JPH06138616A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the method for processing the silver halide photographic sensitive material not deteriorating photographic performance even in the case of rapid processing using an automatic developing machine and capable of obtaining stable photographic performance. CONSTITUTION:The silver halide photographic sensitive material and a developing solution for processing this material are characterized by containing at least one of the compounds represented by formulae I and II in both of which Z is a group necessary to form an N and/or S-containing 5- or 6-membered hetero ring; R1 is H, 1-4C alkyl, aryl, halogen, amino, nitro, carboxy, sulfo, or their salts; and R12 is hydroxy or optionally substituted amino.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a development processing method which does not deteriorate the photographic performance even if it is subjected to a rapid development processing and is capable of low replenishment processing.

[0002]

In recent years, in the field of X-ray photographic light-sensitive materials,
Rapid processing and reduction of processing replenishment amount are rapidly progressing.

In order to accelerate development processing, high-speed rapid processing is carried out by an automatic developing machine, and since the processing is carried out in a short time, a developing material which is excellent in developability and which can be dried in a short time after washing with water is required.

The rapid processing technique has a high conveying speed, but it significantly deteriorates the physical properties of gelatin swollen in a developing solution.

Therefore, as a physical property improving means, a binder,
In particular, there is a method of increasing the amount of gelatin, but it has been found that the residual color is likely to occur in the light-sensitive material after processing due to dyes and the like, and the tendency is remarkable especially when the fixing solution is fresh.

As a means for improving the residual color, for example, a method of adding a mercapto compound described in JP-A-3-101728 to a fixing solution is disclosed. In addition, JP-A-2-71260
JP-A No. 1994-242 discloses a technique of using a heterocyclic compound having 2 to 4 rings in a fixing solution.

However, in a light-sensitive material containing an increased amount of binder, the effect of the above-mentioned method of adding a heterocyclic compound to the fixing solution was insufficient in order to slow the elution rate of the dye.

On the other hand, in a light-sensitive material having a high sensitivity, fog is liable to occur. Therefore, mercaptoazoles such as 1-phenyl-5-mercaptotetrazole are added to the light-sensitive material as a development inhibitor and an antifoggant. The technology to do is known.

However, when the development processing is carried out by the automatic developing machine, these compounds are eluted in the developing solution and accumulated in the developing tank.
It was found that re-adsorption on the photosensitive material causes unfavorable problems such as sensitivity fluctuation, sensitivity deterioration, and gamma reduction, and new measures were required.

[0010]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a method for developing and processing a silver halide photographic light-sensitive material which does not deteriorate in photographic performance even if it is rapidly processed by an automatic processor.

A second object of the present invention is to develop a silver halide photographic light-sensitive material which does not cause residual color contamination and provides stable photographic performance even if the replenishing amount of a processing solution is reduced for environmental protection. It is to provide a processing method. Other objects will be apparent from the following specification.

[0012]

The above object of the present invention is achieved by the following.

(1) Represented by the following general formula [I] and / or the following general formula [II] in a silver halide photographic light-sensitive material and a developing solution for developing the silver halide photographic light-sensitive material. A method of processing a silver halide photographic light-sensitive material, which comprises at least one compound.

[0014]

[Chemical 2]

In the formula, Z represents a 5- or 6-membered heterocycle containing at least one nitrogen atom or sulfur atom,
R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen atom, an amino group, a nitro group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof. R ₂
Represents a hydroxy group or a substituted or unsubstituted amino group.

(2) The above general formula [I] and / or general formula [I
The method for processing a silver halide photographic light-sensitive material according to the item (1), which comprises developing using a starter containing at least one compound represented by the formula [I].

(3) Processing of the silver halide photographic light-sensitive material according to the items (1) and (2), characterized in that the developing replenisher is replenished at a ratio of 325 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. Achieved by the method. Hereinafter, the present invention will be described in detail.

The above general formulas [I] and [II] according to the present invention
The compounds of (1) are well-known compounds as development inhibitors, antifoggants or additives for photography.

Examples of the heterocycles represented by the compound of general formula [I] include indazole, benzimidazole, benzothiazole and triazole. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁ include, for example, methyl, ethyl, allyl, butyl group, the aryl group is, for example, a phenyl group, the halogen atom is, for example, chloro, Examples include brom atoms.

Examples of the salt having a carboxylic acid or sulfonic acid group include alkali metal salts such as sodium salt and potassium salt.

The compound represented by the general formula [II] is adenine and its derivatives, and R _{2 in} the formula is a hydroxy group, an amino group or a substituted amino group such as methylamino, ethylamino, anilino, Represents a naphthylamino, benzylamino group and the like.

The general formulas [I] and [I
Specific examples of the compound represented by I] are shown below, but the present invention is not limited thereto.

[0023]

[Chemical 3]

[0024]

[Chemical 4]

The above compounds are known and can be easily obtained as commercial products.

When the above-mentioned compound according to the present invention is used in a silver halide photographic light-sensitive material, at least one compound represented by the general formula [I] or the general formula [II] may be used alone or in combination. , The amount used is 0.0 per mol of silver halide
The range of 0001 mol to 0.02 mol is preferable, and the range of 0.0001 mol to 0.01 mol is particularly preferable.

The addition method is usually such that it is dissolved in water or methanol, alkali or the like, and dissolved in 0.1% to 1%. The addition time may be any step before the drying step of the photographic light-sensitive material manufacturing step. The silver halide emulsion layer is particularly preferably added, but the silver halide emulsion layer may be added to the intermediate layer, the protective layer, the undercoat layer and other non-photosensitive emulsion layers.

When the compound of the present invention is used in a developing solution or a starter, it may be 0.1 mg to 50 g per liter, and 10 mg to 10 g is particularly preferable.

The starter referred to in the present invention is to be added to the development starter solution to prepare a running solution,
The contents include, for example, acetic acid and KBr.

The running solution is a solution in which the developing or fixing replenisher is supplied to the processing tank in a constant amount per unit area of the light-sensitive material, and the material balance of the processing solution in the processing tank is in equilibrium. .

The starter used in the present invention may contain a pH adjusting agent, a development inhibitor, a development accelerator and the like.

The form before preparation of the starter used in the present invention is preferably a liquid form in which the inhibitors are dissolved in a solvent.

In the light-sensitive material, the developer or the starter, for example, bromcali may be used in combination as an inhibitor.

The replenishing amount of the developing solution of the present invention is 325 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material, preferably 1
It is from 00 ml to 260 ml. The smaller the replenishment amount, the better the effect of the present invention.

The development processing method of a silver halide light-sensitive material according to the present invention includes steps from development to drying when processed by an automatic processor including the steps of development, fixing, washing (or stabilization) and drying. It is preferably completed within 90 seconds.

That is, the time from the time when the tip of the photosensitive material starts to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing steps (so-called Dry to Dry time).
Within 90 seconds, more preferably this Dry to
The dry time is within 60 seconds.

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

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

The drying time is usually 35 to 100 ° C., preferably 4
The automatic developing machine may be provided with a drying zone in which a hot air of 0 to 80 ° C. is blown or a heating means by far infrared rays is provided.

Further, the automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive 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 preparing a developing solution and a fixing solution.

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

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

Examples of the pyrazolidone compound that can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-ethyl-3-pyrazolidone. 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 thereof include pyrazolidone compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

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

The amount of p-aminophenol compound and pyrazolidone compound added is 0.0005 per liter of the developing solution.
It is a mole to 0.2 mole, preferably 0.001 to 0.1 mole.

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. The amount of these sulfites used may be 0.1 mol to 2.0 mol, preferably 0.1 mol to 1.0 mol, per liter of the developing solution. In the case of a concentrated developer solution, the upper limit is preferably 3.0 mol per liter of developer solution.

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

Examples of chelating agents having a chelate stability constant of 8 or more for iron include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds.

Specific examples of these include ethylenediaminedioltohydroxyphenylacetic 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, glycoletheraminetetraacetic 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 Examples thereof include sodium acid salt and sodium hexametaphosphate.

The developing solution of the present invention may contain a hardening agent which strengthens the physical properties of the film by undergoing a hardening reaction with gelatin in the light-sensitive material during the development processing. Examples of the hardener include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde,
α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butyl maleic dialdehyde, or a bisulfite adduct thereof is used.

As additives used in addition to the above components, development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, Antifoggants such as organic solvents such as methanol or mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and benztriazole compounds such as 5-methylbenztriazole May be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, etc. may be contained.

The pH of the developer may be 9.0 to 12, preferably 9.0 to 11.5. The alkaline agent or buffer used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium triphosphate and potassium triphosphate.

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

The fixing solution may contain an aqueous solution aluminum salt as a hardening agent, and further includes aluminum chloride, aluminum sulfate, potassium alum and the like.

As the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or their derivatives 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 the fixing solution, and 0.005 mol to 0.03 mol is particularly effective.

The pH of the fixing solution is 3.8 or higher, preferably 4.2 to
Those having 7.0 are preferred. Considering the fixing dura or odor of sulfite, 4.3 to 4.8 is more preferable.

Examples of the silver halide photographic light-sensitive material applicable to the present invention include direct medical photographic material, medical indirect photographic material, laser imager photographic material, C
Examples thereof include a photosensitive material for RT photography, a photographic material for 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 a highly sensitive material can be obtained. In this respect, silver iodobromide is preferable.

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

The emulsion may be tabular grains having an aspect ratio of 2 or more. The advantage of such tabular grains is that the spectral sensitization efficiency can be improved, and the graininess and sharpness of the image can be improved.For example, British Patent 2,112,157, U.S. Patents 4,439,520, 4,433,048, 4,414,310, and the same.
4,434,226, JP-A-58-113927, 58-127921, 6
No. 3-138342, No. 63-284272, No. 63-305343, etc., and the emulsion can be prepared by the method described in these publications.

In the photographic emulsion of the present invention, a fog other than the compound represented by the general formula [I] or [II] of the present invention is used in order to prevent the deterioration of sensitivity and the occurrence of fog during storage or during the production process of the light-sensitive material. Inhibitors or stabilizers may be included. For example, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles. , Mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazones; thioketo compounds such as oxazolinethione; azaindenes, for example triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes), pentaazaindenes, etc .; benzenesulfinic acid, benzenesulfone Many compounds known as antifoggants or stabilizers such as acid amides and the like can be added.

Examples of additives and the like for silver halide photographic light-sensitive materials include, for example, Research Disclosure (R
D) No.17643 (December 1978), No.18716 (Dec. 1979)
Mon.) and No. 308119 (December 1989). The places where they are written are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII

[0064]

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 Preparation of Seed Emulsion containing hydrogen peroxide treated gelatin at 40 ° C. with vigorous stirring.
A double jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution.
After the liquid temperature was lowered to 5 ° C., 80 ml of ammonia water (28%) was added per mol of silver nitrate, and stirring was continued for 5 minutes. Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was carried out in the same manner as described above, and then an aqueous gelatin solution was added and redispersed.

The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

[Preparation of Emulsion A] Using the above seed emulsion, grains were grown as follows.

To an aqueous solution containing ossein gelatin and polyethyleneoxy / polypropyleneoxy-di-succinate-di-sodium salt vigorously stirred at 75 ° C., an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method. did.

During this period, pH = 5.8 and pH = 9.0 were maintained. After the addition was completed, adjust the pH to 6.0 and use it as a spectral sensitizing dye.
400 mg of anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt
/ Mol AgX was added, desalted in the same manner as above, and then dispersed in an aqueous gelatin solution.

According to this method, a tabular iodobromide having an average silver iodide content of 1.5 mol%, a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness ratio) of 4.0. A silver emulsion was prepared.

The resulting emulsions were each tested at 55 ° C. for 5,5′-
Dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride and 5,5'-di- (butoxycarbonyl) -1,1'-di-ethyl-3 Anhydrous of 3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt was added at a weight ratio of 200: 1, 500 mg each per mole of silver halide.

After 10 minutes, an appropriate amount of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 3 × 10 per mol of silver halide. ^{After the} addition of ^-2 mol, the mixture was dispersed in an aqueous solution containing 70 g of gelatin, and this emulsion was designated as emulsion A.

The following additives were added to each emulsion.
The addition amount is indicated by the amount per mol 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-ammonium sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 1-Phenyl-5-mercaptotrazole 10 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g Dye emulsion dispersion (below) 1.2 g Preparation method of dye emulsion dispersion 10 Kg of the following dye was dissolved in a solvent consisting of 28 l of tricresyl phosphate and 85 l of ethyl acetate at 55 ° C. This is called an oil solution.

On the other hand, the anionic surfactant (AS) was 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 water-based solution, and a dispersion pot were charged, and dispersion was performed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1-dimethylol-bromo-1-nitromethane was added to the obtained dispersion liquid, and the mixture was made up to 240 kg with water.

[0076]

[Chemical 5]

The additives used for the protective layer are as follows. The added amount is shown as an amount per 1 l of the coating liquid.

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

[0079]

[Chemical 6]

The coating solution thus obtained was uniformly coated on an undercoated blue-colored polyethylene terephthalate film base having a thickness of 180 μm and dried.

[0081] The coating amount of 0.99 g / m ² at 2.0 g / m ² emulsion layer per side in terms of silver value, the protective layer is a quantity with gelatin
Every two minutes with two slide hopper type coaters
A sample was obtained by simultaneously coating both sides of the emulsion layer and the protective layer at a speed of 90 m.

The obtained sample was used as a photosensitive material A.

[Preparation of Emulsion B] AgBr having an average particle size of 0.1 μm
I (AgI content 2 mol%) seed emulsion was used to add ammoniacal AgNO ₃ aqueous solution and potassium bromide aqueous solution by double jet method to obtain AgBrI having an average particle size of 0.25 μm (average AgI content 0.4 mol%). The cubic monodisperse emulsion was grown. The coefficient of variation was 0.17.

After this emulsion was divided, one was dissolved just before chemical ripening and when the temperature became constant, the dye (1) below was added to give emulsion (B). The dye amount was 90 mg / mole silver halide. Next, ammonium thiocyanate, chloroauric acid and hypo were added for chemical sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

[0085]

[Chemical 7]

(Backing layer) Coating solution for lower layer of backing Gelatin 400 g i-Amine-n-decylsulfosuccinate sodium 0.4 g Antihalation dye (1) 10 g Diethylene glycol 5.0 g Glyoxal 2.0 g Dye emulsion dispersion (same as above)
33 g

[0087]

[Chemical 8]

Make up to 7 liters with water.

Backing upper layer coating liquid Gelatin 400 g i-amyl-n-decylsulfosuccinate sodium salt 10 g Antihalation dye (1) 10 g Polythymer methacrylate 12 g SAM-1 3.5 g SAM-2 0.75 g Futgent 100 (Neos company Made) 0.3g SMP 2.0g Glyoxal 13.6g

[0090]

[Chemical 9]

Make up to 7 liters with water.

Red-Sensitive Silver Halide Emulsion Layer Coating Solution A red-sensitive silver halide emulsion coating solution was prepared by adding the following to each mole of silver halide of the above emulsion (B).

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg 1,1-Dimethylol-1-bromo- 1-nitromethane
10 mg

[0094]

[Chemical 10]

Coating Solution for Emulsion Side Protective Layer In the solution having the following composition, the addition amount is shown as an amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g i-amyl-n-decylsulfosuccinate sodium 1.4 g Polymethylmethacrylate (particle size 4 μm) Amount shown in Table 1 Silicon dioxide particles (area average particle size 1.2 μm) 0.5 g Ludox AM (colloidal silica [made by DuPont]) 30g 2-4-dichloro-6-hydroxy-1,3,5-triazine sodium (2% aqueous solution) 10ml formalin (35%) 2ml glyoxal (40%) 5ml footer Gent 100 60mg C ₈ F ₁₇ SO ₃ K 180mg Topside 300 (manufactured by Permchem Asia Ltd.) 45mg SAM-1 1.0g SAM-2 0.4g

[0097]

[Chemical 11]

Preparation of Support After a biaxially stretched heat set on both sides of a polyethylene terephthalate support having a thickness of 180 μm, corona discharge treatment was performed. A subbing latex (Synthesis Example 1 compound) described in Example 1 of JP-A-59-18945 was applied thereon.

Then, on one surface of the upper layer, Japanese Patent Laid-Open No. 80744/1992
The following compounds described in No. 1 were applied as an antistatic layer.

Water-soluble conductive polymer (Ex. P4) 0.6 g / m ² Hydrophobic polymer (Ex. HP) 0.5 g / m ² Curing agent (Ex. AH) 2 × 10 ⁻³ mol / dm ² Coating is 30 m / min After coating with a roll-fit coating pan and an air knife at a speed, the activation treatment by corona discharge was performed again in the same manner as above to obtain a support.

Coating of Sample On the side of the obtained support on which the antistatic layer was not coated, the above-described silver halide emulsion B according to the present invention and the emulsion surface protective layer coating solution were coated.

Further, the backing lower layer and the upper layer described above were coated on the surface side coated with the antistatic layer.

The amount of gelatin in the backing layer was 3.0 g in the lower layer.
/ m ² and the upper layer was 1.2 g / m ² at the same time by the slide hopper method at a speed of 90 m / min. A sample was obtained by coating the emulsion layer so that the amount of gelatin was 2.4 g / m ² , the protective layer was 1.2 g / m ² , and the amount of silver was 2.9 g / m ² .

The obtained sample is named photosensitive material B.

The basic compositions of the developing solution and fixing solution used in the present invention are shown below.

Developer Formulation-A Part-A (for 15 l finishing) Potassium hydroxide 470 g Potassium sulfite (50% solution) 3000 g Diethylenetriamine pentaacetic acid 150 g Sodium hydrogencarbonate 150 g Compound represented by general formula [I] Amount of the compound represented by the general formula [II] Amount described in Table 1 Hydroquinone 390 g Water is added to make up to 5000 ml.

Part-B (for 15 l finishing) Glacial acetic acid 220 g Triethylene glycol 205 g 1-Phenyl-3-pyrazolidone 27 g 5-Nitroindazole 0.45 g N-acetyl-D, L-penicillamine 1.5 g Fixer formulation Part-A ( 19l Finishing) Ammonium thiosulfate (70wt / vol%) 5900g Sodium sulfite 175g Sodium acetate trihydrate 400g Sodium citrate 50g Gluconic acid 38g Boric acid 30g Glacial acetic acid 140g Part-B (19l finishing) Aluminum sulfate 65g Sulfuric acid (50wt) %) 105 g The developer and the fixer described above are separately contained in a container for agent A and a container for agent B shown in FIG. 1 described later to form a developer kit and a fixer kit, respectively.

FIG. 1 shows a processing agent bottle, which is shown in FIG.
Is a plan view of the bottle, (b) is a front view, (c) is a side view, and (d) is a bottom view.

A developing solution prepared by adding 100 mg of the exemplified compound I-1 of the general formula [I] per liter of the developing solution was designated as a developing solution A, and a developing solution having a basic composition was designated as a developing solution B.

Using the above developing solution and fixing solution, a light-sensitive material and a starter to which the compound of the present invention and the comparative compound were added, respectively, as shown in the table below, were prepared and developed.

For development, processing was carried out for 45 seconds with the automatic processor shown in FIG.

The treated samples were evaluated as follows.

1. Running Experiment A light-sensitive material containing the compound of the present invention and a comparative compound, which had been exposed to X-rays so that the entire surface of the sample had a density of 1.0, was processed by the automatic processor SRX-502 (manufactured by Konica Corp.). ), The developer replenishment rate is changed as shown in the table, and the fixer replenishment rate is 400 ml / m
^{At 2} , 1000 pieces of 4-cut film were processed. At this time, the photosensitive materials A and B exposed by the following method at the initial stage (0th sheet) and the last stage (1000th sheet) were subjected to development processing, and fog, sensitivity and gamma were measured by the following methods.

(Measurement of Exposure and Sensitivity of Photosensitive Material A) The sample was scissors with two fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), tube voltage: 80 Kv, tube current: 100 mA, irradiation time: 50 msec. Exposure through an aluminum wedge, and after development processing, the reciprocal of the exposure dose required to obtain the density of base density + fog density + 1.0 for the obtained sample was obtained, and the sensitivity after running processing was calculated. It was expressed as relative sensitivity when the initial sensitivity of running was set to 100.

Further, Δγ (gamma) was obtained by calculating the slope of the straight line portion on the characteristic curve and expressing it as the value after the initial running-after the running processing.

The fog value is a value including a base density of 0.13.

(Exposure of Light-sensitive Material B and Measurement of Sensitivity)
After storing at 23 ° C and 55% RH for 3 days, He-Ne laser beam was used to change the light intensity at 1 / 100,000 second for 1 pixel (100μm), and then exposed as in Sample A. ,
Fog and Δγ were determined.

2. Evaluation of residual color property For each film, the unexposed sample was passed through an automatic processor,
The resulting film was visually evaluated for residual color. The evaluation was carried out in the following four grades.

1: No residual color 2: Slight residual color, but no problem 3: Some residual color, no problem in use 4: Some residual color, unusable New treatment after addition of starter to the above treatment Development processing 1000
It performed after one sheet and evaluated. The obtained results are shown in Tables 1 to 4.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

As is clear from the table, according to the method of the present invention, the larger the organic inhibitor (the compound of the general formula [I] or the general formula [II]) in the light-sensitive material, the larger the γ fluctuation. By adding the same inhibitor to the starter, γ fluctuation and sensitivity fluctuation can be reduced. If they are not the same, there is no effect. Further, the combined use of the compounds does not impair the effects of the present invention. Further, the effect is not lost even if the replenishment amount is reduced.

When the comparative compound was added to the starter,
The residual color was not improved. Further, when the replenishment rate was set to 285.5 ml / m ² , the sensitivity decreased and the γ variation occurred.

[0126]

According to the present invention, it is possible to obtain a stable method of processing a silver halide photographic light-sensitive material, in which sensitivity and gamma fluctuations due to running processing are small.

[Brief description of drawings]

FIG. 1 is a view of a treatment agent bottle used in Examples.

FIG. 2 is a configuration diagram of a processing device used in an example.

[Explanation of symbols]

 1 Container for A agent 2 Container for B agent 3 Film detection unit 4 Squeeze 5 Far infrared heater 6 Drying fan 7 Development 8 Fixing 9 Rinsing 10 Drain cock 11 Replenishing pump 12 Processing agent bottle storage 13 Chemical mixer

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material and a developing solution for developing the silver halide photographic light-sensitive material, wherein at least one of compounds represented by the following general formula [I] and / or the following general formula [II] is added. A method for processing a silver halide photographic light-sensitive material, characterized in that [Chemical 1] [In the formula, Z represents a 5- or 6-membered heterocycle containing at least one of a nitrogen atom and a sulfur atom, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen atom. Represents an atom, an amino group, a nitro group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof. R ₂ represents a hydroxy group or a substituted or unsubstituted amino group. ] 2. The general formula [I] and / or the general formula [I
The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the development is carried out by using a starter containing at least one of the compounds represented by I]. 3. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the developing replenisher is replenished at a ratio of 325 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material.