JPH0675178B2 - Silver halide color-color developing solution for photographic light-sensitive materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color developing solution used for processing a silver halide color photographic light-sensitive material, and in particular, a color developing solution for rapid processing in which precipitation and tar are prevented from being generated over time. Regarding

BACKGROUND OF THE INVENTION The processing of a light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilizing treatment, and the like are added as additional treatment steps.

In color development exposed silver halide is reduced to silver while 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 and accumulated in the developer. Separately, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic light-sensitive material as soluble silver salts with a fixing agent. There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

In the color developing solution, the development-inhibiting substance is accumulated by developing the photographic light-sensitive material as described above, while the color-developing agent and benzyl alcohol are consumed or accumulated in the photographic light-sensitive material and taken out. The concentration decreases. Therefore, in the development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic developing machine or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in development finish characteristics due to a change in component concentration. Means are needed. As such means, a method of replenishing a replenisher for diluting unnecessary increasing components and supplementing deficient components is usually adopted. Since the replenishment of this replenisher inevitably causes a large amount of overflow and is discarded,
This method has become a major economic and pollution problem.
Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a developer by an ion exchange resin method or an electrodialysis method, a concentrated low replenishment method, or a method of adding a regenerant to the overflow solution and using it again as a replenisher. Have been proposed and put to practical use.

However, the regeneration of the developing solution is performed by removing bromide which is an unnecessary accumulating component and compensating for the deficient component.
This method (ion exchange resin method and electrodialysis method) has the drawback that the development processing characteristics of the light-sensitive material are impaired unless the developer components are quantified and made constant by chemical analysis, and complicated management is required. However, it is almost impossible to introduce it in a small-scale photo lab or a mini lab without special skills. Further, there is a drawback that the initial cost is extremely high.

Furthermore, the method of adding a regenerant to the overflow solution and reusing it as a replenisher does not require special skills, but it requires a space such as a stock tank, and also has the drawback of being complicated for the photo lab. It is extremely difficult to introduce it into the etc. However, since the concentrated low replenishment method does not require a new device and the process management is easy, it can be said that it is extremely suitable for a small-scale laboratory such as a minilab. However, this method also has some drawbacks. For example, as the replenishment rate is lowered, the eluate from the light-sensitive material into the developing solution is greatly accumulated, and further, a large amount of decomposition products are accumulated due to air oxidation of the color developing solution components.
Under these circumstances, when a small lab such as a minilab with a low throughput is used to perform discontinuous development over a long period of time, the racks and rollers in the color development processing tank of the automatic processor may become dirty. Occurrence of such a stain causes a failure of contaminating the photosensitive material to be processed.

In addition, photo shops that sell short-time processing (one-hour finishing) called 1 Hour Photo have become widespread, and this tendency has become stronger in recent years.

For this reason, studies have been made to accelerate color development.
As means for speeding up, use or increase of benzyl alcohol, increase of color developing agent, selection of color developing agent, increase of pH, increase of developing temperature and the like are generally carried out.

In particular, a color developing solution using benzyl alcohol, which has a large effect of promoting development, has a drawback in solubility and the above-mentioned technique has a drawback of promoting generation of tar over time.

Upon further study, in the above-mentioned rapid technology, when a fluorescent whitening agent for the purpose of improving white background in color development of color photographic paper was used, gray crystalline precipitates of different shapes were observed in racks of automatic developing machines and It was found that it occurs at the bottom of the tank, and for the purpose of accelerating the development in particular, the N-hydroxyalkyl-substituted-former which has been used in the conventional color negative processing of the color developing agent is used.
It was found that the problem was large when the p-phenylenediamine derivative was changed.

Therefore, an object of the present invention is to provide a color developing solution for a silver halide color photographic light-sensitive material, which does not impair rapid processability and prevents the generation of precipitates and tars that occur over time.

[Means for Solving the Problem] The color developer for silver halide color photographic light-sensitive material of the present invention which achieves the above-mentioned object is a p-phenylene amine-based color developing agent and benzyl alcohol and triazinyl stilbene-based fluorescence enhancer. In a color developing solution for a silver halide color photographic light-sensitive material containing a whitening agent, the content of the N-hydroxyalkyl-substituted-p-phenylenediamine type color developing agent contained in the p-phenylenediamine type color developing agent is The weight constant is 5 to 50% with respect to the total amount of the p-phenylenediamine color developing agent, and the stability constant (log KMA) with magnesium ion represented by the following general formula [I] is 3 or more. It is characterized by containing a certain water-soluble chelating agent.

General formula [I] [Here, M represents a magnesium ion and A represents a water-soluble chelating agent. The inventors of the present invention have conducted various studies to achieve the above-mentioned object. As a result, in a system containing a p-phenylenediamine type color developing agent benzyl alcohol and a triazinyl stilbene type optical brightening agent, a p-phenylenediamine type color developing agent was developed. 5 to 50% by weight of N-hydroxyalkyl-substituted-p-phenylenediamine-based color developing agent containing a water-soluble chelating agent having a stability constant with magnesium ion of 3 or more It has been found that this can be prevented.

That is, for example, outside the present invention, when not containing benzyl alcohol, or when not containing a fluorescent whitening agent, a level of practically no problem even if a precipitate, tar is generated over time to some extent, Even if the amount of the N-hydroxyalkyl-substituted-p-phenylenediamine color developing agent to the p-phenylenediamine color developing agent is changed, no effect is obtained, and the stability constant with magnesium ion is 3 This means that the effects of the present invention cannot be obtained even when there is no water-soluble chelating agent as described above.

The present invention generally limits the combined use of the color developing agent and the combined ratio of the limited color developing agent for the color developing agent to be used in one kind, so that the precipitation with time in the color developing solution in a limited composition, tar It is presumed that the mechanism of occurrence of the phenomenon could be prevented in a certain equilibrium state.

The water-soluble chelating agent that can be used in the color developing solution according to the present invention has a chelate stability constant with magnesium ion (log KMA) of 3 or more. The logKMA is preferably 5 or more, and particularly preferably 6 or more, but these stability constants are determined under the conditions of use of the color developing solution, for example,
It varies depending on the hydrogen ion concentration, the amount of other components mixed, etc., and in general, the optimum compound cannot be selected only by the stability constant. Therefore, as long as the stability constant is 3 or more, any one can be used, and the higher the water solubility of the complex and the higher the chelate stability constant, the more preferable.

Examples of these water-soluble chelating agents include diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, diaminopropanoltetraacetic acid, aminopolycarboxylic acid type chelating agents such as transcyclohexanediaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, Aminophosphonic acid type chelating agents such as nitrilotrimethylene, 1-hydroxyethylidene-1,1-diphosphonic acid, organic phosphonic acid type chelating agents such as 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2, 4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid and other phosphonocarboxylic acid chelating agents, catechol-3,5-disulfonic acid and other organic sulfonic acid chelating agents, Sodium pyrophosphate, sodium tetrapolyphosphate Condensed phosphoric acid such as sodium and sodium hexametaphosphate can be used. Preferred chelating agents in the present invention include diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, catechol-3,
Examples thereof include 5-disulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, condensed phosphates and salts thereof.
And as particularly preferable chelating agents, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, catechol-3,
5-disulfonic acid, diethylenetriaminepentaacetic acid, 1-
Examples thereof include hydroxyethylidene-1,1-diphosphonic acid and their alkali metal salts, ammonium salts, and ethanolamine salts. The chelating agent that can be used in the present invention is not limited to these. It is particularly desirable to use two or more chelating agents in combination.

The triazinyl stilbene-based optical brightening agent preferably used in the present invention is a compound represented by the following general formula [II],
Among them, the compound represented by the following general formula [III] is particularly preferable.

General formula [II] In the formula, X ₁₁ , X ₁₂ , Y ₁₁ and Y ₁₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (for example, methoxy, ethoxy, methoxyethoxy, etc.),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
Aryl group (eg phenyl, methoxyphenyl etc.), amino group, alkylamino group (eg methylamino, ethylamino, propylamino, dimethylamino,
Cyclohexylamino, β-hydroxyethylamino,
Di (β-hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino, N- (β-hydroxyethyl-N′-methylamino, etc.), arylamino group (for example, Anilino, o-, m-
p-sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-triidino, o-, m-, p-carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthyl Amino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group or an aryl group. Also R ₁₃ and R ₁₄ and R ₁₅
And R ₁₆ may combine with each other to form a heterocycle. M has the same meaning as M in formula [II].

In the general formula [III], the alkyl group and aryl group represented by R ₁₁ , R ₁₃ , R ₁₄ and R ₁₆ may each have a substituent, and the aryl group is preferably a phenyl group. As the substituent, a hydroxy group, a sulfo group, a sulfoamino group, and a carboxyamino group are preferable. R
_The heterocycle formed by linking ₁₃ and R ₁₄ and R ₁₅ and R ₁₆ is preferably a heterocycle containing an oxygen atom, and examples thereof include a morpholino group.

Specific compounds represented by the general formula [II] are shown below,
It is not limited to these.

[Exemplified compound]

The triazyl stilbene-based optical brightening agent of the present invention is, for example, “Fluorescent brightening agent” edited by Chemical Industry Association (issued in August 1976).
It can be synthesized by the usual method described on page 8.

The triazyl stilbene-based optical brightening agent is preferably used in the range of 0.1 g to 15 g, and particularly preferably in the range of 0.3 g to 8 g, per 1 color developing solution of the present invention.

The developing agents effective in the present invention are quaternary ammonium salts of N-hydroxyalkyl-substituted-p-phenylenediamine compounds, especially those represented by the following general formula.

In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a hydrogen atom or 1 to 4 carbon atoms. Is an alkyl group having R 1 and R ₃ may have a hydrogen group 1
Is an alkyl group having 4 to 4 carbon atoms, A is an alkyl group having at least one hydroxyl group and optionally having a branch, and more preferably Is. R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, and at least one of R ₄ , R ₅ and R ₆ is a hydroxyl group. Alternatively, it is an alkyl group having a hydroxyl group. n ₁ , n ₂ and n ₃ are 0,
1, 2 or 3 and HX represents hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid or phosphoric acid.

Such p-phenylenediamine color developing agents are unstable with their free amines and are commonly used as salts (most commonly identified by the above formula). Typical examples are 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline salt and 4-amino-N-ethyl-N- (β-hydroxyethyl) -aniline salt. Can be mentioned.

Preferably, in the present invention, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate-hydrate [this is commercially available under the name CD-4, Some color photographic methods (for example, Eastman Kodak C41 method and Konishi Roku Photo Co., Ltd. CNK method)
-4 used to develop color negative films, such as system-4), has been found to be particularly effective.

The preferred N-hydroxyalkyl-substituted-p-phenylenediamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds.

[Exemplified compound]

Hydrochloric acid, sulfuric acid, and p-toluenesulfonate of the compounds (1) to (8) are particularly preferable.

Among these exemplified compounds, No. (1), (2),
(6), (7) and (8) are preferably used, especially N
o. (1), (2) and (6) are preferably used. Furthermore, especially 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, it is preferably used in an amount of 1 g to 100 g, and more preferably 2 g to 30 g, per processing liquid.

These N-hydroxyalkyl-substituted-p-phenylenediamine derivatives of the present invention can be easily synthesized by the method described in Journal of American Chemical Society, Vol. 73, page 3100 (1951).

Examples of the color developing agent according to the present invention include N-hydroxyalkyl-substituted-p-phenylenediamine derivative developing agents,
A p-phenylenediamine type is used, and the following are preferred examples.

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, p -Toluenesulfonate, phosphate, etc. Preferably, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline is useful from the viewpoint of photofading.

Furthermore, for example, JP-A Nos. 48-64932, 50-131526 and 5
Journal of the American Chemical Society, No. 1-95849 and Bent, Volume 73, 3100-3125
The one described on page (1951) is also mentioned as a typical one.

In the present invention, N-hydroxyalkyl-substituted-p-
The phenylenediamine derivative is at least 5 to 50 with respect to the total amount of p-phenylenediamine color developing agent in the color developing solution.
%, Preferably 5 to 30%, effectively acts on rapid processing and processing stability.

The color developer of the present invention preferably has a bromide ion concentration of 5 × 10 ⁻³ mol or more, but in the present invention, the higher the bromide content, the more the replenishment amount can be lowered, which is preferable. In the conventional developing method, it was said that bromide was more preferable as it suppressed the development reaction and was lower, but in the combination of the color photographic light-sensitive material and the developing solution of the present invention, the higher the bromide is, the more preferable it is, and the object of the present invention was achieved. To be done. In other words, in the present invention, the replenishment amount can be reduced because it is less affected by bromide.

The bromide is preferably 1 × 10 ^-2 mol or more, particularly preferably
1.5 × is 10 ^-2 mol or more is not preferable due to the effect of bromide ion concentration for bromide ion concentration is too high, the development suppression Dehajimeru 6 × 10 ^-2 mol or more. The chloride concentration has no effect.

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

In addition to the above, the processing method of the photographic light-sensitive material of the present invention is not particularly limited, and any processing method can be applied. For example, as a typical example thereof, a method of performing bleach-fixing treatment after color development and further performing washing treatment and / or stabilizing treatment after washing with water if necessary, and performing bleaching and fixing separately after color development, and if necessary, Method of further washing with water and / or stabilizing treatment; or method of pre-hardening, neutralization, color development, stop fixing, washing, bleaching, fixing, washing, post-hardening, washing in this order, color development, washing, supplement Color development, stopping, bleaching, fixing, washing with water, stabilization, a development method in which developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye formed. You may process using the method of.

In the present invention, a compound preferably used in the stabilizing solution as a substitute for washing with water has a chelate stability constant of 6 with respect to iron ions.
The chelating agents mentioned above can be mentioned, and these are preferably used for achieving the object of the present invention.

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

As the chelating agent having a chelate stability constant of 6 or more with respect to iron ions, which is preferably used in the washing substitute stabilizer of the present invention, organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. Is mentioned. The iron ion means ferric ion (Fe ³⁺ ).

Specific examples of the chelating agent having a chelate stability constant with ferric ion of 6 or more include the following compounds, but are not limited to these. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanol tetraacetic acid, transcyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-
1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate,
Examples thereof include sodium tetrapolyphosphate and sodium hexametaphosphate, and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-
Among them, 1,1-diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

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

When the replenishment amount of the washing alternative stabilizer of the present invention is less than 0.5 times the amount brought from the pre-bath per unit area, the amount of the pre-bath component accumulated in the washing alternative stabilizer of the present invention increases, and the photographic dye image When the storage stability is deteriorated, on the other hand, when it is more than 50 times, the effect of the object of the present invention becomes small. Therefore, in the present invention, it is preferably used in the range of 0.5 to 50 times. Especially when used in the range of 2 to 30 times, the effects of the object of the present invention can be particularly excellently exhibited. Particularly, it is preferable to add 2000 ml or less per 1 m ^{2 of the} light-sensitive material.

The tank for the stabilizing solution for washing with water of the present invention may be one tank,
It is possible to increase the number of tanks up to about 10 and increase the effect of the object of the present invention by increasing the number of tanks. Therefore, the number of tanks may be increased within this range. Further, the replenisher to be supplemented to the washing substitute stabilizer may be replenished in several places, but preferably, it is replenished to a subsequent tank as far as possible from the viewpoint of the processing flow of the light-sensitive material and its overflow ( When the tanks are communicated with each other by a pipe located below the liquid surface, it is preferable to adopt a type in which the bath liquid flows through the pipe) to the tank in front of the tank. More preferably, two or more tanks are used as a substitute for washing with water, and the last stable stabilizing tank is supplemented with a stable replenisher for washing with water, and overflows are successively transferred to the previous tank to replace the solution having fixing ability with the next washing with water. A part or all of the overflow liquid from the stabilizing liquid may be discarded, or a liquid having the fixing ability may be poured.

Examples of means for imparting the anti-vibration property to the water-wash alternative stabilizer used in the present invention include chemical means and physical means for imparting the anti-violation property.

As an example of the chemical means for imparting the anti-vibration property, the anti-vibration agent may be incorporated into the stabilizing solution for washing with water of the present invention. Antifungal agent preferably used is sorbic acid,
Benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds,
They are isoxazole compounds, propanolamino compounds, sulfamide compounds, pyronone compounds and amino acid compounds.

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

Phenolic compounds are compounds that may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (in particular, an alkyl group having an alkyl group of C1 to 6), a phenyl group or the like as a substituent. And preferably orthophenylphenol and orthocyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like.

The thiazole-based compound is a compound having a nitrogen atom and a sulfur atom in its five-membered ring, preferably 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazoline 3
-One, 2-octyl-4-isothiazolin-3-one,
5-chloro-2-methyl-4-isothiazolin-3-none,
2-chloro-thiazolyl-benzimidazole.

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

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

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

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

Quaternary phosphonium compounds include tetraalkylphosphonium salts and tetraalkoxyphosphonium salts,
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-nbutyl-tetradecylphosphonium chloride and tri-phenyl nitrophenylphosphonium chloride.

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

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

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

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

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

Specific examples of the pyronone compound include dehydroacetic acid.

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

Among the above antibacterial agents, compounds preferably used in the present invention are thiazole-based compounds, sulfamide-based compounds, pyronone-based compounds and the like.

The amount of the anti-violent agent added to the washing substitute stabilizer is preferably 0.001 to 30 g, and more preferably 0.003 to 5 g, per 1 washing substitute stabilizer.

On the other hand, examples of physical means include imparting anti-vibration properties by irradiating the stabilizing solution for washing with ultraviolet light with ultraviolet rays or passing a magnetic field.

In the present invention, passing a magnetic field through the washing alternative stabilizing solution means passing the washing alternative stabilizing solution through the magnetic field generated between the positive electrode and the negative electrode of the magnetic field, and the photosensitive material may or may not pass the magnetic field. Good.

The magnetic field used in the present invention is obtained by using a ferromagnetic material such as iron, cobalt, or a permanent magnet made of nickel.
Alternatively, it can be obtained by passing a direct current through a coil or the like, but is not particularly limited, and any means capable of forming a magnetic field can be used. The magnetic field may be formed by using one magnet to form the magnetic force lines, or may be formed by forming two magnetic force lines between the opposing magnets by facing two (positive and negative) magnets.

As a method of passing the washing-replacement stable liquid used in the present invention in a magnetic field, a permanent magnet or the like that forms a magnetic field is used to move (including rotation) a permanent magnet provided in the stable liquid and / or outside the liquid. Alternatively, there is a method of moving the washing substitute stabilizer by stirring or circulating the washing substitute stabilizer. A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of the circulation pipe to circulate the stabilizing liquid. When the permanent magnets are individually fixed to all the pipes, the pipes themselves may be permanent magnets, or the permanent magnets may be attached to all the pipes.

In the case of an automatic processor, the objective can be achieved by installing a permanent magnet or the like in a stabilizing bath as a substitute for washing, but as mentioned above, the circulation system of the stabilizing bath (not limited to the circulation pipe, but the tank and other members in the middle It is preferable to install it. Further, when the washing alternative stabilization treatment step is a multi-stage stabilizing bath, it is most preferable to pass the stabilizing solution of the all-water washing alternative stabilizing bath through a magnetic field. It is also preferable to pass the stabilizing liquid through a magnetic field. A resin lining containing a material capable of generating magnetic lines of force may be applied to the water washing alternative stabilizing bath itself, preferably the water washing alternative stabilizing bath inner surface, and this lining may be applied to a circulation system. In this way, the stabilizing liquid can be passed through the magnetic field.

In the present invention, the method of irradiating the alternative solution for washing with ultraviolet light with ultraviolet rays is carried out by using a commercially available ultraviolet lamp or an ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is preferably 5 to 800 W (tube output). , But is not limited to this.

Further, according to a preferred embodiment of the present invention, the wavelength of ultraviolet rays is in the range of 220 nm to 350 nm. Further, as an irradiation method, there is a method of directly irradiating in a washing substitute stabilizing solution or outside the washing substitute stabilizing solution.

In the color developer used in the present invention, various components that are usually added, for example, sodium hydroxide, an alkali agent such as sodium carbonate, an alkali metal sulfite,
An alkali metal hydrogen sulfite, an alkali metal thiocyanate, an alkali metal halide, a thickener, a development accelerator and the like can be optionally contained.

Examples of the additive other than the above added to the color development liquid include potassium bromide, bromide such as sodium bromide,
Alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, and other compounds for rapid processing liquids, including stain inhibitors, antisludge agents, preservatives, There are multi-layer effect promoters, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Glycol etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt You may contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution, various other additives such as pH buffer, fluorescent whitening agent, defoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. Addition,
It may be contained.

Examples of the silver halide fixing agent include, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, and other water-soluble silver that reacts with silver halide used for ordinary fixing processing. Mention may be made of compounds which form salts.

Processing other than color development of the silver halide color photographic light-sensitive material of the present invention, for example, bleach-fixing (or bleaching / fixing), and if necessary, rapid processing at various processing steps such as washing and stabilization From the point of view of the above, it is preferable to be carried out at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-A-58-1.
No. 4834, No. 58-105145, No. 58-134634 and No. 58-18631
No. 59-126533 and 60-233651, etc., a water-washing alternative stabilizing treatment may be carried out.

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used are British Patent 584,609.
No. 1,277,429, JP-A-48-85130, 49-99620
No. 49, No. 114420, No. 49-129537, No. 52-108115,
59-25845, 59-111640, 59-111641, US Patents 2,274,782, 2,533,472, 2,956,879, 3,1
25,448, 3,148,187, 3,177,078, 3,247,12
No. 7, No. 3,260,601, No. 3,540,887, No. 3,575,704,
3,653,905, 3,718,472, 4,071,312, 4,0
The thing described in 70,352 can be mentioned.

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

The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-61-47959) can also be used.

The 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.

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

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

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

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

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be added for optical sensitization. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080 and U.S. Pat.
No. 2,493,748, 2,503,776, 2,519,001,
2,912,329, 3,656,959, 3,672,897, 3,6
94,217, 4,025,349, 4,046,572, British patent 1,
242,588, Japanese Patent Publication Nos. 44-14030, 52-24844 and the like can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, 2,739,149 and 2,9.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in 45,763 and British Patent 505,979. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Patents 2,269,234, 2,270,378 and
Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes as described in 2,442,710, 2,454,629, 2,776,280 and the like. Furthermore, U.S. Patents 2,213,995 and 2,493,748
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in U.S. Pat.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optionally optically sensitized to a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

A particularly preferable example of the spectral sensitization method is, for example, Japanese Patent Publication No. 43-4936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 42884, No. 45-18433, No. 47-37443, No. 48
-28293, 49-6209, 53-12375, JP-A-52-2393
No. 1, No. 52-51932, No. 54-80118, No. 58-153926, No.
59-116646, 59-116647 and the like.

Further, examples of the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine include, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47-2.
No. 5379, No. 48-38406, No. 48-38407, No. 54-34535,
55-1569, JP-A-50-33220, 50-38526, 51-
107127, 51-115820, 51-135528, 52-10491
No. 6, No. 52-104917 and the like.

Further, as a combination of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanine, for example, Japanese Patent Publication Nos. 44-32753 and 46-11627,
JP-A-57-1483 and merocyanine include, for example, JP-B-48-38408, JP-A-48-41204, and JP-A-50-40662.
No. 56-25728, No. 58-10753, No. 58-91445,
No. 59-116645, No. 50-33828 and the like.

Further, as a combination of thiacarbocyanine with other carbocyanine, for example, Japanese Patent Publication Nos. 43-4932 and 43-4932
No. 4933, No. 45-26470, No. 46-18107, No. 47-8741,
JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and a 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 a fluorinated alcohol described in JP-B-50-40659 can be prepared in advance. It is used by dissolving it in the hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

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

The yellow coupler includes an open-chain ketomethylene compound and an active site called a so-called 2-equivalent type coupler.
o-aryl substituted coupler, active point-o-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine substituted Coupler, active point -o
-Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.Nos. 2,875,057 and 3,265,5.
No. 06, No. 3,408,194, No. 3,551,155, No. 3,582,322
No. 3,725,072, No. 3,891,445, West German Patent 1,547,86
No. 8, West German Application Publication No. 2,219,917, No. 2,261,361, No. 2,4
14,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783,
JP-A-47-26133, 48-73147, 51-102636, 5
0-6341, 50-123342, 50-130442, 51-21827
No. 50, No. 50-87650, No. 52-82424, No. 52-115219, No. 5
Examples thereof include those described in 8-95346.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patents 2,600,788, 2,983,608 and 3,06.
2,653, 3,127,269, 3,311,476, 3,419,391
No. 3,519,429, 3,558,319, 3,582,322,
3,615,506, 3,834,908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665,
2,417,945, 2,418,959, 2,424,467, JP-B-40-6031, JP-A-51-20826, 52-58922, 49-
129538, 49-74027, 50-159336, 52-42121
No. 49-74028, 50-60233, 51-26541, 53
-55122, Japanese Patent Application No. 55-110943 and the like can be mentioned.

The magenta couplers particularly preferably used in the present invention are 2-equivalent type couplers, most preferably JP-A-SHO
The following general formula [IV] or [V] described in No. 62-30252, etc.
The magenta coupler represented by is useful for achieving the effects of the present invention.

General formula (IV) [In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ] General formula [V] In the formula, Ar is a phenyl group and includes a substituted phenyl group. Y represents a group which is released when a dye is formed by coupling with an oxidized product of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative color-forming agent. R represents an acylamino group, an anilino group, or a ureido group.

Further, examples of the cyan coupler used in the present invention include phenol type and naphthol type couplers. And these cyan couplers are 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. Specific examples of cyan couplers include U.S. Pat.
9,929, 2,434,272, 2,474,293, 2,521,908
No., No. 2,895,826, No. 3,034,892, No. 3,311,476,
3,458,315, 3,476,563, 3,583,971, 3,5
91,383, 3,767,411, 3,772,002, 3,933,49
No. 4, No. 4,004,929, West German patent application (OLS) 2,414,830
No. 2,454,329, JP-A-48-59838, 51-26034
No. 48, No. 5055, No. 51-146827, No. 52-69624, No. 52
-90932, 58-95346, JP-B-49-11572 and the like can be mentioned.

The cyan couplers particularly preferably used in the present invention are 2-equivalent type couplers, and most preferably the following general formulas [VI] and [VII] described in the patent application filed on Aug. 16, 1985 by the present applicant. ] And [VIII] are useful in achieving the effects of the present invention.

General formula [VI] In the formula, one of R ₂₀ and R ₂₁ 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 a coupling reaction with an oxidation product of a color developing agent. And R ₂₂ represents a ballast group.

General formula (VII) General formula [VIII] In the formula, Y is —COR ₂₄ , -CONHCOR ₂₄ or -CONHSO ₂ R ₂₄ (wherein R ₂₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₂₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, Represents an aryl group or a heterocyclic group, R ₂₄ and R ₂₅ may combine with each other to form a 5- or 6-membered heterocycle, R ₂₃ represents a ballast group, and Z represents a hydrogen atom. Alternatively, it represents a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent.

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

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

The photographic material of the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surface active agents described in Research Disclosure Magazine No. 17643. Agents, plasticizers, wetting agents and the like can be used.

Specific examples of the magenta couplers represented by the general formulas IV to V are shown in Japanese Patent Application Nos. 60-111694 and 60-13 in addition to those described below.
The magenta coupler described in No. 1590 can be mentioned.

Further, specific examples of the cyan couplers represented by the general formulas VI to VIII include, in addition to those described later, Japanese Patent Application Nos. 60-118444 and 60-1291.
The cyan couplers described in No. 98 can be mentioned.

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

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

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a light-sensitive material for full-color photographic paper, a blue-sensitive silver halide emulsion layer is sequentially formed from the support side,
The arrangement is preferably 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 great when all these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion.

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

[Effect of the Invention] The present invention provides a color developing solution for a silver halide color photographic light-sensitive material, which prevents the generation of precipitates and tars over time without impairing rapid processability.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 The compounds shown in Table 1 were added to the following aqueous solution to prepare a color developer, pH was adjusted to 10.10 with KOH and H ₂ SO ₄ , 1 Erlenmeyer flask was charged with 1 and stored at room temperature. Day, 20th, 30th
The results were shown in Table 2 after observing the condition on days and 40 days.

Aqueous solution Potassium sulfite 3.0 g Potassium carbonate 30.0 g Potassium bromide 1.8 g Hydroxyamine sulfate 4.0 g Pure water was made up to 900 ml, and magnesium chloride hexahydrate 0.6 g was made up to 100 ml with pure water, and both were mixed to make 1.

In Table 2, 0: no precipitation or tar is seen.

1: Very little precipitation or tar is observed.

2: Some precipitation or tar is observed.

3: Significant precipitation or tar is observed.

As is clear from Table 2, precipitation tar does not occur in the absence of comparative No1, 2 and benzyl alcohol and optical brightener, but in the presence of No3 to No6, benzyl alcohol and optical brightener. , Precipitation and tar are found to occur. Further, it is understood that even if a color developing agent is used in combination, precipitation and tar cannot be prevented in Nos. 7, 8 and 14 outside the present invention. However, it can be seen that No9 to No13 and No15 and 16 of the present invention do not cause precipitation or tar and are extremely preferable.

Example 2 A light-sensitive material was prepared by sequentially coating the following layers on a polyethylene-coated paper support from the support side.

The polyethylene coated paper has an average molecular weight of 100,
00, density 0.95 polyethylene 200 parts by weight and average molecular weight 200
A mixture of 20 parts by weight of polyethylene with a density of 0.8 and a density of 0.80 was added with 6.8% by weight of anatase type titanium oxide, and a coating layer of 0.035 mm in thickness was formed on the surface of the fine paper with a weight of 170 g / m ² by the extrusion coating method. The thing which provided the coating layer of thickness 0.040 mm only with polyethylene was used for this. The surface of the support, which was coated with polyethylene, was subjected to pretreatment by corona discharge, and then the following layers were sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 328 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye (a) Sensitized with 2.3 × 10 ⁻⁴ mol (using isopropyl alcohol as a solvent), dissolved in dibutyl phthalate and dispersed, and used as a 2,5-di-t-butylhydroquinone and a yellow coupler. α- [4- (1-
Benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydyl)]-α-pivalyl-2-chloro-5- [γ
-(2,4-Di-t-amylphenoxy) butyramide]
Acetanilide was contained in an amount of 2.2 × 10 ^-1 mol per mol of silver halide, and the amount of silver was 345 mg / m ² .

Second layer: di-t-octylhydroquinone 290 mg / m ² dissolved and dispersed in dibutyl phthalate, and as a UV absorber 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) Gelatin layer containing 205 mg / m ² Gelatin 2100 mg /
It is applied so that it will be m ² .

Third layer: a green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 80 mol% of silver bromide, the emulsion containing 430 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. 2,5-di-t-butylhydroquinone and magenta coupler sensitized with 2.5 × 10 ^-4 mol of sensitizing dye (b) and dissolved and dispersed in a solvent consisting of dibutyl phthalate and tricresyl phosphate 3: 1. As 1- (2,4,6-trichlorophenyl) -3- (2'-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone as 1.6 × 10 ^-1 mol per mol of silver halide Containing, amount of silver 310mg / m
It is applied so that it becomes ² . As an antioxidant, 2,2,4-trimethyl-6-lauryloxy-7-t-
Octyl chroman was used at 0.28 mole per mole of coupler.

Fourth layer: 33 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate and 2-as an ultraviolet absorber
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2-
A mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1.9:
1.5: 1.5: 2.1) a gelatin layer containing 510 mg / m ² ,
It is coated so that gelatin will be 2100 mg / m ² .

Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 78 mol% of silver bromide, the emulsion containing 490 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye (c) 2,5-di-t-butylhydroquinone sensitized with 2.4 × 10 ^-4 mol, dissolved and dispersed in dibutyl phthalate, and 2,4-dichloro-3-methyl as a cyan coupler -6- [γ- (2,4-Diamylphenoxy) butyramide] phenol was contained in an amount of 3.7 × 10 ^-1 mol per mol of silver halide, and the coating amount was 290 mg / m ² .

Sixth layer: It is a gelatin layer and is coated with gelatin so as to be 1100 mg / m ² .

The silver halide emulsion used for each photosensitive emulsion layer (first, third and fifth layers) was prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (2.5 g per mol of silver halide) as a stabilizer, and bis (vinylsulfonylmethyl) ether ( 10 mg per 1 g of gelatin) and saponin as a coating aid.

Sensitizing dye (a) Sensitizing dye (b) Sensitizing dye (C) After exposing the color paper prepared by the above method, the color developing solutions Nos. 1 to 16 of Example 1 were processed using the following processing steps and processing solutions. The maximum density of each dye in the obtained sample was measured with an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) with B (blue sensitive emulsion layer), G (green sensitive emulsion layer) and R (red sensitive emulsion layer). The measured values are shown in Table 3. Further visually observing the white background,
The results are shown in Table 3.

Processing step (1) Color development 38 ° C 2 minutes (2) Bleach fixing 38 ° C 1 minute (3) Stabilization treatment 25 ° C to 35 ° C 1 minute (4) Drying 60 ° C to 80 ° C approx. 1 minute [Bleaching fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with ammonia water or glacial acetic acid and add water. In addition, the total amount is 1.

[Stabilizing solution for washing with water] 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.0g 2-octyl-4-isothiazolin-3-one On 0.01g 1-hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) and 1 3.0 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g of ammonia water (ammonium 25% aqueous hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5g water, ammonia water and sulfuric acid Adjust the pH to 7.0.

From Table 3, No1 and No2 which had no problem in storage with time of Example 1
It is found that No. 9 to No. 13 of the present invention are preferable for both maximum density (rapid processability) and unexposed white background.

Example 3 No11 1-hydroxyethylidene-1.1-diphosphonic acid of Example 1 was converted to diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, nitrilotrimethylenephosphonic acid, catechol-3.5-disulfonic acid.
When the same experiment was performed by changing to a disodium salt, the same result was obtained. Similarly, when hydroxyethylethylenediaminetriacetic acid and ethylenediaminetetramethylenephosphonic acid were subjected to the same experiment, a slight precipitate was observed after 40 days.

Example 4 The same experiment as in Example 1 and Example 2 was conducted by changing No. 11 color developing agent of Example 1.

When the sulfate salt of Exemplified Compound (1) was used instead of the sulfate salt of Exemplified Compound (1), precipitation and tar had similar effects, but the maximum yellow dye concentration was 2.45.

Then 3-methyl-4-amino-N-ethyl-N- (β-
3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidopropyl) aniline sulfate and 3-methyl-4-amino-N-ethyl-in place of methanesulfonamidoethyl) -aniline sulfate. When N-β-methoxyethylaniline-p-triene sulfonate was used, 3-methyl-4-amino-N-ethyl-N- (β-methylsulfonamidopropyl) aniline sulphate was tar Slightly observed in 40 days, tar and precipitation of 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline-p-toluenesulfonate were slightly observed in 30 days and 40 days later. So it happened to some extent.

Example 5 The addition amount of benzyl alcohol of No. 3 and No. 11 of Example 1 was zero, 3 g / l, 5 g / l, 10 g / l, 15 g / l, 19 g / l, 22 g / l, 24.
The same experiment as in Example 1 was conducted by changing the value to g / l and the results are shown in Table 4.
It was shown to.

As is clear from Table 4, the present invention has no effect when the amount of benzine alcohol is zero, and the effect of the present invention is particularly large at 5.0 to 22 g / l.

Example 6 In the method for producing a color paper of Example 2, cyan couplers (1) to (7) represented by the general formulas [VI] to [VIII] are used for the cyan coupler, and a general formula [IV] is used for the magenta coupler. Alternatively, a magenta coupler (1) represented by [V]
Regarding the color paper prepared using (10) and the color paper prepared in Example 2, 4 of No. 11 of Example 1
When developed with a processing solution after a lapse of 0 days, the general formula [VI]-
In the color paper using the cyan coupler [VIII] and the magenta coupler of the general formula [IV] or [V], the stain density was low and the result was favorable.

[Cyan coupler] [Magenta coupler]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kazuhiro Kobayashi 1 Sakura-cho, Hino-shi, Tokyo Photo Konishi Roku Photo Industry Co., Ltd. (72) Masao Ishikawa 1 Sakura-cho, Hino-shi, Tokyo Photo Roku Konishi Photo Co., Ltd. In the company

Claims (8)

[Claims] 1. A color developing solution for a silver halide color photographic light-sensitive material containing a p-phenylene amine color developing agent, benzyl alcohol and a triazinyl stilbene type fluorescent whitening agent, wherein the p-phenylenediamine color developing agent is used. N-hydroxyalkyl-substituted-p contained in the main drug
The content of the phenylenediamine color developing agent is 5 to 50% by weight relative to the total amount of the p-phenylenediamine color developing agent, and magnesium ion represented by the following general formula [I] A color developing solution for a silver halide color photographic light-sensitive material, containing a water-soluble chelating agent having a stability constant (log KMA) of 3 or more. General formula [I] [Here, M represents a magnesium ion and A represents a water-soluble chelating agent. ] 2. A silver halide color photographic light-sensitive material according to claim 1, wherein the content of the p-phenylenediamine type color developing agent is 2.0 g to 15 g per one. Color developer. 3. The content of benzyl alcohol is 5.
The color developing solution for a silver halide color photographic light-sensitive material according to claim 1 or 2, which is in a range of 0 g to 22 g. 4. An N-sulfonamidoalkyl-substituted-p-phenylenediamine color developing agent as a p-phenylenediamine color developing agent other than the N-hydroxyalkyl-substituted p-phenylenediamine color developing agent. A color developing solution for a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, which is characterized. 5. An N-hydroxyne-p-phenylenediamine type color developing agent is 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline salt, and N-
A sulfonamide alkyl-substituted-p-phenylenediamine color developing agent is 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline salt. A color developing solution for a silver halide color photographic light-sensitive material according to item 4. 6. A silver halide color according to any one of claims 1 to 5, wherein the triazinyl stilbene optical brightening agent is represented by the following general formula [II]. Color developer for photographic light-sensitive materials. General formula [II] In the formula, X ₁₁ , X ₁₂ , Y ₁₁ and Y ₁₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group,
It represents an aryloxy group, an aryl group, an amino group, an alkylamino group or an arylamino group. M represents a hydrogen atom, sodium, potassium, ammonium or lithium. 7. Stability constant with magnesium ion (logKM
A) the water-soluble chelating agent having 3 or more is diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminoniacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, catechol-3,5- 7. A color development for silver halide color photographic light-sensitive material according to any one of claims 1 to 6, which is at least one compound selected from disulfonic acid, condensed phosphoric acid or salts thereof. Developer. 8. An N-hydroxyne-p-phenylenediamine type color developing agent in an amount of 5 to 30% by weight based on the total amount of the p-phenylenediamine type color developing agent. A color developing solution for a silver halide color photographic light-sensitive material according to any one of items 5 to 7.