JP3243676B2 - Concentrate of fixer for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing solution for a silver halide photographic light-sensitive material, and more particularly, to a fixing solution for a fixing solution which does not precipitate even at a high concentration rate and does not deteriorate fixing hardening properties.

[0002]

2. Description of the Related Art In recent years, the processing time of silver halide photographic light-sensitive materials has been shortened. For example, in X-ray light-sensitive materials, processing for 45 seconds or less has been performed.

It is desired that a fixing solution be free from defective fixing even if the fixing time is shortened and have high fixing hardening ability. In recent years, it has been desired to improve environmental suitability, improve usability, and improve operability by reducing the replenishment amount of the processing solution.

[0004] Therefore, it is conceivable to increase the concentration of the composition such as the main agent in the fixing solution to increase the reactivity, shorten the processing time, and cope with the processing so that the processing can be performed with a small replenishing amount.

When the replenishing amount is reduced, the amount of the developing solution contained in the photosensitive material is increased with respect to the amount of the replenishing fixing solution, so that the pH of the fixing solution is increased. When the pH rises, the effect of the fixed hardening decreases, which causes poor drying.

For this reason, it is conceivable to increase the buffering capacity of the fixing solution against pH, but for that purpose, it is necessary to increase the amount of acetic acid.

On the other hand, as one of the improvement of usability and operability, it is desired to reduce the preparation of processing chemicals and to reduce the volume and weight of processing chemical kits. Conventionally, treatment chemical kits are often divided into several parts in terms of precipitation properties and reactivity between compositions, but in order to reduce liquid preparation work or simplify the liquid preparation equipment, mixing There is a particular need for a one-part kit that requires only dilution without dilution.

That is, the conventional fixing solution kit is divided into a weak acid to weak alkaline part containing a fixing agent and acetic acid, and an acidic part containing an aluminum compound as a hardener.

One reason for such division is that thiosulfuric acid as a fixing agent is stored at a pH as high as possible to suppress decomposition into sulfur.

Another reason is that if aluminum and thiosulfuric acid, which are hardeners, are present at the same time, precipitation occurs, so that the concentration rate of the concentrated solution cannot be increased, and as a result, the volume of the kit increases. (Here, the concentration ratio refers to a value obtained by dividing the volume of the working solution after dilution by the volume of the concentrated solution.) The higher the composition of the working solution is, the higher the concentration of the kit solution is, and the more preferable it is. However, the volume of the kit solution had to be increased.

According to the present inventors, the precipitate in the concentrated solution of the high-concentration fixing solution is a double salt composed of an aluminum compound, acetic acid and thiosulfuric acid, and tartaric acid suppresses the production of this double salt, and The present invention has been found to be a specific compound that does not deteriorate the drying property, and the present invention has been accomplished.

The addition of a certain amount or more of a mineral acid such as citric acid or tartaric acid to a fixing solution is already known, but it relates to a normal use solution, and it is necessary to add a high concentration concentrated solution as in the present invention. There is no disclosure of suppressing the precipitation of the concentrated solution by using a specific concentration.
Therefore, there has been a demand for a one-part fixing solution that does not precipitate even when the concentration of the fixing solution composition is high and has a high concentration ratio.

[0013]

Accordingly, it is an object of the present invention to provide a fixing solution in which the number of parts in a kit is one, in which no precipitate is generated during the storage of the kit, and the fixing property and the drying property are not deteriorated. It is not to provide a high concentration concentrate.

[0014]

The object of the present invention has been attained by the following.

(1) A silver halide photograph in which the content of aluminum is 0.05 mol / l or more, the content of acetic acid is 0.25 mol / l or more, and the content of thiosulfate is 3.0 mol / l or more. A concentrated solution of a fixing solution for a silver halide photographic material, wherein the concentration of tartaric acid is 0.040 mol / L or more.

(2) The concentrated solution of the fixing solution for a silver halide photographic light-sensitive material according to the above (1), wherein the concentrated solution comprises one kit part and the concentration ratio is 2.5 or more.

(3) The concentrated solution of a fixing solution for a silver halide photographic light-sensitive material according to (2), wherein the product of the thiosulfate concentration and the aluminum concentration is within 500 times the tartaric acid concentration.

Hereinafter, the present invention will be described in detail.

The concentration rate of the fixing solution of the present invention is 2.5 or more, preferably 2.5 to 3.5.

The amount of tartaric acid added is 0.04
It is preferably at least 0.05 mol / l, more preferably at least 0.05 mol / l but not more than 1.0 mol / l.

In the present invention, a combination with other polycarboxylic acids such as citric acid and gluconic acid is also preferable.
As the aluminum compound, for example, aluminum sulfate,
A compound capable of supplying trivalent aluminum ions such as alum is preferably used.

The concentrated solution of the fixing solution of the present invention has a pH of 4.3 to 5.5.
Is more preferable, and more preferably 4.4 to 5.0.

In the present invention, the aluminum content of the concentrated fixing solution is 0.05 mol / l or more, preferably 0.07 mol / l to 0.21 mol / l as aluminum ion.
Contains 1 liter.

The acetic acid content is 0.25 mol / acetic acid as acetic acid.
Liter or more, preferably 0.3 mol / l to 1.0 mol / l. Further, the content of thiosulfate is not less than 3.0 mol / liter as thiosulfate, preferably 3.0 mol / liter.
Mol / l to 3.8 mol / l.

In the concentrated fixing solution of the present invention, the product of the thiosulfate concentration and the aluminum concentration (concentration as aluminum ions) is preferably within 500 times the tartaric acid concentration, more preferably 450 times to 300 times. It is.

As the replenishing solution for the fixing solution in the present invention, the same fixing solution as in the present invention can be used, and the replenishing amount may be 300 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material to be processed. , Preferably from 0 to 200 ml.

In the fixing solution of the present invention, a mesoionic compound disclosed in Japanese Patent Application Laid-Open No. 5-61158 by the same applicant as the present invention can be used in combination. Specific examples of the mesoionic compound used as a fixing agent are described in JP-A-5-61.
Compound No. 1 to 10 described in page 158 of specification No. 158 can be used. The amount of use may be 1 × 10 ⁻⁵ mol to 10 mol, particularly 1 × 10 ⁻³ mol to ³ mol, per liter of fixing solution. Is preferred.

Further, in the fixing solution according to the present invention, a tetrazole compound having a mercapto group can be used in combination. The amount of the tetrazole compound used may be 5 × 10 ^-5 mol to 10 ^-1 mol, particularly 10 ^-3 mol to 1 liter per liter of the fixing solution.
2 × 10 ^-2 mol is preferred.

The fixing temperature and time of the fixing solution of the present invention are preferably from about 20 to 50 ° C. for 6 seconds to 20 seconds, and from 30 to 40 ° C. for 6 seconds to 6 hours.
15 seconds is more preferred.

The development time is 5 seconds to 45 seconds, preferably 8 seconds to 30 seconds. The development temperature is preferably 25 to 50 ° C, and 30 to 40 ° C.
C is more preferred.

The drying time is usually 35 to 100 ° C., preferably 40 to 100 ° C.
A drying zone in which hot air of ~ 80 ° C is blown or heating means by far infrared rays may be provided in the automatic developing machine.

Further, the automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps. Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of adjusting a developing solution and a fixing solution.

The base of the developer is based on a developer containing 1,4-dihydroxybenzenes or, if necessary, a p-aminophenol compound and / or a pyrazolidone compound.

The 1,4-dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, There are 5-dimethylhydroquinone and hydroquinone monosulfonate, but hydroquinone is particularly preferred. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) as a p-aminophenol developing agent
There are -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone-based compound which can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone 1,1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4- Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-
Dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-
Examples include pyrazolidone-based compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

The amount of 1,4-dihydroxybenzene added may be from 0.01 mol to 0.7 mol per liter of the developer, and may be from 0.1 to 0.7 mol.
0.5 mole is preferred.

The addition amount of the p-aminophenol compound and the pyrazolidone compound is per 1 liter of the developing solution.
0.0005 mol to 0.2 mol, preferably 0.001 mol to 0.1 mol.

Examples of the sulfite used in the developer include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metasulfite and the like. The amount of these sulfites used may be from 0.1 mol to 2.0 mol per liter of the developer,
0.1 mol to 1.0 mol is preferred. In the case of the developer concentrate, the upper limit is preferably up to 3.0 mol per liter of the developer.

The developer may contain a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the iron ion means ferric iron (Fe ³⁺ ).

Examples of the chelating agent having a chelate stability constant for iron of 8 or more include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent and a polyhydroxy compound.

Specific examples thereof include, for example, ethylenediaminediorthohydroxyphenylacetic acid, triethylenetetramineacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid,
Ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etheraminetetraacetic acid, ethylenediamine-N , N, N ', N'-tetrakismethylenephosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-
Carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, tetrapolyline And sodium hexametaphosphate.

The developing solution may contain a hardening agent which hardens and reacts with the gelatin in the photosensitive material during the developing process to enhance the film properties. As hardening agents, for example, glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maledialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α
-Dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, or bisulfite adduct thereof are used.

Other additives used in addition to the above-mentioned components include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and the like. Antifoggants such as organic solvents such as methanol or mercapto compounds such as 1-phenyl-5-mercaptotetrazole, sodium salt of 2-mercaptobenzimidazole-5-sulfonic acid, and benzotriazole compounds such as 5-methylbenztriazole And, if necessary, a color tone agent, a surfactant, an antifoaming agent, and the like.

The pH of the developer may be from 9.0 to 12, preferably from 9.0 to 11.5. Examples of the alkaline agent or buffer used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, tribasic sodium phosphate, and tribasic potassium phosphate.
Contains regulators.

In the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate and ammonium thiosulfate can be used as the fixing solution. Of these, ammonium thiosulfate is preferable in terms of fixing speed. These fixing agents are generally used in an amount of about 0.1 mol to 6 mol / l.

The fixing solution may contain an aqueous solution of aluminum salt as a hardening agent, and further includes aluminum chloride, aluminum sulfate, potassium alum and the like.

For the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination. It is effective that these compounds are contained in an amount of 0.001 mol or more per liter of fixing solution, and particularly effective in an amount of 0.005 mol to 0.03 mol.

The pH of the fixing solution is 4.2 or more, preferably 4.3
Those having 7.07.0 are preferred. Taking the fixed hardening film or the odor of sulfurous acid into consideration, 4.5 to 5.5 is more preferable.

The washing water for the development treatment of the present invention may contain a fungicide. For example, it may contain a compound described in Horiguchi's "Chemistry of Bacterial Prevention and Prevention" or JP-A-62-115154, a washing accelerator such as a sulfite, a chelating agent and the like.

The washing of the photosensitive material with water is preferably performed at a temperature of about 20 ° C. to 50 ° C. for about 10 seconds to 3 minutes. The replenishing amount of the washing water may be 1200 ml to 0 ml / m ² .

The washing bath (or stabilizing bath) includes RTKreiman.
J. Image, Tech vo L. 10 No. 6242 (1984), isothiazoline compounds, Research Disclosure (RD) Vo
Isothiazoline compounds described in I20526 (1981, 5), compounds described in JP-A-61-115154 and JP-A-62-209532 can be used in combination as antibacterial agents.

The photosensitive material according to the present invention exhibits excellent performance in rapid processing by an automatic processor in which the total processing time is 15 seconds to 60 seconds. The total processing time referred to here is the time when the leading edge of the film is inserted into the insertion port of the automatic processor and then passed through the developing tank, transition section, fixing tank, transition section, washing tank, transition section, and drying section. Is the time it takes to come out of the drying outlet.

The silver halide photographic light-sensitive material to which the present invention is preferably applied includes silver halide photographic light-sensitive materials for medical use, printing or direct positive. As the silver halide emulsion of these silver halide photographic light-sensitive materials, any silver halide such as silver chloride, silver bromide, silver iodobromide and silver chloroiodobromide may be used.

The halogenated grains may be of any crystal type, for example, those which are all isotropically grown, such as cubic, octahedral, and tetrahedral, or polyhedral crystals such as pearls. Types, twins with plane defects,
Alternatively, it may be a mixed type or a composite type thereof.

The silver halide emulsion may be tabular grains having an aspect ratio of 2 or more.

Such tabular grains can be used, for example, in British Patent 2,112,157 and US Pat. No. 4,414,310 because they can improve the spectral sensitization efficiency and the graininess and sharpness of an image.
No. 4,434,226, etc., and emulsions can be prepared by the methods described in these publications.

The emulsion of the silver halide photographic light-sensitive material to which the present invention is applied may be subjected to steps before and after physical ripening or chemical ripening.
Various photographic additives can be used.

Compounds that can be used in such a step include, for example, Research Disclosure (RD) No. 1764
3, various compounds described in (RD) No. 18716 and (RD) No. 308119 (December 1989) can be mentioned.

[0059]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 Fixing solutions having compositions as compared with the present invention were prepared as shown in Table 1 below by changing the compound concentration of the fixing solution. Each fixer was adjusted to pH 4.80 by adding sulfuric acid, and water was added to 400 ml.
To obtain a concentrated solution. This fixing solution is diluted to 1 liter when used.

Evaluation of Precipitating Property of Fixing Solution For the precipitating property, the presence or absence of the precipitating property was confirmed after leaving each concentrated solution at -5 ° C. for one month. The results are shown in Table 2 below.

[0062]

[Table 1]

Example 2 A running experiment was performed using the nine types of fixing solutions prepared in Example 1 to evaluate the fixing property (measurement of the amount of residual silver) and the drying property. The photosensitive material used for running was prepared as follows.

[0064] The preparation of the photosensitive material 1. Preparation of seed emulsion containing hydrogen peroxide-treated gelatin stirred vigorously at 40 ° C.
To a 05N aqueous potassium bromide solution, an equimolar aqueous potassium bromide solution containing silver nitrate aqueous solution and hydrogen peroxide-treated gelatin was added by a double jet method, and after 1.5 minutes, 25 minutes
After the solution temperature was lowered to 80 ° C., 80 ml of aqueous ammonia (28%) was added per mole of silver nitrate, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalted with an aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and an aqueous solution of magnesium sulfate, and then re-dispersed by adding an aqueous solution of gelatin.

The resulting seed emulsion was spherical with an average particle size of 0.23 μm and a coefficient of variation of 0.28.

2. Growth from Seed Emulsion Using the seed emulsion described above, grains were grown as follows. 75 ℃
Vigorously stirred with ossein gelatin and propyloxy-
An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added to an aqueous solution containing polyethyleneoxy-disuccinate-disodium salt by a double jet method. During this time p
H = 5.8 and pAg = 9.0 were maintained. After the completion of the addition, the pH was adjusted to 6.0, and the sodium salt of 5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) -oxacarbocyanine was used as an ortho-type spectral sensitizing dye. 4 anhydrides (sensitizing dye GD-1)
00 mg / mol AgX was added.

Next, the mixture was desalted at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co., and then redispersed by adding an aqueous solution of gelatin. By changing pAg and potassium iodide by this method, an average silver iodide content of 1.5 mol% and a projected area diameter of 0.96
A tabular emulsion was prepared in which tabular silver iodobromide grains having a μm, a coefficient of variation of 0.25 and an aspect ratio of 5.0 were present in a projected area of 20% or more.

The obtained emulsion was added with GD-1 and 5,5'-di-
Anhydrous (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt (200: 1 weight ratio) in 1 mole of silver halide 500 mg was added per unit.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
Fifteen minutes before the completion of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 3 × 10 ^-2 mol per mol of silver halide, and dispersed in an aqueous solution containing 70 g of gelatin to be stabilized. Then, JP-A-2-301744, page 95, 16
Additives as shown on line 20 to page 20, line 20 were added to prepare an emulsion layer coating solution. Further, a coating solution for the protective layer was prepared in the same manner.

The emulsion layer was 2.0 g / m 2 in terms of silver per one side.
^{2. A} polyethylene terephthalate base with 175 μm reduced at a speed of 90 m / min with two slide hopper coaters so that the amount of gelatin is 2.5 g / m ² and the protective layer is 0.99 g / m ² of gelatin. An emulsion layer and a protective layer were simultaneously coated on both sides, and dried for 2 minutes and 15 seconds to obtain a sample.

The running developing process is performed by an automatic developing machine SRX.
-503 (manufactured by Konica Corporation) was improved, and the obtained photosensitive material was exposed to an optical density of 1.0 after development, and the replenishing amount of the developing solution was reduced to 15 cc / 4, and the fixing solution was fixed. The replenishment amount was processed as a 15 cc / 4 cut size.

The development was performed at a dry to dry time of 45 seconds at a development temperature of 35 ° C. and a fixing temperature of 33 ° C.

The environmental conditions were as follows: room temperature 26 ° C., RH 50%, washing water temperature 21
° C. The used developer is shown below.

Composition of Developer Used Sodium 1,2-dihydroxybenzene-3,5-disulfonate 0.5 g Diethylenetriaminepentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10 g Potassium sulfite 85 g Sodium bromide 6.0 g Diethylene glycol 40 g 5-methyl Benzotriazole 0.2 g Hydroquinone 30 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g Water was added to make up to 1 liter, and the pH was adjusted using NaOH. Was adjusted to 10.5.

The fixability was evaluated by developing the unexposed photosensitive material and evaluating the residual silver concentration as a substitute. That is, a 2.6 × 10 ⁻³ mol / liter aqueous solution of sodium sulfide is dropped as a residual silver evaluation solution, drop by drop, at five locations on a developed sample. After standing for 3 minutes, the solution was thoroughly wiped off, allowed to stand at room temperature and normal humidity for 3 hours, and the blue light transmission density of a portion where the residual silver evaluation solution was dropped and a portion where it was not dropped was measured using a photographic densitometer PDA-65 (manufactured by Konica Corporation). ) Was measured using an interference filter of 436 nm ± 10 nm, and the difference was averaged to obtain the residual silver amount. The larger the difference, the higher the residual silver concentration in the film after processing and the poorer the fixability. Conversely, if the value is 0.03 or less, it can be determined that the film has fixability without practical problems.

The dryness was evaluated by evaluating the dryness of the photosensitive material by touch after continuous processing of 2000 pieces of the photosensitive material in 4-cut size. The criteria are shown below.

A: Completely dry and smooth B: Sensitive material is warm but slightly moist C: Feels sticky, but not so strong that the sensitive materials stick together D: Sticky feeling E: Water droplets are seen on the surface.

The results obtained are shown in Table 2 below.

[0080]

[Table 2]

As is clear from Table 2, according to the fixing solution of the present invention, no precipitation occurred at all even when stored under severe conditions for a long time. In addition, the measurement results of the residual silver show that the toner has excellent fixing performance and good drying properties.

[0082]

According to the present invention, it is possible to obtain a concentrated solution of a fixing solution which does not generate precipitates during storage and has no deterioration in fixability and drying property.

Claims (3)

(57) [Claims] 1. A silver halide photographic light-sensitive material having an aluminum content of 0.05 mol / l or more, an acetic acid content of 0.25 mol / l or more, and a thiosulfate content of 3.0 mol / l or more. A concentrated solution of a fixing solution for a silver halide photographic light-sensitive material, characterized in that the concentration of tartaric acid is 0.040 mol / L or more in the concentrated solution of the material fixing solution. 2. The concentrated solution of a fixing solution for a silver halide photographic light-sensitive material according to claim 1, wherein the kit comprises one kit and the concentration ratio is 2.5 or more. 3. The fixing solution for a silver halide photographic light-sensitive material according to claim 2, wherein the product of the thiosulfate concentration and the aluminum concentration is within 500 times the tartaric acid concentration.