JPH07209823A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To control occurrence of fur in a rinsing bath and to restrain occurrence of residual due stains by incorporating a specified compound in >= one or all of a developing bath, a fixing bath, and a rinsing bath. CONSTITUTION:The photographic sensitive material is imagewise exposed and then developed, fixed, and rinsed in the developing and fixing and rinsing baths containing at least one of the compounds represented by the formula in which X is H, O, S, Se, or Te; R1 is H, optionally substituted amino, nitro, OY (Y being H, Na, or K), -OR7OR8, or -COR9; each of R7-R9 is an alkyl, alkenyl, aryl, or acetyl; and each of R2-R6 is H, 1-5C alkyl, a halogen, nitro, optionally substituted amino, -OR7OR8, or -COR9.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to suppress the adhesion of water stains to a tank wall and a conveying roller in a developing solution, a fixing solution and a washing processing tank. And a method for processing a silver halide photographic light-sensitive material having improved residual color.

[0002]

BACKGROUND OF THE INVENTION Photographic light-sensitive materials are generally processed by an automatic processor after exposure. That is, the film having been photographed is sequentially immersed in, for example, a developing tank, a fixing tank, and a water washing tank to be subjected to development, fixing, and water washing treatments, and then the drying section is completed. In this step, each processing solution is replenished according to the processing of the light-sensitive material so that preferable processing conditions are always maintained. Taking the processing of X-ray photographic material as an example, in places where large-scale processing is required such as in large hospitals, a large amount of replenisher is supplied to overflow the tank solution and replace it with a new processing solution to improve processing efficiency. However, in the recent processing method, the processing liquid is supplied only during the processing of the film by the film detection mechanism, and when the processing is interrupted or finished, the replenishment of the processing liquid is stopped and the processing liquid is stagnant and stored in the processing tank. Further, in an automatic processor of a type in which the processing solution is replaced after the processing solution is not replenished during processing and the processing solution is exchanged, the processing solution is stagnant for many days when the processing amount is small. Among the treatment liquids, in the case of replenishment washing water, a large amount of water is supplied, the tank overflows and is replaced with new water, thus achieving high washing efficiency. Therefore, when the treatment is completed, the replenishment of the washing water is stopped from the standpoint of saving water, and the washing water stays in the treatment tank in the used state. At this time, if the washing water is left stagnant for a long time, water stains will be generated, and when the film is processed next time, it adheres and contaminates the film and affects the diagnosis. A slip phenomenon occurs in the transport rack when transferring to the transport rack, causing transport failure. In addition, water supply failure often occurs due to clogging of the solenoid valve for water supply. For this reason, it is common to add a bactericide to prevent scale stains on the wash water. For example, it is necessary to add a chelating agent or a bactericide to the wash water.
t, "Water Quality Criteria" Phot. Sci. and Eng., Vo
l 9 No.6, 398 (1965), MEBeach, "Microbiological G
routh in Motion-Picture Processing "SMPTE journal
l, Vol.85, Mar. (1976) and RO Deegan, "Photoprocessi.
ng Wash Water Biocides "J. Imaging Tech., Vol.10, No.
6, Dec (1984) et al.

Further, JP-A-57-8542, JP-A-58-105145,
No. 57-157244, addition of various antibacterial agents such as thiazolylbenzimidazole compounds and isothiazolone compounds,
Ultraviolet irradiation method described in JP-A-60-263939, 60-26
A method using a magnetic field described in 3940, a method of making pure water with an ion exchange resin described in 61-131632, JP-A-62-115154, 62-158952, 62-220951, Same as 6
Method using the antibacterial agent described in 2-209532, JP-A-2-269339
The publication discloses a method of eluting Ag ⁺ ions in washing water with a water-soluble glass to prevent the generation of scale by its antibacterial action.

However, in the method of adding these various compounds to the washing water, it is almost difficult to always maintain the concentration at which the antibacterial effect is exhibited in the large volume washing method. The ultraviolet irradiation method and the method using a magnetic field are equipments. Costly and not practical. According to the US Environmental Protection Agency's drinking water regulations, the regulated value in drinking water is 50 μg / liter for the method of eluting Ag ⁺ ions in the washing water with water-soluble glass. You will always have the risk that the cumulative amount at will exceed the regulation value. Also,
Deactivate the activated sludge in the treatment facility for wastewater treatment.
Further, it has a drawback that the effective period is short.

In recent years, in X-ray diagnosis, it has become common to perform centralized processing with a small number of automatic processors due to the widespread use of a darkroom-less system. This is highly evaluated as a method with excellent productivity such as image quality control of images and shortening of work flow lines. In facilities equipped with these facilities, washing water is constantly replaced during the day because the treatment work is performed without interruption. However, for the sake of economy and water saving, the wash water is supplied only during the treatment of the film, and when the treatment is interrupted, the replenishment and the renewal by discharge are often not performed.

Further, in the case of the resource-saving type in which the washing water is automatically controlled by detecting the film, there is no trouble when the treatment amount is large, but when the treatment amount is small, the replacement of the washing water is small, and thus the scale of bacteria is reduced. As described above, the generation is severe, and floating substances and bad odors are generated, which causes slippage, and water stains are attached to the film, and the film is dried and solidified in the drying section in the next step, resulting in a serious defect in the image.

Therefore, there has been a demand for the development of a treatment method which does not generate scale even when the treatment liquid and washing water are retained for a long period of time in the low replenishment treatment or the storage treatment.

On the other hand, the current low replenishment process is liable to cause deterioration of sensitivity and deterioration of image quality (silver tone, graininess, residual color property) due to fatigue of the processing solution, and various measures are taken. Is coming.

The present inventors have surprisingly found that the residual color is improved in the investigation of the compound of the present invention. It has been found that the effect becomes higher especially when the deterioration is severe in the low replenishment treatment system, and these were unexpected.

[0010]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention relates to the development processing step of exposed silver halide photographic light-sensitive material, and particularly, the occurrence of scale in the washing tank when the processing is stagnant in the processing with less replenishment. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which is controlled and has improved residual color.

[0011]

The above-mentioned object is to develop, fix, and fix a silver halide photographic light-sensitive material after imagewise exposure.
In a processing step of washing with water, it is achieved by a processing method of a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula [1] in a developing tank, a fixing tank and a washing tank. Was done. Even more surprisingly, the addition of the compound to the developing tank resulted in a significant improvement in residual color.

General formula [1]

[0013]

[Chemical 2]

In the formula, X represents a hydrogen atom, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, R ₁ represents a hydrogen atom,
Optionally substituted amino group, nitro group, -OY (Y is hydrogen atom, Na or K atom) or -OR ₇ , OR ₈ or-
Represents COR ₉ , and R ₇ , R ₈ and R ₉ represent an alkyl group, an alkenyl group, an aryl group or an acetyl group.

R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group, an amino group which may have a substituent, or -OR. ₇ , OR ₈ or —COR ₉ is represented, and R ₇ , R ₈ and R ₉ represent an alkyl group, an alkenyl group, an aryl group or an acetyl group.

The present invention will be described in detail below.

The preferred substituents in the general formula [1] include the following.

X is an oxygen atom or a sulfur atom, more preferably an oxygen atom. R ₁ is a hydrogen atom hydroxyl group, a nitro group,
It is an amino group, an alkyl group having 3 to 5 carbon atoms, an acetyloxy group, or ONa, and R ₂ is a hydrogen atom, an alkyl group having 3 to 5 carbon atoms, or a phenethyloxy group. R ₃ is a hydrogen atom, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₅ is a hydrogen atom, a hydroxyl group, An alkyl group and a halogen atom.

Representative specific examples of the compound represented by the above general formula [1] are shown below, but the compound of the present invention is not limited thereto.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

The synthetic method of these compounds is as follows. For 2,4,6 cycloheptatriene-1-thione compounds, tetrahedron letter (Tetrahedron Letter) Vol. 28, No. 2, 203-206.
Page 1987, Chemical Letter 1990 4
No. 563 to 566, etc., can be easily synthesized. For 2,4,6-cycloheptatrien-1-one compounds, refer to Tetra
hedron Letter 29 (5) 555-558 1988, Tetrahedron Tetrahedron 43, No. 21, pp. 5031-5038 1987, Bul
l Chim. Soc. Japan Vol. 62, No. 2, 451-454, European Patent 267,
It can be easily synthesized by the method described in JP-A No. 378 and JP-A-63-5048.

Also, tsuyapurisin which is a kind of 2,4,6-cycloheptatrien-1-one compounds (α-tsuyapurisin Exemplified No. 12, β-tsuyapurisin Exemplified No. 13 and γ-tsuyapurisin Exemplified No. 14) ) Is extracted and refined from the natural tree, the Journal of the Wood Science Society of Japan, Vol. 13, No. 3, 123-124, 1967, Vol.
P. 4 1967, Japanese Patent Publication No. 38-8518, Japanese Patent Publication No. 51-23244, Japanese Patent Publication No. 61-278596, Japanese Patent Publication No. 5-86396, Asunaro, Taiwan Hinoki, Aomori Hiba, etc. It can be extracted and purified. The above compounds are easily available as commercial products.

The carrier of these tsuyapurisins includes:
Wood pieces, fibers, fibrin, polymer latex, etc. are preferable, and chips, beads, powder impregnated with these are packaged in non-woven fabric or porous synthetic fiber cloth, or
Alternatively, it is preferably used by leaving it immersed in washing water in the form of chips, beads, or small pieces. Further, an extract concentrate of a natural tree containing these tsuyapurisins may be impregnated in the same manner as above and used.

Further, wood chips containing these compounds, for example, chips of natural trees such as Aomori Hiba and sawdust (referred to as sawdust at the time of sawing wood) may be wrapped in a non-woven fabric or the like and used. As a container to store, nylon, polyester, rayon, polypropylene, vinylon, acrylic,
A non-woven fabric using polyvinyl alcohol or the like is preferable.
Further, a non-woven fabric impregnated with these compounds of the present invention may be directly used.

The compound of the present invention may be added to the processing solution by placing it near the inlet of the replenishing solution in the processing tank, or by adding it to any position in the processing tank when a predetermined processing is completed. It is sufficient to immerse these storage containers.

Further, it may be dissolved and added in advance at the time of preparing the starting solution for the developing solution and the fixing solution and the replenishing solution.

The compound of the general formula [1] of the present invention may be added in all of the developing tank, the fixing tank, and the washing tank, and any two tanks or one tank may be added. From the aspect, the effect is large and preferable. Single and 2 for developing tank and fixing tank
Even if added to the tank, it shows improvement in scale of the washing tank by taking it out with a film. Further, in terms of residual color, the addition of the compound of the present invention to the developing tank exhibits a remarkable residual color effect, so that it is more preferable to add it to two tanks of a developing tank and a fixing tank and to add three tanks including a washing tank.

The residual color is improved even when the fixing bath and the washing bath are used alone or when added to two baths.

The amount used is 20 to 500 mg, preferably 50 to 200 mg, per liter of the developing solution, the fixing solution and the washing water.

The silver halide photographic light-sensitive material applicable to the processing of the automatic processor of the present invention is applied to all silver halide photographic light-sensitive materials such as color light-sensitive materials, black-and-white light-sensitive materials and color photographic papers. , Direct X-ray film, indirect X-ray film, reverse film for X-ray duplication, single-sided film for CT imager, infrared film for laser imager, line drawing film for printing plate making, halftone dot film film, same film film, color film Examples include decomposed films and gravure films.

Although various conventionally known systems can be used for the developing section, fixing section and drying section of the automatic processor of the present invention, the washing method is an automatic washing method and a constant flow rate of water during processing is used. The method of supplying water may be a method of supplying water, a method of controlling the size of the treated film, or a method of controlling the area. Further, it can be used particularly effectively in a small-sized automatic developing machine which is washed with a stored water system.

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferable as the developing agent used in the black and white developing solution used in the present invention because good performance can be easily obtained. Of course, in addition to this, a p-aminophenol type developing agent may be contained.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone and 2,3-dibromohydroquinone. , 2,5-dimethylhydroquinone, etc., but hydroquinone is particularly preferable.

As a developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4- (Hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, and the like, among which N-methyl-p-aminophenol is preferred.

The developing agent is usually preferably used in an amount of 0.01 mol to 1.2 mol / liter. The pH of the developer used in the present invention is preferably in the range of 9 to 13, more preferably 10 to 12.

The alkaline agent used for setting the pH is
Potassium hydroxide, sodium hydroxide, sodium carbonate,
Contains pH regulators such as potassium carbonate, sodium triphosphate, potassium triphosphate. Buffers such as JP-A-61-28708 (borate), JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate may be used.

Additives used in addition to the above components include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. As additives used in addition to the above components, sodium bromide, potassium bromide, a development inhibitor such as potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformaldehyde, methyl cellosolve, hexylene glycol, ethanol, Organic solvents such as methanol, 1-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonate, even antifoggants such as benztriazole compounds such as 5-nitrobenzimidazole Well, if necessary, toning agent, surfactant, defoaming agent, water softener, JP-A-56-10624
It may include the amino compound described in No. 4 and the like.

In the present invention, a silver stain preventing agent such as the compounds described in JP-A-56-24347 can be used in the developing solution.

An amino compound such as an alkanolamine described in JP-A-56-106244 can be used in the developer.

In addition, LFA Messon, "Photographic Processing Chemistry", published by Focal Press (1966), pages 22-229, US Pat. No. 2,193,015,
Those described in JP-A-2,592,364 and JP-A-48-64933 may be used.

The fixing solution is an aqueous solution containing thiosulfate,
It has a pH of 3.8 or higher, preferably 4.2 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / liter.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

In the fixing solution, tartaric acid, citric acid or their derivatives can be used alone or in combination of two or more kinds. 0.005 per liter of fixer for these compounds
Those containing more than 1 mol are effective, and particularly 0.01 to 0.03 mol are particularly effective.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate and ammonium citrate.

If desired, the fixer may contain a preservative (for example,
A sulfite, a bisulfite), a pH buffer (for example, acetic acid, boric acid), a pH adjusting agent (for example, sulfuric acid), and a chelating agent capable of softening water can be contained.

The silver halide emulsion has an aspect ratio of (3.
It is preferably tabular grains of 5) or more, and particularly preferably 3.5 or more and 8.0 or less. The advantage of such tabular grains is that spectral sensitization efficiency can be improved, image graininess and sharpness can be improved, for example, British Patent No. 2,112,157, U.S. Patent No. 4,439,520, No. 4,433,048, No. 4,313, 31
No. 0, 4,434,226, JP-A-58-113927, 58-1279
No. 21, No. 63-138342, No. 63-284272, No. 63-305343, etc., and these emulsions can be prepared by the method described in the publication.

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. May be. In these emulsions, a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, or the like may be used at the stage of physical ripening or grain preparation.

The emulsion has been subjected to a water washing method such as a Noudel water washing method and a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
A method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in 35-16086 or a method using an aggregating polymer agent such as G-3 and G-8 described in JP-A 2-2037 is particularly preferable. The salt method can be mentioned.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978), No. 1
8716 (November 1979) and No. 308119 (December 1989). The types of compounds and the locations where they are described in these three Research Disclosures are listed below.

Additives 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 III Desensitizing dye 23 IV 998 B 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 slip 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 according to the present invention Examples of the support that can be used in the light-sensitive material include the above-mentioned RD-17643, page 28 and RD-308119, 100.
Examples include those described on page 9.

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

[0054]

【Example】

Example 1 Preparation of Type 1 Emulsion 1 A monodisperse cubic crystal of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Particles were prepared.

The resulting reaction solution was desalted at 40 ° C. with an aqueous solution of Demol N and magnesium sulfate solution 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 seed emulsion described above. 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. The pAg was maintained at 9.0 up to 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. Then, the pAg was adjusted to 11.0, and the pH was grown to the target particle size while maintaining the pH at 8.0. Then lower the pH to 6.0 with acetic acid,
Anhydrous 5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt (sensitizing dye GD-1) was added at 400 mg / mol AgX and manufactured by Kao Atlas After desalting with a demol N aqueous solution and a magnesium sulfate aqueous solution, a gelatin solution was added and redispersed.

According to this method, the average silver iodide content was 2.0 mol, and the vertices had a rounded top and the average grain size was 0.40 μm and 0.65.
μm, 1.00 μm, coefficient of variation (δ / γ) of 0.17 and 0.1 respectively
6, 0.16 monodisperse silver iodobromide emulsions (A), (B), (C)
Was prepared.

Preparation of Seed Emulsion 2 0. 0 containing hydrogen peroxide treated gelatin 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 aqueous potassium bromide solution at a temperature of 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.

After that, 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 and redispersed. The resulting seed emulsion has an average grain size of 0.23 μm and a coefficient of variation
It was 0.28 spherical particles.

Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method to an aqueous solution containing ossein gelatin and propyloxy polyethyleneoxy disuccinate disodium salt vigorously stirred at 75 ° C. During this time pH
= 5.8 and pAg = 9.0. After the addition was completed, the pH was adjusted to 6.0, and GD-1 was added at 400 mg / mol AgX. Further, the mixture was desalted at 40 ° C. using a Demol N aqueous solution manufactured by Kao Atlas Co., and then an aqueous gelatin solution was added and redispersed. By this method, the average silver iodide content is 1.5 mol% and the projected area diameter is 0.96 μm.
A tabular silver iodobromide emulsion (D) having a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 4.0 was prepared.

Preparation of Samples Each of the obtained emulsions (A), (B), (C) and (D) at 55 ° C. was GD-1 and 5,5'-di- (butoxycarbonyl)-.
1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride (200: 1
Weight ratio of (A) is 975 mg per mol of silver halide,
(B) 600 mg, (C) 390 mg, and (D) 500 mg were added.

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 ripened emulsions, (A),
(B) and (C) were mixed at a weight ratio of 15:65:20 to prepare Emulsion-I, and (D) was used alone as Emulsion-II.

Additives shown in JP-A-2-301744, page 95, line 16 to page 96, line 20 were added to each of Emulsion-I and Emulsion-II to prepare emulsion coating solutions.

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.

Coating liquid for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (Matting agent having an area average particle size of 3.0 μm) 0.5 g Ludox AM (DuPont colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg

[0068]

[Chemical 5]

The emulsion layer is 1.7 g in terms of silver equivalent per side.
/ M ^2, 2.5 g / m ² as a weight with a gelatin protective layer at a speed per minute 90m by two slide hopper type coater so that the 0.99 g / m ² as a weight with gelatin, glycidyl methacrylate - methyl acrylate -Emulsion on a 175 μm polyethylene terephthalate base coated with an aqueous copolymer dispersion obtained by diluting a butyl methacrylate copolymer (50:10:40 wt%) to a concentration of 10 wt% A layer and a protective layer were simultaneously coated on both sides and dried for 2 minutes and 15 seconds to obtain a sample.

<Sensitometry> Using the obtained sample film as the light source of the standard light source B described in "New Edition, Illumination Data Book", the exposure time was 0.1 seconds, 3.2 cms, and the same light intensity was applied to both sides with no filter. After exposure to, using the automatic processor SRX-501 ((manufactured by Konica [Co.])), the developing solution and the fixing solution were prepared according to the following formulations, and the sensitivity, fog and gamma of each sample were obtained. The results are shown in Tables 1 and 2. Sensitivity was calculated as the reciprocal of the amount of light required to increase the blackening density by 1.0, and was shown as relative sensitivity when the sensitivity of the comparative sample and No. 1 was 100. It is represented by the slope of the straight line portion in the characteristic curve.

[0071]

[Table 1]

[0072]

[Table 2]

<Measurement of antibacterial effect> The compounds exemplified in the present invention were added to a developing tank, a fixing tank and a water washing tank as shown in Tables 1 and 2, and 500 sample films were supposed to be treated at a clinical site. As shown in Table 3, the running treatment was performed for 2 weeks. Immediately after the detection of the film, the addition of washing water was supplied at 4.0 liters / minute, and the supply of the final treated film was stopped 1 minute after the detection.
The stagnant wash water obtained by running for 2 weeks was collected.

[0074]

[Table 3]

Using the collected stagnant wash water as a sample, Sanai Bio Checker (sold by Sanai Petroleum Co., Ltd.) was used for culturing at a culturing temperature of 30 ° C. and a culturing time of 48 hours, and the total number of bacteria was measured. Further, the treatment tank and the bearing of the guide roller were touched and tested for the presence or absence of adhesion of scale.

The obtained results are shown in Tables 1 and 2.

Developing agent Potassium sulfite 70 g Hydroxyethylethylenediamine triacetate trisodium 8 g 1,4-Dihydroxybenzene 28 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1-Phenyl-5-mercaptotetrazole 0.01 g Sodium metabisulfite 5 g Acetic acid (90 %) 13 g Triethylene glycol 15 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Nitroindazole 0.2 g Glutaraldehyde 4 g Potassium bromide 4 g 5-Nitrobenzimidazole 1 g Exemplified compounds of the invention Amount shown in Table 1 and Table 1 It was dissolved in 1 liter of water and adjusted to pH 10.5 with sodium hydroxide.

Starter solution Potassium bromide 300 g glacial acetic acid 144 g An aqueous solution of 1 liter was prepared to give a solution of pH 4.2 with glacial acetic acid.

Preparation of fixer sodium thiosulfate pentahydrate 4.5 g ethylenediaminetetraacetic acid disodium 0.5 g ammonium thiosulfate 150 g anhydrous sodium sulfite 8 g potassium acetate 16 g aluminum sulfate 10-18 hydrate 10 g sulfuric acid (50 wt%) 5 g Compounds shown in Tables 1 and 2 Citric acid 1 g Boric acid 7 g Glacial acetic acid 5 g An aqueous solution of 1 liter was prepared into a solution having pH 4.2 with glacial acetic acid.

(Evaluation of Remaining Coloring Property) For the dye residue caused by the photosensitive dye, the running developer and fixer obtained by processing the unexposed quadrant size film with the above-mentioned 500 sheets by the automatic processor SRX-501 were used. At 35 ° C. for 45 seconds, and the processed film was visually evaluated on a light source stand for photographic observation. The results are shown in Tables 1 and 2.

Evaluation Criteria A: No Dye Remaining B: Dye Remaining Slightly, but Does Not Affect Diagnosis C: Dye Remaining Partially Exists and Exists to a Difficulty in Diagnosis D: Dye Remaining There is a problem in diagnosis. E: Level of color residue is not significant and is not used for diagnosis. As is clear from the table, the treatment in the treatment tank containing the antibacterial agent of the present invention has no influence on photographic performance. However, the residual color was improved. In addition, wash water after processing 500 sample films
Even in the culture test using the liquid that had been stagnant for 8 hours, the antibacterial effect was clearly recognized as compared with the total number of bacteria and the control table attached to the biochecker as compared with the non-added sample washing water.

[0082]

According to the present invention, in the processing of a silver halide photographic light-sensitive material having a small replenishment amount, silver halide photographic in which the generation of scale in the washing tank due to the stagnation of the processing is suppressed and the residual color is improved A method of processing a photosensitive material is obtained.

Claims (1)

[Claims] 1. In a processing step of developing, fixing and washing with water after imagewise exposing a silver halide photographic light-sensitive material, all or one or more tanks among a developing tank, a fixing tank and a washing tank are used. A method of processing a silver halide photographic light-sensitive material, comprising at least one compound represented by the following general formula [1]. General formula [1] In the formula, X represents a hydrogen atom, an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, R ₁ represents a hydrogen atom, an amino group which may have a substituent, a nitro group, -OY (Y is a hydrogen atom. , Na
Or K atom) or --OR ₇ , OR ₈ or --COR ₉ ;
R ₇ , R ₈ and R ₉ represent an alkyl group, an alkenyl group, an aryl group or an acetyl group. R ₂ , R ₃ , R ₄ , R ₅ , R ₆
Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group, an amino group which may have a substituent, or -OR ₇ , OR ₈ or -COR ₉ ; R ₇ , R ₈ and R ₉ represents an alkyl group, an alkenyl group, an aryl group or an acetyl group.