JPH0746216B2 - Method of processing silver halide color photographic light-sensitive material enabling rapid processing - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, a silver halide suitable for rapid processing without stain in an unexposed area even in continuous processing. The present invention relates to a method for processing a color photographic light-sensitive material.

BACKGROUND OF THE INVENTION Development processing of a silver halide color photographic light-sensitive material basically consists of three steps of color development, desilvering and washing with water, and desilvering is performed by bleaching and fixing or bleaching and fixing in the same bath. It will be one of the bleach-fixing steps.

Recently, an anhydrous washing treatment called a stabilizing treatment has been proposed instead of the water washing process, which is used for color development, bleach-fixing and stabilizing treatment.
It is well known that processing consisting of steps is actively carried out. In these color photographic systems, a non-diffusible coupler is generally contained in the photographic emulsion layer and development is carried out with a color developing agent in a color developing solution, but a diffusible water-soluble coupler is contained in the color developing solution. It is also known to cause coupling reactions in photographic materials. The coupler to be contained in the light-sensitive material is generally made non-diffusible by being dispersed in a water-insoluble high boiling point organic solvent and added.

This method is very generally carried out because it is advantageous in terms of color reproducibility, color purity, image storage stability, etc., rather than making a non-diffusive property by introducing a high molecular weight alkyl side chain into a coupler as a ballast group. It is being appreciated. It is well known that a color developing solution for processing such a light-sensitive material contains an aromatic primary amine type color developing agent and a poorly soluble organic solvent (logP 0.4 or more solvent). The best known organic solvent of this type is a poorly soluble alcohol, which accelerates the reaction between the color developing agent and the image forming coupler.
That is, it is used to enhance the efficiency of the coupling reaction. This type of alcohol is often a "development accelerator"
Or called "Development Booster". U.S. Pat.No. 2,304,
Benzyl alcohol is particularly useful for this purpose, as seen in 925 or 3,814,606.

However, the poorly soluble solvent represented by the above benzyl alcohol has a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since the treatment has a problem that it requires a great deal of labor and cost, etc., investigation is being conducted in the direction of reducing or eliminating its use as much as possible.

Further, the stabilization treatment in which a large amount of washing water is supplied to wash the light-sensitive material cleanly, instead of the washing treatment, which is performed with a small amount of liquid, so-called washing substitute stabilization treatment saves water quality sources, pollution, etc. In consideration of the above, there is a strong demand.

These anhydrous washing stabilization treatments are described in JP-A-58-14834 and 58-58.
-105145, 58-134634, 58-18631 and Japanese Patent Application
It is described in detail in the specifications such as 58-2709 and 59-89288.

Further, in recent years, as a part of improving services for users, quick services have become popular, and some services are also provided for processing exposed films on the spot and handing prints to customers. Against the background of the demand of the era of shortening the delivery time, there is also a strong demand for short-time processing, that is, speeding up of processing.

The present inventors have achieved rapid processing without using a poorly soluble solvent represented by benzyl alcohol and using a silver halide color photographic light-sensitive material having a silver chlorobromide emulsion suitable for rapid processing. As a result of various studies on a system for increasing the pH of the color developing solution and a system for increasing the concentration of the main agent, rapid processing was basically possible, but continuous processing was carried out especially using a washing alternative stabilization treatment. In this case, there was a problem that color fog (stain) was generated in the unexposed portion of the light-sensitive material.

The stain in the unexposed area is such that the sensitizing dye contained in the light-sensitive material can be obtained by performing a stabilizing treatment instead of washing with water in a short time without using the poorly soluble solvent represented by benzyl alcohol. It is expected that one of the causes is that it is not washed off sufficiently and remains on the light-sensitive material. Also, it is due to the accumulation of silver or color developer components in the bleach-fix bath due to high pH and high concentration of color developing agent. However, especially when the silver halide is silver chlorobromide, color fog (cyan color) is also expected to occur. Basically, there are some stains that disappear when rewashed with water and some stains that disappear. However, the stain generation mechanism and the like are still unclear, and studies on the prevention of stains are ongoing by trial and error.

While continuing the research on the premise of the rapid processing, the present inventors color-developed a specific sulfonic acid derivative having both a stain which is expected to remain of the sensitizing dye and a stain which is expected to be color fog. The inventors have found that the problems can be solved at the same time by using it in a liquid, and have completed the present invention.

The sulfonic acid derivative described above is obtained from British Patent No. 669,505.
No. 837,491 and JP-A-51-147322, as an aromatic sulfonic acid derivative in which a sulfonic acid or a salt thereof is bound to an aromatic nucleus such as benzene, which is a part thereof, and JP-A-51-8.
No. 0229 is known as an aliphatic sulfonic acid derivative in which a sulfonic acid is bonded to an alkyl group, but in the above publications, both are used as a precipitation inhibitor of a color developing agent, and There is no description about the effect of preventing stain, which is expected to be the above two different causes.

[Object of the Invention] Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material suitable for rapid processing without stain in an unexposed area even in continuous processing using a water-washing alternative stabilizing process which can reduce pollution and cost. It is to provide a method of processing materials.

[Construction of the Invention] The above-mentioned object of the present invention is, after imagewise exposure of a silver halide color photographic light-sensitive material having a plurality of silver halide emulsion layers,
In the method for processing a silver halide color photographic light-sensitive material, which is processed by at least a color developing step, a bleach-fixing step, and a washing and stabilizing alternative stabilizing step, the color developing solution used in the color developing step has a pH of 1
0.3 or more, and the color developing solution contains a p-phenylenediamine compound having a water-soluble group as a color developing agent, and the color developing solution contains a compound represented by the following general formula [1]. general formula [1] in R-SO ₃ X (wherein containing, R represents an alkyl group or a phenyl group having 1 to 8 carbon atoms, having these repeating units in addition R is an ethylenically unsaturated group It may be a polymer, and X represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or an ammonium group.).

[Specific Structure of the Invention] The color developer used in the present invention is a compound represented by the general formula [I] (hereinafter referred to as a sulfonic acid derivative of the present invention).
Contains.

In the general formula [I], the number of carbon atoms represented by R is 1 to
The alkyl group of 8 may be linear or branched, and includes those having a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl group, etc.), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including a salt thereof), a sulfonic acid group (a salt thereof) (Including) and the like. 1 to 8 carbon atoms represented by R
Examples of the alkyl group include methyl group, carboxymethyl group, phenylmethyl group, ethyl group, hydroxyethyl group, sulfonylethyl group, propyl group, butyl group, heptyl group, octyl group and the like.

The phenyl group represented by R includes those having a substituent, and the substituent includes a halogen atom (for example, a chlorine atom,
Bromine atom, etc., alkyl group (preferably having 1 to 1 carbon atoms)
4 alkyl groups such as methyl group, ethyl group, propyl group, butyl group), hydroxyl group, amino group, nitro group, carboxylic acid group (including its salt), sulfonic acid group (including its salt), etc. And the substituent on the phenyl group is 1
The number of substituents may be the same or different, and in the case of 2 to 5, the substituents may be the same or different.

Further, R may be an ethylenically unsaturated group and may be a polymer having these repeating units.

R is preferably a phenyl group and preferably has a substituent, and a preferable substituent has 1 to 1 carbon atoms.
4 alkyl group, hydroxyl group, carboxylic acid group (including its salt), and sulfonic acid group (including its salt).

Specific examples of the sulfonic acid derivative of the present invention represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.

Exemplified compound In the above exemplified compounds, all of the sulfonic acid groups and the carboxylic acid groups are represented by hydrogen atoms, but since they are used in the color developing solution which is an alkaline solution, the sodium salt, potassium salt, lithium salt, etc. of each compound are used. Naturally, the compound of the salt of is included.

Some of the sulfonic acid derivatives of the present invention, the British Patent No. 669,505, 837,491, JP-A-51-147322, 5
No. 1-80229, and can be easily obtained by those skilled in the art.

The sulfonic acid derivative of the present invention may be used alone or in combination of two or more kinds, and the usage amount is 2. per color developing solution.
It is preferably used in 0-200g, more preferably
It is 3.0 to 50 g.

The color developing agent used in the color developing solution of the present invention is a p-phenylenediamine compound having a water-soluble group.

The p-phenylenediamine compound having a water-soluble group is
Compared with para-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, not only does it have the advantage of not contaminating the light-sensitive material and being less prone to skin rash, In the invention, the object of the present invention can be efficiently achieved by combining with the sulfonic acid derivative of the present invention represented by the general formula [I].

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a Gukyu water solubility group _{- (CH 2) n-CH} 2 OH, - _{(CH 2) m-NHSO 2} - (CH 2) n-CH 3, - (CH 2) mO- (CH 2) n-CH 3, - (CH 2 CH 2 O) nCmH2m + 1 (m and n are each 0 The above integers are shown), —COOH group, —SO ₃ H group and the like are preferable.

Specific examples of the water-soluble group-containing color developing agent used in the present invention are shown below, but the present invention is not limited thereto.

Illustrative color developing agent Of the above-illustrated color developing agents, the compounds shown in Exemplified Nos. (1), (3) and (4) are preferable for use in the present invention, and No. (1) is particularly preferable.

The color developing agent is usually used in the form of salt such as hydrochloride, sulfate, p-toluenesulfonate.

The color developing agent having a water-soluble group used in the present invention is
Usually, it can be used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developing solution, but from the viewpoint of rapid processing and solubility of the main agent, 1 × 10 ^-2 to 2 per color developing solution. × 10
^-1 mol is preferred.

In the color developer of the present invention, as a preservative, for example, sodium sulfite, potassium sulfite, sodium bisulfite, sulfite salts such as potassium bisulfite, and further bisulfite adducts of aldehydes or ketones, for example, bisulfite addition of formaldehyde. Bisulfite adduct of glutaraldehyde can be used.

In the present invention, it is preferred that the hydroxylamine conventionally used as a preservative is not substantially contained. Here, hydroxylamine includes free amines and water-soluble acid addition salts such as sulfates, oxalates, hydrochlorides, phosphates, carbonates and acetates. Further, "contains substantially no" means that the concentration of hydroxylamine in the color developer is 1
This means that the amount is 0.007 mol or less, but 0 is most preferable.

By not using this hydroxylamine, the effect of the present invention, that is, the prevention of stain can be efficiently achieved.

The color developer of the present invention can contain the following developer components in addition to the above components.

Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Sodium, tripotassium phosphate, borax and the like can be used alone or in combination. Further, for the purpose of preparation, or for the purpose of increasing ionic strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate,
Various salts such as sodium bicarbonate, potassium bicarbonate and borate can be used.

If necessary, inorganic and organic antifoggants can be added, and as these antifoggants,
For example, inorganic halide compounds such as sodium bromide, potassium bromide, sodium iodide and potassium iodide, 6-nitrobenzimidazoles described in US Pat. No. 2,496,940, and 5 described in US Pat. Nos. 2,497,917 and 2,656,271. -Nitrobenzimidazole, o-phenylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole, or JP-B-46-4
The heterocyclic compounds described in 1675 can be used.

In addition to these various components, Japanese Examined Patent Publication Nos. 46-19039 and 45-614
The development inhibitor compounds disclosed in Japanese Patent No. 9 and US Pat. No. 3,295,976 can be used.

Among the above antifoggants, the bromide ion supplied from sodium bromide, potassium bromide or the like is preferably 0.3 to 3 g / l or less from the viewpoint of rapid processing.

Further, a development accelerator can be used if necessary.
Development accelerators include U.S. Pat. Nos. 2,648,604 and 3,6.
71,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.No. 2,533,990, Second 2,531,832
No. 2,950,970, No. 2,577,127, and Shokoku Sho
Polyethylene glycol and its derivatives described in 44-9504 publication, nonionic compounds such as polythioethers, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also US Patent No. 2,
Examples thereof include benzyl alcohol, phenethyl alcohol described in No. 304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

However, in the color developing solution of the present invention, it is preferable that the organic solvent contains a solvent in the range of the volume ratio defined below.

In the above, logP is a value obtained from the partition coefficient P of n-octanol / water solvent, and the P value is obtained from the following formula.

The above values are values that have been widely used as a measure of lipophilicity. Review (Chemical R
eciew), 1971, Vol. 71, No. 6, 555-613. Further, although it can be determined by the calculation method described in Ecochemistry Vol. 6, pp. 3 to 11, it is preferable to use the actual measured value, and in the present invention, it is shown by the value measured using n-octanol.

Solvents having a log P of 0.4 or more, which are not preferably added to the color developer in the present invention in the above range or more, include aliphatic alcohols having 5 to 20 carbon atoms, aliphatic glycol ethers and alicyclic alcohols, respectively. And aromatic alcohols, and specific examples thereof include benzyl alcohol logP 1.10 o-hydroxyne benzyl alcohol logP 0.73 cyclohexanol logP 1.23 2-benzyloxyethanol logP 0.41 anisyl alcohol logP 0.70 1-pentanol logP 0.4 or more phenylethyl Alcohol logP 1.36 p-tolylcarbinol logP 1.36 n-butanol logP 0.4 or more phenol logP 0.4 or more p-hydroxy benzyl alcohol logP 0.4 or more benzylamine logP 0.4 or more diethylene glycol monobutyl ether logP 0.41 and the like.

Further, examples of the solvent having a logP of less than 0.4 include aliphatic alcohols having 0 to 4 carbon atoms, organic acids and the like, or compounds having 5 or more carbon atoms having a functional group having high polarity. Specific examples include the following solvents.

Acetic acid, ethanol, acetone, propionic acid, propanol, ethylene glycol, diethylene glycol, triethylene glycol, triethanolamine, diethanolamine.

In the above, especially lo represented by benzyl alcohol
For a poorly soluble organic solvent having a gP of 0.4 or more, tar is likely to be generated particularly in a running process in a low replenishment system by using a color developing solution for a long period of time. Adhesion to the product may even cause a serious failure that significantly impairs its commercial value.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome to prepare a stirring device for the preparation of the color developing solution itself, but also the use of such a stirring device results in Due to the badness, the effect of promoting development is limited.

Furthermore, poorly soluble organic solvents have a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since it has problems such as labor and cost,
It is preferable to reduce or eliminate the amount used. In the treatment method of the present invention, a system containing benzyl alcohol can be used, but a system containing no benzyl alcohol is one of the preferred embodiments in a system having a particularly high pH, which is preferable from the viewpoint of rapid processing.

Furthermore, the color developing solution of the present invention contains sodium tetrapolyphosphate, tetrasodium pyrophosphate, polyphosphoric acid such as condensed phosphate, or a salt thereof, as well as various chelating agents as a water softener or a heavy metal sequestering agent. be able to.

Examples of the chelating agent preferably used in the present invention include those described in Research Disclosure (hereinafter referred to as RD) 18837 and 18843.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 described each publication The compound can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

Furthermore, various additives such as an anti-staining agent (fluorescent whitening agent), an anti-sludge agent, and an interlayer effect accelerator for improving the white background of other white background portions can be used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to constant water. In this case, a component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components, each of which can coexist stably, are prepared in a concentrated aqueous solution or in a solid state in a small container, which is prepared by adding and stirring in water to obtain the color developing solution of the present invention. be able to.

In the present invention, the above color developing solution is used at pH 10.3 or higher, but from the viewpoint of rapid processing, it is more preferably pH 10.7 to 13.0.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the quicker the processing can be performed in a shorter time, which is preferable. However, it is preferable that the temperature is not so high from the viewpoint of image storage stability.

Generally, the processing time is generally 3 minutes and 30 seconds for color development, 1 minute and 30 seconds for bleach-fixing, and 3 minutes for stabilizing washing with water. In the present invention, the color development time is preferably within 2 minutes, particularly preferably 30 seconds to 1 second.
The present invention is particularly effective when the processing time is within the range of minutes and 30 seconds and the total processing time is within 6 minutes.

In the present invention, any system can be applied as long as it is a system using a color developing solution containing the sulfonic acid derivative of the present invention. For example, one-bath treatment and other various methods, for example, the treatment solution is sprayed. It is also possible to use various processing methods such as a spray method, a wet method by contact with a carrier impregnated with a processing solution, or a developing method with a viscous processing solution, but the processing steps are substantially color development and bleach-fixing. , Stabilization processing and the like.

In the bleach-fixing step, the bleaching step and the fixing step may be separately provided, or a bleach-fixing bath in which bleaching and fixing are processed in one bath may be used.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is obtained by coordinating a metal ion such as iron, cobalt or copper with an organic acid such as aminopolycarboxylic acid or acid or citric acid. The most preferred organic acid used to form such a metal acid salt of an organic acid includes a polycarboxylic acid.
These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine Citric acid (or tartaric acid) [9] Ethyl Etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethalenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [ 15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are preferably 5-450 g / l. 20-250g
Use with / l. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent, or conversely, a halide such as ammonium bromide. Use a bleach-fixing solution with a composition containing a large amount of added, and a special bleach-fixing solution with a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. You can As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 70 g to 250 g / l are used.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compounds, organic chelating agents such as aminopolycarborinic acid or stabilizers such as nitroalcohol and nitrates, organic compounds such as methanol, dimethylsulfamide and dimethylsulfoxide. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention includes JP-A-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 8.5, further stated the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or lower and 3 ° C. or higher, preferably 5 ° C. higher than the processing solution temperature in the color developing tank.
Although it is used at a lower temperature, it is preferably used at 55 ° C or lower while suppressing evaporation and the like.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, a stabilizing treatment by washing with water is performed subsequent to the color developing step using the color developing solution containing the sulfonic acid derivative of the present invention, the bleach-fixing step. .

Hereinafter, the stabilization treatment in place of the water washing applied to the present invention will be described.

In the present invention, examples of the compound preferably used in the stabilizing solution for washing with water include a chelating agent having a chelate stability constant for iron ions of 8 or more, and these are preferably used for achieving the object of the present invention.

Here, the chelate stability constant is LG Sillen / AEMart.
ell, “Stability Constants of Metalion Complexe
s ", The Chemical Society, London (1964). S. Chaberek
・ AEMartell, “Organic Sequestering Agents”, Wi
It means a constant generally known by Ley (1959).

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions, which is preferably used in the water-washing alternative stabilizing solution of the present invention, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds and the like. Is mentioned. The iron ion means the second fixing ion (Fe ³⁺ ).

Specific examples of the chelating agent having a chelate stability constant of 8 or more with ferric ion include, but are not limited to, the following compounds. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanol tetraacetic acid, transcyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-
1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate,
Sodium tetrapolyphosphate, sodium hexametaphosphate can be mentioned, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like, among which 1-hydroxyethylidene-1. Most preferred is 1,1-diphosphonic acid.

The amount of the above chelating agent used is 0.01 per 1 stabilizing solution for washing with water.
˜50 g is preferred, more preferably 0.05 to 20 g.

Furthermore, as a compound to be added to the washing alternative stabilizing solution of the present invention,
Ammonium compounds are mentioned as particularly preferred compounds.

These are supplied by ammonium salts of various inorganic compounds. Specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluorinated ammonium, etc. Ammonium, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride,
Ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium sulfate, ammonium pentaborate,
Ammonium acetate, ammonium adipate, ammonium laurate tricarboxylate, ammonium benzoate,
Ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid second Ammonium iron, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium etc. . Among these ammonium compounds, ammonium thiosulfate is particularly preferable for achieving the effect of the present invention.

The addition amount of the ammonium compound is preferably 1.0 × 10 ⁻⁵ or more, more preferably 0.001 to 5.0 mol, and further preferably 0.002 to 1.0 mol per 1 stabilizer.

Further, it is desirable that the stabilizing solution for washing with water in the present invention contains a sulfite in a range that does not violate the purpose of the present invention, that is, in a range where bacteria are not generated.

In the present invention, the sulfite salt contained in the washing alternative stabilizing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and a preferable specific compound is sodium sulfite, Potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite,
Examples thereof include sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, hydrosulfite, cartaraldehyde bis sodium bisulfite, and succinic aldehyde bis sodium bisulfite.

The above sulfite should be at least 1.0 × 1 in the stabilizing solution for washing with water.
The amount is preferably 0 ^-5 mol / l, more preferably 5 × 10 ^-5 mol / l to 1.0 × 10 ^-1 mol / l.
Is added. The method of addition may be such that it is added directly to the stabilizing solution for washing replacement, but it is preferable to add it to the stabilizing solution for washing replacement.

The stabilizing solution for washing with water used in the present invention preferably contains a fungicide, which can further improve the prevention of sulfuration and the image storability.

Preferred antifungal agents added to the stabilizer of the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, triazole compounds, morpholine compounds. , Quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamino compounds, sulfamide compounds, pyronone compounds and amino acid compounds.

Examples of the benzoic acid compound include salicylic acid, hydroxybenzoic acid, and hydroxybenzoic acid ester compounds such as methyl ester, ethyl ester, propyl ester, and butyl ester, and preferably n-butyl ester and isobutyl ester of hydroxybenzoic acid. , Propyl ester and salicylic acid, and more preferably a mixture of the three hydroxybenzoic acid esters.

The phenol compound is a compound which may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (in particular, an alkyl group having a C _{1 to} 6 alkyl group), a phenyl group or the like as a substituent. And preferably orthophenylphenol and orthocyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like.

The thiazole-based compound is a compound having a nitrogen atom and a sulfur atom in the 5-membered ring, preferably 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazoline 3
-One, 2-octyl-4-isothiazolin-3-one,
5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloro-thiazolyl-benzimidazole.

Specific examples of the pyridine compound include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium-2-pyridinethiol-1-oxide and the like, but preferably sodium-2-pyridinethiol-1. -Is oxide.

Specifically, the guanidine-based compound is cyclohexidine,
There are polyhexamethylene biguanidine hydrochloride, dodecyl guanidine hydrochloride and the like, and dodecyl guanidine and salts thereof are preferable.

Specific examples of the carbamate compound include methyl-1- (butylcarbamoyl) -2-benzimidazole carbamate and methylimidazole carbamate.

Specific examples of the morpholine compound include 4- (3-nitrobutyl) morpholine and 4- (3-nitrobutyl) morpholine.

Quaternary phosphonium compounds include tetraalkylphosphonium salts and tetraalkoxyphosphonium salts,
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride and tri-phenylnitrophenylphosphonium chloride.

Specific examples of the quaternary ammonium compound include benzalkonium salt, benzethonium salt, tetraalkylammonium salt and alkylpyridinium salt, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride and laurylpyridinium. There are chlorides.

The urea-based compound is specifically N- (3,4-dichlorophenyl) -N '-(4-chlorophenyl) urea, N- (3
-Trifluoromethyl) -N '-(4-chlorophenyl) urea and the like.

Specific examples of the isoxazole-based compound include 3-hydroxy-5-methyl-isoxazole.

Propanolamino compounds include n-propanols and isopropanols, and specifically, DL-2-benzylamino-1-propanol and 3-diethylamino-1.
-Propanol, 2-dimethylamino-2-methyl-1
-Propanol, 3-amino-1-propanol, isopropanolamine, diisopropanolamine, N, N
-Dimethyl-isopropanolamine and the like.

Specific examples of the sulfamide compound include o-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, α-amino-p-toluenesulfamide. Famide, sulfanilamide, acetosulfeguanidine, sulfathiazole, sulfadiazine, sulfamerazine, sulfamethazine, sulfisoxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, Examples include succinyl sulfathiazole.

Specific examples of the pyronone compound include dehydroacetic acid.

Specific examples of the amino acid compound include N-lauryl-β-alanine.

Specific examples of the triazole-based compound include 2-amino-triazole, benzotriazole, and 5-methyl-benzotriazole.

The compounds preferably used in the present invention among the above antibacterial agents are thiazole compounds, sulfamide compounds, and pyronone compounds.

The amount of anti-fungal agent added to the stabilizer is 0.001 per stabilizer.
It is preferably used in the range of ~ 30 g, more preferably 0.003 g to 5 g.

It is preferable that the stabilizing solution for washing with water in the present invention contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Bi, Ca, Ce, Co, In, Mn, Mg, Ni, Pb, Sn,
Examples thereof include metal salts of Zn, Ti, Zr, Al, and Sr, which can be supplied as an inorganic salt such as a halide, a hydroxide, a sulfate, a carbonate, a phosphate, an acetate, or a water-soluble chelating agent. Particularly preferred metal salts are Bi, Mg, Ni and Zn metal salts, and the amount used is in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, preferably 2 × 10 ^-4 to ¹ mol of the stabilizing solution. It is in the range of 5 × 10 ^-2 mol.

Other commonly known stabilizing bath additives include surface active agents, organic sulfur compounds, onium salts, hardeners such as formalin and chromium, and the addition amount of these compounds is stable according to the present invention. Any compound may be used in any combination as long as it is necessary to maintain the pH of the bath and does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. .

The pH of the washing alternative stabilizing solution applied to the present invention is preferably
It is in the range of 5.5 to 10.0, more preferably in the range of pH 6.3 to 9.5, and particularly preferably in the range of pH 7.0 to 9.0.
As the pH adjusting agent that can be contained in the stabilizing solution for washing with water applicable to the present invention, any of generally known alkali agents or acid agents can be used.

The treatment temperature for stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ~ 45 ℃ is good. Also, the treatment time is preferably as short as possible from the viewpoint of rapid treatment, but is usually 20 seconds to 10 minutes, most preferably 30 seconds to 3 minutes. However, it is preferable that the treatment time is longer in the latter-stage tank. In particular, it is desirable to perform the treatment sequentially with a treatment time that is 20% to 50% longer than that of the previous tank. No washing treatment is required after the stabilization treatment applied to the present invention, but rinsing by a small amount of washing in a very short time, surface washing, etc. can be optionally performed.

When the multi-tank counter current method is used as the method for supplying the stabilizing solution for washing with water in the stabilization treatment step applicable to the present invention, it is preferable to supply the stabilizing solution to the post-bath and cause the overflow from the pre-bath. Of course, it can also be processed in a single tank. As a method of adding the above compound, the compound and other additives are added to the stabilizing tank as a concentrated solution, or the above washing alternative stabilizing solution supplied to the stabilizing tank is added to the washing alternative stabilizing replenisher. There are various methods such as whether to use the supply liquid, but any addition method may be used.

In the present invention, the amount of replenishment to the processing bath with the washing substitute stabilizing solution is based on the unit area of the photosensitive material to be processed from the pre-bath of the processing bath with the washing substitution stabilizing solution to the processing bath with the washing substitution stabilizing solution. The effect of the present invention is advantageously exhibited when the amount is 1.5 to 30 times the carry-in amount, and the effect is more remarkable when the amount is 2 to 20 times. Amount carried on the type of light-sensitive material, the conveying speed of the automatic developing machine, the conveying system, varies depending squeeze method, etc. of the photosensitive material surface, if normal, the amount of carryover of color paper is ^{25ml / m 2 ~100ml / m 2} .

Therefore, the replenishment rate effect is more pronounced of the present invention to carry amount in this range is in the range of ^{50ml / m 2 ~2000ml / m 2} , the effect is particularly significant replenishment rate 75ml / m ² ~900ml It is in the range of / m ² .

In the case of a color film (roll film), the carry-in amount is usually 50 ml / m ^{2 to} 150 ml / m ² , and the replenishing amount at which the effect of the present invention is more remarkable for this carry-in amount is 100 ml / m ² to
3.0 l / m is in the range of ^2, the effect is particularly noticeable replenishment rate 150ml
It is in the range of / m ^{2 to} 950 ml / m ² .

As described above, in the present invention, the treatment with the stabilizing solution refers to the treatment for the stabilizing treatment in which the stabilizing treatment is carried out immediately after the treatment with the bleach-fixing solution and substantially no washing treatment is carried out,
The treatment liquid used for the stabilization treatment is called a water-washing substitute stabilizer,
The treatment tank is called a stabilizing bath or stabilizing tank.

The stabilizing tank in the stabilizing treatment applied to the present invention is 1 to 5
In the case of a tank, the effect of the present invention is great, and particularly preferably 1
~ 3 tanks, and preferably at most 9 tanks or less.

In the present invention, a p-phenylenediamine compound having a water-soluble group is contained as the color developing agent, at least one of the sulfonic acid derivative of the present invention is contained in the color developing solution, and the pH is adjusted to 10.3 or more. Using a color developer, a silver halide color photographic light-sensitive material having at least one imagewise exposed silver halide emulsion layer is subjected to a process including a color developing process.

The silver halide used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material includes silver chloride, silver bromide,
Any of silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures thereof can be used, but the effects of the present invention can be achieved more efficiently. It is preferably substantially silver chlorobromide.

The term "substantially silver chlorobromide" as used herein means that a small amount of silver iodide may be contained in addition to silver chlorobromide, for example, 0.3 mol% or less, and more preferably 0.1 mol% or less of silver iodide. Means silver chlorobromide. However, silver chlorobromide containing no silver iodide is most preferred in the present invention.

The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, and any ratio of [100] plane to [111] plane can be used. 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. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

The silver halide grains used in the present invention may be those obtained by any of the acid method, the neutral method and the ammonia method.

In addition, 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 grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-aurothio-3-.
Methylbenzothiazolium chloride or the like or a sensitizer of a water-soluble group such as ruthenium, palladium, platinum, rhodium or iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention is preferably a ring-extinguishing dye represented by the following general formulas [II] and [III] in order to impart photosensitivity to a desired light-sensitive wavelength region.

General formula [II]Where Z₁And Z₂Are benzochiosazole nucleus and naphtho, respectively
Oxazole nucleus, benzothiazole nucleus, naphthothiazo
Le nucleus, benzoselenazole nucleus, naphthoselenazole nucleus,
Benzimidazole nucleus, naphthimidazole nucleus, pyridi
Group of atoms necessary to form a quinine or quinoline nucleus
And R₁And R₂Are alkyl, alkenyl or a
Represents a reel group, R₃Is a hydrogen atom, a methyl group or ethyl
Represents a group, X₁ Represents an anion, l is 0 or
Represents 1.

General formula [III]Where Z₃And Z_FourIs an oxazole ring or thiazo
Benzene ring or naphthalene ring fused to the aryl ring
Represents the atomic group necessary for_FourAnd R_FiveAre each
Represents a kill group, an alkenyl group or an aryl group, and R₆Is
Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X₁
Represents an anion, l represents 0 or 1, and A₁Over
And A₂Each represents an oxygen atom or a sulfur atom.

In the sensitizing dye represented by the general formula [II] preferably used in the present invention, the nuclei represented by Z ₁ and Z ₂ may be substituted, and the substituent is a halogen atom (eg chlorine), alkyl Groups (eg methyl, ethyl), alkoxy groups (eg methoxy, ethoxy), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl), aryl groups (eg phenyl),
Examples thereof include a cyano group.

The alkyl group and alkenyl group represented by R ₁ and R ₂ preferably have 5 or less carbon atoms, and preferably R ₁ and R ₂ are alkyl groups.

In the sensitizing dye represented by the general formula [II] used in the present invention, the heterocyclic nucleus formed by condensing Z ₃ and Z ₄ with the oxazole ring or the thiazole ring is substituted with various substituents. However, these preferable substituents are a halogen atom, an aryl group, an alkenyl group, an alkyl group and an alkoxy group. More preferable substituents are a halogen atom, a phenyl group and a methoxy group, and the most preferable substituent is a phenyl group.

Preferably, Z ₃ and Z ₄ are both a benzene ring or a thiazole ring fused to an oxazole ring, and at least one of these benzene rings has a 5-position substituted with a phenyl group, or one benzene ring is A phenyl group, or the other 5-position of the benzene ring is substituted with a halogen atom. R ₄ and R ₅ are R in the general formula [II]
_{1 has} the same meaning as R ₂ .

Preferably, R ₄ and R ₅ are an alkyl group substituted with a carboxyl group or a sulfo group, most preferably a sulfoalkyl group having 1 to 4 carbon atoms, and most preferably a sulfoethyl group. R ₆ is preferably a hydrogen atom or an ethyl group.

General formula [II] or [III] preferably used in the present invention
The sensitizing dye represented by can also be used as a so-called supersensitizing combination in combination with other sensitizing dyes.
In this case, each sensitizing dye may be dissolved in the same or different solvent, and these solutions may be mixed or added separately to the emulsion prior to addition to the emulsion. When they are added separately, the order and time interval can be arbitrarily determined according to the purpose.

Specific compounds of the sensitizing dye represented by the general formula [II] or [III] are shown below, but not limited thereto.

The addition amount of the sensitizing dye represented by the general formula [II] or [III] to the emulsion is 2 × per mol of silver halide.
A range of 10 ^-6 to 1 × 10 ^-3 mol is suitable, and preferably 5
It is from × 10 ^{-6 to} 5 × 10 ^-4 mol.

Many of the above-mentioned sensitizing dyes are sensitizing dyes having a spectral sensitizing ability in a wavelength range called green-sensitivity or blue-sensitivity in a light-sensitive material. Spectral sensitization with the above-mentioned sensitizing dye is desirable, and it is preferable that most (50 mol% or more) of the sensitizing dye is at least the above-mentioned sensitizing dye in total of the green-sensitive emulsion and the blue-sensitive emulsion. .

When a light-sensitive material using the sensitizing dye represented by the general formula [II] or [III] is processed with the color developer of the present invention,
The effect of the present invention, that is, the contamination of the unexposed portion, particularly the contamination concentration at 440 nm, can be favorably reduced.

To add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 is prepared in advance. It is used by dissolving it in a hydrophilic organic solvent such as.

The time of addition may be any time from the start of chemical ripening of the silver halide emulsion, during ripening, and at the end of ripening, and in some cases,
You may add in the process just before emulsion coating.

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 584,60.
No. 9, 1,277,429, JP-A-48-85130, 49-99620
No. 49, No. 114420, No. 49-129537, No. 52-108115,
59-25845, 59-111640, 59-111641, U.S. Pat.Nos. 2,274,782, 2,533,472, 2,956,079.
No. 3,125,448, 3,148,187, 3,177,07
No. 8, No. 3,247,127, No. 3,260,601, No. 3,540,8
No. 87, No. 3,575,704, No. 3,653,905, No. 3,718,
Examples thereof include those described in No. 472, No. 4,071,312 and No. 4,070,352.

These AI dyes are generally 2x per mole of silver in the emulsion layer.
It is preferable to use 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mol.

The silver halide emulsion layers according to the present invention may each contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the coupler usable in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and it is also possible to use diffusible dye releasing type couplers in combination with these couplers.

The yellow coupler includes an open-chain ketomethylene compound and an active site called a so-called 2-equivalent type coupler.
o-aryl substituted coupler, active point-o-acyl substituted coupler, active point hydantoin compound substitution coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine Substitution coupler, active point -o
-Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.Nos. 2,875,057 and 3,26.
5,506, 3,408,194, 3,551,155, 3,5
82,322, 3,725,072, 3,891,445, West German Patent 1,547,868, West German Published Application 2,219,917, 2,261,
No. 361, No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Unexamined Patent Publication No. 47-26133, No. 48-73147, No. 51.
-102636, 50-6341, 50-123342, 50-130442
No. 51, No. 21-21827, No. 50-87650, No. 52-82424, No. 52
-115219, 58-95346 and the like can be mentioned.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of the magenta coupler, U.S. Patent No. 2,600,788, No. 2,983,608,
No. 3,062,653, No. 3,127,269, No. 3,311,476
Issue No. 3,419,391, No. 3,519,429, No. 3,558,31
No. 9, No. 3,582,322, No. 3,615,506, No. 3,834,9
08, 3,891,445, West German Patent 1,810,464, West German Patent Application (OLS) 2,408,665, 2,417,945, 2,41
8,959, 2,424,467, JP-B-40-6031, JP-A-51-
20826, 52-58922, 49-129538, 49-74027
No. 50, No. 50-159336, No. 52-42121, No. 49-74028, No. 5
No. 0-60233, No. 51-26541, No. 53-55122, Japanese Patent Application No. 55-11
Those described in No. 0943 and the like can be mentioned.

Further, as the cyan coupler useful in the present invention, compounds represented by the following general formulas [IV], [V] and [VI] are preferably used.

General formula [IV] In the formula, one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or an oxidation of an aromatic primary amine color developing agent. Represents a group capable of splitting off by a coupling reaction with the body, and R ₂ represents a ballast group.

General formula [V] General formula [VI] In the formula, Y is -COR ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group. Or a heterocyclic group, R ₄ and R ₅ may combine with each other to form a 5- or 6-membered ring), R ₃ represents a ballast group, and Z represents a hydrogen atom or an aromatic group. It represents a group capable of splitting off upon coupling with an oxidized product of a primary amine color developing agent.

The number of carbon atoms represented by R and R ₁ in the general formula [IV] is 2 to 12
The linear or branched alkyl group of is, for example, an ethyl group, a propyl group, or a butyl group.

In the general formula [IV], the ballast group represented by R ₂ has a size that gives the coupler molecule sufficient bulkiness so that the coupler cannot substantially diffuse from the layer to which the coupler is applied to other layers. It is an organic group having a shape. A typical ballast group has a total carbon number of 8 to
Examples thereof include 32 alkyl groups or aryl groups, and preferably have 13 to 28 total carbon atoms. Substituents for these alkyl groups and aryl groups include, for example, alkyl groups, aryl groups, alkoxy groups, allyloxy groups, carboxy groups, acyl groups, ester groups, hydroxy groups, cyano groups, nitro groups, carbamoyl groups, carbonamide groups. , An alkylthio group, an arylthio group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, and a halogen, and examples of the substituent of the alkyl group include the substituents of the aryl group except the alkyl group.

The preferred ballast group is represented by the following general formula.

R ₁₂ represents an alkyl group having 1 to ₁₂ carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, a halogen atom, an alkylsulfonamide group and the like, and the most preferable one is a branched alkyl group such as a t-butyl group.

The group capable of splitting off upon coupling with the oxidation product of the color developing agent, which is defined by X in the above general formula [IV], determines the number of equivalents of the coupler, as well known to those skilled in the art. It affects the reactivity of the ring. As typical examples, halogen represented by chlorine and fluorine, aryloxy group, substituted or unsubstituted alkoxy group, acyloxy group, sulfonamide group, arylthio group, heteroylthio group, heteroyloxy group, sulfonyloxy group, carbamoyloxy group. Groups and the like. More specific examples include JP-A Nos. 50-10135, 50-120334, and 50-1304.
No. 14, No. 54-48237, No. 51-146828, No. 54-14736,
47-37425, 50-123341, 58-95346, and Shogun 4
8-36894, U.S. Pat.Nos. 3,476,563 and 3,737,316
And the groups described in JP-A No. 3,227,551.

Next, exemplary compounds of the cyan coupler represented by the general formula [IV] will be shown, but the invention is not limited thereto.

In the general formulas [V] and [VI], Y is —COR ₄ , A group represented by —CONHCOR ₄ or —CONHSO ₂ R ₄ .
Here, R ₄ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (eg, an allyl group). , Heptadecenyl group, etc.),
A cycloalkyl group, preferably a 5- to 7-membered ring (eg cyclohexyl), an aryl group (eg phenyl group, tolyl group, naphthyl group etc.), a heterocyclic group, preferably a nitrogen atom, an oxygen atom or a sulfur atom It represents a 5-membered to 6-membered heterocyclic group containing 4 to 4 members (for example, a furyl group, a thienyl group, a benzothiazolyl group, etc.). R ₅ represents a hydrogen atom or a group represented by R ₄ . R ₄ and R ₅ may combine with each other to form a 5-membered to 6-membered heterocycle containing a nitrogen atom. In addition, arbitrary substituents can be introduced into R ₂ and R ₃ , for example, an alkyl group having 1 to 10 carbon atoms (eg, ethyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.). , Aryl groups (eg phenyl,
Naphthyl etc.), halogen atom (fluorine, chlorine, bromine etc.), cyano, nitro, sulfonamide group (eg methanesulfonamide, butanesulfonamide, p-toluenesulfonamide etc.), sulfamoyl group (eg methylsulfamoyl, phenyl) Sulfamoyl etc.), sulfonyl group (eg methanesulfonyl, p-toluenesulfonyl etc.), fluorosulfonyl, carbamoyl group (eg dimethylcarbamoyl, phenylcarbamoyl etc.), oxycarbonyl group (eg ethoxycarbonyl, phenoxycarbonyl etc.), acyl group (Eg, acetyl, benzoyl group), heterocyclic group (eg, pyridyl group, pyrazolyl group, etc.), alkoxy group, aryloxy group, acyloxy group and the like.

In the general formulas [V] and [VI], R ₃ is necessary or ballast for imparting diffusion resistance to the cyan coupler represented by the general formulas [V] and [VI] and the cyan dye formed from the cyan coupler. Represents a group. Preferably, it is an alkyl group having 4 to 30 carbon atoms, an aryl group or a heterocyclic group. Examples thereof include linear or branched alkyl groups (for example, t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5-membered or 6-membered heterocyclic groups, and the like.

In the general formulas [V] and [VI], Z represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidation product of a color developing agent. For example, halogen atom (eg chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, sulfonyloxy group, alkylthio group, arylthio group, heterocycle Thio group, sulfonamide group and the like, and further specific examples include U.S. Pat.No. 3,741,563, JP-A-47-37425, JP-B-48-36894, and JP-A-50-10135. 50-117422, 5
0-130441, 51-108841, 50-120343, 52-183
No. 15, No. 53-105226, No. 54-14736, No. 54-48237,
55-32071, 55-65957, 56-1938, 56-1264
No. 3, No. 56-27147, No. 59-146050, No. 59-166956, No. 6
0-24547, 60-35731, and 60-37557 can be mentioned.

In the present invention, among the cyan couplers represented by the general formula [V] or [VI], the following general formula [VIII],
Cyan couplers represented by [IX] or [X] are more preferred.

General formula [VIII] General formula [IX] General formula [X] In the general formula [VIII], R ₁₃ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent is -SO.
₂ R _16, halogen atoms (e.g. fluorine, bromine, chlorine, _{etc.), - CF 3, -NO 2} , -CN, -COR 16, -COOR 16, -SO 2
OR ₁₆ , At least one substituent selected from is included.

Here, R ₁₆ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group such as methyl, ethyl, tert-butyl, dodecyl, etc.), an alkenyl group, preferably 2 carbon atoms.
To 20 alkenyl groups (eg, allyl group, heptadecenyl group, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (eg, cyclohexyl group, etc.), aryl groups (eg, phenyl group, tolyl group, naphthyl group, etc.) , R ₁₇ is a hydrogen atom or a group represented by R ₁₆ .

A preferred compound of the phenolic cyan coupler represented by the general formula [VIII] is a compound in which R ₁₃ is a substituted or unsubstituted phenyl group, and cyano, nitro, —SO ₂ R ₁₈ (R ₁₈ Is an alkyl group), a halogen atom,
A compound such as trifluoromethyl.

In the general formulas [IX] and [X], R ₁₄ and R ₁₅ are alkyl groups, preferably alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl, tert-butyl, dodecyl, etc.), alkenyl groups, preferably carbon. An alkenyl group having a number of 2 to 20 (eg, allyl, oleyl, etc.), a cycloalkyl group, preferably a 5- to 7-membered ring group (eg, cyclohexyl etc.), an aryl group (eg, phenyl group, tolyl group, naphthyl group etc.), a heterocycle Represents a group (a 5-membered to 6-membered heterocycle containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms is preferable, and examples thereof include a furyl group, a thienyl group, and a benzothiazolyl group).

Any substituent can be further introduced into R ₁₆ and R ₁₇ and R ₁₄ and R ₁₅ in the general formulas [IX] and [X]. Specifically, specific formulas [II] and [III] can be used. ], A substituent that can be introduced into R ₄ or R ₅ . As the substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable.

Z and R in the general formulas [VIII], [IX] and [X]
Each of ₃ has the same meaning as in general formulas [II] and [III]. A preferred example of the ballast group represented by R ₃ is a group represented by the following general formula [XI].

General formula [XI] In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, l represents 0 or 1, and when K is 2 or more, two or more R _{20 s} are the same. R ₁₉ may represent a linear or branched alkylene group having 1 to 20 carbon atoms and a substituted alkylene group such as an aryl group, R ₂₀ represents a monovalent group, preferably a hydrogen atom,
Halogen atoms (eg chromium, bromine), alkyl groups,
Preferably, a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl and the like groups), aryl group (for example, phenyl group) ), A heterocyclic group (preferably a nitrogen-containing heterocyclic group), an alkoxy group, preferably a linear or branched alkoxy group having 1 to 20 carbon atoms (eg, methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyl). Each group such as oxy), aryloxy group (eg phenoxy group), hydroxy, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (eg acetoxy group, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably Is a linear or branched alkyl group having 1 to 20 carbon atoms. Aryloxycarbonyl group, an aryloxycarbonyl group, preferably phenoxycarbonyl,
An alkylthio group, preferably 1 to 20 carbon atoms, an acyl group,
Preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably 1 to 20 carbon atoms
A linear or branched alkylcarboxamide, benzenecarboxamide or sulfonamide group, preferably having 1 to 1 carbon atoms.
20 linear or branched alkylsulfonamide group or benzenesulfonamide group, carbamoyl group, preferably C 1-20 linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group, sulfamoyl group, preferably carbon It represents a linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group of the number 1 to 20 and the like.

Next, specific compound examples of the cyan coupler represented by the general formula [V] or [VI] will be shown, but the cyan coupler is not limited thereto.

[Compound example] These cyan couplers can be synthesized by a known method, for example, U.S. Pat.Nos. 2,772,162 and 3,75.
8,308, 3,880,661, 4,124,396, 3,2
22,176, British Patents 975,773, 8,011,693, 8,011,694, JP-A-47-21139, 50-112038, and
55-163537, 56-29235, 55-99341, 56-1160
No. 30, 52-69329, 56-55945, 56-80045, 56
50-134644, and British Patent No. 1,011,940, U.S. Patent Nos. 3,446,622, 3,996,253, and JP-A-56-65134.
57-204543, 57-204544, 57-204545, Japanese Patent Application No. 5
6-131312, 56-131313, 56-131314, 56-131
No. 309, No. 56-131311, No. 57-149791, No. 56-130459
No. 59-146050, No. 166956, No. 60-24547,
It can be synthesized by the synthesis method described in No. 60-35731, No. 60-37557 and the like.

In the present invention, the cyan coupler represented by the general formula [IV], [V] or [VI] can be used in combination with a conventionally known cyan coupler. In addition, the general formula [I
V], [V] and [VI] cyan couplers can also be used in combination.

When the cyan coupler represented by the general formulas [IV] to [VI] is contained in the silver halide emulsion layer, it is usually about 0.005 to 2 mol, preferably 0.01 to 1 mol, per mol of silver halide.
Used in the range of 1 mol.

Further, couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers and diffusible DIR compounds may be used in combination in the silver halide emulsion layer and other photographic constituent layers of the present invention. Non-diffusible DIR compound,
For the colored magenta or cyan coupler, the description in Japanese Patent Application No. 59-193611 by the present applicant can be referred to, and for the polymer coupler, the description in Japanese Patent Application No. 59-172151 by the present applicant can be referred to.

The method of adding the above-mentioned coupler which can be used in the present invention to the photographic constituent layer of the present invention is the same as before, and the addition amount of the above-mentioned coupler is not limited, but it is 1 × 10 ^-3 per mol of silver.
~ 5 mol is preferred, more preferably 1 x 10 ^{-2 to} 5 x 10
^-1 .

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 17643, A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

Examples of the support of the silver halide color photographic light-sensitive material of the present invention include, for example, transparent paper, polyethylene coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or a transparent support such as a glass plate and cellulose. Examples thereof include polyester films such as acetate, cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and other usual transparent supports may be used. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Pat.No. 2,761,79
A simultaneous coating method of two or more layers by the method described in No. 1 and No. 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

[Specific effects of the invention] As described above, in the present invention, it is possible to satisfactorily reduce the stain in the unexposed portion, which is a problem when performing continuous treatment in rapid water washing alternative stabilization treatment. It was possible to provide an excellent method for processing a silver halide photographic light-sensitive material in processing and anhydrous washing.

[Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 An experiment was conducted with the following color paper, processing solution and processing steps.

[Color paper] Polyethylene mixture by extrusion coating on both sides of 80 g / m ² basis weight fine paper whose inside is sized by a general method.
About 12 g / m ² was coated. This polyethylene mixture contains 10 parts by weight of titanium dioxide.

The following layers were sequentially coated on this polyethylene-coated paper support from the support side to prepare a light-sensitive material.

The polyethylene coated paper has an average molecular weight of 100,
000, density 0.95 polyethylene 200 parts by weight and average molecular weight 2,
000, 6.8 wt% of anatase type titanium oxide was added to a mixture of 20 parts by weight of polyethylene having a density of 0.80, and a coating layer having a thickness of 0.035 mm was formed on the surface of the fine paper having a weight of 170 g / m ² by the extrusion coating method, The back side was provided with a coating layer of 0.040 mm thickness made of polyethylene only. After pretreatment by corona discharge on the polyethylene-coated surface of this support, each layer was sequentially coated.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide (average grain size: 0.3 μm) emulsion containing 80 mol% of silver bromide, the emulsion containing 350 g of gelatin per mol of silver halide, and a halogen. Sensitizing dye having the following structure per mol of silver halide Sensitized with 7.5 × 10 ^-4 mol (using isoprovir alcohol as solvent), dissolved in dibutyl phthalate and dispersed in 2,5-di-t-butylhydroquinone 200 mg
/ m ² , and as a yellow coupler α- [4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydyl)] α-pivalyl-2-chloro-5- [γ-
(2,4-Di-t-amylphenoxy) butylamido] acetanilide was contained in an amount of 2 × 10 ⁻ mol per mol of silver halide, and the amount of silver was 330 mg / m ² .

Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, and as a UV absorber 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
(2'-Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-bezotriazole mixture 200 mg / m ²
It is coated so that the amount of gelatin will be 2000 mg / m ² in the gelatin layer containing.

Third layer: a green-sensitive silver halide emulsion layer comprising a silver chlorobromide (average grain size: 0.3 μm) emulsion containing 80 mol% of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide, and a halogen. Sensitizing dye having the following structure per mol of silver halide Sensitized with 7.5 × 10 ^-4 mol, 2,5-di-t-butylhydroquinone 150 mg dissolved and dispersed in a 2: 1 mixed solvent of dibutyl phthalate and tricresyl phosphate
/ m ² and 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone as a magenta coupler at 1.5 per mol of silver halide. × 10 ^-1 mol content, silver amount 300 mg / m ²
Is applied so that As an antioxidant
0.3 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was contained per mol of the coupler.

Fourth layer: di-t-octylhydroquinone 30 mg / m ² dissolved and dispersed in dioctyl phthalate and 2 as an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5'-chlorobenzotriazole and 2
A mixture of-(2'-hydroxy-3 ', 5'-t-butylphenyl) -5-chloro-benzotriazole (2: 1.
5: 1.5: 2) and the amount of gelatin is 500 mg / m ^{2, and} the amount of gelatin is 2000 mg / m ² .

Fifth layer: a red-sensitive silver halide emulsion layer consisting of silver chlorobromide (average grain size: 0.3 μm) containing 60 mol% of silver bromide, and the emulsion contains 500 g of gelatin per mol of silver halide. , Exemplified sensitizing dye per 1 mol of silver halide (No. I-12 and II-13)
Sensitized using 2.5 × 10 ⁻⁵ mol, 2,5-di-t-butylhydroquinone dissolved in dibutyl phthalate and dispersed, and cyan coupler exemplified as cyan coupler (N
oC-18) is contained in an amount of 3.5 × 10 ⁻⁴ mol per mol of silver halide, and the coating amount is 300 mg / m ² .

Sixth layer: The gelatin layer is coated so that the amount of gelatin is 1000 mg / m ² .

The silver halide emulsion used for each photosensitive emulsion layer (1,3,5 layers) was prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized with 4-hydroxy-6-methyl-
It contained 1,3,3a, 7-tetrazaindene, bis (vinylsulfonylmethyl) ether as a hardener and saponin as a coating aid.

After the stepwise exposure of the photosensitive material sample prepared above, in the following processing solutions and processing steps, the processing solution was continuously processed until the total replenishment amount of the color developing solution became equal to the volume of the tank solution, and then unexposed. The contamination concentration of each part was measured. The results are shown in Table-1.

Development process Temperature time [1] Color development 35 ° C As shown in Table-1 [2] Bleach-fixing 33 ° C 50 seconds [3] Washing with water or 33 ° C 18 seconds × 3 tanks Stabilization treatment (in case of stabilization treatment) [4] ] Drying 90 ° C. to 100 ° C. for 1 minute Processing liquid composition <Color developing tank liquid> Benzyl alcohol Table-1 amount Amount potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Sulfonic acid derivative table of the present invention- 1 described amount Color developing agent (described in Table-1) Table-1 described amount Chelating agent 1 0.3g Chelating agent 2 2.0g Add water to make the total amount 1 and adjust pH with KOH to the value described in Table-1. .

<Color development replenisher> [Bleaching fixer] Benzyl alcohol 1.3 times the amount described in Table-1 Potassium sulfite 3.0 g Potassium carbonate 30.0 g Sulfonic acid derivative of the present invention Table-1 described amount Color developing agent (described in Table-1) 1.3 times the amount described in Table-1 Chelating agent 1 0.3 g Chelating agent 2 2.5 g Water was added to make the total amount 1 and pH was adjusted to the value shown in Table 1 with KOH, and then 2 g of KOH was added.

<Bleach-fixing tank liquid> Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust pH to 7.1 with potassium carbonate or glacial acetic acid. And add water to bring the total amount to 1.

<Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 260g Potassium carbonate 42g Water is added to bring the total amount to 1.

The pH of this solution is 6.7 ± 0.1.

<Bleach-fixing replenisher B> Ammonium thiosulfate (70% solution) 500 ml Ammonium sulfite (40% solution) 250 ml Ethylenediaminetetraacetic acid 17 g Glacial acetic acid 85 ml Add water to bring the total volume to 1.

The pH of this solution is 4.6 ± 0.1.

<Stabilizer tank liquid or replenisher> Benzotriazole 2.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.03 g 2-Methyl-4-isothiazolin-3-one 0.03 g Nitriromethylenephosphonic acid 2.0 g 2 - octyl-4-isothiazolin-3-one 0.01 g 1-hydroxy ethylidene-1, and the total volume of 1 by addition of 1-diphosphonic acid 2.0g of ammonia water (28%) 3.0 g of bismuth chloride 0.2g water, H ₂ SO ₄ And adjust to pH 7.5 with KOH.

Fill the automatic developing machine with the above color developing tank solution, bleach-fixing tank solution and stabilizing solution, and replenish the color paper with 1 m ²
As a replenishing amount for each color developing tank, 300 ml,
100 ml each of bleach-fixing replenisher A and B as replenishing amounts to the bleach-fixing tank, 300 stabilizer as replenishing amount to the stabilizing bath.
Replenished with ml.

The stabilization processing bath of the automatic processor is a stabilizing bath that is the first to third baths in the direction of the flow of the photosensitive material, replenishment is performed from the final bath, and overflow is allowed to flow from the final bath to the preceding bath. In addition, a multi-tank countercurrent system in which this overflow liquid is allowed to flow into the previous tank is also adopted.

The structures of chelating agents 1 and 2 are as follows.

Chelating agent 1 Chelating agent 2 In addition, the contamination concentration of the unexposed area is measured by Hitachi spectrophotometer.
The 330 was used to measure the reflection density at 440 nm and 640 nm.

As is clear from the results in Table 1, in Comparative Experiments 1 to 7 in which the sulfonic acid derivative of the present invention was not used, at low pH, the unexposed portion was less contaminated but the treatment took longer,
In the system with increased benzyl alcohol, the effect is basically obtained by using a large amount of benzyl alcohol, which is a problem in terms of pollution, but in the system with reduced benzyl alcohol and the system without it, the degree of contamination of the unexposed area is high. . Further, the washing of water reduces the contamination of the unexposed area to some extent, but it is not sufficient. On the other hand, in Experiment Nos. 8 to 16 using the sulfonic acid derivative of the present invention, depending on the type of the sulfonic acid derivative of the present invention, there are some in which the contamination of the unexposed area is not sufficiently removed. It can be seen that the contamination of the unexposed area is reduced.

Further, it can be seen from Experiment Nos. 17 to 25 that the effects of the present invention are obtained even if the color developing agent is changed or the concentration thereof is changed.

Example-2 Under the same light-sensitive material sample and processing conditions as in Example-1, the color development processing time was changed as shown in Table-2, and the color developing agent was exemplified as the compound of No. 1 at 2.0 × 10 ^-2. used in g / l,
No benzyl alcohol was used, the pH value was set to 11.5, the presence or absence of the sulfonic acid derivative of the present invention, and washing with water or anhydrous were as shown in Table 2 below. The concentration was measured. In addition, the maximum yellow density at that time was measured with blue light of an optical densitometer (PDA-65, manufactured by Konishi Roku Photo Industry Co., Ltd.). The results are also shown in Table-2.

As can be seen from the results in Table 2, the effect of the present invention can be achieved even if the treatment time is extended. By increasing the time, the maximum density increases, but the density of contamination in the unexposed area also increases accordingly. Usually, the maximum concentration is sufficient if it is 2.50 or more, and the contamination concentration of the unexposed portion is preferably 0.12 or less, more preferably 0.11 or less.
It is understood that the effect of the present invention can be sufficiently obtained even if the treatment time is lengthened and the maximum concentration is increased. In addition, when viewing this table from another viewpoint, a result that can be sufficiently put to practical use is obtained in a short time treatment of 45 seconds, and a preferable result is shown even in a short time treatment, and the present invention is It turns out that this method is suitable for rapid processing.

It was confirmed that the same effect of the present invention was obtained even when the treatment was performed for a time longer than 150 seconds.

Example-3 In the photosensitive material sample of Example-1, the first, third and fifth
The silver chlorobromide having a silver bromide content of 80 mol% in the layer was changed to a silver halide having the composition shown in Table 3, and the processing conditions were changed to those in Example 1.
Experiment No. 4 (comparative treatment method not using the sulfonic acid derivative of the present invention) and Experiment No. 13 (treatment method of the present invention using the sulfonic acid derivative of the present invention (Ex. I-32)), The contamination density of the unexposed area was measured in the same manner as in Example-1. The results are also shown in Table-3.

As is clear from the results in Table 3, the effects of the present invention can be obtained basically regardless of the silver halide composition, but in particular, Experiments 37, 39, 41, 43 using substantially silver chlorobromide, In 45, it can be seen that the effect of the present invention is achieved more efficiently.

Example-4 In the light-sensitive material sample of Example-1, the cyan coupler used in the fifth layer was changed to the coupler shown in Table-4, and the experiment No. 4 of Example-1 was carried out in the same manner as in Example-3. And Experiment No.1
3 were treated respectively. The contamination density at 640 nm in the unexposed area was measured in the same manner as in Example-1. The results are also shown in Table-4.

As is clear from Table 4, the contamination of the unexposed area at 640 nm is closely related to the cyan coupler used, and it can be seen that the effects of the present invention can be efficiently achieved particularly in the specific cyan coupler.

In addition, with respect to the cyan coupler 1, general formulas [IV] to [VI]
The cyan coupler represented by is particularly a coupler excellent in dark fading.

Furthermore, other exemplary cyan couplers C-9, C-11, C-
It was confirmed that similar effects were obtained with 12, C-17 to 22, C-29, C-51, and C-111.

Example-5 In the photosensitive material sample of Example-1, the sensitizing dyes are shown in Table-5.
Experiment No. of Example-1 except that the sensitizing dye of the layer shown in Table 5 was changed as shown in Table 5 and the addition amount was not changed, and the sulfonic acid derivative of the present invention was changed as shown in Table 5. The same process as in .4 was performed. The contamination density of 440 nm in the unexposed area was measured in the same manner as in Example-1. The results are also shown in Table-5.

The structures of sensitizing dyes 1 and 2 used in Table-5 are as follows.

As can be seen from Table-5, the contamination of the unexposed area of 440 nm is
It can be seen that there is a close relationship with the sensitizing dye. Further, in the present invention, it can be seen that the effects of the present invention are efficiently achieved particularly in combination with the sensitizing dyes represented by the general formulas [II] and [III].

In Experiments 56 and 57, the sensitizing dye of I-16 was added to I-
Similar results were obtained by changing to 2 and I-5.
Furthermore, in Experiments 58 and 59, the sensitizing dye of II-11 was added to II-
Similar results were obtained by changing to 3 and II-15.

Example-6 Example-1 using the photosensitive material sample prepared in Example-1, except that the sulfonic acid derivative of the present invention and hydroxylamine were added to the color developing solution as shown in Table-6.
It was processed under the same conditions as Experiment No. 4 of. The contamination density of the unexposed area was measured in the same manner as in Example-1. The results are also shown in Table-6.

As is clear from the results of Table 6, the effects of the present invention can be achieved even in the presence of hydroxylamine, but it can be seen that the effects of the present invention are particularly excellent especially in a system not using hydroxylamine.

Claims (3)

[Claims] 1. A silver halide color obtained by image-wise exposing a silver halide color photographic light-sensitive material having a plurality of silver halide emulsion layers, and then performing at least a color development step, a bleach-fixing step and a water washing alternative stabilizing step. In the method for processing a photographic light-sensitive material, the color developing solution used in the color developing step has a pH of 1
0.3 or more, and the color developing solution contains a p-phenylenediamine compound having a water-soluble group as a color developing agent, and the color developing solution contains a compound represented by the following general formula [1]. general formula [1] in R-SO ₃ X (wherein containing, R represents an alkyl group or a phenyl group having 1 to 8 carbon atoms, having these repeating units in addition R is an ethylenically unsaturated group A polymer may be used, and X represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or an ammonium group.) The method for processing a silver halide color photographic light-sensitive material. 2. The silver halide according to claim 1, wherein the silver halide contained in the plurality of silver halide emulsion layers is substantially silver chlorobromide. Color photographic light-sensitive material processing method. 3. The color developing solution according to claim 1, wherein the solution contains a solvent in a volume ratio range represented by the following formula. Method for processing silver halide color photographic light-sensitive material.