JP3379032B2 - Fixer for processing silver halide photographic light-sensitive material and processing method - 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 and a processing method for processing a silver halide photographic light-sensitive material, and more particularly to low replenishment and rapid stable processing of a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, it has been desired that a processing solution for processing a silver halide photographic light-sensitive material (hereinafter, light-sensitive material) can be stably and rapidly processed with low replenishment.

For example, in a silver halide photographic light-sensitive material for X-ray photography, the so-called Dry to D is used mainly in the ortho system.
It started to be processed by ry in 30 seconds. In such a case, the time allotted for developing and fixing processing is about 5 to 10 seconds,
Such a short-time treatment inevitably causes deterioration of covering power (CP), drying property, and residual color. In particular, the deterioration of the fixing solution lowers the hardness of the light-sensitive material, and slipping in the automatic processor causes conveyance failure and drying failure during finishing.

Therefore, various hardeners are added to the fixing solution in order to suppress the degree of film swelling during the washing process of the light-sensitive material and reduce the amount of water brought into the transport slip and the drying section to improve the drying property. Has been added. As the hardener, a water-soluble aluminum salt such as aluminum sulfate or potassium alum is used.

Since a developing solution having a high pH is usually brought into the fixing solution with running, the pH of the running equilibrium solution becomes higher than that of the fresh solution. For this reason, aluminum ions become aluminum hydroxide or aluminum oxide, and the concentration of aluminum ions (hereinafter, also referred to as free aluminum ions) present alone decreases. In addition, it is possible to use aluminum chelating agents such as citric acid and gluconic acid, which are added to reduce the white precipitation of acetate hydroxide used as a buffering agent and the drying and precipitation of aluminum hydroxide around fixing tanks and crossover racks. The ion concentration is decreasing.

[0006] Recently, with the downsizing of the processor, the space saving and simplification of the liquid preparation device, the processing agent composition has been reduced, and it has been proposed to use a single fixing solution. A strong aluminum chelating agent such as tartaric acid is used to suppress the life, but the concentration of free aluminum ions is significantly reduced even in such a fixing solution. On the other hand, free aluminum ions in the fixing solution react with gelatin in the light-sensitive material and exhibit a hardening effect, so that they are consumed during running and the concentration decreases. Therefore, the smaller the replenishment amount is, the larger the reduction amount of aluminum ions is.

It is known that when the concentration of free aluminum ions is lowered as described above, the deterioration of the drying property is usually remarkable, but surprisingly, when various developing and fixing processes are examined, free aluminum is It has been found that the gradation characteristic, especially the shoulder portion (middle and high concentration portion) of the characteristic curve is significantly changed due to the decrease of the ion concentration. Almost no influence of this phenomenon on drying (effect width of dry-down due to over-drying, non-drying, etc.) is detected.

Further, the decrease in the concentration of free aluminum ions is easy to catch a minute hunting, a fluctuation in developing agitation property, a minute hunting in the fixing temperature and the like which may occur during normal processing, and the sensitivity (fog + 1. It was found that the fluctuation is large even in the concentration range where 0) is taken.

As a result of various studies for solving such a problem, we have found that the problem can be solved by using the fixing solution according to claim 1. In particular, when the replenishing amount of the fixing replenisher is 400 ml / m ² or less and the processing concentration is largely reduced, the effect becomes more remarkable.

Regarding the replenishment amount of the developing solution, the processing sensitivity due to low replenishment (decrease in the concentration of the main agent, increase in the amount of the inhibitor accumulated due to the elution of the constituents of the photosensitive material) and oxidation fatigue (oxidation due to the increase in the residence time) causes a running sensation. Fluctuations in tomometry performance (increase in sensitivity and gradation) were solved by combining the fixing process of the present invention.

Furthermore, by using a light-sensitive material in which the melting point and the amount of silver attached are defined as described in claim 4, it is possible to provide a very stable running processing stability and a processing method with improved residual color. 6. A tabular grain is used.
It has also been found that the processing method of the silver halide photographic light-sensitive material described above enables stable processing while maintaining sensitivity and high CP.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive material sensitization due to minute hunting of processing conditions or fatigue of processing solution in low replenishment and rapid stabilization processing of an automatic developing machine of a silver halide photographic photosensitive material. It is an object of the present invention to provide a fixing solution for processing a silver halide photographic light-sensitive material and a processing method in which there is no change in tomometry, drying property, and residual color contamination.

[0013]

[Means for Solving the Problems] The ratio of the amount of aluminum present as a single ion to the total amount of aluminum contained in the fixer is 0.6 to 1.0,
And the amount of aluminum present as a single ion (mol / l)
A fixing solution for processing silver halide photographic light-sensitive material, characterized in that the running equilibrium fixing solution / fixing fresh solution ratio is 1.0 to 0.8.

The replenishing amount of the fixing solution described is 400 ml / m ²
A method of processing a silver halide photographic light-sensitive material, characterized in that:

The method of processing a silver halide photographic light-sensitive material as described above, wherein the replenishment amount of the developing solution is 270 ml / m ² or less.

The silver halide photographic light-sensitive material has a melting time of 60 minutes or more at 60 ° C. and / or a silver adhesion amount of 30 g / m ² or less per side, or the silver halide photographic light-sensitive material Material processing method.

The method of processing a silver halide photographic light-sensitive material as described above, wherein the silver halide emulsion layer of the silver halide photographic light-sensitive material comprises tabular silver halide grains having an average aspect ratio of 3 or more.

The present invention will be specifically described below.

The aluminum ion existing as a single ion of the present invention means an aluminum ion (Al ³⁺ ) which does not form a chelate compound, and the abundance ratio thereof in the fixing solution is 0.6 with respect to the total amount of aluminum. The range is from 1.0 to 1.0, and preferably from 0.7 to 1.0.

With respect to the fixing replenisher, the range of 0.8 to 1.0 is preferable, and this range is particularly preferable when the replenishing amount is small. Further, in the fixing running equilibrium solution, the ratio of single aluminum ion to the total amount of aluminum is 0.7 to
The range of 1.0 is more preferable.

A new solution of a single aluminum ion fixing solution /
The running equilibrium liquid ratio is 1.0 to 0.8, but preferably 0.9 or more, so that fluctuations of the fixing solution due to pH and running fluctuations are more controlled.

The single aluminum ion can be determined by measurement using an aluminum ion selective electrode. Examples of the method of adjusting the ratio of the single ions to 0.6 to 1.0 include a method of lowering the pH of the fixing solution, an appropriate amount of the chelating agent, an adjustment of the amount of aluminum, or a combination thereof.

A new fixing solution for a single aluminum ion /
The running equilibrium liquid ratio can be adjusted by a method such as increasing the pH of the running equilibrium liquid by suppressing the amount of a buffering agent, and using an aluminum chelating agent having a chelating ability depending on pH.

The replenishing amount of the fixing solution of the present invention is 400 ml / m ² , more preferably 350 to 50 ml / m ² , but 400 ml / m ^2.
/ M ² or less further increased the running change improvement in 350 ml / m ² or less, the fixability at 50 ml / m ² or less, residual color deteriorates.

The fixing agent of the present invention may be a commonly used fixing material, for example, an aqueous solution containing thiosulfate.

Specifically, it is a thiosulfate such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of the fixing speed.

The concentration of thiosulfate in the fixer is preferably
The range is preferably 0.1 to 5 mol / liter, more preferably 0.8 to 3 mol / liter.

The processing conditions of the fixing solution of the present invention are preferably a fixing time of 3.6 to 150 seconds, a processing temperature of 15 to 45 ° C., and particularly preferably 25 to 38 ° C.

A surfactant may be added to the fixing solution of the present invention. Preferred surfactants include, for example, anionic surfactants such as sulfate ester and sulfonate, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. To be

The fixer contains various acids in addition to the above compounds.
Additives such as salts, chelating agents and wetting agents can be included.

Examples of the acid include salts of 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 salt include salts of these acids such as lithium, potassium, sodium and ammonium.

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

Examples of the wetting agent include alkanolamine and alkylene glycol.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferable. The preferable additive amount of the additive is 0.5 to 20 g / liter.

The replenisher used in the present invention comprises the same components as the above-mentioned fixer, and the replenisher replenishes the amount corresponding to the fatigue of the processing agent. As a replenishment method, width replenishment described in JP-A-55-126243, replenishment by feeding speed, area replenishment described in JP-A-60-104946, or area replenishment controlled by continuous processing number described in JP-A-1-149156 Good.

As the developing agent of the developer of the present invention, it is preferable to use dihydroxybenzenes, 3-pyrazolidones described in JP-A-4-15641 and JP-A-4-16841, or a combination thereof. Also, para-aminophenols,
3-aminopyrazolones may be used.

The total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones is preferably 0.1 mole / liter or less.

Preservatives may include sulfites such as calcium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / liter, more preferably 0.3 to 0.6 mol / liter. Further, addition of a large amount of ascorbic acid also leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

Further, borate described in JP-A-61-28708, saccharose described in JP-A-60-93439, acetoxime, 5-
A buffering agent such as sulfosalicylic acid, phosphate or carbonate may be used. The contents of these agents are selected so that the pH of the developer is 9.0 to 13, preferably pH 10 to 12.5.

Polyethylene glycols and their esters are used as dissolution aids in the developing solution, and quaternary ammonium salts, development accelerators, hardeners, surfactants and the like are contained as sensitizers. be able to. As the silver sludge inhibitor, for example, a silver stain inhibitor described in JP-A-56-106244, a sulfide described in JP-A-3-51844, a disulfide compound, a cystine derivative described in Japanese Patent Application No. 4-92947, or a triazine compound is disclosed. Etc. may be used.

As the antifoggant, for example, an indazole type, imidazole type, benzimidazole type, triazole type, benztriazole type, tetrazole type or thiadiazole type compound may be used in the developer.
Also, as an inorganic inhibitor, sodium bromide, potassium bromide,
You may use potassium iodide etc. In addition, LFA Menson's "Photographic Processing Chemistry" published by Focal Press (1966), pages 226-229,
U.S. Patents 2,193,015 and 2,592,364, JP-A-48-54933
You may use those described in No.

Further, as a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, for example, as an organic chelating agent, a chelate stabilization constant with iron described in JP-A 1-193853 is 8 or more. The chelating agent of is preferably used. Further, as the inorganic chelating agent, there are sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate and the like.

The preferred processing conditions for the development of the present invention are a development temperature of 25 to 50 ° C., more preferably 30 to 40 ° C.
The developing time is 5 to 20 seconds, more preferably 5 to 11
Seconds. The total treatment time is preferably 20 to 60 seconds, more preferably 23 to 45 seconds.

The developer replenisher is composed of the same components as the developer described later, and the replenisher replenishes the treatment agent fatigue and the oxidation fatigue equivalent. As the replenishment method, as described in the fixing solution replenishment method, replenishment according to the width and the feed speed described in JP-A-55-126243,
Area replenishment described in JP-A-60-104946 and controlled area replenishment by continuous processing number described in JP-A-1-149156 may be used, and the replenishment amount is preferably 270 ml / m ² or less, more preferably 200 ml / m ² The following is a large reduction in the amount of waste liquid and stable processability is obtained.

The melting time referred to in the present invention is 60
It means the time until the emulsion layer of the light-sensitive material begins to dissolve by immersing the light-sensitive material in a 1.5% sodium hydroxide solution at ℃ and allowing it to stand.

Melting time 15 at 60 ° C.
If it is more than 5 minutes, the drying property and the transport property are improved but the developing property is deteriorated.If it is 15 or less, the developing property is improved but the transport property is significantly deteriorated, but the developing property does not deteriorate in the constitution of the present invention. Dryability and transportability are improved.

Drying is usually 35 to 100 ° C., preferably 40
The automatic developing machine may be provided with a drying zone in which hot air at a temperature of 80 ° C. to 80 ° C. is blown or a heating means by far infrared rays is provided.

The automatic developing machine has a function of applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during each of the developing, fixing and washing steps (special feature). Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of preparing a developing solution and a fixing solution.

The processing agents of the present invention are various black and white halogens for X ray, printing plate making, black and white general use, film for laser light source, CRT photographing, duplication, II or a photosensitive material for indirect photographing such as a mirror. It can be applied to silver halide photographic materials.

In the present invention, the tabular silver halide grains having an average aspect ratio of 3 or more are the grain diameter of silver halide grains /
The particle thickness ratio is 3 or more, more preferably 5 to 20, and further preferably 5 to 12.

The silver halide emulsion applicable to the processing method of the present invention may have any halogen composition such as silver chloride, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. However, from the viewpoint of high sensitivity, silver chloroiodobromide is preferable, the average silver iodide content is 0 to 4.0 mol%, particularly preferably 0.2 to 3.0 mol%, and the average silver chloride content is 0. To 5.0
Mol%.

In the silver halide emulsion, the halogen composition may be uniform within the grains or silver iodide may be localized, but the one localized in the central portion is preferably used. .

Further, the method for producing a silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like. As a method for producing a monodisperse tabular silver halide emulsion, reference can be made to JP-A No. 61-6643.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halide are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

In the silver halide emulsion of the silver halide photographic light-sensitive material applicable to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research
Disclosure No.17643 (December 1978), No.18716
(November 1979), and compounds described in No. 308119 (December 1989). The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 to 4 XXII Support 28 XVII 1009 XVII Used for photosensitive materials Examples of the support that can be used include those described on page 28 of RD-17643 and page 1009 of RD-308119.

A suitable support is polyethylene terephthalate or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, or ultraviolet irradiation in order to improve the adhesion of the coating layer.

[0060]

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

Example 1 <Preparation of silver halide photographic light-sensitive material> Preparation of seed emulsion 1 Silver iodide 2 having an average grain size of 0.3 μm by a double jet method while controlling at 60 ° C., pH = 8 and pH = 2.0. Monodisperse cubic crystal grains of silver iodobromide containing mol% were prepared.

The resulting reaction solution was desalted at 40 ° C. using an aqueous solution of Demol N and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then an aqueous solution of gelatin was added and redispersed to obtain a seed emulsion.

Growth from Seed Emulsion 1 Grains were grown as follows using the above seed emulsion. First, disperse the seed emulsion in a gelatin aqueous solution kept at 40 ° C,
Further, the pH was adjusted to 9.7 with aqueous ammonia and acetic acid.

To this solution, an aqueous ammoniacal silver nitrate ion solution and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method. During the addition, pAg = 7.3 and pH were controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method.

Up to 95% of the target particle size, pAg = 9.0 is maintained and p
H was continuously changed from 9.0 to 8.0. Then pA
The g was adjusted to 11.0 and grown to the target particle size while maintaining pH 8.0. Then, the pH was lowered to 6.0 with acetic acid, and 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride (sensitizing dye GD-1) was added.
400 mg / mol AgX was added, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then a gelatin solution was added to redisperse the mixture.

By this method, the average grain size was 0.40 μm, 0,65 in a tetrahedron having a rounded top with an average silver iodide content of 2.0 mol.
μm, 1.00 μm, coefficient of variation (δ / r) 0.17, 0.
16, 0.16 monodisperse silver iodobromide emulsions (A), (B),
(C) was prepared.

Preparation of Seed Emulsion 2 Including hydrogen peroxide treated gelatin which was vigorously stirred at 40 ° C.
A double-jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution, and the temperature was 25 ° C for 1.5 minutes to 30 minutes.
The liquid temperature was lowered to 80 ml of ammonia water (28%) per mol of silver nitrate, and stirring was continued for 5 minutes.

Then, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added to re-disperse. The resulting seed emulsion had an average grain size of 0.23 μm and a coefficient of variation of 2
It was 8% spherical particles.

Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. 75 ° C
Vigorously stirred with ossein gelatin and propyloxy
An aqueous solution of potassium bromide and potassium iodide and an aqueous silver nitrate solution were added to an aqueous solution containing polyethyleneoxydisuccinate disodium salt by a double jet method.

During this period, pH = 5.8 and pAg = 9.0 were maintained. After the addition was completed, the pH was adjusted to 6.0 and GD-1 was 400 mg / mol A
gX was added. After further desalting at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas, gelatin aqueous solution was added and redispersed.

By this method, a tabular iodobromide having an average silver iodide content of 1.5 mol% and a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 2.5, 4.5 and 8.0. Silver emulsion (D-1), (D-2), (D-
3) was prepared.

Preparation of Samples Obtained Emulsions (A), (B), (C), (D-1),
GD-1 at 55 ° C for each of (D-2) and (D-3)
And 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-
Anhydrous 3,3′-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt (weight ratio of 200: 1) was 975 mg (A) and 600 m (B) per mol of silver halide.
g, (C) was added at 390 mg, and (D) was added at 500 mg.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
15 minutes before the end 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.

Of the four types of emulsions that have been aged, (A),
(B) and (C) are mixed at a weight ratio of 15:65:20 to form an emulsion (R-1), and (D-1), (D-2), (D-
3) was used alone.

For each of the emulsions, JP-A-2-301744,
Additives as shown on page 95, line 16 to page 96, line 20 were added.

Further, 1.2 g of the dye emulsion dispersion shown below was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresylphosphate and 85 liters of ethyl acetate.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) is called an aqueous solvent.

Next, the oil-based solvent and the water-based solvent were placed in a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C.

[0079]

[Chemical 1]

The additives used for the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (area average particle size) 3.0 μm matting agent) 0.5 g Ludox AM (DuPont colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) Melting time preparation amount shown in Table 2 CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent ) Melting time preparation amount shown in Table 2

[0082]

[Chemical 2]

The coating solution thus obtained was uniformly coated on a blue-colored polyethylene terephthalate film base having a thickness of 175 μm, which had been undercoated, and dried.

The emulsion amount was such that the emulsion layer per one side was the amount shown in Table 1 in terms of silver equivalent, the gelatin coating amount was 2.5 g / m ² , and the protective layer was gelatin coating amount 0.99 g / m ^2. The emulsion layer and the protective layer were simultaneously coated on both sides with two slide hopper type coaters at a speed of 90 m / min, and dried for 2 minutes and 15 seconds to obtain a sample.

For all the obtained samples, 3.5 mm × 0.5 mm
The test piece cut to size was heated to 60 ° C in a constant temperature bath.
It was immersed in 1000 ml of 1.5% NaOH solution and the time until the emulsion dissolved out was measured. The melting time is shown in Table 2.

Next, the compositions of the developing solution and the fixing solution are shown.

Developer Formulation Part-A (for finishing 12 liters) Potassium hydroxide 580 g Potassium sulfite (50% solution) 2280 g Diethylenetetramine 5 acetic acid 120 g Sodium hydrogen carbonate 132 g Boric acid 36 g 5-Methylbenzotriazole 1.6 g 4-Hydroxymethyl-4 -Methyl-1-phenyl-3-pyrazolidone 86g 1-phenyl-5-mercaptotetrazole 0.25g 5-nitroindazole 0.55g 1,4-dihydroxybenzene 390g diethylene glycol 550g Add water to make 6000ml Part-B (12l finish) ) Glacial acetic acid (90%) 70 g 5-Nitroindazole 1.2 g Glutaraldehyde (50% solution) 78 g N-acetyl-D, L-penicillamine 1.8 g Starter solution HO (C ₂ H ₄ ) S (C ₂ H ₄ ) S _{(C 2 H 4) OH 0.5g} CH 3 N (C 3 H 6 NHCONHC 2 H 4 SC 2 H 5) 2 0.5g glacial acetic acid (90%) of 270g of potassium bromide 300 g 5-methylbenzotriazole 1.40g water was added Preparation of developer finish 1000ml above in about 5 liters of water Part-A, Part
-B was added at the same time, water was added while stirring and dissolved to make 12 liter, and the pH was adjusted to 10.55. This was used as a developer replenisher, and the starter was added to 1 liter of this developer.
20 ml / l was added and the pH was adjusted to 10.30 to prepare a developing solution.

Fixer Formula Fixer A Part-A (for 18 l finishing) Ammonium thiosulfate (70 wt / Vol%) 6000 g Sodium sulfite 150 g Boric acid 30 g Acetic acid (90%) Amount shown in Table 1 Sodium acetate Amount shown in Table 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Sodium citrate Amount shown in Table 1 Gluconic acid (50% liquid) Amount shown in Table 1 Part-B (for 18l finishing) Aluminum sulfate 860g Sulfuric acid (50wt %) 100 g To prepare the fixing solution, add Part-A and Part-B to approximately 5 liters of water at the same time, add water while stirring and dissolve to make 18 liters, and use sulfuric acid and ammonia water to adjust the pH of Table 1 to I adjusted it like this. This is the fixing replenisher.

Fixing solution B 1 solution (for 18 l finishing) Ammonium thiosulfate (70 wt / Vol%) 6000 g Sodium sulfite 150 g Boric acid 30 g Acetic acid (90%) Amount shown in Table 1 Sodium acetate Amount shown in Table 1- (N, N -Dimethylamino) -ethyl-5-mercaptotetrazole 18g Tartaric acid Amount shown in Table 1 Aluminum sulfate 860g Add water to make 7200ml Fixer B is prepared by adding tap water to 18L while stirring and dissolving. The pH was adjusted as shown in Table 1 using aqueous ammonia.

[0090]

[Table 1]

Using the film selected as shown in Table 2, the development temperature was 35 ° C. with an automatic processor SRX-501 (manufactured by Konica Corporation).
The fixing temperature was 33 ° C, and the washing water was supplied at 3.5 ° C / min at a temperature of 18 ° C, and the whole treatment process was run at a drying temperature of 50 ° C until the running equilibrium (replacement rate of 90% or more) was reached.

Table 2 also shows the ratio of the amount of aluminum present as single ions in the fixing replenisher / total amount of aluminum and the ratio of the amount of run liquid of aluminum present alone / the ratio of new liquid.

[Treatment Process] Process Treatment temperature (° C.) Treatment time (sec) Treatment time (sec) Replenishment amount Insertion-1.8 1.0 Development + crossover 35 14.6 8.2 Amount shown in Table 2 Fixing + crossover 33 9.8 5.5 Table 2 Quantity Washing + crossing 18 8.0 4.5 Squeeze 40 4.1 2.3 Drying 45 6.7 3.8 Total −45.0 25.3 <Evaluation of running stability> As described above, the substitution rate is 0%, 30% in the process of short-term running treatment until running equilibrium is reached. , 50%, 70%, and 95%, and sensitometric evaluation was performed 1 and 3 days after running.

The obtained sample film was used as a fluorescent intensifying screen KO-250.
It was sandwiched between (Konica Corp.), irradiated with X-rays at a tube voltage of 110 kVP and 20 mA for 0,05 seconds, and a sensitometric curve was created by the distance method to determine the sensitivity. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0. The result is a sample
It is expressed as relative sensitivity when the sensitivity of No. 1 is 100.

The gradation is represented by ΔD / ΔlogE in the range of fog + 0.25 to fog + 0.20.

Further, the density of the sensitometric curve is 2.6
The reciprocal of the required X-ray dose of (shoulder concentration) was obtained and expressed as shoulder sensitivity.

<Evaluation of Covering Power (CP)> Appropriate exposure was performed so that the density of the sample after development became the maximum density, and then the same treatment as in the above sensitometry was performed using a fixing solution and a running equilibrium solution. went.

The density (D) and the developed silver amount (Av
[Mg / dm ² ]) was measured and calculated by the following formula.

CP = (D) / (Av) × 100 <Evaluation of Dryability> The sample was cut into four pieces and exposed to light so that the density after development would be 1.0, and then the above processing conditions were applied. The fixing solution was rapidly processed using a running equilibrium solution, and the sample film immediately after passing through the drying section of the automatic processor was touched by hand to evaluate the degree of drying in the following five stages.

Evaluation Criteria 1: The entire surface is wet.

2: More than half of the film is damp and the film easily sticks and scratches easily. 3: Partially moist but no sticking 4: Slightly damp feeling, cold surface 5: Touch Although there is no problem in practical use in the above-mentioned evaluation criteria 3 to 5 which are free and warm,
2 is unusable for practical use <Evaluation of residual color> Development processing of unexposed sample film,
The residual color was evaluated according to the following evaluation criteria.

Evaluation Criteria 5: No Contamination of Residual Color 4: Slight Contamination of Residual Color 3: Slight Contamination of Residual Color but No Practical Problems 2: Slight Contamination of Residual Color but Limit of Practical Range 1: Residual Color The results are summarized in Tables 2, 3, and 4 because of the large amount of contamination and impracticality.

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

[Table 4]

As is clear from Tables 2, 3 and 4, sensitometric performance due to running fatigue in low replenishment and rapid processing was observed in processing by an automatic processor using the fixing solution for processing a light-sensitive material and the processing method of the present invention. It can be seen that there is a fixing solution having no change in drying property and no residual color contamination, and a processing method using them.

[0107]

According to the present invention, in the low replenishment rapid processing of the silver halide photographic light-sensitive material by the automatic processor, there is no fluctuation of the sensitometric performance such as sensitivity and covering power due to running fatigue of the processing liquid, and the drying property is improved. Excellent,
A fixing solution and a processing method for processing a silver halide photographic light-sensitive material having no residual color contamination were obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 5/38 G03C 1/035 G03C 1/74 G03C 5/31 G03C 5/395

Claims (5)

(57) [Claims] 1. The ratio of the amount of aluminum present as a single ion to the total amount of aluminum contained in the fixer is 0.6 to.
1.0 and the ratio of running equilibrium fixer / fixer new fixer of the amount of aluminum (mol / l) present as a single ion is 1.0.
A fixing solution for processing a silver halide photographic light-sensitive material, characterized in that it is 0.8 to 0.8. 2. The replenishing amount of the fixer according to claim 1 is 400 ml.
/ M ² or less, a method for processing a silver halide photographic light-sensitive material. 3. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the replenishment amount of the developing solution is 270 ml / m ² or less. 4. A silver halide photographic light-sensitive material having a melting time of not less than 15 minutes at 60 ° C. and / or a silver adhesion amount of not more than 30 g / m ² per side.
Or the processing method of the silver halide photographic light-sensitive material as described in 3 above. 5. The halide according to claim 1, 2, 3 or 4, wherein the silver halide emulsion layer of the silver halide photographic light-sensitive material comprises tabular silver halide grains having an average aspect ratio of 3 or more. Processing method of silver photographic light-sensitive material.