JPH05249625A - Agent for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the agent for processing the silver halide photographic sensitive material superior in storage stability and running stability and remarkably enhanced in photographic performance. CONSTITUTION:This agent for processing the silver halide photographic sensitive material having at least one silver halide emulsion layer on a support contains a compound represented by formula in which R is H, alkyl, or aryl, and n is an integer of 1-10. It is preferred to incorporate this compound in a developer or a fixing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing agent for silver halide photographic light-sensitive materials, and more particularly to a processing agent for silver halide photographic light-sensitive materials excellent in stability over time or running.

[0002]

BACKGROUND OF THE INVENTION Processing agents for silver halide photographic light-sensitive materials contain various additives at high concentrations depending on the purpose. In most cases, a large amount of inorganic salt is contained for the purpose of adjusting pH or imparting a buffer property, and the ionic strength in the liquid is very high. Of these additives in the liquid, those having a very low solubility cause precipitation in the processing layer of the automatic processor or in the replenishing tank with running or with the passage of time, resulting in a marked deterioration in photographic quality. In order to solve this problem, various water-soluble solvents have been investigated, but as described above, they are not dissolved due to their high ionic strength and pH conditions, and most of them do not adversely affect the photographic performance. Only a few species can withstand.
However, even in such a water-soluble solvent, the addition amount is limited, and if it is added more than that, the photographic performance is adversely affected. Therefore, the addition amount of the low-solubility additive is also limited, and it is impossible to add a large amount, and it is not possible to expect further improvement in photographic performance.

[0003]

SUMMARY OF THE INVENTION To solve the above problems, it is an object of the present invention to provide a processing agent for silver halide photographic light-sensitive materials which is excellent in stability over time or running and has markedly improved photographic performance.

[0004]

The above object of the present invention is represented by the following general formula [I] in a processing agent for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. It is achieved by a processing agent for silver halide photographic light-sensitive materials, which comprises a compound containing

[0005]

[Chemical 2]

[In the formula, R represents a hydrogen atom, an alkyl group or an aryl group. n represents an integer of 1 to 10. The compound of the general formula [I] is preferably contained in the developer or the fixing agent.

The present invention will be specifically described below.

First, the compounds represented by the general formula [I] are listed below, but the present invention is not limited thereto.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

The amount of the above compound added is not particularly limited,
It is preferably used in an amount of 300 g or less per liter of the used liquid.

The silver halide photographic light-sensitive material treating agent of the present invention includes a color developing agent, a black and white developing agent, a bleaching agent, a fixing agent, a bleaching stabilizer, a stabilizer and the like, and the effects of the present invention are excellently exhibited. What is done is a black and white developer and a fixing agent.

A combination of a dihydroxybenzene chain and 1-phenyl-3-pyrazolidones is most preferable for 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-based developing agent may be contained.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone,
Brom hydroquinone, isopropyl hydroquinone,
Methyl hydroquinone, 2,3-dichlorohydroquinone,
There are 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

The developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention is 1-phenyl-4,4-
There are dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

The p-aminophenol-based developing agent used in the present invention includes N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxy). Phenyl) glycine, 2-methyl-
There are p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The developing agent is usually preferably used in an amount of 0.01 mol / l to 1.2 mol / l.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.2 mol / l or more, more preferably 0.4 mol / l or more. The upper limit is preferably up to 2.5 mol / l.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably pH 10 to 1
The range is up to 2.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Includes pH regulators such as potassium carbonate, sodium triphosphate, potassium triphosphate.

JP-A-61-28708 (borate), JP-A-60
-93439 (eg saccharose, acetoxime, 5-
Sulfur salicylic acid), phosphates, carbonates and other buffering agents may be used.

As additives used in addition to the above components, 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 ethinol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole
Mercapto-based compounds such as sodium 5-sulfonate, 5
-Indazole-based compounds such as nitroindazole, may contain an antifoggant such as benztriazole-based compounds such as 5-methylbenztriazole, and if necessary, toning agents, surfactants, defoaming agents, water softeners, JP-A-56
The amino compound described in No. 106244 may be included.

In the present invention, a silver stain preventing agent is added to the developer.
For example, the compounds described in JP-A-56-24347 can be used.

Amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer of the present invention.

Besides this, L. F. A. Meson's "Photographic Processing Chemistry", Focal
Press (1966), pages 226-229, U.S. Pat. No. 2,193,01
Nos. 5, 2,592,364 and JP-A-48-64933 may be used.

The development temperature and time are about 25 ° C. to 50 ° C. and 90 seconds or less, preferably 30 ° C. to 40 ° C. and 10 seconds to 40 seconds.
The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher,
Preferably it has 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which have thiosulfate ion and ammonium ion as essential components, 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 / l.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, ammonium sulfate and potassium alum. Tartaric acid, citric acid or their conductors can be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / l to 0.03 mol / l is particularly effective.

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

Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, nitric acid), pH adjusting agents (eg, sulfuric acid), chelating agents having a water softening ability can be used in the fixer if desired. And the compounds described in Japanese Patent Application No. 60-213562.

The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. for 10 seconds to 1 minute, more preferably 30 ° C. to 40 ° C. for 10 seconds to 40 seconds. When the fixer concentrate is replenished to the automatic processor by the method of the present invention along with the water used to dilute it as the light-sensitive material is processed, it is most preferred that the fixer concentrate consist of one agent. Is the same as in the case of the developing solution.

It is at pH 4.5 or higher, more preferably at pH 4.65 or higher, that the fixer actual solution can exist stably as one agent. If the pH is less than 4.5, the thiosulfate will be decomposed and eventually sulfided, especially when the fixer is left for many years until it is actually used. Therefore, in the range of pH 4.5 or higher, the generation of sulfurous acid gas is small and the working environment is improved. The upper limit of pH is not so strict, but if it is fixed at an excessively high pH, the pH of the film will be high even if it is washed with water thereafter, the film swelling will be large, and the drying load will be large.
The limit is up to.

The present invention may be a so-called working solution in which either the developing solution or the fixing solution does not require the above-mentioned dilution water (that is, the undiluted solution is replenished).

The amount of each concentrated solution to be supplied to the treatment tank solution and the mixing ratio with the dilution water can be variously changed depending on the composition of the concentrated solution. In the ratio of 8, the total amount of each of the developing solution and the fixing solution is preferably 50 ml to 1500 ml per 1 m ² of the light-sensitive material.

In the present invention, the light-sensitive material is subjected to washing with water or stabilization after fixing with the actual solution. For the washing or stabilizing treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as washing water or a stabilizing solution. By using anti-mold water as the washing water or stabilizing solution, not only the water saving process of replenishing amount of 3 liters or less per 1 m ² of the light-sensitive material is possible, but also the pipe for installing the automatic processing machine is unnecessary. This further reduces the stock tank. That is, the preparation diluting water for the developing solution and the fixing solution and the washing water or the stabilizing solution can be supplied from the common one stock tank, and the automatic developing machine can be further compacted.

When water treated with antifungal means is used in combination with washing water or a stabilizing solution, the occurrence of scale can be effectively prevented.
0 to 3 liters, preferably 0 to 1 per 1 m ^{2 of} light-sensitive material
It can save liters of water.

Here, when the replenishment amount is 0, no replenishment is performed at all, that is, substantially no replenishment except that the amount of the wash water in the wash tank decreased by natural evaporation or the like is appropriately replenished. "Tempered water" refers to the case where the treatment method is performed.

As a method of reducing the replenishment amount, a multi-stage countercurrent system (eg, two-stage, three-stage) has been known for a long time. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material of the fixing solution is gradually processed in the clean direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially contacted and processed.
Further efficient water washing is performed. According to this, unstable thiosulfate and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more remarkable stabilizing effect is obtained. The amount of flush water is much smaller than before.

When washing with a small amount of washing water, Japanese Patent Application No. 60
It is more preferable to provide a squeeze roller cleaning tank described in No. -172968.

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 water depending on the treatment, is disclosed in JP-A-60-235133. As described above, it can also be used for a processing solution having a fixing ability, which is the previous processing step. This is more preferable because the stock water can be saved and the amount of waste liquid is reduced.

As the antifungal means, the ultraviolet irradiation method described in JP-A-60-263939, the method using a magnetic field described in JP-A-60-263940, and the ion exchange resin described in JP-A-61-131632 Method for making pure water by using, Japanese Patent Application Nos. 60-253807 and 60-
The methods using the antibacterial agents described in 295894, 61-63030 and 61-51396 can be used.

Furthermore, LEWest "Water Quality Criter
ia ”Photo Sci & Eng. Vol.9No.6 (1965), MW Beach
“Microbiological Growths in Motion Picture Proces
sing "SMPTE Journal Vol.85, (1976) .RODeegan," Pho
to Processing Wash Water Biocides ”J.Imaging Tech.
Vol 10, No. 6 (1984) and JP-A-57-8542 and 57-58143.
No. 58, No. 58-105145, No. 57-132146, No. 58-18631,
Antibacterial agents, antifungal agents, surfactants and the like described in Nos. 57-97530 and 57-157244 can also be used in combination.

Further, for the washing bath, RT Kreiman, J. Image,
Tech 10, (6) 242 (1984), isothiazoline compounds, RESEARCH DISCLOSURE Volume 205, Item 20526 (1
981, May issue), isothiazoline compounds,
The isothiazoline compound described in Vol. 228, Item 22845 (April, 1983), the compound described in Japanese Patent Application No. 61-51396, and the like can also be used together as a bacteriostatic agent (Microbiocide).

Further, specific examples of the antifungal agent include phenol, 4-chlorophenol, pentachlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloroacetamide, p-hydroxybenzoic acid. Acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluorodichloromethylthio) -phthalimide, 2,4,4'-trichloro-2 ′ -Hydroxydiphenyl ether and the like.

The water stored in the water stock tank after being treated with a mildew proofing agent is preferably the diluting water of the processing solution stock solution such as the developing solution fixing solution and its addition amount is 0.01 to 10 g / l, more preferably
It is 0.1 to 5 g / l.

Further, in addition to the silver image stabilizer, various surfactants may 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 are added to the above stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg borate, etc.) for adjusting the membrane pH (eg pH 3-8).
Typical examples are aldehydes such as metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. Can be mentioned. In addition, chelating agents, antiseptic agents (thiazole-based, isothiazole-based, halogenated phenol,
Various additives such as a sulfanilamide and benzotriazole), 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 as a film pH adjusting agent for the treatment liquid in order to improve the image storability.

A preferred silver halide photographic light-sensitive material used in the processing liquid of the present invention is a black-and-white photographic light-sensitive material which requires a fixing hard film. More preferably, it is a photolithographic material. Most preferably, JP-A-52-18317, JP-A-53-95618,
No. 58-173737, No. 58-106493, Photographic plate-making photosensitive material containing tetrazolium salt as described in JP-A Nos. 61-223734 and 61-223834, and photoengraving plate containing hydrazine derivative. It is a photosensitive material.

[0049]

EXAMPLES The effects of the present invention will be illustrated below with reference to examples.

Example 1 (Production of Evaluation Film) An evaluation film was produced by the method described in JP-A-2-226143, page 15, lower right column, line 7 to page 16, lower left column, line 4. As the tetrazolium compound, Exemplified Compound T-2 (50 mg / m ² ) was used. This film is S
Ample 1

[0051]

[Chemical 5]

The developer samples shown below were prepared and their storage stability and running stability were evaluated. To evaluate the storability, put 50 ml of each developer sample in a 100 ml beaker at 5 ° C.
The solution was left in an open system for 14 days under the conditions of 30% RH, 23 ° C. 50% RH, 40 ° C. 50% RH, and evaluated by the blackening level and the amount of precipitation. The blackening level was evaluated by visual rank. The 5th rank is the best, there is no color change at all, the 1st rank is black, the 3rd rank is brown, and it cannot be used in a photographic image unless it is 3 ranks or more. Running stability is evaluated by a blackening rate of 80.
% Sample 1 film (252 x 303 mm) 30 per day
0 Using Konica GR-27 automatic processor, the following developer 1 and fixer 1 were processed under the following processing conditions, and the photographic performance (sensitivity, fog, halftone dot quality) on the 14th day was evaluated. I went with that.

The photographic performance was evaluated by subjecting the sample for evaluation to wedge exposure with a bright room printer (HMW-215 manufactured by Oak Manufacturing Co., Ltd.) and then processing the sample with an automatic processor. The sensitivity was measured by measuring the density of an evaluation sample treated with the developer of Experiment No. 1 in Table 2 with an optical densitometer (PDA-65 manufactured by Konica), and shown as a relative sensitivity with the sensitivity at a density of 2.5 as 100. .. The fogging is indicated by the density measurement value of the unexposed area. Evaluation of halftone dot quality is 100
The evaluation was carried out by visual evaluation using a magnifying glass of 5 times. The highest rank is 5, the lowest rank is 1, and 3 or more are practically usable levels. The results are shown in Tables 1 and 2.

<Developer formulation 1> (1 liter of solution used) Hydroquinone 15 g Phenidone 0.5 g K ₂ SO ₃ 49.5 g KBr 4.5 g K ₂ CO ₃ 66 g KHCO ₃ 3 g 5-Nitroindazole 0.20 g 5-Methylbenzotriazole 0.16 g 1-Phenyl-5-mercaptotetrazole 0.03 g EDTA.2Na 1 g Diethylene glycol 100 g Compound of general formula [1] The amount pH shown in Table 1 was 10.40 (25 ° C.).

<Fixer Formula 1> Ammonium thiosulfate (72.5w% aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90w% aqueous solution) 13.6ml (Composition B) ) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50 w% aqueous solution) 3.0 g Aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1 w%) 20 g When using the fixer, the above composition A and composition B are added to 500 ml of water. They were melted in order and finished to 1 l for use. The pH of this fixer was about 5.6 (25 ° C).

[0056]

[0057]

[Table 1]

[0058]

[Table 2]

As is clear from Tables 1 and 2, the time-dependent and running stability of the present invention are remarkably improved.

Example 2 A fixing solution sample was prepared according to the following fixing solution formulation 2, and the storage stability with time and running stability were evaluated. To evaluate the storability with time, put 50 ml of each developer sample in a 100 ml beaker at 5 ° C and 30%.
RH, 23 ° C. 50% RH, 40 ° C. 50% RH conditions were left for 14 days in an open system to evaluate the amount of precipitation. Precipitation The amount of precipitation was measured by a precision electronic balance after filtering a fixing solution sample with filter paper and drying. The running stability was evaluated by using the following developer 2 and fixer 2 under the same conditions as in Example 1. Sample 1 film (252 x 303 mm) described in Example 1 with a blackening rate of 80%
300 sheets per day were processed by using a GR-27 automatic developing machine manufactured by Konica Corporation, and the film drying property on the 14th day was evaluated. The drying property of the film was evaluated by measuring the water content after squeezing with a squeeze roller after finishing the water washing step of the automatic developing machine.

(Sample size: 252 × 303 mm) This evaluation is based on the fact that the water content depends on the hardening effect of fixing. In other words, if the hardening effect is small, the water content increases and the film becomes scratched during the drying process, resulting in no commercial value. The results are shown in Table 3.

<Fixing solution formulation 2> (1 liter of working solution) (Composition A) Ammonium thiosulfate (72.5 wt% aqueous solution) 240 ml Natrium sulfite 17 g Natrium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2g Acetic acid (90% aqueous solution) 13.6ml Compound of general formula [1] Amount shown in Table 3 (Composition B) Pure water 30ml Sulfuric acid (50wt% aqueous solution) 3.2g Aluminum sulfate (Al ₂ O ₃ conversion content 81wt% aqueous solution) (Amount shown in Table 3) When the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and finished to 1 liter. Of this fixer
The pH was about 5.6 (25 ° C).

<Developer formulation 2> (1 liter of solution used) Hydroquinone 15 g Phenidone 0.5 g K ₂ SO ₃ 49.5 g KBr 4.5 g K ₂ CO ₃ 66 g KHCO ₃ 3 g 5-Nitroindazole 0.11 g 5-Methylbenzotriazole 0.20 g 1-Phenyl-5-mercaptotetrazole 0.02 g EDTA.2Na 1 g diethylene glycol 100 g pH was 10.40 (25 ° C).

[0064]

[Table 3]

As is clear from Table 3, the running stability of the present invention is remarkably improved as compared with the comparison.

[0066]

According to the present invention, it is possible to provide a processing agent for silver halide photographic light-sensitive materials, which has excellent stability over time or running and has markedly improved photographic performance.

Claims (3)

[Claims] 1. A processing agent for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, containing a compound represented by the following general formula [I]. A characteristic treating agent for silver halide photographic light-sensitive materials. [Chemical 1] [In the formula, R represents a hydrogen atom, an alkyl group, or an aryl group. n represents an integer of 1 to 10. ] 2. A developer for silver halide photographic light-sensitive materials according to claim 1, wherein the compound of the formula [I] is contained in the developer. 3. A fixing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the fixing agent contains a compound represented by the general formula [I].