JPH0534872A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make fixing speed high to rapidly process photographic sensitive material without sacrificing other performance by using both the specified sodium thiosulfate and mesoionic compound as a fixing agent. CONSTITUTION:Fixing liquid where 0.5-2.0mol/l sodium thiosulfate and 0.003-0.3mol/l mesoionic compound represented by the formula I are included and the quotient of mols of the compound and the sodium thiosulfate is 0.003-0.2 is used for processing. In the formula I, Z represents a five-or six-membered ring composed of a carbon atom, nitrogen atom, oxygen atom, sulfur atom or selenium atom. X<-> represents -O<->,-S<-> or-N<->R (where R represents an alkyl radical, cycloalkyl radical, alkenyl radical, alkinyl radical, allyl radical or heterocyclic radical).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method of a silver halide photographic light-sensitive material, and more particularly to a fixing processing suitable for a rapid processing method of a black-and-white silver halide light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the delivery period has been shortened in the printing and platemaking industry.
There is an increasing demand for reduction of processing time in order to improve work efficiency. The fixing time is preferably 19 seconds or less in order to achieve a total processing time of 60 seconds or less. When processing a large-sized photosensitive material such as a scanner film, a return film and a facsimile film used in the plate making field, there is a case where the central portion of the photosensitive material is insufficiently fixed especially in a fixing time of 19 seconds or less. In addition, the washing time becomes short, so that the washing performance may be poor and the image storability may be poor. As a countermeasure against this, it is conceivable to reduce the amount of silver halide in the light-sensitive material, but this generally brings about a decrease in maximum density.
Especially in the field of printing light-sensitive materials, there is a reduction work, and the amount of silver is preferably 2.0 g / m ² or more, and there is a limit to the reduction of the amount of silver.

Further, as fixing means for improving the fixing speed, there are an increase in the fixing temperature and an increase in the amount of agitation in the fixing tank. The problem of evaporation occurs, and the problem that the evaporated sulfurous acid gas corrodes indoor equipment occurs. There is also a method of increasing the circulation amount of the fixing solution. In this case, the fixing property is improved in the vicinity of the solution outlet, but the effect is diminished in the central part. In order to improve the fixing property in the central portion, it is necessary to considerably increase the circulation amount, and at both ends, it becomes excessive and energy is wasted.

On the other hand, from the viewpoint of the composition of the fixing solution, it is common to increase the concentration of the fixing agent (usually thiosulfate) in order to increase the fixing speed, but (a) the thiosulfate concentration is 2 mol / mol. On the other hand, if it is more than 1 liter, fixing is suppressed. (B) Washing time is shortened due to rapid processing. Therefore, if the concentration of the fixing agent is high, the washing property is deteriorated, the amount of residual hypo is increased, and the image storability is deteriorated. . (C) The pollution load of the fixer and washing water increases. (D) There is a limit in practical use due to restrictions such as difficulty in concentrating the fixing solution and high cost. Also, the use of an organic compound instead of thiosulfate as a fixing agent has been studied. As a fixing agent replacing thiosulfate, US Pat. No. 4,378,424, JP-A-57-150.
No. 842 and the like describe the use of a mesoionic compound, 1,2,4-triazolium-3-thiolate, but these documents only describe a mode in which only a mesoionic compound is used as a fixing agent.

Further, JP-A-1-201659 discloses that a mesoionic thiolate compound is added as a bleaching accelerator to a bleaching bath or a bleach-fixing bath.
-44355 discloses the use of a bleaching solution using diethylenetriaminepentaacetic acid ferric salt and a fixing agent containing a 1,2,4-triazolium-3-thiolate compound in the processing of color light-sensitive materials. There is no description of use as a fixing solution for rapid processing of black-and-white silver halide light-sensitive materials that does not use a bleaching solution as in the present invention, and no mention is made of the effects intended by the present invention. Other than the above, as the mesoionic compound, US Pat.
003,910, 4,675,276, 4,6
24,913, 4,631,253, JP-A-62.
-217237, 64-3641, 60-14
No. 4737, No. 62-253161, No. 62-287.
No. 239, No. 61-176920, No. 62-9694.
No. 3 and JP-A No. 1-154056 are disclosed,
All of them are added to the photographic light-sensitive material or added to the developing solution, and no mention is made of the effects intended by the present invention.

Ammonium thiosulfate has been used as a fixing solution for rapid processing, but there is a problem that ammonia gas is generated in the ammonium thiosulfate when the developing solution is brought in. Furthermore, in recent years, there has been a demand for a low replenishment of the processing liquid due to environmental reasons such as low discharge of the waste liquid and reduction of the processing work.

[0007]

SUMMARY OF THE INVENTION With respect to the above problems, an object of the present invention is to provide a rapid and low replenishment processing method for silver halide photographic light-sensitive materials. Further, the present invention relates to a fixing solution for rapid processing, which has a good fixing property even in the rapid and low replenishment processing and does not generate ammonia gas.

[0008]

Conventionally, ammonium thiosulfate has been used as a fixing solution for rapid processing from the viewpoint of the fixing speed, but there is a problem that ammonia gas is generated in the ammonium thiosulfate by bringing in a developing solution. is there. Further, sodium thiosulfate has no problem with respect to generation of ammonia gas, but when the fixing solution is a new solution, the fixing speed is inferior to that of ammonium thiosulfate. But,
As a result of diligent study by the present inventor, the fixing rate of sodium thiosulfate approaches the fixing rate of ammonium thiosulfate when the replenishment of the fixing solution is processed at a low replenishment rate, and when the replenishment rate of the fixing solution is further lowered, the fixing rate becomes I found the speed reversed.

The above object of the present invention is 0.5 to 2.0 mol / mol.
Liter of sodium thiosulfate, 0.003-0.3
A value obtained by dividing the number of moles of the compound represented by the general formula (I) by the number of moles of sodium thiosulfate is 0.003 to 0. It was achieved by a method of processing a silver halide black and white light-sensitive material characterized by processing with a fixing solution such as 2. The mesoionic compound represented by the general formula (I) works as a solvent for silver halide even if it is used alone, and has a fixing action. However, the complex salt when silver and mesoion is an emulsion as compared with the complex salt of silver and thiosulfate ion. It has a drawback that the diffusion speed in the film is slow and that it remains as residual silver in the emulsion film during rapid processing. In addition, the mesoionic compound has a longer clearing time in fixing (time until the photosensitive material becomes transparent in the fixing solution) when used alone, and is inferior to thiosulfate as compared with thiosulfate. However, as a result of earnest studies on the speeding up of the fixing speed, the present inventors have found that the fixing speed is increased by using the mesoionic compound in combination with the thiosulfate in the ratio of the present invention. That is, when a part of sodium thiosulfate was replaced with a mesoionic compound so that the total molar concentration of the fixing agent was matched, fixing using a mesoionic compound in combination with sodium thiosulfate rather than a fixing solution using only sodium thiosulfate It has been found that the liquid has a significantly higher fixing speed. There is a preferable range for the ratio of the mesoionic compound to sodium thiosulfate, and 0.003 to 0.2 is preferable,
Furthermore, 0.01-0.15 is more preferable. 0.003
When both are smaller than 0.2 and larger than 0.2, the fixing speed is equal to or inferior to the case where the total amount of the fixing agent is sodium thiosulfate.

The concentration of sodium thiosulfate in the present invention is preferably 0.5 to 2.0 mol / liter, and more preferably 0.8.
~ 1.5 mol / l is preferred. The above general formula (I)
The compound of the present invention represented by 0.003 to 0.3 mol /
The concentration is liter, preferably 0.004 to 0.2 mol / liter, and more preferably 0.005 to 0.1 mol / liter. The pH of the fixer is 5.0 to 7.5,
Preferred is 5.3 to 6.5. It is known and widely used to incorporate a water-soluble aluminum compound in a fixing solution in order to harden the film surface of a light-sensitive material and improve the drying property. However, the water-soluble aluminum compound delays the fixing speed due to the hardening effect. Further, in order for the water-soluble aluminum compound to be stably present in the fixer, the pH value of the fixer must be lowered, and the odor caused by acetic acid and sulfurous acid gas in the fixer and the rust-prone machine can easily be rusted. There's a problem. Furthermore, when the processing is performed with a low replenishment amount of the fixing solution containing a water-soluble aluminum compound,
There is also a problem that precipitation of aluminum hydroxide occurs. Thus, a fixing solution containing no or only a small amount of a water-soluble aluminum salt can be added
H can be set to 5.0 or more, there is no problem of odor and rust peculiar to the fixing solution, and a good fixing speed can be obtained even if the replenishment amount per square meter of silver halide black and white photosensitive material is 0.3 liters or less. A fixer having was obtained. The compound represented by formula (I) used in the present invention will be described.

[0011]

[Chemical 2]

[0012] In the formula, Z represents a carbon atom, a nitrogen atom, an oxygen atom, 5 or 6-membered ring composed of a sulfur atom or a selenium atom, X ^- is ^-O -, -S ^- or -N ^-
R 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. General formula (II)

[0013]

[Chemical 3]

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-, -N
Represents (R ₃ )-, R ₃ is 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,
It represents an ureido group or a sulfamoylamino group. R
₁ and R ₂ , and R ₂ and R ₃ may be bonded to each other to form a ring.

Next, the general formula (I) will be described in detail. Examples of the 5-membered heterocycle represented by Z include imidazoliums, pyrazoliums, oxazoliums, thiazoliums, triazoliums, tetrazoliums, thiadiazoliums, oxadiazoliums, thiatriazoliums, and oxatriazoliums. Kind and the like. R is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, n-octyl group, carboxyethyl group, ethoxycarbonylmethyl group, dimethylaminoethyl group, etc. ), A substituted or unsubstituted cycloalkyl group (eg, cyclohexyl group, 4-methylcyclohexyl group, etc.), a substituted or unsubstituted alkenyl group (eg, propenyl group,
Etc.), a substituted or unsubstituted alkynyl group (eg, propargyl group, 1-methylpropargyl group, etc.), a substituted or unsubstituted aralkyl group (eg, benzyl group, 4-
Methoxybenzyl group, etc.), a substituted or unsubstituted aryl group (eg, phenyl group, 3-methoxyphenyl group,
Etc.), a substituted or unsubstituted heterocyclic group (eg, pyridyl group, imidazolyl group, morpholino group, triazolyl group,
A tetrazolyl group, a thienyl group, etc.).

The heterocycle represented by Z is a nitro group,
Halogen atom (eg chlorine atom, bromine atom, etc.), mercapto group, cyano group, substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group) , Trimethylammonioethyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group, etc.), aryl group (for example, phenyl group, 4-sulfophenyl group, etc.), Alkenyl group (eg allyl group etc.), cycloalkyl group (eg cyclohexyl group etc.), alkenyl group (eg propargyl group etc.), aralkyl group (eg benzyl group, 4-
Methylbenzyl group, etc.), alkoxy group (eg methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (eg phenoxy group, etc.), alkylthio group (eg methylthio group, ethylthio group, etc.), arylthio group (Eg, phenylthio group, etc.), sulfonyl group (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), thiocarbamoyl group (eg, dimethylthiocarbamoyl group) , Etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (eg, acetamide group, benzamide group, methoxypropionamide group, etc.), sulfonamide group (Eg methane Rufonamide group, benzenesulfonamide group, etc.), acyloxy group (eg acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg methanesulfonyloxy group, etc.), ureido group (eg unsubstituted ureido group, methyl) Ureido group, ethylureido group, methoxyethylureido group, etc.), thioureido group (eg, unsubstituted thioureido group, methylthioureido group, methoxyethylthioureido group,
Etc.), a sulfamoylamino group (for example, an unsubstituted sulfamoylamino group, a dimethylsulfamoylamino group,
Etc.), an acyl group (eg acetyl group, 4-methoxybenzoyl group, etc.), a thioacyl group (eg thioacetyl group, etc.), a heterocyclic group (eg 1-morpholino group, 1-
Piperidino group, 2-pyridyl group, 4-pyridyl group, 2-
Thienyl group, 1-pyrazolyl group, 1-imidazolyl group,
2-tetrahydrofuryl group, tetrahydrothienyl group,
Etc.), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group, methoxyethoxycarbonyl group, etc.), oxycarbonylamino group (eg methoxycarbonylamino group, etc.), amino group (eg unsubstituted amino group, dimethylamino group) , Etc.), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxyl group and the like.

Further, the compound represented by the general formula (I) may form a salt (eg, acetate, nitrate, salicylate, hydrochloride, iodate, bromate, etc.). In general formula (I), X ⁻ preferably represents —S ⁻ .

The compound represented by the general 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 (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 (for example, 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, dimethylamino group). Ethylthioethyl 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 groups (eg propargyl groups,
Etc.) a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, 4-methoxybenzyl group,
Etc.), aryl groups (eg 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) Group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, etc.), substituted or unsubstituted amino group (eg, unsubstituted amino group, dimethylamino group, methylamino group, etc.) , An acylamino group (eg, acetylamino group, benzoylamino group, methoxypropionylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, 4-toluenesulfonamide group, etc.), ureido group (eg, , Unsubstituted ureido group, 3-methylureido group, etc.), sulfamoylamino group (eg, In unsubstituted sulfamoylamino group,
3-methylsulfamoylamino group, etc.).

In the general formula (II), Y is preferably --N (R
₃ )-, 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. Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0021]

[Chemical 4]

[0022]

[Chemical 5]

The compounds represented by the above general formula (I) or (II) of the present invention are described in Journal of Heterocyclic Chem.
5 (1965), Journal of Organic Chemistry (J.Org.Chem.) 32, 2245 (196).
7), Journal of Chemical Society (J.
Chem.Soc.) 3799 (1969), Journal of.
American Chemical Society (J.Am.Chem.So
c.) 80, 1895 (1958), Chemical Communication (Chem.Commun.) 1222 (1971), Tetrahedron Lett. 2939
(1972), JP-A-60-87322, Berichte.
Der Germany Cheso Hemischen Gesellschaft (Berichte der Deutschen Chemischen Gesellschaft)
38, 4049 (1905), Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 1224 (1971), JP-A-60-122936, JP-A-60-117240.
Issue, Advances in Heterocyclic Chemistry 1
9, 1 (1976), tetrahedron, letters (Tetr
ahedron Letters) 5881 (1968), Journal of Heterocyclic Chemistry (J. Hetero
Cyclic Chem.) 5, 277 (1968), journal
Of Chemical Society Perkin Transaction I (J.Chem.Soc., Perkin Trans. I) 627 (1
974), Tetrahedron Le
tters) 1809 (1976) and 1578 (197).
1), Journal of Chemical Society (J.
Chem. Soc.) 899 (1935), ibid 2865 (195)
9), Journal of Organic Chemistry (J. Org. Chem.) 30, 567 (1965) and the like.

The compounds of the present invention are preferably used in fixers or fixer replenishers. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid, boric acid), pH adjuster (eg, ammonia). , Sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators. 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.
As the fixing accelerator, for example, JP-B-45-35754
Nos. 58-122535 and 58-122536, thiourea derivatives described therein, alcohols having a triple bond in the molecule, and thioether compounds described in US Pat. No. 4,126,459. As the pH buffer, for example, organic acids such as acetic acid, malic acid, succinic acid, tartaric acid and citric acid, and inorganic buffering agents such as boric acid, phosphate and sulfite can be used. It is preferable to use an inorganic buffering agent from the viewpoint of suppressing odor and rusting of equipment materials. Where pH
The buffer is used for the purpose of preventing the pH of the fixing solution from rising due to the carry-in of the developing solution, and is used in an amount of 0.1 to 1.0 mol / liter, more preferably 0.2 to 0.6 mol / liter.

Hardeners in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. and 5 seconds to 1 minute. The replenishing amount of the fixing solution is 300 ml / m ² or less, preferably 180 ml / m ² or less.

The developer used in the development processing of the light-sensitive material of the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffer, preservative, chelating agent). . Any known method can be used for the development processing of the present invention, and a known development 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, and in view of developing ability, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or A combination of dihydroxybenzenes and p-aminophenols is preferred. Hydroquinone as a dihydroxybenzene developing agent used in the present invention,
Chlorohydroquinone, isopropylhydroquinone,
There are methylhydroquinone and the like, but hydroquinones are particularly preferable. As the developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 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-based developing agent is preferably used usually in an amount of 0.05 mol / liter to 0.8 mol / liter. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.0
5 mol / l to 0.5 mol / l, the latter of 0.
It is preferably used in an amount of 06 mol / liter or less.

Examples of preservatives 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 / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is 1.2 mol / liter. Is desirable. 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.
Additives used other than the above include development inhibitors such as sodium bromide and potassium bromide; ethylene glycol, diethylene glycol, triethylene glycol,
Organic solvents such as 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, and benzotriazole-based compounds as 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, the compound described in JP-A-62-212651 can be used as the development unevenness preventing agent, and the compound described in JP-A-61-267759 can be used as the dissolution aid.

In the developer used in the present invention, boric acid described in JP-A-62-186259, saccharides (eg saccharose) and oximes (eg acetoxime) described in JP-A-60-93433 are used as a buffer. , Phenols (eg 5-sulfosalicylic acid), tertiary phosphates (eg sodium salt, potassium salt), etc. are used,
Boric acid is preferably used. Transportation cost of processing liquid,
For the purpose of 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.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment may be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only is it possible to save water,
It is possible to eliminate the need for piping for the automatic processor. When the washing with water is carried out with a small amount of water, JP-A-63-18350 and JP-A-6-18350.
It is more preferable to provide a washing tank for a squeeze roller or a crossover roller described in JP-A-2-287252. In addition, various oxidants may be added or filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means by the method of the present invention depending on the treatment is disclosed in JP-A-60- As described in No. 235133, it can also be used for a processing liquid having a fixing ability which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, a dye adsorbent described in JP-A-63-163456 may be installed in a water washing tank to prevent contamination by dyes eluted from the light-sensitive material.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and as an example thereof, JP-A-2-201357 is used.
The baths containing the compounds described in JP-A Nos. 2-132435, 1-1022553, and JP-A-46-44446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). Preference is given to using.

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 25 ° C.
-50 degreeC is preferable and 30 degreeC-40 degreeC is more preferable.
The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. and 19 seconds or less, more preferably 30 ° C. to 40 ° C. and 6 seconds to 15 seconds. The temperature and time for washing or stabilizing bath are more preferably 0 to 50 ° C. According to the method of the present invention, the developed, fixed and washed (or stabilized) photographic material is squeezed out of the washing water, that is, dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as a silver halide, a conventional halogenated silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide or the like. Any silver halide emulsion may be used, and preferably, a negative silver halide emulsion containing 60 mol% or more of silver chloride or a positive silver halide emulsion of 6 mol.
Silver chlorobromide, silver bromide, and silver iodobromide containing 0 mol% or more of silver bromide. The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method. The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside and the surface layer of the grain, and the latent image is mainly on the surface. Even if the particles are formed in
Further, particles that are mainly formed inside the particles may be used. The silver halide grains according to the present invention may have any shape. One preferable example is {10
It is a cube having a 0} plane as a crystal surface. US Pat. Nos. 4,183,756 and 4,225,666,
Methods described in JP-A-55-26589, JP-B-55-42737, and the like, and the Journal of Photographic Science (J.Photgr.Sci.), 21-39 (1973), and the like. , Octahedron, 14-sided, 1
Particles having a shape such as a dihedron can be prepared and used. Further, grains having twin planes may be used. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes. In the present invention, a monodisperse emulsion is preferred. As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained within a grain size range of ± 10% around the average grain size γ is 60% of the total weight of silver halide grains.
% Or more is preferable.

The silver halide grains used in the emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt in the course of forming grains and / or in the process of growing. , An iron salt or a complex salt may be used to add a metal ion, and the metal ion may be included inside the particle and / or on the surface of the particle. The photographic emulsion used in the present invention may be used in combination with sulfur sensitization, gold / sulfur sensitization, reduction sensitization using a reducing substance: noble metal sensitization using a noble metal compound, and the like. As the photosensitive emulsion, the above emulsions may be used alone, or two or more kinds of emulsions may be mixed. In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene, 5-mercapto-1
Various stabilizers can be used including phenyltetrazole and 2-mercaptobenzothiazole. Further, if necessary, a silver halide solvent such as thioether, or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used. In the present invention, particularly in the case of a photosensitive material for printing, a preferable effect is exhibited for a photosensitive material to which a so-called contrast-increasing agent such as a tetrazolium compound, a hydrazine compound or a polyalkylene oxide compound is added.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion may be spectrally sensitized with a sensitizing dye into blue light, green light, red light or infrared light having a relatively long wavelength. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. The silver halide photographic light-sensitive material according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation and prevention of halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are West German Patent 616,00.
7, British Patent 584,609, 1,117,42
No. 9, Japanese Patent Publication No. 26-7777, No. 39-22069
No. 54-38129, JP-A-48-85130.
No. 49-99620, No. 49-114420,
49-129537, PB Report 74175,
Photographic Abstract (Photo.Abstr.)
128 ('21) and the like. In particular, it is preferable to use these dyes in a bright room reversal light-sensitive material. In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like. Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. Further, a technique of incorporating a polymer latex into a silver halide emulsion layer or a backing layer to improve dimensional stability can also be used. These technologies are
For example, Japanese Examined Patent Publication Nos. 39-4272 and 39-17702.
No. 43-13482, and the like. Gelatin is used as the binder of the light-sensitive material used in the present invention. However, gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins,
A hydrophilic colloid such as a sugar derivative, a cellulose derivative, a synthetic hydrophilic polymer such as a single or copolymer, or the like can also be used in combination.

Various additives can be further used in the light-sensitive material of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure No. 17
Volume 6 Item 17643 (December 1978) and 18
Volume 7 Item 18716 (November 1979), the relevant parts are summarized in the table below. Additive type R17643 RD18716 1. Chemical sensitizer page 23 page 648 right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggant, pages 24 to 25, page 649, right column, and stabilizer 6. Light absorbers, filters Pages 25-26 649 Right column-Dyes, UV absorbers 650 Left column 7. Anti-staining agent, page 25, right column, page 650, left to right column 8. Dye image stabilizer, page 25 9. Hardener, page 26, page 651, left column 10. Binder p. 26 Same as above 11. Plasticizer, lubricant Page 27, 650, right column 12. Coating aids / surfactants pp. 26-27 Same as above 13. Antistatic agent Page 27 Same as above

The support used in the light-sensitive material of the present invention is a flexible reflective support such as paper laminated with α-olefin polymer (eg polyethylene, polypropylene, ethylene / butene copolymer) or synthetic paper, Cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
Films made of semi-synthetic or synthetic polymers such as polyamide, and flexible supports provided with a reflective layer on these films,
Metals etc. are included. Among them, polyethylene terephthalate is particularly preferable. As the undercoat layer which can be used in the present invention, an undercoat layer containing an organic solvent system containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-49-11118 and JP-A-52-104913. , And the like, and the aqueous latex undercoating layer described in. or,
The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, and other surface activation treatments. The present invention can be applied to various photosensitive materials for printing, X-ray, general negative, general reversal, general positive, direct positive and the like.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .

[0038]

EXAMPLES The present invention will be specifically described below 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 ⁻⁸ mol of K ₃ IrCl ₆ and 3 × 10 ⁻⁷ mol of (NH ₄ ) ₃ RhCl were added per mol of silver. A monodispersed silver chlorobromide emulsion having an average grain size of 0.15 μm was prepared by simultaneously adding an aqueous solution of sodium chloride and sodium bromide containing ₆ for 30 minutes and maintaining the potential at 200 mV during that period. To this emulsion, 0.1 mol% potassium iodide aqueous solution was added per mol of silver for conversion, followed by desalting by flocculation method and dispersion in gelatin to prepare Emulsion A. (AgCl _69.9 Br ₃₀ I _0.1 , dispersion coefficient 10
%). Hypo and N, N-dimethylselenourea were added to this emulsion, and the emulsion was kept at 60 ° C. for chemical ripening, and then 4-hydroxy-6-methyl-1,3,3 as a stabilizer.
30 ml of a 1% solution of a, 7-tetrazaindene was added per mol of silver.

To 1 kg of these emulsions, a compound having the following structural formula was used as an infrared sensitizing dye, and 60 ml of a 0.05% solution thereof was added to carry out infrared sensitization. For the purpose of supersensitization and stabilization of the emulsion, 0,4'-bis- [4,6-di (naphthoxy-pyrimidin-2-ylamino] -stilbene-2,2'-disulfonic acid disodium salt was added to the emulsion. .5
% Methanol solution (50 ml), 2,5-dimethyl-3-allyl-benzothiazole iodo salt (0.5% methanol solution 90 ml) and potassium bromide (1% aqueous solution) (15 ml).

Further, hydroquinone 100 mg / m ² , polyethyl acrylate as polymer latex 25% in gelatin binder ratio, and 2-bis (vinylsulfonylacetamide) ethane as hardener were added, and 3.5 g / silver on PET support. It was applied so as to be m ² . The gelatin was 1.3 g / m ² . 0.6g of gelatin on this
m ^2, the particle size 3~4μ polymethyl methacrylate 60 mg / m ² as a matting agent, colloidal silica 40 mg / m ² of particle size 10～20Emumyu, silicone oil 100 mg / m ^2, the dye 20 mg / m ² of the following structural formula, Dye 10 mg / m ² was added, and dodecylbenzene sulfonic acid sodium salt as a coating aid, a fluorine-containing surfactant of the following structural formula was added to the protective layer and the back surface of the support: 0.7 g / m ² , gelatin; acrylate latex 225 mg / m ^2, average particle diameter polymethyl methacrylate 40 mg / m ² of 5μ dye having the structural formula shown below 70 mg / m ^2, and as a matting agent, and sodium dodecyl benzene sulfonate salt as a coating aid and 2mg / A back layer containing m ² was simultaneously applied to prepare a light-sensitive material.

[0041]

[Chemical 6]

The light-sensitive material thus produced was processed using the following developing solution, fixing solution, and developing machine without exposing it to light. The fixing liquid tank and washing water tank of the automatic developing machine are of the same type, and the number of opposed rollers is 7. The size of the photosensitive material is 20 × 24
Inches were used.

(Developer) g / liter (Used solution) Potassium hydroxide 24 Potassium sulfite 70 Diethylenetriaminepentaacetic 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 (fixing solution) Ammonium thiosulfate Addition amount shown in Table 1 Sodium thiosulfate Addition amount shown in Table 1 The compound types and addition amounts of the present invention are shown in Table 1. Description Sodium acetate 15 g / liter Sodium sulfite 9.0 g / liter Sodium bisulfite 15 g / liter Disodium ethylenediaminetetraacetate dihydrate 0.025 g / liter Adjust pH to 5.5 with sodium hydroxide (treatment of automatizer) Condition) Fixing time 10 seconds Down speed (mm / sec) 28 fixer circulation rate (m / min) 48 fixer circulation rate (%) 54 roller 7 logs developer temperature is 38 ° C., fixer temperature was set at 37 ° C..
The fixing process results are shown in Table 1.

[0044]

[Table 1]

In the evaluation of the fixing loss, in the sample of 20 × 24 inch size, good fixing is made possible, and defective fixing is caused even in a part of the defective xx. The residual silver amount is the measured silver amount in the center of the sample. The amount of residual silver is preferably as small as possible and should be 10 mg / m ² or less. As is clear from Table 1, the use of the compound of the present invention in the fixing solution improves the fixing loss. When the concentration of sodium thiosulfate is low, fixing is slow, and when the concentration of sodium thiosulfate is increased, the fixing loss is improved, but when the concentration is further increased, the fixing loss is deteriorated again. It can be seen that the addition amount of the compound of the present invention has a preferable addition amount range as well as the concentration of sodium thiosulfate. The NH ₃ amount (ppm) is a measure of the amount of ammonia gas generated when the photosensitive material passes through the fixing tank. In the case of ammonium thiosulfate, ammonia gas is generated when the developing solution is brought in by the photosensitive material. , Sodium thiosulfate does not generate ammonia gas.

Example 2 Using the light-sensitive material prepared in Example 1, the following developing solution and fixing solution were used without exposing to light, using an automatic developing machine having the processing conditions shown in the table below. The automatic machine is line speed,
The fixer circulation speed and circulation amount were designed to be variable. The fixer tank and the washing water tank are of the same type. The size of the processed photosensitive material was 20 × 24 inches. (Developer) g / liter (Used solution) Potassium hydroxide 24 Potassium sulfite 70 Diethylenetriaminepentaacetic acid 2.4 Boric acid 10 Hydroquinone 35 Diethylene glycol 11.2 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2 0.5 5-methylbenzotriazole 0.06 pH 10.05 (fixing solution) Fixing solution ABCD sodium thiosulfate 200 g / liter 200 g / liter 200 g / liter 200 g / liter Compound of the present invention-1 5.0 g / liter 5.0 g / liter 5.0 g / liter-sodium sulfite 31 g / liter 31 g / liter 31 g / liter 31 g / liter Boric acid 12 g / liter 12 g / liter 12 g / liter 12 g / liter Tartaric acid 4.3 g / liter 4.3 g / liter 4.3 g / liter 4.3 g / liter acetic acid 46g / liter 46g / liter 46g L 46g / L Ethylenediaminetetraacetic acid disodium dihydrate 0.025g / L 0.25g / L 0.25g / L 0.25g / L Aluminum sulphate 10g / L --- Adjust pH with sodium hydroxide pH = 4.5 pH = 4.5 pH = 6.0 pH = 6.0 (Processing condition of developing machine) Fixing time 10 seconds Line speed (mm / sec) 27 Fixing solution circulation speed (m / min) 48 Fixing solution circulation amount (%) 54 Roller log number 7 Development 38 The temperature was 15 seconds, the fixing was 37 degrees C, and the total dry-to-dry processing time was 50 seconds. The fixer tank capacity is 10 liters and the developer tank capacity is 10 liters. The concentration of sodium thiosulfate in the fixer is 1.
27 mol / liter. The value obtained by dividing the concentration of the mesoionic compound 1 of the present invention by the concentration of sodium thiosulfate is 0.028.
Is. The replenisher was replenished at a constant rate each time the light-sensitive material was processed. For the fixing solution and the developing solution, a solution having the same composition as the replenisher was used in the tank of the developing machine. Sensitive material (20 x 2)
Evaluation was performed on the 500th sheet of the light-sensitive material, which was obtained by replenishing 500 sheets of 4 inch) each time. The results are shown in Table 2.

[0047]

[Table 2]

The evaluation of fixing loss and the amount of residual silver were carried out by the same evaluation method as in Example 1. From the results shown in Table 2, the fixing solution of the present invention has no problem in fixing loss and residual silver amount even when the replenishing amount is 0.2 liter / m ² . Since the hardening type fixing solution A has a problem of aluminum hydroxide precipitation, it is necessary to keep the pH at 5.0 or less. pH 4.5
There is no practical problem with the fixing solutions A and B,
There is concern that SO ₂ gas will be generated and the parts of the automatic processing machine may be rusted. S
From the viewpoint of O ₂ gas generation, preferable fixing solutions are fixing solutions C and D having a high pH, but fixing solutions satisfying the performances of fixing loss and residual silver amount are the fixing solutions C of the present invention.

Example 3 Using the light-sensitive material prepared in Example 1, the following developing solution and fixing solution were used without exposure to light, using an automatic processor having the processing conditions shown in the table below. The automatic machine is line speed,
The fixer circulation speed and circulation amount were designed to be variable. The fixer tank and the washing water tank are of the same type. The size of the processed photosensitive material was 20 × 25 inches. (Developer) g / liter (Used solution) Potassium hydroxide 12 Sodium hydroxide 8.6 Potassium sulfite 35 Sodium sulfite 27.9 Diethylenetriaminepentaacetic acid 2.4 Boric acid 10 Hydroquinone 35 Diethylene glycol 11.2 4-Hydroxymethyl-4 -Methyl-1-phenyl 2.5-3-pyrazolidone 5-methylbenzotriazole 0.06 2,3,5,6,7,8-hexahydro-2-thioxo 0.180 pH adjusted to 10.65 with sodium hydroxide. (Fixing solution) Fixing solution AB Naliteum thiosulfate 200 g / liter-Ammonium thiosulfate-187 g / liter Compound of the present invention-3 5.0 g / liter 5.0 g / liter Sodium sulfite 31 g / liter 31 g / liter Boric acid 12 g / liter 12g / liter Tartaric acid 4.3g / liter 4.3g / liter Lu acetic acid 46 g / liter 46 g / liter Ethylenediaminetetraacetic acid 0.025 g / liter 0.025 g / liter Disodium dihydrate Adjust the pH with sodium hydroxide pH = 5.5 pH = 5.5 (processing conditions of the developing machine) Fixing time 10 seconds Line speed (mm / sec) 28 Fixer circulation speed (m / min) 48 Fixer circulation rate (%) 54 Roller pairs 7 Development 38 ° C 15 seconds, fixing 37 ° C, Dyr to Dry total processing time 50 Processed in seconds. The tank volume of the fixer is 10 liters, and the tank volume of the developer is also 10 liters. The value obtained by dividing the concentration of the mesoionic compound 1 of the present invention by the concentration of sodium thiosulfate is 0.028.
The replenisher was replenished at a constant rate each time the light-sensitive material was processed. For the fixing solution and the developing solution, a solution having the same composition as the replenisher was used in the tank of the developing machine. When replenishing the above sensitive material (20 x 24 inches) while processing 500 sheets each,
Measure the amount of ammonia when passing through the 500th photosensitive material,
The fixing speed of the liquid after processing 500 sheets was measured.
The results are shown in Table 3.

[0050]

[Table 3]

The fixing solution of ammonium thiosulfate has a problem of generation of ammonia gas. With the fixing solution A of the present invention, the problem of the generation of ammonia gas has been solved, and the fixing rate, which is the most important in the fixing solution, becomes the same as the fixing rate of ammonium thiosulfate as the replenishment rate becomes lower, and there is a practical problem. There is no range.

Example 4 Preparation of Emulsion 30 g of gelatin and 6 g of potassium bromide were added to 1 liter of water, and an aqueous silver nitrate solution (5 g as silver nitrate) and 0.15 g of potassium iodide were added to a container kept at 60 ° C. with stirring. The aqueous potassium bromide solution was added by the double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 2.1 g of potassium iodide were added by the double jet method. At this time, the flow rate of the addition was accelerated so that the flow rate at the end of the addition was 5 times that at the start of the addition. After the addition was completed, the soluble salts were removed at 35 ° C by the precipitation method, the temperature was raised to 40 ° C, and 75 g of gelatin was added to adjust the pH.
Was adjusted to 6.7. The obtained emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm. This emulsion was chemically sensitized by combining gold and ion sensitization.

In addition to gelatin, an average molecular weight of 8,000 was used as a surface protective layer for adjusting photographic materials.
An aqueous gelatin solution containing polyacrylamide, sodium polystyrene sulfonate, fine particles of polymethylmethacrylate (average particle size: 3.0 μm), polyethylene oxide, and a hardening agent was used. Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt was added to the above emulsion as a sensitizing dye in an amount of 500.
200 mg / 1 mol Ag of potassium iodide at a ratio of mg / 1 mol Ag
Was added. Furthermore, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6bis (hydroxyamino) -4-diethylamino-1,3,5-triazine and nitrone as stabilizers, anti-dry fog A photographic material was prepared by adding trimethylolpropane as an agent, a coating aid and a film hardener to obtain a coating solution, and coating and drying the coating solution on both sides of a polyethylene terephthalate support simultaneously with the surface protective layers. The coating silver amount of this photographic material is 3.5 g / m ² . The thickness of the emulsion surface was 4.0 μm and the swelling ratio was 180%.

LD-745 (manufactured by Fuji Photo Film Co., Ltd.) was used as the developing solution, and the fixing solution having the following formulation was used. The automatic developing machine was designed so that the line speed, the fixing solution circulation speed, and the circulation amount could be changed. The fixer tank and the washing water tank are of the same type. The size of the processed photosensitive material was 20 × 24 inches. (Fixer) AB Sodium thiosulfate 203 g 203 g Compound of the present invention 8-0.2 mol Sodium sulfite 22.0 g 22.0 g Disodium ethylenediaminetetraacetate 0.1 g 0.1 g Tartaric acid 1.0 g 1.0 g Ammonia water ( 27%) 5g 5g Acetic acid (90%) 30.0g 30.0g Add water to 1 liter, add sodium hydroxide to pH
Adjust to 5.5.

The processing conditions of the used automatic processing machine are as follows. The developer temperature was 35 ° C., the fixing solution temperature was 35 ° C., and the washing water temperature was room temperature. (Processing conditions of automatic processing machine) (1) (2) (3) Fixing time 16 "16" 16 "Line speed (mm / sec) 20 20 20 Fixer circulation speed (m / min) 40 40 110 Fixer circulation Amount (%) 42 42 125 roller pair 2 6 6 In fixing solution B, the concentration of sodium thiosulfate is 1.28.
It is mol / liter and the value obtained by dividing the concentration of the compound 8 of the present invention by the concentration of sodium thiosulfate is 0.16. The processing results are shown in Table 4. The fixing failure and the evaluation of the amount of residual silver were performed in the same manner as in Example 1.

[0056]

[Table 4]

It can be seen from Table 4 that the fixing solution of the present invention has good fixing omission even in rapid processing and is excellent in rapid processing property.

[0058]

According to the present invention, by using sodium thiosulfate and a mesoionic compound together in a fixed ratio,
With low replenishment, quick fixing process with less gas generation becomes possible.

Claims (2)

[Claims] 1. A sodium thiosulfate of 0.5 to 2.0 mol / liter and a mesoionic compound of the following general formula (I) of 0.003 to 0.3 mol / liter are contained, and A value obtained by dividing the number of moles of the compound represented by the formula (I) by the number of moles of sodium thiosulfate is 0.003 to 0.
2. A method of processing a silver halide black-and-white light-sensitive material, which comprises processing with a fixing solution of 2. 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 - represents a ^R. R
Represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. 2. A treatment using an automatic processor, the pH of the fixer is 5.0 to 7.5, and the concentration of the water-soluble aluminum compound in the fixer is 0 to 0.01 mol / liter.
2. The processing method according to claim 1, wherein the replenishing amount of the fixing solution is 0.3 liter or less when processing 1 square meter of the silver halide black-and-white light-sensitive material.