JP3030589B2 - Processing agents for black and white silver halide photographic materials, developers for black and white silver halide photographic materials and fixing agents for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for a black-and-white silver halide photographic light-sensitive material, and more particularly to a processing agent for a black-and-white silver halide photographic light-sensitive material excellent in aging or running stability.

[0002]

BACKGROUND OF THE INVENTION A processing agent for a silver halide photographic light-sensitive material contains various additives in high concentrations depending on the purpose. In particular, in most cases, a large amount of an inorganic salt is contained for the purpose of adjusting pH or imparting a buffer property, and the ionic strength in a liquid is extremely high. Among these in-liquid additives, those having a very low solubility cause precipitation in the processing layer of the automatic developing machine or in the replenishment tank with running or aging, resulting in remarkable deterioration of photographic quality. In order to solve this problem, various types of water-soluble solvents have been studied. However, as described above, most of them do not dissolve due to high ionic strength and pH conditions, and most of them do not adversely affect photographic performance even if dissolved. Only a few are able to survive.
However, even in such a water-soluble solvent, the amount of addition is limited, and if it is added in excess, the photographic performance is adversely affected. Therefore, the amount of the low-solubility additive is also limited, cannot be added in a large amount, and further improvement in photographic performance cannot be expected at present.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a processing agent for a silver halide photographic light-sensitive material which has excellent stability over time or running and has remarkably improved photographic performance.

[0004]

The object of the present invention is to provide a black-and-white silver halide photographic material for processing a black-and-white silver halide photographic material having at least one silver halide emulsion layer on a support.
In the material for treatment agent is achieved by the treatment agent contains a compound represented by the following general formula [I].

[0005]

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

Hereinafter, the present invention will be described specifically.

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

[0009]

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[0010]

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The amount of the above compound is not particularly limited,
It is preferable to use 300 g or less per liter of working liquid.

The processing agent for a silver halide photographic light-sensitive material 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. What is done is a black and white developer and a fixer.

The combination of a dihydroxybenzene chain and 1-phenyl-3-pyrazolidones is most preferred as the developing agent used in the black-and-white developer used in the present invention, since good performance is easily obtained. Needless to say, a p-aminophenol-based developing agent may also be contained.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone,
There are 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferred.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention is 1-phenyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

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

The sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfite is preferably at least 0.2 mol / l, particularly preferably at least 0.4 mol / l. 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
Range up to 2.

Alkali agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Includes pH regulators such as potassium carbonate, sodium triphosphate and potassium triphosphate.

JP-A-61-28708 (borate), JP-A-60-28708
No. -93439 (for example, saccharose, acetoxime, 5-
Buffering agents such as sulfosulfylic acid), phosphates and carbonates may be used.

Additives other than the above-mentioned components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, Organic solvents such as ethinol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole
Mercapto compounds such as -5-sulfonic acid sodium salt, 5
-Indazole compounds such as nitroindazole, and antifoggants such as benzotriazole compounds such as 5-methylbenztriazole may be further contained, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, JP 56
-106244 or the like.

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

In the developer of the present invention, an amino compound such as an alkanolamine described in JP-A-56-106244 can be used.

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

The development temperature and time are from about 25 ° C. to 50 ° C. for 90 seconds or less, preferably from 30 ° C. to 40 ° C. for 10 seconds to 40 seconds.
Fixing solution is an aqueous solution containing thiosulfate, pH 3.8 or more,
Preferably it has 4.2-5.5.

As the fixing agent, there are sodium thiosulfate and ammonium thiosulfate, and thiosulfate ion and ammonium ion are essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6
Mol / l.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, 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 at least 0.005 mol per liter of fixing solution, particularly 0.01 mol / l to 0.03 mol / l.

Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or nitric acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water. And the compounds described in Japanese Patent Application No. 60-213562.

The fixing temperature and time are preferably from about 20 ° C. to about 50 ° C. for 10 seconds to 1 minute, and more preferably from 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 together with water for diluting the photosensitive material as it is processed, it is most preferable that the fixer concentrate is composed of one agent. Is the same as in the case of the developer.

The fixing solution can be stably present as one agent at a pH of 4.5 or more, more preferably at a pH of 4.65 or more. If the pH is lower than 4.5, the thiosulfate is decomposed and finally sulfided when the fixing solution is left for many years until it is actually used. Accordingly, in the range of pH 4.5 or more, the generation of sulfurous acid gas is small and the working environment is improved. The upper limit of the pH is not so severe, but if the pH is fixed at an excessively high pH, the film pH will increase even after washing with water, and the film will swell and the drying load will increase.
The order is the limit.

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

The supply amount of each concentrate to the treatment tank solution and the mixing ratio with the dilution water can be variously changed depending on the composition of the concentrate. At a ratio of 8, the total amount of each of these developing solution and 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 or stabilizing treatment after the present solution and fixing. Any method known in the art can be applied to the washing or stabilizing treatment, and water containing various additives known in the art can be used as the washing water or the stabilizing solution. The use of water which has been subjected to antifungal means in the washing water or stabilizing solution, not only the possible water saving processing of the photosensitive material 1 m ² per 3 liters or less replenishing rate, automatic processor installed in piping required Therefore, the stock tank can be further reduced. That is, the preparation dilution water and the washing water or the stabilizing solution for the developing solution and the fixing solution can be supplied from one common stock tank, so that the automatic developing machine can be made more compact.

When water that has been subjected to fungicide is used in combination with washing water or a stabilizing solution, the occurrence of scale can be effectively prevented.
Photosensitive material 1 m ² per 0-3 liters, preferably 0-1
1 liter of water-saving treatment can be performed.

Here, the case where the replenishment amount is 0 means that no replenishment is carried out except that the washing water in the washing tank is appropriately replenished by an amount reduced by natural evaporation or the like. It means the case where the "water" treatment method is performed.

As a method for reducing the amount of replenishment, a multi-stage countercurrent system (for example, two-stage or three-stage) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material of the fixing solution is gradually processed in a clean direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted.
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 washing water is very small compared to the conventional method.

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

Further, part or all of the overflow liquid from the washing or stabilizing bath generated by replenishing the washing or stabilizing bath with antifungal water according to the treatment is described in JP-A-60-235133. As described, it can be used for a processing solution having a fixing ability, which is the preceding processing step. By doing so, it is more preferable because the stock water can be saved and the waste liquid can be reduced.

Examples of the antifungal means include an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion exchange resin described in JP-A-61-131632. Method of making pure water using, Japanese Patent Application No. 60-253807, 60-253807
No. 295894, No. 61-63030 and No. 61-51396 can be used.

Further, LEWest "Water Quality Criter"
ia ”Photo Sci & Eng. Vol. 9 No. 6 (1965), MWBeach
“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, 57-58143
No. 58-105145, No. 57-132146, No. 58-18631, No.
Antibacterial agents, antibacterial agents, surfactants, and the like described in Nos. 57-97530 and 57-157244 can also be used in combination.

Further, in the washing bath, RTKreiman, J. Image,
Isothiazoline compounds described in Tech 10, (6) 242 (1984), RESEARCH DISCLOSURE Vol. 205, Item 20526 (1
981, May issue),
Isothiazoline-based compounds described in Vol. 228, Item 22845 (April, 1983), the compounds described in Japanese Patent Application No. 61-51396, and the like can also be used in combination as antibacterial agents (Microbiocide).

Further, specific examples of the anti-binder include phenol, 4-chlorophenol, pentachlorophenol, cresol, O-phenylphenol, chlorophen, dichlorophen, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoate. 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 the antifungal means is diluted with the stock solution of the processing solution such as the developer fixing solution and the amount thereof is preferably 0.01 to 10 g / l, more preferably 0.01 to 10 g / l.
0.1 to 5 g / l.

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

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, for adjusting the membrane pH (for example, pH 3 to 8))
Aldehydes such as metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin Can be mentioned. In addition, chelating agents, detergents (thiazoles, isothiazoles, halogenated phenols,
Various additives such as a sulfanilamide and a 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.

It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a film pH adjuster of the processing solution in order to improve image storability.

Preferred silver halide photographic materials used in the processing solution of the present invention are black-and-white photographic materials requiring a fixed hardening film. More preferred is a photomechanical photosensitive material. Most preferably, JP-A-52-18317, JP-A-53-95618,
JP-A-58-173737, JP-A-58-106493, and JP-A-61-223734, and JP-A-61-223734, and photoengraving containing a hydrazine derivative as described in JP-A-61-223834. It is a photosensitive material.

[0049]

EXAMPLES The effects of the present invention will now be illustrated by examples.

Example 1 (Preparation of Evaluation Film) An evaluation film was prepared 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
ample1.

[0051]

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The following developer samples were prepared and evaluated for storage stability over time and running stability. The storage stability evaluation over time was performed by placing 50 ml of each developer sample in a 100 ml beaker and 5 ° C
The solution was allowed to stand in an open system for 14 days under the conditions of 30% RH, 23 ° C., 50% RH, and 40 ° C., 50% RH, and evaluated by the blackening level and the amount of precipitate of the liquid. The blackening level was evaluated by visual rank. Five ranks are the best, there is no color change at all, one rank is black, three ranks are brown, and if not more than three ranks, they cannot be used on photographic images. Running stability was evaluated at a blackening ratio of 80.
% Sample1 film (252 × 303mm) 30 times a day
0 Using a GR-27 automatic developing machine manufactured by Konica Corporation, process using the following developing solution 1 and fixing solution 1 under the following processing conditions, and evaluate the photographic performance (sensitivity, fog, halftone dot quality) on the 14th day. I went by that.

The photographic performance was evaluated on a processed sample which was subjected to wedge exposure on a sample for evaluation using a bright room printer (Oak Seisakusho HMW-215) and then processed by an automatic developing machine. The sensitivity was measured by using an optical densitometer (PDA-65, manufactured by Konica Corporation) to measure the density of an evaluation sample treated with the developer of Experiment No. 1 in Table 2, and expressed as a relative sensitivity with the sensitivity at a density of 2.5 being 100. . Fog was indicated by a density measurement value of an unexposed portion. The dot quality rating is 100
It was visually evaluated using a magnifying glass with a five-step rank. The highest rank is 5, the lowest rank is 1, and 3 or more are practically usable levels. Tables 1 and 2 show the results.

[0054] <Developer Formulation 1> (using 1 liter minute) hydroquinone 15g phenidone _{0.5g K 2 SO 3 49.5g KBr 4.5g} K 2 CO 3 66g KHCO 3 3g 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 the general formula [1] The amount shown in Table 1 was 10.40 (25 ° C.).

<Fixing Solution Formulation 1> Ammonium thiosulfate (72.5 w% aqueous solution) 240 ml Sodium sulfite 17 g sodium acetate trihydrate 6.5 g boric acid 6 g sodium citrate dihydrate 2 g acetic acid (90 w% aqueous solution) 13.6 ml (composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50 w% aqueous solution) 3.0 g Aluminum sulfate (aqueous solution having an equivalent content of 8.1 w% in terms of Al ₂ O ₃ ) 20 g When using a fixing solution, the above composition A and composition B were mixed in 500 ml of water. It melted in order and finished to 1 liter for use. The pH of the fixing solution was about 5.6 (25 ° C.).

[0056]

[0057]

[Table 1]

[0058]

[Table 2]

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

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

(Sample size: 252 × 303 mm) This evaluation is based on the fact that the water content is influenced by the hardening effect of fixing. In other words, if the hardening effect is small, the water content increases, and the film is scratched in the drying step, resulting in no commercial value. Table 3 shows the results.

<Fixing solution formulation 2> (1 liter of working solution) (Composition A) Ammonium thiosulfate (72.5 wt% aqueous solution) 240 ml Naurium sulfite 17 g Naurium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate amounts indicated in compound table 3 2g acetate (90% solution) 13.6 ml formula [1] (composition B) pure water 30ml sulfate (50 wt% aqueous solution) 3.2 g aqueous aluminum sulfate (Al ₂ O ₃ in terms content of 81 wt% ) Amount shown in Table 3 When the fixing solution was used, the composition A and the composition B were dissolved in 500 ml of water in this order, and finished to 1 liter. This fixer
pH was about 5.6 (25 ° C).

<Developer Formulation 2> (1 liter of working solution) 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 The pH was 10.40 (25 ° C.).

[0064]

[Table 3]

As is evident from Table 3, the present invention has significantly improved running stability as compared with the comparison.

[0066]

According to the present invention, it is possible to provide a processing agent for a silver halide photographic light-sensitive material which is excellent in aging or running stability and has remarkably improved photographic performance.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 5/305 G03C 5/38 G03C 11/00

Claims (3)

(57) [Claims] 1. A black-and-white silver halide photographic light-sensitive material for processing agent characterized by containing a compound represented by the following general formula [I]. Embedded image [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 a black- and- white silver halide photographic material, comprising a compound represented by the above general formula [I] . 3. Characteristics and be Ruha androgenic halide photographic light-sensitive material fixer to have containing <br/> a compound represented by the general formula [I].