JP2694381B2 - Processing method of black and white silver halide photographic material - Google Patents

Description

The present invention relates to a method for processing a black and white silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) using an automatic processor (hereinafter referred to as an automatic processor). In particular, the present invention relates to a method for processing a black-and-white silver halide photographic light-sensitive material in which there is no fixing delay even when the replenishing amount of the fixing solution is reduced.

(Prior Art) The processing of a black-and-white light-sensitive material includes a developing process, a process of removing unexposed silver halide (that is, a fixing process), and a process of washing or stabilizing the light-sensitive material after fixing.

In recent years, with the progress and development of various industrial fields, rapidity has been required in all fields, and the field of silver halide photographic processing is no exception. In particular, in the development processing of sheet-shaped photosensitive materials such as photosensitive materials for plate making, photosensitive materials for X-rays, and photosensitive materials for scanners,
The need for rapid processing is ever increasing.

The fixing step is the rate-determining step in rapid processing. Increasing the fixing speed is most effective for speeding up.

On the other hand, resources, generated gas, wastewater, waste, and the like are being reviewed in many fields from the viewpoint of environmental protection. In the field of photographic processing, the necessity of reducing the replenishment amount of a processing solution used for processing a photosensitive material is increasing in terms of resource saving, reduction of waste water amount, reduction of containers used, and the like.

However, if the replenishing amount of the fixer is reduced, the amount of silver accumulated in the fixer, halogen ions, and the amount of the developer brought in from the developing bath rapidly increase, which generally slows down the fixing speed. Is. Therefore, it is the actual situation that a large amount of fixing solution has been conventionally used (500 to 800 ml per 1 m ^{2 of} light-sensitive material).

To increase the fixing speed, raise the fixing temperature,
Measures to strengthen the stirring conditions of the automatic machine are being studied,
There is a problem in that it causes odor and increases the cost of the device, and it is difficult to realize.

Thus, it has been difficult to achieve both low replenishment of the fixing solution and rapid processing.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a method for processing a photosensitive material, which is excellent in fixability and enables rapid processing without delaying the fixing speed even when the replenishment amount is reduced. To provide.

(Means for Solving the Problems) The above object is to expose a black-and-white silver halide photographic light-sensitive material, and then at least develop and fix it using an automatic developing machine, in an amount of 80 mol% of the salt component of the developer. The above is a salt having potassium ion as a cation, the replenishing amount of the fixing solution is 350 ml or less per 1 m ^{2 of the} light-sensitive material, and the fixing solution is
The problem has been solved by a method of processing a black-and-white silver halide photographic light-sensitive material, which contains at least one mesoionic compound as a fixing agent.

By the way, JP-A-57-150842 discloses a meso-ion.
It is described that the developed silver halide light-sensitive material is dipped in a fixing solution composed of a 1,2,4-triazolium-3-thiolate compound, an organic acid and water for fixing. However, in this publication, there is no description about the use of this fixing solution in the processing of the developing machine and the replenishment amount.

The present inventors have found that the main cause of the running fatigue of the fixer, especially the increase in fixing delay when the replenishment amount of the fixer is reduced,
It has been found that this is due to the relative increase in the amount of the developer (particularly, the developer containing a large amount of potassium ions for concentration) brought into the fixer. As a result of studying various compounds, the present inventors have found that by using the above mesoionic compound in a processing method using a low replenishing amount, rapid processing can be performed without delaying the fixing rate, and the present invention It has been completed.

The mesoionic compound used in the present invention is preferably a compound represented by the following general formula (I).

Wherein, Z is a carbon atom, a nitrogen atom, an oxygen atom, a 5 or 6-membered ring composed of a sulfur atom or a selenium atom, X ^- is -O ^-, -S ^-, or -N ^- R (wherein X represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group).

Among these, compounds represented by the following general formula (II) are more preferable.

In the formula, R ₁ and R ₂ represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. However, R ₂ may be a hydrogen atom. Y is -O-, -S-, And R ₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, a ureido group or a sulfamoylamino group. R ₁ and R ₂ , R ₂ and
R _3's may be bonded to each other to form a ring.

The compound represented by formula (II) will be described in detail.

In the formula, R ₁ and R ₂ are substituted or unsubstituted alkyl groups (for example, methyl group, ethyl group, n-propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group). , Dimethylaminoethylthioethyl group, diethylaminoethyl group, aminoethyl group, methylthiomethyl group, trimethylammonioethyl group, carboxymethyl group, carboxyethyl group,
Carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group, etc.), substituted or unsubstituted cycloalkyl group (eg, cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group, etc.), substituted or unsubstituted Alkenyl group (eg, allyl group, 2-methylallyl group, etc.) Substituted or unsubstituted alkynyl group (eg, propargyl group, etc.) Substituted or unsubstituted aralkyl group (eg, benzyl group,
Phenethyl group, 4-methoxybenzyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 4-sulfophenyl group, etc.) or substituted Or an unsubstituted heterocyclic group (eg, 2-pyridyl group, 3-
Pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, etc.).

However, R ₂ may be a hydrogen atom.

R ₃ is a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylaminoethylthioethyl Group, diethylaminoethyl group, aminoethyl group,
Methylthiomethyl group, trimethylammonioethyl group,
Carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group, etc., substituted or unsubstituted cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group, etc.) ),
A substituted or unsubstituted alkenyl group (for example, an allyl group,
2-methylallyl group, etc.) Substituted or unsubstituted alkynyl group (eg, propargyl, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, 4-methoxybenzyl group, etc.), aryl group ( For example, phenyl group, naphthyl group, 4-methylphenyl group, 4
-Methoxyphenyl group, 4-carboxyphenyl group, 4
-Sulfophenyl group, etc.) or a substituted or unsubstituted heterocyclic group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2 A tetrahydrofuryl group,
Etc.), a substituted or unsubstituted amino group (eg, unsubstituted amino group, dimethylamino group, methylamino group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, methoxypropionylamino group, etc.), sulfonamide Group (for example, methanesulfonamide group, benzenesulfonamide group, 4-toluenesulfonamide group,
Etc.), ureido group (eg, unsubstituted ureido group, 3-methylureido group, etc.), sulfamoylamino group (eg, unsubstituted sulfamoylamino group, 3-methylsulfamoylamino group, etc.) May be.

In the general formula (II), preferably, Y is And R ₁ and R ₃ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group. R ₂ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group.

Hereinafter, specific examples of the compound of the present invention are shown, but the present invention is not limited thereto.

The compound of the present invention is 1 × 10 ⁻⁵ mol / to 10 mol /,
Particularly, it is preferably used in the fixing solution or the fixing solution replenishing solution in the range of 1 × 10 ⁻³ mol / to 3 mol /.

Here, when the halogen composition of the silver halide emulsion in the light-sensitive material to be processed is silver iodobromide, it is preferably used in an amount of 0.5 to 2 mol / mol. Silver bromide, silver chlorobromide, or high silver chloride emulsion In the case of (silver halide containing 80 mol% or more of silver chloride), it is preferably used in the range of 0.05 to 1 mol /.

The fixing solution of the present invention may use a known fixing agent in addition to the above mesoionic compound. Examples thereof include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The use amount of these known fixing agents can be appropriately changed, and is generally about
0.1 to about 5 mol / min.

The fixing solution may optionally contain a hardener (for example, a water-soluble aluminum compound), a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), or a pH adjuster (for example, ammonia). , Sulfuric acid), chelating agents, surfactants,
Wetting agents and fixing accelerators may be included.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6840. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include Japanese Examined Patent Publication Nos. 45-35754, 58-122535, and 58-12253.
Examples thereof include thiourea derivatives described in JP-A-6, alcohols having a triple bond in the molecule, and thioether compounds described in US Pat. No. 4,126,459.

Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, and citric acid; and inorganic buffers such as boric acid, phosphate, and sulfite. Odor,
It is preferable to use an inorganic buffering agent from the viewpoint of suppressing rusting of equipment materials.

Here, the pH buffer is the pH of the fixer when the developer is brought in.
It is used for the purpose of preventing the increase, and is used in an amount of 0.1 to 1.0 mol / r, more preferably 0.2 to 0.6 mol / l.

Examples of the hardening agent in the fixing solution of the present invention include ethylenediaminetetraacetic acid complex using a water-soluble aluminum salt, a chromium salt and a trivalent iron compound as an oxidizing agent. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol /, more preferably
It is 0.03 to 0.08 mol /.

The effects of the present invention are exhibited regardless of the presence or absence of a hardener.

The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. and 5 seconds to 1 minute.

The fixer replenishment rate is 350 ml / m ³ or less, especially 300 ml / m ^3.
The effect of the present invention becomes remarkable at m ³ or less. Particularly preferred range is ^{50ml / m 3 ~300ml / m 3} .

The developer used in the development processing of the light-sensitive material according to the present invention contains additives usually used (for example, a developing agent, an alkaline agent,
pH buffers, preservatives, chelating agents) can be included. In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used. There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable that the developing agent contains dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality. A combination of -phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols is preferred.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred.

The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. Among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene developing agent is usually 0.05 mol /
It is preferably used in an amount of .about.0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / -0.5 mol / and the latter is 0.0
It is preferable to use it in an amount of 6 mol / or less.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is used in an amount of 0.20 mol / mol or more, particularly 0.3 mol / mol or more, but if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is preferably 1.2 mol / mol.

As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

As additives used other than the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as imidazole or its derivatives; mercapto-based compounds such as 1-phenyl-5-mercaptotetrazole, indazole-based compounds such as 5-nitroindazole, benzotriazole-based compounds, antifoggants or black pepper prevention It may be contained as an agent and may further contain a color toning agent, a surfactant, an antifoaming agent, a water softening agent, a film hardening agent and the like, if necessary.

Further, compounds described in JP-A-56-24347 as silver stain inhibitors, compounds described in JP-A-62-212651 as development unevenness inhibitors, compounds described in JP-A-61-267759 as dissolution aids. Can be used.

In the developer used in the present invention, a buffer agent is used.
62-186259, boric acid, saccharides (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphate (for example, sodium) described in JP-A-60-93433. (Salt, potassium salt) or the like is used, and boric acid is preferably used.

For the purpose of transportation cost of the treatment liquid, packaging material cost, space saving, etc., it is preferable to concentrate the treatment liquid and dilute it before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

However, the conventional fixer using thiosulfate has a problem that fixing is delayed when a developer containing a large amount of potassium ion component is introduced.

When the mesoionic compound of the present invention is used as a fixing agent, there is no delay in fixing due to potassium ions. Therefore, in the processing system of the present invention, the salt component of the developer is
80 mol% or more can be used as a salt having potassium ion as a cation, which is extremely advantageous for concentration of the developer.

The photosensitive material that has been developed and fixed is then washed or stabilized.

Washing or stabilizing treatment is performed with silver halide light-sensitive material 1 m ²
Alternatively, the replenishment amount of 3 or less (including 0, that is, washing with water) can be performed. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated.

When washing with a small amount of water, JP-A-63-18350,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-62-287252. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water.

Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in As described in JP-A-235133, it can also be used for a processing solution having a fixing ability, which is a preceding processing step.

In addition, it prevents unevenness of water bubbles that easily occur when washing with a small amount of water and /
Alternatively, a water-soluble surfactant or an antifoaming agent may be added in order to prevent the transfer of the treatment agent component attached to the squeeze roller to the treated film.

Also, to prevent contamination by dyes eluted from the photosensitive material,
The dye adsorbent described in JP-A-63-163456 may be installed in the water washing tank.

In addition, there is a case where a stabilizing treatment is performed subsequent to the water washing treatment, and examples thereof include JP-A-2-201357 and JP-A-2-132435.
The baths containing the compounds described in JP-A No. 1-102553 and JP-A No. 46-44446 may be used as the final bath of the light-sensitive material.

Ammonium compounds, B as needed in this stabilizing bath
Metal compounds such as i and Al, optical brighteners, various chelating agents, film pH adjusting agents, hardening agents, bactericides, fungicides, alkanolamines and surfactants (preferably silicon-based) can also be added. . As the water used in the washing step or the stabilizing step, it is preferable to use tap water, water deionized to an ion concentration of 5 mg / or less, or water sterilized by halogen, an ultraviolet sterilization lamp or the like.

In the present invention, the term "development step time" or "development time" refers to the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the time when it is immersed in the next fixing solution, the "fixing time" What is the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution) "Washing time"
The time during which it is immersed in the washing tank liquid.

Further, the "drying time" usually means a time when the drying machine is provided with a drying zone and is in the drying zone.

In the developing treatment of the present invention, the developing time is 25 seconds or less, preferably 6 seconds to 15 seconds, and the developing temperature is preferably 25 ° C to 50 ° C, more preferably 30 ° C to 40 ° C.

The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. and 25 seconds or less, more preferably 30 ° C. to 40 ° C. and 6 seconds to 15 seconds.

Washing or stabilizing bath temperature and time is 0 to 50 ° C for 5 seconds to 30
Seconds are preferable, and 15 to 40 ° C. and 5 to 20 seconds are more preferable.

According to the method of the present invention, the developed, fixed and washed (or stabilized) photographic material is squeezed out of the washing water, i.e., dried through a squeeze roller. Drying is about 40 ° C ~ about
The drying is carried out at 100 ° C, and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 2 minutes, and particularly preferably 40 ° C to 80 ° C for about 5 seconds to 30 seconds.

The silver halide photographic light-sensitive material applicable to the fixing solution of the present invention generally comprises a support and at least one silver halide emulsion layer coated thereon. The silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, a back layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer) and the like can be provided if necessary. The silver halide emulsion is a hydrophilic colloid such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide or silver chloroiodobromide, which is a hydrophilic colloid such as gelatin, modified gelatin or colloid. Albumin, casein,
It is dispersed in carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, acrylic acid ester, methacrylic acid ester or a mixture thereof.

The silver halide emulsion is generally prepared by mixing a water-soluble silver salt (for example, silver nitrate) and a water-soluble halogen salt with water by a method well known in the art (for example, single jet method, double jet method, control jet method, etc.). It is produced by mixing in the presence of a hydrophilic colloid, followed by physical ripening and chemical ripening such as gold sensitization and / or sulfur sensitization. Emulsions thus obtained include cubic, octahedral, spherical,
Research Disclosur
e) High aspect ratio tabular silver halide grains described in 22534 (January1953) can be used,
Further, the internal latent image type silver halide grains and the surface latent image type silver halide grains described in JP-B No. 41-2065 may be used in combination.

The silver halide emulsion contains a spectral sensitizer (for example, a cyanine dye, a merocyanine dye or a mixture thereof), a stabilizer (for example, 4-hydrohydroxy-6-methyl-1,3,3a) during the production process or immediately before coating. , 7-Tetrazaindene),
Sensitizers (for example, compounds described in US Pat. No. 3619198), antifoggants (for example, benzotriazoles such as 5-nitrobenzimidazole, polyethylene oxide, hardeners (formalin, glyoxal, etc.,
Mucochloric acid, 2-hydroxy-4,6-dichloro-s-
Triazine), a coating aid (for example, saponin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide) and the like can be added. The silver halide emulsion produced in this manner is applied to a support such as baryta paper, resin coated paper, cellulose acetate film, and polyethylene terephthalate film by the dip method, air knife method, bead method, extrusion doctor method, double-sided method. It is applied and dried by a coating method or the like.

Although the silver halide photographic light-sensitive materials exemplified above have different silver halide compositions, additives, types of supports, etc. depending on their applications, the silver halide photographic light-sensitive materials to which the fixing solution of the present invention is applied are , Black-and-white photographic light-sensitive materials (for example, medical or industrial X-ray photographic light-sensitive materials, photomechanical photographic light-sensitive materials, micro photographic light-sensitive materials, X-ray micro reversal photographic light-sensitive materials, computer type paper photographic light-sensitive materials, general photography There are negative photographic light-sensitive materials, photographic paper, etc.).

The silver coating amount of the silver halide photographic light-sensitive material to which the fixing solution of the present invention is applied is preferably 1 to 25 g / m ² . It is more preferably 1.5 to 12 g / m ² , and is effective for a structure having a high fixing rate. Most preferably, it is 2.0 to 6 g / m ² .

The preferred coating amount of the hydrophilic colloid in the silver halide photographic light-sensitive material to which the fixing solution of the present invention is applied is 1 to 5 g / m ² per one side of the support. More preferably, the total amount of both sides of the support is 1.5 to 4.5 g / m ^2, which is a preferable result with good swelling restriction. The most preferable hydrophilic colloid coating amount is
The total amount on both sides of the support is 1.5 to 3.5 g / m ² .

A silver halide photographic light-sensitive material preferable for processing using the fixing solution of the present invention is a black-and-white photographic light-sensitive material because swelling restriction is required. Photosensitive material for photolithography is more preferred, and it is suitable because the swelling of the film surface is not large. Most preferably, the Japanese Examined Patent Publication Nos. 52-18317 and 53
-95618, 58-173737, 58-106493, a photolithographic material containing a tetrazolium salt, and RESEARCH DISCLOSUR.
E Item 23516 (November 1983, p. 346) and documents cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,269,929.
No., No. 4,276,364, No. 4,278,748, No. 4,385,108,
4,459,347, 4,560,638, 4,478,928, British Patent 2,011,391B, JP-A-60-179,734, 62-270,948.
No. 63, No. 63-29,751, No. 61-170,733, No. 61-270,744
No. 62-270,948, EP217,310, EP356,898, US
4,686,167, JP-A-62-178,246, 63-32,538,
63-104,047, 63-121,838, 63-129,337
63, 223,744, 63-234,244, 63-234,24
No. 5, 63-234,246, 63-294,552, 63-306,4
No. 38, JP-A-1-100,530, No. 1-105,941, No. 1-
105,943, JP-A-64-10,233, JP-A-1-90,439
JP-A-1-276,128, 1-280,747, 1-28
3,548, 1-283,549, 1-285,940, Japanese Patent Application No. 6
3-147,339, 63-179,760, 63-229,163, Japanese Patent Application Nos. 1-18,377, 1-18,378, 1-18,379,
1-15,755, 1-16,814, 1-40,792, 1-42,615, 1-42,616, 1-123,693, use the hydrazine derivative described in 1-126,284. You can

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ⁻⁶ mol to 5 × 10 ⁻² mol, and particularly 1 × 10 ⁻⁵ to 2 × per mol of silver halide.
The range of 10 ^-2 mol is a preferable addition amount.

The treatment liquid used in the present invention is preferably stored in the packaging material having low oxygen permeability described in JP-A-61-73147.

When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

US Patent No. 30 for roller transport type automatic developing machine
No. 25779, No. 3,554,971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. .

<Example> Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 Preparation of Emulsion A In a gelatin aqueous solution kept at 40 ° C., an aqueous silver nitrate solution and 3 × 10 ⁻⁷ mol of K ₃ IrCl ₆ per mol of silver, and 3 × 1
An aqueous solution of sodium chloride and sodium bromide containing 0 ^-7 mol of (NH ₄ ) ₃ RhCl ₆ was added simultaneously for 30 minutes, and the potential between them was adjusted to
A monodisperse silver chlorobromide emulsion having an average particle size of 0.15 μm was prepared by keeping the voltage at 200 mV. 0.2 mol per mol of silver in this emulsion
Emulsion A was prepared by adding a mol% potassium iodide aqueous solution for conversion, desalting by a flocculation method, and dispersing in gelatin.

Hypo and chloroauric acid were added to this emulsion, and the mixture was kept at 60 ° C. for chemical ripening, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1 was added as a stabilizer. % Solution was added at 30 ml per mole of silver. (AgCl _69.8 Br ₃₀ I _0.2 dispersion coefficient 10%).

A compound was used as an infrared sensitizing dye in 1 kg of these emulsions, and 60 ml of a 0.05% solution thereof was added to perform sensitization in the infrared region. This emulsion has 4,4'- for the purpose of supersensitization and stabilization.
0.5 of bis- (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt
70% methanol solution and 2,5-dimethyl-3-allyl-
90 ml of 0.5% methanol solution of benzothiazole iodo salt
Was added.

Furthermore, hydroquinone 100 mg / m ² and polyethyl acrylate as polymer latex were used in the gelatin binder ratio.
25%, 2-bis (vinylsulfonylacetamide) ethane as a hardener was added and coated on a PET support so as to have a silver content of 2.9 g / m ² . Gelatin was 1.3 g / m ² .

On this, gelatin 0.6g / m ² , particle size 3 ~
4μ polymethyl methacrylate 60mg / m ² , particle size 10-20m
μ colloidal silica 70 mg / m ² , silicone oil 100 mg
/ m ² was added, and dodecylbenzene sulfonic acid sodium salt as a coating aid, a protective layer to which a fluorine-based surfactant having the following structural formula was added, and gelatin on the back side of the support 0.7 g / m
^2, polyethyl acrylate latex 225 mg / m ^2, the dye 20 mg / m ² of the following structural formula, the dye 10 mg / m ² and sodium dodecylbenzenesulfonate simultaneously applying a back layer added as a coating aid, a photosensitive material It was made.

The photosensitive material thus prepared was subjected to scanning exposure for 10 ^-7 seconds using a semiconductor laser having a wavelength of 780 nm, and then the following developing solution, fixing solution and washing solution were formulated,
The following processing was performed with an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd., which was modified so that the replenishing amount of the fixing solution could be changed.

Treatment process Process treatment time Treatment temperature Replenishment amount (amount per m ² ) Development 13.7 seconds 35 ℃ 390ml Fixing 12.5 seconds 32 ℃ 500ml 230ml Washing 6.2 seconds 20 ℃ 500ml (Developer) g / (use solution) Potassium hydroxide 24 Sulfite Potassium 70 Diethylenetriamine pentaacetic acid 2.4 Boric acid 10 Hydroquinone 35 Diethylene glycol 11.2 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.5 5-Methylbenzotriazole 0.06 pH 10.05 50 sheets in quarter size per day (developing blackening rate of 1 sheet of film
40%) running treatment was continued for 6 days.

When the photosensitive material is subjected to the development processing, the amount of the circulating stirring liquid of the developer is set to 20 / min.
Set to minutes.

The developing solution and the fixing solution were prepared as 2.5 times and 4 times concentrated solutions of the above formulations, respectively, and the stock solution and water were added by the immediately preceding mixing method.

After completion of the running process, the same sample as the sample for running process was used to measure the time until it became transparent at 32 ° C.

Further, the presence or absence of precipitation in the fixing bath was visually examined. The results are shown in Table 1.

It can be seen from Table 1 that when the compound of the present invention is used, precipitation is not generated even during the running process, the liquid stability is good, and desilvering is possible with a fixing time of 12.5 seconds. Clearly superior to single use.
This effect is particularly remarkable when fixing replenishment is used.

Further, since the fixing solution of this embodiment does not contain an organic acid, it has no odor as compared with the existing fixing solution containing an organic acid (for example, the fixing solution A of Example 3) and the iron parts of the equipment. There was no rust.

In this example, comparison was made with the case where the total amount of potassium sulfite in the developer formulation was replaced with 60 g of sodium sulfite (preparation as a working solution).

In the fixing solution A using only ammonium thiosulfate, the larger the amount of potassium ions in the developing solution, the larger the fixing speed delay at the time of low replenishment of the fixing solution, but the fixing solution B using the compound of the present invention causes the fixing delay. You can see that it is suppressed.

Example 2 The same test as in Example 1 was conducted by replacing Compound-1 in Example 1 with Compounds-4 and 5. As a result, as in the case of Example 1, good results were obtained in that the fixing ability was high even in the running liquid and no precipitation was generated during the running treatment.

Further, this effect was particularly remarkable at a low replenishing amount.

Example 13 (Preparation of photosensitive emulsion) 4 × 10 ⁻⁷ per mol of silver was added to an aqueous gelatin solution kept at 50 ° C.
In the presence of moles of iridium (III) potassium chloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide are added simultaneously for 60 minutes, and the pAg between them is kept at 7.8. A cubic monodispersed emulsion having an average silver iodide content of 0.3 mol% was prepared. The emulsion was desalted by flocculation, and then 40 g of inert gelatin per mole of silver was added.
5,5'-dichloro-9-ethyl- as sensitizing dye
3,3'-Bis (3-sulfopropyl) oxacarbocyanine and a KI solution of 10 ^-3 mol per mol of silver were added, and the mixture was aged for 15 minutes and then cooled.

(Coating of photosensitive emulsion layer) This emulsion was redissolved, and the following hydrazine derivative was added at 40 ° C. Further, 5-methylbenztriazole, 4-hydroxy-1,3,3a, 7-tetrazaindene, the following compound (a),
(B) and 30% by weight of gelatin relative to polyethyl acrylate and the following compound (c) as a gelatin hardener were added, and an undercoat layer (0.5%) of a vinylidene chloride copolymer was added.
μ) of polyethylene terephthalate film (15
0 μ) and the amount of silver was 3.4 g / m ² .

(Coating of protective layer) As a protective layer, gelatin 1.5 g / m ² , polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g / m ² , and AgCl fine particles (0.08 μ) prepared by the following method were applied thereon. 0.3g / m in Ag amount
² was applied using the following surfactant.

These samples were cut into a large size (50.8 cm x 61.0 cm), exposed to 50% blackening with 3200 ° K tungsten light, and then processed with 200 sheets according to the following processing recipe.

Processing process Processing time Processing temperature Replenishment amount Image 30 seconds 34 ° C 240ml Fixing 30 seconds 34 ° C 390ml 250ml Water wash 30 seconds 20 ° C 2 Replenishment amount is shown as amount per 1 m ² of photosensitive material.

Add water and add potassium hydroxide to adjust pH to 11.7 Add water to add 1 and sodium hydroxide to adjust to pH 4.8.

The presence or absence of precipitates in the fixer after this series of continuous treatments was visually inspected. Further, with respect to the fixing solution after the completion of the series of processing, the clearing time was measured at 34 ° using the processed sample.

 The results are shown in Table 2.

As shown in Table 2, by using the compound of the present invention together, the fixing speed is increased, and the fixing speed is less delayed during running, and the effect becomes remarkable especially when the replenishment amount is reduced. It was found that no precipitation was observed in any of them and the stability was excellent.

Claims (4)

(57) [Claims] 1. After exposing a black-and-white silver halide photographic light-sensitive material,
In the method of at least developing and fixing using an automatic processor, 80 mol% or more of the salt component of the developer is a salt having potassium ion as a cation, and the replenishing amount of the fixer is 350 ml or less per 1 m ^{2 of the} light-sensitive material. And a fixing solution containing at least one mesoionic compound as a fixing agent, the method for processing a black-and-white silver halide photographic light-sensitive material. 2. The method according to claim 1, wherein the mesoionic compound is represented by the following general formula (I):
The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, which is a compound represented by: General formula (I) (Wherein, Z is a carbon atom, a nitrogen atom, an oxygen atom, a 5 or 6-membered ring composed of a sulfur atom or a selenium atom, X ^- is -O ^-, -S ^- or -N ^- R (wherein R is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group,
Represents an aralkyl group, an aryl group or a heterocyclic group). 3. The mesoionic compound is represented by the following general formula (II):
The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, which is a compound represented by: General formula (II) (In the formula, R ₁ and R ₂ represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, provided that R ₂ may be a hydrogen atom. -O -, - S -, - N (R 3) - ( wherein R ₃ is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, A sulfonamide group, a ureido group or a sulfamoylamino group), R ₁ and R ₂ , R ₂ and
R _3's may be bonded to each other to form a ring. 4. The method of processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the pH buffer used in the fixing solution is substantially only an inorganic compound.