JPH087410B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rapid and / or simple processing method for silver halide color photographic light-sensitive materials.

More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material having improved processability, process dependence and image fastness in a quick and / or simple process.

(Prior Art) In recent years, in the photographic processing of a color photographic light-sensitive material, it has been desired that the processing time be shortened as the delivery time for finishing and the labor for laboratories are reduced. As a method for shortening the time of each treatment step, a temperature increase and a replenishment amount increase are general methods, but in addition, many methods of strengthening stirring or adding various accelerators have been proposed.

Among them, a color photographic light-sensitive material containing a silver chloride emulsion in place of a silver bromide emulsion or a silver iodide emulsion which has been widely used conventionally is processed for the purpose of accelerating color development and / or embodying a replenishing amount. It is known how to do it. For example, in International Publication No. WO87-04534, a silver halide color photographic light-sensitive material having a high silver chloride content (hereinafter referred to as a high silver chloride color photographic light-sensitive material) contains substantially sulfite ion and benzyl alcohol. A method of rapid processing with a color developing solution is described.

However, based on the above method, it has been found that there is an unexpected problem such as an increase in fog due to pressure sensitization when developing is performed.

Further, during continuous processing, fluctuations in photographic properties, poor desilvering, white background contamination (residual color), and deterioration of image storability were observed. In a rapid processing method using high silver chloride color photographic light-sensitive material, fluctuations in photographic characteristics due to continuous processing (especially fog)
As a method of reducing the above-mentioned problems, Japanese Patent Laid-Open Nos.
It is known to use organic antifoggants for 32342. However, the fog preventing effect is insufficient, and it is difficult to suppress the minimum density by increasing the residual color in continuous processing.

Further, Japanese Patent Laid-Open No. 61-70552 discloses a method for lowering the replenishment rate of a developing solution, in which a high silver chloride color photographic light-sensitive material is used and a replenishing amount is added during development so that overflow does not occur in a developing bath. Has been described.

Further, in JP-A-63-106655, for the purpose of stabilizing the processing, a silver halide color photographic light-sensitive material in which the silver halide emulsion layer has a high silver chloride content is used with a hydroxyamine compound and a predetermined concentration or more. The method of developing with a color developing solution containing a chloride is disclosed. However, in these methods, there is a problem in that variations in photographic properties (in particular, variations in photographic properties due to influences of developer components, pH, temperature, etc.) are recognized, and improvements have been demanded.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a development processing method using a high silver chloride color photographic light-sensitive material, which is quick and prevents fogging from occurring.

A second object of the present invention is to provide a color photographic light-sensitive material using a high silver chloride color photographic light-sensitive material, which is quick and simple and has little fluctuation in photographic properties, and a development processing method.

A third object of the present invention is to provide a method for forming an image of a color photographic light-sensitive material, which uses a high silver chloride color photographic light-sensitive material and is quick and simple and has good image storability (decrease in density and increase in density of white background). It is to be.

(Means for Solving the Problem) As a result of examining various anti-fading agents and the composition of the treatment liquid, the present inventors have found that this problem can be solved by the following means.

That is, in the method of processing a silver halide color light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, the silver halide color photographic material contains 80 mol% or more of silver chloride. At least one layer containing a silver halide emulsion comprising at least one compound represented by the following general formula (I) and having a total coated silver amount of 0.75 g / m ² or less. The color developer contains chlorine ions in an amount of 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol.
/ l and contains 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol of bromide ion
The problem was solved by a processing method of a silver halide color photographic light-sensitive material characterized by containing / l.

General formula (I) In the formula, R ₁ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, —OR ′ ₁ , —SR ′. ₁ , It represents a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group and a formyl group.

R _'1 represents the same meaning as R _1. R ₇ and R ₈ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group or a sulfonyl group.

_{OR 1, R 2, R 3} , R 4, R 5 and may form a 5- to 7-membered ring by bonding group at the ortho position to each other among the R _6, also with R ₇
R ₈ may combine with each other to form a 5- to 7-membered ring.

The present invention will be described in detail below. The silver halide emulsion of the present invention has a silver chloride content of 80 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, based on the total amount of silver halide. From the viewpoint of rapidity, the higher the silver chloride content, the better.

The coating amount of silver halide light-sensitive material of the present invention is 0.75 g / m ²
It must be: When the amount of coated silver is more than 0.75 g / m ² , the photographic property varies so much that the object of the present invention is not achieved.

In the present invention, chlorine ions are added to the color developer.
It is necessary to contain 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l. It is preferably 4 × 10 ^-2 to 1 × 10 ^-1 mol / l. When the chlorine ion concentration is more than 1.5 × 10 ⁻¹ mol / l, it has a drawback that development is delayed, and it does not achieve the object of the present invention that the concentration is high and the maximum concentration is high.

On the other hand, if it is less than 3.5 × 10 ^-2 mol / l, the object of the present invention cannot be achieved because the photographic property varies greatly due to the process variation.

In the present invention, a bromine ion of 3.0 is contained in the color developer.
It is necessary to contain x10 ^-5 mol / l to 1.0 x 10 ^-3 mol / l. It is preferably 5.0 × 10 ^{−5 to} 5.0 × 10 ⁻⁴ mol / l.
When the bromine ion concentration is more than 1.0 × 10 ⁻³ mol / l, the development is delayed and the purpose of rapid processing cannot be achieved.

On the other hand, when the amount is less than 3.0 × 10 ⁻⁵ mol / l, the process variation (particularly the process liquid component and pH variation) is large and the object of the present invention is not achieved.

Here, chlorine ion and bromine ion may be directly added to the developing solution and / or may be eluted from the light-sensitive material in the developing solution.

When directly added to a color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, of which the preferred ones Are sodium chloride and potassium chloride.

It may also be supplied from a fluorescent whitening agent added to the developing solution. As a source of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide,
Examples thereof include calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and thallium bromide, of which potassium bromide and sodium bromide are preferred.

When it is eluted from the photosensitive material in the developing solution, chlorine ions,
Both bromine ions may be supplied from the emulsion, or may be supplied from other than the emulsion.

 The compound represented by formula (I) will be described in detail.

R ₁ is an alkyl group (a linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, sec-butyl, tert-hexyl, benzyl, cyclohexyl, octyl, isooctyl, decyl, dodecyl, hexadecyl, octadecyl). , An alkenyl group (for example, vinyl, allyl), an aryl group (for example, phenyl, naphthyl), a heterocyclic group (a heterocyclic ring composed of an atom selected from a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom, for example, 2- Pyridyl, 2-piperidyl, 2-morpholinyl, 4
-Chromanyl).

_{R 2, R 3, R 4} , R 5 and R ₆ may be the same or different, each represents a hydrogen atom, an alkyl group (straight-chain, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, sec -Butyl, tert-hexyl, benzyl, cyclohexyl, octyl, isooctyl, decyl, dodecyl, hexadecyl, octadecyl), an alkenyl group (e.g. vinyl, allyl), an aryl group (e.g. phenyl,
Naphthyl), a heterocyclic group (a heterocycle composed of an atom selected from a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom, such as 2-pyridyl, 2-piperidyl, 2-morpholinyl, 4-chromanyl), halogen Atom (eg fluorine atom, chlorine atom, bromine atom), -OR ' ₁ , -S
R ′ ₁ , , A sulfonyl group (eg, methanesulfonyl, toluenesulfonyl), a sulfinyl group (eg, dodecanesulfinyl, benzenesulfinyl), an alkoxycarbonyl group (eg, methoxycarbonyl, octyloxycarbonyl, octadecyloxycarbonyl), an aryloxycarbonyl group ( For example, phenyloxycarbonyl,
Naphthyloxycarbonyl), an acyl group (eg acetyl, benzoyl), a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group and a formyl group. R '
₁ has the same meaning as R ₁ . R ₇ and R ₈ may be the same or different, and each is a hydrogen atom, an alkyl group (for example, a linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, sec-butyl, tert-hexyl, benzyl, Selected from cyclohexyl, octyl, isooctyl, decyl, dodecyl, hexadecyl, octadecyl), alkenyl group (eg vinyl, allyl), aryl group (eg phenyl, naphthyl), heterocyclic group (carbon atom, oxygen atom, sulfur atom or nitrogen atom) A heterocyclic ring composed of atoms such as 2-pyridyl, 2-piperidyl, 2-morpholinyl, 4-chromanyl), an acyl group (eg acetyl, benzoyl), a carbamoyl group, and a sulfonyl group (eg benzenesulfonyl, methane). Sulfonyl, dodecanesulfonyl).

_{OR 1, R 2, R 3} , R 4, R 5 and may form a 5- to 7-membered ring by bonding group at the ortho position to each other among the R _6, also with R ₇
R ₈ may combine with each other to form a 5- to 7-membered ring.

Among the compounds represented by the general formula (I), preferred compounds from the viewpoint of the effect of the present invention are those in which at least one of R _{2 to} R ₆ is —OR ′ ₁ , —SR ′ ₁ , When it is a group selected from.

More preferred compounds are represented by the following general formulas (Ia), (Ib),
It can be represented by (Ic), (Id), (Ie) and (If).

General formula (Ia) General formula (Ib) General formula (Ic) General formula (Id) General formula (Ie) General formula (If) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ′ ₁ are represented by the general formula (I)
Has the same meaning as. R ″ ₁ and R ₁ have the same meaning as R ′ _1. R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₀ ′, R
₁₁ 'may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₁₄ and R ₁₅ further represent an alkoxy group, an aryloxy group, a substituted or unsubstituted or cyclic amino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group and an aryloxycarbonyl group. R _'2 and R' ₅ has the same meaning as R _2.

The compounds of the present invention are specifically exemplified below, but the present invention is not limited thereby.

These compounds can be easily synthesized according to the method described in Japanese Patent Application No. 62-158342.

The compound represented by formula (I) of the present invention may be used in any layer of the light-sensitive material. It is preferably used in a layer containing a coupler.

The compound represented by the general formula (I) of the present invention is 1 × 10 ⁻² to 10 mol, preferably 1 × 10 ⁻¹ to 1 mol per mol of the coupler.
It is in the range of 5 mol.

 The processing liquid will be described in more detail below.

In the present invention, it is preferable that the color developing solution contains substantially no sulfite ion from the viewpoint of processing stability and prevention of fogging, but the developing solution is not used for a long time in order to suppress deterioration of the developing solution, and air oxidation. In order to suppress the influence of the above, use a floating pig, use a physical means such as reducing the opening of the developing tank, suppress the temperature of the developer, add a chemical means such as adding an organic preservative. Can be used.
Among them, the method using an organic preservative is advantageous from the viewpoint of simplicity.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, although it is an organic compound having a function of preventing the oxidation of the color developing agent by air or the like, among them, a hydroxylamine derivative (excluding hydroxylamine; hereinafter the same), hydroxamic acids, hydrazines, hydrazides, phenols, Particularly, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. It is an effective organic preservative. These are disclosed in Japanese Patent Application Nos. 61-147823, 61-173595 and 61-173595.
-165621, 61-188619, 61-197760, 61-
186561, 61-198987, 61-201861, 61-18
6559, 61-170756, 61-188742, 61-1887
No. 41, U.S. Pat.Nos. 3,615,503 and 2,494,903,
52-143020 and JP-B-48-30496.

Regarding the preferred organic preservatives, the general formula is given below, but the organic preservatives that can be used in the present invention are:
It is not limited to these.

The amount of the following compounds added to the color developer is 0.005
Mol / l to 0.5 mol / l, preferably 0.03 mol / l to 0.1 mol
It is desirable to add so that the concentration becomes / l.

Particularly, addition of hydroxylamine derivative and / or hydrazine derivative is preferable.

The hydroxylamine derivative is preferably one represented by the following general formula (II).

General formula (II) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R ¹¹ and R ¹² do not become hydrogen atoms at the same time and may be linked to each other to form a heterocycle together with the nitrogen atom. The ring structure of the hetero ring is a 5- to 6-membered ring and is constituted by a carbon atom, a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

The following are preferred as hydrazines and hydrazides.

General formula (III) In the formula, R ³¹ , R ³² , and R ³³ are hydrogen atoms, substituted or unsubstituted,
Represents an alkyl group, an aryl group, or a heterocyclic group,
R ³⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. The heterocyclic group is a 5- to 6-membered ring,
It is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. X ³¹ is -CO-, -SO ₂
-Or Represents a divalent group selected from, and n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

Use of the compound represented by the general formula (II) or (III) and the amine represented by the following general formula (IV) or (V) in combination improves the stability of the color developer. Is more preferable from the viewpoint of improving stability during continuous treatment.

General formula (IV) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R ⁷³
May be linked to each other to form a nitrogen-containing heterocycle.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent.
As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferable. Further, as the substituent, a hydroxyl group, a sulfo group,
Carboxyl group, halogen atom, nitro group, amino group,
Etc. can be mentioned.

General formula (V) In the formula, X represents a trivalent atom group necessary for completing a condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R ¹ and R ² may be the same or different from each other.

The organic preservative can be obtained as a commercial product, but can also be synthesized by the method described in Japanese Patent Application Nos. 62-124038 and 62-24374.

Hereinafter, the color developer used in the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N -[Β-Hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
[Β-C methanesulfonamido) ethyl] aniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 g to about 10 g per developer.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-nobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1 -Diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfo Salicylic acid, 4-sulfosalicylic acid, and these chelating agents may be used in combination of two or more, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution.

As a development accelerator, Japanese Patent Publication Nos. 37-16088 and 37-598.
No. 7, No. 38-7826, No. 44-12380, No. 45-9019 and thioether compounds represented by U.S. Pat. -Phenylenediamine compounds, JP-A-50-13
7726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, quaternary ammonium salts, p-aminophenols described in U.S. Pat. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Japanese Patent Sho 4
1-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in JP-B-3.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-41-23883 and U.S. Pat.
Polyalkylene oxides represented by 532, 501, etc.,
In addition, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

The color developer preferably contains substantially no benzyl alcohol. Substantially per color developer
The amount is 2.0 ml or less, more preferably, it is not contained at all.
When the content is not substantially contained, the fluctuation of photographic characteristics during continuous processing is small, and more preferable results are obtained.

In the present invention, any antifoggant can be added in addition to chlorine ion and bromine ion, if necessary. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole,
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Typical examples are nitrogen-containing heterocyclic compounds such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, imidazole, hydroxyazaindolidine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightening agent, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 10 g / l, preferably 0.1 to 6 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

Usually, in color development, the developer is replenished. The replenishment amount depends on the photosensitive material to be processed, but is generally about 180 to 1000 ml per square meter of the photosensitive material. Replenishment is a means for keeping the components of the color developing solution constant in order to avoid a change in the development finish characteristics due to a change in the component concentration in a development processing method in which a large amount of a light-sensitive material is continuously processed with an automatic developing solution or the like. For replenishment, a large amount of overflow liquid is inevitably generated, and it is preferable that the replenishment amount is small in terms of economy and pollution. The preferable replenishing amount is ^{20 to} 150 ml per 1 m ² of the light-sensitive material. The replenishment amount of 20 ml per 1 m ² of the light-sensitive material is an amount at which the carry-out amount of the processing liquid by the light-sensitive material and the replenishment amount are substantially equal to each other, though the overflow is substantially eliminated, although the amount of replenishment varies depending on the light-sensitive material. The present invention is effective even in such a treatment with low replenishment.

In the present invention, desilvering processing is performed after color development.
The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferred that they are performed simultaneously.

The bleaching solution or bleach-fixing solution used in the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), chloride (eg, potassium chloride, sodium chloride, ammonium chloride), or iodide ( For example, a rehalogenating agent such as ammonium iodide) may be included. One or more inorganics with pH buffering capacity, such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary. Acids, organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas. These are used alone or in admixture of two or more. can do. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5.
The range is up to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is
3 to 10 are preferable, and 5 to 9 are particularly preferable. pH
If it is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution and the fixing solution in the present invention, as a preservative, sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, Etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound is contained. These compounds are converted to sulfite ion
The content is preferably 0.02 to 0.50 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, carbonyl bisulfite adduct, sulfinic acid, carbonyl compound, sulfinic acid and the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added if necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, and then washing with water and / or a stabilizing step.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), the application, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture and
Television Engineers) Volume 64, p.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isothianurate, other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide", It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Sanitary Technology Association, "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-10.
And preferably 5-8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. Is done.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14834 are used.
No. 59, No. 184343, No. 60-220345, No. 60-238832
No. 60, No. 60-239784, No. 60-239749, No. 61-4054,
All known methods described in JP-A-61-118749 and the like can be used. Especially 1-hydroxyethylidene-1,1-
A stabilizing bath containing diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and as an example, it is used as a color photosensitive material for photographing and a final bath. A stabilizing bath containing formalin and a surfactant can be mentioned.

The processing time of the present invention is defined as the time from the time when the photosensitive material comes into contact with the color developer to the time when it leaves the final bath (usually a washing or stabilizing bath). The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 4 minutes or less.

Next, the silver halide color photographic light-sensitive material used in the present invention will be described in detail.

The silver halide emulsion of the present invention has a silver chloride content of 80 mol% or more, preferably 95 mol%, based on the total amount of silver halide.
Or more, more preferably 98 mol% or more. From the viewpoint of quickness, the higher the content of silver chloride is, the more preferable. The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. There are many useful points in terms of photosensitivity, such as increasing the light absorption amount, enhancing the adsorption of the spectral sensitizing dye, or weakening the desensitization by the spectral sensitizing dye.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have a different phase between the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a whole grain structure. It may consist of a homogeneous phase. Moreover, they may be mixed.

Silver halide grains in photographic emulsions are cubic, octahedral,
Those having a regular crystal form such as tetradecahedron, spherical,
It may be a material having an irregular crystal such as a plate, a material having a crystal defect such as a twin plane, or a compound thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978).
Dec.), pp. 22-23, "I. Emulsion preparat
ion and types) ”and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No. 1
7643 and No. 18716, the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760 and the like are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3,725,064, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, US Pat. No. 4,500,630,
No. 4,540,654, No. 4,556,630, WO (PCT) 88/0479
Those described in No. 5 and the like are particularly preferable.

Cyan couplers include phenol and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
No. 3,446,622, No. 4,333,999, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212,
No. 4,296,199, European Patent No. 161,626A, JP 61-4
Those described in No. 2658 and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the above-mentioned RD17643, VII-F.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in U.S. Pat.
Examples of the coupler include a DIR redox compound releasing coupler described in JP-A-185950, and a coupler that releases a dye that restores color after separation described in EP 173,302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No.17643, page 28, and RD.No. 18716, page 647 From right column 64
It is described in the left column on page 8.

(Examples) Examples of the present invention are specifically shown below, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper (01) having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene.
The coating liquid was prepared as follows.

Preparation of 1st layer coating solution 60.0g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) 28.0 g of ethyl acetate 150 cc and solvent (Solv-
3) Add 1.0 cc and 3.0 cc of solvent (Solv-4) and dissolve, then add 10 cc of this solution containing sodium dodecylbenzene sulfonate.
% Gelatin aqueous solution (450 cc) and then dispersed with an ultrasonic homogenizer. The resulting dispersion is 420 g of silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye.
To prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-Bis (vinylsulfonyl) ethane was used as a gelatin hardener for each layer.

The following were used as the spectral sensitizing dyes in each layer.

Blue-sensitive emulsion layer; anhydro-5-5'-dichloro-3,
3'-Disulfoethylthiacyanine hydroxide ... 6
X10 ^-4 mol / Agl mol Green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide ... 4 x 10 ^-4 mol / Agl mol red Sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9,9 '
-(2,2'-Dimethyl-1,3-propano) thiacarbocyanine iodide ... 2.1.times.10.sup.- ⁴ mol / Agl mol The following substances were used as stabilizers for each emulsion layer.

The following dyes were used as the anti-irradiation dye.

[3-Carboxy-5-hydroxy-4- (3- (carboxy-5-oxo-1- (2,5-disulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1- Birazolyl] benzene-2,5-disulfonate-sodium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7
-Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy-4- (3- (3-cyano-5-oxo-1- ( 4-sulfonatophenyl)-
2-pyrazolin-4-ylidene) -1-pentanyl)-
1-Pyrazolyl] benzene-4-sulfonato-sodium salt (Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion (silver chlorobromide emulsion) represents the coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene 1st layer (blue sensitive layer) Silver halide emulsion (AgBr: 0.7 mol%, cubic average grain size 0.9μ) 0.27 Gelatin 1.80 Yellow coupler (ExY) 0.61 Anti-fading agent (Cpd) -1) 0.28 solvent (Solv-3) 0.015 solvent (Solv-4) 0.03 second layer (color mixing prevention layer) gelatin 0.80 color mixing inhibitor (Cpd-2) 0.055 solvent (Solv-1) 0.03 solvent (Solv-2) 0.015 Third layer (green layer) Silver halide emulsion (AgBr: 1.2 mol%, cubic grain size)
0.45μ) 0.28 Gelatin 1.40 Magenta coupler (EXM) 0.65 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.02 Fourth layer (color mixing prevention layer) Gelatin 1.70 Color mixing inhibitor (Cpd-2) 0.085 Ultraviolet absorber (UV) -1) 0.45 UV absorber (UV-2) 0.23 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red sensitive layer) Silver halide emulsion (AgBr: 2 mol%, cubic grain size 0) .
5μ) 0.19 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.13 Anti-fading agent (Cpd-1) 0.23 Solvent (Solv-1) 0.14 Solvent (Solv-2) 0.10 Compound (Cpd-4) 0.13 Sixth layer (UV absorbing layer) Gelatin 0.70 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 Seventh layer (protective layer) Gelatin 1.07 (ExY) Yellow coupler α-pivalyl-α- (3-benzyl-1-hydantoinyl) -2-chloro-5- [β- (dodecylsulfonyl) butylamido] acetanilide (ExM) Magenta coupler 1- (2,4 , 6-Trichlorophenyl) -3 [2-chloro-5 (3-octadecenylsuccinimide) anilino] -5-pyrazolone (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5
[2- (2,4-di-tert-amylphenoxy) -3-methylbutyramidephenol (ExC-2) cyan coupler 2,4-dichloro-4-methyl-6- [α- (2,4-di-
tert-amylphenoxy) butylamide] phenol (Cpd-1) anti-fading agent 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate (Cpd-2) anti-fading agent 2,5-di- tert-octylhydroquinone (Cpd-4) p- (p-dodecylphenylsulfonamide) toluene (Solv-3) solvent di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide methoxy-2 , 4-ge-t
-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-di) -Tert-Butylphenyl) benzotriazole (Solv-1) solvent di (2-ethylhexyl) phthalate (Solv-2) solvent dibutylphthalate (Preparation of color photographic paper 02) As a color fading inhibitor in the third layer of color photographic paper 01 Further, a color photographic paper 02 was prepared in the same manner as the color photographic paper 01 except that the following comparative compound (A) was added at 0.25 g / m ² .

(Preparation of color photographic paper 03) The amount of silver halide emulsion in the first layer of color photographic paper 01 was adjusted to 0.
The amount of the silver halide emulsion in the third layer was 0.34 g / m ² to 31 g / m ^2.
2 , the amount of the silver halide emulsion in the fifth layer was 0.21 g / m ² , and the following comparative compound (A) was further added as a fading inhibitor in an amount of 0.25 g / m ^2.
A color printing paper 03 was prepared in the same manner as the color printing paper 02 except that m ^{2 was} added.

(Preparation of Color Printing Paper 04) Instead of the following comparative compound (A), the compound (A-48) of the present invention was used as the anti-fading agent in the third layer of the color printing paper 03.
A color photographic paper 04 was prepared in the same manner as the color photographic paper 03 except that 0.23 g / m ² was used.

(Preparation of Color Printing Paper 05) The same as Color Printing Paper 01 except that the compound (A-48) of the present invention was further added to the third layer of Color Printing Paper 01 at 0.23 g / m ² as an anti-fading agent. , Color photographic paper 05 was produced.

(Preparation of Color Printing Paper 06-14) In the same manner as for the color printing paper 05, the compound (A-
2), (A-7), (A-21), (A-27), (A-3)
9), (A-42), (A-50), (A-54), and (A-72) except that 0.23 g / m ^{2 was} added in the same manner as the color printing paper 05, the color printing paper 06 to 14 was produced.

(Preparation of color photographic paper 15 and 16) Color photographic paper 14 except that the silver halide emulsion composition of the first, third and fifth layers of color photographic paper 14 was changed as shown in Table 1. Color paper, similar to paper 14.
15 and 16 were produced.

(Preparation of color photographic paper 17) Color photographic paper 01 was prepared in the same manner as color photographic paper 01 except that the following comparative compound (B) was further added to the third layer of color photographic paper 01 at 0.23 g / m ^2. Paper 17 was made.

Comparative compound (A) Comparative compound (B) The following experiments were conducted on the above color photographic papers (01) to (18).

First, the coated sample was subjected to sensitometric gradation exposure using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time is 1 /
The exposure was performed so that the exposure amount was 250 CMS with an exposure time of 10 seconds.

Next, the sample was treated with the following treatment step and the following treatment liquid composition (A). Moreover, it processed similarly with the processing liquid composition (B). However, the chlorine ion concentration and the bromine ion concentration of the color developing solution were changed as shown in Table 1 below.

The maximum yellow color density (Y-Dmax) in the treatment liquid composition (A) is summarized in Table 1 as an index of color developability. In addition, as an index of processing dependence, Table 1 summarizes the decrease in density (ΔD _y ) when the processing liquid composition (B) is processed at an exposure amount that gives a yellow density of 1.0 in the processing liquid composition (A). It was

In addition, after treating with the treatment liquid composition (A), irradiating with a xenon fade meter (45,000Lux) for 450 hours,
Increase in yellow density (Δd _y ) of the white background and image residual rate (ΔD _m ) at initial magenta density D _m = 2.0
Table 1 shows the image retention rate (ΔD _c ) at an initial cyan density D _c = 2.0 when the sample was left in a dark room at 90 ° C. for 150 hours as an index of image storability. Step Temperature Time Color developing 38 ° C. 45 seconds blix 30 to 36 ° C. 45 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 seconds Drying 70 to 80 ° C. 60 seconds each processing solution The composition of is as follows.

Color developer Water 800ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 3.0g Diethylhydroxylamine Sodium chloride See table 1 Potassium bromide See table 1 Potassium carbonate 19.0g N-ethyl- N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0g Triethanolamine 10.0g Fluorescent brightener (4,4'-diaminostilbene type) 2.0g Sodium sulfite 0.13g Water added 1000ml pH (25 ° C) 10.05 Bleach-fixing solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Glacial acetic acid 9 g Water added 1000 ml pH (25 ° C) 5.40 Rinse solution Ion-exchanged water (3 ppm or less for each of calcium and magnesium) However, the amount of diethylhydroxylamine in the color developer is 3.1 g / l for the A treatment and 5.7 g / l for the B treatment.

By defining the halogen composition, the anti-fading agent, the coating silver amount, and the halogen ion of the present invention, the color developability, the processing dependence,
It can be seen from Table 1 that both the image storability and the image storability can be solved.

Comparison of A and Z when no anti-fading agent is used and when using a comparative anti-fading agent, and B, C and D
As can be seen from the comparison, even if the chlorine ion concentration and the bromine ion concentration are within the range of the present invention, the processing dependence (ΔD _y ) is greatly reduced without significantly lowering the color forming property (yellow maximum color forming density; ΔDmax). It can be improved (the fluctuation range becomes smaller). However, the increase of stain due to light (△ D _y
Increase) is a problem. This is used for comparison as an anti-fading agent. It can be seen from the comparison of Z, D, and I that the addition of amine compounds (B, C, and D) is worsened by the addition, but it is reduced when the compounds of the present invention are used. This photo stain is seen even when the chloride ion concentration and the bromine ion concentration are outside the range of the present invention, as can be seen from the comparison of A, B, K, Z, D, and I. It is understood that the effect is more remarkable (the difference is larger) in the case. Furthermore, when the combination (I, etc.) of the present invention was used, the comparative anti-fading agent was able to significantly improve the processing dependence which could not be sufficiently improved.

 This effect is unexpected.

Example 2 A multilayer color photographic printing paper (51) having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene.
The coating liquid was prepared as follows.

1st layer coating solution preparation 19.7 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 4.4g and (Cpd-7) 0.7g to ethyl acetate 27.2cc
And 8.7 g of a solvent (Solv-3) were added and dissolved. This solution was emulsified and dispersed in 18.5 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, in a silver chlorobromide emulsion (cubic average grain size 0.88μ, grain size distribution variation coefficient 0.08, containing 0.2% mol of silver bromide on the grain surface), the following blue-sensitizing sensitizing dyes were each added 2.0 × After addition of 10 ⁻⁴ mol, a sulfur-sensitized product was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. As a gelatin hardening agent for each layer, 1-oxy-3,5
-Dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

Blue-sensitive emulsion layer (2.0 × 10 ^-4 moles per mole of silver halide) Green-sensitive emulsion layer (4.0 × 10 ⁻⁴ mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv -1) 0.16 Solvent (Solv-4) 0.08 Third Layer (Green Sensitive Layer) Silver chlorobromide emulsion (1: 3 mixture (Ag mole) ratio of cubic average grain size 0.55μ and 0.39μ). Coefficients of variation of particle size distribution 0.10, 0.08, and AgBr 0.8 mol% were contained locally on the particle surface. 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-3) 0.13 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-2) 0.54 Fourth layer ( UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic average particle size 0.58) with μ,
A 1: 4 mixture of 0.45μ (Ag molar ratio). Coefficients of variation of particle size distribution 0.09, 0.11 and AgBr 0.6 mol% were locally contained in a part of the particle surface. 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer ( UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.16 Anti-color mixing agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protecting layer) Gelatin 1.33 Polyvinyl alcohol acrylic 0.17 Modified copolymer ( Degree of denaturation 17%) Liquid paraffin 0.03 R = H, C ₂ H ₅ , C ₄ H ₉ 1: 3: 6 mixture by weight (Preparation of Color Printing Paper 52) A color printing paper 52 was prepared in the same manner as the color printing paper 51 except that the color mixing inhibitor (Cpd-3) in the third layer of the color printing paper 51 was omitted.

(Preparation of Color Printing Paper 53) Except that the color mixing inhibitor (Cpd-3) in the third layer of the color printing paper 51 was replaced with the comparative compound (A) of Example 1 in an equal weight.
A color photographic paper 53 was produced in the same manner as the color photographic paper 51.

(Preparation of Color Printing Paper 54-60) The color mixing inhibitor (Cpd-3) in the third layer of the color printing paper 51 was used as the compound (A-4), (A-19), (A-25) of the present invention,
(A-27), (A-31), (A-50), and (A-6
Color photographic papers 54 to 60 were produced in the same manner as the color photographic paper 51 except that 6) was replaced by the same weight.

The following experiments were conducted on the above color photographic papers (51) to (60).

The color photographic paper (51) was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., light source color temperature 3200 ° K), and color development was performed according to the following processing steps. The treatment was carried out until the replenishment amount of the liquid became twice the tank volume. After that, color paper (5
1) to (60) were treated with the treatment liquid after running (treatment A). However, the chlorine concentration and the bromine ion concentration of the color developing solution were changed as shown in Table 2.

After the treatment, it was irradiated with a xenon fade meter (45,000Lux) for 450 hours, and then the increase in yellow density (ΔD _y ) in the white background and the residual ratio of color image density at the initial magenta density D _m = 2.0. (ΔD _m ) is summarized in Table 2.

Further, the pH of the color developing solution after the running was readjusted to 9.80, and the color photographic papers (51) to (60) were processed (Process B). Table 2 summarizes the magenta density (DM _2.0 ) in the treatment B in the exposure that gives the magenta density D _m = 2.0 in the treatment A as an index of the treatment dependence.

The composition of each treatment liquid is as follows.

Color developer Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Glacial acetic acid 9g Water added 1000ml pH (25 ℃) 5.40 Stable Liquid (same as tank liquid and replenisher) Formalin (37%) 0.1g Formalin-sulfite adduct 0.7g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-Methyl-4-isothiazoline-3 -ON 0.01g Copper sulfate 0.005g Ammonia water (28%) 2.0ml Add water to 1000ml pH (25 ℃) 4.0 As can be seen from the comparison between Experiments D and E in Table 2, there is no particular effect on the color developability (YDmax) even when the chloride ion concentration and the bromine ion concentration are within the range of the present invention, but the value of DM _2.0 It is clear that the processing dependency tends to improve as the value of is close to 2.0. However, in that case, an increase in stain (ΔDy) due to light is observed. On the other hand, when the combination of the present invention is used, it is recognized that both processing dependence and image storability are good.

Claims (1)

[Claims] 1. A silver halide color light-sensitive material having a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer is treated with a color developing solution containing at least one aromatic primary amine color developing agent. In the method described above, each of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer is a high silver chloride emulsion comprising 80 mol% or more of silver chloride, and at least one of the emulsion layers is Contains at least one compound represented by formula (1) and has a total coated silver amount of 0.75 g / m ²
The following, the color developer, chloride ion 3.5 × 1
0 ^{-2 to} 1.5 x 10 ^-1 mol / l and 3.0 x 1 bromine ion
A method for processing a silver halide color photographic light-sensitive material, which comprises 0 ^{-5 to} 1.0 x 10 ^-3 mol / l. General formula (1): In the formula, R ₁ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, -OR ' ₁ , or -SR'. ₁ , It represents a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group and a formyl group. R _'1 represents the same meaning as R _1. R ₇ and R ₈ may be the same or different and each represents a hydrogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group and a sulfonyl group. OR ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ may be bonded to each other at the ortho positions to form a 5- to 7-membered ring, or R ₇ and R ₈
May combine with each other to form a 5- to 7-membered ring.