JP2000181028A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method of a silver halide photographic sensitive material prevented from corrosion of the metal parts of an automatic developing mmachine due to a gas emitted from a fixing solution and also from the occurrence of uneven processing. SOLUTION: The silver halide photographic sensitive material is processed with the automatic developing machine at least by the developing process and the fixing process, and at that time, the developing solution to be used contains a silver halide dissolving agent and the fixing solution to be used is controlled so as to restrain drop in pH to within 0.25 or less, when the fixing solution is added with 10 weight % of the developing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A commonly used black-and-white silver halide photographic material is developed, and an image is formed by a process comprising fixing, washing and drying steps. Among the processing solutions used in these steps, particularly, the conventional fixing solution contains thiosulfate as a fixing agent and sulfite, acetic acid, boric acid and the like as a buffer in addition to the above, and in some cases, is water-soluble. Those containing a hardening agent composed of an aluminum salt are generally used. In these fixing solutions, a large amount of a sulfite or the like is used as a preservative.

However, on the other hand, sulfites, acetic acid,
Because it contains a large amount of boric acid, etc., and there is a problem that the metal part of the automatic developing machine itself is corroded by a trace amount of gas generated from the fixing solution during operation of the automatic developing machine. It is generally practiced to exhaust a small amount of gas generated from the fixing solution to the outside, so that the mechanism of the automatic developing machine becomes complicated or the number of parts increases. However, when these sulfites, acetic acid, boric acid, etc. are reduced, the pH buffering capacity cannot be secured. A technique using succinic acid, maleic acid, or the like as a pH buffer instead of acetic acid is known.

However, with such a pH buffer, a sudden drop in pH at the early stage of the fixing step, that is, a so-called stop effect cannot be obtained, and processing unevenness occurs.

[0005]

The problem to be solved by the present invention is that the amount of gas generated from the fixing solution is small, and even if a fixing solution which does not corrode the metal part of the automatic developing machine itself is used, the processing unevenness is reduced. An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material free of generation.

[0006]

The above object is achieved by the following items which specify the present invention. (1) In a method for processing a silver halide photographic light-sensitive material in which at least a developing step and a fixing step are performed on the silver halide photographic light-sensitive material using an automatic developing machine, the fixing solution used in the fixing step has the following characteristics. A method for processing a silver halide photographic light-sensitive material, characterized in that the developing solution to be filled and used in the developing step contains a silver halide dissolving agent. Characteristics: pH of the developing solution when the fixing solution used in the fixing step is added at 10% by weight to the developing solution used in the developing step is 0.25 or less. (2) The silver halide dissolving agent is sodium thiosulfate,
The method for processing a silver halide photographic material according to the above (1), which is selected from potassium thiosulfate and ammonium thiosulfate. (3) The fixing solution contains 0.01 to 0.10 mol / sulfite.
Liter, acetic acid 0-0.05 mol / l, and a compound selected from succinic acid, maleic acid and malonic acid.
Containing 15-0.50 mol / l, pH 4.2-
6. The method for processing a silver halide photographic material according to the above (1) or (2), which is 6.2. (4) processing method of any of the silver halide photographic light-sensitive material of the replenishing amount of the silver halide photographic light-sensitive material 1 m ² per developer and fixer is 50~250ml (1) ~ (3) .

[0007]

Embodiments of the present invention will be described below in detail. In the present invention, a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material or a light-sensitive material) is processed using an automatic developing machine, and is subjected to processing steps including a developing step and a fixing step. Between the developing solution and the fixing solution used in the developing step and the fixing step, a fixing solution is added to the developing solution.
It is necessary to satisfy a relationship such that a decrease in pH of the developer when added at 0% by weight is 0.25 or less, preferably 0.20 to 0.10. The fixing solution is prepared so as to satisfy such characteristics. And the developer contains a silver halide dissolving agent. As described above, even when a fixing solution which is considered to have a small decrease in pH at the time of entering the fixing process from the developing process and it is considered difficult to obtain the processing unevenness preventing effect by the stop effect is used, the developing solution contains a silver halide dissolving agent. Thereby, processing unevenness can be prevented.

Conventionally, pH buffers used in fixing solutions are sulfites, acetic acid, and boric acid, and when these are used in large amounts, gas is generated. Rust occurs in parts. Therefore, it must be ventilated outdoors. It is preferable to use sulfite, acetic acid, and boric acid at a low concentration because the amount of generated gas can be reduced, but the pH buffering ability in a pH range of 4.2 to 6.2 as a fixing solution is reduced. Succinic acid, maleic acid, malonic acid, etc. are considered to be those which have an effective pH buffering ability in the pH range of 4.2 to 6.2 of the fixer but do not generate gas.
There is a fixing solution used at a concentration of 15 mol / liter or more. Such a fixing solution generates little gas which causes rust on a metal portion, and eliminates the need to exhaust air from an automatic developing machine to the outside.
However, such a fixing solution has a drawback that processing unevenness easily occurs. This is presumably because the pH decrease in the early stage of fixing is not sufficient. In such a processing system, the use of a silver halide dissolving agent in the developing solution enables processing of a silver halide photographic light-sensitive material free of processing unevenness.

The fixing solution used in the present invention is an aqueous solution containing a thiosulfate, and preferably has a pH of 4.2 to 6.2, more preferably 4.8 to 6.2. Examples of the thiosulfate include sodium thiosulfate and ammonium thiosulfate. The amount used can be appropriately changed, and is generally from 0.3 to 1.5 mol / l.

As a compound having a sufficient pH buffering capacity in the above pH range, one or more compounds selected from succinic acid, maleic acid and malonic acid are used in an amount of 0.15 to 0.15.
It is preferable to contain at 0.50 mol / l.
By using such a compound, there is no generation of gas which causes the generation of rust on the metal portion, and it becomes unnecessary to install an exhaust system in the automatic developing machine. Further, the content is set to the above-mentioned value because if the content is too small, the effect cannot be obtained. Considering the chemical cost and the difficulty in preparing the concentrated solution due to the limitation of the solubility, the content is 0.50 mol / liter. The following is preferred. Succinic acid, maleic acid,
Malonic acid may be a salt, and the salt is preferably an alkali metal salt (such as a lithium salt, a sodium salt, or a potassium salt), or an ammonium salt. In particular, it is preferable to use succinic acid.

The fixing solution of the present invention contains a sulfite (including bisulfite) as a preservative in an amount of 0.01 to 0.10.
The content is preferably in the range of mol / l, more preferably 0.01 to 0.05 mol / l. Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. Also,
The reason for setting the content to the above range is to develop a function as a preservative and to suppress gas generation.

The fixing solution may contain a water-soluble aluminum salt acting as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum. When adding the water-soluble aluminum salt,
Usually, the range of 0.01 to 0.15 mol / liter is preferable.

In the fixing solution, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and in particular, they contain 0.1 mol.
01 mol / l to 0.03 mol / l is particularly effective. However, these compounds are used in small amounts for stabilizing aluminum.

The fixing solution of the present invention preferably does not substantially contain acetic acid (including salts) and boric acid (including salts). That is, the content of acetic acid and boric acid is 0 to
Preferably it is 0.05 mol / l.

In the fixing solution of the present invention, for example, sodium hydroxide or sulfuric acid can be used as a pH adjuster. Further, a chelating agent having a water softening ability and a chelating agent disclosed in JP-A-62-7855 can be used.
The compound described in No. 1 can be included.

The replenishing amount of the fixing solution is 50 ml or more and 250 ml or less, preferably 60 ml or more and 230 ml or less per 1 m ² of the photosensitive material as a diluted fixing solution (ie, used solution).
More preferably, it is 70 ml or more and 200 ml or less.

The fixing temperature and the fixing time in the fixing process are 4 to 48 seconds at 20 ° C. to 50 ° C., respectively.
It is preferably 7 to 40 seconds at 25 ° C to 40 ° C, and more preferably 8 to 30 seconds at 32 ° C to 38 ° C.

The above contents, replenishment amounts and the like are based on the used liquid.

The fixing solution of the present invention can be used as a fixing agent in the form of a concentrated solution in order to reduce transportation costs and storage space. When the concentrated solution is used as a transport solution, the concentration is preferably 4 times or less, and more preferably 3 times or less, for the purpose of preventing precipitation of the fixing solution components at low temperatures. The components can also be stored in several parts. The storage container at this time has an oxygen permeability at 20 ° C. and 65% RH of 50 ml / m ² · atm · day or less, usually 1.0 to 50 ml / m ^2.
・ Made of atm / day materials can also be used.

The fixing solution may be prepared by using a solid chemical, that is, a powdery fixing agent, and supplying it.

The developer or developer used in combination with the fixing solution of the present invention contains a silver halide dissolving agent.

As a silver halide dissolving agent, thiosulfate,
Mesoionic compounds, thioether compounds and the like can be mentioned.

As specific examples of the mesoionic compound, compounds described on page 11 of JP-A-8-248582 can be used. Further, as specific examples of the thioether-based compound, compounds described on pages 4 to 7 of JP-A-8-82899 can be used.

Of these, thiosulfates are preferable, and sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate and the like are preferably used.

The amount of these silver halide dissolving agents used in the developer (working solution) is from 0.001 mol / L to 0.05 mol / L, particularly preferably from 0.001 mol / L to 0.1 mol / L. It is preferable to use it at not more than 03 mol / liter. Such a usage amount is
If the amount is too small, the effect of preventing processing unevenness cannot be obtained, and if the amount is too large, the function as a developer is adversely affected, such as an increase in fog, a decrease in the maximum density, or a decrease in gradation.

The developing agent preferably used in the developer or the developer of the present invention is an ascorbic acid-based developing agent or a dihydroxybenzene-based developing agent. Of these, ascorbic acid-based developing agents are preferred. Specific examples of the compounds include the following.

L-ascorbic acid D-ascorbic acid L-erythroascorbic acid D-glucoascorbic acid 6-deoxy-L-ascorbic acid L-rhamnoascorbic acid D-glucoheptoascorbic acid imino-L-erythroascorbic acid imino -D-glucoascorbic acid imino-D-glucoheptoascorbic acid sodium isoascorbate L-glycoascorbic acid D-galactascorbic acid L-araboascorbic acid sorboascorbic acid sodium ascorbate

On the other hand, dihydroxybenzene-based developing agents include hydroquinone, hydroquinone monosulfonic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
5-dimethylhydroquinone and the like.

In the present invention, in particular, the above-mentioned ascorbic acid-based developing agent or dihydroxybenzene-based developing agent together with 1
It is preferable to use an auxiliary developing agent such as -phenyl-3-pyrazolidone or p-aminophenol in combination. In particular, in the present invention, it is preferable to use an ascorbic acid-based developing agent in combination with such an auxiliary developing agent.

The 1-phenyl-3-pyrazolidones include 1-phenyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like.

Examples of the p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, and 2-methyl-p-aminophenol. Examples include aminophenol and p-benzylaminophenol. Further, N, N-disubstituted aminophenols described in Japanese Patent Application No. 8-70908 can be used. The developing agent in the developer is usually preferably used in an amount of 0.01 mol / l to 0.8 mol / l, particularly preferably in an amount of 0.05 mol / l to 0.5 mol / l. preferable.

When an ascorbic acid-based developing agent or a dihydroxybenzene-based developing agent is used in combination with an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol, the former is used in an amount of 0.05 mol / liter. 0.5 to 0.5 mol / l, the latter being 0.001 to 0.
06 mol / l (particularly 0.003 to 0.06 mol / l
Liters).

The developer or the developer preferably contains a sulfite as a preservative. As sulfites,
Sodium sulfite, potassium sulfite, lithium sulfite,
There are ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The sulfite in the developer is 0.0
It is preferably at least 3 mol / l. The upper limit is preferably up to 1.0 mol / l, especially up to 0.8 mol / l.

The developer or the developer may contain an amino compound for accelerating the development. In particular, JP-A-56-10624
No. 4, JP-A-61-267759 and JP-A-2-208652 may be used.

The pH of the developer is from 8.0 to 13.0, preferably from 8.3 to 12, more preferably from 8.5 to 1
0.5.

The developer or developer has a pH value setting
It is preferable to contain a carbonate (for example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate) as a pH buffer. The amount of the carbonate used in the present invention is preferably 0.1 mol / L or more, particularly preferably 0.3 mol / L or more and 2 mol / L or less, and more preferably 0.4 mol / L or more and 1 mol / L. The following are most preferred.

As the alkaline agent used for setting the pH of the developer or the developer, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) may be used in addition to the above carbonate. it can.

The developer or the developer further includes boric acid,
Borax, dibasic sodium phosphate, dibasic potassium phosphate,
PH like sodium monophosphate and potassium monophosphate
A buffer, and furthermore, a pH buffer described in JP-A-60-93433 can be used. Further, potassium bromide, a development inhibitor such as potassium iodide, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol,
Organic solvents such as methanol, diethylene glycol and triethylene glycol, benzotriazole derivatives,
Nitroindazole and the like can be used. Benzotriazole derivatives include 5-methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, benzotriazole and the like. Examples of nitroindazole include 5-nitroindazole, 6-nitroindazole,
-Nitroindazole, 7-nitroindazole, 3-
And cyano-5-nitroindazole.

Further, if necessary, a color tone agent, a surfactant and the like may be contained.

The developer or the developer may contain a chelating agent. Specific examples of the compound include the following compounds. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid,
Nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid Acetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid,
-Hydroxyethylidene-1,1-diphosphonic acid, 1,
1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, Examples thereof include sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid. 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydro Shipuropiriden 1,1-diphosphonic acid, 1-amino-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

It is preferable that potassium ion is 10 mol% or more and 90 mol% or less, sodium ion is 10 mol% or more and 90 mol% or less, and sodium ion is 20 mol% or less of all cations contained in the developer. Not less than 50 mol%, potassium ion is not less than 50 mol% and not more than 80 mol%.
More preferably, it is at most mol%.

The developer may be used as a concentrated solution to reduce transportation costs and storage space. When a concentrated solution is used, the concentration is preferably 3 times or less, more preferably 2 times or less, for the purpose of preventing precipitation of the developer components at low temperatures. In addition, components having different solubilities may be stored in several parts, and mixed and diluted at the time of use. The receiving container 20 ° C. In this case, the following oxygen permeability 50ml / m ² · atm · day at 65% RH, normal 1.0~50ml / m ² ·
The one made of atm day material is preferable.

The developer can be supplied as a solid chemical, that is, a powder.

The replenishment amount of the developing solution is 50 ml or more and 250 ml or less, preferably 60 ml or more and 230 ml or less per m ² of the photosensitive material as a diluted developing solution (ie, used solution).
More preferably, it is 70 ml or more and 200 ml or less.

The development processing temperature and development processing time in the development processing are respectively 20 ° C. to 50 ° C. and 5 to 60 seconds.
It is preferably 8 to 45 seconds at 25 ° C to 40 ° C, and more preferably 10 to 35 seconds at 32 ° C to 38 ° C.

The total processing time (Dry to Dry) is from 20 seconds to
Preferably, it is 180 seconds.

The silver halide photographic light-sensitive material is processed using an automatic developing apparatus (automatic developing machine). The opening ratio of the developing tank is 0.04 cm ^-1 or less, usually 0.01 to 0.04.
It is preferably cm ⁻¹ . Further, each replenisher of the developing solution and the fixing solution is preferably supplied by a mixed dilution method immediately before being supplied from each of these concentrated solutions diluted with water in each of the tanks to be used, and each of the concentrated solutions is It is also preferred that it consists of one part. Further, it is preferable that the containers for the concentrated developing solution and the concentrated fixing solution are an integrated packaging material.

Further, when a chemical mixer is incorporated in the automatic developing apparatus, it is preferable to have a mechanism in which the cartridges for the developing solution and the fixing solution can be used simultaneously.

Examples of the automatic developing machine suitable for performing the developing processing of the present invention include FPM-9000, CE manufactured by Fuji Photo Film Co., Ltd.
PROS-M2, CEPROS-30, CEPROS-S, CEPROS-SV, CEPROS-
P, FPM-800A, FL-IMD and the like.

In the present invention, the developing step and the fixing step are usually followed by a washing and / or stabilizing step and a drying step. Such a step is carried out according to a conventional method, and preferred embodiments are as described below. In addition, for example,
Paragraph Nos. “0106” to “011” of No. 0-207919
2 "can be referred to.

The silver halide photographic light-sensitive material used in the present invention is preferably the paragraph numbers "0019" to "0022" and "0033" to "006" in JP-A-7-120895.
0 ", JP-A-8-57712, JP-A-10-2070
No. 19, paragraphs “0040” to “0079” and the like.

Preferred embodiments of the present invention, including those described above, are as follows.

1. A developer and a fixing agent, wherein the developing solution and the fixing solution used in claim 1 are a one-solution concentrate. 2. A developer in which potassium ions are 80 mol% or more (usually 98 mol% or less) of all cations in the developer used in claim 1. 3. The developing method according to (1) above, wherein a silver halide photographic light-sensitive material is used in which the amount of silver applied to both sides of the photographic light-sensitive material is 3.5 g or less (normally 0.1 g or more) per 1 m ² . 4. 10-100 mol% of silver chloride in silver halide grains,
The above (1) using a silver halide photographic light-sensitive material having 10 to 100 mol% of silver bromide and 0 to 0.5 mol% of silver iodide.
Development method. 5. The developing method according to the above (1), wherein the total processing time (Dry to Dry) is 20 seconds to 180 seconds. 6. The developing method according to the above (1), wherein the processing is carried out using an automatic developing machine having an infrared and / or far infrared drying means in a drying section of the automatic developing machine. 7. The developing method according to (1) above, wherein the automatic developing machine has a mechanism in which the developer and fixing solution cartridges are used up simultaneously when the chemical mixer is incorporated in the automatic developing machine. 8. developing method for an automatic opening ratio of the developing apparatus in the developing tank 0.04 cm ^-1 or less (0 cm ^-1 or more) in the above (1). 9. A processing method in which a developing concentrated solution and a fixing concentrated solution are composed of one part, and each concentrated solution and water are diluted into a working solution in each tank and supplied as a replenisher (just-in-time mixing dilution method). 10. A processing method in which the container for the developing concentrate and the fixing concentrate is an integrated packaging material. 11. A processing method using an automatic developing machine provided with a rinsing tank and a rinsing roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the washing tank. 12. A processing method using an automatic developing machine equipped with a water stock tank in which various water rust preventive agents (antibacterial agents) are supplied to a washing tank and a rinsing tank. 13. A processing method using an automatic processor equipped with a solenoid valve at the drain of the washing tank. 14. The developing method according to the above (1), wherein the liquid is prepared from a powdery developer. 15. A processing method in which the developer and the fixing agent are of the used liquid type. 16. A processing method in which the washing tank of the automatic processor has a multi-chamber tank and a multi-stage countercurrent washing tank. 17. Oxygen permeability is 50ml / m ²・ atm ・ day (20 ℃ 65%
RH) A method in which the liquid developer of the above (1) is stored and processed in a container of not more than [0 ml / m ² · atm · day].

[0054]

Next, the present invention will be described in more detail with reference to examples, but the examples of the present invention are not limited to these examples.

Example 1 Preparation of Development Replenisher A Diethylenetriaminepentaacetic acid 16.0 g Potassium carbonate 120.0 g Sodium bicarbonate 80.0 g Sodium sulfite 40.0 g Sodium erythorbate monohydrate 120.0 g 4-methyl-4- Hydroxymethyl-1-phenyl-3-pyrazolidone 24.0 g diethylene glycol 100.0 g 3,3'-dithiobis- (3,3'-diphenyl) -propionic acid 2.00 g 2,5-dimercapto-1,3,4- Thiadiazole 0.20 g 2- (1,2-dicarboxyethyl) thio-5-mercapto-1,3,4-thiadiazole 0.60 g Water was added to make 2 liters, sodium hydroxide was added and the pH was 10.10 g. To

Preparation of Development Replenisher B To development replenisher A was added 4.00 g of sodium thiosulfate pentahydrate.
Added.

Preparation of development replenisher C A solution obtained by adding 3.10 g of potassium thiosulfate to development replenisher A.

Preparation of Development Replenisher D A solution obtained by adding 2.39 g of ammonium thiosulfate to Development Replenisher A.

Preparation of Developing Mother Solution 2 liters of water was added to 2 liters of each of the developing replenishers A, B, C, and D to make a total of 4 liters, and 30.0 g of acetic acid and 30.0 g of potassium bromide were added as a starter. What was dissolved to make 240 ml was added (pH =
9.65).

Preparation of Fixer Replenisher E Ethylenediaminetetraacetic acid disodium dihydrate 0.1 g Succinic acid 160.0 g Sodium bisulfite 12.0 g Sodium thiosulfate 800.0 g In addition, bring the pH to 5.00.

Preparation of Fixing Replenisher F To Fixing Replenisher E, 312.0 g of sodium bisulfite was added.

Preparation of fixer replenisher G Fixer replenisher E added with 180.0 g of acetic acid.

Preparation of fixing mother liquor Two liters of water was added to 2 liters of each of the fixing replenishers E, F and G to make a total of 4 liters.

The above developing replenisher and fixing replenisher were filled as concentrates in a processing agent packaging material of a CEPROS-P development processing system manufactured by Fuji Photo Film Co., Ltd. The developing mother liquor and the fixing mother liquor were used as CEPROS manufactured by Fuji Photo Film Co., Ltd.
-P Filled the developing tank and the fixing tank of the automatic developing machine.

As shown in Table 1, a combination of the developing solutions A, B, C, and D and the fixing solutions E, F, and G was used in an amount of 130 ml / m ² of the photosensitive material.
Treated with replenishment. Washing was performed using tap water with a water washing amount of 1.5 liters per minute for the film processing time. Development was performed at 35 ° C. for 32 seconds, fixing was performed at 34 ° C. for 28 seconds, water washing was performed at 18 ° C. for 25 seconds, and drying was performed at 50 ° C. for 35 seconds.

[0092] Fuji-Medical X-ray Film PX was converted to Dry to Dry.
Processed in 120 seconds. At this time, a large-angle size (35 cm × 35 cm) which was given uniform exposure so that the blackening density after processing was about 1 was processed. The processing unevenness and the rusting of the metal were evaluated as follows. Table 1 shows the results.

(Processing unevenness) An image which is not preferable as an image in which the density unevenness is visually visible on the processed film is set to "1", and an image in which the density unevenness is visually invisible is "5". Was evaluated on a five-point scale. "3"
Is the practical limit.

(Situation of rust generation on metal) An iron nail whose surface was polished well was placed in the vicinity of the fixing tank for one week, and the influence of the fixing solution on rust was evaluated. A sample having no weight increase and almost no change was evaluated as "5", and a state in which the weight increased by about 0.5% and the surface was rusted was evaluated as "1" on a five-point scale. "3" is a practical limit, with a weight gain of about 0.1 to about 0.2%.

[0069]

[Table 1]

As shown by the results in Table 1, the results of Experiment No. 1 and
In Nos. 2 and 3, when the fixing solutions E, F, and G were added at 10% by weight to the developing solution A, the pHs were 0.12, 0.40, and 0.
The lower the pH and the larger the pH drop, the better the unevenness of the treatment is, but the rust of the iron nail is worsened and incompatible. On the other hand, as shown in Experiment Nos. 4, 7, and 10, the developing solutions B, C, and D in which thiosulfate is added to the developing solution show good processing in the fixing solution E which gives good results due to rust of iron nails. It is possible to obtain a result relating to the unevenness, and it is possible to obtain a good result in which both the unevenness of the treatment and the rust of the iron nail are compatible.

Example 2 In Example 1, instead of Fuji-Medical X-ray Film PX, Fuji-Medical X-ray Film Super HRS30, Super HRG30,
Super HRA30, Super HRHA30, Super HRC30, Super HRL3
0, UR-1, UR-2, UR-3, Fuji-Medical Imaging Film MI-
When the same treatment was performed using FA, MI-FG, and Fuji-Medical X-ray Film UM-MA, the same result as in Example 1 was obtained.

[0072]

According to the present invention, it is possible to prevent processing unevenness in processing using a fixing solution that generates little gas which causes corrosion of a metal portion of an automatic developing machine.

Claims (4)

[Claims] 1. A method for processing a silver halide photographic light-sensitive material, wherein at least a developing step and a fixing step are performed on the silver halide photographic light-sensitive material using an automatic developing machine, wherein the fixing solution used in the fixing step is as follows: A method for processing a silver halide photographic light-sensitive material, characterized in that the developer satisfies the characteristics and the developing solution used in the developing step contains a silver halide dissolving agent. Characteristics: pH of the developing solution when the fixing solution used in the fixing step is added at 10% by weight to the developing solution used in the developing step is 0.25 or less. 2. The method for processing a silver halide photographic material according to claim 1, wherein the silver halide dissolving agent is selected from sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate. 3. The fixing solution according to claim 1, wherein the sulfite is 0.01 to 0.10.
Mol / l, acetic acid 0-0.05 mol / l, and 0.15-0.50 mol / l of a compound selected from succinic acid, maleic acid and malonic acid,
3. The method for processing a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the number is 4.2 to 6.2. 4. A processing method of the developing solution and the replenishing amount of the silver halide photographic light-sensitive material 1 m ² per fixer is a is any one of claims 1 to 3 50～250Ml silver halide photographic light-sensitive material.