JP2949879B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

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 color photographic light-sensitive material, and more particularly, to a rapid processing even in continuous processing, no generation of stains in unexposed areas, and an improvement in processing stability. The present invention relates to a method for processing an excellent silver halide color photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Generally, in order to obtain a color image by processing an imagewise exposed light-sensitive material, a processing step of desilvering the generated metallic silver after a color development step, followed by washing or stabilization, etc. is carried out. Provided. In recent years, photosensitive materials have been subjected to running processing by an automatic developing machine provided in a development laboratory. In the processing of such photosensitive materials, as a part of improving services to users, development processing is performed within the day when development is received. Is required to be returned to
Development of rapid processing technology is required. In recent years, it has been required to even return the product within a few hours from the reception, and the development of rapid processing technology has been increasingly required. Against this background, Eastman Kodak has proposed a rapid processing of color paper called Process RA-4. That is, this method comprises three steps of color development 45 seconds, bleach-fix 45 seconds, and stability 90 seconds, and is a method of processing at a processing temperature of 35 ° C. for a development time of 3 minutes.

[0003] As for the rapid processing of these photographic materials, the prior arts are described as follows.
The techniques are broadly classified into techniques based on physical means at the time of development processing, and techniques based on (3) improvement of the composition of the processing solution used in the development processing. A fine graining technique of silver halide described in JP-A-77223, a technique for reducing silver bromide of silver halide described in JP-A-58-18142, and JP-B-56-18939, and the use of additives (for example, JP-A-56-64
No. 339, JP-A-57-144547, JP-A-58-50534, and JP-A-58-50534, in which a 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-339-339 is added to a photosensitive material.
No. 1 as described in JP-A-50535 and JP-A-58-50536.
A technique of adding aryl virazolidones to a light-sensitive material), a technique using a high-speed reactive coupler (for example, Japanese Patent Publication No. 51-10783, Japanese Patent Application Laid-Open No. 50-123342),
No. 51-102636, a technique using a high-speed reactive yellow coupler), a technique for thinning a photographic constituent layer (for example, a technique for thinning a photographic constituent layer described in Japanese Patent Application No. 60-204992), and the like. Regarding the above (2), there is a processing liquid stirring technique (for example, a processing liquid stirring technique described in Japanese Patent Application No. 61-23334), and the above (3).
Regarding the above, there are known a technique using a development accelerator, a technique for increasing the concentration of a color developing agent, and a technique for reducing the concentration of halogen ions, particularly bromide ions.

In the above-mentioned rapid processing technique, a technique using a photosensitive material using a high concentration of silver chloride according to the technique (1) (for example, JP-A-58-95345, JP-A-60-95345).
19140, 58-95736, etc.)
Provides particularly good speedup performance. However, the above technology is not sufficiently satisfactory for users who demand further speed. In the photographic industry, there is a demand for further speeding up as seen in the waiting time for cup noodles in the food industry.

On the other hand, in recent years, environmental problems have been highlighted, and in the photographic industry, products with low replenishment and reduced amount of waste liquid have been marketed for the purpose of reducing pollution load. However, if the replenishment is to be promoted in addition to the rapid processing, there has been a major problem that the maximum concentration varies during continuous processing, and the value as a product is lost. In particular, this problem is serious in a color developing solution. In addition, it has been found that a problem that yellow stain occurs also occurs.

Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is capable of rapid processing in continuous processing, prevents stain in unexposed areas, has excellent processing stability, and is capable of continuous processing for a long period of time. Is to provide a processing method.

[0007]

The present inventors have conducted intensive studies and as a result, have found that the object of the present invention is to provide a silver halide emulsion having a mean silver chloride content of 80 mol% or more in a silver halide emulsion coated on a support. In a processing method in which the material is imagewise exposed and then subjected to color development processing, the chloride concentration in the processing solution for color development processing is 4 × 10 ⁻² mol / l or more and the color developing agent concentration is 1.0 × 1 liter of a processing solution for the color development processing , wherein the compound represented by the formula (1) is 10 ^-2 mol / l or more and is represented by the following general formula (1):
It has been found that this can be achieved by a method for processing a silver halide color photographic light-sensitive material, characterized in that the processing is carried out with a color development processing time of 5 seconds or more and 35 seconds or less, containing 10 g to 80 g per silver.

Formula (1) R-SO ₃ X (wherein, R represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R is an ethylenically unsaturated group, and these repeating units are X represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or an ammonium group.) In the above, the amount of silver in the silver halide color photographic light-sensitive material is 0.75 g / m 2. it is ² or less, also found that achievable more effectively the above-mentioned object by containing a compound represented by the following general formula (2).

[0009]

Embedded image In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group,
Aryl group or However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

[0010]

When a light-sensitive material containing a high silver chloride emulsion is used and low replenishment processing is performed, the Cl ^- concentration in the color developing solution is 4%.
It was found that when the content was more than × 10 ^-2 mol / l, the above problem became remarkable. As a result of the examination, the color developing agent was 1.
It has been found that it can be improved by treating with a processing solution of 0 × 10 ⁻² mol / l or more, but a new problem has arisen.
This is a problem that the solubility of the color developing agent is poor and the color developing agent is not dissolved unless it is heated to a high temperature or precipitates at a low temperature, and furthermore, the developing agent precipitates during a running experiment. In order to solve these problems, it has been found that the presence of the compound of the formula (1) in the developing solution improves the solubility and precipitation of the color developing agent to obtain stable performance, thereby achieving the object of the present invention. I was able to. Unexpectedly, some effects such as the generation of tar in the color developing solution were improved.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred processing steps to which the processing method using the processing solution of the present invention is applied include: (1) color development → bleaching fixation → stable (2) color development → bleaching → fixing → stable (3) Color development → Bleaching → Bleaching → Stable (4) Color development → Bleaching → Fixing → Stable (5) Color development → Bleaching → Bleaching → Stable (6) Color development → Bleaching → Bleaching → Fixing → Stable But preferably (1), (2) and (3)
It is a process of.

The color developing solution used in the present invention contains a compound represented by the general formula (1). General formula (1)
In the above, examples of the alkyl group having 1 to 8 carbon atoms represented by R include a methyl group, a carboxymethyl group, a phenylmethyl group, an ethyl group, a hydroxyethyl group, a sulfonylethyl group, a propyl group, a butyl group, a heptyl group,
An octyl group; These may be linear or branched and include those having a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl group, etc.), a hydroxyl group, an amino group,
Examples include a nitro group, a carboxylic acid group (including its salt), a sulfonic acid group (including its salt), and the like.

The phenyl group represented by R includes those having a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom and a bromine atom), an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms). And, for example, methyl group, ethyl group, propyl group, butyl group, etc.), hydroxyl group, amino group, nitro group, carboxylic acid group (including its salt), sulfonic acid group (including its salt), and phenyl. The number of substituents on the group may be one or 2 to 5, and in the case of 2 to 5, the substituents may be the same or different. Further, R may be a polymer having an ethylenically unsaturated group and having these repeating units. R is preferably a phenyl group,
Those having a substituent are preferable, and preferable substituents are an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxylic acid group (including a salt thereof), and a sulfonic acid group (including a salt thereof).
Is mentioned. Hereinafter, the general formula (1) used in the present invention
Specific examples of the sulfonic acid derivative of the present invention represented by are shown below, but the present invention is not limited thereto.

[0014]

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[0015]

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[0016]

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[0017]

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The compounds having a sulfonic acid group and a carboxylic acid group in the above exemplified compounds are used in a color developing solution which is an alkaline solution. Therefore, the sodium salt, potassium salt and lithium salt of each compound are used. And the like. Some of the sulfonic acid derivatives of the present invention are described in British Patent Nos. 669,505 and 83.
7,491, JP-A-51-147322 and JP-A-51-147322.
No.-80229, which are readily available to those skilled in the art. The sulfonic acid derivative of the present invention may be used alone or in combination of two or more, and the amount used is 10 g to 80 g per liter of the color developing solution. Particularly preferred is 20 g to 70 g. That is, in the present invention, 10 g of the sulfonic acid derivative represented by the general formula (1) is used.
As described above, by using more preferably 20 g or more, the concentration of the color developing agent in the processing solution such as the color developing replenisher and the color developing solution can be maintained at a high level, and the performance can be stabilized. In particular, the effect of the present invention is remarkable in a color developing solution having a high chloride concentration.

Next, the processing liquid used in the present invention will be described. In the present invention, the color developing solution used for the developing process is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. As the color developing agent, a paraphenylenediamine compound is preferable, and typical examples thereof include 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N- (β-hydroxyethyl) aniline, 3-
Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β-methoxyethyl) aniline and sulfates thereof, hydrochloric acid Salt, phosphate or p-
Toluenesulfonate and the like can be mentioned. These diamines are generally more stable in the form of a salt, and are preferably used in a salt form. Among these salts, p-toluenesulfonic acid salt is useful for increasing the concentration of the color developing agent. Among the above color developing agents, (1) 3-methyl-4-amino-N-ethyl-N- (β
-Hydroxyethyl) aniline (2) 3-methyl-4-amino-N-ethyl-N- (β
-Methanesulfonamidoethyl) aniline is preferable, and it may be preferable to use both depending on the purpose.

The color developing agent used in the present invention is usually 1 × 10 ^-2 to 2 × 10 per liter of color developing solution.
It can be used in the range of ^-2 mol, but when it is used in a color developing replenisher, it is 1.5 × 10 ^{−2 to} 2.0 × 10 ⁻¹
Mol / liter, preferably 2.0 × 10 ^{-2 to} 1.0 ×
10 ^-1 mol / l.

Preservatives used in the color developing solution used in the present invention include sulfites, and examples of the sulfites include sodium sulfite, sodium bisulfite, potassium sulfite and potassium hydrogen sulfite. 0
× 10 ⁻² mol / l or less, preferably 50 × 10 ⁻³ mol / l
1 or less, particularly preferably 0 from the viewpoint of rapidity. Further, preservatives other than sulfites include hydroxylamine and JP-A-63-146043 and JP-A-63-32547.
No., 63-146042, 63-146041
Nos. 63-146040 and 63-135938
And hydroxylamine derivatives described in JP-A-63-118748 and JP-A-64-62639,
No. 226,862, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes , Diamide compounds, condensed amines and the like are preferably used as organic preservatives. Among these, in the present invention, when the compound represented by the following general formula [2] or the general formula [B] and a dialkylhydrazine are used in a color developing solution, the effect of the present invention is particularly improved in terms of preventing stain. Plays well.

[0022]

Embedded image In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group,
Aryl group or However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring. In the general formula [2], R ₁ and R ₂ are not hydrogen atoms at the same time The alkyl groups represented by each may be the same or different,
Each is preferably an alkyl group having 1 to 3 carbon atoms. R 'represents an alkoxy group, an alkyl group or an aryl group.
The alkyl group and aryl group of R ₁ , R ₂ and R ′ include those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, piperidine, pyridine, triazine and morpholine. And a heterocyclic ring such as

[0023]

Embedded image In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ₁₄ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group. , An alkyl group, an aryl group, a heterocyclic group,
Represents an alkoxy group, an aryloxy group, a carbamoyl group or an amino group. The heterocyclic group is a 5- to 6-membered ring and is composed of atoms of C, H, O, N, S and a halogen atom. And n is 0 or 1. Especially n = 0
When, R ₁₄ represents an alkyl group, an aryl group, a group selected from the heterocyclic group, R ₁₃ and R ₁₄ may form a heterocyclic ring in cooperation.

Specific examples of the hydroxylamine compound represented by the general formula [2] are described in US Pat. No. 3,287,12.
Nos. 5, 3,293,034 and 3,287,12
No. 4, No. 4, etc., and particularly preferred specific exemplary compounds are described in Japanese Patent Application No. 2-172374, 51st.
-Diethylhydroxylamine, N-hydroxymorpholine and dimethoxyethylhydroxylamine on pages 53 to 53.

In the above general formula [B], R ₁₁ , R ₁₂ and R ₁₃
Is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably, R ₁₁ and R ₁₂ are each a hydrogen atom. In the general formula [B], R ₁₄ is preferably an alkyl group, an aryl group, a carbamoyl group or an amino group, particularly preferably an alkyl group and a substituted alkyl group. Here, preferable substituents of the alkyl group include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group and the like. Specific examples of the compound represented by the general formula [B] include 55 to 5 of Japanese Patent Application No. 2-172374.
The compounds described on page 9 are mentioned.

The compounds represented by the general formula [2] or [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonate, oxalate, phosphate, acetate and the like. The concentration of the compound represented by the general formula [2] or the general formula [B] in the color developing solution is
Usually 0.4 to 100 g / l, preferably 1.0 to 60 g
/ L, more preferably 2 to 30 g / l. Also,
The compound represented by the general formula [2] or the general formula [B] can be used in combination with a conventionally used hydroxylamine and various organic preservatives. It is preferable from the viewpoint of properties. Further, these compounds represented by the general formula [2] or [B] may be used alone or in combination of two or more. The color developing solution of the present invention preferably contains a triazinylstilbene-based fluorescent whitening agent from the viewpoint of the effects of the present invention, and is disclosed in Japanese Patent Application No. 2-172374, pages 65 to 67. Nylstilbene-based optical brighteners are particularly preferred.

The triazinylstilbene-based whitening agent preferably used in the present invention can be prepared by the usual method described in page 8 of "Fluorescent Whitening Agent" (published in August 1976, edited by the Chemical Industry Association of Japan). Can be synthesized. Japanese Patent Application No. 2-17
Among the exemplified compounds of the general formula (E) in JP-A-2374, particularly preferred are E-4, E-24, E
-34, E-35, E-36, E-37 and E-41. These triazinylstilbene-based brighteners are preferably in the range of 0.2 to 10 g, more preferably 0.4 to 5 g per liter of the color developing solution.

Further, the color developing solution used in the present invention may contain methyl cellosolve, methanol,
Acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, 44-95
No. 09 can be used as an organic solvent for increasing the solubility of the developing agent. Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexaulfate (methol), phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl -P-Phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably from 0.01 to 1.0 g / l. Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

In the present invention, the concentration of chloride (for example, potassium chloride, sodium chloride,
Ammonium chloride, etc.) is at least 4 × 10 ^-2 mol / l, preferably 6.0 × 10 ^-2 mol / l.
It is in the range of 3.0 × 10 ^-1 mol / l. 4.0x
If it is less than 10 ^-2 mol / l, the effect of the present invention is not sufficient, and if it is 3.0 × 10 ^-1 mol / l or more, the concentration is reduced even if the color developing agent has a high concentration. Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, cyclohexanediaminetetraacetic acid, etc., aminopolyphosphonic acids such as ethylenediaminetetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxy as a precipitation inhibitor Various metal chelate-forming compounds such as alkylidene diphosphonic acids represented by ethylidene-1,1-diphosphonic acid are used. The addition amount of these chelating agents is in the range of 0.1 to 20 g, preferably 0.2 to 8 g, per liter of the color developing solution.

Further, the color developing solution of the present invention preferably contains anionic, cationic, amphoteric or nonionic surfactants, and particularly the general formula described in Japanese Patent Application No. 2-38072. The compound [I] is useful for enhancing the effects of the present invention. In the present invention, the above color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0. Can be The treatment temperature is 36.0 ° C or higher, preferably 38.0 to 43.0 ° C, particularly preferably 38.5 to 41.
° C, and the processing time is 5 seconds or more and 35 seconds or less.

In the practice of the present invention, a nitrogen-containing heterocyclic compound, a compound containing a mercapto group, an aromatic compound, an onium compound, a compound having an iodine atom in the substituent, or the like can be used as an organic inhibitor. The replenishment amount of the color developing solution according to the present invention is generally 160 ml or less per 1 m ² of the light-sensitive material, preferably in the range of 20 ml to 120 ml, more preferably in the range of 30 ml to 100 ml, and most preferably. It ranges from 35 ml to 90 ml.

In the present invention, it is preferable that after the color development, processing is carried out with a processing solution having a bleaching ability, and the bleaching agent used in the bleaching solution or the bleach-fixing solution is an organic acid represented by the following formula (C) or (D): Ferric complex salts are preferably used in practicing the present invention.

[0033]

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The ferric organic acid complex represented by formula (C) or (D) is disclosed in JP-A-1-206340 and JP-A-1-20340.
No. 6342, each gazette, and Japanese Patent Application No. 2-240400,
No. 2-240401 are described in each specification, and among them, 1,3 diaminopropanetetraacetic acid ferric complex salt and glycol ether diaminetetraacetic acid ferric complex salt are particularly preferable.

That is, when the above-mentioned ferric organic acid complex salt is used for speeding up, bleaching fog is remarkable, and particularly remarkable in a mixing treatment, but can be effectively prevented by the practice of the present invention, and the effect is remarkable. Becomes

In the present invention, a complex salt with an aminopolycarboxylic acid iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, etc. is used in addition to the above-mentioned ferric organic acid complex salt. May be. These complex salts are available from Research Disclosure Nos. As described in No. 24023 (April 1984), various combinations can be used.

However, from the viewpoint that the effects of the present invention can be more favorably achieved, substantially the above-mentioned general formula (C) or (D)
A bleaching solution using only a ferric complex salt of the compound represented by formula (1) is preferred. Here, “substantially” means at least 70% (in terms of mol) or more of all the ferric complex salts. The ratio is preferably 80% or more, more preferably 90% or more,
Most preferably, it is 95% or more.

The ferric complex salt of the compound represented by the general formula (C) or (D) is used in an amount of at least 0.10 mol per liter of the bleaching solution, preferably from 0.15 mol to 1 mol.
It is in the range of 0.6 mol, more preferably in the range of 0.18 mol to 0.5 mol. When used in a bleach-fix solution, the amount is in the range of 0.03 mol to 0.3 mol, preferably 0.05 to 0.25 mol, per liter.

The processing solution having a bleaching ability according to the present invention includes the general formulas [I] to [I] described in Japanese Patent Application No. 2-41549.
It can contain the compound of the formula (IX) imidazole and its derivatives, and is preferably used because it has not only a bleach accelerating effect but also another effect of improving silver sludge.

These bleaching accelerators may be used alone or in combination of two or more, and good results are generally obtained in the range of about 0.01 to 100 g per liter of bleaching solution. . However, in general, when the amount is too small, the effect of accelerating bleaching is small, and when the amount is too large, precipitation may occur to contaminate the silver halide color photographic light-sensitive material to be processed. The amount is preferably 0.05 to 50 g, more preferably 0.05 to 15 g, per liter of the processing solution having the function.

When the bleaching accelerator is added, the bleaching accelerator may be added and dissolved as it is, but it is general to dissolve it in water, an alkali, an organic acid or the like in advance and then add it. And an organic solvent such as acetone or the like.

The bleaching solution is preferably used in a pH range of from 2.0 to 5.5, more preferably from 3.0 to 5.0. When the pH of the bleaching solution is 5.5 or more, bleaching fog cannot be sufficiently prevented, and when the pH is 2 or less, bleaching fog is prevented but photographic performance may be affected. The temperature for the treatment is preferably used at 20 ° C to 50 ° C, more preferably at 25 ° C to 45 ° C.

To the bleaching solution, a halide such as ammonium bromide is usually added and used. The bleaching solution contains a pH buffer consisting of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. May be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents, surfactants and deterrents can be added.

In the bleaching solution, ammonium ion accounts for 50 mol% or less of all cations, preferably 20 mol% or less,
In particular, it is preferably at most 10 mol%, in which case bleaching fog is prevented.

The preferred replenishing amount of the bleaching solution is from 20 ml to 400 ml, particularly preferably from 30 ml to 350 ml, more preferably from 40 ml to 300 ml, most preferably from 50 ml to 300 ml per m ^{2 of the} silver halide color photographic light-sensitive material. 250 ml.

The above-mentioned bleaching solution is preferably used immediately after color development during the processing step.

In the present invention, from the viewpoint of rapid processing, processing is preferably carried out with a bleaching solution and then with a fixing solution or a bleach-fixing solution.

A so-called fixing agent is essential for the fixing solution and the bleach-fixing solution. As the fixing agent, a compound which reacts with silver halide to form a complex salt in an aqueous solution, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate, sodium thioocyanate and ammonium thiocyanate Thiocyanate, or thiourea, thioether and the like, but preferably thiosulfate and thiocyanate,
Particularly preferred is thiocyanate. In the practice of the present invention, it is a preferred embodiment that the ammonium ion of the fixing solution or the bleach-fixing solution is 50 mol% or less, preferably 20 mol% or less of all cations as in the bleaching solution. Is effective in preventing stain.

In the fixing solution and the bleach-fixing solution, in addition to these fixing agents, ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite PH buffer consisting of various salts such as sodium sulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. May be used alone or in combination of two or more.

Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Borate, oxalate,
PH buffers such as acetates, carbonates and phosphates, alkylamines, polyethylene oxides and the like which are known to be added to ordinary fixing solutions and bleach-fixing solutions can be appropriately added. The fixing agent is used as a fixing agent in an amount of 0.1 mol or more per liter of processing solution, and preferably 0.1 mol.
3 mol to 4 mol, particularly preferably 0.5 mol to
It is used in a range of 3.0 mol, particularly preferably in a range of 0.6 mol to 2.0 mol.

In the present invention, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank, if desired, in order to increase the activity of the bleaching solution or bleach-fixing solution. Agents such as hydrogen peroxide, bromate, persulfate and the like may be added as appropriate.

In the present invention, silver may be recovered from the fixing solution or the bleach-fixing solution by a known method. For example, an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, German Patent No. 2,3)
31 and 220) Ion exchange method (Japanese Unexamined Patent Publication No.
-17114, German Patent 2,548,237
And the metal substitution method (British Patent 1,353,
805) can be used effectively.

It is particularly preferable to recover silver in-line from the tank liquid because the suitability for rapid processing is further improved, but silver may be recovered from the overflow waste liquid and reused.

In the present invention, the replenishing amount of the fixing solution and the bleach-fixing solution is preferably 800 ml or less per m ^{2 of the} light-sensitive material, and particularly good results are obtained when the replenishment amount is ^{20 to} 650 ml, particularly 30 to 400 ml per m ^{2 of the} light-sensitive material. obtain.

Further, iodide (ammonium iodide, potassium iodide, sodium iodide,
When the content of lithium iodide (0.1 g / L) is 0.1 g / L to 10 g / L, the effect of the present invention is further promoted.

Good results are obtained especially at 0.3 g / l to 5 g / l, especially at 0.5 g / l to 3 g / l, most preferably at 0.8 g / l to 2 g / l.

The fixing solution or the bleach-fixing solution is disclosed in Japanese Patent Application No. 2-41.
Use of the general formula [FA] or [FB] described in the specification of JP-A No. 549 is preferably used for achieving ammonia-free.

Further, a sulfurous acid adduct is preferably used in the fixing solution and the bleach-fixing solution. Examples of the sulfite adduct include general formulas (AI) to (A) described in Japanese Patent Application No. 41549/1990.
-II) is preferably used.

These sulfurous acid addition compounds are preferably used in the range of 0.1 g to 80 g, more preferably in the range of 0.5 g to 40 g, per liter of the processing solution.

The processing time of the bleaching solution and the processing solution having fixing ability (fixing solution or bleach-fixing solution) is preferably 3 minutes and 45 seconds or less in total, and more preferably 20 seconds or less.
It is within a range of 3 minutes 20 seconds or less, particularly preferably 40 seconds to 3 minutes, and particularly preferably 60 seconds to 2 minutes 40 seconds.

The bleaching time can be arbitrarily selected within the range of the above total time, but is preferably 1 minute 30 seconds or less, particularly preferably 10 seconds to 70 seconds, particularly preferably 20 seconds to 55 seconds. The processing time of the processing solution having a fixing ability can be arbitrarily selected, but is preferably 3 minutes and 10 seconds or less, and particularly preferably in the range of 10 seconds to 2 minutes and 40 seconds.

The crossover time between the color developing solution tank and the bleaching solution tank is preferably 10 to prevent bleaching fog.
In a preferred embodiment, the time is within seconds, particularly preferably within 7 seconds.

In the present invention, it is preferable to apply forced stirring to the bleaching solution, fixing solution and bleach-fixing solution.

Here, the forced stirring of the liquid means not the ordinary diffusion movement of the liquid but the forced stirring by adding a stirring means.

Means for forcibly stirring include the following methods. 1. 1. High pressure spraying method or spray stirring method 2. Air bubbling treatment method Ultrasonic oscillation processing method 4. Vibration treatment method The above specific method is described in Japanese Patent Application No. 2-41549.

Next, the stabilizer used in the present invention will be described. The stabilizing solution used in the present invention can be applied to a stabilizing solution used in a stabilizing process which is a final processing step of a silver halide color photographic light-sensitive material. Further, the present invention can also be applied to a case where a silver halide color photographic light-sensitive material is processed with a processing solution having a fixing ability, for example, a fixing solution or a bleach-fixing solution, and subsequently a stabilizing process is performed without substantially washing with water. .

The replenishing amount of the stabilizing solution is preferably 1 to 80 times the carry-in amount per unit area of the color light-sensitive material to be processed from the pre-bath. In the present invention, the pre-bath component (the bleach-fixing solution) in the stabilizing solution is used. Or fixing solution) in the final tank of the stabilizing solution tank is 1/100 or less.
/ 100 to 1/100000, preferably 1/200 to
It is preferable to configure the treatment tank of the stabilization tank so as to be 1 / 50,000.

The stable treatment tank may be composed of a plurality of tanks, and it is preferable for the present invention that the number of the plurality of tanks is two or more and six or less.

In the present invention, in the case of two or more tanks, it is particularly preferable to use a counter current method (a method in which the solution is supplied to a post-bath and overflows from a pre-bath), particularly from the viewpoint of low pollution and improvement of image preservation.

The carry-in amount varies depending on the type of the photosensitive material, the transport speed of the automatic developing machine, the transport system, the squeezing method on the surface of the photosensitive material, and the like. For a color photosensitive material, the carry-in amount is usually 50 ml / m ^{2 to} 150 ml / m ^{2. 2} , and the replenishment amount at which the effect of the present invention on the carry-in amount is more remarkable is 5
The range is from 0 ml / m ^{2 to} 4.0 liters / m ² , and the replenishment amount with a particularly remarkable effect is from 100 ml / m ^{2 to} 1500 ml / m ^2.
It is in the range of ² .

The treatment temperature of the treatment with the stabilizing solution is 15 to 60.
° C, preferably in the range of 20 to 45 ° C. The stabilizer used in the present invention preferably contains a chelating agent represented by any one of the general formulas [CH-I] to [CH-III] described in Japanese Patent Application No. 2-41549.

The chelating agent preferably used in the above-mentioned stabilizing solution is used in an amount of 0.1 to 1 liter of the stabilizing solution used in the present invention.
The amount is preferably from 0.1 to 100 g, more preferably from 0.05 to 50 g, particularly preferably from 0.1 to 2 g.
0 g.

The pH value of the stabilizer is preferably in the range of 4.0 to 9.0, more preferably 5.5 to 9.0, for the purpose of improving image storability.

As the pH adjusting agent that can be contained in the stabilizing solution, any of generally known alkali agents and acid agents can be used.

The stabilizing solution includes organic acid acids (citric acid, acetic acid,
Succinic acid, oxalic acid, benzoic acid, etc.), pH adjuster, (phosphate, borate, hydrochloric acid, sulfate, etc.), surfactant, preservative, Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr
And the like can be added. The amount of addition of these compounds is the amount necessary to maintain the pH of the stabilizing bath,
Any combination may be used as long as it does not adversely affect the stability of the color photographic image during storage and the occurrence of precipitation. C in the stabilizer
It is also preferable that a and Mg ions be 5 ppm or less in order to achieve the above-mentioned effects.

The antifungal agent preferably used in the stabilizer used in the present invention is a hydroxybenzoate compound,
Phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds,
Morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, and benztriazole compounds.

More preferred are phenolic compounds, thiazole compounds and benzotriazole compounds in view of their liquid preservability.

Specific examples include 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazoline3-one.
On, 2-octyl-4-isothiazoline 3-one, 5
-Chloro-2-methyl-4-isothiazolin-3-one,
Examples thereof include sodium 0-phenylphenol and benztriazole. The amount of these fungicides to be added to the stabilizer is preferably in the range of 0.001 g to 20 g per liter, particularly preferably in the range of 0.005 g to 10 g.

Further, in the stabilizing solution, Japanese Patent Application No. Hei.
Nos. 6 and 2-234780, for example, formalin, hexamethylenetetramine, triazine compounds, N-methylol compounds (dimethylolurea, trimethylolurea, dimethylolguanidine,
N-hydroxymethylhydroxyethylamine, trimethylol melamine, etc.), aliphatic aldehyde and the like can be used in combination, but it is preferable to reduce formalin to substantially 0 from the viewpoint of pollution, This is also a preferred embodiment.

The stabilizer used in the present invention contains surfactants represented by the general formulas [I] and [III] described in Japanese Patent Application No. 2-41549, triethanolamine and polyvinylpyrrolidones. Is preferred.

The addition amount of these surfactants and water-soluble organic siloxane compounds is 0.0
Good results are obtained when used in the range of 1 to 20 g.

When the amount is less than 0.01 g, stains on the surface of the light-sensitive material are conspicuous, and when the amount is more than 20 g, a large amount of the organic siloxane compound adheres to the surface of the light-sensitive material and becomes dirty.

The above water-soluble organosiloxane compounds are described, for example, in JP-A-47-18333 and JP-B-55-511.
No. 72, JP-B-51-37538, JP-A-49-62
No. 128 and U.S. Pat. No. 3,545,970 and the like, and mean a general water-soluble organic siloxane compound. These water-soluble organic siloxane compounds can be generally obtained from UCC (Union Carbide), Shin-Etsu Chemical Co., Ltd., or the like.

Next, the photosensitive material to which the processing method of the present invention is applied will be described. The color light-sensitive material of the present invention is silver chloride-based silver halide grains containing silver chloride at least 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and most preferably 99 mol% or more. Those containing at least mol% are used. Such a silver chloride-based silver halide emulsion can contain silver bromide as a silver halide composition in addition to silver chloride.
Silver bromide is preferably at most 20 mol%, more preferably 1 mol%.
0 mol% or less, more preferably 3 mol% or less;
When silver iodide is present, it is preferably at most 1 mol%, more preferably at most 0.5 mol%, most preferably zero. Such silver halide grains mainly comprising silver chloride of 80 mol% or more may be applied to at least one silver halide emulsion layer, but are preferably applied to all silver halide emulsion layers. Is Rukoto.

The crystal of the silver halide grain may be a normal crystal, a twin crystal or other crystal, and may have [1,0,0] plane and [1,0] plane.
[1,1] Any ratio can be used for the plane. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and the outside are different. Also,
These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain.
Furthermore, tabular silver halide grains (JP-A-58-1139)
No. 34, Japanese Patent Application No. 53-17070) can also be used. Japanese Patent Application Laid-Open Nos. 64-26837 and 64-6437.
Silver halides described in JP-A-26838 and JP-A-64-77047 can be used.

Further, the silver halide grains may be prepared by an acid method,
It may be obtained by any adjustment method such as a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method, and further grown by an ammonia method having a high growth rate to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ion corresponding to the growth rate of the silver halide grains as described in, for example, JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention has a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color coupler is advantageously incorporated in or in close proximity to the photosensitive layer in non-diffusible form.

Thus, the red-sensitive layer can contain, for example, a non-diffusible color coupler for forming a cyan partial color image, generally a phenol or α-naphthol coupler. The green light-sensitive layer can include, for example, at least one non-diffusible color coupler that produces a magenta partial color image, usually a 5-pyrazolone-based color coupler and a pyrazolotriazole. The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a color coupler having an open chain ketomethylene group. The color coupler can be, for example, a 6, 4 or 2 equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred. Suitable couplers are disclosed, for example, in the following publications: Agfa's work report (Nitteilunglnaus)
den Forschungslaboratorien der Agfa), Leverkusen / Munchen, Vol.
III. P. 111 (1961), "Color coupler" by W. Pelz (Farbkuppler);
K. Venkataraman, "The Chemistry of Synthetic Soy" (The Ch
emistry of Synthetic Dyes), Vol. 4, 341-3
87, Academic Press, The Theory of the Photographic Process, 4
Edition, pages 353-362; and Research Disclosure No. 17643, section VII.

In the present invention, in particular,
No. 106655, p. 26, a magenta coupler represented by the general formula [M-1] (a specific example of these magenta couplers is described in JP-A-63-106).
No. 655, p. 1 to No.
77. ), And a cyan coupler represented by the general formula [C-I] or [C-II] also described on page 34 (specific examples of cyan couplers are described in the same specification,
(C′-1) to (C′-82) described on pages 37 to 42,
(C "-1) to (C" -36)) and the high-speed yellow coupler also described on page 20 (specific examples of cyan couplers include (Y ') described on pages 21 to 26 of the same specification). -1) to (Y'-39)) are preferred from the viewpoint of the effects of the present invention.

When a nitrogen-containing polycyclic mercapto compound is used in a light-sensitive material, not only the effect of the present invention is exerted well, but also the photographic performance caused when a bleaching solution or a bleach-fixing solution is mixed in a color developing solution. This has another effect of making the influence on the surface extremely small, and thus can be cited as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing bicyclic mercapto compounds are described in JP-A-63-106655,
(I'-1) to (I'-87) described on pages 42 to 45.

The silver halide emulsions can be prepared by conventional methods (eg, single or double inflow with constant or rapid acceleration of the material). Particularly preferred is the method of adjustment by the double inflow method while adjusting the pAg; 17643, see sections I and II.

Emulsions can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, such as those described in Belgian Patents 493,464 and 56;
Silver compounds as described in US Pat. No. 8,687, and polyamines or aminomethylsulfinic acid derivatives such as, for example, diethylenetriamine according to Belgian Patent 547,323. Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is described in the article by R. Kosiovsky in Z. Wiss. Photo 46 , 65-72 (1951). Research Disclosure N
o. See also 17643, Section III.

Emulsions are prepared in optically known manner, for example using conventional polymethine dyes such as neuthocyanins, basic or acidic carbocyanines, rhodocyanines, hemicyanines, styryl dyes, oxonols and the like.
Can sensitize: FM Hammer (FM Ha
mer) 「Cyanine Dyes and related Compoun」
ds) (1964) Ullmanns Enzyklpadie der
technischen Chemie) 4th edition, volume 18, page 431 and the following, and the above-mentioned Research Disclosure No. 17
643, see section IV.

For the emulsion, conventional antifoggants and stabilizers can be used. Azaindene is a particularly suitable stabilizer, preferably tetra and pentaazaindene, especially those substituted with a hydroxyl or amino group. Compounds of this kind are described, for example, in Birr, Zeitschrift Für, Z. Wiss. Photo 47, 195.
2, p. Nos. 2 to 58 and Research Disclosure Nos. 17643, section IV.

The components of the light-sensitive material can be contained by a conventional method; for example, US Pat.
027, 2,533,514, 3,689,2
Nos. 71, 3,764, 336 and 3,765, 8
See No. 97. Components of photosensitive material such as couplers and UV
The absorbent can also be contained in the form of a charged latex; see DE 2,541,274 and EP 14,921. The components can also be fixed in the light-sensitive material as polymers; for example, DE 2,044,992, U.S. Pat.
See Nos. 70,952 and 4,080,211. In the present invention, the amount of silver in the silver halide color photographic light-sensitive material is preferably 0.75 g or less per 1 m ^{2 of the} photographic material, and more preferably 0.2 to 0.7 g.

As the support of the light-sensitive material, an ordinary support can be used. For example, in the case of color paper, reflective supports are used, such as paper supports, and these can be coated, for example, with polyolefins, especially polyethylene or polypropylene; 17643 section VVI
reference.

If the light-sensitive material is a light-sensitive material containing a coupler and processed by a so-called internal developing method, color paper, color negative film, color positive film, color reversal film for slide, color reversal film for movie,
The present invention can be applied to any photosensitive material such as a color reversal film for TV and a reversal color paper.

[0101]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. Example 1 Each layer having the following constitution was coated on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side. A color photographic light-sensitive material (1) was prepared. The coating solution was prepared as described below. First layer coating solution Yellow coupler (Y-1) 26.0 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67
g and 0.53 g of the additive (HQ-1) were dissolved in 6.3 g of a high boiling point organic solvent (DNP) by adding 60 ml of ethyl acetate.
This solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of a 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. (H-1) was added to the second and fourth layers as a hardener, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) as coating aids
Was added to adjust the surface tension.

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[Method for Preparing Blue-Sensitive Silver Halide Emulsion] 4
The following (Solution A) and (Solution B) were added in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C. with pAg = 6.5 and pH = 3.0.
Over 30 minutes while controlling at the same time.
Solution) and (D Solution) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, pA
g was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Silver nitrate 10 g Add water 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water 600 ml (Solution D) 300 g of silver nitrate Water was added and after the addition of 600 ml, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. 0.85μ particle size
m, coefficient of variation (σ / r) = 0.07, silver chloride content 9
A 9.5 mol% monodispersed cubic emulsion EMP-1 was obtained. The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-1).
-B) was obtained. Sodium thiosulfate 0.8 mg / mol Ag X chloroauric acid 0.5 mg / mol Ag X stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol Ag X sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol Ag X sensitizing dye BS-2 1 × 10 ^-4 mol / mol Ag X

[Preparation Method of Green-Sensitive Silver Halide Emulsion]
(Solution A) and (solution B) addition time and (solution C) and (solution D)
Except for changing the addition time of EMP-1,
Average particle size 0.43 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained. EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G). Sodium thiosulfate 1.5 mg / mol Ag X chloroauric acid 1.0 mg / mol Ag X stabilizer STAB-1 6 × 10 ^-4 mol / mol Ag X sensitizing dye GS-1 4 × 10 ^-4 mol / mol Ag X [Preparation method of red-sensitive silver halide emulsion] (solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodisperse cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation (σ / r) of 0.08, and a silver chloride content of 99.5 mol% was obtained.
EMP-3 was subjected to chemical ripening at 60 ° C. for 90 minutes using the following compounds to give a red-sensitive silver halide emulsion (Em-R).
I got Sodium thiosulfate 1.8 mg / mol Ag X chloroauric acid 2.0 mg / mol Ag X stabilizer STAB-1 6 × 10 ^-4 mol / mol Ag X Sensitizing dye RS-1 1 × 10 ^-4 mol / mol Ag X

[0112]

Embedded image

[0113]

Embedded image The color paper sample thus prepared contained 99.5 mol% of silver chloride. The silver chloride content was varied as shown in Table 3 below to prepare and use color paper samples for experiments. This sample was exposed to a wedge according to a conventional method, and then subjected to a running process according to the following processing step (1).

[0114]

[Table 3]

(Color developing tank solution) Diethylene glycol 10 g Potassium bromide 0.03 g Potassium chloride It was added so as to have a Cl ^- concentration shown in Table 4. Potassium sulfite (50% solution) 0.5 ml Color developing agent (described in Table 4) Described in Table 4 Compound represented by general formula (1) Described in Table 4 (described in Table 4) Diethylhydroxylamine 5 g Triethanolamine 10 g Potassium carbonate 30 g Diethylenetriaminepentaacetic acid 2 g Fluorescent whitening agent (Exemplified compound E-34) 2 g Water was added to make the whole volume 1 L, and the pH was adjusted to 10.15 with potassium hydroxide or sulfuric acid.

(Color developing replenisher) Diethylene glycol 17 g Potassium sulfite (50% solution) 1.0 ml Color developing agent (described in Table 4) Compound shown in Table 4 Compound represented by general formula (1) described in Table 4 (Table 4) 7 g) Diethylhydroxylamine 7 g Triethanolamine 10 g Potassium carbonate 40 g Diethylenetriaminepentaacetic acid 2 g Fluorescent whitening agent (Exemplary compound E-34) 2.5 g Water was added to bring the total volume to 1 liter, and the pH was adjusted to 11.1 with potassium hydroxide or sulfuric acid. Adjusted to zero. (Bleaching tank liquid) 1,3-diaminopropanetetraacetic acid ferric ammonium 0.35 mol ethylenediaminetetraacetic acid 2 g ammonium bromide 125 g glacial acetic acid 50 ml ammonia water (25%) 38 ml Add water to make 1 liter, and add ammonia water or Adjust the pH appropriately to 4.5 using glacial acetic acid. (Bleaching replenisher) Ferric ammonium 1,3-diaminopropanetetraacetic acid 0.42 mol Ethylenediaminetetraacetic acid 2 g Ammonium bromide 178 g Glacial acetic acid 50 ml Ammonia water (25%) 23 ml Add water to make 1 liter, add ammonia water or Adjust the pH appropriately to 3.2 using glacial acetic acid.

(Fixing Tank Solution and Fixing Replenisher) Ammonium thiosulfate 250 g Sodium metabisulfite 20 g Ethylenediaminetetraacetic acid 0.8 g Water was added to make 1 liter, and the pH was adjusted to 6.5 using acetic acid and aqueous ammonia. (Stabilizing tank solution and stabilizing replenisher) ortho-phenylphenol 0.15g ZnSO ₄ · 7H ₂ O 0.2g bismuth chloride 0.5g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60% solution) 3.8 g Ethylenediaminetetraacetic acid 2.0 g Fluorescent brightener (Tinopearl SFP Ciba-Geigy) 2.0 g Adjust the pH to 7.8 with aqueous ammonia or 50% sulfuric acid and make up to 1 liter with water. In the running process, the automatic developing machine is filled with the above-described color developing tank solution, and the bleaching tank solution, the fixing tank solution and the stabilizing tank solution are filled. The solution, fixing replenisher and stable replenisher were replenished through a metering pump.

The magenta density (reflection density) of the unexposed portion and the yellow dye density (reflection density) of the exposed portion (maximum density portion) of the processed color paper sample immediately after the completion of the running process were measured. Subsequently, a running process was continuously performed until the total replenishment amount of the developing solution became three times the developing tank solution. At the end, the wedge-exposed color paper sample was processed to measure the yellow-dye density (reflection density) of the exposed portion (maximum density), and the density difference from the pretreatment was determined and evaluated. Further, the state of precipitation (crystal precipitation) of the solution at the end of the running process and the developing tank solution after the completion of the running process were allowed to stand at room temperature for 10 days, and the occurrence of tar in the developing tank solution tank was observed. Table 5 summarizes the results.

[0119]

[Table 4]

[Table 5] As shown in Table 5, a silver halide color photographic light-sensitive material having an average silver chloride ratio of 80 mol% or more in a silver halide emulsion, a Cl ^- concentration of 4 × 10 ^-2 mol / l or more, and a color developing agent of 1.0 or more were used. By processing with a color developer containing at least × 10 ^-2 mol / l and the compound represented by the general formula (1) I-32, rapid processing is possible, stain is prevented, and excellent processing stability is obtained. It turns out that it is possible.

(Example 2) Using the photosensitive material prepared in Example 1 and the color developing solution used in Example 1, a running process was performed with the following processing solution according to the following processing step (2). Processing step (2) Temperature Processing time Replenishment rate (ml / m ² ) (1) Color development 39 ° C. 25 seconds 40 (2) Bleaching and fixing 39 ° C. 30 seconds 51 (3) Stable * 30 ° C. First layer 25 seconds 120 2 Layer 25 seconds (4) Drying 60-80 ° C. 30 seconds * The first and second layers of the stabilization tank are of counter current type, and the replenisher was replenished to the second layer.

[Bleach-fixing tank solution and replenisher] Ferric ammonium salt of ethylenediaminetetraacetic acid 53.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 123.0 g Ammonium sulfite (40% solution) 51.0 g Ammonia Adjust the pH to 5.4 with water or glacial acetic acid and add water to make the total volume 1 liter. [Stabilizing tank and Replenisher] ortho-phenyl phenol 0.1g Uvitex (Ciba _{Geigy) 1.0g ZnSO 4 · 7H 2 O} 0.1g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1 -Diphosphonic acid 3.0 g (60% volume solution) Ethylenediaminetetraacetic acid 1.5 g Adjust pH to 7.8 with aqueous ammonia or sulfuric acid and add 1 with water.
Liters.

In the running process, an automatic developing machine is filled with the above-mentioned processing solution and the color paper sample is processed while being processed.
The color developing replenisher, the bleach-fix replenisher and the stable replenisher were replenished through a metering pump at every minute interval.
The running process was performed until the total amount of the color developing solution replenisher replenished in the color developing tank solution was three times the volume of the color developing tank solution. The evaluation was performed in exactly the same manner as in Example 1. The results were exactly the same as those in Example 1, and it was found that the present invention exhibited an effect even in the case of performing bleach-fixing-stabilizing processing after color development.

Example 3 Based on Sample 1 having an average silver chloride content of 99.5 mol% prepared in Example 1, the following Table 6 was used.
The color paper samples 2-1 to 2-4 for experiments were prepared by changing the amount of silver applied as shown in FIG. These samples were prepared in Example 1.
In the processing step (1). The treatment liquid used in Experiment 1-7 of Example 1 was used.

[Table 6] The experiment and evaluation were performed in the same manner as in Example 1, and the results are summarized in Table 7.

[0124]

[Table 7] Table 7 shows that the effect of the present invention is favorably exhibited when the coated silver amount of the photosensitive material sample is 0.75 g / m ² or less.

(Example 4) Using the color paper sample prepared in Example 1 and wedge exposure according to a conventional method, a running process was performed according to the processing step (1) of Example 1, and
Experiments and evaluations were performed in the same manner as in Example 1. Table 8 shows the results. The processing solutions used in the experiments were as follows. Of [color developing tank solution] Diethylene glycol 15g Potassium bromide 0.03g Potassium chloride Table 8 [Cl ^-]
Was added so that Potassium sulfite (50% solution) 0.5 ml Color developing agent listed in Table 8 Triethanolamine 10 g Potassium carbonate 30 g Diethyleneamine pentaacetic acid 2 g Fluorescent brightener (Exemplary compound E-34) 2 g General formula (2) or (B) (Described in Table 8) The compound represented by Table 8 is represented by the general formula (1) (Described in Table 8) The description is described in Table 8 The total amount is made up to 1 liter by adding water, and the pH is adjusted to 10.15 with potassium hydroxide or sulfuric acid. did.

[Color developing replenisher] Diethylene glycol 17 g Potassium sulfite (50% solution) 1.0 ml Color developing agent Described in Table 8 Compound represented by general formula (1) Described in Table 8 (described in Table 8) Preservative Described in Table 8 Triethanolamine 10 g Potassium carbonate 40 g Diethylenetriaminepentaacetic acid 2 g Fluorescent whitening agent (Exemplified compound E-34) 2.5 g Water was added to make the total volume 1 L, and the pH was adjusted to 12.0 with potassium hydroxide or sulfuric acid. did. [Bleaching tank, replenisher] [Fixing tank, replenisher] and [stabilizing tank and replenisher] used in Example 1 were used.

[0127]

[Table 8] It can be seen that the effects of the present invention can be more favorably obtained by adding the compound represented by the general formula (2) or (B), and it is particularly preferable to add 2 g or more.

(Example 5) Using the color paper sample prepared in Example 1 and wedge exposure according to a conventional method, Example 1
A running process was performed in accordance with the processing step (1), and experiments and evaluations were performed in the same manner as in Example 1. Table 9 shows the results. The processing liquid used in the experiment was the same as that of Experiment No. 1-13 of Example 1.
The processing solution used in the above was used. However, the fluorescent whitening agent (Exemplified Compound E-34) was changed as shown in Table 9.

[0129]

[Table 9] As can be seen from Table 9, the effect of the present invention can be obtained more favorably by using the compound (fluorescent whitening agent) represented by the general formula [E] in combination in the color developer used in the processing method of the present invention. You can see that.

Example 6 The same evaluation as in Example 5 was carried out, except that the compound I-32 of the present invention used in Example 5 was replaced with I-2, I-21, I-20 or I-37. As a result, almost the same tendency as that of I-32 was obtained, but the generation of sediment and tar after the running treatment was slightly inferior.

[Table 5]

Experiment No. 1 of Example 1 The same experiment as in Example 1 was performed except that the processing time of the color development processing step used in 1-26 was changed to the processing time shown in Table 10 below. Table 10 shows the results.

[Table 10] From Table 10 above, when the color development processing time is 5 to 35 seconds, the magenta density (stain) of the unexposed portion, the yellow density of the exposed portion, the yellow density difference of the exposed portion of the continuously processed wedge, It can be seen that good results can be obtained in all of the occurrence of sediment after the running treatment and the occurrence of tar after standing at room temperature for 10 days.

Continued on the front page (72) Inventor Masao Ishikawa 1 Konica Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (56) References JP-A-2-96138 (JP, A) JP-A-2-77743 (JP, A JP-A-62-234161 (JP, A) JP-A-62-242938 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/407 G03C 7/413

Claims (3)

(57) [Claims] 1. A method according to claim 1, wherein the silver halide emulsion coated on the support has an average silver chloride content of 80 mol% or more. The chloride concentration in the processing solution for color development processing is 4 × 10 ^-2 mol / l or more, the color developing agent concentration is 1.0 × 10 ^-2 mol / l or more, and the following general formula (1)
1 liter of the processing solution for color development processing
Contains 10g to 80g per Torr , 5 to 35 seconds
A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed for a color development processing time of Formula _{(1) R-SO 3 X} ( wherein, R is a polymer having these repeating units represent an alkyl group or a phenyl group having 1 to 8 carbon atoms, still more R a ethylenically unsaturated group X represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or an ammonium group.) 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the amount of silver in the silver halide color photographic light-sensitive material is 0.75 g / m ² or less. 3. A method for processing a silver halide color photographic material according to claim 1, wherein the processing solution for color development processing contains a compound represented by the following general formula (2). . Embedded image (Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an aryl group or . However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may combine to form a ring. )