JPH07159939A - Developing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce silver stains occurring in the development processing of the photosensitive material without adversely affecting other photographic performances. CONSTITUTION:The developing solution for this photosensitive material contains at least one kind of compound represented by the general formula in which X is S or imino, and when X is imino,(m) is 0 and A is H; L is optionally substituted alkenyl; A is H, carboxy, nitrile, acetyl, or carbamoyl: and (m) is 0, 1, 2, or 3 and only when (m)is 0, A is H.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of developing and processing a silver halide photographic light-sensitive material, and more particularly to a developer used therein.

[0002]

2. Description of the Related Art Generally, it is well known that a developer used for developing a silver halide photographic light-sensitive material contains a sulfite for the purpose of enhancing the storage stability of the developer. In some cases, a developing solution containing a compound having a strong dissolving action for silver halide such as thiosulfate such as a developing solution for silver salt diffusion transfer or a one-bath developing / fixing solution is also used. When a light-sensitive material is treated with a developing solution containing a compound having a dissolving effect on silver halide such as sulfite or thiosulfate, a large amount of silver complex is easily reduced and accumulated as silver sludge. Especially when continuously processing the photosensitive material using an automatic processor, not only the silver sludge floats but also adheres to the rollers and belts and the light reflection on the photosensitive material called silver stain on the roller stripes. As a result, yellow or brown stains are generated due to the precipitated silver. 2-Mercapto-1,3,4-as an agent to prevent silver sludge and liquid stains
Thiadiazoles (British Patent No. 940169), 2-
Mercapto-1,3,4-oxadiazoles or 1-
Phenyl-5-mercaptotetrazole (US Pat. No. 3,
173,789), D, L-6,8-dithiooctanoic acid (U.S. Pat. No. 3,318,701), O-mercaptobenzoic acid (British Patent No. 1144481), aliphatic mercaptocarboxylic acid (U.S. Pat. No. 3,628,955), L
-Thiazolidine-4-carboxylic acid (J. Photogr. Sci., 13,
233 (1976)), disulfide compound (Japanese Patent Laid-Open No. 52-36029), 2-benzoxazole thiol, 2-benzimidazole thiol (Photogr. Sci. Eng., 20, 220 (196).
5)), acetylene glycols (JP-A-55-95947), 2-mercaptobenzothiazole-5-sulfonic acid (JP-A-56-72441) and the like are known. However, these compounds are used in a developing solution having a dissolving action on silver halide, particularly in a high concentration of sulfite (for example,
When used as an anti-sludge agent in a developer containing 0.2 mol / l or more), the anti-sludge effect is lost due to air oxidation, or the sludge-inhibiting effect is weak and needs to be used in large amounts. There is a problem that it is difficult to say that it is sufficiently satisfactory, because it adversely affects photographic characteristics such as suppression, is expensive, or has an unpleasant odor.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to sensitize a developing solution having a dissolving action for silver halide, particularly a stable developing solution containing a high concentration of sulfite, by using an automatic processor. Provide a developer that can prevent liquid stains due to silver sludge and stains on rollers and belts of automatic processors when processing materials and can obtain photographic images with excellent finish quality without silver stain, yellow fog, etc. Especially. Still another object of the present invention is to provide a method for processing a silver halide black-and-white photographic light-sensitive material with a developer which prevents the generation of silver sludge without the above-mentioned problems.

[0004]

The above objects of the present invention have been achieved by incorporating at least one compound represented by the following general formula (I) into a developer for silver halide photographic light-sensitive materials.

[0005]

[Chemical 2]

[Wherein X is a sulfur atom or an imino group (when X is an imino group, m is 0 and A is a hydrogen atom);
Is a substituted or unsubstituted alkylene group, A is a hydrogen atom, a carboxy group, a nitrile group, an acetyl group, or a carbamoyl group, m is 0, 1, 2 or 3 (A is hydrogen only when m is 0). Atom) is shown. ] Specific examples of the compound represented by formula (I) are described below. However, it is not limited to these.

[0007]

[Chemical 3]

Of the above compounds, Compound 1 is known and can be easily obtained. Other compounds can be obtained by reacting the general formula (II) with the general formula (III) in water or an organic solvent.

[0009]

[Chemical 4]

[Wherein L represents a substituted or unsubstituted alkylene group, A represents a carboxy group, a nitrile group, an acetyl group, or a carbamoyl group, and m represents 1, 2 or 3 respectively. ] An example of synthesis is shown below. Synthesis Example 1 3-Carboxymethylthio-1,2,4-triazoline-5
-Thion (Compound 2) 20 g of 3-sodiumthio-1,2,4-triazoline-5-
The thione was dissolved in 174 ml of water and 12.3 g of monochloroacetic acid was added with stirring. After stirring at room temperature for 1.5 hours, the mixture was concentrated under reduced pressure. Ethanol was added to the concentrate to remove insoluble matter. The ethanol solution was concentrated to obtain crude crystals. Yield 8.1g. Preparative purification is carried out by column chromatography using a mobile phase of benzene / acetone = 1/1 and a stationary phase of Wakogel C-200 to obtain the desired product, which is then recrystallized with ethanol / water = 1/1, mp144- White needle crystals at 145.5 ℃ 4.6g
(18.7%) was obtained. Also, the Weilstein test method gave a halogen (-), and the Lassene test method gave a sulfur (+). Infrared absorption spectrum is NH (3230cm ^-1 ), CH ₂
(2930,2800cm ^-1 ), COOH (1730cm ^-1 ), NH-C = S (1530cm
^-1 ) was shown. Synthesis Example 2 3-acetonylthio-1,2,4-triazoline-5-thione (Compound 4) 10 g of 3-sodiumthio-1,2,4-triazoline-5-
Thion was dissolved in 123 ml of methanol, and 6 g of acetyl chloride was added to this methanol solution with stirring, and a white precipitate was formed immediately. The mixture was stirred at room temperature for 1.5 hours, then heated to 50 ° C. and stirred for 20 minutes. The precipitate was filtered off and the filtrate was concentrated to give crude crystals. Repeat the reconstitution three times with ethanol, mp160
2.5 g (20.5%) of white crystals were obtained at ˜161 ° C. (single product was confirmed by thin layer chromatography). The Beilstein test method gave halogen (-), and the Lasagne test method gave sulfur (+). The infrared absorption spectrum is NH (30
10-3050cm ^-1 ), CH ₃ , CH ₂ (2990-2890cm ^-1 ), CO (1700
cm- ¹ ) and NH-C = S (1530 cm- ¹ ).

The preferred concentration of the compound of the present invention in the developing solution (working solution) is about 0.005 to about 5 g, and more preferably about 0.01 g to about 2 g per liter of the developing solution (working solution). The development processing of the present invention is carried out by using a conventional black and white photographic developing agent such as hydroquinone, alkylhydroquinone (for example, t-butylhydroquinone, methylhydroquinone,
Dimethylhydroquinone), catechol, chlorohydroquinone, dichlorohydroquinone, alkoxyhydroquinone (eg methoxy or ethoxyhydroquinone), aminophenol developing agent (eg N-methyl-
p-aminophenol, 2,4-diaminophenol, N
-Methyl-p-aminophenol sulphate), ascorbic acid developing agent, pyrazolones (eg 4-aminopyrazolone), 3-pyrazolidone developing agent (eg 1-
Phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-
Pyrazolidone, 1,5-diphenyl-3-pyrazolidone,
1-p-tolyl-3-pyrazolidone, 1-phenyl-2
-Acetyl-4,4-dimethyl-3-pyrazolidone, 1-
An alkaline aqueous solution containing p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone) or a combination thereof. Preferably there is. Especially with hydroquinone
A combination of pyrazolidones or hydroquinone and aminophenols is useful for rapid treatment at high temperature. However, it may be a so-called activator type developer which does not substantially contain a developing agent.

The developer containing the general formula (I) used in the present invention exhibits a particularly remarkable sludge preventing effect when it contains a large amount of sulfite ions. At this time, specifically, 0.1 mol or more, preferably 0.2 to 1.0 mol of sulfite ion is contained per 1 liter of the developing solution. Specific examples of sulfites that give sulfite ions include alkali metal sulfites such as sodium sulfite, potassium sulfite, and potassium metabisulfite. The silver sludge generated in the developing solution is particularly likely to be deposited on the roller or belt in the developing solution, and the silver sludge deposited on the roller or belt is likely to contaminate the photosensitive material. Therefore, the present invention is particularly useful when processed by an automatic processor. As such an automatic developing machine, for example, a facing roller system (for example, Pakorol Super G24 manufactured by PAKO) is used.
-2, Fuji Photo Film Co. G-14LFG-24SQ, RN, etc. Staggered roller system (eg Eastman Kodak Kodalith Proc
essor, M6 Processor, Fuji Photo Film Co. RU, etc.),
Belt transfer method (for example, LD-241D from Log-E-tronics) and others (such as Cronalith 24L from dupont).

If necessary, the developing solution may further contain a buffering agent (eg, carbonate, boric acid, borate, alkanolamine),
Alkaline agents (eg hydroxides, carbonates), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium) Salt), a development accelerator, a surfactant, a hardener and the like. The developer may further include an antifoggant (eg, benzotriazole such as 5-nitroindazole, 5-nitro-benzimidazole, 5-methyl-benzotriazole, 5-nitrobenzotriazole, benzothiazole, 1-phenyl-5-). Tetrazole such as mercaptotetrazole, thiazole or compounds described in British Patent No. 1,269,268), chelating agent (eg ethylenediaminetetraacetic acid, alkali metal salt thereof, polyphosphate salt, nitriloacetate salt) . PH of developer
Is selected to give the desired density and contrast, but is preferably in the range of about 8-13.
Developer processing temperature and time are interrelated and are determined in relation to the total processing time, generally 10 to 40 ° C.
Seconds to 3 minutes, but about 25 to 45 ° C for high-temperature rapid processing
Is the temperature of.

In the present invention, such a component of the developing solution may contain components necessary for use, and the form before treatment before use as a use liquid may be, for example, a mixture of solid components or a concentrate. , A solution, an emulsion or a suspension. For example, the components of the developing solution may be divided into several parts to have the same or different forms, or may be in the form of a powder or liquid preparation liquid prepared in advance. If necessary, the prepared liquid can be dissolved in water or diluted with water to prepare a use liquid. On the other hand, the fixing solution is a solution containing thiosulfate and a water-soluble aluminum compound, preferably
It has a pH of about 3.8 to 5.5 (20 ° C). In the method of the present invention, a stopping step may be provided after the development, but the stopping step is generally omitted in a roller-conveying type automatic developing machine. Therefore, the developing solution is brought into the fixing solution, and the pH of the fixing solution rises. For that reason, the pH of the fixer is about 3.8-
It is desirable to adjust to 5.0 (20 ℃). The fixing agent is a thiosulfate such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of the fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to 5 mol / liter. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound known as a hardening agent for an acidic hardening fixing solution, for example, aluminum chloride, aluminum sulfate,
There is potash alum.

According to the method of the present invention, the developed and fixed photographic material is washed and dried. Wash with water at about 5-50 ° C
10 seconds to 3 minutes is preferable. Drying is performed at about 30-180 ℃,
About 5 seconds to 3 minutes and 30 seconds may be sufficient. The light-sensitive material processed by the method of the present invention may be of any use, but is preferably a black and white light-sensitive material, that is, an X-ray light-sensitive material,
It is applied to micro sensitive materials, sensitive materials for ANRIS, photographic sensitive materials, and black and white sensitive materials for general amateurs. The silver halide of the photosensitive layer includes silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and the like. The light-sensitive material used in the present invention may be either a negative type or a direct positive type.

The silver halide photographic light-sensitive material applicable to the method of the present invention comprises a support and at least one silver halide emulsion layer coated thereon. The silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, it may have a back layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer), etc., if necessary. The silver halide emulsion is a dispersion of silver halide in a hydrophilic colloid (eg, gelatin, modified gelatin, colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone or a mixture thereof). Is. The silver halide emulsion is generally prepared by mixing a water-soluble silver salt (for example, silver nitrate) and a water-soluble halogen salt with water by a method well known in the art (for example, single jet method, double jet method, control double jet method, etc.). And in the presence of a hydrophilic colloid, followed by physical ripening and chemical ripening such as gold sensitization and / or sulfur sensitization. The silver halide emulsion contains a spectral sensitizer (for example, a cyanine dye, a mesylocyanine dye, or a mixture thereof), a stabilizer (for example, 4-hydroxy-6) during the production process or immediately before coating.
-Methyl-1,3,3a, 7-tetrazaindene), sensitizers (eg, compounds described in US Pat. No. 3,619,198), antifoggants (eg, benzotriazole, 5
-Nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole), a hardener (eg formalin,
Glyoxal, mucochloric acid, 2-hydroxy-4,6
-Dichloro-s-triazine), a coating aid (for example, saponin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide) and the like can be added. The silver halide emulsion produced in this manner is applied to a support such as baryta paper, resin coated paper, cellulose acetate film and polyethylene terephthalate film by dipping method, air knife method, bead method,
It is applied and dried by an extrusion doctor method, a double-sided application method or the like.

[0017]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but of course the present invention is not limited thereto. Example 1 The following developers (A) to (D) were prepared. <Development concentrate> Pure water 640 ml Potassium sulfite 259 g Ethylenediaminetetraacetic acid tetrasodium salt 4.8 g Potassium hydroxide 34.2 g Hydroquinone 80 g Potassium carbonate (anhydrous) 57.7 g 4,4-Dimethyl-1-phenyl-3-pyrazolidone 1.6 g Methylcellosolve 38.7 ml 1-phenyl-5-mercapto-1,2,3,4-tetrazole 0.2 g potassium bromide 10 g Pure water is added to bring the total volume to 1 liter. The pH at this time is
11.40. The developer is prepared by diluting the above concentrate as follows.
(A). Development concentrate 500 ml + pure water 1500 ml = developer (A) developer (B); developer (A) 1 mg of compound 1 300 mg
What was added Developer (C); Developer (A) 300 mg of compound 2 per liter
What was added Developer (D) ； Developer (A) 1 liter of compound 4 300mg
What was added Next, using various developing solutions (A) to (D), a roller transport automatic developing machine Gevaset 437N machine (manufactured by Agfergewert Akchengezelshaft) at a developing time of 30 seconds and a developing temperature of 32 ° C. HLF-100 (manufactured by Oriental Photography Co., Ltd.,
A film for a scanner using a He-Ne laser as a light source was processed. The replenishment rate was 40 ml / 10 inches × 12 inches (quarter size) of developing solution, 60 ml / 10 inches × 12 inches (quarter size) of fixing solution, and 3.5 liters / min of washing water. The fixer is GF-500 (Oriental Photo Industry Co., Ltd.)
Manufactured) was used. To check the photographic properties of this light-sensitive material, a sensitometer was used to perform stepwise exposure with an optical wedge. The automatic developing machine was operated for 6 days a week, and 50 half-exposed four-cut size (10 inch × 12 inch) sheets were processed per day on the working day. The above running experiment was continued for 2 weeks. The total number of processed sheets was 600. Table 1 shows the results of photographic properties and silver stains obtained by running experiments. The sensitivity was obtained as the relative value of the reciprocal of the exposure amount required to obtain the blackening degree of +3.52 and the comparison sensitivity was set to 100. Fog value was measured as the net increase in density corrected for base density. Average gradation is 90% of DM on the characteristic curve
And the area of fogging value +0.1 was regarded as a straight line and expressed as the slope. DM represents maximum concentration.

[0018]

[Table 1]

As shown in Table 1, the developer containing the compound used in the present invention has good silver sludge prevention performance and does not adversely affect photographic performance.

[0020]

INDUSTRIAL APPLICABILITY According to the present invention, silver sludge produced in a developing solution containing a silver halide solvent such as sulfite can be satisfactorily used by using at least one compound represented by the general formula (I). It can be prevented and does not adversely affect photographic performance.

Claims (1)

[Claims] 1. A developer for a silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula (I). [Chemical 1] [Wherein X is a sulfur atom or an imino group (when X is an imino group, m is 0 and A is a hydrogen atom), L is a substituted or unsubstituted alkylene group, and A is a hydrogen atom, a carboxy group or a nitrile group. Group, acetyl group or carbamoyl group, m is 0, 1, 2 or 3 (only when m is 0, A
Represents a hydrogen atom). ]