JP2955906B2 - Developer 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 photographic developer, and more particularly to a silver halide photographic light-sensitive material capable of producing a high-sensitivity, high-density image without silver sludge even when a low-replenishment developer is used. The present invention relates to a developing solution for use.

[0002]

BACKGROUND OF THE INVENTION Sulfites such as sodium sulfite and potassium sulfite used as antioxidants in photographic developers have a dissolving effect on silver halide.

For this reason, when a photographic material is processed, a large amount of a silver complex with a sulfite is generated and eluted into a developer. The eluted silver complex is easily reduced by the active ingredient, and accumulates precipitated silver, which is called silver sludge.

[0004] In continuous processing by an automatic developing machine, the silver sludge floats in a developing solution and adheres to a film or adheres to a roller or a belt of the automatic developing machine.

[0005] Therefore, serious obstacles such as generation of yellow-brown streaky stains and scratches on the conveyed film are caused.

In particular, in recent years, the amount of replenishment of a photographic processing solution has been reduced from the viewpoint of environmental protection, and thus the residence time of the processing solution in a developing machine bath has increased. For this reason, the amount of silver sludge accumulated is currently increasing as compared with the conventional case.

There have been many reports on techniques intended to prevent silver sludge. For example, JP-A-58-114035 using thiouracils, JP-A-63-2043 using mercaptobenzoic acids, JP-B-47-14953 using mercaptocarboxylic acids, JP-A-62-178959, JP-A-3-51844 using disulfides, JP-A-46-26136 using sulfur-containing α-amino acids Further, various mercaptoazoles and the like are disclosed, and all of these compounds are listed as compounds which easily form a water-soluble silver salt.

However, many of these conventional techniques have the following disadvantages, and few of them are practically satisfactory.

That is, (1) the sludge prevention effect is reduced by air oxidation in a developing solution. (2) A large amount of use is required to obtain the sludge prevention effect. (3) The use of a large amount deteriorates the sensitivity and gamma of the film. 4) Generates unpleasant odor. In addition, the processing solution is expensive, and the development of a new technology that clears these has been strongly desired.

[0010]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to prevent the generation of silver sludge and the contamination of a developing solution or a roller even when a large amount of continuous processing is carried out by an automatic developing machine using a developing solution with a reduced replenishing amount. It is an object of the present invention to provide a developer which can easily obtain an image having excellent finish quality without causing contamination of the belt or belt.

A second object of the present invention is to provide a developer for a silver halide photographic light-sensitive material having a sludge preventing effect without adversely affecting photographic performance. Other objects will be apparent from the following description.

[0012]

The above objects of the present invention have been found to be achieved by the following present invention.

That is, the following general formula [1] or general formula [2]
This is achieved by a developer for a silver halide photographic light-sensitive material containing at least one of the compounds represented by the formula:

[0014]

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In the formula, R ₁ and R _{2 each} represent a hydrogen atom and have 1 to 3 carbon atoms.
Represents an alkyl group up to However, R ₁ and R ₂ are not hydrogen atoms at the same time. R ₃ and R _{4 each} represent a hydrogen atom and carbon number 1
Represents an alkyl group up to 3, and R ₅ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₆ and R _{7 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 carbon atoms, or a —COOM ₂ group. However, R ₆ and R ₇ are not hydrogen atoms at the same time. M ₁ represents a hydrogen atom, an alkali metal atom, or an ammonium group.

M ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group, or an aralkyl group having 15 carbon atoms.

M represents 0, 1 or 2.

Hereinafter, the present invention will be described in detail. In the above, the alkyl group having 1 to 4 carbon atoms includes, for example, a methyl, ethyl, propyl or butyl group.

The acyl group having up to 18 carbon atoms includes, for example, an acetyl group and a benzoyl group, and the aralkyl group having up to 15 carbon atoms includes, for example, a benzyl group and a phenethyl group. The aryl group includes a phenyl group, a naphthyl group and the like.

The alkali metal atom of M ₁ is, for example, a sodium ion or a potassium ion.

Various methods for synthesizing the compound of the present invention are known. For example, a Strecker amino acid synthesis method known as an amino acid synthesis method may be used. The reaction is performed by alternately adding acetic anhydride.

Next, specific examples of the compounds represented by the general formulas [1] and [2] of the present invention are shown, but the present invention is not limited to these.

[0023]

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[0024]

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The above compounds of the present invention may be used alone or in combination. Further, at least one compound of the general formulas [1] and [2] may be used in combination.

The amount of the compound represented by the general formula [1] or the general formula [2] of the present invention is 1 × 10 ⁻⁵ mol / l to 1 liter of the developer.
It is used at a concentration of × 10 ⁻² mol, preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. The replenishing amount of the developing solution containing the compound of the present invention is not uniform due to the type of light-sensitive material and the automatic processor is particularly preferably 0.10l~0.35l a normal photosensitive material 1 m ² per 0.05 to 0.651.

The process for developing a silver halide light-sensitive material according to the present invention comprises the steps of developing, fixing, washing with water (or stabilizing), and drying. Preferably, it is completed within 90 seconds.

That is, the time from when the tip of the photosensitive material begins to be immersed in the developing solution to when the tip comes out of the drying zone through a processing step (so-called dry-to-dry time).
Is less than 90 seconds, more preferably, this Dry to
Dry time must be within 60 seconds.

The fixing temperature and time are about 20 ° C. to 50 ° C. for 6 seconds to
20 seconds are preferable, and 6 seconds to 15 seconds at 30 ° C to 40 ° C are more preferable.

The development time with the developing solution of the present invention is 5 seconds to 45 seconds, preferably 8 seconds to 30 seconds. Development temperature is 25-50 ℃
Is preferable, and 30 to 40 ° C is more preferable.

The drying time is usually 35 to 100 ° C., preferably 40 to 100 ° C.
A drying zone in which hot air of ~ 80 ° C is blown or heating means by far infrared rays may be provided in the automatic developing machine.

Further, the automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps. Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of adjusting a developing solution and a fixing solution.

The developer of the present invention is based on containing 1,4-dihydroxybenzenes or, if necessary, p-aminophenol compounds and / or pyrazolidone compounds as a developer.

The 1,4-dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, There are 5-dimethylhydroquinone and hydroquinone monosulfonate, but hydroquinone is particularly preferred. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) as a p-aminophenol developing agent
There are -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone-based compound which can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone 1,1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4- Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-
Dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-
Examples include pyrazolidone-based compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

The amount of 1,4-dihydroxybenzene to be added may be from 0.01 mol to 0.7 mol, preferably from 0.1 to 0.5 mol, per liter of the developer.

The addition amount of the p-aminophenol compound and the pyrazolidone compound is 0.0005 per liter of the developing solution.
The molar amount is from 0.2 to 0.2 mol, preferably from 0.001 to 0.1 mol.

Examples of the sulfite used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metasulfite and the like. These sulfites may be used in an amount of 0.1 mol to 2.0 mol, preferably 0.1 mol to 1.0 mol, per liter of the developer. In the case of the developer concentrate, the upper limit is preferably up to 3.0 mol per liter of the developer.

The developer may contain a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the iron ion means ferric iron (Fe ³⁺ ).

Examples of the chelating agent having a chelate stability constant for iron of 8 or more include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent and a polyhydroxy compound.

Specific examples thereof include, for example, ethylenediaminediorthohydroxyphenylacetic acid, triethylenetetramineacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid,
Ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etheraminetetraacetic acid, ethylenediamine-N , N, N ', N'-tetrakismethylenephosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-
Carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, tetrapolyline And sodium hexametaphosphate.

The developing solution of the present invention may contain a hardening agent which hardens and reacts with gelatin in the light-sensitive material during the development processing to enhance film properties. As hardening agents, for example, glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maledialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde,
α, α-Dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, or a bisulfite adduct thereof are used.

Other additives used in addition to the above-mentioned components include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and the like. Antifoggants such as organic solvents such as methanol or mercapto compounds such as 1-phenyl-5-mercaptotetrazole, sodium salt of 2-mercaptobenzimidazole-5-sulfonic acid, and benzotriazole compounds such as 5-methylbenztriazole And, if necessary, a color tone agent, a surfactant, an antifoaming agent, and the like.

The pH of the developer may be from 9.0 to 12, preferably from 9.0 to 11.5. Examples of the alkaline agent or buffer used for setting the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium tertiary phosphate and potassium tertiary phosphate.

In the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate and ammonium thiosulfate can be used as the fixing solution. Of these, ammonium thiosulfate is preferable in terms of fixing speed. These fixing agents are generally used in an amount of about 0.1 mol to 6 mol / l.

[0046] The fixing solution may contain a water-soluble aluminum <br/> beam salt as hardener, further aluminum chloride, aluminum sulfate, potassium alum is.

For the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination. It is effective that these compounds are contained in an amount of 0.001 mol or more per liter of fixing solution, and particularly effective in an amount of 0.005 mol to 0.03 mol.

The pH of the fixing solution is 3.8 or more, preferably 4.2 to
Those having 7.0 are preferred. In consideration of the fixed hardening film or the odor of sulfurous acid, 4.3 to 4.8 is more preferable.

The emulsion of the silver halide photographic light-sensitive material used in the present invention includes a photographic material for medical radiation, a photographic material for printing plate making, and a direct positive photographic material.

The silver halide photographic light-sensitive material to which the present invention can be applied may have a silver halide composition such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc., and high sensitivity can be obtained. In this respect, silver iodobromide is preferred.

The emulsions of the silver halide photographic light-sensitive material used in the present invention include, for example, JP-A-59-177535 and JP-A-61-177535.
Internally high iodine type monodisperse particles disclosed in 802237, 61-132943, 63-49751 and the like. The habit of the crystal is cubic, tetradecahedral, octahedral and intermediate (111)
The plane and the (100) plane may be arbitrarily mixed.

The emulsion may be tabular grains having an aspect ratio of 2 or more. The advantages of such tabular grains are as follows: improvement in spectral sensitization efficiency, improvement in graininess and sharpness of an image, and the like, for example, UK Patent No. 2,112,157, US Patent Nos. 4,439,520, 4,433,048, 4,414,310,
4,434,226, JP-A-58-113927, 58-127921, 6
Emulsions are disclosed in JP-A-3-138342, JP-A-63-284272 and JP-A-63-305343, and emulsions can be prepared by the methods described in these publications.

Examples of the additives for the silver halide photographic light-sensitive material include Research Disclosure (R)
D) No. 17643 (December 1978), No. 18716 (November 1979)
And No. 308119 (December 1989). The locations of those descriptions are listed below.

[0054]

[Table A]

[0055]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 (Preparation of emulsion 1) 1) Preparation of seed emulsion While controlling 60 ° C., pAg = 8 and pH = 2.0, 2 mol% of silver iodide having an average grain size of 0.3 μm was prepared by a double jet method. Monodispersed cubic grains of silver iodobromide were prepared. The obtained reaction solution is made at 40 ° C by Kao Atlas Co., Ltd.
After desalting using an aqueous solution of -N and an aqueous solution of magnesium sulfate, an aqueous solution of gelatin was added and redispersed to obtain a seed emulsion. 2) Growth from seed emulsion Grains were grown as follows using the seed emulsion described above. First
The seed emulsion was dispersed in an aqueous gelatin solution maintained at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid.
Aqueous ammoniacal silver nitrate and aqueous solutions of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, the pAg was controlled to 7.3 and the pH to 9.7 to control the silver iodide content.
A layer of 35 mol% was formed. Next, an aqueous ammonium nitrate solution and an aqueous potassium bromide solution were added by a double jet method. Maintain pAg = 9.0 up to 95% of the target particle size, and the pH is 9.0 ~
It was continuously changed to 8.0. Thereafter, the pAg was adjusted to 11.0, and growth was performed to the target particle size while maintaining the pH at 8.0.
Subsequently, the pH was lowered to 6.0 with acetic acid, and then 5,5'-dichloro-9 was added.
Anhydrous sodium salt of -ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine was added in an amount of 400 mg per mol of silver halide, and the mixture was desalted with the above-mentioned aqueous solution of demol and magnesium sulfate. A gelatin solution was added and redispersed.

According to this method, the apexes having an average silver iodide content of 2.0 mol% and having a rounded top were 0.40 μm in average grain size and 0.40 μm in average.
65 μm, 1.00 μm, coefficient of variation 0.17, 0.16, 0.16 respectively
To prepare monodispersed silver iodobromide emulsions (A), (B) and (C).

(Preparation of Emulsion 2) 1) Preparation of Seed Emulsion 1 A hexagonal tabular seed emulsion was prepared by the following method.

Solution A 60.2 g of ossein gelatin Distilled water 20 l Polyisopropylene-polyethyleneoxy disuccinate sodium salt (10% aqueous solution of ethanol) 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml Solution B 2.5 N AgNO ₃ aqueous solution 3500 ml Solution C KBr 1029g Kl 29.3g Make up to 3500ml with distilled water Solution D 1.75N KBr aqueous solution Solution A using the mixing stirrer described in JP-B-58-58288 and 58-58289 at the following silver potential control amount at 35 ° C 64.1 ml of each of the solution B and the solution C were added thereto over 2 minutes by a double jet method to form nuclei.

After stopping the addition of the solution B and the aqueous solution C,
It takes 60 minutes to raise the temperature of the solution A to 60 ° C., and the solution B and the solution C are again mixed at 68.5 ml / min by the simultaneous mixing method.
For 50 minutes. The silver potential during this period (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to +6 mv using Solution D.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. The obtained emulsion was used as seed emulsion E
Let m be 0. In this emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The average thickness of the hexagonal tabular grains is 0.07 μm, and the average diameter (in terms of circular diameter) is It was found by an electron microscope to be 0.5 μm.

Using the following four kinds of solutions, 1.53 mol%
A tabular silver iodobromide emulsion D containing Agl was prepared.

Solution A 29.4 g of ossein gelatin Seed emulsion Em Equivalent to 1.6 mol Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.5 ml Make up to 1400 ml with distilled water.

Solution B 3.5N AgNO ₃ aqueous solution 2360ml Solution C KBr 963g KI 27.4g Make up to 2360ml with distilled water Solution D 1.75N KBr aqueous solution At the following silver potential control amount of 60 ° C, the same as in JP-B-58-58288, 58 -582
The total amount of the solution B and the solution C was added to the solution A by a simultaneous mixing method at a flow rate of 21.26 ml / min over a period of 111 minutes using a mixing stirrer described in the specification of No. 89 for growth.

During this period, the silver potential was controlled to +25 mv using solution D. After the addition was completed, the following spectral sensitizing dyes (A) and (B) were each added in an amount of 300 m / mol of silver halide.
g and 15 mg were added.

Next, in order to remove excess salts, precipitation and desalting were carried out using the same aqueous solution of Demol and magnesium sulfate as described above, and a gelatin aqueous solution containing 92.2 g of ossein gelatin was added, followed by stirring and redispersion.

By this method, a tabular silver iodobromide emulsion D having an average silver iodide content of 1.5 mol%, a projected area diameter of 0.96 μm, a variation coefficient of 0.25 and an aspect ratio of 4.0 was prepared.

Sensitizing dye (A) 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) oxacarboxyanine sodium salt anhydrous sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,1'-
Anhydrous sodium salt of diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine (Preparation of sample) Emulsions A, B, C and D obtained were each subjected to the above sensitization at 55 ° C. A mixture of dyes (A) and (B) in a weight ratio of 200: 1 was used to prepare emulsion A per mole of silver halide.
975mg, Emulsion B 600mg, Emulsion C 390mg, Emulsion D 500mg
Was added.

After 10 minutes, an appropriate amount of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to carry out optimal chemical ripening. Fifteen minutes before the completion of ripening, 200 mg of potassium iodide was added per mole of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaiden was added at 3 × 10 ^-2 per mole of silver halide. Mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

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

The following additives were added to the emulsions.
The amount of addition is shown in an amount per mole of silver halide.

1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g nitrophenyl-triphenyl phosphonium chloride 50 mg 1,3-dihydroxybenzene-4-sulfonic acid ammonium 4g sodium 2-mercaptobenzimidazole-5-sulfonic acid 15 mg 1-phenyl-5-mercapto tiger tetrazole _{10mg C 4 H 9 OCH 2 CH} (OH) CH 2 N (CH ₂ COOH) ₂ 1g

[0073]

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Dye Emulsified Dispersion (Below) 1.2 g Method for Preparing Dye Emulsified Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 l of tricresyl phosphate and 85 l of ethyl acetate. This is called an oil-based solution.

On the other hand, anionic surfactant (AS) was added to 1.35
270 l of a 9.3% gelatin aqueous solution containing kg was prepared. This is called an aqueous solution. Next, the oil-based solution, the aqueous-based solution and the dispersing vessel were put into the vessel and dispersed while keeping the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1-dimethylol-bromo-1-nitromethane was added to the obtained dispersion, and the dispersion was adjusted to 240 kg with water.

[0076]

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The additives used in the protective layer are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethyl methacrylate Matting agent having an area average particle diameter of 3.5 μm 1.1 g Silicon dioxide particles having an area average particle diameter of 1.2 μm Matting agent 0.5 g Ludox AM (manufactured by DuPont) Colloidal silica 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml Bis (vinylsulfonylmethyl) ether (hardening agent) 500 mg

[0079]

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[0080]

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[0081]

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The obtained coating solution was uniformly applied to a subbed blue colored polyethylene terephthalate film base having a thickness of 180 μm and dried.

The coating amount of the emulsion layer per side was 1.7 g / m ² in terms of silver, and the protective layer was 0.99 g / m ^{2 in} terms of gelatin per one side.
Every minute with two slide hopper type coaters
The emulsion layer and the protective layer were simultaneously coated on both sides at a speed of 90 m to obtain a sample.

In the table, "Development sample 1" refers to a sample obtained from Emulsion 1, and "Development sample 2" refers to a sample obtained from Emulsion 2.

Next, the compositions of the developing solution and the fixing solution used in the present invention are shown.

Developer Formulation Part-A (for 12 liter finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5- Mercaptotetrazole 0.2g Hydroquinone 340g Add water to make up to 5000ml.

Part-B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 L.

Fixer Formulation Part-A (for 18l finishing) Ammonium thiosulfate (70wt / vol%) 6000g Sodium sulfite 110g Sodium acetate trihydrate 450g Sodium citrate 50g Gluconic acid 70g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18g Part-B Aluminum sulphate 800g To prepare a developer, add Part A and Part B simultaneously to about 5 l of water, add water while stirring and dissolving, and add 12 l to finish with glacial acetic acid.
H was adjusted to 10.40. This is used as a development replenisher.

The above-mentioned starter was added to 1 liter of the developing replenisher at 20 ml / l to adjust the pH to 10.26 to prepare a working solution.

The fixer was prepared by adding Part A and Part B to about 5 liters of water.
Was added at the same time, water was added while stirring and dissolving to make up to 18 l, and the pH was adjusted to 4.4 with sulfuric acid and NaOH. This is used as a fixing replenisher.

The above-mentioned developing solution and fixing solution are used as a basic composition.
As shown in Table 1 below, a developing solution to which the compound of the present invention and the comparative compound were added was prepared and developed.

For development, an automatic developing machine of the roller transport type shown below was used.

[0093] Processing is performed at 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing and 50 ° C. for drying.

The following evaluation was performed on the processed sample.

1. Measurement of sensitivity The sample was scissored with two fluorescent intensifying screens KO250, tube voltage: 80KV,
After performing exposure through an aluminum wedge at a tube current of 100 mA and an irradiation time of 50 msec, development processing was performed using the automatic developing machine. With respect to the obtained sample, the reciprocal of the exposure amount required to obtain a density of (base density + fog density + 1.0) was obtained. Sensitivity (Experiment No. 15) when treated with liquid is 10
It was expressed as a relative sensitivity when 0 was set.

The density of the unexposed portion of the exposed sample was measured with a PDA-65 manufactured by Konica Corporation, and the value obtained by subtracting the base density was defined as Fog density, and the maximum density was defined as Dm.

2. Evaluation of silver sludge Next, the developing samples exposed to X-rays so that the entire surface of the samples had a density of 1.0 were subjected to the replenishment of the developing solution and the samples to be developed by the automatic developing machines Nos. 1, 2, and 3 in Table 1. Developing was performed 70 times a day for 30 days under the conditions of a fixer replenishment rate of 300 cc / m ² .

As the developing samples, the above-mentioned samples Nos. 1 and 2 were used.

At that time, stains on the developing rack and rollers, stains on the wall surface, and the developed samples were visually evaluated. The following four-step evaluation was performed.

○ Little silver sludge was observed, and no dirt was found on the rollers and the wall. △ The developer was turbid and slight dirt was seen on the processing tank wall. × Silver sludge was generated and even if the developing rack was washed. Dirty is not easily removed. XX: A large amount of silver sludge was generated in the developer tank, adhered to the film to be processed, and caused image contamination.

3. Evaluation of Residual Silver The above-prepared Sample 2 was developed without being exposed to obtain a sample for evaluating residual silver. Evaluation of residual silver was performed by the following method.

A 2.6 × 10 ⁻³ mol / l aqueous solution of sodium sulfide was dropped as a residual silver evaluation liquid onto the above-mentioned film for evaluating residual silver, and after leaving for 3 minutes, the liquid was thoroughly wiped off, and then room temperature and normal humidity were applied. Let sit for 15 hours underneath.

Thereafter, a PDA-65 type densitometer (Konica Corporation)
Using Ltd.), and added dropwise to a portion of the residual silver test solution, and measuring the transmission density of the blue light of the portion not drip, and the eye depreciation of residual silver drives out the difference. The larger this difference, the more
The residual silver concentration in the processed film is high.

The obtained results are shown in Tables 1 to 3 below.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

As is clear from the table, according to the present invention, even if the replenishing amount of the developing solution is reduced, photographic performance is not impaired and silver sludge is prevented.

That is, from Table 1, it can be seen that the sensitivity and Dm (maximum density) do not decrease even when the compound of the present invention is added to the developing solution, while the comparative compound has an effect of preventing silver sludge when the replenishing amount is large. Although having a slight amount, the sensitivity was significantly reduced.

Further, according to Experiments Nos. 1 to 10, in the developer containing the compound of the present invention, even if the replenishment rate was reduced to 200 ml / m ^{2, the} effect of preventing silver sludge was not deteriorated, and the effect was extremely excellent. You can see that it is. Experiments Nos. 12 and 14 also show that there is no difference in the effect of preventing silver sludge even if the automatic developing machine is different.

Furthermore, it has been surprisingly found that the present invention has little residual silver and has improved fixability.

[0112]

According to the present invention, it is possible to obtain a developing solution for a silver halide photographic light-sensitive material which can prevent the generation of silver sludge even with a low replenishing developing solution and does not deteriorate the sensitivity and the maximum density. Was. Further, according to the present invention, the fixing performance is also improved.

Claims (1)

(57) [Claims] 1. A developer for a silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula [1] or [2]: In the formula, R ₁ and R ₂ represent a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. R ₃ and R _{4 each} represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₅ represents a hydroxyl group, an amino group or 1 to 3 carbon atoms.
Represents up to 3 alkyl groups. R ₆ and R _{7 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 carbon atoms, or a —COOM ₂ group. However, R ₆ and R ₇ are not hydrogen atoms at the same time. M ₁ represents a hydrogen atom, an alkali metal atom, or an ammonium group. M ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group,
Represents up to 15 aralkyl groups. m represents 0, 1 or 2.