount exceeding 0.01 mol / L.

The fixing solution may contain a preservative (for example,
Sulfites, bisulfites), pH adjusters (eg, sulfuric acid,
Sodium hydroxide), a chelating agent capable of softening water and compounds described in JP-A-62-78551.

In the processing of the present invention, the replenishing amounts of the developing solution, the replenishing solution and the stabilizing solution are 65 to 325 ml / m ^{2 of the} photographic material, respectively, in order to reduce the amount of waste solution.
And more preferably 65 to 220 per m ²
ml.

In the present invention, when water is supplied in the washing step, the amount is preferably 0.5 to 15 L per 1 m ^{2 of} the light-sensitive material.
Furthermore, it is 1 to ¹⁰ L per m ² .

The replenishing amount of the developing solution and the replenishing amount of the fixing solution are, specifically, the replenishing amounts of the developing solution and the fixing solution when the same solution is replenished. This is the total amount of each concentrated solution and water when replenishing with the solution diluted in. When the solid processing agent is replenished with a solution dissolved in water, the replenishing amount is the total amount of each solid processing agent volume and water volume, and when the solid processing agent and water are separately replenished, the replenishing amount is It is the total amount of each solid processing agent volume and water volume.

The solid processing agent used in the present invention may be a solid formed of two or more components constituting the processing liquid, a single solid containing all of the processing liquid components, or a processing liquid containing two or more solid components. However, it is preferable that there is at least one solid formed of at least two compounds, and a single substance other than the formed solid may be used.

As a method for producing 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 with 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 0 to the amount of the whole material.
Preferably it is 2%. A briquetting machine is an example of a system in which a raw material is directly compression-molded without performing granulation to form a granular solid processing agent. As a means for granulating, there is a method using a generally used stirring granulator or Henschel mixer.

From the viewpoint of rapid processing, in the present invention,
The total processing time (Dry to dr) from when the tip of the photosensitive material is inserted into the automatic developing machine to when it comes out of the drying zone
y) is preferably from 10 to 90 seconds, more preferably from 15 to 50 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is preferably 2 to 30 seconds, more preferably 5 to 18 seconds.

As an automatic developing machine, a heat transfer material of 60 ° C. or more (heat roller of 60 ° C. to 130 ° C. or the like) or 150 ° C.
The above radiating objects (tungsten, carbon, nichrome, zirconium oxide, a mixture of yttrium oxide, 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 “00”
58 "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) In the case where two or more stabilizing tanks are provided, it is preferable to use a multi-stage countercurrent method as a means for reducing the replenisher amount of washing water, which has been known previously. 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.

According to the present invention, the capacity of the entire washing tank is 5 to 40 L.
And more preferably 10 to 20 L.

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 grain size of the silver halide grains is 1.2 μm
Hereinafter, 0.1 to 0.8 μm is particularly preferable. 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 preferred. Such emulsions are described in U.S. Pat. Nos. 5,264,337, 5,314,798 and 5,320,958. Can be obtained with reference to the description in 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. It is preferable to dope one kind in the range of 10 ^-9 to 10 ^-3 mol per mol 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 for carrying out the processing of 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 JP-A-5-224330, paragraph (0017), page (3)
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) Hydrazine derivative JP-A-7-114126, page (23), paragraph “011”
1) to page (32), paragraph “0157” 7) Nucleation accelerator JP-A-7-114126, page (32), paragraph “015”
8 "to page (36), paragraph" 0169 "8) Tetrazolium compound JP-A-6-208188, page (8), paragraph" 0059 "
To page (10), paragraph "0067" 9) Pyridinium compounds JP-A-7-110556, page (5), paragraph "0028"
To page (29), paragraph [0068] 10) Redox compounds JP-A-4-245243, pages 235 (7) to 250
(22) page 11) Syndiotactic polystyrene support JP-A-3-131843, pages 324 (2) to 327
(5) For pages and other additives, for example,
Disclosure No. 17643 (December 1978
No.) and the same No. No. 18716 (November 1979) and the same No. 308119 (December 1989).

[0095]

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 >> Aqueous solution of silver nitrate and NaCl
A silver halide grain having a silver chloride content of 70 mol% and the remainder consisting of silver bromide was grown by a simultaneous mixing method using a mixed aqueous solution of KBr and KBr. Mixing at 50 ° C., pAg 7.8, p
Under the conditions of H3.0, a water-soluble rhodium salt was added at 2 × 10 ⁻⁷ mol per mol of silver during grain formation. Then, the product is washed with desalinated water by flocculation method and the following compound [A]
[B] A bactericide comprising the mixture of [C] and ossein gelatin were added and redispersed. EAg after redispersion is 220 m
V. The resulting emulsion was an emulsion of monodisperse cubic grains having an average grain size of 0.19 μm and a coefficient of variation (standard deviation divided by the average grain size and multiplied by 100) of 12%.

After adjusting the pH of the obtained emulsion with citric acid,
The pAg was adjusted with KBr, and 5 mg of chloroauric acid and 0.5 mg of sulfur white were added per mole of silver, and the mixture was chemically ripened at 53 ° C. for 50 minutes. After ripening, 300 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mole of silver.

<< Preparation of silver halide photographic light-sensitive material >> One of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941). The following formulations (1) to (3) were simultaneously coated on the undercoat layer in the order close to the undercoat layer.
On the other subbing layer on the opposite side, a backing layer was coated according to the following formula (4) so that the amount of gelatin became 2.0 g / m ² , and further, the protection of the following formula (5) was applied thereon. The layer was applied so that the amount of gelatin became 1.0 g / m ² to obtain a sample.

Formulation of hydrophilic colloid layer (1) Gelatin 0.6 g / m ² Surfactant: saponin 100 mg / m ² Dye: D-1 17 mg / m ² Silver halide emulsion layer formulation (2) Gelatin 1.5 g / m ² silver halide emulsion Silver amount 3.5 g / m ² sensitizing dye: Sd-1 0.5 mg / m ² sensitizing dye: Sd-2 0.5 mg / m ² hydrazine derivative: H 3 × 10 ^-5 mol / M ² Quaternary onium salt compound: P 1 × 10 ⁻⁴ mol / m ² Polymer latex: l 0.5 g / m ² Colloidal silica 0.25 g / m ² Water-soluble polymer: V-1 20 mg / m ² Surface activity Agent: saponin 0.1 g / m ² : Sodium sulfosuccinate isopentyl-n-decyl ester 8 mg / m ² Formula for protective layer of silver halide emulsion (3) Gelatin 0.9 g / m ² Matting agent: Average particle size 3.5 μm Polymethyl meta Crylate beads 30 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Surfactant: F-1 0.6 mg / m ² Hardener: HA-1 150 mg / m ² Backing Layer formulation (4) Gelatin 2.0 mg / m ² Surfactant: saponin 0.12 g / m ² Dye: D-2 18.9 mg / m ² Dye: D-3 67.2 mg / m ² Colloidal silica 0.3 g / M ² Hardener: HA-1 110 mg / m ² Hardener: K 110 mg / m ² Backing protective layer formulation (5) Gelatin 1.0 mg / m ² Matting agent: Polymethyl methacrylate having an average particle size of 4.0 μm 50 mg / m ² surfactant: sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² hardener: ^HA-2 0.14g / m 2 hardener: HA-3 100 m / M ²

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<< Preparation of Solid Processing Agent >> Preparation of Developing A Parts (Per L of Working Solution) Exemplary Compound of General Formula (1): A-18 60 g Compound of General Formulas (2) to (9) 20 shown in Table 1 Compound having an acid dissociation constant pk1 at 9.degree. C. of 9.80 or less: a 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1.75 g benzotriazole 0.45 g sodium sulfite 15 g 1-octane shown in Table 1. Sodium sulfonate 1.88 g Raw material for developing B parts (per liter of working solution) Potassium carbonate 24.2 g Anhydrous sodium carbonate 55.6 g Sodium sulfite 10 g Sodium 1-octanesulfonate 0.12 g Preparation of fixing A parts (per liter of working solution) ) Sodium thiosulfate 131 g Sodium metabisulfite 14 g Sodium sulfite g anhydrous sodium acetate 19.4 g sodium 1-octanesulfonate 2.6 g Preparation of fixing B parts (per liter of working solution) sodium gluconate 1 g aluminum sulfate 11.5 g anhydrous sodium acetate 10.0 g sodium 1-octanesulfonate 26 g succinic acid 14.7 g tartaric acid 3.0 g The raw material for the developing A part, the raw material for the fixing A part, and the raw material for the fixing B part were respectively mixed with a Henschel mixer FM10C.
After mixing for 10 minutes using Model No./1 (manufactured by Mitsui Mining Co., Ltd.), 300 kg of granules having a diameter of 3 to 5 mm were molded using Briquetta BSS-IH type (manufactured by Shinto Kogyo Co., Ltd.).
These granules and the raw material for developing B parts were packaged in aluminum pillows each in an amount of 10 L to form a kit.

The pH when the developer was dissolved in water was 10.2, and the pH when the fixing agent was dissolved in water was 5.4.

The light-sensitive material prepared as described above was subjected to a blackening ratio of 10%.
The automatic developing machine is equipped with a GR-26SR and a liquid processing agent mixer SM-11 (both manufactured by Konica Corporation).
Using a developer and a fixing agent of the above-mentioned formulation, 130 ml of a replenisher for developing per 1 m ^{2 of} the photosensitive material.
/ M ² and 130 ml / m ² of the fixing replenisher, and 1500 sheets of large size (505 × 600 mm) were added for 3 days for 50 days.
0 sheets / day were processed.

Processing Conditions (Step) (Temperature) (Time) Developing 38 ° C. for 12 seconds Fixing 35 ° C. for 10 seconds Rinse at room temperature 10 seconds Drying 48 ° C. for 10 seconds Total 42 seconds << Evaluation Method >> (Evaluation Method for Sensitivity) 633
Through an interference filter having a peak at nm, exposure was performed through a step wedge with xenon flash light having a light emission time of 10 ⁻⁶ sec, and processing was performed under the above conditions. Here, the sensitivity was measured in Experiment No. The relative value of the reciprocal of the exposure amount that gives a density of 1.5 is shown based on the case of processing with the new solution No. 1. The change in sensitivity may be within ± 10 as a relative value.

(Method of Evaluating Contrast) As an index indicating the contrast of an image, fog + density of the characteristic curve is set to 0.1.
The point of fog + 3.0 was connected from the point 3 by a straight line, and the slope of this straight line was represented as a γ value (gradation).

That is, γ = (3.0−0.3) / ｛log
(Exposure amount giving a density of 3.0) -log (exposure amount giving a density of 0.3)｝, and a larger γ value indicates harder photographic characteristics, and a value of less than 18 is not practical.

Table 1 shows the above results.

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[Table 1]

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As is evident from Table 1, according to the processing method using the developer of the present invention, the fluctuation in sensitivity and the decrease in contrast are small even when running with a small amount of replenishment.

Example 2 The procedure of Example 1 was repeated except that the preparation of the developer was changed as follows.

Preparation of Developed A Parts (Per 1 L of Working Solution) Exemplary Compound of General Formula (1): A-18 60 g Compound of General Formulas (2) to (9) Half-wave potential at 20 ° C. and pH 10 shown in Table 2 Compound whose E _1/2 is 130 mV or more: b 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1.75 g benzotriazole 0.45 g sodium sulfite 15 g shown in Table 2 1-sodium 1-octanesulfonate 1 .88 g Raw materials for developing B parts (per liter of liquid used) Potassium carbonate 24.2 g Anhydrous sodium carbonate 55.6 g Sodium sulfite 10 g Sodium 1-octanesulfonate 0.12 g The results are shown in Table 2.

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[Table 2]

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As is clear from Table 2, according to the processing method using the developer of the present invention, the fluctuation in sensitivity and the decrease in contrast are small even when running at a low replenishment rate.

Example 3 The procedure of Example 1 was repeated, except that the preparation of the developer was changed as described below.

Preparation of Developed A Parts (per L of Working Solution) Exemplary Compound of General Formula (1): A-18 60 g Compound of General Formulas (2) to (9) The solubility product log P shown in Table 3 is 0.75 or less. 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1.75 g benzotriazole 0.45 g sodium sulfite 15 g sodium 1-octanesulfonate 1.88 g shown in Table 3 (Per liter of liquid used) Potassium carbonate 24.2 g Anhydrous sodium carbonate 55.6 g Sodium sulfite 10 g 1-Sodium 1-octanesulfonate 0.12 g The results are shown in Table 3.

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[Table 3]

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As is evident from Table 3, according to the processing method using the developer of the present invention, the fluctuation in sensitivity and the decrease in contrast are small even when running at a low replenishment rate.

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According to the present invention, a low replenishing amount can be realized in consideration of the environment, and a black-and-white silver halide photographic material can be processed without causing a fluctuation in sensitivity and a decrease in contrast in running processing.

Claims (18)

[Claims] 1. The method according to claim 1, which is substantially free of hydroquinone.
A compound represented by the general formula (1),
At 20 ° C. and a compound represented by a general formula selected from
Including a compound having an acid dissociation constant pk1 of 9.80 or less.
For black and white silver halide photographic light-sensitive materials, characterized by
Agent. Embedded image[Wherein, R₁And R_TwoAre substituted or unsubstituted
Alkyl group, substituted or unsubstituted amino group,
Is an unsubstituted alkoxy group, or a substituted or unsubstituted
Represents an alkylthio group;₁And R_TwoAre connected to each other
A ring may be formed. k represents 0 or 1, and k = 1
X represents -CO- or -CS-. M ₁And M_TwoHaso
Each represents a hydrogen atom or an alkali metal. [Chemical formula 2][Wherein, R_{twenty one}And R_{twenty two}Is a hydrogen atom or carbon number 1
Represents an alkyl group of 1 to 3. Where R_{twenty one}And R_{twenty two}Is water at the same time
And the alkyl group is a substituent
May be provided. R_{twenty three}And R_{twenty four}Is a hydrogen atom
Or an alkyl group having 1 to 3 carbon atoms;_{twenty five}Is hydroxy
A sil group, an amino group, an alkyl group having 1 to 3 carbon atoms or
Represents a nyl group. R₂₆And R₂₇Are hydrogen atom and carbon, respectively
An alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 18 carbon atoms, or
-COOM_{twenty two}Represents Where R₂₆And R ₂₇Is a hydrogen atom at the same time
Never be. M_{twenty one}Is a hydrogen atom, an alkali metal atom
Or an ammonium group. M_{twenty two}Is hydrogen atom, carbon number 1
To 4 alkyl groups, alkali metal atoms, aryl groups or
Represents an aralkyl group having 15 or less carbon atoms. m is 0, 1 or
2 is represented. [Chemical formula 3][Where X₄₀Is hydrogen atom, hydroxyl group, lower alkyl
Group, lower alkoxy group, halogen atom, carboxyl
Group or a sulfo group;₄₁And M₄₂Are hydrogen sources
Represents an atom, an alkali metal atom or an ammonium group. [Formula 4][Wherein, R₅₁~ R₅₅Represents a hydrogen atom or a substituent, and is the same
Or at least one may be different from -SM₅₀
Group. M₅₀Is a hydrogen atom, an alkali metal atom or
Represents a monium group. X₅₀And Y₅₀Is a nitrogen atom or
Represents a carbon atom. [Chemical formula 5][Wherein, R₆₀Represents an alkylene group having 1 to 12 carbon atoms,
M₆₁, M₆₂And M₆₃Are hydrogen atoms or alkali gold, respectively
Represents a genus atom. ] 2. The method according to claim 1, wherein the composition is substantially free of hydroquinone.
A compound represented by the general formula (1),
At 20 ° C. and a compound represented by a general formula selected from
Including a compound having an acid dissociation constant pk1 of 9.80 or less.
For black and white silver halide photographic light-sensitive materials, characterized by
Agent. Embedded image[Where B₇₀Is a hydrogen atom, a hydroxyl group or -CH_Two
COOM₇₀Represents B₇₀A is a hydrogen atom, A₇₁~ A₇₉
Is a hydrogen atom, -C_nH_{2n + 1}Or-(CH_Two)_mX
₇₀(Where n is an integer of 1-3, m is an integer of 0-3, X
Represents -COOM, an amino group or a hydroxyl group)
N71 and n72 are such that n71 + n72 is 1 to 4.
A represents an integer₇₁~ A₇₅Are all hydrogen atoms
There is no. B ₇₀Is a hydroxyl group or -CH_TwoCOOM₇₀
, N71 = 0, n72 = 1, and A₇₁, A
₇₈And A₇₉Represents a hydrogen atom, and A₇₂~ A₇₅Haso
Hydrogen atom, hydroxyl group, -COOM₇₀, -P
O_Three(M₇₀)_Two, -CH_TwoCOOM₇₀, -CH_TwoOH, -C
H_TwoNH_TwoOr a lower alkyl group. Where A₇₂~ A₇₅
At least one is -CH_TwoCOOM₇₀, -COOM₇₀
Or -PO_Three(M₇₀) _TwoIt is. M₇₀Is a hydrogen atom, an alka
Represents a metal atom or an ammonium group. [Formula 7][Where A₈₁~ A₈₄Is -COOM₈₀Or hydro
Represents a xyl group, and n81 to n84 each represent an integer of 0 to 2.
Represents a number. R₈₁~ R₈₄Is a hydrogen atom, hydroxy
A lower alkyl group or a lower alkyl group. X₈₀Is 2 to 2 carbon atoms
6 alkylene groups or-(B₁O)_m-B_Two− (Where
B₁And B_TwoIs an alkylene having 1 to 5 carbon atoms.
And m represents an integer of 1 to 5). M₈₀Is hydrogen field
Represents an atom, an alkali metal atom or an ammonium group. Embedded image[Where B₉₀Is-(CH_Two)_mCH_ThreeOr-(CH_Two)_nS
O_ThreeM₉₀(Where m is an integer of 0 to 3 and n is 1 to 4
And n91 and n92 each represent 1.
And n93 and n94 each represent an integer of 0 to 3.
A₉₁~ A₉₈Represents a hydrogen atom, a hydroxyl group, -C
OOM₉₀, -PO_Three(M₉₀)_Two, -CH_TwoCOOH, -C
H_TwoOH, -CH_TwoNH_TwoOr a lower alkyl group. M
₉₀Represents a hydrogen atom, an alkali metal atom or an ammonium group
Represent. ] 3. The developer for a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the compound having a pk1 of 9.80 or less is a polyhydroxybenzene. 4. The method according to claim 1, wherein the substance is a solid.
4. The developer for a black-and-white silver halide photographic light-sensitive material according to 2 or 3. 5. A method for processing a black-and-white silver halide photographic material, comprising developing using the developer according to claim 1, 2, 3, or 4. 6. A replenishing amount of a developing replenisher is 220 ml / m ^2.
The processing method according to claim 5, wherein: 7. A compound substantially free of hydroquinone and represented by the general formula (1), a compound represented by the general formula selected from the above (2) to (6), and a pH of 20 ° C.
10. A developer for a black-and-white silver halide photographic light-sensitive material, which comprises a compound having a half-wave potential E _1/2 of 130 mV or more in No. 10. 8. A compound substantially free of hydroquinone and represented by the general formula (1), a compound represented by the general formula selected from the above (7) to (9), and a pH of 20 ° C.
10. A developer for a black-and-white silver halide photographic light-sensitive material, which comprises a compound having a half-wave potential E _1/2 of 130 mV or more in No. 10. 9. The developer for a black-and-white silver halide photographic material according to claim 7, wherein the compound having an E _1/2 of 130 mV or more is a polyhydroxybenzene. 10. The developer for a black-and-white silver halide photographic material according to claim 7, wherein the developer is a solid. 11. A method for processing a black-and-white silver halide photographic light-sensitive material, comprising developing using the developer according to claim 7, 8, 9 or 10. 12. The replenishment rate of a development replenisher is 220 ml / m.
The processing method according to claim 11, wherein the number is ² or less. 13. The compound represented by the general formula (1), which is substantially free of hydroquinone, and the compound represented by the above (2) to (6).
A compound represented by a general formula selected from the group consisting of
A developer for a black-and-white silver halide photographic material, which comprises a compound having an ogP of 0.75 or less. 14. The compound represented by the general formula (1), which is substantially free of hydroquinone, and the compounds represented by the above formulas (7) to (9).
A compound represented by a general formula selected from the group consisting of
A developer for a black-and-white silver halide photographic material, which comprises a compound having an ogP of 0.75 or less. 15. The developer for a black-and-white silver halide photographic light-sensitive material according to claim 13, wherein the compound having a log P of 0.75 or less is a polyhydroxybenzene. 16. The method according to claim 1, wherein the material is a solid.
16. The developer for a black-and-white silver halide photographic light-sensitive material according to 3, 14, or 15. 17. A processing method for a black-and-white silver halide photographic light-sensitive material, wherein the processing is carried out using the developer according to claim 13, 14, 15, or 16. 18. A replenishment rate of a development replenisher is 220 ml / m.
18. The processing method according to claim 17, wherein the number is ² or less.