JPH0882899A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To reduce the use of a developing replenisher soln., to ensure high sensitivity even in the case of rapid processing and to prevent the color tone of developed silver from being tinged with yellowish red by incorporating a specified amt. or more of halogen ions and two kinds of specified compds. into a developing soln. CONSTITUTION: A developing soln. contg. >=0.05mol/l halogen ions, >=0.02mol/l compd. represented by formula I and a compd. represented by formula II and a developing replenisher soln. are used. In the formula I, R is aryl and each of R1 -R4 is H, alkyl, etc. In the formula II, each of X and Y is H, hydroxy, etc., each of R1 and R3 is alkylene which may have an ether bond and R2 is alkylene which may have an ether bond, etc.

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 reduce the amount of replenisher and to provide a highly sensitive silver tint of developed silver with a yellow-red tint even when it is rapidly processed. The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art When a silver halide photographic light-sensitive material is run-processed by an automatic processor, the processing solution is deteriorated in proportion to the increase in the processing amount. There are two factors that cause deterioration in the case of a developing solution, one of which is "processing fatigue" in which a component in a light-sensitive material reacts with a developing solution component to lose its activity, and the other is a cause of deterioration in the air. The decrease in pH due to absorption of carbon dioxide, and the "air oxidation fatigue" due to the oxidation of the developing agent are mentioned. The above-mentioned "processing fatigue" means that halogen ions, which are components of the light-sensitive material, are eluted into the developing solution, and among these halogen ions, iodine ions are replaced with bromine ions of silver bromide. Is mainly the accumulation of bromine ions, which acts as an inhibitor and adversely affects photographic performance. In order to process the photographic light-sensitive material stably, it is necessary to eliminate such deterioration factors. To that end, from the purpose of supplementing useful substances and diluting unnecessary substances,
At present, the photographic performance is kept constant by supplying a replenishing liquid in an amount corresponding to deterioration.

A number of techniques have been proposed as replenishing methods for such a processing solution, for example, Japanese Patent Laid-Open No. 55-126242.
No. 55, No. 55-126243, No. 57-195245, No. 57-195246,
No. 59-195247, No. 60-104946, No. 62-238559, JP-A No. 1-140156 discloses that the developer replenisher is continuously or intermittently replenished depending on the development processing amount to reduce fatigue. Means for recovery are disclosed.

Further, these photographic processing waste liquids have hitherto been discharged as they are to sewers, causing water pollution of rivers, lakes and marine water. In recent years, in order to reduce the environmental pollution load and simplify the processing work, it has been desired to reduce the discharge amount of the photographic processing waste liquid. Specifically, there is a reduction in the replenishment amount, or a method of recycling and reusing it. Listed. However, for example, when the replenishment amount of the developing replenisher is reduced, the halogen ions accumulate and the sensitivity decreases, and the color tone of the obtained image loses the pure black tone property, causing a drawback of degrading to a yellowish reddish color tone, It was practically impossible to reduce the amount of replenishment.

On the other hand, in recent years, the consumption of silver halide photographic light-sensitive materials has been increasing. Therefore, the number of processed silver halide photographic light-sensitive materials increases, and there is a strong demand for speeding up the processing.

Although the processing speed can be increased by increasing the amount of the developing agent, if the amount of the pyrazolidone-based developing agent is increased, the silver tone is deteriorated. On the other hand, the addition of thioether to a developing starter to achieve running sensitivity stability is disclosed in JP-A-6-138591, but a means of improving the silver tone by adding it to a developing replenisher has been found so far. I didn't.

From the above background, it has been desired to develop a processing method for a silver halide photographic light-sensitive material which has a reduced replenisher and has a high sensitivity even when it is rapidly processed and does not give a yellowish red tint to the developed silver. It was

[0008]

In contrast to the problems described above, the object of the present invention is to reduce the developer replenisher, to provide high sensitivity even with rapid processing, and the developed silver tones have a yellow-red tint. An object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material which is not tinged.

[0009]

The above object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the developing solution contains 0.05 mol / min of halogen ions. a developing solution and a developing replenishing solution containing at least 0.02 mol / l of a compound represented by the following general formula [I] and further containing a compound represented by the general formula [II]. And a method for processing a silver halide photographic light-sensitive material.

The average grain size or thickness of the silver halide grains is 0.3 μm or less, and the developer replenishment amount is 220 m.
l / m ² or less and total processing time (dry to dry) is 35
What is done within seconds is a preferred embodiment of the invention.

The present invention will be described in detail below.

The developer used in the developing method according to the present invention contains 10 to 40 g / l of hydroquinone and 0.02 to 0.08 m of at least one compound represented by the general formula [I].
ol / l, 0.16 mol / l of the compound represented by the general formula [II]
Hereinafter, it is preferable to further contain halogen ions in an amount of 0.05 to 0.2 mol / l.

In the general formula [I], R represents an aryl group (eg phenyl, naphthyl group). R ₁ , R ₂ , R
₃ and R ₄ each represent a hydrogen atom, an alkyl group (eg, methyl, ethyl, propyl, isopropyl and higher alkyl groups), an aryl group (eg, phenyl, naphthyl group), and an aralkyl group (eg, benzyl group).

Further, the aryl group of R and the alkyl group, aryl group and aralkyl group of R _{1 to} R ₄ may each have a substituent, and each substituent is, for example, a hydroxy group, an alkoxy group or a hydroxyalkyl. Group, amino group,
Examples thereof include a nitro group, a sulfonic acid group, a carboxyl group, and a halogen atom.

In the above general formula, R ₁ is preferably a hydrogen atom, an alkyl group substituted with an amino group, or a hydroxyalkyl group. R ₄ is preferably a hydrogen atom.

More preferably, R ₂ is a hydroxyalkyl group, R ₃ is a hydroxyalkyl group, an alkyl group, or a substituted alkyl group, and R is an aryl or substituted aryl group.

The alkyl group preferably has 4 or less carbon atoms.

The examples of the compounds represented by the general formula of the present invention are shown below, but the present invention is not limited thereto.

I-1 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone I-21-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidone I-3 1-phenyl-4-hydroxymethyl -4-Methyl-3-pyrazolidone I-4 1-phenyl-4,4-dimethyl-3-pyrazolidone I-5 1-phenyl-2-hydroxymethyl-4,4-dimethyl-
3-pyrazolidone I-6 1-phenyl-2-morpholinomethyl-4,4-dimethyl-
3-pyrazolidone I-7 1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone I-8 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone I-9 1-phenyl-5, 5-Dimethyl-3-pyrazolidone I-10 1-phenyl-5-methyl-3-pyrazolidone I-11 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone I-12 1-p-hydroxy Phenyl-4,4-dimethyl-3-pyrazolidone I-13 1-o-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone I-14 1-p-methoxyphenyl-4-methyl-4-hydroxymethyl -3-Pyrazolidone I-15 1- (3,5-dimethyl) phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone The compound represented by the above general formula [I] is a developing solution and a developing replenishing solution each 1 Add 0.02 mol / l or more per liter.

In the practice of the present invention, the following developing agents can be used in the developing solution.

Typical examples of HO- (CH = CH) n-OH type developing agents include hydroquinone. In addition, catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone and methylhydroquinone. , 2,
Examples include 3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone.

Further, as the HO- (CH = CH) n-NH ₂ type developing agent, ortho and para aminophenols are typical ones, such as N-methyl-p-aminophenol and other 4-aminophenols. There is also.

Further, H ₂ N- (CH = CH) _n -NH ₂ type developing agents include 4-amino-2-methyl-N, N-diethylaniline and p-phenylenediamine.

As the heterocyclic developing agent, 1-phenyl is used.
-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
There is pyrazolidone.

The above developing agents may be used alone,
It is also possible to use two or more kinds in combination.

The compound represented by the general formula [II] will be described.

In the formula, X and Y may be the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an amino group, an ammonio group, a carboxyl group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group. X and Y may form a ring. As the substituents of X and Y, a hydrogen atom,
Alkyl group having 1 to 5 carbon atoms which may have a substituent, for example, methyl group, ethyl group, amino group which may have a substituent, for example, dimethylamino group, diethylamino group, di-
Cyanoethylamino group, morpholino group, ammonio group,
For example, trimethylammonio group, aminocarbonyl group,
For example, a dimethylaminocarbonyl group and an aminosulfonyl group, for example, a dimethylaminosulfonyl group are preferable.

The compound represented by the general formula [II] may be a salt of an inorganic or organic acid. Preferred salts include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like.

R ₁ and R ₃ represent alkylene groups, and these alkylene groups may have an ether bond.

R ₂ represents R ₅ —CO—NH—R ₆ —NH—CO—R ₇ or an alkylene group which may have an ether bond.

[0031] R ₆ is _{- (CH 2) n1 -N (} R 8) - (CH 2) n2 - or _{-O- (CH 2) n3 -S- (} CH 2) represents an _n4 -O-.

R ₅ and R ₇ represent an alkylene group which may have an ether bond, R ₈ represents a hydrogen atom or an alkyl group,
_{n 1, n 2, n 3} , n 4 represents an integer of 1 to 5.

Specific examples of the compounds represented by the general formula [II] are shown below, but the present invention is not limited to these compounds.

[0034]

Embedded image

[0035]

[Chemical 3]

[0036]

[Chemical 4]

[0037]

[Chemical 5]

[0038]

[Chemical 6]

The compound represented by the general formula [II] can be synthesized by a general method, for example, US Pat.
3,021,215, British Patent 950,089, Journal of
Organic Chemistry Vol. 26, pp. 1991-1995 (1961
), New Experimental Chemistry Course, Vol. 14, pp. 1713 to 1726, Maruzen (published in 1978).

These compounds of the present invention may be used in combination. The addition amount of the compound of the present invention to the developing solution and the developing replenishing solution is preferably 1.6 × 10 ^{−6 to} 1.6 × 10 ⁻¹ mol / l, particularly preferably 1.6 × 10 ^{−4 to} 7.8 × 10 ⁻² mol / l.
It is l.

In the developer, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine, etc.), alkaline agents (eg, Carbonates, etc., solubilizers (polyethylene glycols and their esters, etc.), pH adjusters (eg organic acids such as citric acid),
A sensitizer (for example, quaternary ammonium salt), a development accelerator, a hardener (for example, dialdehydes such as glutaraldehyde), a surfactant and the like can be contained. Further as an antifoggant azole organic antifoggant (e.g. indazole, imidazole, benzimidazole, triazole, benztriazo, tetrazole, thiadiazole), calcium ions mixed in the tap water used in the treatment liquid. There are masking agents for masking sodium, such as sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

In processing the developer used in the present invention
The pH is preferably in the range of 9.00 to 13.00 and more preferably treated with a developer pH of 10.00 to 12.00. As the developing solution, a developing replenishing solution having the same composition or a composition similar thereto is used, and the replenishing amount is 220 ml / m ² or less, preferably 50
It is processed with a developing replenisher solution of about 200 ml / m ² , more preferably 80 to 190 ml / m ² .

The fixing agent preferably contains thiosulfate. The thiosulfate is supplied as a solid, specifically, as a salt of lithium, potassium, sodium, or ammonium, but is preferably supplied as sodium thiosulfate or ammonium thiosulfate and used by dissolving. More preferably, a fixing solution having a high fixing rate can be obtained by supplying and dissolving it as an ammonium salt, but sodium is preferable from the viewpoint of holding property.

The concentration of thiosulfate is preferably 0.1-5 mol.
l / l, more preferably 0.5-2 mol / l,
More preferably, it is 0.7 to 1.8 mol / l. Other fixing agents such as iodide salts and thiocyanates can also be used.

The fixing agent contains a sulfite, and the concentration of the sulfite is 0.2 mol / l or less when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent. As the sulfite, solid lithium, potassium, sodium, ammonium salt or the like is used, and it is used by dissolving with the solid thiosulfate.

Further, the fixing solution preferably contains citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof.

Examples of these salts include potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate and ammonium tartrate. Potassium, potassium sodium tartrate, sodium malate, ammonium malate, sodium succinate,
Lithium, potassium, sodium, ammonium salts and the like typified by ammonium succinate and the like are mentioned as preferable ones, and among these, one kind or a combination of two or more kinds can be used.

More preferred among the above compounds are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The above-mentioned citric acid, tartaric acid, malic acid, succinic acid, etc. may be used as a solid even if they are supplied as a solid. The preferred content in the fixer after dissolution is 0.05 mo.
l / l or more, and the most preferable content is 0.2 to 0.6 mol /
It is l.

Examples of the acid include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid, with boric acid and aminopolyacid being preferred. Acids and salts such as carboxylic acids. The preferable addition amount is 0.5 to 20 g / l.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

As the surfactant, for example, anionic surfactants such as sulfuric acid ester compounds and sulfonate compounds, nonionic surfactants such as polyethylene glycol and ester compounds, and amphoteric surfactants described in JP-A-57-6840. And so on.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of fixing accelerators include those disclosed in JP-A-45-357.
No. 54, JP-B-58-122535 and JP-A-58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, and thioethers described in US Pat. No. 4,126,459.

The silver halide emulsion according to the present invention has a total processing time (dry t) from the start of development to fixing, washing with water, and completion of drying.
It is preferable that the o dry) is processed in 35 seconds or less.

The developing temperature is 18 to 50 ° C., especially 30 to 45 ° C.
The developing time is preferably 6 to 15 seconds.

Next, the silver halide grains used in the silver halide light-sensitive material of the present invention will be described. The emulsion used in the present invention may be a single emulsion or a mixture of two or more kinds of emulsions. The emulsion to be mixed may be either tabular grains or normal grains or twin grains having an aspect ratio of less than 2. The emulsion layer may be a single layer or a plurality of layers.

For the emulsion used in the present invention, grains having an average grain size or a thickness of 0.3 μm or less are preferably used. The thickness of the silver halide grain in the present invention is defined as the minimum distance between the two parallel principal planes constituting the tabular grain.

The thickness of the tabular silver halide grains was determined by vapor-depositing a metal from a diagonal direction of the grains together with a comparative latex.
The shadow length can be calculated on an electron microscope and calculated with reference to the shadow length of the latex, or it can be obtained from an electron micrograph of a sample slice obtained by coating and drying a silver halide emulsion on a support. .

As the silver halide emulsion, those having monodispersion are preferably used, and those having an average grain size of 50% by weight or more of silver halide grains contained in the central grain size range of ± 20% are particularly preferably used. To be

The silver halide emulsion may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., but from the viewpoint of high sensitivity, silver bromide or iodo Silver bromide is preferred, and the average silver iodide content is 0 to 5.0 mol%, particularly preferably 0.1 to 3.0 mol%.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like.

Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halide are simultaneously added to a gelatin aqueous solution having pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution. The aspect ratio can be controlled by the method of preparing the seed crystal, the thickness, the pAg and pH during growth, the halogen composition, the aging time and the temperature. The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide. In addition, a silver halide solvent such as ammonia, thioether or thiourea can be used, if necessary, during the production of tabular silver halide grains.

The grain growth may be performed by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions.
It may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution, and a silver ion-containing solution can be supplied.

As the silver halide emulsion, core / shell type or double structure type grains having a silver halide composition whose surface is different from the inside of the grain are also preferably used. A method for obtaining a core / shell type emulsion is described in, for example, US Pat.
5,068, 4,444,877, British Patent 1,027,146, JP-A-60-14331 and the like. In the core / shell type grains of the silver halide emulsion, the silver iodide content of the outermost shell layer of the grains is less than 5 mol%, preferably less than 3 mol%.

The silver iodide content of the outermost shell layer of the silver halide grain of the present invention can be detected by various surface elemental analysis means. It is useful to use methods such as XPS (X-ray Photoelectron Spectroscopy), Auger electron spectroscopy, and ISS. XPS is the simplest and highly accurate means, and the silver iodide content of the outermost shell layer of the present invention can be defined by the value measured by this method.

The depth analyzed by the XPS surface analysis method is said to be about 10Å. Regarding the principle of the XPS method used for the analysis of iodine content near the surface of silver halide grains, see Aihara Soichi et al. "Electron spectroscopy" (Kyoritsu Library 1
6, published by Kyoritsu Shuppan, 1978).

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. You may. In these emulsions, a cadmium salt, a lead salt, a zinc salt, a thallium salt, a ruthenium salt, an osmium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, etc. may be used at the stage of physical ripening or grain preparation.

The emulsion may be subjected to a water washing method such as a Noudel water washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or G3, G8 as an aggregation polymer agent described in JP-A-63-158644, etc. The method used is mentioned as a particularly preferable desalting method.

The chemical sensitization applied to the emulsion of the present invention includes so-called sulfur sensitization, sensitization with Se compounds, sensitization with Te compounds, gold sensitization, and noble metals of Group VIII of the periodic table (for example,
Sensitization by Pd, Pt, Id, etc.) and a combination of these can be used. Above all, a combination of gold sensitization and sulfur sensitization or a combination of gold sensitization and Se compound sensitization is preferable. Further, it is also preferable to use it in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the time of completion, from the viewpoint of sensitivity and dye adsorption. A method of adding in the form of fine grains of silver iodide is particularly preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferred compounds are azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having a mercapto group and compounds having a benzene ring.

In the present invention, the reduction treatment, so-called reduction sensitization, is called a method of adding a reducing compound, silver ripening.
Method to pass silver ion excess state with pAg = 1 to 7, high p
It is applied to a silver halide emulsion by a method called H ripening, in which a high pH state of pH = 8 to 11 is passed. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfite. Examples thereof include salts, and particularly preferable examples include thiourea dioxide, stannous chloride and dimethylamine borane. The addition amount of these reducing compounds varies depending on the reducing property of the compound, the type of silver halide, the emulsion production conditions such as the dissolution conditions, and is 1 × 10 ⁻⁸ per mol of silver halide.
A range of up to 1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

It is also preferable to subject any portion and / or shell layer other than the outermost shell layer of the silver halide grain to a reduction treatment and further grow the grain as it is. From the viewpoint of effect control, the surface of the inner shell layer to be laminated in multiple stages is preferable. For example, it is preferably applied to the surface of the seed emulsion grains or the surface of the shell layer at the time of growth suspension.

The reduction treatment is carried out according to JP-A-2-135439 and 2-1368.
It may be carried out in the presence of a thiosulfonic acid compound as shown in No. 52 or the like.

The silver halide photographic light-sensitive material applied to the present invention is spectrally sensitized with methine dyes and other spectral sensitizing dyes. The dyes used are cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobolacyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes.
Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes can be applied to any of the commonly used nuclei.
That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., a nucleus in which an aliphatic hydrocarbon ring is fused to these nuclei, that is, India. The renin nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has pyrazoline-5 as a nucleus having a ketomethine structure.
-One nucleus, thiobitantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These patents are, for example, German patents 929,
080, U.S. Patent No. 2,231,658, No. 2,493,748, No. 2,503,776, No. 2,519,001, No. 2,912,329,
No. 3,655,394, No. 3,656,959, No. 3,672,897
No. 3,649,217, British Patent No. 1,242,588, Japanese Patent Publication Sho
44-14030.

These sensitizing dyes may be used alone or in combination. Sensitizing dyes are often used in combination. As typical examples thereof, U.S. Pat.Nos. 2,688,545, 2,977,299, and 3,
No. 397,060, No. 3,522,052, No. 3,527,641, No. 3
No. 3,617,293, No. 3,628,964, No. 3,666,480, No. 3,679,428, No. 3,703,377, No. 3,837,862,
It is described in British Patent No. 1,344,281 and Japanese Patent Publication No. 43-4936.

The sensitizing dye may be added at any time during grain formation, before and after chemical sensitization, during the sensitization, and during coating, but it is preferably added at several points.

<Crossover Cut: Undercoat Dye Layer,
Solid Disperse Dye Layer> In the light-sensitive material applied to the present invention, a crossover cut layer may be provided between the support and the emulsion layer. This layer may be an undercoat layer provided between the support and the hydrophilic colloid layer, or a dye layer may be provided between the undercoat layer and the emulsion layer. The dye used in the undercoat layer includes an oxonol dye having a pyrazolone nucleus or a barbituric acid nucleus, an azo dye, an azomethine dye, an anthraquinone dye,
Examples thereof include arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes and cyanine dyes. The dye used in the dye layer may be dispersed in the form of fine particles. Specific examples of the dyes include the exemplified compounds (-2, 4, 6, 8, and 8) described on pages 6 to 12 of JP-A-2-264247.
9,10,11,12,13-27, -2,5,6, -3,4
6,8,9,10,11,12,14-28, -3,5,6,8,
10 to 16, -3, 5, 6, 7) and the like can be mentioned and used.

Further, these compounds are described in International Patent Publication 88
/ 04794, European Patent Nos. 0274723A1, 276,566, and
299,435, JP-A-52-92716, 55-155350, 55-1
55351, 61-205934, 48-68623, U.S. Pat.
527,583, 3,486,897, 3,746,539, 3,933,7
It can be easily synthesized according to the method described in No. 98, No. 4,130, 429, No. 4,040, 841 and the like.

The emulsion can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978) and No. 187.
16 (November 1979) and No. 308119 (December 1989). These three research
The types of compounds shown in the disclosure and the place of description 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 In the present invention, the developing solution means a developing solution that enters a developing tank of an automatic developing machine and indicates a processing solution that actually develops a photosensitive material,
The development replenisher is a replenisher replenished during the development of the light-sensitive material.

[0088]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these.

Example 1 Using a silver iodobromide (silver iodide content of 2 mol%) seed emulsion having an average grain size of 0.1 μm, an aqueous ammoniacal silver nitrate solution and an aqueous potassium bromide solution were added by the double jet method, and the average Particle size 0.25μ
A cubic monodisperse emulsion of silver iodobromide (average silver iodide content: 0.1 mol%) of m was grown. The coefficient of variation (σ / r) was 0.17.

The above emulsion was dissolved immediately before chemical ripening, and when the temperature became constant, the sensitizing dye I was added, and ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added to carry out chemical sensitization. 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added.

[0091]

[Chemical 7]

The following additives were added to the obtained emulsion coating solution per mol of silver halide.

Nitrophenyl-triphenylphosphonium chloride 30 mg 1,3-dihydroxybenzene-4-sulphonic acid ammonium 1 g 2-mercaptobenzimidazole-5-sodium sulfonate 10 mg 2-mercaptobenzothiazole 10 mg trimethylolpropane 9 g 1,1- Dimethylol-1-bromo-1-nitromethane 10mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g

[0094]

Embedded image

(Emulsion side protective layer liquid) It has the following composition. The added amount is shown as an amount per 1 liter of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decyl-sulfosuccinate 1 g Polymethylmethacrylate 4 μm particles Silicon dioxide particles (matting agent having an average particle size of 1.2 μm) 0.5 g Ludox AM (DuPont) 30g 2-4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 2% aqueous solution (hardener) 10cc 35% formalin (hardener) 2cc glyoxal 40% aqueous solution ( Hardener) 1.5cc (Backing layer, coating solution for backing protection layer) As a backing layer, 400 g of gelatin, 2 g of polymethylmethacrylate having an average particle size of 6 μm, 24 g of potassium nitrate, 6 g of sodium dodecylbenzenesulfonate, 120 g of the following antihalation dye 120 g 2 g / m ^{2 of} dye emulsion dispersion,
And a backing layer solution consisting of glyoxal,
A glycidyl methacrylate-methyl acrylate-butyl methacrylate copolymer (50:10:40 weight ratio) was diluted to a concentration of 10 wt% and the resulting aqueous copolymer dispersion was applied as an undercoat liquid. A backed support obtained by coating one side of the polyethylene terephthalate base with a protective layer liquid containing gelatin, a matting agent, glyoxal, and sodium dodecylbenzenesulfonate was prepared.

The coating amount for both the backing layer and the protective layer is 2.0 g / m ² as the gelatin coating amount.

[0098]

[Chemical 9]

(Preparation of Sample) On the backed base,
The emulsion coating solution and the protective layer were simultaneously coated in two layers with a slide hopper to obtain a sample. Coating amount is 3.0g in terms of silver amount
/ M ² , gelatin amount is 3 g / m ^{2 for} emulsion layer, 1.2 g / m for protective layer
^{Was 2} .

(Processing Solution) The compositions of the developing solution, developing replenishing solution and fixing solution used in the present invention are shown below.

Development Replenisher Solution Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetramine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-phenyl-5 -Mercaptotetrazole 0.2g Hydroquinone 340g Add water to finish to 5 liters Part-B (for 12 liter finish) Glacial acetic acid 170g Triethylene glycol 185g Compound [I] 5-nitroindazole 0.4g Compound [II] shown in Table 1 Amount shown in Table 1 Fixer formulation Part-A (for 18 liter finish) 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 (for 18 liter finish) Sulfuric acid Preparation of aluminum 800g developer replenisher added simultaneously Part A, the PartB water about 5l, finish 12l adding water with stirring dissolved, p with KOH
The H was adjusted to 10.40. This is used as a development replenisher.

2.4 g of glacial acetic acid was added to 1 liter of this development replenisher.
/ l, add potassium bromide in the amount shown in Table 1 and adjust the pH to 1 with KOH.
The developer was adjusted to 0.15 to prepare a developer.

The fixing solution was prepared by adding Part A and Part B to approximately 5 liters of water.
Was simultaneously added, water was added while stirring and dissolving to make 18 l, and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is the fixing replenisher.

(Evaluation method) <Silver color tone> Regarding the silver color tone, uniform exposure was performed with tungsten light so that the transmitted light blackening density was 1.0, and the following four-level evaluation was performed visually with a light source for photographic observation. It was The processing is carried out by the X ray automatic developing machine S containing the developing solution and the fixing solution.
RX-502 (manufactured by Konica Co., Ltd.) is running in a 45-second mode at a replenishment rate of 180 ml / m ² (processing 2,000 sheets in 4 cuts) until the processing level reaches equilibrium. Was used. As the replenisher, a developer replenisher and a fixer were used. The processing temperature was a developing temperature of 35 ° C, a fixing temperature of 33 ° C, a water washing temperature of 20 ° C, and a drying temperature of 45 ° C.

The evaluation criteria of the silver color tone are as follows: A: Black B: Reddish black C: Reddish black D: Yellowish red black The results are shown in Table 1.

[0106]

[Table 1]

From the results shown in Table 1, it can be seen that even if the concentration of halogen ions is high, the processing method of the present invention causes little deterioration in silver tone.

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

<Solution A> Ocein gelatin 60.2 g Distilled water 20.0 l Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml <Solution B> AgNO ₃ 1487.5g Distilled water to 3500ml <Solution C> KBr 1029g KI 29.3g Distilled water to 3500ml <Solution D> 1.75N KBr aqueous solution At the following silver potential control amount 35 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58 Using the mixing stirrer shown in No. 58289, 64.1 ml of each of Solution B and Solution C was added to Solution A by the simultaneous mixing method for 2 minutes to perform nucleation.

After stopping the addition of Solution B and Solution C, 60
The temperature of solution A is raised to 60 ° C. in a minute, and solution B and solution C are mixed again by the simultaneous mixing method at a flow rate of 68.5 ml / min to 50 ° C., respectively.
Added for minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D. 3% KOH after addition
Then, the pH was adjusted to 6 and the mixture was immediately desalted and washed with water to obtain a seed emulsion EM-0. Seed emulsion EM- thus prepared
0 means that 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains with a maximum adjacent side ratio of 1.0 to 2.0, the hexagonal tabular thickness is 0.07 μm, and the average diameter (circular diameter conversion) is 0.5 μm. It was found by electron microscope observation that there was. (Preparation of tabular emulsion) A tabular silver iodobromide emulsion EM-1 containing 1.53 mol% AgI was prepared using the following four kinds of solutions.

<Solution A> Ocein gelatin 29.4 g Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 2.5 ml Seed emulsion EM-0 0.588 mol equivalent Distilled water to 1400 ml.

<Solution B> AgNO ₃ 1404.2 g Distilled water to 2360 ml <Solution C> KBr 963 g KI 27.4 g Distilled water to 2360 ml <Solution D> 1.75N KBr aqueous solution Using the mixing stirrer shown in JP-A-58-58288 and JP-A-58-58289, the total amount of solution B and solution C was added to solution A by the simultaneous mixing method at a flow rate of 21.26 ml / min for 111 minutes for growth. It was

During this period, the silver potential was controlled to be +25 mV by using the solution D.

After the completion of the addition, the following sensitizing dyes (A) and (B) were added at 200 mg / Ag 1 mol and 15 mg / Ag 1 mol, respectively, and then, in order to remove excess salts, Demol N (manufactured by Kao Atlas) aqueous solution. And desalting were performed using an aqueous magnesium sulfate solution, an aqueous gelatin solution containing 92.2 g of ossein gelatin was added, and the mixture was stirred and redispersed.

Approximately 3000 particles of EM-1 were observed and measured by an electron microscope, and the shape was analyzed. As a result, the average particle thickness was 0.25.
It was found that the particles were hexagonal tabular grains having a diameter of 1.0 μm and an average particle diameter of 1.05 μm and a distribution of 18%.

The resulting emulsion was sensitized with the sensitizing dye (A) at 55 ° C.
And sensitizing dye (B) 300 mg and 15 mg per mol of silver halide
mg was added.

Sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium anhydride Sensitizing dye (B): 5, 5'-di- (butoxycarbonyl) -1,
Anhydrous of 1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt 10 minutes later, chemically ripened with an appropriate amount of chloroauric acid, sodium thiosulfate and ammonium thiocyanate. I went. 15 minutes before the end of ripening, potassium iodide was added per mol of silver halide.
Add 0.8 mmol of silver iodide fine particles (average particle size 0.05 μm),
Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 3 × 10 ^-2 mol per mol of silver halide, and dispersed in an aqueous solution containing 70 g of gelatin.

The emulsion after chemical sensitization was A: B: C =
A mixture of 1: 6: 3 emulsion E, H: A: D: C = 1:
A mixture of 6: 3 was designated as I.

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution described below was also prepared.

The additives used in the emulsion are as follows.
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 Nitrophenyl-triphenylphosphonium chloride 50 mg 1 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 2g 2-Mercaptobenzimidazole-5-sulfonic acid sodium 1.5g

[0122]

[Chemical 10]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg Protective Layer Solution Next, the following was prepared as a protective layer coating solution. The additive is shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size 1.2 μm matting agent) 0.5 g Ludox AM (DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2mg C ₁₂ H ₂₅ CONH ( CH ₂ CH ₂ O) ₅ H 2.0 g The obtained coating solution was uniformly applied onto a blue-colored polyethylene terephthalate film base which had a thickness of 180 μm and which had been undercoated, and dried.

The coating amount was 1.7 g / m ² in terms of silver equivalent on the emulsion layer on one side, and 0.99 g on the protective layer as the gelatin coating amount.
FILM 1 was obtained by simultaneously coating both sides of the emulsion layer and the protective layer with two slide hopper type coaters at a speed of 90 m / min so that the surface area became / m ² . In the same manner, FILM2 was obtained so that the amount of silver per side was 2.25 g / m ² .

The developer used in Example 1 (provided that the compound
(I and II are the amounts shown in Table 2), and an automatic processor for X-ray SRX-502 (manufactured by Konica Corp.) containing a fixing solution is used in a 45-second mode until the processing level reaches an equilibrium state and the processing amount is replenished. The film was changed (2000 pieces were cut in a size of 4 cuts) and running was performed to obtain an equilibrium level processing solution. Processing temperature is development temperature
35 ℃, Fixing temperature 33 ℃, Washing temperature 20 ℃, Drying temperature 45
℃ was made. The treated film used was one in which FILM 1 and 2 were uniformly exposed so that the transmitted light blackening density was 1.0. The replenishment amount of the development replenisher is shown in Table 2. 18 for treated film I
0 ml / m ^2, in the case of processing the film II was 360 ml / m ^2. The bromine ion concentration of the obtained running solution was 180 ml / m
² for 0.1 mol / l, 360 ml / m ² for 0.07 mol / l
Met. The replenishing amount of the fixing solution was 400 ml / m ² .

The following evaluations were carried out using the running liquid obtained as described above.

<Sensitometry> As for photographic characteristics, FILM1 was sandwiched between two fluorescent intensifying screens SRO250, and a wedge image was printed at a tube voltage of 80 KV, a tube current of 100 mA, and an irradiation time of 50 msec.
Evaluation was made with a film of 4 × 17 cm. The relative sensitivity of Table 2 is NO.10
The relative sensitivity is shown when the sensitivity of is set to 100.

<Silver color tone> Regarding the silver color tone, FILM1 was uniformly exposed with tungsten light so that the transmitted light blackening density was 1.0, and visually observed on a light source for photographic observation in four steps as in Example 1. An evaluation was made.

The treatment was carried out by modifying the obtained running solution so that it could be treated in 25 seconds by changing the conveying speed with an automatic processor for X ray SRX-502 (manufactured by Konica Corporation).
Processed in seconds and 45 seconds mode. The processing temperature is 35
℃, fixing temperature 33 ℃, washing temperature 20 ℃, drying temperature 45 ℃
And The replenishment amount is as shown in Table 2 for developer and 400 m for fixer.
It was set to l / m ² .

[0131]

[Table 2]

As described above, according to the present invention, it is possible to obtain an image having a low replenishment, a high sensitivity even if the processing speed is increased, and a good silver tone.

[0133]

According to the present invention, there is provided a method for processing a silver halide photographic light-sensitive material which has a reduced replenisher, has a high sensitivity even when it is rapidly processed, and does not have a yellow-red tint in the silver tone of developed silver. I was able to.

Claims (4)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein a developer contains halogen ions in an amount of 0.05 mol / l or more, and further the following general formula [I ] The compound represented by 0.0
A method of processing a silver halide photographic light-sensitive material, which comprises using a developer and a developer replenisher containing 2 mol / l or more of the compound represented by the general formula [II]. Embedded image [In the formula, R represents an aryl group. R ₁ , R ₂ , R ₃ , and R _{4, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. ] Formula (II) _{X-R 1 -S- (R 2} ) -S-R 3 -Y [wherein, X and Y good hydrogen atoms be the same or different, a hydroxyl group, an alkyl group, an amino group, Ammonio group,
It represents a carboxyl group, a sulfo group, an aminocarbonyl group, or an aminosulfonyl group. R ₁ and R ₃ represent an alkylene group, and these alkylene groups may have an ether bond. R ₂ represents an alkylene group which may have _{R 5 -CO-NH-R 6} -NH-CO-R 7, or an ether bond. R ₆ is _{- (CH 2) n1 -N (} R 8) - (CH 2) n2 - or -O- (CH _{2) n3} -S-
(CH ₂₎ represents an _n4 -O-. R ₅ and R ₇ represent an alkylene group which may have an ether bond, R ₈ represents a hydrogen atom or an alkyl group, and n ₁ , n ₂ , n ₃ and n ₄ represent integers of 1 to 5. ] 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material having an average grain size or a thickness of 0.3 μm or less is processed. 3. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the replenishing amount of the developing replenisher is 220 ml / m ² or less. 4. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the total processing time (dry to dry) is within 35 seconds.