JPH0740129B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, a sensitization which occurs when a silver halide color photographic light-sensitive material is continuously processed. The present invention relates to a processing method for improving stains by dyes, particularly yellow stains, and further obtaining a photographic image without color turbidity and achieving low pollution.

[Prior Art] Generally, a light-sensitive material is subjected to processing steps such as color development, bleach-fixing (or bleaching / fixing) and washing with water after imagewise exposure. In these processing steps, the depletion of water resources and the increase in the cost for washing due to the increase in the price of crude oil have become more and more serious problems in the photofinisher that automatically and continuously develops photosensitive materials. It is becoming.

Furthermore, recently, the issue of environmental protection has been emphasized, and processing with a processing solution having fixing ability (fixing or bleach-fixing processing)
It is desired to reduce or eliminate a large amount of washing water used in the following washing step. Therefore, after fixing or bleach-fixing treatment, a technique of directly stabilizing without washing with water has been proposed. For example, JP-A-57-8542,
Nos. 57-132146, 57-14834, and 58-18631 disclose isothiazoline derivatives, benzisothiazoline derivatives,
A technique for treating with a substitute solution for washing with water containing a soluble iron complex salt, a polycarboxylic acid or an organic phosphonic acid is described.

However, when the photosensitive material is continuously processed for a long period of time in the processing using such a water-washing alternative stabilizing solution, stains are likely to occur in the processed photosensitive material, and especially in a color paper, an unexposed portion is unexposed. Because it is a white background,
There is a problem that even a small amount of stain causes a serious drawback and the product value is remarkably reduced.

As a result of diligent study on this stain, the present inventor has found that when a light-sensitive material is continuously processed for a long period of time, a bleaching component and a fixing component are brought in by the light-sensitive material, and the concentration of the bleaching component and the fixing component in a stabilizing bath instead of washing increases. It was found that there is a stain caused by the sensitizing dye and a stain caused when the sensitizing dye is used in the light-sensitive material.

It has been clarified by the study of the present inventor that the generation of stains caused by bringing a bleaching component or a fixing component into a washing substitute stabilizer can be greatly reduced by incorporating the polycarboxylic acid or organic phosphonic acid in the washing substitute stabilizer. became. However, although stains, especially yellow stains, which occur when a sensitizing dye is contained in a light-sensitive material, cause almost no problem in conventional water washing treatments, the above-mentioned water-washing treatment is a substitute solution for washing with water in order to secure water resources and protect the environment. The fact that is caused by the above is a completely unexpected problem for the present inventor, and therefore, the present situation is that no effective solution has been proposed yet.

As a method for preventing stains, particularly yellow stains, by the sensitizing dye, a method of increasing the replenishment amount of the washing substitute stabilizer and a method of reducing or eliminating the blue sensitizing dye can be considered, but the former is from the viewpoint of low pollution. The latter is not preferable because it impairs the sensitivity of the light-sensitive material.

The present inventor has made diligent studies in view of such a current situation and found that the film swelling speed of the binder of the photosensitive material is related, and the stain of the sensitizing dye is set by setting the film swelling speed T 1/2 to 30 seconds or less. It has been found that can be greatly reduced.

Usually, most of the blue-sensitizing sensitizing dye flows out in the color developing solution, hardly flows out from the light-sensitive material in the bleach-fixing solution (or bleaching solution, fixing solution), and partly flows out in the wash-stabilizing alternative solution. Alternatively, it remains in the light-sensitive material, but by adjusting the film swelling speed of the binder, the outflow is further promoted in the color developing solution or the water-washing alternative stabilizing solution, and it also flows out in the bleach-fixing solution (or bleaching solution, fixing solution). It has become possible to

However, the inventor faced new difficulties. That is, it was found that when the film swelling speed of the binder was increased, color turbidity was likely to occur and the photographic performance was remarkably reduced. In particular, the present inventor has revealed that color turbidity due to the blue-sensitive emulsion layer is a problem.

[Object of the Invention] Accordingly, an object of the present invention is to provide a processing method which suppresses the generation of yellow stain when a water-washing alternative stabilizing solution is used and does not cause color turbidity in the obtained photographic image,
Another object of the present invention is to provide a processing method capable of realizing the low pollution required by the times without deteriorating the photographic performance.

[Structure of the Invention] As a result of intensive studies, the present inventor has carried out a color development processing after exposure of a light-sensitive material containing a sensitizing dye represented by the following general formula [I] and processed it with a processing solution having fixing ability. After that, when subsequently processed with a wash substitute stabilizer which has a replenishment amount of 1 to 50 times the carry-in amount from the previous bath, the photosensitive material contains a yellow coupler represented by the following general formula [II], It has also been found that the object of the present invention can be achieved by a method for processing a light-sensitive material characterized in that the film swelling speed T 1/2 of the binder is 30 seconds or less.

General formula [I]Where Z₁And Z₂Are the benzoxazole nucleus and naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, naphthoselenazole nucleus,
Nzoimidazole nucleus, naphthimidazole nucleus, pyridine
Represents the atomic group necessary to form a nucleus or a quinoline nucleus,
R₁And R₂Are alkyl, alkenyl or aryl
Represents a group, R₃Represents a hydrogen atom, a methyl group or an ethyl group
Then X₀ Represents an anion, and l represents 0 or 1.

General formula (II) X ₁ represents a halogen atom, an alkoxy group or an alkyl group.

Y ₁ represents an aryloxy group or a heterocyclic oxy group which is released when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent.

R ₄ ; tert-butyl group or R ₅ and R ₆ represent a group capable of substituting on the benzene ring, and n represents an integer of 1 or 2. When n is 2, R ₅ or R ₆ may be the same or different.

As a preferred embodiment for achieving the effect of the present invention,
The following are listed. That is, the film swelling speed T of the binder
1/2 is 20 seconds or less, and the replenishing amount of the stabilizing solution for washing instead of 2 to 20 times as much as the amount of the processing solution brought in from the previous bath when the photosensitive material is continuously processed is processed, for example, 5 per 1 m ^{2 of the} photosensitive material. ~ 20
The present inventor has found that the effect of the present invention is more remarkable by supplementing about 0 ml.

Hereinafter, the present invention will be described in more detail.

General formula [I]Where Z₁And Z₂Are the benzoxazole nucleus and naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, naphthoselenazole nucleus,
Nzoimidazole nucleus, naphthimidazole nucleus, pyridine
Represents the atomic group necessary to form a nucleus or a quinoline nucleus,
R₁And R₂Are alkyl, alkenyl or aryl
Represents a group, R₃Represents a hydrogen atom, a methyl group or an ethyl group
Then X₀ Represents an anion, and l represents 0 or 1.

In the sensitizing dye represented by the above general formula [I] used in the present invention, the nucleus represented by Z ₁ and Z ₂ may be substituted, and the substituent is a halogen atom (for example, chlorine) or alkyl. Groups (eg methyl, ethyl), alkoxy groups (eg methoxy, ethoxy), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl),
An aryl group (for example, phenyl), a cyano group and the like can be mentioned.

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

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

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

[Exemplified compound] The addition amount of the sensitizing dye represented by the general formula [I] to the silver halide emulsion is 1 × 10 ⁻⁸ to 1 × per mol of silver halide.
A range of 10 ^-3 is suitable, and preferably 5 x 10 ^{-6 to} 5 x 10
^-4 mol.

The yellow couplers preferably used in the present invention include those represented by the following general formula (I).

General formula (I) X ₁ represents a halogen atom, an alkoxy group or an alkyl group.

Halogen atom: chlorine atom, etc. Alkoxy group: methoxy group, ethoxy group, etc. Alkyl group: methyl group, ethyl group, etc. Y ₁ ; When a dye is formed by coupling with an oxidation product of an aromatic primary amine color developing agent. Represents a group capable of splitting off (sometimes referred to simply as a splitting component). The following groups are preferred. That is, they are an aryloxy group and a hetrocyclic oxy group.

R ₄ ; tert-butyl group or Represents

R ₅ , R ₆ ; represents a group capable of substituting on the benzene ring, and n represents 1 or 2. When n is 2, R ₅ and R ₆ may be the same or different.

R ₅ and R ₆ are halogen atoms (for example, fluorine, chlorine, bromine, etc.), Here, R ₁ ′, R ₁ ″ and R ₁ may be the same or different, each is a hydrogen atom, an alkyl group which may have a substituent,
It represents an aryl group or a heterocyclic group. R ₅ and R ₆ are preferably
_{R '1 CONH-, R 1'} SO 2 NH-, R 1 ' is OCONH-, R _1' represents an alkyl group which may have a substituent.

Most preferably, it is R ₁ ′ CONH—, and R ₁ ′ represents an alkyl group having a substituent. R ₆ preferably represents R ₁ ′ O—.

Next, Y ₁ will be described. The aryl moiety of the aryloxy group or arylthio group represented by Y ₁ is preferably a phenyl group, but this phenyl group may have a substituent. Specific examples of the aryloxy group and the arylthio group include a phenoxy group, a phenylthio group, a 4-carboxyphenyloxy group, a 4-carboxyphenylthio group, and a 4-carboxyphenylthio group.
(4-benzyloxybenzenesulfonyl) phenyloxy group, 4- (4-benzyloxybenzenesulfonyl) phenylthio group and the like.

Examples of the heterocyclic oxy group and the heterocyclic thio group include a 1-phenyl-5-tetrazolyloxy group, a 1-phenyl-5-tetrazolylthio group, an isoxazolyloxy group, an isoxazolylthio group, and 4-pyridinyloxy group. Group, 4-pyridinylthio group and the like.

Also For example, Etc.

The specific examples of the yellow couplers preferably used in the invention are shown below, but the invention is not limited thereto.

However, in the following yellow couplers, Y-5, Y-6, Y
-7, Y-8, Y-9, Y-10, Y-11, Y-12, Y-13, Y-1
4, Y-15, Y-16, Y-17, Y-18, Y-19, Y-20, Y-21, Y-2
2, Y-23, Y-25, Y-28, Y-29, Y-30, Y-31, Y-34, Y-3
5, Y-38, Y-39, Y-46, Y-47, Y-48, Y-49, Y-50, Y-51
Is a comparative compound outside the invention.

[Exemplified compound]

In the above formula, Y ₁ is as follows.

The above-mentioned yellow coupler used in the present invention is effective in preventing color turbidity, which is the effect of the present invention, but particularly as the yellow coupler preferably used in exhibiting the effect of the present invention, it is represented by the general formula [II]. Aromatic No. 1
A group that is released when a dye is formed by coupling with an oxidized product of a primary amine color developing agent is an aryloxy group or a heterocyclic oxy group.

The yellow coupler used in the present invention can be added to the photographic constituent layers by various methods. The addition amount is not limited, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 1 mol per mol of silver halide. It is 10 ^{−2 to} 5 × 10 ⁻¹ mol.

The hydrophilic binder used for coating the silver halide of the light-sensitive material is usually gelatin, but in some cases high molecular polymers are used, and the film swelling speed T 1/2 must be less than 30 seconds. No, binder film swelling speed T
1/2 can be measured according to any method known in the art, for example, A. Green Photo.Sci. Eng., Vo.
It can be measured by using a swellometer (swelling meter) of the type described in L.19, No.2, P124-129, and T 1/2 is at 30 ° C for 3 minutes and 30 seconds in color development. 90% of the maximum swollen film thickness reaching
It is defined as the time to reach the film thickness (see FIG. 1).

The swelling speed T 1/2 of the binder of the photographic constituent layer used in the light-sensitive material of the present invention is 30 seconds or less, and the smaller it is, the more preferable. However, it is preferably 2 seconds or more due to scratch failure or the like.
Particularly preferred is 20 seconds or less, and most preferred is 15 seconds or less.

By adding the compound represented by the general formula [III] to the stabilizing solution for washing with water of the present invention, the effect of the present invention becomes more remarkable.

General formula (III) 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-toluidino, o-, m-, p-
Carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino and the like). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned, but not limited to these.

[Exemplified compound] The triazyl stilbene-based whitening agent of the present invention can be synthesized, for example, by the usual method described on page 8 of "Fluorescent Whitening Agent" edited by Chemical Industry Association (August 1976).

These triazyl stilbene-based brighteners are preferably used in an amount of 0.2 to 15 g, and particularly preferably 0.4 to 8 g, per 1 water washing substitute stabilizing solution of the present invention.

The method of addition may be such that it is added directly to the wash-replacement stabilizing solution, but it is preferably added to the wash-replacement stabilizing replenisher.

Further, when the above compound is added to the washing substitute stabilizer and / or the washing substitute stabilizer replenisher, it can be added after being dissolved in water or an organic solvent such as methanol, ethanol, acetone, ethylene glycol or polyethylene glycol.

In the present invention, "processing with a processing solution having a fixing ability" refers to a step using a fixing bath or a bleach-fixing bath for the purpose of fixing a light-sensitive material, and is a processing step performed after ordinary development. . Details of the processing liquid having the fixing ability will be described later.

In the present invention, "after processing with a processing solution having fixing ability,
`` Continuous treatment with an alternative stabilizing solution for washing with water '' refers to a treatment for stabilizing treatment in which a stabilizing treatment is carried out immediately after the treatment with a treating solution having fixing ability and substantially no washing treatment is carried out. The treatment liquid used is referred to as a washing substitute stabilizer, and the treatment tank is referred to as a washing substitute stabilizing bath (tank) or a stabilizing bath (tank).

However, the concentration of the fixing solution or the bleach-fixing solution brought in to the stabilizing bath (tank) as a substitute for washing [when the stabilizing bath consists of two or more baths (tanks) is 1/2000]
As long as it does not fall below, it may be possible to perform rinsing treatment by a single-tank or multi-tank countercurrent method for a very short time, auxiliary water washing, and water washing accelerating bath.

In the present invention, the number of stabilizing baths for substituting with water may be one, but it is preferably two to three, and at most nine or less. That is, if the replenishment amount is the same, the more the tanks are, the lower the concentration of pollutant components in the final stabilizing bath for washing with water is.

As described above, the treatment with the water-washing alternative stabilizing solution of the present invention is performed after the fixing treatment. That is, as long as it is a processing solution after the fixing process and a replenishing amount of 1 to 50 times the amount of the processing liquid carried from the pre-bath and a stabilizing solution which replaces washing with water, it is a stabilizing solution as a substitute for washing with water of the present invention. As long as this condition is satisfied, the solution containing the compound of the present invention in the washing water is a stabilizing solution as a substitute for washing.

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 8 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).

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

Specific examples of the chelating agent having a chelate stability constant of 8 or more with ferric ion include, but are not limited to, the following compounds. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, hydroxyethylglycine, 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.

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

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

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

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

In the present invention, the sulfite salt to be contained in the washing alternative stabilizing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but it is a preferable inorganic salt, and preferable specific compounds include sodium sulfite and sulfite. Potassium, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde sodium bisulfite, succinic acid bisbisbisulfite Sodium and the like can be mentioned.

The above sulfite should be at least 1.0 × 10 in the stabilizing solution for washing.
^-5 mol / l is preferably added in an amount such that,
More preferably, it is added in an amount of 5 × 10 ⁻⁵ mol / l to 1.0 × 10 ⁻¹ mol / l. The method of addition may be such that it is added directly to the stabilizing solution for washing replacement, but it is preferable to add it to the stabilizing solution for washing replacement. Further, sulfite may be added as an adduct of the compound of the present invention.

It is preferable that the stabilizing solution as a substitute for washing with water according to the present invention contains a fungicide. Antifungal agents preferably used are salicylic acid, sorbic acid, dehydroacetic acid, hydroxybenzoic acid compounds, alkylphenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium. Compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamino compounds,
Sulfamide derivatives and amino acid compounds.

Examples of the hydroxybenzoic acid-based compound include hydroxybenzoic acid and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester and butyl ester, but preferably n-butyl ester of hydroxybenzoic acid, isobutyl ester and propyl ester. It is an ester, and more preferably a mixture of the three hydroxybenzoic acid esters.

The alkylphenol compound is a compound having an alkyl group having an alkyl group of C1 to 6 as a substituent, preferably orthophenylphenol and orthocyclohexylphenol.

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-one,
2- (4-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 clonides, etc.

The urea 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 derivative include fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, sulfanilamide, acetosulfaguanidine,
Sulfathiazole, sulfadiazine, sulfamelazine, sulfamethazine, sulfisoxazole,
Examples include homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, and succinylsulfathiazole.

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

The compounds preferably used in the present invention among the above antibacterial agents are thiazole compounds, pyridine compounds, guanidine compounds and quaternary ammonium compounds.

The amount of the anti-violent agent added to the washing substitute stabilizer is used in the range of 0.001 to 50 g per 1 washing substitute stabilizer, preferably 0.
Used in the range of 003g-10g.

In the present invention, the pH of the stabilizing solution for washing with water is preferably in the range of 3.0 to 9.5, and more preferably adjusted to pH 3.5 to 9.0 for the purpose of preventing precipitation, which is one of the objects of the present invention.

Further, other compounds that can be added to the washing substitute stabilizer in the present invention include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH buffers (phosphoric acid, borate, hydrochloric acid, Sulfuric acid, etc.) or surfactant, preservative, B
There are metal salts such as i, Mg, Zn, Ni, Al, Sn, Ti, Zr, etc., but the addition amount of these compounds is necessary for maintaining the pH of the washing substitute stabilizer according to the present invention and a color photographic image. Any compound may be used in any combination as long as it does not adversely affect the stability during storage and the occurrence of precipitation.

The present invention has a great effect when the replenishing amount of the stabilizing solution for washing with water in the stabilizing bath is small, and the replenishing amount is treated in the range of 1 to 50 times the carried-in amount of the treating solution from the previous bath, and further 2 to 20 times. Within the range, the effect of the present invention is particularly remarkable.

As described above, the treatment temperature during the stabilizing treatment is 50 ° C. or less, particularly preferably 15 ° C. to 50 ° C., more preferably 20 ° C.
The range of 45 ℃ is good. Also, the treatment time is preferably shorter from the viewpoint of rapid treatment, but is usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes. However, it is preferable that the treatment time is longer in the latter-stage tank. In particular, it is desirable to sequentially perform the treatments with a treatment time that is 20% to 50% longer than that in the previous tank. After the stabilization treatment according to the present invention, washing treatment is not required at all, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

In the stabilizing treatment step according to the present invention, when the stabilizing solution for washing with water is supplied in a multi-tank counter current system, it is preferable that the solution is supplied to the post-bath and allowed to overflow from the pre-bath. Of course, it can also be processed in a single tank. As a method of adding the compound or the like of the present invention, the compound of the present invention and the other additives are added to the stabilizing tank as a concentrated solution, or to the washing substitute stabilizing solution supplied to the stabilizing tank, This is used as a supply liquid for the washing replacement stable replenisher,
There are various methods such as the above, but any addition method may be used.

Aromatic No. 1 used in the color developer of the light-sensitive material of the present invention
The primary amine color developing agents include various types widely used in various color photographic processes.
These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example hydrochlorides or sulphates. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, preferably at a concentration of about 1 g to about 1.5 g for color developer 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful aromatic primary amine color developing agents are N, N'-dialkyl-p-phenylenediamine compounds, and the alkyl group and phenyl group may be substituted with any substituents. Among them, particularly useful compounds are N, N ′.
-Diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-
p-phenylenediamine hydrochloride, 2-amino-5- (N
-Ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4- Amino-3-methyl-N, N'-diethylaniline, 4-amino-N- (2
-Methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate and the like can be mentioned.

In the color developing solution, in addition to the aromatic primary amine-based color developing agent, various components that are usually added to the color developing solution, for example, alkali agents such as sodium hydroxide, sodium carbonate, potassium carbonate, An alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softening agent, a thickening agent and the like can be optionally contained.
The pH value of this color developing solution is usually 7 or higher, most commonly about 10 to about 13.

When the processing solution having fixing ability used in the present invention is a fixing solution, the fixing solution may be, for example, a thiosulfate (described in JP-A-57-185435) or a thiocyanate (UK Patent 565,135) as a fixing agent. , JP-A-54-137143), halides (JP-A-52-130639), thioethers (Belgium Patent 626970), thiourea (UK Patent 1,189,416), etc. Can be used.
Among these fixing agents, it is thiosulfates that effectively exert the effect of the present invention. When the processing solution having fixing ability is a bleach-fixing solution, the bleaching agent is a ferric organic acid complex salt (Japanese Patent Publication Nos. 54-38895, 55-500704, JP-A-56-52748).
No. 59-149358).

Further, the processing solution having a fixing ability used in the present invention is a processing solution intended only for fixing processing, and any bleaching agent can be used as the bleaching agent in the case of performing the bleaching processing in the preceding step, for example, Red blood salt, iron chloride (UK Patent 736,
881, Japanese Patent Publication No. 56-44424), persulfuric acid (German Patent 2,141,199), hydrogen peroxide (Japanese Patent Publication 58-11).
Nos. 617 and 58-11618), ferric organic acid complex salts (described in JP-A-57-70533 and 58-43454, and Japanese Patent Application No.
58-40633 and 59-170070, etc.) and the like can be used.

In the processing of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution and a bleach-fixing solution as well as a stabilizing solution for washing with water. In this case, for example, the electrolysis method (described in French Patent 2,299,667),
Precipitation method (described in JP-A-52-73037 and German Patent 2,331,220), ion exchange method (JP-A-51-17114, German patent)
2,548,237) and metal replacement method (UK Patent 1,3
53,805) can be effectively used.

Regarding the processing method of the light-sensitive material of the present invention, for example, as a typical example thereof, a method of performing bleach-fixing treatment after color development and performing an alternative stabilizing treatment with water, and after color development, bleaching and fixing are separately performed Alternate stabilization treatment; or method of pre-hardening, neutralization, color development, stop fixing, washing alternative stabilization treatment, bleaching, fixing, washing alternative stabilization treatment, post-hardening, washing alternative stabilization treatment, color development Development, washing, supplementary color development, stop, bleaching, fixing, stabilizing by washing, and stabilizing treatment in this order.Halogenation bleaching of developed silver generated by color development, then color development again to increase the amount of dye formed. Processing may be performed using any method such as a developing method.

The photographic constituent layers of the light-sensitive material of the present invention may be added with a dye soluble in water or decolorized with a color developer (AI dye). Azo dyes are included. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patents 584,609, 1,277,429, JP-A-48-85130, 49-99620, 49-114420 and 49-12.
9537, 52-108115, 59-25845, 59-111640
No. 59-111641, U.S. Patent Nos. 2,274,782 and 2,533,47.
No. 2, No. 2,956,879, No. 3,125,448, No. 3,148,187,
3,177,078, 3,247,127, 3,260,601, 3,5
40,887, 3,575,704, 3,653,905, 3,718,47
No. 2, No. 4,071,312, No. 4,070,352 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 be different from the inside to the outside. 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. Furthermore, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-
No. 170070) 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 optically sensitized by adding a mole. 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.

Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, and
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in 2,739,149, 2,945,763, British Patent 505,979 and the like. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
Issue 2, Issue 2,270,378, Issue 2,442,710, Issue 2,454,629,
Cyanine dyes such as those described in No. 2,776,280,
Typical examples thereof include merocyanine dyes and complex cyanine dyes. Furthermore, US Patent 2,
213,995, 2,493,748, 2,519,001, West German patent 9
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in No. 29,080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The 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.

The light-sensitive material according to the present invention may contain a coupler other than the yellow coupler of the present invention, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a magenta or cyan dye.

The magenta coupler and the cyan coupler which can be used in the present invention may be so-called 2-equivalent type or 4-equivalent type, but it is preferable to use the 2-equivalent type in order to obtain the effect of the present invention.

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 couplers but also 2-equivalent couplers. Specific examples of magenta couplers include U.S. Pat.
788, 2,983,608, 3,062,653, 3,127,269
No. 3,311,476, 3,419,391, 3,519,429,
3,558,319, 3,582,322, 3,615,506, 3,8
34,908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,41
8,959, 2,424,467, JP-B-40-6031, JP-A-51-
20826, 52-58922, 49-129538, 49-74027
No. 50, No. 50-159336, No. 52-42121, No. 49-74028, No. 5
No. 0-60233, No. 51-26541, No. 53-55122, Japanese Patent Application No. 55-11
Those described in No. 0943 and the like can be mentioned.

The magenta coupler which is particularly preferably used in the present invention is a 2-equivalent type coupler, but most preferable is Japanese Patent Application No.
Magenta couplers represented by the following general formula [IV] or [V] described in JP-A No. 60-169226 and the like are useful in 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
No. 90932, No. 58-95346, and Japanese Patent Publication No. 49-11572.

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 , (However, R ₂₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
It represents an aryl group or a heterocyclic group, and 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 or a group capable of splitting off by a coupling reaction with an oxidation product of a color developing agent.

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

The amount of the above-mentioned coupler that can be used in the present invention is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ mol, per mol of silver. The photographic material of the present invention may further contain various photographic additives, for example, Research Disclosure Magazine 17
No. 643, antifoggant, stabilizer, ultraviolet absorber, color stain preventing agent, fluorescent whitening agent, color image fading inhibitor, antistatic agent, hardening agent, surfactant, plasticizer, wetting agent Agents and the like can be used.

In the light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, protein such as casein, hydroxyethyl cellulose derivative, carboxymethyl cellulose. And the like, such as cellulose derivatives, starch derivatives, polyvinyl alcohol, polyvinyl imidazole, polyacrylamide, and other single or copolymer synthetic hydrophilic polymers.

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

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. 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 which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

[Effect of the Invention] According to the present invention, it is possible to prevent yellow stain when a stabilizing solution as a substitute for washing with water is used, to prevent color turbidity in the obtained photographic image, and to reduce the pollution without degrading the photographic performance. It is possible to provide a method of processing a light-sensitive material that can realize the following.

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

Example 1 Photosensitive material samples Nos. 1 to 12 were prepared by sequentially coating the following layers from the support side on a polyethylene-laminated paper support.

Layer 1: Gelatin of 1.5 g / m ² , silver amount of 0.35 g / m ² (converted to silver, the same applies hereinafter), and sensitizing dye exemplified compound (I-21) 1.0 × 10 per mol of silver halide Blue-sensitive silver chlorobromide gelatin emulsion color-sensitized at ^-3 mol (silver bromide 50 mol%, average particle size
0.6 μm monodisperse spherical particles), 1.5 g / m ² yellow coupler dissolved in 0.50 g / m ² dioctyl phthalate (Table 1)
A blue-sensitive silver halide emulsion layer containing the above).

Layer 2 ... an intermediate layer consisting of 0.70 g / m ² of gelatin.

Layer 3 ... Gelatin of 1.30 g / m ² , silver amount of 0.30 g / m ² and the following sensitizing dye (II) 7.0 × 10 per mol of silver halide
-Green-sensitive silver chlorobromide gelatin emulsion color-sensitized at ^-4 mol (70 mol% silver bromide, monodisperse spherical particles having an average particle size of 0.5 μm),
A green-sensitive silver halide emulsion layer containing 0.80 g / m ² of magenta coupler (M-1) dissolved in 0.35 g / m ² of dioctyl phthalate.

Layer 4 ... an intermediate layer consisting of 1.2 g / m ² of gelatin.

Layer 5: 1.4 g / m ² of gelatin, 2.06 g / m ² of silver and 2.0 × 10 per mole of silver halide of the following sensitizing dye (III):
-Red-sensitive silver chlorobromide gelatin emulsion color-sensitized at ^-5 mol (70 mol% silver bromide, monodisperse spherical particles having an average particle size of 0.5 μm),
A red sensitive silver halide emulsion layer containing 0.60 g / m ² of cyan coupler (C-1) dissolved in 0.20 g / m ² of dioctyl phthalate.

Layer 6 ... A layer containing a UV absorber (UV-1) dissolved in 1.0 g / m ² of gelatin and 0.30 g / m ² of dioctyl phthalate.

Layer 7 ... A protective layer containing 0.50 g / m ² of gelatin.

As a hardening agent, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to Layers 2, 4 and 6 and, after drying, the gelatin film swelling rate at 30 ° C using the following color developing solution. It was prepared so that the measured value of T1 / 2 was as shown in Table 1. The measurement was performed using a Lebenzone type swelling meter.

Each of the photosensitive material sample Nos. 1 to 12 shown in Table 1 was subjected to picture printing by a conventional method and then continuously processed by a modified automatic developing machine according to the following steps.

Processing process (38 ℃) Color development 180 seconds Bleach fixing 60 seconds Water washing alternative stability 90 seconds Dry 60-80 ℃ 120 seconds Processing solution composition [Color development tank solution] Benzyl alcohol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxyamine sulfate 3.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.6 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate Salt 5.5g Optical brightener (4,4 'diaminostil benzene sulfonic acid derivative Exemplified compound (A-8) 1.0g Potassium hydroxide 2.0g Water was added to make 1.

[Color development replenisher] Benzyl alcohol 20 ml Ethylene glycol 20 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxyamine sulfate 4.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g 3-Methyl-4-amino-N- Ethyl-N- (β-methanesulfonamide ethyl) -aniline sulfate 7.0g Optical brightener (4,4 'diaminostil benzenesulfonic acid derivative 1.5g Exemplified compound (A-8) 1.0g Potassium hydroxide 3.0g Water Was added to make the total amount 1.

[Bleaching and fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to bring the total amount to 1 and potassium carbonate or With glacial acetic acid
The pH was adjusted to 7.10.

[Bleach-fixing replenisher A] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260 g Potassium carbonate 42 g Water was added to bring the total amount to 1. The pH of this solution is 6.7 ± 0.1
Is.

[Bleach-fixing replenisher B] Ammonium thiosulfate (70% aqueous solution) 500 ml Ammonium sulfite (40% aqueous solution) 250 ml Ethylenediaminetetraacetic acid 17 g Glacial acetic acid 85 ml Water was added to bring the total amount to 1. The pH of this solution is 4.6 ± 0.1
Is.

[Stabilizer (Replenisher)] 5-Chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 1.0g Ammonium hydroxide (28% aqueous solution) 3.0g 1-Hydroxyethylidene-1,1-diphosphone Acid 2.0 g Ammonium sulfite 3.0 g Fluorescent brightener (4,4 'diaminostil benzene sulfonic acid derivative 1.5 g Exemplified compound (A-8) 1.0 g Water was added to 1 and the pH was adjusted to 7.2 with sulfuric acid.

A modified automatic developing machine was filled with the color developing tank solution, the bleach-fixing tank solution and the stabilizing solution, and the color developing replenishing solution and the bleach-fixing replenishing solution A and B were processed every 3 minutes while processing color paper. A running test was conducted while replenishing a predetermined amount of stable replenisher. Replenishment amount is 1 m ² of color paper
182 ml as a replenishment amount to the color developing tank,
Bleach-fixing replenisher A, B for replenishing the bleach-fixing tank
Each was 25 ml.

The carry-on amount of the bleach-fixing solution to the water-washing alternative stabilizing solution per 1 m ^{2 of} color paper was 50 ml.

The stabilization process is a two-tank counter-current system in which the stabilizing bath of the automatic processor is a stable bath that can perform continuous processing in two tanks, and the replenishment is performed from the final tank (second tank) and the overflow flows into the previous tank. And Replenishment amount of color paper 1m ² per 250m
It was l.

Continuous processing was carried out until the total amount of the bleach-fix replenisher A and B used was three times the capacity of the bleach-fix replenisher tank.

Next, this sample was subjected to an optical wedge exposure post-treatment through an interference filter (KL-46) to obtain a developed sample. The reflection density of the unexposed portion of this developed sample at 440 nm was measured with a self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and used as a representative characteristic of yellow stain. Further, the green density at a blue density of 1.0 was measured using a PDA-65 spectral reflection densitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) and used as a representative characteristic of color turbidity. The results are shown in Table 1.

As is clear from the results in Table 1, the yellow stain is greatly improved by increasing the film swelling speed T 1/2 of the binder to 30 seconds or less, while the sample using the coupler of the comparison is used. It can be seen that Nos. 1 to 7 have large color turbidity, and Samples Nos. 8 to 14 using the coupler (Y-1) of the present invention have small color turbidity. When a coupler other than the present invention is used, the degree of color turbidity is greatly affected by the film swelling speed T 1/2, and both color turbidity and yellow stain cannot be sufficiently satisfied. On the other hand, it can be seen that Sample Nos. 11 to 14 of the present invention have remarkable effects on both the characteristics of yellow stain and color turbidity.

Example 2 Instead of the coupler (Y-1) of the present invention used in Example 1, (Y-2), (Y-5), (Y-10), (Y-36),
Using (Y-37), (Y-40), and (Y-49), the following yellow coupler was used as a comparative coupler, and the same evaluation as in Example 1 was performed.

However, all the samples used had a film swelling speed T 1/2 of 10 seconds.

In addition, among the exemplified compounds of the yellow coupler in Table 2, Y-5,
Y-10 and Y-49 are comparative compounds not included in the present invention.

As is clear from the results in Table 2, as in Example 1, when the coupler of the present invention was used, remarkable effects were observed in both yellow stain and color turbidity prevention as compared with the yellow couplers other than the present invention, and the fragrance was also obtained. Particularly good results were obtained when the group leaving when the dye was formed by coupling with the oxidation product of the group 1 primary amine color developing agent was an aryloxy group.

Example 3 Replacing the sensitizing dye (I-21) used in Example 1 (I-12),
The sample added with (I-16) was also evaluated by the same method as in Example 1, but the same result as in Example 1 was obtained.

Example 4 The sensitizing dye (I-21) of the first layer of the silver halide photographic light-sensitive material used in Sample No. 13 of Example 1 was replaced with the following (RS-1) or (RS
-2) was replaced with a photosensitive material. The stabilizing solution used in the treatment step was replaced with water washing (the replenishing amount for water washing was 2500 ml per 1 m ^{2 of} color paper), and otherwise the same experiment and evaluation as in Example 1 were carried out. The results are summarized in Table 3.

[Brief description of drawings]

FIG. 1 is a graph showing the film film swelling speed T 1/2 of the binder.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-132146 (JP, A) JP-A-57-8542 (JP, A) JP-A-57-14834 (JP, A) JP-A 58- 18631 (JP, A) JP 59-184344 (JP, A) JP 58-115438 (JP, A) JP 51-80224 (JP, A) JP 57-8543 (JP, A)

Claims (3)

[Claims] 1. A sensitizing dye represented by the following general formula [I] is contained.
The developed silver halide color photographic material develops color after exposure.
After image processing and processing with a processing solution with fixing ability, continue
The amount of replenishment is 1 to 50 times the amount of processing solution brought in from the previous bath.
When processing with a certain washing substitute stabilizer, the silver halide solution
Color photographic light-sensitive material is represented by the following general formula [II]
-Containing coupler and film swelling speed of binder T 1 /
Silver halide color characterized in that 2 is less than 30 seconds
-Processing method for photographic light-sensitive materials. General formula [I]Where Z₁And Z₂Are the benzoxazole nucleus and naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, naphthoselenazole nucleus,
Nzoimidazole nucleus, naphthimidazole nucleus, pyridine
Represents the atomic group necessary to form a nucleus or a quinoline nucleus,
R₁And R₂Are alkyl, alkenyl or aryl
Represents a group, R₃Represents a hydrogen atom, a methyl group or an ethyl group
Then X₀ Represents an anion, and l represents 0 or 1. General formula (II)X₁Represents a halogen atom, an alkoxy group or an alkyl group. Y₁Oxidants and capri of aromatic primary amine color developing agents
Aryloxy that leaves when the dye is formed
Represents a Si group or a heterocyclic oxy group. R_Fourtert-butyl group orR_Five, R₆A benzene ring-substitutable group, n is 1 or
Represents an integer of 2. R when n is 2_FiveOr R₆Is that
These may be the same or different. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the film swelling speed T 1/2 of the binder is 20 seconds or less. 3. A silver halide color photographic light-sensitive material is continuously processed at a replenishing amount of 2 to 20 times as much as the amount of the processing solution carried in from the prebath when it is processed in a continuous manner. 5. The method for processing a silver halide color photographic light-sensitive material according to item 1 or 2.