JPH086215A - Developing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the method of processing the silver halide photographic sensitive material by using the developing solution prevented from occurrence of silver sludge. CONSTITUTION:The developing solution for the silver halide photographic sensitive material contains a compound represented by the formula in which R is nonsubstituted alkyl or aryl; A is alkylene or arylene; and M is an H or alkali metal atom or ammonium group, thus permitting the developing solution to be prevented from occurrence of silver sludge, staining of the rollers and belts of an automatic developing machine to be prevented, when the photosensitive material is processed by using the developing solution having dissolution action to silver halide, especially, the stable developing solution containing highly concentrated sulfite, and a photographic image free from silver sludge and superior in finished quality to be obtained.

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 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 the field of photolithography for printing, an image forming system showing photographic characteristics of high contrast (gamma value of 10 or more) is required in order to reproduce a continuous tone image by a halftone dot image and a line image. is there.

Recently, a high concentration of sulfite has been used in a developer,
A method of developing a silver halide light-sensitive material in the presence of a hydrazine derivative and an amino compound to obtain a high-contrast image has been put into practical use. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since a high concentration of sulfite can be added to the developer, the stability of the developer against air oxidation is higher than that of the lith developer. improves.

Further, a developing solution for other purposes such as a silver salt diffusion transfer developing solution and a developing solution containing a compound having a strong dissolving action for silver halide such as thiosulfate such as a one-bath developing and fixing solution are also used. There is.

However, when the light-sensitive material is treated with a developing solution containing a compound having a dissolving effect on silver halide such as sulfite, amino compound and thiosulfate, a large amount of silver complex is eluted in the developing solution, The eluted silver complex is easily reduced and accumulated as silver sludge. Especially when continuously processing photosensitive materials using an automatic processor,
Not only the silver sludge floats but also adheres to a roller, a belt or the like, and the light-sensitive material called a roller-striped silver stain causes a stain due to precipitated silver which is yellow or brown due to reflection of light.

As an agent for preventing silver sludge and liquid stain, 2-
Mercapto-1,3,4-thiadiazoles (British Patent No. 940,169), 2-mercapto-1,
3,4-oxadiazoles or 1-phenyl-5
-Mercaptotetrazole (US Pat. No. 3,173,7
89), D.I. L-6,8-dithiooctanoic acid (US Pat. No. 3,318,701), O-mercaptobenzoic acid (GB Pat. No. 1,144,481), aliphatic mercaptocarboxylic acid (US Pat. Third and sixth
28,955), L-thiazolidine-4-carboxylic acid (J. Photogr. Sci., 13 , 233).
(1965)), a disulfide compound (JP-A-52-3
6029), 2-benzoxazolthio-
2-Benzimidazolethiol (Photog
r. Sci. Eng. , 20 , 220 (1976)),
2-Mercapto-5-sulfamoyl-n-octylbenzimidazole (Japanese Patent Publication No. 47-25385, 2538)
6), acetylene glycols (JP-A-55-55)
95,947), 2-mercaptobenzothiazol-5-sulfonic acid (JP-A-56-72,441), 2-mercaptobenzimidazole-5-sulfonic acid (JP-A-56-72,441). 60-258,537), 4.
6-dimercapto-2-substituted-S-triazine (JP-A-1-19031, JP-A-3-282457), 4.6
-Dimercapto-2- (dicarboxyphenyl) amino-S-triazine (JP-A-4-32248) and the like are known.

[0007]

However, these compounds are sludges in a developing solution having a dissolving action on silver halide, particularly in a developing solution containing a high concentration of sulfite (0.2 mol / L or more). When it is used as an inhibitor, it loses its sludge prevention effect due to air oxidation, its sludge prevention effect is weak and it requires the use of a large amount, and when it is developed in the presence of a hydrazine derivative, it adversely affects the effects of sensitization and high contrast. It is difficult to say that it is sufficiently satisfactory, because it adversely affects the photographic characteristics such as desensitization, softening, suppression of development, occurrence of fog, etc., and is expensive or has an unpleasant odor. There was a problem.

Therefore, an object of the present invention is to process a light-sensitive material using an automatic processor with a developing solution having a dissolving action on silver halide, particularly a stable developing solution containing a high concentration of sulfite. Another object of the present invention is to provide a developer capable of preventing a liquid stain due to silver sludge and a stain on a roller and a belt of a developing machine and obtaining a photographic image having excellent finish quality without silver stain. 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. Still another object is to provide a method for forming a high-contrast negative image with a hydrazine derivative which prevents the generation of silver sludge.

[0009]

[Means for Solving the Problems]

The above objects of the present invention have been achieved by containing a compound represented by the following chemical formula 2 in a developer for silver halide photographic light-sensitive materials. Further, a method of developing an exposed negative-working silver halide photographic light-sensitive material in the presence of a hydrazine derivative to form a high-contrast negative image can also be achieved by containing a compound represented by the following chemical formula 2 in the developer. It was

[0011]

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In the formula, R represents an unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, etc.) or aryl group (eg, phenyl group, etc.), A represents an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, etc.) or arylene group (eg, phenylene group, etc.), and M represents a hydrogen atom, an alkali metal atom (eg, sodium, potassium, etc.). ) Or an ammonium group.

Specific examples of the compound represented by Chemical formula 2 used in the present invention will be given, but the compound used in the present invention is not limited to these.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

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[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

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[0026]

[Chemical 15]

[0027]

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[0028]

[Chemical 17]

Intermediate (A) 4.6-Dichloro-2 of Chemical formula 3
-(N-methyl-N-carboxymethyl) amino-S-
Synthesis of triazine

A mixture of 18.44 g of cyanuric chloride, 100 ml of acetone and 100 g of ice water was kept at an internal temperature of 5 ° C. or lower and agitated vigorously to give N-methylglycine 8.91.
A solution prepared by dissolving g in 100 ml of M / 2-sodium carbonate and a solution prepared by dissolving 5.30 g of sodium carbonate in 50 ml of water were simultaneously added dropwise over 20 minutes, and then stirred at the same temperature for 2 hours. The crystallized product was filtered off, washed with cold water, the filtrate and the washing solution were combined and acidified with 6N hydrochloric acid under ice cooling, and the crystallized product was collected by filtration.
After washing with cold water and drying, 15.7 g of the desired product was obtained. Melting point: 127.0 ° C to (decomposition).

Synthesis of Chemical Formula 3

A solution prepared by dissolving 14.2 g of the intermediate (A) of Chemical formula 3 in 120 ml of dimethylformamide was maintained at an internal temperature of 15 ° C. or lower and under stirring, 70% -sodium hydrosulfide 14.4.
After adding g to a small amount in about 20 minutes, the mixture was stirred at the same temperature for 1.5 hours and further at room temperature for 1.5 hours, and then water 300 m
After adding 1 liter and further adding 6 N-hydrochloric acid 10 m, the liquid was almost concentrated, water was added to the residue, the mixture was ice-cooled, the crystallized product was collected by filtration, washed with water, and then washed with 50 ml of methanol and warmed. After cooling with ice, the precipitated crystal was collected by filtration and dried to obtain 11.0 g of the desired product. Melting point: 174.0 ° C. (decomposition).

The other compounds of the present invention can be synthesized by the same synthetic method or known synthetic methods.

The addition amount of the mercapto compound of the present invention to the developer is 0.005 g or more per liter of the developer, but the addition amount is preferably 0.01 g to 2 g.

The developing agent used in the developing solution of the present invention is not particularly limited, but preferably contains dihydroxybenzenes, and from the viewpoint of developing ability, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones. Alternatively, a combination of dihydroxybenzenes and p-aminophenols is preferable.

As the developing agent used in the present invention, hydroquinone, alkylhydroquinone (for example, t-butylhydroquinone, dimethylhydroquinone, methylhydroquinone, potassium hydroquinone monosulfonate, etc.), catechol, virazole, chlorohydroquinone, dichlorohydroquinone, alkoxyhydroquinone ( For example, methoxyhydroquinone, ethoxyhydroquinone, etc., aminophenol developing agent (eg, N
-Methyl-P-aminophenol, 2,4-diaminophenol, ascorbine developing agent, N-methyl-P-aminophenol sulfate, etc.), pyrazolones (for example, 4-aminopyrazolone, etc.), 3-pyrazolidone developing agent (for example, 1-phenyl) -3-pyrazolidone, 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1,5
-Diphenyl-3-pyrazolidone, 1-p-tolyl-3
-Pyrazolidone, 1-phenyl-2-acetyl-4,4
-Dimethyl-3-pyrazolidone, 1-P-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1-
(2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., and these are used alone or in combination.

Particularly, a combination of hydroquinone and 3-pyrazolidones or hydroquinone and aminophenols is useful for high temperature rapid treatment. However, it may be an activator type developer which does not substantially contain a developing agent.

The developing agent is usually 0.1 mol / L to 0.8.
It is preferably used in an amount of mol / L. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.1 mol / L to 0.5 mol / L and the latter is 0.06 mol. It is preferably used in an amount of / L or less.

The developer containing the compound represented by Chemical formula 2 used in the present invention exerts a remarkable sludge preventing effect when it contains a large amount of sulfite ion. At this time, specifically, the developer contains 0.1 mol / L to 1.0 mol / L of sulfite ion. Specific examples of sulfites that give sulfite ions include alkali metal sulfites such as potassium sulfite, sodium sulfite, and potassium metasulfite.

The amino compound used in the present invention has an effect of promoting contrast enhancement in the presence of a hydrazine derivative. This amino compound is described in JP-A-56-1062.
No. 44, No. 61-267759, No. 61-23014.
5, No. 62-211647, and JP-A No. 2-50150.
No. 2,208,652 and the like can be used.

The typical ones are listed below. (Representative example) 1) N-n-butyldiethanolamine 2) 3-dimethylamino-1,2-propanediol 3) 2-diethylamino-1-ethanol 4) 2-diethylamino-1-butanol 5) 3-diethylamino-1 , 2-Propanediol 6) 3-Dimethylamino-1-propanol 7) 3-Diethylamino-1-propanol 8) Triethanolamine 9) 3-Dipropylamino-1,2-propanediol 10) 2-Dioctylamino- 1-ethanol 11) 3-amino-1,2-propanediol 12) 1-diethylamino-2-propanol 13) n-propyldiethanolamine 14) 2-diisopropylaminoethanol 15) N, N-di-n-butylethanolamine 16) 3-Dibutylamino-1,2-propanediol 17) 2 Methylamino-1-ethanol 18) 4-Dimethylamino-1-butanol 19) 1-Dimethylamino-2-butanol 20) 1-Dimethylamino-2-hexanol 21) 5-Dimethylamino-1-pentanol 22) 6 -Dimethylamino-1-hexanol 23) 1-Dimethylamino-2-octanol 24) 6-Dimethylamino-1,2-hexanediol

The amount of addition may be any amount as long as it promotes contrast enhancement.
Generally, an amount of 0.005 to 1.0 mol / L can be added.

The pH of the developing solution used in the present invention may be selected to an extent sufficient to give a desired density and contrast to the light-sensitive material, but is preferably in the range of 10 to 13.

The alkaline agent used for setting the pH is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate, potassium silicate, or the like. Contains agents and buffers. Also, as a buffer agent, JP-A-62
-186259, Boron compound, JP-A-60-934
Compounds of No. 33 having a dissociation constant of 1 × 10 ^{−11 to} 3 × 10 ⁻¹³ can also be used.

As additives used in addition to the above components, sodium bromide, potassium bromide, sodium chloride,
Potassium chloride, potassium iodide, ethylene glycol,
Examples include diethylene glycol and triethylene glycol.

The developing solution further contains an antifoggant (for example,
Benzotriazoles such as 5-nitroindazole, 5-nitrobenzimidazole, 5-methylbenzotriazole and 5-nitrobenzotriazole, thiazoles such as benzothiazole, tetrazoles such as 1-phenyl-5-mercaptotetrazole or British patents Nos. 1,269,268), 3- (5-mercaptotetrazole) benzenesulfonic acid and its derivatives and chelating agents described in JP-A-62-212651 as development unevenness preventing agents. (For example, ethylenediaminetetraacetic acid, alkali metal salts thereof, polyphosphate salts, nitriloacetate salts, etc.) can be contained.

The developing treatment temperature is usually selected from 18 ° C to 50 ° C, more preferably 25 ° C to 40 ° C. The processing method of the present invention is particularly suitable for rapid processing using an automatic developing machine, and as the automatic developing machine, any of a roller-conveying type, a belt-conveying type and the like can be used.
The processing time may be short, and the development processing time is within 15 to 60 seconds, preferably within 20 to 40 seconds.

As the fixing solution, those having a generally used composition can be used. The fixing solution includes sodium thiosulfate and ammonium thiosulfate as a fixing agent, and water-soluble aluminum (such as aluminum sulfate, a hardener) as a hardening agent.
Aluminum chloride, potassium alum, etc.), dibasic acid (eg tartaric acid, potassium tartrate, sodium tartrate, sodium citrate, lithium citrate, potassium citrate, etc.) as an aluminum precipitation inhibitor, and sulfite as a preservative. , Bisulfite, and acetic acid, boric acid or the like as a pH buffering agent. The pH of the fixing solution is 3.8 or higher, and more preferably 4.5 to 5.0 in view of the stability of the solution.

According to the method of the present invention, the developed and fixed photographic material is washed with water and dried. Washing with water is performed to almost completely remove the silver salt dissolved by fixing, and the washing is performed at about 5 ° C to 5 ° C.
10 seconds to 3 minutes at 0 ° C is preferable. Drying is about 30 ℃ -80
The drying time may be varied depending on the ambient conditions, but is usually about 5 seconds to 3 minutes and 30 seconds.

The silver sludge generated in the developing solution is particularly likely to adhere to the roller or belt in the developing solution, and the silver sludge adhering to the roller or belt is likely to contaminate the photosensitive material. Therefore, the present invention is particularly effectively used when processing with an automatic processor. Examples of the automatic developing machine include P-710 automatic developing machine manufactured by Mitsubishi Paper Mills Ltd., LD280Q, LD381, LD4 manufactured by Dainippon Screen Mfg. Co., Ltd.
80Q, FG680A, FG manufactured by Fuji Photo Film Co., Ltd.
950A, FG710A and the like.

Examples of the hydrazine derivative used in the development processing method of the present invention include hydrazine sulfate and hydrazine hydrochloride, and US Pat. Nos. 4,224,405 and 4,2.
43,734, 4,272,614, 4,
385,108, 4,269,929, 4,323,643 and JP-A-53-16623.
53-20921, 53-20922, 53
-49429, 53-66732, 55-90.
No. 940, No. 56-67843, No. 56-10624.
No. 4, No. 57-99635, No. 60-179734.
No. 61-267759 and No. 61-230145.
No. 62, No. 62-948, No. 62-73256, No. 62
-270953, 62-178246, 62-
180361, 62-275247, 63-1
21838, 63-223744, 63-23
No. 4244, No. 63-253357, No. 63-265.
No. 239, 64-90439, JP-A-1-1059.
No. 43, No. 2-25843, No. 2-120736,
No. 2-37, No. 2-8834, No. 3-125134
No. 3-184039, No. 4-51143, Japanese Patent Application Nos. 1-92356, 1-99822, etc., and there are hydrazine derivatives which can be used in the present invention. .

The above-mentioned hydrazine derivative may be contained in the developer or in the emulsion layer of the light-sensitive material and / or the adjacent layer thereof. When contained in the developing solution, 5 mg to 5 per 1 L
g, when contained in the light-sensitive material, 1 per mol of silver
It is 0 ^{-6 to} 5 x 10 ^-2 mol, preferably 10 ^-5 to 2 x 10 ^-2 mol.

As a preferred embodiment of the present invention, it is preferable to incorporate the hydrazine derivative described in the above patent specifications into the light-sensitive material.

Representative examples of the hydrazine derivative are shown below, but the invention is not limited to these representative examples.

[0055]

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[0056]

[Chemical 19]

[0057]

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[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

[0067]

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[0068]

[Chemical 31]

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

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[0072]

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[0073]

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Further, there has been proposed a developing system in which a compound which promotes contrast enhancement is contained in a light-sensitive material in the presence of a hydrazine derivative, and development is performed at ultralow contrast at a relatively low pH (pH 11 or less). The anti-sludge agent of the present invention is also effective in these development systems. There are the following compounds as the contrast enhancing agents, and typical examples thereof are shown, but the compounds are not limited to these representative examples.

[0075]

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[0076]

[Chemical 38]

[0077]

[Chemical Formula 39]

[0078]

[Chemical 40]

[0079]

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[0080]

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[0081]

[Chemical 43]

[0082]

[Chemical 44]

[0083]

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[0084]

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[0085]

[Chemical 47]

[0086]

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[0087]

[Chemical 49]

[0088]

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[0089]

[Chemical 51]

The silver halide light-sensitive material processed by the method of the present invention can be processed for any purpose.

These silver halide light-sensitive materials include those having a silver halide composition such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride. The effect of the present invention is There is no effect on their silver halide composition. Generally, it shows a remarkable effect in the processing of a photographic light-sensitive material having a high silver chloride content. The light-sensitive material used in the present invention may be either a negative type or a direct positive type silver halide light-sensitive material.

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, if necessary, a back layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer, etc.) can be provided. The silver halide emulsion can be prepared by converting silver halide into a hydrophilic colloid (eg, gelatin, modified gelatin, colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone or a mixture thereof). It is dispersed. The silver halide emulsion is usually prepared by a method well known in the art (for example, single jet method, double jet method,
Control jet method, etc.) is used to mix a water-soluble silver salt (for example, silver nitrate) and a water-soluble halogen salt in the presence of water and a hydrophilic colloid, followed by physical ripening and chemical sensitization such as gold sensitization and / or sulfur sensitization. It is manufactured after aging.

The silver halide emulsion contains a spectral sensitizer (for example, a cyanine dye, a merocyanine dye or a mixture thereof) and a stabilizer (for example, during the production process or immediately before coating).
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, etc.), a sensitizer (for example, US Pat. No. 3,6).
19, 198, etc.), antifoggants (eg, benzotriazole, 5-nitrobenzimidazole, 1-phenyl-5-mercaptotetrazole, etc.), hardeners (eg, formalin, glyoxal, mucochrome). Acid, 2-hydroxy-4,6-dichloro-s-triazine, etc.), coating aid (for example, saponin,
Sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide, etc.) can be added.

The silver halide emulsion thus produced is applied to a support such as baryta paper, resin coated paper, cellulose acetate film or polyethylene terephthalate film by a dipping method, an air knife method, a bead method, an extrusion doctor method, It is applied and dried by a double-sided application method or the like.

[0095]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 The following developers (A) to (G) were prepared. Both pH
It was 10.65. Developer (A) Sodium sulfite 67 g Hydroquinone 23 g 1-Phenyl-3-pyrazolidone 0.4 g Potassium hydroxide 11 g Sodium carbonate (monohydrate) 11 g Potassium bromide 3 g Benzotriazole 0.1 g Water is added to make 1 L. pH 10.65

Developers (B) to (G) were prepared as shown in Table 1.

[0097]

[Table 1]

[0098]

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[0099]

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[0100]

[Chemical 54]

The following fixer was used. Ammonium thiosulfate 150 g Sodium sulfite (anhydrous) 20 g Boric acid 10 g Tartaric acid 3 g Potassium aluminum sulfate 10 g Acetic acid (90%) 30 g Water is added to make 1 L. Adjust pH to 4.8-5.0.

Next, the following experiments were carried out for the developers (A) to (G) thus prepared.
22 L of developing solution was placed in a roller-conveying type automatic developing machine (P-710 manufactured by Mitsubishi Paper Mills), and a black-and-white photographic film (silver amount: 4; silver chlorobromide (silver bromide 10 mol%) emulsion layer was formed on a polyethylene terephthalate film). 0.5 g / m ² ) was imagewise exposed and then inserted into the above developing machine for development. The development temperature is 38 ° C and the development time is 20 seconds.
0 inch x 24 inch) 2 developer solution for every 1 sheet development
It was automatically replenished at a rate of 00 ml. 100 sheets of a full-size paper size were developed per day for 5 hours, and this processing operation was continued for one week.

Table 2 shows the processing results.

[0104]

[Table 2]

Example 2 A gelatin-silver chloride emulsion consisting of cubic crystals having an average grain size of 0.1 micron was prepared by the double jet method, and was desalted, washed with water and redissolved by the flocculation method.
4 mg of the hydrazine derivative of 4 was added per 1 g of silver nitrate, and further 1-phenyl-5-mercaptotetrazole, poly (ethyl acrylate) latex, 2-hydroxy-4,6-
After adding dichloro-1,3,5-triazine sodium salt and sodium dodecylbenzenesulfonate, the amount of silver (1% with silver nitrate was added to the polyethylene terephthalate film).
The coating amount was 5 g (per square meter) and the amount of gelatin was 3 g (per square meter). On top of this, as a protective layer, the amount of gelatin is 0.8 g (per 1 square meter), 400
To a yellow dye with an absorption maximum wavelength of 450 to 80 m
g (per square meter), a surfactant and a hardener were added and coated to obtain a film. The film was processed with the following developers (H to O).

Composition of Developer Solution Developer solution (H) Sodium ethylenediamine diacetate 1 g Sodium hydroxide 48 g Potassium sulfite 108 g Hydroquinone 55 g N-methyl-P-aminophenol 1/2 sulfate 0.8 g 5-Sulfosalicylic acid 40 g 5-Methyl Benzotriazole 0.4 g 3- (5-mercaptotetrazole) benzenesulfonic acid 0.2 g Potassium bromide 4 g N-n-butyldiethanolamine 12 g PH is adjusted to 11.8 with potassium hydroxide. Add water to make 1L

Developers (I) to (O) were prepared as shown in Table 3.

[0108]

[Table 3]

The treatment was carried out by exposing the produced film through a wedge for sensitometry with a light room printer (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.) and then using a developing solution (H to O) of the above composition for 38 times. It was developed at 20 ° C for 20 seconds, fixed, washed with water and dried. For this processing, an automatic processor (Dainippon Screen Mfg. Co., LD221Q
T) was used.

With respect to silver sludge, under the same conditions as above, a developer (H to O) was imagewise exposed to a full-scale film (20 inches × 24 inches) and continuously processed for 2 square meters per liter. The developer was not replenished during processing. After the processing, the automatic developing machine was stopped, and after 24 hours, 5 pieces of Daisen film were processed, and the dirt of the film and the dirt of the developing tank were observed. Regarding the photographic characteristics, the relative sensitivity was determined from the sensitometric wedge. The relative sensitivity was expressed as 100 when the anti-sludge agent was not added. Fog is represented by the transmission density of the unexposed area.

Table 4 shows the processing results.

[0112]

[Table 4]

Example 3 A test was conducted according to the conditions of Example 1 except that a black-and-white photographic film having a silver chloride emulsion layer on polyethylene terephthalate (amount of silver: 3.5 g / m ² ) was used. The following developer (P) was prepared. Developer (P) EDTA disodium tetraacetate 2g hydroquinone 24g potassium sulfite 100g potassium bromide 0.52g sodium hydroxide 14g triethylene glycol 4.3g 5-nitroindazole 0.1g 5-methylbenzotriazole 0.05g potassium hydroxide Add 3.5 g water to make 1 liter. pH 11.5

Developers (Q) to (V) were prepared as shown in Table 5.

[0115]

[Table 5]

Table 6 shows the processing results.

[0117]

[Table 6]

[0118]

As shown in Table 2, Table 4 and Table 6, the developer containing the compound of the present invention can prevent silver sludge very well without impairing the photographic characteristics.

Claims (1)

[Claims] 1. A developer for a silver halide photographic light-sensitive material, comprising a compound represented by the following chemical formula 1. Embedded image In the formula, R represents an unsubstituted alkyl group or an aryl group, A represents an alkylene group or an arylene group, and M represents a hydrogen atom, an alkali metal atom or an ammonium group.