JPH0429137A - Fixer for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To eliminate the generation of precipitate and to attain a higher fixing speed and better film hardening property by incorporating an acetic acid ion at a specific amt. into the fixer contg. thiosulfate, water-soluble aluminum salt and sulfite. CONSTITUTION:The acetic acid ion is incorporated at >=0.35mol/l into the fixer contg. the thiosulfate at least at the ratio to attain 0.60 to 1.7mol/l thiosulfuric acid ion, the water-soluble aluminum salt at the ratio to attain 0.60 to 3.0g/l in terms of aluminum and the sulfite at least at the ratio to attain 0.03 to 0.13mol/l sulfite content at the time of dissolving and mixing of the sulfite and the thiosulfate on the occasion of use of the fixer. The high fixing speed and the good film hardening property are obtd. in this way and the generation of the precipitate is prevented.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a fixing solution for silver halide photographic light-sensitive materials (hereinafter simply referred to as fixing solution). The present invention relates to a fixing solution for silver halide photographic materials having good properties.

[Background of the invention]

Silver halide photographic light-sensitive material (hereinafter simply referred to as light-sensitive material)
After development, it is known to fix with a thiosulfate-containing fixer or a sulfite-containing fixer to prevent decomposition of the thiosulfate. It is also known and widely used to include a water-soluble aluminum compound in the fixing solution in order to harden the film surface of the photosensitive material.

In recent years, large quantities of photosensitive materials have come to be processed by automatic processing apparatuses, and there has been a desire to shorten the processing time. Therefore, it is desired to shorten the fixing time as well. Therefore, due to the increase in fixing speed, the concentration of thiosulfate has been on an increasing trend.

In addition, in order to speed up processing and reduce the drying load, a hardening fixer containing a water-soluble aluminum salt is usually used as a fixer, and therefore it generally contains a large amount of aluminum salt. be.

Under these circumstances, a large amount of white precipitate is generated in the fixing tank and circulation system of automatic processing equipment, which not only adheres to the surface of the photosensitive material film but also clogs the circulation system. Improvement of the problem was strongly desired.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a fixing solution which does not cause precipitation, has a high fixing speed, and has good film hardening properties.

[Structure of the invention]

The above object of the present invention is as follows: (1) Thiosulfate ion 0.60 to 1.
7 mol/(2) of thiosulfate and ■ 0.60 to 3.0 g/(in terms of aluminum) of water-soluble aluminum salt and (2) the sulfite during dissolution and mixing of sulfite and thiosulfate. The amount is 0.03 when using fixer
This was achieved by using a fixer solution for silver halide photographic light-sensitive materials, which contains at least an amount sufficient to obtain acetate ions of 0.13 mol/12 or more, and is characterized by containing 0.35 mol #2 or more of acetate ions.

The present invention will be explained in detail below.

The fixing solution of the present invention has a fast fixing speed, good hardening properties, and prevents precipitation.

There is a method of incorporating boric acid in order to prevent the formation of trace amounts of aluminum hydroxide compounds due to alkaline components in the developer brought in by the photographic light-sensitive material from the developing process, but this method also does not improve the situation. could not. The composition of the precipitate analyzed by the present inventor was found to be the following double salt.

(1:M(NH4), (SO3), (OH).

Although the details of the mechanism of occurrence of precipitation are unknown, it is thought that it is due to the formation of double salts in the case of a specific ion ratio in the fixing solution.

Therefore, in the present invention, by regulating the amounts thereof, it was possible to suppress the occurrence of precipitates, even though the hardness was good and the fixing speed was fast.

As the sulfite/thiosulfate of the present invention, any salt can be used as long as it dissociates sulfite ions and thiosulfate ions in the fixer, but lithium, potassium,
Examples include sodium and ammonium salts. Preferred are sodium salts and ammonium salts. Thiosulfates are most preferably ammonium salts because of their high fixing speed.

As the water-soluble aluminum salt, aluminum sulfate, ammonium aluminum sulfate, potassium aluminum sulfate, aluminum chloride, etc. are used.

Examples of the acetate include sodium, potassium, lithium, and ammonium salts, with sodium salt being preferred.

The preferred amount of thiosulfate in the present invention is 0.80
-1.7mol/12, more preferably 0.90-
It is 1.50 mol/ff. Most preferably 1.0-
At 1.35 mol/Q, a fixing agent with an extremely high fixing speed and in which precipitation is prevented can be obtained.

The amount of sulfite is 0.039-0.095 mol/
(2, more preferably 0.055 to 0-087
mol, l, most preferably 0.055-0.071 m
ol/(2 improves the precipitation prevention effect. As for sulfite, the time of dissolving and mixing thiosulfate may be any time when thiosulfate and sulfite are dissolved and mixed; therefore, it can be used only once. is not limited.

The preferred amount of the water-soluble aluminum salt is 0.6 g to 1.8 g/Q, more preferably 0.6 g/Q to 1.8 g/Q in terms of aluminum.
．． It is 8 to 1.70 g/Q. Most preferably 1.0~
It is 1.6g/Q.

The preferred concentration of the acetate ion is Q, 4 mol/Q or more, preferably 0.5 mol/ff or more, which improves the precipitation prevention effect and improves film hardness.

The preferred concentration of acetate is 0.25 mo 1 /
0 or more, more preferably 0.30 mol/4
As described above, the effect of preventing the occurrence of precipitation is improved, and the hardening performance of the photosensitive material is improved.

In addition to the above compounds, the fixing agent of the present invention can contain various additives such as acids, salts, chelating agents, surfactants, wetting agents, and fixing accelerators.

Examples of acids include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid, and malic acid.

Examples of the salts include lithium, potassium, sodium, and ammonium salts of these acids.

Examples of the chelating agent include aminopolycarboxylic acids such as tartaric acid, citric acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, nonionic surfactants such as polyethylene glycol and ester, and JP-A-57-
Examples include amphoteric surfactants described in No. 6840 (title of the invention, photographic fixing agents).

Examples of wetting agents include alkanolamines and alkylene glycols.

Examples of the fixing accelerator include JP-B No. 45-35754, JP-A No. 58-122535, and JP-A No. 58-122536.
Examples thereof include thiourea derivatives described in No. 1, alcohols having a triple bond in the molecule, and thioethers described in U.S. Pat. No. 4,126,459.

Among the additives, acids and salts such as boric acid and aminopolycarboxylic acids are preferred because they have the effect of promoting the object of the present invention. More preferred is a fixing agent containing boric acid (salt).

The preferred amount of the boric acid (salt) added is 0.5 to 20 g/
It is Q.

The pH of the fixer of the present invention is 3.8 to 6.0. For higher hardness and ability of the film surface of the silver halide photographic light-sensitive material and ability to prevent precipitation, the pH is preferably 4.0 to 5.3.
The pH is most preferably 4.1 to 5.0.

Silver halide photographic materials to which the fixer of the present invention can be applied can be produced by methods known in the art.

However, in order to further enhance the effect of the fixing solution with a high fixing speed of the present invention, the preferable amount of coated silver in the photosensitive material to be applied is 1 to 1.
25g/+n”. More preferably 1.5 to 12
g/m”, most preferably 2.0 to 6 g/[11
It is 2.

The above-mentioned light-sensitive materials differ in silver halide composition, additives, types of supports, etc. depending on their uses, but the light-sensitive materials to which the fixer of the present invention is applied are black-and-white photographic materials (for example, medical or industrial There are photosensitive materials for photoengraving such as line photographic materials and lithographic photographic materials, microphotographic materials, microreversal photographic materials for X-ray, vapor for computer typesetting, negative photographic materials for general photography, photographic paper, etc.), and color photosensitive materials. .

A preferred silver halide photographic light-sensitive material used in the fixing solution of the present invention is a black-and-white photographic light-sensitive material that requires a fixing hardening film. More preferred is a photolithographic light-sensitive material. Most preferably, JP-A-52-18317 and JP-A-53-95618.
No. 58-173737 and No. 58-106493, it contains a tetrazolium salt. Photolithographic light-sensitive materials and JP-A-61-223734
As described in No. 61-223834, it is a photolithographic light-sensitive material containing a hydrazine derivative.

The photographic material described above is developed with a developer before being processed with the fixer of the present invention. The developer is a solution containing the following developing agent. As a black and white developing agent, dihydroquinone benzenes (e.g. hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate) ), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, l-722-4.
4-dimethyl-3-pyrazolidone, 1-phenyl-4-
Ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, l-phenyl-4-methyl-4-
hydroxymethyl-3-pyrazolidone, l-)dinyl-4,4-dihydroxymethyl-3-pyrazolidone, etc.)
, aminophenols such as 0-aminophenol, p
-aminophenol, N-methyl-〇-aminephenol, N-methyl-p-aminophenol, 2゜4-diaminophenol, etc.), l-aryl-3-aminopyrazolines (such as 1-(p-hydro quinphenyl)-
3-Aminopyrazoline, 1-(p-methylaminophenyl)-3-aminopyrazoline, 1-(p-amino-m-
(methylphenyl)-3-aminopyrazoline, etc.) or a mixture thereof.

Furthermore, as a color developing agent, known primary aromatic amine developers, such as phenylene diamines (for example, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N, N-diethylaniline, -amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methanesulfonamidoethylaniline, 4-amino-
3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.).

In addition, Mason's Photographic Processing Chemistry (L, F, A, Mason Photo
graphic processing chemis
Try, Focal Press, 1966), pages 226-229, Japanese Patent Application Laid-Open No. 48-64933, etc. may be used.

The developing agent used for these is usually about 0.1 to 80 g/(1, preferably 2 to 50 g/Q).

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A silver chlorobromide emulsion with an average grain size of 0.30 μm to which hexachlororhodium salt was added during physical ripening was mixed with sodium thiosulfate,
4-Hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added and chemically heated to form a photosensitive dye, 2.3.
5-triphenyl-2H-tetrazolium chloride,
Dipropyl-naphthalene disulfonium was added to deposit 4.5% silver on polyethylene terephthalate film. Og/m
, apply the gelatin amount to 3.3g/m,
A photosensitive material for photolithography was prepared.

The following developing solution and the fixing solution of the present invention were used in an automatic developing machine GR27R.
(Konica Corporation) (fixing process 28°C 20 seconds)
The photosensitive material was then exposed to light using known means and developed. (Amount of replenishment, fixer 28 mg / 4 slices 1 sheet) Developer disodium ethylenediaminetetraacetic acid 2 g Potassium sulfite 50 g Potassium carbonate hydroquinone phenidone 5-nitroindazole l-phenyl-5-mercaptotetrazole 0 g 5 g 0, 4 g 0, 12g 0.03g Diethylene glycol Finish to IQ with 120m4 pure water.

Fixer Ammonium thiosulfate 170g Sodium sulfite 8.5g Boric acid
7g Sodium citrate di-salt 2g Aluminum sulfate aqueous solution (Ac, (so.) Adjust to pH 4.35.

The amount of ammonium thiosulfate in this fixer is 1.15 mol
/+2, the amount of aluminum is 1.15 g/β, and the amount of sulfite is 0.067 mol/(l).

Table 1 shows the results.

(Evaluation method) Swelling amount used in Examples 1; silver halide photographic light-sensitive material sample (1
00cm') is fixed with the developed sample and test liquid and washed with water. Immediately after washing with water, absorb moisture with filter paper, place in a sealed container, and measure the weight (as A gram). The samples were then dried at room temperature for 1-2 hours and then weighed. (Defined as B gram) The amount of swelling was determined using the following formula.

Swelling amount (g/4 cut) = (A-B) X (25.2X3
0.3)/100 A freshly prepared solution (swelling amount obtained by performing the same operation with a fresh solution and a fatigued solution) of 0.95 or more is a practical problem.

Here, the fatigue solution is a fixing solution that was used to process about 600 sheets of exposed size (50 x 60 Cll+) in the automatic developing machine J used in the examples under the condition that the replenishment amount was 212 cc/one sheet.

Touch the surface of the photosensitive material immediately after it comes out of the drying automatic processor to check how dry it is.

Visually check the occurrence of precipitates at the bottom of the fixing tank of the automatic processor.

Measurement Results From the results shown in Table 1, it was found that the fixers 1 to 4 of the present invention did not cause precipitation even after 3 weeks. In addition, the swelling degree of the silver halide photographic light-sensitive material film surface is 0.8 in the case of a new solution.
0 to 0.85 (grams/4 pieces), and 0.85 to 0.91 (grams/4 pieces) for fatigue liquid, indicating that the swelling limiting effect is good. Further, all of the fixing solutions of the present invention had good drying properties.

Comparative Example Development Process As shown in Table 1, the same development process as in the example was carried out using fixers 5 to 7.

Measurement result Table 1 shows the measurement results.

Fixer 5.6 formed a white precipitate at the bottom of the fixing tank after 3 weeks and was found to be unusable.

In addition, the amount of swelling is large and the drying properties are poor, so that it is not suitable for practical use.

Example 2 The tetrazolium compound in the emulsion layer in Example 1 was replaced with the following hydrazine compound, and the same study as in Example 1 was carried out by processing with the following high pH developer, and the same results as in Example 1 were obtained. Ta.

Developer composition Hydroquinone 45g N-methyl-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18g Potassium hydroxide 55g 5-sulfosalicylic acid
45g boric acid
25g potassium sulfite 1
10g ethylenediaminetetraacetic acid disodium salt 1g potassium bromide 6g 5-methylbenzotriazole 0.6gn-butyl-jetanol 15g Add water to make 112. However, the pH is set to 11.6.

〔Effect of the invention〕

According to the present invention, it was possible to provide a fixing solution in which the occurrence of precipitation is prevented and a silver halide photographic light-sensitive material is hardly swollen and the drying property of the light-sensitive material is also good.

Claims (2)

[Claims] (1) [1] Thiosulfate ion 0.60-1.7 mol/
[2] A water-soluble aluminum salt sufficient to give 0.60 to 3.0 g/l in terms of aluminum; and [3] the sulfite when the sulfite and thiosulfate are dissolved and mixed. The amount is 0.03 to 0.13 mol when using fixer
1. A fixing solution for silver halide photographic light-sensitive materials, characterized in that the fixing solution contains at least an amount sufficient to make the amount of acetate ions equal to or more than 0.35 mol/l. (2) The fixing solution for silver halide photographic materials according to claim 1, characterized in that it contains 0.20 mol/l or more of acetate.