JPH05341457A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To render processing rapid, to reduce waste water amount and environmental pollution, to improve image storage stability, and to prevent occurrence of residual dye stains and processing unevenness by processing an exposed photosensitive material with a developing solution specified in concentration and replenishing a specified amount of a fixing solution specified in concentration. CONSTITUTION:The developing solution has a potassium ion concentration of <=0.3mol/l, preferably, 0-0.2mol/l, and the fixing solution has a potassium ion concentration of <=0.1mol/l preferably, 0-0.05mol/l. The photosensitive material is processed for 3-14sec in the fixing process in which the fixing solution is replenished in an amount of 0.5-0.05, preferably, 0.6-0.05mol/m<2> of the photosensitive material. The potassium ions are given mainly by a pH controller and a preservative but their concentration can be controlled by using sodium ions or ammonium ions. It is preferred to use sodium ions from the viewpoint of odor. The preservative is used, preferably, in an amount of 0.05-1mol/l.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of processing a silver halide photographic light-sensitive material. The present invention can be used as a means for forming an image by processing a silver halide photographic light-sensitive material for various uses.

[0002]

2. Description of the Related Art It is desired to reduce the processing time of photographic light-sensitive materials. Therefore, the processing speed of the photosensitive material has been rapidly increased in recent years. In order to increase the processing speed, it is necessary to shorten each process step time.
However, in each process, shortening the processing time causes various problems. If the fixing time is shortened, the fixing cannot be completed and the silver halide remains, resulting in the generation of colloidal silver in the image.
There is a problem in image storability such as discoloration.

On the other hand, in recent years, due to environmental problems, interest in waste liquid has increased. Even in the photographic industry, in order to deal with this problem, it is effective means to reduce the pollution of the processing waste liquid and to reduce the waste liquid itself.

When the replenishing amount of the fixing solution is reduced, the fixing solution becomes fatigued and residual silver due to defective fixing deteriorates the storability of the image. When the fixing speed is shortened, the degree becomes worse, and there are problems such as residual color and stepwise unevenness.

[0005]

It is an object of the present invention to solve the above problems and to obtain an image which can realize rapid processing and low pollution by reducing waste liquid, has good image storability, and is free from color residue and unevenness. Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which can be used.

[0006]

The above object is to provide a photographic light-sensitive material having at least one silver halide emulsion layer which is processed through at least development, fixing, and washing or stabilizing processing steps. After development with a developing solution having a concentration of 0.3 mol / liter or less, 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 an amount of 0.5.
~ 0.05 liter / m ^{2 3} ~ 14 in fixing process
It was achieved by a processing method of a silver halide photographic light-sensitive material characterized by processing in seconds.

The present invention is described in more detail below. The developer used in the present invention has a potassium ion (K ⁺ ) concentration of 0.3 mol / liter or less, preferably 0.
Is about 0.2 mol / liter. The fixing solution used in the present invention has a potassium ion content of 0.1 mol / liter or less, preferably 0 to 0.05 mol / liter. In addition, this fixing solution is added to the photosensitive material to be processed at 0.5 to
0.05, preferably 0.6 to 0.05 liter / m ²
In the replenishing fixing step, the processing is performed in 3 to 14 seconds.

The potassium ion mainly depends on the pH adjuster and preservative, but the concentration of potassium ion can be adjusted by using sodium salt or ammonium salt instead of potassium salt. From the viewpoint of odor, it is preferable to use sodium salt.

The potassium ion concentration of the developer used in the present invention is 0.3 mol / liter or less, and particularly preferably 0.1 mol / liter or less (including zero, that is, the case where potassium ion does not exist). ..

In the practice of the present invention, the following developing agents can be used in the developing solution.

A typical example of the HO- (CH = CH) n-OH type developing agent is hydroquinone, and in addition, catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone and methylhydroquinone. , 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone.

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

Further, H ₂ N- (CH = CH) n-NH ₂
4-Amino-2-methyl-N, N as a type developing agent
-Diethylaniline, p-phenylenediamine and the like.

As the heterocyclic developing agent, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4 are used.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1
-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,
It is also possible to use two or more kinds 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 developing solution include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.1 mol / liter or more, particularly preferably 0.3 mol / liter or more. The upper limit is preferably 2.5 mol / liter.

The pH of the developer is preferably in the range of 9 to 13. More preferably, it is in the range of pH 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 triphosphate and potassium triphosphate.

JP-A-61-28708 (borate),
Buffering agents such as JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol. , Organic solvents such as ethanol and methanol. Further, mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole. Antifoggants such as Further, if necessary, a hardening agent such as nermaldehyde or glutaraldehyde may be contained. Further, a color tone agent, a surfactant, a defoaming agent, a water softener, JP-A-56-
The amino compound described in No. 106244 may be included.

A silver stain preventing agent in the developer, for example, JP-A-56
The compounds described in No. 24347 can be used.

An amine compound such as an alkanolamine described in JP-A-56-106244 can be used in the developer. In addition, L. F. A. Meson's "Photographic Processing Chemistry", published by Focal Press, Inc. (1966), pages 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364.
Nos. 4,483,849, and JP-A-48-64933 may be used.

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 halogen composition of silver halide is silver chloride, silver bromide or chlorobromide. It may be silver or those containing iodine therein, which is optional. When iodine is included, the ratio of iodine is 0
-4 mol% is preferable. The layer containing silver halide may be provided on one side or both sides of the light-sensitive material.

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

The fixing solution used in the present invention may optionally contain various fixing agents. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, bromides such as lithium bromide and sodium bromide, halogen compounds such as iodides such as sodium iodide,
Alternatively, thiourea and thioether are typical ones. These representative fixatives may be used alone or in two
It is possible to use a combination of two or more kinds as appropriate, and in the case of using them in combination, the mixing ratio of these combinations is arbitrary. The ratio with potassium ions is also arbitrary.

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

As the thiosulfate, sodium salt and potassium salt are preferable, and 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,
The preferred amount is generally about 0.1 to about 6 mol / liter.

The fixer may also contain water-soluble aluminum salts which act as hardeners, such as aluminum chloride, aluminum sulphate, potassium alum and the like.

The fixer used in the present invention contains tartaric acid, citric acid, malic acid, succinic acid or their derivatives, or aminopolycarboxylic acid, aminopolyphosphonic acid or salts thereof, either alone or in combination of two or more. Preference is given to using. 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. Further, 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 tartrate, ammonium hydrogen tartrate, Lithium typified by magnesium hydrogen tartrate, potassium boron tartrate, ammonium tartrate, potassium ammonium tartrate, potassium aluminum tartrate, antimony potassium 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 A in page 10 of JP-A-63-182650.
Compounds such as -1 to A-12 can be used.

If desired, a preservative (sulfite,
(Bisulfite), pH buffering agents (acetic acid, nitric acid), pH adjusting agents (eg sulfuric acid), and chelating agents capable of softening with water. The amount of preservative used can be changed appropriately,
It is preferably about 0.05 to 1 mol / liter. The pH of the fixing solution is preferably 3.8 or more, and particularly 4.0 to 5.
5 is preferable.

In the present invention, the replenishing amount of the fixing solution in the fixing step is 0.5 to 0.05 liter / m ² with respect to the light-sensitive 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
When the temperature is from 0 to 35 ° C, the effect of the present invention is remarkably exhibited.

In the present invention, a washing or stabilization treatment step is carried out. For these treatments, any method known in this field can be applied, and water containing various additives known in this field can also be used as washing water or a stabilizing solution. By using anti-mildew water for washing or as a stabilizing solution, not only a water-saving treatment of a replenishing amount of 3 liters or less per 1 m ² of the light-sensitive material is possible, but also a pipe for installing an automatic processor is unnecessary. It is possible to reduce the stock tank.

When washing with a small amount of washing water
It is more preferable to provide the squeeze roller cleaning tank described in No. 2-32460.

Further, a part or all of the overflow liquid from the washing or stabilizing bath, which is produced by supplementing the washing or stabilizing bath with antifungal means depending on 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 as a pretreatment step.

Further, antibacterial agents, antifungal agents, surfactants and the like described in JP-A-57-8542 may be used in combination.

Further, in the washing bath, R. T. Kreima
n by J. Image, Tech 10. (6) 242
(1984) and the like, isothiazoline compounds,
The compounds described in Japanese Patent Application No. 61-51396 can also be used together as an antibacterial agent (Microbiocide).

The water stored in the water stock tank after being treated with the mildew-proofing agent can be used both as the diluting water for the stock solutions of the developing solution and the fixing solution and as the rinsing water, but the space is small. Is preferred. However, it is possible to separately store the diluting water and the washing water (or the stabilizing solution) which have been subjected to the mildew-proofing means in separate tanks, or to take only one of them directly from the tap water.

When stored separately in different tanks, various additives can be added to the washing water (or stabilizing bath) in addition to, for example, antifungal means.

For example, a chelate compound having a chelate stability log K value with aluminum of 10 or more may be contained. These are effective in preventing whitening in the wash water when the fixing solution contains an aluminum compound as a hardening agent.

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 (Same as 19.
7) and the like and their sodium salts, potassium salts and ammonium salts, and the addition amount thereof is preferably 0.01 to 1
It is 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 unevenness of water droplets. As the surfactant, any of cation type, anion type, nonionic type and amphoteric type may be used. Specific examples of the surfactant include compounds described in "Surfactant Handbook" published by Engineering Book Co., Ltd.

Various compounds may be added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffer agents (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, mono) for adjusting the membrane pH (eg pH 3 to 8). Representative examples include carboxylic acids, dicarboxylic acids, polycarboxylic acids and the like) and aldehydes such as formalin. Others, chelating agents, bactericides (thiazole-based, isothiazole-based, halogenated phenols, 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 the image storability.

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

The washing (stabilizing) treatment time is the time during which the photosensitive material to be treated is immersed in washing water (or stabilizing solution). In the case of an automatic processor, the washing tank solution (or stabilizing tank) is used. It is the time of immersion in 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, that is, dried through a squeeze roller method. Drying in this case is generally about 40 ° C to
It is carried out at about 100 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but 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 of various fields. The silver halide grains used in the photosensitive silver halide emulsion layer for constituting the light-sensitive material to be processed are not particularly limited and are arbitrary.

That is, as the silver halide, any of silver bromide, silver iodobromide, silver chlorobromide, silver chloride and the like used in ordinary silver halide emulsions can be appropriately used. Silver iodobromide is preferably used. The crystal habit and grain size of the silver halide grains are not limited and are arbitrary.

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 one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used. Even if each is independent, several kinds thereof are mixed. It may be the one. Monodisperse emulsions can be preferably used.

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

In the light-sensitive material, the support to which the emulsion layer and other layers are applied is preferably a flexible support generally used in light-sensitive materials (polyethylene terephthalate, cellulose triacetate, paper, etc.). Useful as flexible supports include cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
It is a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate or polycarbonate, baryta paper, or paper coated or laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer) or the like. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports may be subjected to a subbing treatment in order 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 undercoat treatment.

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

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

[0057]

[Table 1]

The light-sensitive material to which the present invention is applied may be, for example, various light-sensitive 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 the processing of an X-ray photographic light-sensitive material.

[0059]

EXAMPLES Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 (1) Preparation of Monodisperse Grains 30 mol% of silver iodide was prepared by using monodispersed grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain size of 0.2 μm as a core. A silver iodobromide containing the above is grown at pH 9.8 and pAg 7.8,
After that, equimolar amounts of potassium bromide and silver nitrate were added at pH 8.2 and pAg 9.1 to obtain silver iodobromide grains having an average silver iodide content of 2.2 mol%.
((1) -1), 0.64 μm ((1) -2), 1.4
2 μm ((1) -3) monodisperse emulsion particles were prepared. The emulsion was desalted from excess salts by a conventional flocculation method. Ie 4
The temperature was maintained at 0 ° C., a formalin condensate of sodium naphthalenesulfonate and an aqueous magnesium sulfate solution were added, and the mixture was aggregated to remove the supernatant. The dispersion method of the obtained three kinds of particle size is S
With /r<0.16, it had good dispersibility (r represents an average particle size).

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

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

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

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 molar solution of potassium bromide containing 0.55 moles of potassium iodide was added along with the silver nitrate solution over 13.3 minutes. During this time, the pBr was maintained at 1.7 and the flow rate was accelerated at the end to 1.5 times the start (consuming 35.9% of the total silver nitrate used). Sodium thiocyanate (1.5 g / mol Ag) was added to this emulsion and held for 25 minutes. A solution of 0.60 mol of potassium iodide and silver nitrate in a double jet method at an equal flow rate for about 5 minutes, pBr
Was added until it reached 3.0 (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
An emulsion containing tabular silver iodobromide grains having an aspect ratio of about 16: 1 was prepared. The tabular grains accounted for 80% or more of the total projected area of the silver iodobromide grains. The resulting emulsion was used as tabular grains (2).

(3) Preparation of polydisperse particles No. 1 liquid H ₂ O 17 liters KI 126 g Gelatin 210 g No. 2 liquid H ₂ O 14 liter KBr 3.5 Kg glacial acetic acid 0.35 liter No. 3 liquid H ₂ O 9.45 liters AgNO ₃ 4.25Kg NH ₄ OH (concentrated ammonia water) 3.1 liters No. 4 liquid NarlCl ₆ 1.0 ml H ₂ O 100 ml

No. Keep 1 liquid at 46 ℃, 800 rpm
While stirring at No. 3% of the volume of 3 liquids was added at a constant rate over 1 minute, and after leaving for 1 minute, the remaining No. 2 liquid and No.
No. 3 solution was added at the same time. 2 solutions over 8 minutes, No.
Solution 3 was added at a constant rate over 14 minutes. No. No. 1 minute after addition of 3 liquids. Solution 4 was added rapidly, and after aging for 2 minutes, acetic acid was added to adjust the pH to 6.0. No. 2 liquids and
No. The pAg changed from 11 to 10.5 while the 3rd solution was added.

Then, the monodisperse emulsion was desalted at the same time, gelatin was added thereto, and the pH was adjusted to 5.90 at pAg of 8.7.
Emulsion 14.5 kg was obtained. The average particle size r is r =
It was confirmed from an electron micrograph that the twinned emulsion had a grain size of 0.51 μm, a grain size dispersibility of S / r = 0.24, and a (111) plane of 99% or more. The obtained emulsion was designated as polydisperse grains (3).

(Preparation, Treatment and Evaluation of Sample) Pure silver was added to each of the obtained silver halide grains of (1), (2) and (3) so that the volume per mol of silver was 500 ml. Then, the total amount of the spectral sensitizing dyes A and B shown below at a weight ratio of 200: 1 is 820 mg of (1) -1 and 6 of (1) -2 per mol of silver halide.
00 mg and (1) -3 were added so as to be 360 mg, 600 mg was added to the tabular grains (2) and 700 mg was added to the polydisperse grains (3).

After 10 minutes, ammonium thiocyanate was added to 4 × 10 ^-3 mol of (1) -1 per mol of salt, (1)-
2 is 2 × 10 ⁻³ mol, (1) -3 is 1 × 10 ⁻³ mol,
(2) is 2 × 10 ^-3 mol, (3) in addition 3 × 10 ^-3 mol, was started more appropriate amount of added chemical ripening and chloroauric acid hypo. At this time, pH was 6.15 and silver potential was 50 m.
It was conducted under the condition of v.

15 mg before the end of chemical ripening (70 minutes after the start of chemical ripening), 200 mg of potassium iodide per mol of silver
5 minutes later, 10% (wt / vol) acetic acid was 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. Completed chemical ripening.

15% of (1) -1 of the obtained particles,
(1) -2 was mixed at a ratio of 50% and (1) -3 was mixed at a ratio of 35%, and the emulsion additives described below were added to prepare a monodisperse emulsion preparation liquid (Emulsion 1). In addition, (2) tabular grains and (3)
Similarly for the polydisperse particles of, by adding the additive for emulsion,
A tabular emulsion preparation liquid (emulsion 2) and a polydisperse emulsion preparation liquid (emulsion 3) were used, respectively.

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

[0074]

[Chemical 1]

[0075]

[Chemical 2]

That is, the dispersion (a) was prepared as described in JP-A-61-2854.
According to the method described in Example 1 (3) of No. 45, the dispersion (b) dispersed according to the method described in JP-A-60-243654, page 15, line 15 et seq. Was added in the above-mentioned amount.

[0077]

[Chemical 3]

Emulsion liquid (light-sensitive silver halide coating liquid)
The additives used for are as follows. The addition amount is indicated by the amount per mol of silver halide. 1,1-Dimethylol-1-bromo-1-nitromethane 65 mg

[Chemical 4]

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 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg

[0080]

[Chemical 5]

The additives used in the protective layer liquid are as follows. The addition amount is shown as an amount per 1 liter of the coating liquid. Lime treated inert gelatin 68g Acid treated gelatin 2g

[Chemical 6]

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

[0083]

[Chemical 7]

The emulsion has a silver conversion value of 1.48 g / m ² ,
The amount of hydrophilic colloid was 1.98 g / m ^2, and the protective layer had a gelatin coating amount of 0.99 g / m ² with two slide hopper type coaters at 6 min / min.
Glycidyl methacrylate 50wt at 0m speed
%, Methyl acrylate 10 wt%, butyl methacrylate 40 wt%, a copolymer of three monomers was diluted to a concentration of 10 wt%, and an aqueous copolymer dispersion was applied as an undercoat liquid. It was uniformly coated on one side 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 40g Hydroquinone 25g 1-Phenyl-3-pyrazolidone 1.2g Boric acid 10.0g Sodium hydroxide 21.0g Triethylene glycol 17.5g 5-Nitrobenzimidazole 0.10g Glutaraldehyde bisulfite 15.0g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylenetetramine 6-acetic acid 2.5 g Water was adjusted to 1 liter and adjusted to pH 10.45 with NaOH and acetic acid.

Fixing solution Ammonium thiosulfate 130.0 g Anhydrous sodium sulfite 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 Water was adjusted to 1 liter, and the pH was adjusted to 4.5 with NaOH and sulfuric acid.

The sample using the above-prepared monodisperse particles was exposed to give a density of 1.0, and processed in a size of four. That is, the above-mentioned developing solution and fixing solution are used for processing, and the fixing processing is performed with the capacity of the fixing tank equal to 4
Running was performed in four-cut size until the double amount of liquid was replenished, and the conditions were as shown in Table 2.

The potassium ion concentration was adjusted by the ratio of sodium ion and potassium ion in the compositions of the developing solution and the fixing solution so that the values shown in Table 2 were obtained.

The developing temperature is 35 ° C. and the fixing temperature is 32.
Performed at ° C.

As the automatic processor, the one shown in FIG. 1 is used.
Fixing time is the size of the fixing rack (fixing line length)
Changed and changed.

Development unevenness was evaluated on this sample. The evaluation criteria are as follows. No Occurrence 5 Occurrence is minor, no problem at all 4 Occurrence is no problem in practical use 3 Occurrence becomes a problem 2 Occurrence is severe and unusable 1

For the color residue, 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 produced by residual silver ions and sodium sulfide. Specifically, the following method was used. 0.2 ml of an aqueous solution of sodium sulfide (0.5 N) was dropped on the light-sensitive material that had been subjected to the development treatment without being exposed, and after 2 minutes, the surface liquid was absorbed with a blotter paper and dried for 30 minutes. After drying, the blue densities of the sodium sulfide dropping portion and the portion not dropping were measured with PDA65 (manufactured by Konica Corporation), and the difference was evaluated as residual silver.

As can be seen from Table 2, when the treatment of the present invention is used, even if the treatment time is short, there is almost no deterioration in unevenness, residual color and residual silver, and excellent results can be obtained. Similar results were also obtained with samples using tabular grains and samples using polydisperse grains.

[0095]

[Table 2]

[0096]

As described above, according to the processing method of the present invention, since rapid processing is possible and a low replenishing amount step is used, low pollution can be realized by reducing waste liquid, and yet image storability is maintained. Is good, and an effect that a good image can be formed with no residual color or image unevenness can be obtained.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A processing method in which a photographic light-sensitive material having at least one silver halide emulsion layer is processed through at least development, fixing, and washing or stabilizing processing steps, and a potassium ion concentration is 0.3 mol / liter. After the development treatment 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 treated in an amount of 0.5 to 0.05.
A method of processing a silver halide photographic light-sensitive material, which comprises processing in a fixing step of replenishing l / m ² in 3 to 14 seconds.