JPS62166336A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid and stable processing by developing a sensitive material contg. a silver chlorobromide emulsion as a photosensitive emulsion, a binder having a specified rate of swelling in the form of a film and a specified cyan coupler with a color developer. contg. a specified deriv. but not contg. benzyl alcohol. CONSTITUTION:A sensitive material contg. a silver chlorobromide emulsion as a silver halide emulsion, a binder having <=30sec rate T1/2 of swelling in the form of a film and at least one kind of cyan coupler represented by formula I, II or III in a photosensitive emulsion layer is developed with a color developer contg. an N-hydroxyalkyl substituted p-phenylenediamine deriv. by >=30mol% of the total amount of p-phenylenediamine type color developer is the soln. but no contg. benzyl alcohol. The development temp. is >=30 deg.C. In the formula I, one of R and R1 is H, the other is 2-12C straight chain or branched alkyl, X is H or a group eliminable by a coupling reaction with the oxidized produce of an N-hydroxyalkyl substituted p-phenylenediamine deriv. as a color developer, and R2 is a ballast group. A concrete example of the cyan coupler represented by the formula II or III is represented by formula A.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials). Dye images with low dependence on bromide ion concentration fluctuations and processing time dependence, without impairing speed, excellent ancestral color and stain, and high storage stability were obtained, and were also excellent in low pollution. The present invention relates to a new processing method, and particularly to a method that provides a processing method that requires a small amount of replenishment and has high processing stability.

[Zen Nakabayashi] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

In color development, the exposed silver halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted into the color developing solution and accumulated. In the desilvering step, silver produced during development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are combined and recycled.

In color developing solutions, development inhibitory substances accumulate when photographic light-sensitive materials are developed as described above, but the -1 color developing agent and benzyl alcohol are consumed or accumulated in the photographic light-sensitive materials and taken out. In a developing method in which a large amount of silver halide photographic material is continuously processed by an automatic processor or the like, the component concentration decreases.

In order to avoid changes in development finish characteristics due to changes in component concentration, a means is required to maintain the components of the color developer within a constant concentration range. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components.

The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, a so-called concentrated and low replenishment method has been widely used, in which the replenisher is concentrated and refilled in small amounts, and another method is to add a regenerating agent to the overflow liquid and use it again as a replenisher. has also been proposed and put into practical use.

[Problems to be Solved by the Invention] All of these methods substantially reduce the amount of replenishment. If the amount of replenishment is extremely reduced, the concentration of organic inhibitors and halogen ions eluted into the developer will be subject to large changes due to even a slight error in the amount of replenishment.
It is also more susceptible to the effects of concentration due to evaporation (1) Normally, the concentration of the fatigue accumulation mentioned above will increase (0) For example, if the halogen ion concentration increases, the development reaction will be suppressed, or the legs of the characteristic curve will be more suppressed. This causes the problem of high contrast. To avoid this, halogen ions are removed from the overflow solution using an ion exchange resin or electrodialysis, and a regenerating agent is added to compensate for the missing components generated during development and missing components lost during regeneration processing, and the solution is regenerated as a replenisher. Is there a suggested way to use it?

These regeneration and concentrated low replenishment methods using ion exchange resins and electrodialysis are affected by evaporation and regeneration operations, and are susceptible to fluctuations in bromide ion concentration. The difference between the beginning and the weekend when the order quantity is low, and the high season and the high season is expressed as a difference of up to 1:5, and the composition of the processing liquid is affected by evaporation and the difference in the amount of replenisher. There is a drawback that the width is different.

Therefore, in low replenishment processing and regeneration methods, efforts are made to quantitatively analyze the components and make the composition constant each time the product is regenerated. Therefore, it is difficult for photo labs and minilabs without special skills to carry out these regeneration processing and low replenishment processing. It is often difficult.

These problems are mainly caused by changes in bromide ions, which are development inhibitors. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to errors in the amount (see Japanese Patent Application Nos. 59-173189 and 59-205540, etc.).

It is also presumed that these problems can be solved by improving developability by, for example, reducing the average grain size of silver halide in photographic materials or reducing the amount of coated silver, or by using conventional developing agents. certain 3-methyl-4-
Improving the developability of a color developer using amino-N-ethyl-N-β-methanesulfonamide ethylaniline makes it easier to absorb the effects of fluctuations in the bromide ion concentration in the developer, making processing easier. The result is the opposite of the expected stability loss.

However, it is an important issue to improve processing stability while shortening processing time.

Conventionally, in color paper processing consisting essentially of a silver chlorobromide emulsion, one color development was performed at 33°C for 3 minutes and 30 seconds - bleaching and fixation.
°C for 11 minutes and 30 seconds - washing with water for 3 minutes (or stabilizing for 3 minutes) - drying. The total processing time is about 8 minutes, which is the standard processing time, but the current strong demand is for the above-mentioned low replenishment from an economical point of view, but there is also a strong demand for short processing times from the perspective of shortening delivery times. has been done.

However, as described above, speeding up the process and stabilizing the process or reducing replenishment are contradictory issues and can be said to be a trade-off relationship.

That is, if the replenishment level is low, the concentration of bromide ion, which is an inhibitor, and the concentration of sulfur compounds and mercapto compounds, which are emulsion stabilizers, increase, impairing rapidity and processing stability.

However, various measures have been taken to speed up color development. In particular, the above-mentioned developing agent, which has been used for a long time as the most suitable crude drug for developing silver chlorobromide emulsions, has low hydrophilicity.

Penetration of a color developing agent into a light-sensitive material is slow, and various penetrants have been studied to speed up the penetration.1 For example, a method of speeding up color development by adding benzyl alcohol to a color developer is widely used. However, this method
Unless treated with C for 3 minutes or more, the color did not develop sufficiently, and it also had the disadvantage that it was easily affected by the subtle bromide ion concentration. Is there also a known method of increasing the pH of the color developing solution?When the pi is over 1000, the oxidation of the color developing agent becomes extremely rapid, and since there is no suitable buffer solution, it becomes more susceptible to changes in pl+ and becomes stable. There were problems in that photographic characteristics could no longer be obtained and processing time became highly dependent.

A method of increasing the activity by increasing the color developing agent in the color developing solution is known, but the color developing agent is very expensive, resulting in a relatively expensive processing solution, and at the same time, the main agent is difficult to dissolve in water and tends to precipitate. It also causes instability and cannot be used practically.

On the other hand, in order to speed up color development, a method is known in which a color developing agent is incorporated into a light-sensitive material in advance. For example, there is a known method of incorporating a color developing agent in the form of a metal salt (U.S. Pat. No. 3,719,492); however, this method has poor storage stability for photosensitive materials, and is difficult to store before use. Another drawback was that it was prone to fogging during color development.

Furthermore, in order to inactivate the amine part of the color developing agent,
For example, a method of incorporating a color developing agent into a Schiff salt (US Pat. No. 142,559).

Research Disclosure, 197
No. 6, No. 15159) is also known, but these methods have the disadvantage that color development cannot begin until after the color developing agent has been alkaline hydrolyzed, and rather the color development is delayed.

Furthermore, when the color developing agent is directly contained, the color developing agent is unstable, which causes the emulsion to overlap during storage, and the quality of the emulsion film becomes weak, which can lead to various processing problems. there were.

Furthermore, it is known that 3-pyrazolidones are added to a black and white developer solution containing a developer such as pytroquinone to accelerate development (for example, F, A).

Author: Photographic Process
The fact that this compound is incorporated into photosensitive materials is disclosed in British Patent No. 767.7.
However, in the technology described in the above patent specification, the technology is incorporated into a black-and-white photosensitive material or a one-inversion color photosensitive material, and its purpose is to promote only black-and-white development. Japanese Patent Publication No. 53-52422 discloses that 3-pyrazolidones are added to a photosensitive material for the purpose of preventing a decrease in sensitivity in an unexposed state of a color photosensitive material containing a 2-equivalent magenta coupler having an oxy-type organic split-off group at its active site. However, these techniques are not suitable as a rapid method of stabilizing color development processing with low replenishment processing.

Further, as a conventionally known method of accelerating color development using an accelerator, US Pat. No. 2,950,970;
No. 2,515,147, No. 2,496,903, No. 4,038.075, No. 4,119,462,
British Patent No. 1.4:10.998, No. 1,455,41
No. 3, JP-A-53-15831, JP-A No. 55-62450
No. 55-62451, No. 55-62452, No. 55-62453, Special Publication No. 51-12322, No. 5
The compounds described in No. 5-49728, etc. have been studied, but most of the compounds have insufficient accelerating effects, and the compounds that show a high accelerating effect not only have the drawback of forming fog, but also require treatment. This was not suitable as a method for improving stability.

Further, it is known that a silver halide emulsion layer which is substantially non-photosensitive is provided in a light-sensitive material to accelerate development.
No. 23225, No. 56-14236, British Patent 1. :
No. 178,577, OLS No. 2,622,922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers and DAR couplers. There is nothing that actively promotes development, and its development promotion effect is not only small, but even though it is effective against fluctuations in iodide ion concentration, the process is completely stable against fluctuations in bromide ion concentration. No effect was obtained.

On the other hand, the speed of color development varies depending on the type of paraphenylenediamine derivative used and is said to depend on the oxidation binary potential. Among these color developing agents, N
, N-diethyl-p-phenylenecyamine sulfate and 3-
Color development with low water solubility of N-alkyl substituted drugs such as methyl-4-amino-N,N-diethylaniline hydrochloride ↑ Is the development activity high and is it possible to speed up the development? Dark fading of the coloring dye after processing It is known that it has low sex and is undesirable. On the other hand, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl is said to be preferable because of its high development activity (see U.S. Pat. No. 3,656.950, U.S. Pat. No. 658,525, etc.) Aniline-C-p-toluenesulfonate does indeed provide rapid processing speed, but it does not provide stable bromide ion concentration, and yellow stain occurs significantly in the unexposed areas of photographic materials after processing, especially during short processing times. When this is done, the color developing agent remains and causes rough staining, so it cannot be used in rapid processing.

On the other hand, 3-methyl-4-amino-N-ethyl-β-methanesulfonamitoethylaniline sesquisulfate monohydrate and 3- Methyl-4-amino-N-β-hydroxyethylaniline sulfate k12, etc., are available from Photocratic Science Ant Encinia Song Vol. 1.8. No: 1.
As seen in May-June, 1964, P, 125-137, it was said that there was not much difference in half-wave potential indicating the oxidation-reduction potential, and that both had weak developing activity.

Therefore, there are few color developing agents that can provide substantial development activity of silver chlorobromide emulsions and have excellent storage stability of dye images; generally, 3-methyl-1-amino-N-ethyl-N
-β-methanesulfonamitoethylaniline sulfate,
The above objective was achieved by using it with benzyl alcohol.

However, in this case, as mentioned above, it is easily affected by changes in bromide ion concentration. Further, in the concentrated low replenishment process in which the amount of replenisher is reduced, another problem is an increase in the contamination and accumulation of other processing liquid components.

This is because the rate at which the tank liquid is replaced with replenisher becomes lower due to the decrease in the amount of replenishment, and also because the period of use of the liquid becomes longer. Contamination with other processing solutions is caused by so-called back contamination, in which processing solution components immediately after development are brought into the color developer by splashes from adjacent processing solutions in the processing machine, transport leaders, belts, hangers for hanging the film, etc. It will be done. Among these contaminant components that accumulate, thiosulfate ion, which is a fixing agent, accelerates development. That is, this problem occurs particularly when bleach-fixing is performed directly after one-color development. In particular, by promoting the shoulder portion of the photographic characteristic curve, remarkable high contrast is produced. Further, increased contamination of metal salts as bleaching agents, especially ferric salts, accelerates the decomposition of hydroxylamine as a preservative, producing ammonia ions. This decomposition reaction is greatly accelerated at temperatures above 30°C. The generation of ammonia ions, like thiosulfate ions, has the disadvantage of accelerating physical development and increasing contrast.

Therefore, even if the amount of replenishment is reduced in order to improve economical and environmental pollution, iJ! , a color developing solution that can be processed quickly, maintains constant photographic performance, and does not degrade the active ingredients or change the photographic processing performance even if the processing solution is used for a long period of time. The current situation is that its appearance is strongly desired.

It is an object of the present invention to maintain constant appropriate photographic performance over a long period of time without any change in bromide ion concentration even when processed with a color developing solution at a low replenishment amount, and to produce a color developing agent and To provide a rapid and stable method for processing a photosensitive material in which uncolored areas do not fade or change color even when stored for a long period of time.

Other objects of the invention will become apparent from the description below.

[Means for Solving the Problem] As a result of various studies to achieve the above-mentioned object of the present invention, the present inventor has developed a unique color development that is almost unaffected by the bromide ion concentration when developing a specific silver halide. Although we succeeded in finding the main drug, we also encountered the problem that the storage stability of the obtained coloring dye decreased, and we further investigated ways to solve this problem. As a result, in the method for developing a photosensitive material, the silver halide emulsion in at least one photosensitive emulsion layer is substantially a silver chlorobromide emulsion;
Binder v11! A photographic material having a wettability rate T I/2 of 30 seconds or less and containing at least one cyan coupler represented by the following general formula (I), (II) or (m) is Development processing is carried out at 30°C or higher using a color developing solution containing 30 mol% or more of a p-phenylenecyamine derivative based on the p-phenylenediamine color developing agent in the color developing solution and substantially free of pencil alcohol. It has been found that the above object can be achieved by a method of processing a photosensitive material characterized by the following.

General formula ([) In the formula, one of R and R1 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 N-hydroxyalkyl substituted -p
-phenylenediamine derivative represents a group that can be released by a coupling reaction with an oxidized form of a color developing agent, and R2 represents a ballast group.

General formula (II) H General formula (m) OH In the formula, Y is -COR4, (However, R4 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Rg is a hydrogen atom, an alkyl group, alkenyl group, cycloalkyl group,
represents an aryl group or a heterocyclic group, and R4 and Rs may be bonded to each other to form a 5- to 6-membered heterocycle)
, R3 represents a ballast group, and Z represents a hydrogen atom or a group that is separated by a coupling reaction with an oxidized product of a hydroxyalkyl-substituted -ρ-phenylenecyamine derivative color developing agent.

The present inventor has discovered that a specific silver halide, namely silver chlorobromide-based (
In particular, when developing a color photographic light-sensitive material using an emulsion with a silver bromide content of 90 mol% or less, the bromide ion concentration changes when an N-hydroxyalkyl-substituted p-phenylenediamine conductor is used as the color developing agent. The first and most important fact has been discovered that there is almost no change in the density of the dye obtained. The above-mentioned characteristics of this color developing agent include silver iodide of 0.5
This cannot be obtained with color photographic materials that use silver iodobromide emulsions containing more than mol% of silver iodobromide, and conventionally this type of color developing agent has been used exclusively for the development of silver iodobromide emulsions. In particular, the fact that the development speed is not delayed even if the bromide ion concentration is greatly increased when developing a color photographic light-sensitive material using a substantial silver chlorobromide emulsion is unexpected. This is not something that can be understood from the oxidation-reduction potential or half-wave potential of common color developing agents, and it is surprising that this phenomenon cannot occur unless an optimal balance between development speed and coupling speed is maintained. It was the right thing to do.

However, the inventor encountered the following problem. When an N-hydroxyalkyl-substituted-p-phenylenediamine color developing agent is used, it is rapid and unaffected by changes in bromide ion concentration, and can be developed especially under high bromide ion concentrations, so it is necessary to replenish it during continuous processing. Although it has the great advantage of being able to greatly reduce the amount of color and having extremely high processing stability, the storage stability of the resulting coloring dye is affected, especially the reduction in photofading resistance and the occurrence of staining, especially cyan staining. I found out that there is a drawback.

The storage stability of dye images has become a critical and major obstacle, especially in the case of print materials.

As a result of further efforts by the inventor to resolve this issue,
The photofading property is not due to the low storage stability of the dye itself, but is caused by the fact that single-color developing agents and oxidized products of color developing agents tend to remain in color photographic materials. It has been found that the above problem occurs when the benzyl alcohol used is present in the color developer. However, substantially freeing benzyl alcohol from the color developing solution cannot be achieved unless the development processability of the color photographic material is sufficiently improved.

Regarding cyan stain, it largely depends on the structure of the coupler, and in order to achieve low replenishment and processing stability without impairing the photobleaching properties and stain characteristics of the dye image, the coupler of the present invention must be used, and the coupler of the present invention must be used. It has been found that it is necessary to use a color developing solution substantially free of benzyl alcohol.

In this case, if conventional photographic materials are used as they are, the problem arises that developing time is insufficient and sufficient photographic images cannot be obtained. Therefore, the inventors of the present invention have made further studies and found that in order to perform low replenishment processing without being affected by the increase in bromide ion concentration by using the color developing agent of the present invention, at least one layer, preferably all photosensitive emulsion layers, can be processed. The silver halide emulsion is substantially a silver chlorobromide emulsion, and the binder film swelling rate T l
/2 or less than 30 seconds in a color photographic light-sensitive material, a developer containing at least 30 mol % or more of an N-hydroxyalkyl di-substituted-p-phenylenediamine derivative based on the p-phenylenediamine color developing agent in the color developer. By processing, the development speed was improved and the object of the present invention was successfully achieved without impairing the stability of the one-dye image.

In this specification, the term "substantially silver chlorobromide emulsion" may include a WL amount of silver iodide in addition to silver chlorobromide, for example, 0.3 mol% or less, more preferably means that it may contain 0.1 mol or less of silver iodide. However, in the present invention, silver chlorobromide emulsions containing no silver iodide are most preferred.

The present invention will be described in further detail below.

The hydrophilic binder used to coat silver halide in color photographic light-sensitive materials is usually gelatin, or sometimes a high molecular weight polymer, and the film swelling rate T
The film swelling rate T1/2 of the binder can be measured according to any technique known in the art, for example,
een and G, LP.

Lcvenson, J. photo, sci., 2
0. It can be measured by using a swellometer (swelling film) of the type described in p. The saturation film thickness is defined as 90%, and is defined as the time required to reach 112 thickness of 1/2 (see FIG. 1).

The binder of the photographic constituent layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate T1/2 of 30
The lower limit is less than 2 seconds, and the smaller the better, but the lower limit is preferably 2 seconds or more because if it is too small, failures such as scratches may occur without hardening.

Particularly preferably, the time is 20 seconds or less, most preferably 15 seconds or less. If it is longer than 30 seconds, not only will the storage stability of the dye image be low, but also sufficient dye formation will not be obtained in a short period of time.
The membrane swelling rate Tl/Z can be determined by the amount of hardener used.

The light-sensitive emulsion layer of the light-sensitive material processed according to the present invention is
It is sufficient that at least one layer consists essentially of a silver chlorobromide emulsion, but it is preferable that all of the light-sensitive emulsion layers consist of a silver chlorobromide emulsion, and the silver chlorobromide is contained in a mol% of silver bromide. The smaller the silver bromide content is, the more sufficient dye formation can be obtained even with short one-color development, so the silver bromide content is preferably 80 mol% or less, and 70 mol%.
The most preferable results are below 40 mol% or more.

The cyan coupler according to the present invention has the general formulas CI) to (I
The general formula CI) can be represented by II), and the general formula CI) will be further explained.

In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R+ and R in the general formula CI) is, for example, an ethyl group, a propyl group, or a butyl group.

In general formula (I), the ballast, represented by R2, is of a size that provides the coupler with sufficient bulk to prevent the coupler from being substantially dispersed elsewhere from the layer to which it is applied. A typical palust group, which is an organic group with a shape, has a total carbon a8 to 3
2 alkyl groups or aryl groups, preferably having a total carbon number of 13 to 28. These alkyl groups and 7-aryl groups may have a substituent, and examples of the substituent for this aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a carboxy group, an acyl group,
Examples of substituents for alkyl groups include ester groups, hydroxy groups, cyanide groups, nitro groups, carbamoyl groups, carbonamide groups, alkylthio groups, arylthio groups, sulfonyl groups, sulfonamide groups, sulfamoyl groups, and halogens. The substituents listed above for the aryl group excluding the group may be mentioned.

A preferable example of the palast group is the following general formula: % R12 represents an alkyl group having 1 to 12 carbon atoms, Ar represents a 7-aryl group such as a phenyl group, and even if this aryl group has a substituent, Good substituents include alkyl groups,
Hydroxy group, halogen atom.

Examples include alkylsulfonamide groups, and the most preferred are branched alkyl groups such as t-butyl.

The group defined by X in the above general formula CI) that can be split off upon coupling with the oxidized form of the color developing agent determines the number of equivalents of the coupler and also controls the coupling reaction, as is well known to those skilled in the art. Typical examples of 0 that affect gender are:
Halogens represented by chlorine and fluorine, aryloxy groups, substituted or unsubstituted flukoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups,
Heteroyloxy group, sulfonyloxy group.

Examples include carbamoyloxy group. More specific examples include JP-A-50-10135 and JP-A-50-12.
No. 0334, No. 50-130414, No. 54-482
No. 37, No. 51-146828, No. 54-14736
No. 47-37425, No. 50-123341,
Examples include groups described in US Pat. No. 58-95345, Japanese Patent Publication No. 48-36894, US Pat. Exemplary compounds of the cyan coupler represented by the general formula CI) are listed below, but are not limited to these. In the general formula CI), R1, X,
Examples include those in which R2 and R are specified.

The synthesis method of the exemplified compounds of the present invention is shown below in the margins, but other exemplified compounds can also be synthesized by the same method.

Synthesis Example of Exemplified Compound C-5 [(1)-t ] Synthesis of 2-nitro-4.8-dichloro-5-ethylphenol 33 g of 2-nitro-5-ethylphenol, 0.6 iodine
8 and 1.5 g of ferric chloride were dissolved in 150 g of glacial acetic acid.

To this, 75+jL of sulfuryl chloride was added dropwise over 3 hours at 40° C. The precipitate formed during the 0 dropwise addition was reacted and dissolved by heating and refluxing after the completion of the dropwise addition of sulfuryl chloride. Heating and refluxing takes about 2 hours.The reaction solution is poured into water, and the resulting crystals are purified by recrystallization with methanol.

(1)-a was confirmed by nuclear magnetic resonance spectroscopy and elemental analysis.

[(1)-b 1 2-nitro-4,6-dichloro-5
-Synthesis of ethylphenol [(1)-a 21.2g of compound 1 was added to 300+sjL
A catalytic amount of Raney nickel was added thereto, and after hydrogen was passed through the reaction at normal pressure until hydrogen absorption disappeared, the Raney nickel was removed and the alcohol was distilled off under reduced pressure. The residue [(1)-b] was subjected to the next acylation without being purified.

[(1)-c] 2[(2,a-di-tert-acylphenoxy)acetamide]-4,6-dichloro-
Crude amide compound 1B-5g obtained by synthesis of 5-ethylphenol [(1)-b]
was dissolved in a mixture of 500a+1 glacial acetic acid and 18.7g of sodium acetate, and 28.0g of 2,4-di-tert-acylphenoxyacetic acid chloride was added to 50mJl of acetic acid.
A solution of acetic acid dissolved in is added dropwise at room temperature. The mixture was added dropwise over 30 minutes, and after stirring for an additional 30 minutes, one reaction solution was poured into ice water. The generated precipitate is collected by filtration, dried, and then recrystallized twice from acetonitrile to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectroscopy.

The following margin is CnHsN (hCQ) Next, the general formula (n) or (III
) will be explained. In the general formulas (n) and (m), Y is -(:OR4
.

It is a group represented by However, R4 is an alkyl group, preferably a furkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (allyl group, heptadecenyl group, etc.). group, etc.), cycloalkyl group, preferably 5-
Seven-membered rings (for example, cyclohexyl, etc.), aryl groups (for example, phenyl, tolyl, naphthyl, etc.), and heterocyclic groups.

Preferably 1 nitrogen atom, oxygen atom or sulfur atom
R represents a 5- to 6-membered heterocyclic group containing ~4 members (e.g., furyl group, chenyl group, benzothiazolyl group, etc.)
s represents a hydrogen atom or a group represented by R4, R
4 and R5 may be combined with each other to form a 5- to 6-membered heterocycle. Furthermore, any substituent can be introduced into R2 and R3, such as an alkyl group having 1 to 10 carbon atoms. (e.g. methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.), aryl groups (e.g. phenyl,
naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.)
.

Cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (e.g. methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p-toluenesulfonamide, etc.) ) luenesulfonyl, etc.), fluorosulfonyl groups, carbamoyl groups (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl groups (e.g. acetyl, benzoyl, etc.), heterocyclic groups (e.g. pyridyl group, pyrazolyl group, etc.), alkoxy group, aryloxy group, acyloxy group, etc.

In the general formula (Il) and the general formula (m), R3 imparts diffusion resistance to the cyan coupler represented by the general formula (n) and the general formula (III) and the cyan dye formed from the cyan coupler. represents a ballast group necessary for 6, preferably an alkyl group, aryl group or heterocyclic group having 4 to 30 carbon atoms, such as a straight-chain or branched alkyl group (
For example, t-butyl, n-octyl, t-octyl, n-
dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, and the like.

In the general formula (n) and the general formula [■], Z represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized product of the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent 0 For example, a halogen atom (e.g. chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy groups,
Examples include aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfone 7-mido groups, and more specific examples include U.S. Pat. , No. 741.5+1t3, JP-A-47-37425
No., JP 4B-36894, JP 50-1013
No. 5, No. 50-117422, No. 50-130441
No. 51-108841, No. 50-120343, No. 52-18315, No. 53-105226, No. 54-14736, No. 54-48237, No. 55-
No. 32071, No. 55-65957, No. 56-193
No. 8, No. 56-12643, No. 56-27147,
No. 59-146050, No. 59-166956, No. 60-24547, No. 60-35731, No. 60-
Examples include those described in No. 37557 and the like.

In the present invention, among the cyan couplers represented by the general formula (n) or (III), the following general formula (IT),
Cyan couplers represented by (V) or (VI) are more preferred.

General formula (IV) H General formula (V) H General formula (1) In the general formula (rV), Rt3 is a substituted or unsubstituted aryl group (particularly preferably a phenyl group), and the aryl group has a substituent. In this case, the substituent is S02
Rls, halogen atom (fluorine, chlorine, bromine, etc.),
CF3, -NO2, -CM, -CORti.

-COOIhs, -8020Rts.

At least one substituent selected from is included.

Here, RIG is an alkyl group, preferably a carbon number 1
~20 alkyl 2&i (e.g. methyl, ethyl.

tert-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (e.g. cyclohexyl, etc.) , represents an aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), and Rly is a hydrogen atom or a group represented by Ru.

In a preferred compound of the cyan coupler of the present invention represented by the general formula (IV), Ru is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -
9O2RLI (Lm is an alkyl group), halogen atom,
A compound that is trifluoromethyl.

In general formulas (V) and (Vl), R14 and Ris are an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (
For example, methyl, ethyl, tert-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, oleyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups. (e.g. cyclohexyl, etc.), aryl groups (e.g. phenyl, tolyl, naphthyl, etc.), heterocyclic groups (e.g. 5- to 6-membered heterocyclic groups containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms) A ring is preferred, such as a furyl group, a chenyl group, a benzothiazolyl group, etc.).

Said Rt, R1? and R1 of general formulas (V) and (VI)
4. An arbitrary substituent can be further introduced into Ra. Specifically, in general formulas (It) and (m), R
4 or Rs. As a substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable.

In general formula [■], (V) and (VI), Z and R3
have the same meanings as in general formulas (II) and (m), respectively. A preferred example of the ballast group represented by R:I is a group represented by the following general formula (■).

General formula [■] In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, represents an integer from 0 to 4, one sentence represents 0 or l, and when K is 2 or more, two or more are present. Rn may be the same or different; Rt represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group; Rn represents a monovalent group, preferably a hydrogen atom or a halogen atom(
For example, chromium, bromine), alkyl groups, preferably linear or branched alkyl groups having 1 to 20 carbon atoms (for example, methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.) ), aryl groups (e.g., phenyl groups), heterocyclic groups (e.g., nitrogen-containing heterocyclic groups), alkoxy groups, preferably linear or branched alkoxy groups having 1 to 2 o carbon atoms (e.g., methoxy,
ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (e.g. phenoxy groups), hydroxy groups, acyloxy groups, preferably alkylcarbonyloxy groups, arylcarbonyloxy groups (e.g. acetoxy groups, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably a straight-chain or branched furkylcarbonyl group having 1 to 20 carbon atoms, preferably phenoxycarbonyl group,
Alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, acylamino group, preferably 1 to 20 carbon atoms
20 straight chain or branched furkylcarboamide group, benzenecarboxamido group, sulfonamide group, preferably straight chain or branched furkylsulfonamide group having 1 to 20 carbon atoms, benzenesulfonamide group, carbamoyl group, preferably Represents a straight or branched fluorylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, a sulfamoyl group, preferably a straight or branched fluorylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms. .

Next, specific examples of cyan couplers represented by formula (n) or (III) will be shown, but the invention is not limited thereto.

Margin below [Exemplary compounds] 0 -2ri O.J.

0-noke -J5 -J7 C-C C-Tsuku I C-ri θ Oh.

C-Hiro 1 -P2 C-Illusion C-kai ψ C-%” C-ril a-<x7 OH C-ri? C-+ri (t)OsHu 0-da1 H -f2 H H3 -1j C-f Hiromu C-fri t -sj -f7 H -si H 4H9 0-f mail l O-〆θ 06H.

f-1 C4H.

C-/2 ρI C-ρ j a- as a partner H 06H,.

c-1ap c-/;1 H 2H5 C-? 1 H u c -7s O-ri l O-’t8 c-’? '1 -S.O. (t) O, H.

OCH20H20 (3H.

c-gb C-87 〇-minute 8 C-8? 0-'l.

H 04H.

04H,”’ −qF H 2H5 0H (t)O,H,1 -1o0 H O-101 NH80, (3H.

a-(o3 2Hs O-10 cow H c −tOr 0-+o'b C-IO p 04H,,5o2NB Oμ SO□NH (OH2)200zHs o-/Iri t 0-/l Hiro 0-//,! ; t O-//6 t O-/19 0-1zl.

H r"0- /2J O-/2ri0-7.Z! N C-/2〆N -1z7 H These cyan couplers of the present invention can be synthesized by a known method, and have the general formula [■] In the case of compounds represented by, for example, U.S. Pat.
8. [T22, 3,998,253, British Patent 1
．． It can be synthesized by the synthesis method described in No. 011,940 and the like. In addition, in the case of a compound represented by general formula (III) 1, for example, U.S. Pat. No. 2,772,182;
758.308, 3,880,881, 4.1
No. 24,3118, British Patent No. 975,773, 8.
No. 011,893, No. 8,011,884, JP-A-4
No. 7-21139, No. 50-112038, No. 55-
No. 163537, No. 56-29235, No. 55-99
No. 341, No. 56-116030, No. 52-6932
No. 9, No. 56-55945, No. 56-80045,
No. 50-134644 and British Patent No. 1,011,9
No. 40, U.S. Patent No. 3,448,822, U.S. Patent No. 3,998
, No. 253, JP-A-56-65134, JP-A No. 57-20
No. 4543, No. 57-204544, No. 57-204
No. 545, Japanese Patent Application No. 56-131309, No. 56-13
No. 1311, No. 56-131312, No. 56-131
No. 313, No. 56-131314, No. 56-1304
No. 59, No. 57-149791, JP-A No. 59-146
No. 050, No. 59-166956, No. 60-2454
No. 7, No. 60-35731, No. 60-37557, etc.

The cyan coupler represented by the general formula (I), (n) or (III) can be used in combination with a cyan coupler other than the one according to the invention to the extent that it does not contradict the object of the invention.

Furthermore, one or more cyan couplers of the general formulas CI), (It) and (m) can be used in combination.

When the cyan coupler according to the present invention represented by general formulas (I) to (III) is contained in the silver halide emulsion layer, it is usually about 0.005 to 2 mol per mol of silver halide,
It is preferably used in a range of 0.01 to 1 mol.

In the present invention, the processing temperature is raised to complete the development in a short time rather than to maintain the storage stability of the dye.The higher the temperature is from 30°C to 50°C, the shorter the processing time, and the faster the process. From this point of view, the temperature is preferably 33°C or higher and 48°C or lower, and most preferably 35°C or higher and 43°C or lower.

An effective developing agent in the present invention is a quaternary ammonium salt of a hydroxyalkyl-substituted p-phenylenediamine compound, particularly one that can be represented by the following general formula.

In the formula, R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R2 is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. is an alkyl group, R3 is an alkyl group having 1 to 4 carbon atoms which may have a water group,
A is an alkyl group that has at least one hydroxyl group and may have a branch, and is more preferably R4, R5, and R6 are each a hydrogen atom, a hydroxyl group, or 1 to 1 that may have a hydroxyl group. represents an alkyl group having 3 carbon atoms, at least one of R4, Rs, R6 is a hydroxyl group or an alkyl group having a hydroxyl group, R2, R3 are each O, l, 2 or 3, and where HX represents hydrochloric acid, sulfuric acid, P-)luenesulfonic acid, nitric acid or phosphoric acid.

Such P-7 nylenediamine color developing agents are unstable with their amines and are commonly used as salts (most commonly those specified by the formula above), typical An example is 4-amino-3-methyl-
Examples include N-ethyl-N-(β-hydroxyethyl)-aniline salt and 4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline salt.

Preferably, in the present invention, 4-amino-7-3-methyltoethyl-N-(β-hydroxyethyl)-aniline sulfate hydrate [which has been reprinted under the name CD-4 and is mostly In the color photographic system of
1, which is used for developing color negative films such as the K-4 system, has been found to be particularly effective.

Preferred N-hydroxyfurkyl substituted-p-7-functional nylene diamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds.

[Exemplary compounds]

H2 H2 H2 H2 (or N1-12 H2 Space below) Hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid salts of the compounds (1) to (8) above are particularly preferred.

Among these exemplified compounds, No., (1), (2),
(6).

(7) and (8) are preferably used, especially No., (1
), (2) and (6) are preferably used. moreover,
In particular, No. (1) is preferably used in the present invention.Since the solubility of the color developing agent of the present invention in water is extremely high, the amount used is preferably in the range of 1 g to 100 g per 11 of the processing solution. , more preferably 2g to 3
Used in the range of 0g.

These N-hydroxyalkyl-substituted-p-phenylenediamine derivatives of the present invention are described in the Journal of American
Chemical Society Vol. 73, p. 3100 (195
It can be easily synthesized by the method described in 1).

In addition to the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent, the color developing agent according to the present invention includes:
A p-phenylene diamine type is used, and a primary type is mentioned as a preferable example.

4-Amino-N, N-diethylaniline, 3-methyl-
4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methoxy-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-dimethylaniline, N-ethyl-N-β-(β-(β-methoxyethoxy)ethoxy) Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochlorides, sulfites, Examples include p-toluenesulfonate and phosphate. Preferably, dimethyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline is useful from the viewpoint of chromaticity.

Further 1, for example, JP-A No. 48-64932, JP-A No. 50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.

In the present invention, N-hydroxyalkyl substituted -p-
The phenylenediamine derivative has an effective effect on rapid processing and processing stability when it is contained at least 30 mol% or more, preferably 40 mol% or more, based on the total amount of p-phenylenediamine color developing agent in the color developer.

The color developing solution of the present invention needs to be substantially free of benzyl alcohol, and most preferably it is O per 11 parts of the color developing solution, or it is preferable from the viewpoint of image preservation, or if the content is too much for image preservation. Benzyl alcohol can be added to an extent that does not have any effect. Specifically, in carrying out the present invention, it is preferable to use 5II1 or less, preferably 2+*Jl or less, per color developer ti. Furthermore, by substantially freeing benzyl alcohol, it is possible to further reduce the concentration and replenishment and make the kit size more compact, which is preferable from the viewpoint of non-polluting properties and cost.

The color developing solution of the present invention has a bromide ion concentration of 5 x 10-''
It is preferable that the amount is r moles or more, and in the present invention, the higher the bromide, the lower the replenishment amount, so it is preferable. In conventional development methods, bromide inhibits the development reaction, and the lower the bromide content, the better; however, in the combination of the color photographic light-sensitive material and developer of the present invention, the higher the bromide content, the more preferable it is. achieved. In other words, in the present invention, the amount of replenishment can be reduced because it is less susceptible to the effects of bromide.

The bromide is preferably present in an amount of l x 10-2 mol or more, particularly preferably 1. If the bromide ion concentration is too high, development will be inhibited, so it is not preferable to have a bromide ion concentration of 6 x 10-2 mol or more due to the influence of the bromide ion concentration. Note that the concentration of chloride has no effect.

The color photographic light-sensitive material of the present invention is a multilayer color photographic light-sensitive material having three or more layers including each of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. That is, the maximum effect is exhibited when the membrane swelling rate T l/2 is 30 seconds or less, but the thickness of the gold membrane when dry is 147 ts or less.

It is preferably 13% or less, particularly preferably 12 gm or less, but in any case it is preferred that T l/2 is 30 seconds or less.

In the processing method of the photographic light-sensitive material of the present invention, it is possible to use a color developing bath containing the color developing agent according to the present invention. In addition, various other methods including bath treatment 1
For example, various processing methods can be used, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid.

In addition to the above, there are no particular limitations on the processing method for the photographic light-sensitive material of the present invention, and any processing method can be applied.

After color development, bleach-fixing is performed, and if necessary, washing with water and/or stabilizing treatment as an alternative to washing is performed. Method 5: After color development, bleaching and fixing are performed separately, and if necessary, washing with water and/or stabilizing treatment are performed. ; or a method of performing in the order of pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water, color development, washing with water, supplementary color development, stop, P: 4 white; Method of fixing, washing with water, and stabilizing in that order.

The developed silver produced by color development may be subjected to halogenation bleaching, and then color development may be performed again to increase the amount of produced dye, or any other method may be used for processing.

In the present invention, compounds preferably used in the water washing alternative stabilizer have a chelate stability constant of 6 for iron ions.
The above-mentioned chelating agents are mentioned, and these are preferably used to achieve the object of the present invention.

Here, the chelate stability constants are L, G, 5illen
・A-E, Martell, “5tabi
ity Con5tants of Meta
l-ion Complexes”, The
Chemical 5ociety, London
(1964), S., Chaberek-A., E., Ma.
"Organic Sequester" by Rtell
ing Agents'', a constant commonly known by Wiley (1959) and others.

Examples of chelating agents having a chelate stability constant of 6 or more for iron ions that are preferably used in the water washing alternative stabilizer of the present invention include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. can be mentioned. Note that 1. Iron ion means ferric ion (Fe'').

Specific examples of compounds of chelating agents having a chelate stability constant of 6 or more with ferric ions include, but are not limited to, the following compounds: ethylenediaminediorthohydroxyphenyl Acetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetosoaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, Trans-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, ■, 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, hexamethalin Particularly preferred are diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and -hydroxyethylidene-1,1-diphosphonic acid, among which l-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above-mentioned chelating agent used is 0.00.
01-50g is preferable, more preferably 0.05-2
It is in the range of 0g.

If the amount of replenishment of the water washing alternative stabilizer of the present invention is less than 0.5 times the amount brought in from the prebath per unit planting area, the prebath components will accumulate in the water washing alternative stabilizer of the present invention, and the photo The storage stability of the dye image deteriorates, and on the other hand, if it is more than 50 times, the desired effect of the present invention becomes smaller. For this reason, in the present invention, it is preferable to use the amount in a range of 0.5 to 50 times.

In particular, when used in a range of 2 to 30 times, the desired effects of the present invention can be particularly well achieved. Especially photosensitive material 1
It is preferable to add 20005 M or less per m''.

The tank for the water washing alternative stabilizing solution of the present invention may be 1 tank, but may be 2 to 1 tank.
The number of tanks can be increased up to about 1O2 tank, and the effect of the present invention becomes greater as the number of tanks increases, so the number of tanks may be increased within this range. Further, the replenisher to be added to the water-washing alternative stabilizing solution may be replenished in several places, but it is preferable to replenish it to a later tank as far as possible in terms of the processing flow of the photosensitive material, so that the overflow ( When the species are communicated by a tube located below the liquid surface, it is preferable to use a type in which the bath liquid (including the case where the bath liquid passes through a chain tube) flows into a tank in front of the nuclide, and more preferably two tanks. With the above-mentioned washing alternative stabilizer, replenish the washing alternative stabilizing replenisher to the last stabilizing tank, transfer the overflow to the previous tank sequentially, and collect the overflow from the washing alternative stabilizer after the solution with fixing ability. A part or all of the liquid may be discarded, or a liquid having the fixing ability may be poured into the liquid.

Means for imparting anti-spill properties to the water-washing alternative stabilizer used in the present invention include chemical means and physical means for imparting anti-spill properties.

A specific example of chemical means for imparting anti-spill properties is to include an anti-spill agent in the water washing alternative stabilizing solution of the present invention. Preferably used anti-high agents include sorbic acid,
Benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds 1 Morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds,
These are isoxazole-based compounds, propatoolamino-based compounds, sulfamide-based compounds, pyronone-based compounds, and amino acid-based compounds.

The benzoic acid compounds include salicylic acid, hydroxybenzoic acid, and hydroxybenzoic acid ester compounds such as methyl ester, ethyl ester, propyl ester, and butyl ester.

Preferred are n-butyl ester, isobutyl ester, propyl ester and salicylic acid of hydroxybenzoic acid, and more preferred is a mixture of the three hydroxybenzoic acid esters.

The phenolic 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 (especially alkyl 21i where the alkyl group is Ct-S), or a phenyl group as a substituent. Among them, preferred are ortho-phenylphenol, ortho-cyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, or 2-benzisothiazolin 3-one. These are isothiazolin 3-one, 5-chloro-2-methyl-4-isothiacyli-3-one, and 2-chloro-thiazolyl-benzimidazole.

Specifically, pyridine compounds include 2. dimethylpyridine, 2,4,6-drimethylpyridine, radium-2-
Examples include pyridinethiol-1-oxide, but radium-2-pyridinethiol-1-oxide is preferred.

Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine salt, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred.

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

Specific examples of morpholine compounds include: 4-(:l-nitrobutyl)morpholine, 4-(3-nitrobutyl)morpholine, and the like.

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

Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium. There are chloride etc.

Specifically, the urea-based compounds include N-(:1,4-dichlorophenyl)-N7-(4-chlorophenyl)urea, N-
(:l-trifluoromethyl)-N''-(4-chlorophenyl)urea and the like.

Specific examples of inxazole compounds include 3-hydroxy-5-methyl-isoxazole.

Proptool amino compounds include n-proptools and isoproptools, specifically DL-2-benzylamino-1-proptool, 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
■-Propatur, 3-amino-1-propatur, idopropaturamine, diisopropaturamine, N
, N-dimethyl-isopropanolamine, and the like.

Specifically, the sulfamide-based compounds include 0-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-abminor p-toluenesulfamide. Dosulfanilamide, acetosulfaguanidine, sulfathiazole, sulfadiazine, sulfamerazine, sulfamethacine, sulfaine oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfa There are thiazoles, etc.

Specific examples of pyronone compounds include dehydroacetic acid and the like.

A specific example of the amino acid compound is N-lauryl-β-alanine.

Among the anti-spill agents mentioned above, compounds preferably used in the present invention include thiazole compounds, sulfamide compounds, and pyronone compounds.

The amount of anti-piping agent added to the washing substitute stabilizer is 1! It is preferably used in a range of 0.001 to 30 g per L, more preferably in a range of 0-003 g to 5 g.

On the other hand, physical means include irradiating the water washing alternative stabilizer with ultraviolet rays or passing it through a magnetic field to impart anti-piping properties.

In the present invention, passing a magnetic field through the water-washing alternative stabilizer means passing the water-washing alternative stabilizer through a magnetic field generated between the positive and negative poles of the magnetic field, and the photosensitive material may pass through the magnetic field or not. good.

The magnetic field used in the present invention is obtained by using a permanent magnet made of ferromagnetic materials such as iron, cobalt, and nickel.
Alternatively, it can be obtained by passing a direct current through a coil or the like, but there is no particular limitation, and any means capable of forming a magnetic field can be used. Note that the magnetic field may be formed by using one magnet to form lines of magnetic force, or by opposing two magnets (a positive pole and a negative pole) to form lines of magnetic force between the opposing magnets.

The method of passing the water-washing alternative stabilizing solution used in the present invention through a magnetic field includes moving (including rotation) a permanent magnet that is placed inside and/or outside the stabilizing solution using a permanent magnet that forms a magnetic field. Alternatively, there is a method of moving the washing alternative stabilizing liquid by stirring or circulating the washing alternative stabilizing liquid. A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of the circulation system pipe and circulate the stabilizing liquid.

When permanent magnets are individually fixed to all of the pipes, the pipes themselves may be permanent magnets, or the permanent magnets may be attached to all of the pipes.

In the case of an automatic developing machine, is it possible to achieve the purpose by installing a permanent magnet etc. in the stabilizing bath instead of washing with water? In the case of a water washing alternative stabilization treatment process or a multi-stage stabilization bath, it is most preferable to pass the stabilizing solution of the all water washing alternative stabilization bath through a magnetic field.
It is also preferable to pass the stabilizing liquid of a stabilizing bath other than the water washing alternative stabilizing bath closest to the processing liquid having fixing ability through the magnetic field. In addition, the washing alternative stabilizing bath itself, preferably the inner surface of the washing alternative stabilizing bath! ! A resin lining containing a material capable of generating lines of force may be applied, and this lining can also be applied to the circulation system. In this way the stabilizing liquid can be passed through a magnetic field.

In the present invention, the method of irradiating the washing alternative stabilizer with ultraviolet rays is generally carried out using a reprinted ultraviolet lamp or ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is 5 to aoow (tube output). , but is not limited to this.

According to a preferred embodiment of the present invention, the wavelength of the ultraviolet rays is in the range of 220 nm to 350 nm.

Further, as an irradiation method, there is a method of placing the product in the washing substitute stabilizing solution or outside the washing substitute stabilizing solution and irradiating it directly.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A thickening agent, a development accelerator, etc. may optionally be included.

Further, in the present invention, chelating agents represented by the following general formulas (IT), (V), and (VI) are preferably used because they further exhibit the effects of the present invention on low replenishment and processing stability.

General formula (TV) A-COOM General formula [V] 0 B-P-82 B.

General formula (VI) ￥:c-on In the formula, A is a monovalent organic residue, B, B+ and B2 each represent a -valent organic residue or atom, which may be an inorganic substance or an organic substance. It may be.

D represents an aromatic ring or heterocycle which may have a substituent, and M
represents a hydrogen atom or an alkali metal atom.

Surface general formula ([V), (V) or (
Among the chelating agents represented by VL), preferred chelating agents for the present invention are compounds represented by any of the following general formulas [■] to (XVOI).

General formula [■] MIIIPI110301 general formula [
■) Mn+ tPnosn + is expressed by the general formula (fK
) A+ Rt Z Rt C00H General Formula (X) In the formula, E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -Rt-0R7-, -Rt-
OR? Represents OR,- or -RtZR,-, where Z is > N
-Rv A * or >N-A, R, ~R7
each represents a substituted or unsubstituted alkylene group, A1 to 80 are each a hydrogen atom, -08, -COOM or -POpM
represents x, M represents a hydrogen atom or an alkali metal atom,
m represents an integer of 3 to 6, and n represents an integer of 2 to 20.

General formula [scale] RsN (CIItPOaM't), where R1 is a lower alkyl group, an aryl group, an aralgyl group, a nitrogen-containing 6-membered ring group [as a substituent: 10t-r, -OR,
-COOM), and M represents a hydrogen atom or an alkali metal atom.

General formula (1) %Formula% In the formula, R, ~R1 are hydrogen atoms, -〇H1 lower alkyl (
-OH, -COOM, unsubstituted or as a substituent.

P OsM t), 81 to B are hydrogen atoms, -O
tl-COOM,-PO3M! , -NJz, where J is a hydrogen atom, a lower alkyl group, and C! H40[4,-PO
, M represents a hydrogen atom or an alkali metal, n
, m does not represent 0 or 1.

General formula (XII) OM R,,-0-P-ORIs ■ During the ceremony, RI! and R13 is a hydrogen atom or an alkali metal.

01 to C11 alkyl group, alkenyl group represents a cyclic alkyl group.

General formula (XN) In the formula, Ro is CI~1. an alkyl group of C1 to Io, a monoalkylamino group of C,X, , C1
~, dialkylamino group, amino group, CI~2. represents an aryloxy group, a C1-4 arylamino group, and an amyloxy group, and Q and ~Q are -OH.

C1 to 4 alkoxy group, aralkyloxy group, amyloxy group, -0M3 (M is a cation), amino group, morpholino group, cyclic amino group, alkylamino group, dialkylamino group, arylamino alkyloxy group .

General formula (X'/) General formula [application] In the formula, n 4g, R++, Rr7 and R1 are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a substituted or unsubstituted alkyl having 1 to 7 atoms. or unsubstituted phenyl group.

Rl#+ Rtar R*r and R11 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

In the formula, Rt and R1 represent a hydrogen atom, a halogen atom, or a sulfonic acid group.

General formula [X■] In the formula, R1゜ and R2゜ are respectively a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -Cl1tCOOII, -CIl*
PO51 (* or a salt thereof; xl represents a hydroxyl group or a salt thereof; W, Z, and Y each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group) represents a group or a salt thereof, an alkoxy group, or an alkyl group. Ill is 0 or l.

nl is an integer from 1 to 4, [1 is! or 2, pl represents an integer of 0 to 3, and ql represents an integer of 0 to 2.

Specific examples of the chelating agents represented by the general formulas [■] to [X■] include the following.

[Exemplary chelating agent]; (1) Na5P*0ta (2) Na
5P30゜(3) II-how (4)
Ir5PsO+.

(5) Na5P*0ta CIl, C00I+ CIls (15) (+10Cyo ■4) YoNCIIINC
llIC0OI I (16 ) (2I ) (22) (lx (OON (24) PG!I
AI POIIIz (29)
(3G) POllt2
CH2-POllt2POIIl,
P.O., II.

CII2POilb po=I+
.

PG, II, Cll
2COOIIPO1ff2
POlltCII2P(hlh
POilhPO, 11° (51) (52) (52'
) PO112 (Ill 0il
0ilOll ■ 11yOiP-C-POJlh ■ C2110] +IOC12CI(011)-CII2G-P-(ON
m) 2l 110CII2C1hO-P-(Ollh110C11
2CI-0-P-(ONa)2cn, ot+ 110-C112-CIl-C1lz-0-P-(Ol
l) 201! ++00C-C11-C112-0-P-(011).

(67) (6g) COO
to C00I+112
N-CII2CI+2-OP-(OH)2l211-C
oo-P-(OK)2 HIC-COO-P-(01112 IIooC-Cl12CI12NllC-Cll0II
-C-Cl120- P-(OH)tl11 0K 0+1 C21160-P-0CzH& NaOONm 011 0i1 (8[) Oll 011 011Oll
011 011Oll 011
0i+ OCIl, OCIl.

01+ 0il (8g) (89)C1
ni0011 CIItCOOllCIgCOOII
CIzCOOHCIl, C00II Cl
l2COOIICOOII C
OO11CIIzPChNphantom CII2COONa CI12COONmCl12
C OON, COOff CIItCOOllCTo
COONa CIlzCOCllzCOON C1l, C00II In the present invention, general formula [■], (Vff[), (IX)
(X), (Xl), (XII), (XV) and [X■]
It is effective to use chelating agents shown in

The chelating agent represented by any of the above general formulas (IV) to (Vl) used in the present invention has an amount of i x per stable liquid ifL.
It can be added in the range of to-'mol-1 mole,
Preferably, it is added in a range of 2 x 10-' mol to 1 x 10-' mol, more preferably 5XI
It can be added in the range of O-4 mol to s x to-2 mol.

Examples of additives other than the above that may be added to the color developing solution include bromides such as potassium bromide and sodium bromide, alkali iodide, nitropenzimitazole, mercaptobenzimitazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing solutions such as l-phenyl-5-mercaptotetrazole, there are anti-stain agents, anti-sludge W agents, preservatives, interlayer effect promoters, chelating agents, and the like.

As bleaching agents used in bleaching solutions or bleaching qualitative solutions in the bleaching process, those in which total ion such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid are generally known. ing. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol etherdiaminetetraacetic acidethylenediaminetetraprobionic acidethylenediaminetetraacetic aciddisodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may also contain additives. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the bleach solution mentioned above, additives from other companies such as PU buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. It may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Processing processes other than color development of the silver halide color photographic light-sensitive material of the present invention, such as bleach-fixing (or bleaching, fixing), as well as various processing steps such as water washing and stabilization as necessary, are also rapidly processed. From this point of view, it is preferable to carry out the process at a temperature of 30°C or higher.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 5B-105145, 58-1
No. 34634 and No. 5B-18631 and patent application No. 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that is decolorized by a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 58
No. 4.509, No. 1,277.429, Japanese Unexamined Patent Publication No. 1977-
No. 85130, No. 49-99620, No. 49-114
No. 420, No. 49-129537, No. 52-1081
No. 15, No. 59-25845, No. 59-111640
No. 59-111641, U.S. Patent No. 2,274,7
No. 82, No. 2,533,472, No. 2,956,87
No. 9, same: l, 125,448, same: 1.148,1
No. 87, No. 3,177.078, No. 87, No. 3,177.078, Same: l, 247,
No. 127, No. 3,260,601, No. 3.540,
No. 887, No. 1,575,704, No. 1, 65
No. 3,905, No. 3,718,472, No. 4,071
．． :112 and No. 4,070.352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-' to 5 X 10-' moles, more preferably l x 10-'' to l X t
o-' moles are used.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0] planes to [1,1,1] planes may 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 outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Roughly plate-shaped silver halide grains (Japanese Patent Application Laid-open No. 113934/1982, Japanese Patent Application No. 1983)
9-170070) may also be used.

Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, seed particles may be produced using an acid method, and then grown using an ammonia method, which has 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 suitable for the growth rate of silver halide grains is controlled, for example, as described in JP-A-5.4-48521. It is preferable to simultaneously implant and mix silver ions and halide ions.

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

These silver halide emulsions contain active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers: reduction sensitizers such as stannous salts, thiourea dioxide, Polyamine kg: Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol 3
- Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these They act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination 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 this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention contains an appropriate sensitizing dye in an amount of 5 x 10-' to 3 x 1 per mole of halide in order to impart photosensitivity to a desired wavelength range.
Optical sensitization may be achieved by adding 0-'mol.

Various sensitizing dyes can be used, and each sensitizing dye may be used alone or in combination. Examples of the sensitizing dyes advantageously used in the present invention include the following: I can list things like this.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and U.S. Pat.
, No. 231,658, No. 2,493,748, No. 2.
50:1.776, 2,519,001, 2,
No. 912,329, No. 3.556,959, No. 3,
No. 672,897, same: l, No. 694,217, same: 41
Examples include those described in Japanese Patent Publication No. 25,349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, and the like. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 2,945.763 and British Patent No. 505,979. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, for example, US Pat.
No. 9,234, No. 2,270,378, No. 2,442
, No. 710, No. 2,454,629, No. 2,776.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 280 and the like. Furthermore, U.S. Patent 2,21
No. 3,995, No. 2,493,748, No. 2,519
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Pat.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized to a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 5t-t
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828, etc. may be mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications No. 43-4932, No. 43-4933, No. 45-, No. 6470, No. 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order 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 fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

Each of the silver halide emulsion layers according to the present invention may 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 above-mentioned couplers that can be used in the present invention, yellow couplers, magenta couplers and cyan couplers can be used without any particular limitations. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers.

The yellow coupler includes an open-chain ketomethylene compound and a so-called two-equivalent type coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine co-substituted coupler, active point chlorine or bromine Substituted coupler, active point -〇-
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. No. 2,875.057;
l, No. 265,506, No. 3,408,194, No. 3
．． No. 551,155, 1,582. : No. 122, No. 3,725,072, No. 3,891,445, West German Patent No. 1,547,868, West German Application Publication No. 2,219
, No. 917, 2,261. : No. 161, 2,414
．． No. 006, British Patent No. 1,425,020, Special Publication No. 5
No. 1-10783, JP-A-47-26133, JP-A No. 48
-73147, 51-102636, 50-6
No. 341, No. 50-123342, No. 50-1304
42, No. 51-21827, No. 50-87650, No. 52-82424, No. 52-115219, No. 58-95346, and the like.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon 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 magenta couplers include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3,062,653, No. 3,127,
No. 269, Ill., No. 476, No. 3,419.
．． Co No. 91, same: l, 519,429, same 3.558
．． No. 119, same, 51112. : No. 122, same: l
, No. 615,506.

No. 3,834,908, No. 3,891,445, West German Patent No. 1,810.464, West German Patent Application (OL S
) No. 2,408,565, No. 2,417,945
No. 2,418,959, No. 2,424.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826/1982, No. 52-58922, No. 49-129538, No. 49-74027 , No. 50-159336, No. 52
-42121, 49-74028, 50-60
No. 233, No. 51-26541, No. 53-55122
and Japanese Patent Application No. 55-110943.

The magenta coupler particularly preferably used in the present invention is a 2-equivalent type coupler, but from the viewpoint of processing stability and image storage stability, it is most preferably
Magenta couplers represented by the following general formula (XX) or (XX) described in No. 1, etc. are useful in achieving the effects of the present invention.

General Formula (XIX) [In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing wood ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a coloring agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula (XX) ■ Ar In the formula, Ar is a phenyl group and includes a monosubstituted phenyl group, and Y is an N-hydroxyalkyl-substituted p-phenylenediamine derivative that is linked with an oxidized form of a coloring agent to form a pigment. represents a group that leaves when a compound is formed. R represents an acylamino group, anilino group, or ureido group.

In the silver halide emulsion layer of the present invention and other photographic constituent layers, couplers such as a non-diffusible DIR compound, a sicard magenta cyan coupler, a polymer coupler, and a diffusible DIR compound may be used in combination. The chemical compound Sicard magenta cyan coupler is described in Japanese Patent Application No. 59-193611 by the present applicant, and the polymer coupler is described in Japanese Patent Application No. 59-198 by the present applicant.
72151 can be referred to.

The method of adding the above coupler that can be used in the present invention into the photographic constituent layer of the present invention is the same as before, and the amount of the above coupler added is not limited, but I x 1 per mole of silver.
0-” to 5 mol is preferable, more preferably l x 1
0-2 to 5 x 10-'.

The light-sensitive material of the present invention may contain various other photographic additives.
Stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like may be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a reflective layer. Or a transparent support used in combination with a reflector, such as a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and other ordinary transparent supports. Good too,
These supports are appropriately selected depending on the intended use of the photosensitive material.

The silver halide emulsion layer and other photographic constituent layers used in the present invention can be coated using various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,761
, No. 791 and No. 2,941,898 may be used to coat two or more layers simultaneously.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily.For example, in the case of a full-color photosensitive material for photographic paper, the blue-sensitive silver halide emulsion layer,
It is preferable to arrange a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. Each of these light-sensitive silver halide emulsion layers may consist of two or more layers. The effect of the present invention is most significant when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as a structural layer. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

[Effects of the Invention] According to the present invention, even when processed using a color developing solution at a low replenishment amount, the bromide ion concentration does not change and constant appropriate photographic performance can be maintained over a long period of time. To provide a rapid and stable method for processing a photosensitive material in which colored dyes and uncolored areas do not fade or change color even when stored for a long period of time. Furthermore, a treatment method capable of reducing pollution can be provided.

[Example] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Silver halide color photographic light-sensitive material samples Nos. 1 to 25 were prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1---1.2 g/rn' gelatin, 0. :l
Blue-sensitive silver halide gelatin emulsion of Og/rn' (in terms of silver, the same applies hereinafter) (silver halide composition and average grain size are shown in Table 1)
Shown below. ), a blue-sensitive silver halide emulsion layer containing 0.85 g/rn' of yellow coupler (Y-■) dissolved in 0.50 g/rn' dioctyl phthalate.

Layer 2---0.70 g/m' gelatin, lflog
/m' anti-irradiation dye (AI-1), So
Intermediate layer consisting of (AI-2) of +g/rn'.

Layer 3---1.25g/rn' gelatin, O,:
lOg/rn' green-sensitive silver halide gelatin emulsion (
The silver halide composition and average grain size are shown in Table 1. ),
Q: Contains 0.62 g/m' of magenta coupler (M-1) dissolved in lOg/rrr' of dioctyl phthalate and 0.04 g/m' of antioxidant (AO-1) dissolved in dibutyl phthalate. green-sensitive silver halide emulsion layer.

Layer 4: Intermediate layer consisting of gelatin at 1.2 g/rn' and anti-tarnishing agent (As-1) at 0,05 g/rn' dissolved in dibutyl phthalate.

Layer 5---1.4g/rn' gelatin, 0.25g
/rr+' red-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.20
0.45 g dissolved in g/m' dioctyl phthalate
/rn' cyan coupler (C-1) and 0.15g/
A red-sensitive silver halide emulsion layer containing a black cyan coupler (C-2).

Layer 6: Protective layer containing 0.50 g/rn' of gelatin and ultraviolet absorber (UV-1).

The silver halide in each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer was one whose color had been increased by a general sensitizing dye.

(Y-1) t t (1)・(Indicative dog C-) (U-2) t (AI-1) Nap3SCH2NHO0H (AI-2) (AO-1) H (As-+) (UV- 1) 05H,, (t) As a hardening agent, 2.4-dichloro-6-hydroxysodium S-t-riazine was added in layers 2.4 and 6 at a rate of 0.02 per gelatin Ig, respectively. After drying, the gelatin film*111 speed TI/2 was measured at 30°C using the following color developing solution, and the result was about 6 seconds. Measured using Lebenzon Y! 1. A swelling degree meter was used.

Each of the photosensitive material samples Nos. 1 to 25 shown in Table 1 was exposed through an optical wedge and then processed in the following steps.

Processing steps (38°C) Color development 150 seconds Bleach-fixing 60 seconds Washing 60 seconds Drying 60-80°C 120 seconds The composition of each processing solution is as follows.

[Color developer] Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g Color developing agent (shown below) 0.030 mol l-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution)
1.5a+magnesium exchange chloride
0.3g potassium carbonate
32gKaycoll-PK-Conc
PK-rink) (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.)
Add 2M pure water to make it 1M, and adjust the pH to 115 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[PM white fixer] Pure water 550a Iron ethylenediaminetetraacetate (TI) Ammonium salt 65g Ammonium thiosulfate (70% aqueous solution) 85g Sodium bisulfite 10g Sodium metabisulfite
Add 2g ethylenediaminetetraacetic acid-disodium 20g pure water to make 141, and adjust the pH to 7.0 with aqueous ammonia or dilute sulfuric acid.

Separately, the potassium bromide concentration of the above color developer is 0.6 g/l.
The same sample No. 1 to 2 as above was prepared using a color developing solution with the only difference that the amount was 1.5 g/or and 1.5 g/view.
Each of No. 5 was subjected to development processing.

Sensitometry was performed on each sample obtained by a conventional method. When the potassium bromide concentration was 0.6 g/l, the concentration of each sample in the exposed region around the concentration of 1.0 was set as 100, and Table 1 shows the concentration changes when the potassium bromide concentration was varied. As for the color density ratio, only the cyan density is shown in Table 1.

[Color developing agent] A mixture of a developing agent (sulfate of exemplified compound (1)) and CD-3, the molar ratio of which is exemplified compound (1): CD-3 = 1: 1 [C
D-3]: 3/2 H2SO4・T ■20 As is clear from the results in Table 1, compared to Samples No. 1 to No. 12, which contain substantially no silver halide or silver chlorobromide, Sample No., l:l or No. when it is silver chlorobromide
, 25 is the bromide ion concentration in the color developer, O, 6gl
It can be seen that even when changing from 1.5 g/i to 3.5 g/i, there was not much change in color density, indicating high processing stability. Table 1 shows that as the bromide ion concentration increases, the amount of replenishment is reduced, which indicates that the amount of replenishment can be significantly reduced in the treatment of the present invention.

Example 2 Using the silver halide photographic light-sensitive material sample No. 21 of Example 1, exposure was carried out in the same manner using the same processing solution as in Example 1 except that the color developing agent or pencil alcohol was changed as shown in Table 2. Developed. The treatment temperature was 38°C.

The obtained sample was stored at 75° C. and relative humidity 90% R11, and changes in cyan concentration were measured. At that time, when using the color developing agent Toshi C[l-3 and using 20 ni of benzyl alcohol per 11 color developing solutions, the sample initial concentration of 1.0 deteriorated by about 0.3. The concentration reduction in the same concentration range of the treated samples was measured and shown in Table 2. At this time, the 1-stain density of the unexposed portion of the same sample was measured and is also shown in Table 2.

Further, in the same manner as above, the maximum color density of each sample was measured using CD-3 as a color developing agent and 2 hJl of benzyl alcohol.

As is clear from the results in Margin Table 2 below, if benzyl alcohol is present at 1oe12,20-, the color developing agent is CD-
3 or CD-4 or a mixture of CD-3 and CD-4, the discoloration property is not much different, and it can be seen that the discoloration property is particularly large when a large amount of benzyl alcohol is used in CD-14. This means that the stain density of the unexposed area (D m1n
).

However, when benzyl alcohol is 5- or less, especially 2-
In the case of +a12 or less, the fading property and stain density (Dmin) of the unexposed area are also significantly improved. This is predicted to indicate that the color developing agent, especially in the case of CD-4, tends to remain in the film due to benzyl alcohol.

Also, the maximum color density depends largely on the amount of benzyl alcohol when using CD-3, but when CD-3/CD-4
When the ratio is about 2/1, good color density is exhibited without being greatly dependent on the amount of benzyl alcohol.

Example 3 Using sample No. 26 No. 40 of Example 2, blue,
Samples were prepared in which the amount of silver halide in the green and red-sensitive emulsion layers was the same as in Example 1, and the amount of hardener added was varied. The membrane swelling rate T of the sample after drying was measured using the above-mentioned color developer using a Lebenzon type swelling meter.
1/2 was measured. Membrane swelling rate TI/2 is 2 seconds, 5 seconds,
Samples that took 10 seconds, 15 seconds, 30 seconds, 40 seconds, and 60 seconds were selected and used in the experiment. This sample was exposed to light in the same manner as in Example 1 and treated with the same processing solution as in Example 1. The maximum density when color development was performed at 38° C. for 10 minutes was defined as lOO, and the processing time required to reach the maximum density of 80 is shown in Table 3.

This result shows the rapidity of the development completion point.

Margin Table 3 below As is clear from the results in Table 3, when the color developing agent of the present invention is used and the film swelling rate T1/2 is 30 seconds or less, the development completion time is extremely fast, and the development is completed quickly. It can be seen that development processing is possible.

Example 4 Exemplary compounds C-2 and C-36 of the present invention were used in place of the cyan coupler (exemplified compound C-8) of the photosensitive material used in Example 1.
-1C-86, C-111 and comparative couplers (described below) were evaluated using the treatment method No. 39 of Example 2. The results are shown in Table 4.
c(Cr)-17lLehich1tech1;1quiet.

r:-RayenAyyyf)- 〇CH2CH25o2cH3 As is clear from the results in Table 4, when the cyan coupler of the present invention is used, the fading property and the cyan stain in the unexposed area (
Dakin) has been improved.

Example 5 Instead of the water washing treatment used in Example 1, a water washing substitute stabilizing solution (
The same evaluation as in Example 2 was conducted using the following composition, but
Compared to washing with water, the fading property was improved by about 0.03, and the stain in the unexposed area was improved by 0.01 to 0.02.

[Water washing alternative stabilizer]

5-Chloro-2-methyl-4~Isothiazolin-3-one 0.02g2-Methyl-4-isothiazolin=3-one 0.02gEthylene glycol 1g2 Octyl-
4-Isothiazolin-3-one 0.01g Exemplary chelating agent (1112) 3.0gB
I CQco (45% aqueous solution) 0.6
5g ammonia water (ammonium hydroxide 25% aqueous solution) 3.0g exemplary chelating agent (44) 1.5g water! Q
and adjust the pH to 8.0 with HtSO4 and KOH.

Example 6 The following magenta coupler was used instead of the magenta coupler used in Example 1, and the same evaluation as in Example 5 was performed using the following comparative magenta coupler as a comparison, but compared to the comparative magenta coupler, Example 1 and the following When a magenta coupler was used, it was effective in reducing yellow stain.

[Magenta coupler]

t [Comparison magenta coupler]

[Brief explanation of drawings]

FIG. 1 is a graph showing the membrane swelling rate T I/2 of the binder.

Claims (13)

[Claims] (1) In a method for developing a silver halide color photographic light-sensitive material, the silver halide emulsion in at least one photosensitive emulsion layer is substantially a silver chlorobromide emulsion, and the film swelling rate of the binder is T1/2. is 30 seconds or less and contains at least one cyan coupler represented by the following general formula (I), (II) or (III). A color developing solution containing a phenylenediamine derivative at 30 mol % or more based on p-phenylenediamine color developing agent in a color developer and substantially free of benzyl alcohol is used for development processing at 30°C or higher. A method for processing a silver halide color photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 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 Hydrogen atom or N-hydroxyalkyl substitution-
R_2 represents a ballast group. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, Y is -COR_4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, - SO_2R_4
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COHHCOR
_4 or -COHHSO_2R_4 (where R_4 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, and R_5 represents a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group) , R_4 and R_5 may combine with each other to form a 5- to 6-membered heterocycle.),
R_3 represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an N-hydroxyalkyl-substituted p-phenylenediamine color developing agent. (2) The silver halide emulsion of at least one photosensitive emulsion layer is a silver chlorobromide emulsion having a silver bromide content of 90 mol% or less. A method for processing silver halide color photographic materials. (3) Claim 1, characterized in that the color developer contains at least 5 x 10^-^3 moles of bromide.
2. A method for processing a silver halide color photographic light-sensitive material according to either item 1 or 2. (4) The silver halide according to any one of claims 1 to 3, wherein the color developer contains a compound represented by the following general formulas (IV) to (VI). A method of processing color photographic materials. General formula (IV) A-COOM General formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is a monovalent organic residue , B, B_1 and B_2 each represent a monovalent organic residue or atom, and may be an inorganic substance or an organic substance. D represents a nonmetallic atom group necessary to form an aromatic ring or heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. ] (5) The halogen according to any one of claims 1 to 4, wherein the film swelling rate T1/2 of the photographic constituent layer of the silver halide color photographic light-sensitive material is 20 seconds or less. Processing method for silver chemical color photographic materials. (6) A claim characterized in that the N-hydroxyalkyl-substituted p-phenylenediamine color developing agent is contained in an amount of 40 mol% or more based on the amount of the p-phenylenediamine color developing agent in the color developer. A method for processing a silver halide color photographic material according to any one of items 1 to 5; (7) The silver halide color photographic light-sensitive material according to any one of claims 1 to 6, characterized in that the amount of benzyl alcohol in the color developer is 5 ml or less per 1 liter of the color developer. Processing method. (8) The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the benzyl alcohol in the color developer is 2 ml or less per 1 liter of the color developer. Processing method. (9) Claim 3, characterized in that processing is performed with a color developing solution containing 1 x 10^-^2 moles or more of bromide.
A method for processing a silver halide color photographic light-sensitive material as described in . (10) A method for processing a silver halide color photographic light-sensitive material according to claim 3, which comprises processing with a color developing solution containing 1.5 x 10^-^2 moles or more of bromide. (11) N-hydroxyalkyl-substituted-p-phenylenediamine color developing agent is 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline salt.The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 10. (12) The silver halide color according to any one of claims 1 to 11, characterized in that the color photographic material is processed at a replenishment amount of 250 ml/m^2 or less during continuous processing. Method of processing photographic materials. (13) A method for processing a silver halide color photographic material according to claim 12, wherein the color photographic material is processed at a replenishment amount of 200 ml/m^2 or less during continuous processing.