JP3141216B2 - Processing method of silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic material. INDUSTRIAL APPLICABILITY The present invention can be used as a means for processing a silver halide photographic light-sensitive material for various uses to form an image.

[0002]

2. Description of the Related Art It is desired to reduce the processing time of photographic light-sensitive materials. For this reason, the processing speed of photosensitive materials has been rapidly increased in recent years. In order to increase the processing speed, it is necessary to shorten the time of each step of the processing.
However, shortening the processing time in each step causes various problems. If the fixing time is reduced, colloidal silver is generated in the image as a result of remaining silver halide without fixing,
Problems such as discoloration occur in image storability.

On the other hand, in recent years, due to environmental problems, interest in waste liquid has been increasing. Even in the photographic industry, it is effective to address this problem by reducing the pollution of the processing waste liquid and reducing the waste liquid itself.

[0004] When the replenishment amount of the fixing solution is reduced, the fixing solution becomes fatigued, and the storage stability of an image is deteriorated due to residual silver due to poor fixing. When the fixing speed is shortened, the degree becomes worse, and in addition, problems such as remaining color and stepped unevenness occur.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to realize an image which can realize low pollution by rapid processing and reduction of waste liquid, and which has good image storability and does not cause color remaining or unevenness. It is intended to provide a method for processing a silver halide photographic light-sensitive material which can be used.

[0006]

An object of the present invention is to provide a method for processing a photographic material having at least one silver halide emulsion layer through at least a developing, fixing and washing or stabilizing step. After developing with a developing solution having a concentration of 0.3 mol / l or less, a fixing solution having a potassium ion concentration of 0.1 mol / l or less is added to a photosensitive material to be processed in a concentration of 0.5 mol / l.
Method for processing a silver halide photographic material which comprises treating a fixing time of 3 to 14 seconds at 0.05 l / m ² replenished fixing step (although bromine ions in the fixing solution
When the concentration is 0.02 to 0.09 mol / L
except. ) Was achieved.

Hereinafter, the present invention will be described in more detail. The developer used in the present invention has a potassium ion (K ⁺ ) concentration of 0.3 mol / liter or less, preferably 0 mol / l.
０．２0.2 mol / liter. In the fixing solution used in the present invention, potassium ion is 0.1 mol / l or less, preferably 0 to 0.05 mol / l. Further, the fixing solution is used in an amount of 0.5 to
0.05, preferably 0.6 to 0.05 l / m ²
In the fixing step of replenishment, the processing is performed in 3 to 14 seconds.

[0008] Potassium ions mainly depend on a pH adjuster or a preservative, but the concentration of potassium ions can be adjusted by using sodium salts or ammonium salts instead of potassium salts. From the viewpoint of odor, it is preferable to use a sodium salt.

The potassium ion concentration of the developer used in the present invention is 0.3 mol / l or less, but is particularly preferably 0.1 mol / l or less (including zero, that is, the case where no potassium ion is present). .

In the practice of the present invention, the following can be mentioned as developing agents which can be used in the developer.

Representative HO- (CH ＝ CH) n-OH type developing agents include hydroquinone, and catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone. , 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone.

As HO- (CH ＝ CH) n-NH ₂ type developing agents, ortho- and para-aminophenols are typical, such as N-methyl-p-aminophenol and other 4-aminophenols. There is also.

Further, H ₂ N— (CH ＝ CH) n—NH ₂
Type developing agents include 4-amino-2-methyl-N, N
-Diethylaniline, p-phenylenediamine and the like.

As the heterocyclic developing agent, 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,
-Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-morpholinomethyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone, 1-phenyl-2
-Hydroxymethyl-4-methyl-3-pyrazolidone,
1-phenyl-5,5-dimethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1-o-tolyl-4-methyl-4-hydroxymethyl-3- Pyrazolidone, 1-p
-Methoxyphenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1- (3,5-dimethyl) phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like.

The above developing agents may be used alone,
Two or more can be used in combination.

The developing agent is usually 0.01 mol / liter to
It is preferably used in an amount of 1.2 mol / l.

Preservatives preferably used in the developer include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. The sulfite is preferably at least 0.1 mol / l, particularly preferably at least 0.3 mol / l. The upper limit is preferably up to 2.5 mol / l.

The pH of the developer is preferably in the range of 9 to 13. More preferably, the pH is in the range of 9.5 to 12.

The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.

JP-A-61-28708 (borate),
A buffer such as JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate, carbonate and the like may be used.

Additives other than the above-mentioned components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol. , Ethanol and methanol. Also, mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole And the like. Further, if necessary, a hardening agent such as nermaldehyde and glutaraldehyde may be contained. Further, a color tone agent, a surfactant, an antifoaming agent, a water softener,
It may contain an amino compound described in No. 106244.

A silver stain inhibitor such as disclosed in
No. 24347 can be used.

As the developer, an amine compound such as an alkanolamine described in JP-A-56-106244 can be used. In addition, L. F. A. Messon, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364.
And those described in JP-A-48-64933.

The light-sensitive material processed in the present invention preferably contains silver halide in an amount of ² to 6 g / m ^{2 in} terms of silver. The silver halide has a halogen composition of silver chloride, silver bromide, chlorobromide. Silver or those containing iodine may be used arbitrarily. When iodine is contained, the ratio of iodine is 0
~ 4 mol% is preferred. The layer containing silver halide may have only one side or both sides of the light-sensitive material.

In the development processing, the replenishing amount of the developing solution is preferably 0.1 to 0.4 l / m ² , and the development processing temperature and time are generally preferably about 25 ° C. to about 50 ° C. and 5 to 90 ° C.
Second, more preferably 8 seconds to 1 minute at 30 ° C to 40 ° C.

Various fixing agents can be optionally contained in the fixing solution used in the present invention. For example, sodium thiosulfate, thiosulfate such as ammonium thiosulfate, sodium thiocyanate, thiocyanate such as ammonium thiocyanate, lithium bromide, bromide such as sodium bromide, halogen compound such as iodide such as sodium iodide,
Alternatively, thiourea, thioether and the like are typical examples. These representative fixing agents may be used alone or
More than one kind can be used in appropriate combination, and when used in combination, the mixing ratio of these combinations is arbitrary. The ratio with the potassium ion is also arbitrary.

In the present invention, it is preferable to use a thiosulfate or a halogen compound alone or in combination as a fixing agent.

As the thiosulfate, a sodium salt and a potassium salt are preferable, and a sodium salt is particularly preferable. As the halogen compound, iodide, particularly sodium iodide is preferable.

The amount of the fixing agent used can be appropriately changed.
Preferred amounts are generally from about 0.1 to about 6 mol / l.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, such as aluminum chloride, aluminum sulfate, potassium alum and the like.

The fixing solution used in the present invention may contain tartaric acid, citric acid, malic acid, succinic acid or a derivative thereof, or aminopolycarboxylic acid, aminopolyphosphonic acid or a salt thereof alone or in combination of two or more. It is preferred to use. When these compounds are used, the effect of the present invention can be further enhanced by adding 0.004 mol or more per liter of the fixing solution.

Specifically, citric acid, isocitric acid, malic acid, succinic acid and optical isomers thereof can be used. Also, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, lithium tartrate, potassium tartrate, sodium tartrate, potassium sodium tartrate, lithium hydrogen tartrate, lithium potassium tartrate, potassium hydrogen tartrate, sodium bitartrate, ammonium bitartrate, Lithium represented by magnesium hydrogen tartrate, potassium potassium tartrate, ammonium tartrate, potassium ammonium tartrate, aluminum potassium tartrate, potassium antimonyl tartrate, sodium antimonyl tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc. , Potassium, sodium, ammonium salts and the like can be used. Further, specific examples of aminopolycarboxylic acid and aminopolyphosphonic acid include those described in page 10 of JP-A-63-182650.
Compounds such as -1 to A-12 can be used.

The fixing solution may optionally contain a preservative (sulfite,
Bisulfite), a pH buffer (acetic acid, nitric acid), a pH adjusting agent (for example, sulfuric acid), and a chelating agent capable of hardening water. The amount of preservative used can be changed as appropriate,
Preferably it is about 0.05-1 mol / l. The pH of the fixing solution is preferably 3.8 or more, particularly preferably 4.0 to 5.0.
5 is preferred.

In the present invention, the replenishment rate of the fixing solution in the fixing step is 0.5 to 0.05 liter / m ² with respect to the photosensitive material to be processed, and the fixing time is 3 to 14 seconds.
The fixing temperature is preferably 15 to 40 ° C, more preferably 2 to 40 ° C.
When the temperature is 0 to 35 ° C., the effect of the present invention is particularly remarkably exhibited.

In the present invention, a washing or stabilizing treatment step is performed. As these treatments, any method known in the art can be applied, and water containing various additives known in the art can be used as the washing water or the stabilizing solution. By using the water treated with antifungal means for washing or stabilizing solution, not only water saving treatment of not more than 3 liters per 1 m ² of the photosensitive material can be achieved, and piping for installing an automatic developing machine becomes unnecessary. Stock tanks can be reduced.

When washing with a small amount of washing water, see
It is more preferable to provide a squeeze roller washing tank described in 2-32460.

Further, part or all of the overflow liquid from the washing or stabilizing bath generated by replenishing the water subjected to the antifungal means to the washing or stabilizing bath according to the treatment is disclosed in JP-A-60-235113. As described in (1), it can also be used for a processing solution having a fixing ability, which is a pre-processing step.

Further, a bactericide, a fungicide, a surfactant and the like described in JP-A-57-8542 and the like can be used in combination.

Further, R.I. T. Kreima
n. Image, Tech10. (6) 242
(1984) and the like,
Compounds described in Japanese Patent Application No. 61-51396 can also be used in combination as antibacterial agents (microbiocides).

The water stored in the water stock tank after the antifungal means is used as a diluting water for the stock solution of the processing solution such as the developing solution and the fixing solution and also as a washing water, but the space is small. Is preferred. However, the diluted water and the washing water (or the stabilizing solution) provided with the antifungal means can be separately stored in separate tanks, or only one of them can be taken directly from the tap water.

When stored separately in a separate tank, various additives can be contained in the washing water (or stabilizing bath), for example, after being subjected to fungicide means.

For example, a chelate compound having a log K value of 10 or more in chelation stability with aluminum may be contained. These are effective for preventing white precipitation in the washing water when the fixing solution contains an aluminum compound as a hardener.

Specific examples of the chelating agent include ethylenediaminetetraacetic acid (log K16.1), cyclohexanediaminetetraacetic acid (17.6), diaminopropanoltetraacetic acid (13.8), and diethylenetriaminepentaacetic acid (18.4). ) Triethylenetetramine hexaacetic acid (19.
7) and the like, and sodium salts, potassium salts, and ammonium salts thereof.
0 g / liter, more preferably 0.1 to 5 g / liter.

Further, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. As the surfactant, any of a cationic type, an anionic type, a nonionic type and a zwitterionic type may be used. Specific examples of the surfactant include, for example, compounds described in “Surfactant Handbook” issued by Kogyo Tosho Co., Ltd.

Various compounds may be added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monohydrate) for adjusting the membrane pH (for example, pH 3 to 8) Typical examples include aldehydes such as carboxylic acid, dicarboxylic acid and polycarboxylic acid) and formalin. In addition, chelating agents, fungicides (thiazole, isothiazole, halogenated phenol, sulfanilamide, benzotriazole, etc.),
Various additives such as a surfactant, an optical brightener and a hardener may be used, and two or more kinds of the same or different target compounds may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storability.

The temperature and time of the washing or stabilizing bath by the above method are preferably from 0 ° C. to 50 ° C. for 6 seconds to 90 seconds.

The rinsing (stabilizing) processing time refers to the time during which the photosensitive material to be processed is immersed in rinsing water (or stabilizing solution). For an automatic developing machine, the rinsing tank solution (or stabilizing tank) is used. Liquid).

In the practice of the present invention, the photographic material which has been developed, fixed and washed or stabilized is preferably squeezed out of washing water or a stabilizing solution, ie, dried via a squeeze roller method. In this case, drying is generally performed at about 40 ° C.
The drying is performed at about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions, but it is usually about 5 seconds to 90 seconds, more preferably 40 ° C. to 80 ° C. for about 5 seconds to 60 seconds.

The light-sensitive material processed by the processing method of the present invention may be any material in various fields. The silver halide grains used in the photosensitive silver halide emulsion layer to constitute the light-sensitive material to be processed are not particularly limited and are optional.

That is, any silver halide, such as silver bromide, silver iodobromide, silver chlorobromide, and silver chloride, which are used in ordinary silver halide emulsions, can be used as appropriate. Preferably, silver iodobromide is used. The crystal habit and grain size of the silver halide grains are also not limited and are optional.

The silver halide emulsion used may be spectrally sensitized. For example, ortho sensitization, panchromatic sensitization, and infrared spectral sensitization can be performed.

As the silver halide photographic emulsion, any emulsion such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used. May be done. Monodisperse emulsions can be preferably used.

The binder (binder, protective colloid) used in the non-photosensitive layer such as the photosensitive silver halide emulsion layer and the protective layer of the photosensitive material, and other hydrophilic colloid layers include, for example, quartz-treated gelatin, acid It is preferable to use gelatin such as treated gelatin, derivative gelatin, and gelatin / graft polymer. In addition, hydrophilic colloids such as hydroxyethyl cellulose, polyvinyl alcohol, and polyvinyl imidazole can also be used.

In the light-sensitive material, the support on which the emulsion layer and other layers are coated is preferably a flexible support generally used for the light-sensitive material (polyethylene terephthalate, cellulose triacetate, paper, etc.). Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
Examples thereof include films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate and polycarbonate, baryta paper, and paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports may be subbed to improve the adhesion to the emulsion layer and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

The light-sensitive material may contain other optional additives, which are described in Research Disclosure, Vol. 17643 (December 1978) and 187, No. 18716 (November 1976), and the relevant locations are summarized in the following table.

Known photographic additives which can be used in the preparation of emulsions of the light-sensitive material are also described in the above two Research Disclosures, and their locations are shown in the following table.

[0057]

[Table 1]

The photosensitive material to which the present invention is applied may be, for example, various photosensitive materials for printing, X-ray, general negative, general reversal, general positive, and direct positive. For example, the processing method of the present invention can be suitably applied to processing of an X-ray photographic material.

[0059]

Embodiments of the present invention will be described below. However, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (1) Preparation of monodisperse grains Monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain size of 0.2 μm were used as nuclei, and 30 mol% of silver iodide was used. Is grown at pH 9.8, pAg 7.8,
Thereafter, equimolar amounts of potassium bromide and silver nitrate were added at pH 8.2 and pAg 9.1, and the average grain size was 0.375 μm so that silver iodobromide grains having an average silver iodide content of 2.2 mol% were obtained.
((1) -1), 0.64 μm ((1) -2), 1.4
Monodisperse emulsion particles of 2 μm ((1) -3) were prepared. The emulsion was subjected to desalting of excess salts by a usual aggregation method. That is, 4
While maintaining the temperature at 0 ° C., a formalin condensate of sodium naphthalenesulfonate and an aqueous solution of magnesium sulfate were added to cause aggregation, and the supernatant was removed. The dispersion method of the obtained three kinds of particle sizes is S
/R<0.16, indicating good dispersibility (r indicates the average particle size).

Further, it was confirmed by X-ray diffraction that each silver halide grain had a portion having silver iodide of 20 mol% or more inside the grain.

(2) Preparation of tabular grains A bromide was added to 5.5 liters of a 1.5% gelatin solution containing 0.17 mol of potassium bromide by stirring at 80 ° C. and pH 5.9 by the double jet method. Potassium 2.1
Moles and 2.0 moles of silver nitrate were added in solution over 2 minutes. pBr was maintained at 0.8 (consumes 0.53% of total silver nitrate used).

The addition of the potassium bromide solution was stopped and the silver nitrate solution was continued for 4.6 minutes (8.6% of the total silver nitrate used).
Consume). Then, a potassium bromide solution and a silver nitrate solution were added simultaneously for 13 minutes. During this time, the pBr was maintained at 1.2, and the addition flow rate was accelerated so that the completion was 2.5 times that at the start (consuming 43.6% of the total silver nitrate used).

The addition of the potassium bromide solution was stopped and the silver nitrate solution was added for 1 minute (consuming 4.7% of the total silver nitrate used).

A 2.0 mole solution of potassium bromide containing 0.55 mole of potassium iodide was added along with the silver nitrate solution over 13.3 minutes. During this time, pBr was maintained at 1.7 and the flow rate was accelerated at completion to 1.5 times that at the start (consuming 35.9% of the total silver nitrate used). 1.5 g / mol Ag of sodium thiocyanate was added to this emulsion and kept for 25 minutes. A solution of potassium iodide 0.60 mol and silver nitrate in a double jet method at an equal flow rate of about 5 minutes with pBr
Until 3.0 was reached (consuming about 6.6% of the total silver nitrate used). The amount of total silver nitrate consumed was about 11 moles. Thus, the average particle diameter is 1.62 μm
To prepare an emulsion containing tabular silver iodobromide grains having an aspect ratio of about 16: 1. In this grain, tabular grains accounted for 80% or more of the total projected area of the silver iodobromide grains. The resulting emulsion was designated as tabular grains (2).

(3) Preparation of Polydisperse Particles One solution H ₂ O 17 liter KI 126 g Gelatin 210 g No.2 H ₂ O 14 liter KBr 3.5 kg Glacial acetic acid 0.35 liter No. 3. Liquid H ₂ O 9.45 liter AgNO ₃ 4.25 Kg NH ₄ OH (concentrated aqueous ammonia) 3.1 liter No. 4 liquids NarlCl ₆ 1.0 ml H ₂ O 100 ml

No. One solution is kept at 46 ° C and 800 rpm
No. while stirring with 3% of the volume of the three solutions was added at a constant speed over 1 minute, and after leaving for 1 minute, the remaining No. 3 solution was added. No. 2 solution and No.
No. 3 solution was added at the same time. The two solutions were applied for 8 minutes.
The three solutions were added at a constant speed over 14 minutes. No. After addition of the three solutions, No. The four solutions were rapidly added, and after aging for 2 minutes, acetic acid was added to adjust the pH to 6.0. No. Two liquids and
No. The pAg changed from 11 to 10.5 during the addition of the three solutions.

Next, desalting was carried out simultaneously with the monodispersed emulsion, gelatin was added, and the pH was 5.90 and the pAg was 8.7.
As a result, 14.5 kg of emulsion No. 1 was obtained. The average particle size r is r =
An electron micrograph confirmed that the emulsion was 0.51 μm, the dispersibility of the particle size was S / r = 0.24, and a twin emulsion having 99% or more (111) planes. The resulting emulsion was designated as polydisperse particles (3).

(Preparation, processing and evaluation of sample) Pure water was added to each of the obtained silver halide grains (1), (2) and (3) so that the volume per mole of silver was 500 ml. And the total amount of the spectral sensitizing dyes A and B described below in a weight ratio of 200: 1 was 820 mg for (1) -1 and 6 for (1) -2 per mole of silver halide.
00 mg and 360 mg of (1) -3 were added, and 600 mg was added to tabular grains (2) and 700 mg to polydisperse grains (3).

After 10 minutes, ammonium thiocyanate was added with 4 × 10 ⁻³ mol of (1) -1 per mol of salt, and (1)-
2 is 2 × 10 ^-3 mol, (1) -3 is 1 × 10 ^-3 mol,
(2) was added in an amount of 2 × 10 ⁻³ mol, and (3) was added in an amount of 3 × 10 ⁻³ mol. Further, appropriate amounts of chloroauric acid and hypo were added to initiate chemical ripening. At this time, the pH was 6.15, and the silver potential was 50 m.
v.

Fifteen minutes before the completion of chemical ripening (70 minutes after the start of chemical ripening), potassium iodide was added in an amount of 200 mg per mole of silver.
5 minutes later, 10% (wt / vol) acetic acid is added to lower the pH to 5.6 and maintain the pH for 5 minutes,
Thereafter, a 0.5% (wt / vol) solution of potassium hydroxide was added to return the pH to 6.15, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. Chemical ripening was completed.

(1) -1 of the obtained particles was 15%,
(1) -2 was mixed at 50% and (1) -3 was mixed at 35%, and the emulsion additives described later were added to obtain a monodisperse emulsion preparation (emulsion 1). Further, (2) the tabular grains, and (3)
For the polydisperse particles of the above, an additive for emulsion was similarly added,
A tabular emulsion preparation (emulsion 2) and a polydisperse emulsion preparation (emulsion 3) were prepared.

In the coating solution, in addition to the additives described below, the following compounds (1), (2) and (3) were dispersed to form oil droplets having a particle size of 0.12 μm (a), and the compound (2) (3)
Dispersion (2) in which (4) was dispersed to form oil droplets having a particle size of 0.09 μm was added in the following amount per mol of silver halide.

[0074]

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[0075]

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That is, the dispersion (a) was prepared by the method described in JP-A-61-2854.
In accordance with the method described in Example 1, (3) of No. 45, the dispersion (b) was dispersed according to the method described in JP-A-60-243654, page 35, line 15 et seq. And the above amount was added.

[0077]

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Emulsion solution (photosensitive silver halide coating solution)
The additives used are as follows. The amount of addition is shown in an amount per mole of silver halide. 1,1-dimethylol-1-bromo-1-nitromethane 65 mg

Embedded image

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-hydroxybenzene-4-sulfonic acid Ammonium 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5mg

[0080]

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The additives used in the protective layer solution are as follows. The amount of addition is indicated by the amount per liter of the coating solution. Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g

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Polymethyl methacrylate, matting agent having an area average particle diameter of 3.5 μm 1.1 g Matting agent having silicon dioxide particles having an area average particle diameter of 1.2 μm 0.5 g Ludox AM (manufactured by DuPont) (colloidal silica) 30 g 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution 2% (hardener) 10 ml Glyoxal aqueous solution 40% (hardener) 1.5 ml

[0083]

Embedded image

The emulsion was 1.48 g / m ² in terms of silver,
The amount of the hydrophilic colloid is 1.98 g / m ² and the protective layer is 0.99 g / m ^{2 in} terms of gelatin weight.
At a speed of 0m, glycidyl methacrylate 50wt
%, Methyl acrylate 10 wt%, and butyl methacrylate 40 wt% of a copolymer composed of three kinds of monomers were diluted to a concentration of 10 wt%, and an aqueous dispersion of the copolymer was applied as a subbing liquid. One side was uniformly coated on a 175 μm polyethylene terephthalate film base.

In this example, a developing solution and a fixing solution having the following compositions were prepared. Developer Sodium sulfite 40 g Hydroquinone 25 g 1-Phenyl-3-pyrazolidone 1.2 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Nitrobenzimidazole 0.10 g Glutaraldehyde bisulfite 15.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylenetetramine hexaacetic acid 2.5 g Finished to 1 liter with water and adjusted to pH 10.45 with NaOH and acetic acid.

Fixing solution Ammonium thiosulfate 130.0 g Sodium sulfite anhydrous 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Sodium acetate trihydrate 25.8 g Aluminum sulfate 18 hydrate 2.5 g Sulfuric acid (50 wt%) 6.77 g gluconic acid 4.5 g Finished to 1 liter with water and adjusted to pH 4.5 with NaOH and sulfuric acid.

A sample using the monodisperse particles prepared as described above was exposed to give a density of 1.0, and processed to a size of a quarter. That is, processing is performed using the above-described developing solution and fixing solution, and the fixing process is performed with the capacity of the fixing tank of 4 times.
Until the doubled amount of the liquid was replenished, the running was performed in four cut sizes, and the running was performed under the conditions described in Table 2.

The concentration of potassium ion was adjusted by the ratio of sodium ion to potassium ion in the composition of the developing solution and the fixing solution so that the concentration was as shown in Table 2.

The developing temperature was 35 ° C. and the fixing temperature was 32.
C. was performed.

The automatic developing machine shown in FIG. 1 was used.
Fixing time is the size of the fixing rack (fixing line length)
Was changed and changed.

The development unevenness was evaluated for this sample. The evaluation criteria were as follows. No occurrence 5 Occurrence but slight, no problem at all 4 Occurs, but no practical problem 3 Occurs and causes problems 2 Occurs severely and does not endure use 1

For the remaining color, a sample which was not exposed was processed, and the condition was visually evaluated. The evaluation criteria were the same as those described above.

The residual silver was evaluated by the blue optical density of silver sulfide formed by the remaining silver ions and sodium sulfide. Specifically, the following method was used. 0.2 ml of an aqueous sodium sulfide solution (0.5 N) was dropped on the unexposed and developed photosensitive material. Two minutes later, the liquid on the surface was blotted with blotting paper and dried for 30 minutes. After drying, the blue density of the portion where the sodium sulfide was dropped and the portion where the drop was not dropped were measured with a PDA65 (manufactured by Konica Corporation), and the difference was evaluated as residual silver.

As can be seen from Table 2, when the processing of the present invention is used, even when the processing time is short, unevenness, residual color, and residual silver are hardly deteriorated, and excellent results can be obtained. Similar results were obtained with a sample using tabular grains and a sample using polydisperse grains.

[0095]

[Table 2]

[0096]

As described above, according to the processing method of the present invention, rapid processing is possible and a low replenishing amount step is employed, so that low pollution can be realized by reducing waste liquid, and the image storability is improved. And the effect of forming a good image free of color residue and image unevenness can be obtained.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a processing apparatus used in an embodiment.

Claims (1)

(57) [Claims] 1. A processing method for processing a photographic material having at least one silver halide emulsion layer through at least a developing, fixing and washing or stabilizing step, wherein a potassium ion concentration is 0.3 mol / l. After a developing process with the following developing solution, a fixing solution having a potassium ion concentration of 0.1 mol / liter or less is added to the photosensitive material to be processed in a range of 0.5 to 0.05.
A processing method for a silver halide photographic light-sensitive material, wherein the processing is performed with a fixing time of 3 to 14 seconds in a fixing step of replenishing liter / m ² . However, the bromine ion concentration in the fixing solution is 0.1.
Excluding the case of 02 to 0.09 mol / liter.