JP2000250176A - Developer for black-and-white silver halide photographic sensitive material and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a treating method of a black-and-white silver halide photographic sensitive material which does not cause contamination in a developing tank of an automatic developing machine or in a dissolving tank or stock tank of an automatic replenishing device by developing a photosensitive material with a developer containing a specified developing agent and a specified compd. and having a specified pH or lower. SOLUTION: A black-and-white silver halide photographic sensitive material is developed with a developer which substantially does not contain a hydroquinone but contains a developing agent expressed by formula I and a compd. expressed by formula II and which has <=9.4 pH. In formula I, each of R1 and R2 is independently a substd. or unsubstd. alkyl group or the like, k is 0 or 1, and when k=1, X is -CO- or -CS-, and each of M1 and M2 is a hydrogen atom or alkali metal. In formula II, R is at least one group selected from -SO3M, -COOM, substd. or unsubstd. ammonio groups or the like, (n) is an integer 1 or 2 and (m) is an integer 1, 2, or 3.

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 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 safer developing agent is disclosed in US Pat.
A method using ascorbic acids as described in US Pat. No. 6,816 is known. These ascorbic acid-based developers are easily oxidized by air, and the lower the pH, the higher the stability.

[0003] On the other hand, it is known that ascorbic acids contain sugar derivatives in the process of decomposition. When a developing solution containing ascorbic acid is placed in a developing tank of an automatic developing machine or a dissolving tank or a stock tank of an automatic replenishing device for a long period of time, a sugar derivative, which is a decomposition product thereof, becomes a nutrient, and fungi and fungi propagate, thereby causing contamination. They adhere to the film and cause deterioration of the finished photographic performance, causing a problem. In particular, when the pH is lowered to enhance the stability of the liquid, the growth of fungi and fungi increases, and the stain deteriorates.

[0004] There is also interest in reducing the amount of photographic processing waste liquid. Photographic effluents cannot normally be discharged into public sewers, and effluents are collected and destroyed by a cumbersome and expensive incineration method. From these points, it has been strongly desired to reduce the photographic processing waste liquid. As a means for achieving such reduction of the photographic processing waste liquid, it is conceivable to reduce the replenishing amount of the developing solution when processing is performed using an automatic developing machine.
When the replenishing amount of the developer is reduced, the number of days of the developer remaining in the developing tank of the automatic developing machine or the dissolving tank or the stock tank of the automatic replenishing device becomes longer, and the degree of contamination is further deteriorated. Especially when the replenisher is prepared from the solid processing agent, after the developer is sent from the dissolution tank of the automatic replenisher to the stock tank, the next solid processing agent is dissolved in the dissolution tank where a small amount of the developer remains. Of water, so that fungi and fungi can be more easily propagated.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to prevent generation of dirt in a developing tank of an automatic developing machine, a dissolving tank of an automatic replenishing apparatus, and a stock tank. An object of the present invention is to provide a processing agent and a processing method for a black-and-white silver halide photographic light-sensitive material.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a black-and-white silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, which is substantially free of hydroquinone. A developing method containing a developing agent represented by the general formula (1) and a compound represented by the general formula (2) and having a pH of 9.4 or less; A developer for a black-and-white silver halide photographic light-sensitive material containing a developing agent represented by the general formula (1) and a compound represented by the general formula (2) without containing hydroquinone, and In the method for processing a black-and-white silver halide photographic light-sensitive material subjected to development processing using a developer, the replenishment rate of the development replenisher is 220 ml / m ^2.
The following is achieved.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for preparing a black-and-white silver halide photographic material by using a developing agent represented by the general formula (1) and a compound represented by the general formula (2) substantially without containing hydroquinone. It is characterized by containing a developing solution having a pH of 9.4 or less, and suppressing the generation of fungi and molds caused by sugar derivatives by solidifying the developer. The replenishment amount of the development replenisher is 220 ml
In a treatment system in which the replenishing amount is reduced to not more than / m ² , the effect is regretfully exhibited.

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.

[0010]

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In the formula, 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, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . 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 general formula (1) or the general formula [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 substitutable group 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] according to the present invention are shown below.
The present invention is not limited to these.

[0014]

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[0015]

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

Hereinafter, specific examples of the compound represented by the general formula (2) are shown below, but it should not be construed that the invention is limited thereto.

[0018]

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The compound represented by the general formula (2) can be easily synthesized by a known synthesis method.

The amount of the compound represented by the general formula (2) of the present invention ranges from 0.02 mol to 0.1 mol / L of the developer solution.
It is preferably 5 mol, more preferably 0.025 mol to 0.3 mol.

In the present invention, the developer contains substantially no hydroquinone. "Substantially not contained" refers to an amount of less than 0.01 mol per liter of developer.

In the present invention, the developing agent of the general formula (1) according to the present invention and 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) can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are preferably used in an amount of usually 0.01 to 1.4 mol per liter of developer.

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 concentrated solution, and a working solution. Is preferred. 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. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol / L.
It is in the range of not less than 1 mol and not more than 1.5 mol. If necessary, silver sludge inhibitor (mercapto group-containing compound, etc.), dissolution aid (polyethylene glycols, their esters,
Alkanolamines), sensitizers (nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoamers, antifoggants (halogens such as potassium bromide and sodium bromide) Compound, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazole, thiazole, etc., chelating agent (ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development acceleration Agents (US Pat. No. 2,304,025;
A compound described in JP-B-47-45541, 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 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. 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 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.

The fixing solution is an aqueous solution containing thiosulfate (preferably sodium thiosulfate for the purpose of preventing generation of odor) as a fixing agent, and the pH of the fixing start solution is 4.0 or more, preferably 4.2 to 4.2. 7.0, and more preferably,
4.2 to 5.5. 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 optionally 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 amount of the developing solution, the replenishing amount of the fixing solution, and the replenishing amount of the stabilizing solution are 65 to 325 ml / m ^{2 of the} photosensitive material, respectively, in order to reduce the amount of waste liquid.
And more preferably 65 to 220 per m ²
ml.

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

Specifically, the replenishing amount of the developing solution and the replenishing amount of the fixing solution are the replenishing amounts of the respective solutions when replenishing the same solution as the developing mother solution and the fixing mother solution. 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 developer of the present invention may be a solid formed of two or more components constituting the developer, a single solid containing all the components, or a solid containing two or more components of the developer. Any of those which can be constituted may be used, but it is preferable that there is at least one kind of solid formed of at least two kinds of compounds, and a single substance other than the formed solid may be used.

As a method for preparing a solid processing agent, including the solid developer of the present invention, a method of adding water, granulating and then drying to obtain granules, and reducing the amount of water to be added. There is a method of performing granulation without adding water at all and directly forming without passing through a drying step. The amount of water added is preferably 0 to 2% by weight based on the total amount of the raw materials. 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 commonly 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 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 paragraph (8), page "0058" Wastewater 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), "0071".

When two or more stabilizing tanks are provided, it is preferable to use a multi-stage countercurrent method, which has been known as a means for reducing the amount of replenisher for washing water. 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 of 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.

For the silver halide photographic light-sensitive material subjected to the processing of the present invention, it is preferable to employ the following techniques.

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 (22)" 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"
10) Redox compounds JP-A-4-245243, 235 (7) to 250
(22) 11) 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).

[0046]

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 a 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 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-55 3 × 10 ^-5 mol / m ² Nucleation accelerator: P-27 1 × 10 ⁻⁴ mol / m ² Polymer latex L 0.5 g / m ² Colloidal silica 0.25 g / m ² Hydroquinone 50 mg / m ² Water-soluble polymer V-1 20 mg / m ² surfactant: saponin 0.1 g / m ² surfactant: sodium sulfosuccinic acid isopentyl -n- decyl ester 8 mg / m ² silver halide emulsion protective layer formulation (3) gelatin 0.9 g / m ² matting agent: Rights Particle size 3.5μm polymethylmethacrylate beads 30 mg / m ² Surfactant: Sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² Surfactant: F-1 0.6mg / 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: average particle size 4.0μm polymethylmethacrylate 50 mg / m ² surfactant: sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² hardener: HA-2 0.14 / M ² Hardener: HA-3 100 mg / ^{m 2}

[0051]

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[0052]

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[0053]

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<Preparation of Processing Agent> Formulation of developer (per liter of working solution) 50 g of exemplified compound A-18 of general formula (1) Compound of general formula (2) 1-phenyl-5-mercaptotetrazole shown in Table 1 03 g 8-mercaptoadenine 0.11 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.5 g benzotriazole 0.42 g sodium sulfite 30 g DTPA / 5Na 4 g potassium carbonate 97 g potassium bromide 5 g water and sulfuric acid In addition, p is adjusted to pH 9.3 when used.
H was adjusted to make the whole 500 ml. At the time of use, 500 ml of water was added to make 1 L of a working solution.

Fixing agent formulation (per liter of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium sulfite 22 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Boric acid 10 g Tartaric acid 3 g Sulfuric acid Aluminum (27% aqueous solution) 25 ml Add water and sulfuric acid and adjust the pH to 4.9 when used.
It was adjusted to make the whole 500 ml. At the time of use, 500 ml of water was added to make a 1 L fixing solution.

The light-sensitive material prepared as described above was subjected to a blackening ratio of 10%.
And an automatic developing machine using GR-26SR equipped with a liquid processing agent mixer SM-8 (both manufactured by Konica Corporation), using a developer and a fixing agent of the above-mentioned formulation. , 130 ml of developer replenisher per m ^{2 of} photosensitive material,
130 ml of fixer replenisher was replenished, and the whole size (505
(× 600 mm) 1500 sheets were processed at 30 sheets / day for 50 days.

Processing Conditions (Step) (Temperature) (Time) Developing 35 ° C. 12 seconds Fixing 35 ° C. 10 seconds Rinse at room temperature 10 seconds Drying 48 ° C. 10 seconds Total 52 seconds (Evaluation method) <Evaluation of water scale> The evaluation was performed, and rank 5 was the best, and rank 3 or higher was a level that could withstand practical use.

Rank 1: The roller and the developing tank wall are slimy due to water scale, and the scale is floating in the liquid. Rank 2: The roller and the developing tank wall are slimy due to water scale, but the suspended matter is in the liquid. No Rank 3: The roller is slimy only, and the developing tank wall is not slimy. Rank 4: Part of the roller is slimy. Rank 5: No scale is generated.

Table 1 shows the above results.

[0060]

[Table 1]

As is clear from Table 1, according to the processing method of the present invention, a developing solution having a pH of 9.4 or less and containing ascorbic acid substantially free of hydroquinone as a developing agent is used to reduce the replenishment amount of development. Also, the contamination of the developing tank can be suppressed.

Example 2 Processing and evaluation were performed in the same manner as in Example 1 except that the preparation and replenishment methods of the developer and the fixing agent were changed as follows.

<Preparation of Solid Processing Agent> Preparation of Developing A Parts (per L of Working Solution) 50 g of Exemplified Compound A-18 of General Formula (1) Compound of General Formula (2) 1-phenyl-5-mercapto shown in Table 2 Tetrazole 0.03 g 8-mercaptoadenine 0.11 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.5 g benzotriazole 0.42 g sodium sulfite 5 g D-sorbitol 5 g 1-sodium 1-octanesulfonate 1 g Production of B parts (per liter of liquid used) DTPA · 5Na 4 g Potassium carbonate 97 g Potassium bromide 5 g Sodium bisulfite 11.3 g Sodium sulfite 10 g D-mannitol 11.7 g D-sorbitol 5 g Sodium 1-octanesulfonate 2 g Fixing A Production of parts (use Sodium thiosulfate 180 g Sodium sulfite 33 g Trisodium citrate dihydrate 11.9 g Pine flow (manufactured by Matsutani Chemical Co., Ltd.) 9 g 1-sodium 1-octanesulfonate 4 g Preparation of fixing B parts (per liter of liquid used) GLUCON Sodium acid 10g Citric acid 11.8g D-mannitol 2.5g D-sorbitol 1.2g Macrogol PEG @ 4000 0.75g Na-octanesulfonic acid 0.5g Raw material for developing A parts, raw material for developing B parts and fixing The raw materials for the A parts and the raw materials for the fixing B parts are mixed for 10 minutes using a Henschel mixer FM10C / 1 type (manufactured by Mitsui Mining Co., Ltd.), and then the briquette BSS-IH type (manufactured by Shinto Kogyo Co., Ltd.) is used. 300 kg of granules with a diameter of 3 to 5 mm
Was molded. Each of these granules was packaged in an aluminum pillow in an amount of 10 L to form a kit.

The pH when the developer is dissolved in water is 1
0.1, 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 mixer SM-11 for solid processing agents (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.

Table 2 shows the above results.

[0067]

[Table 2]

As is evident from Table 2, according to the processing method of the present invention, the replenishing amount of development was reduced by using a developing solution prepared from a solid processing agent containing ascorbic acid substantially free of hydroquinone as a developing agent. However, the contamination of the developing tank can be suppressed.

[0069]

As has been demonstrated in the examples, according to the processing method of the present invention, even if the replenishment amount of the development is reduced, the contamination of the developing tank can be suppressed.

Claims (4)

[Claims] 1. A black-and-white silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support is represented by the following general formula (1) substantially without containing hydroquinone. When developing with a developing solution containing a developing agent, the developing solution contains a compound represented by the following general formula (2), and the pH of the developing solution is 9.4 or less. A processing method for black-and-white silver halide photographic materials. Embedded image [Wherein R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group; ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. [Chemical formula 2] [Wherein, R represents a —SO ₃ M group or a —COOM group (where M
Represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonio group), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group. n represents an integer of 1 or 2, and m represents an integer of 1, 2 or 3. ] 2. The method according to claim 1, wherein the developing agent represented by the general formula (1) and the compound represented by the general formula (2) are substantially contained without containing hydroquinone, and are solid. For black and white silver halide photographic light-sensitive materials. 3. 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 2. 4. A replenishing amount of a developing replenisher is 220 ml / m ^2.
The method for processing a black-and-white silver halide photographic material according to claim 1 or 3, wherein: