JP2533362B2 - Silver halide color-processing method of photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color light-sensitive material, and more particularly to a method for processing a silver halide color light-sensitive material in which the replenishment amount of a color developer is remarkably reduced. About.

(Prior Art) The processing of a silver halide color photographic light-sensitive material basically consists of two steps of color development (in the case of a color reversal material, first black and white first development) and desilvering. The bleaching and fixing step or the one-bath bleaching and fixing step used in combination with or alone. If necessary, other additional processing steps, that is, washing, stopping processing, stabilizing processing, pretreatment for promoting development, and the like are added.

In color development exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. In this process, halogen ions generated by decomposition of silver halide are eluted and accumulated in the developing solution. On the other hand, the color developing agent is consumed by the reaction with the coupler described above. Further, other components are carried out by being held in the photographic light-sensitive material, and the concentration of the components in the developer decreases. Therefore, in a development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic processor or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in development finish characteristics due to a change in the component concentration. Means is needed.

For example, when the effect of the concentration of a consumable component such as a developing agent or a preservative is small, the concentration in the replenisher is generally increased. In some cases, the eluate having an effect of suppressing development, such as halogen, is reduced in concentration or not contained in the replenisher. Further, a compound may be contained in the replenisher to remove the influence of the eluate. Also
In some cases, the pH or the concentration of the alkali or chelating agent is adjusted. As such means, a method is usually employed in which a replenisher for replenishing the insufficient component and diluting the increased component is replenished. The replenishment of the replenisher inevitably generates a large amount of overflow, which is a serious problem in terms of economy and pollution.

In recent years, a reduction in the replenishment amount of the color developer has been strongly desired for the purpose of saving resources and reducing pollution as well as speeding up the development processing. However, if the replenishment amount of the color developing solution is simply reduced, the development activity is lowered and the rapidity is impaired due to the accumulation of eluate from the light-sensitive material, particularly bromine ion which is a strong development inhibitor, and various organic compounds. The problem arises.

As a solution to this, a development accelerating technique is required, and many speeding-up techniques for reducing the replenishment amount of the developer are being studied. For example, as one of the methods, there is known a speeding-up means for increasing the pH and the processing temperature of a color developer to promote development. However, this method has a serious problem that the fog is high, the stability of the developer is deteriorated, and the fluctuation of the photographic characteristics is increased during continuous processing. Further, as another accelerating technique, a method of adding various development accelerators is described, but the accelerating effect is insufficient and it is not satisfactory.

For the purpose of reducing the accumulation of bromine ion, which is a strong development inhibitor, and speeding up the development, JP-A-58-95345 and 59-2
32342, 61-70552, and International Patent Publication W087-04534 disclose a method of using a silver halide light-sensitive material having a high silver chloride content, which is effective for reducing the replenishing amount of a developer without impairing speeding up. Considered a means. However, if we try to reduce the amount of developer replenishment without sacrificing speed,
During continuous processing, the photographic characteristics fluctuate significantly, and floating substances considered to be silver eluted from the light-sensitive material are generated in the developer.
It was found that it could not be put to practical use due to new problems such as contamination of rollers of the processor, clogging of filters, scratches and contamination of the photosensitive material.

Another major factor in continuous processing when the replenishment rate is low is high fog when a silver photographic color photographic material is developed. For photosensitive materials with high fog, when the temperature of the developer rises or the pH rises and the developing conditions are such that fog tends to occur, the temperature and
The difference in the fog tends to increase when the developing conditions are such that the pH is lowered and fog is less likely to occur, and as a result, the variation in the development finish characteristics tends to increase.

It is known to add various antifoggants to a light-sensitive material as one of means for preventing the fog of the silver halide color photographic light-sensitive material. That is, benzotriazole, 6-nitrobenzimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
It is known that compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaquindridine, and adenine have a remarkable effect in preventing fog.

The above antifoggants and stabilizers have the effect of preventing fog and reducing the change in development finish characteristics when the usual developer replenishment is carried out. On the contrary, when the amount of the antifoggant and the stabilizer added to the light-sensitive material are significantly reduced, there is a problem that the development finish characteristics, especially the sensitivity, are greatly varied and the silver developing rate is remarkably reduced. .

(Problems to be Solved by the Invention) Currently, the replenishing amount of the color developing solution is somewhat different depending on the photosensitive material to be developed, but is generally about 180 to 1000 ml per 1 m ^{2 of} the photosensitive material to be processed. Because, if the replenishment amount is further reduced without impairing the speediness, a very serious problem that the photographic characteristics are greatly changed and floating substances are generated in the developing solution occurs during continuous processing as described above. Therefore, no technology has been found that can fundamentally solve these problems.

Therefore, the first object of the present invention is to reduce variations in photographic characteristics, particularly minimum density, maximum density, and sensitivity during continuous processing even when the replenishing amount of the color developing solution is significantly reduced without impairing speediness. A development processing method is provided. A second object of the present invention is to provide a processing method using a high silver chloride light-sensitive material, in which even if the replenishing amount of the color developing solution is remarkably reduced, floating substances are not generated in the developing solution during continuous processing. It is a thing.

(Means for Solving the Problem) The object of the present invention has been achieved by the methods described below. That is, in a method of continuously processing a silver halide color photographic light-sensitive material having a reflective support with a color developing solution containing at least one aromatic primary amine color developing agent, it is composed of 80 mol% or more of silver chloride. A silver halide color photographic light-sensitive material for reflection having a silver halide emulsion of high silver chloride in at least one layer and having a coated silver amount of 0.8 g / m ² or less is prepared from a compound represented by the following general formula (I): In the presence, a color developer containing substantially no benzyl alcohol is used, and the replenishing amount of the color developer is 20 to 120 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. Color photographic light-sensitive material processing method.

General formula [I] Z-SM In the formula, M represents a hydrogen atom, a cation (for example, an alkali metal ion, an ammonium ion, etc.) or -S-Z, and Z is a hetero residue free of one or more nitrogen atoms. Represents

In the present invention, a method of reducing the replenishment amount of the color developing solution to 20 to 120 ml per 1 m ² of the light-sensitive material without impairing the speediness by using a high silver chloride color photographic light-sensitive material having a silver chloride content of 80 mol% or more is , Conventionally, during continuous processing, photographic characteristics, especially sensitivity, maximum density and minimum density fluctuate significantly,
Moreover, floating substances that are thought to be caused by silver eluted from the high-silver chloride light-sensitive material are generated in the developer, which causes failure such as contamination of the processor roller, clogging of the filter, scratches and contamination of the light-sensitive material. There was a problem and it was unrealistic. However, as in the present invention, a silver chloride content of 80
A high silver chloride color photographic light-sensitive material having a mol% of not less than 1 is continuously processed with a color developing solution containing substantially no benzyl alcohol in the presence of the compound of the general formula [I], so that the replenishing amount of the color developing solution is increased. , Even if it is reduced to 20 to 120 ml per 1 m ^{2 of} light-sensitive material, the fluctuation of photographic characteristics is very small.
The fact that the generation of the above-mentioned suspended solids in the treatment liquid was significantly prevented was totally unexpected.

The range of the replenishment amount of the color developing solution in the present invention is ^{20 to} 120 ml per m ^{2 of the} silver halide light-sensitive material. The replenishment amount of the developing solution to 120 ml or less is unrealistic in the prior art due to the above-mentioned problems, and was made possible for the first time by the present invention. Replenishment amount 120ml / 1m photosensitive material
² is a value located at the boundary between the range that can be achieved for the first time by the present invention and the range that is possible by the combination of conventional techniques other than the present invention. Also, depending on the light-sensitive material, if the developer replenishment amount is 20 ml / light-sensitive material 1 m ² or less, the amount of processing liquid carried out by the light-sensitive material exceeds the replenishment amount, and the processing liquid decreases Makes continuous processing impossible. The replenishment amount of 20 ml / light-sensitive material 1 m ² indicates 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, although the amount is slightly different depending on the light-sensitive material.

A rapid processing method using a high silver chloride light-sensitive material comprising 80 mol% or more of silver chloride in the present invention is known. International Publication W087-04534 discloses a method for treating a high silver chloride light-sensitive material with a developer which does not substantially contain benzyl alcohol and sulfite ion, but in the absence of the compound of general formula (I). Further, there is no description about the problem in the case where such a light-sensitive material is subjected to development processing by remarkably reducing the replenishment amount of the developing solution, and further, there is no description about whether or not the above-mentioned problem can be solved. Not
The technology of the present invention cannot be analogized. JP-A-61-
No. 70552 discloses continuous processing of a high silver chloride light-sensitive material with a developer containing substantially no benzyl alcohol and a replenishing amount so as not to cause overflow into the developing bath. The above-mentioned problems and their solutions that occur when the development replenishment amount is remarkably reduced are not described, and the technique of the present invention cannot be analogized.

The heterocyclic residue represented by Z in the general formula (I) may be further condensed, and specific examples thereof include imidazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzoxazole, benzthiazole, Thiadiazole,
Oxadiazole, benzselenazole, pyrazole,
Pyrimidine, triazine, pyridine, naphthothiazole, naphthimidazole, naphthoxazole, azabenzimidazole, purine, azaindene (eg, triazaindene, tetrazaindene, pentazaindene, etc.) and the like are preferable.

Further, these heterocyclic residue and condensed ring may be substituted with an appropriate substituent. Examples of the substituent include an alkyl group (for example, methyl, ethyl, hydroxyethyl,
Trifluoromethyl, sulfopropyl, di-propylaminoethyl, adamantane), alkenyl group (eg allyl), aralkyl group (eg benzyl, p-chlorophenethyl), aryl group (eg phenyl, naphthyl,
p-carboxyphenyl, 3,5-di-carboxyphenyl, m-sulfophenyl, p-acetamidophenyl,
3-capramide phenyl, p-sulfamoyl phenyl, m-hydroxy phenyl, p-nitro phenyl, 3,
5-dichlorophenyl, 2-methoxyphenyl), heterocyclic residue (eg pyridine, furan, thiophene), halogen atom (eg chlorine, bromine atom), mercapto group,
Cyano group, carboxyl group, sulfo group, hydroxy group,
Carbamoyl group, sulfamoyl group, amino group, nitro group, alkoxy group (eg methoxy), aryloxy group (eg phenoxy), acyl group (eg acetyl), acylamino group (eg acetylamino, capramide, methylsulfonylamino), substituted amino Groups (eg diethylamino, hydroxyamino), alkyl or arylthio groups (eg methylthio, carboxyethylthio, sulfobutylthio), alkoxycarbonyl groups (eg methoxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl) and the like. .

The heterocyclic residue represented by Z in the general formula (I) needs to contain at least one nitrogen atom, but preferably the heterocyclic residue contains at least two nitrogen atoms, more preferably at least three nitrogen atoms. And those containing four nitrogen atoms are particularly preferable.

Of the general formula (I), particularly preferred are those of the general formula (I
-I), (I-II) and (IIII).

General formula (II) In the formula, R represents an alkyl group, an alkenyl group or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor.

The alkali metal atom is, for example, a sodium atom, a potassium atom or the like, and the ammonium group is, for example, a tetramethylammonium group or a trimethylbenzylammonium group. The precursor is X under alkaline conditions.
= H or a group which can be an alkali metal, and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group or the like.

Of the above R, the alkyl group and the alkenyl group include an unsubstituted group and a substituted group, and further include an alicyclic group. The substituent of the substituted alkyl group includes a halogen atom, nitro group, cyano group, hydroxyl group, alkoxy group, aryl group, acylamiki group, alkoxycarbonylamino group, ureido group, amino group, heterocyclic group, acyl group, sulfamoyl group. , Sulfonamide group, thioureido group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, and further carboxylic acid group, sulfonic acid group or salts thereof.

The ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amiki group each include an unsubstituted group, an N-alkyl substituted group, and an N-aryl substituted group. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and substituents of the alkyl groups listed above.

General formula (I-II) In the formula, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. The alkyl group, alkenyl group and X of R have the same meanings as those in formula (II).

Specific examples of the divalent linking group represented by L above include: And combinations thereof.

n represents 0 or 1, and R ⁰ , R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aralkyl group.

General formula (I-III) In the formula, R and X have the same meaning as in general formula (II), and L has the same meaning as that in general formula (I-II). R ³ has the same meaning as R, and may be the same or different.

Specific examples of the compounds of the general formula (II), the general formula (I-II) and the general formula (I-III) are listed below, but the invention is not limited thereto.

In the present invention, the compound represented by the general formula (I) is
It may be present in the silver halide color photographic light-sensitive material, or may be present in the color developing solution,
It may be present in both the silver halide color photographic light-sensitive material and the color developing solution.

In particular, it is more preferably present in the silver halide color photographic light-sensitive material.

The compound represented by formula (I) used in the present invention can be contained in any layer or / and a color developing solution in a silver halide color photographic light-sensitive material.
By any layer in a silver halide color photographic light-sensitive material is meant a light-sensitive and light-insensitive hydrophilic colloid layer.

When the compound represented by the general formula (I) is added to the silver halide color photographic light-sensitive material, it is preferably added in an amount of 1 × 10 ^{−5 to} 5 × 10 ⁻² mol per mol of silver halide. Further, 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol is preferable. When it is contained in the color developing solution, 1 × 10 ^-6 1 × 1
0 ^-3 mol / l is preferable, and further 5 × 10 ^{-6 to} 5 × 10 ^-4 mol / l
l is preferred.

If the addition amount is less than the above amount, the fog prevention for the silver halide emulsion is not sufficient and causes color turbidity. On the other hand, when the amount is larger than the above, on the other hand, the color reproduction becomes poor because the sensitivity is lowered or the development is suppressed to lower the density.

The color developer used in the present invention will be described in detail.

In practicing the present invention, it is necessary to use a developing solution containing substantially no benzyl alcohol.
Here, the term "substantially free from" means that the concentration of benzyl alcohol is preferably 2 ml / or less, more preferably 0.5 ml / or less, and most preferably benzyl alcohol is not contained at all.

The developer used in the present invention more preferably contains substantially no sulfite ion. The sulfite ion has a function as a preservative of the developing agent, and at the same time, has a function of dissolving a silver halide and a function of reacting with an oxidized product of the developing agent to reduce the dye forming efficiency. It is presumed that such an action is one of the causes of an increase in fluctuations in photographic characteristics and the occurrence of the above-mentioned suspended matter, which occurs when the replenishment amount of the color developing solution is reduced.
Here, the term “substantially free from” means preferably 5.0 × 10 ^−3.
It has a sulfite ion concentration of not more than mol / mol, and most preferably contains no sulfite ion at all. However, in the present invention, a small amount of sulfite ion is excluded as it is used for preventing the oxidation of the processing agent kit in which the developing agent is concentrated before preparing the working solution.

The developer used in the present invention preferably contains substantially no sulfite ion, and more preferably contains substantially no hydroxylamine. this is,
This is because hydroxylamine functions as a preservative for the developer and has silver developing activity at that time, and fluctuations in the concentration of hydroxylamine are thought to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

The developer used in the present invention more preferably contains an organic preservative in place of the hydroxylamine and sulfite ion.

Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing the oxidation of the color developing agent due to air, etc. Among them, hydroxylamines (excluding hydroxylamine), hydroxamate,
Hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds Polycondensed amines are particularly effective organic preservatives. These are Japanese Patent Application No. 61-147823,
Japanese Patent Application Nos. 61-173595, 61-165621 and 61-1888619
No. 61-197760, No. 61-186561, No. 61-198987
No. 61, No. 61-201861, No. 61-186559, No. 61-170756,
No. 61-188742, No. 61-188741, U.S. Pat.
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

With respect to the preferred organic preservatives, general formulas and specific compounds are shown below, but the present invention is not limited thereto.

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

 The following are preferred as the hydroxyamines.

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 are not hydrogen atoms at the same time and may be linked to each other to form a heterocyclic ring 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, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

It is preferable that R ¹¹ and R ¹² are an alkyl group or an alkenyl group, and the carbon number is preferably 1 to 10, and particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by connecting R ¹¹ and R ¹² include a piperidyl group, a pyrrolidylyl group, an N-alkylipiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents of R ¹¹ and R ¹² are hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amido group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound example The following are preferable hydroxamic acids.

General formula (III) In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted Alternatively, it represents an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group or a hydroxyaminocarbonyl group. Examples of the substituent include a halogen atom, an aryl group, an alkyl group, an alkoxy group, and the like.

A ²¹ is preferably a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, or aryloxy group. Particularly preferred examples are a substituted or unsubstituted amino group, an alkoxy group, and an aryloxy group. The number of carbon atoms is preferably 1-10.

X ²¹ is -SO ₂ -, or represents -SO-. Preferably X ²¹ is Is.

R ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. At this time,
A ²¹ and R ²¹ may be linked to form a ring structure. The substituent is the same as the substituents mentioned in A ^21. Preferably R ²¹
Is a hydrogen atom.

Y ²¹ represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

Compound example The following are preferred as hydrazines and hydrazides.

General formula (IV) In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group, Represents an 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.

In formula (IV), R ³¹ , R ³² , and R ³³ are hydrogen atoms or C ₁ to C.
_It is preferably an alkyl group of ₁₀ , particularly preferably R ³¹ and R ³² are hydrogen atoms.

In the general formula (IV), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group or an amino group. Particularly, the case of an alkyl group or a substituted alkyl group is preferable. Here, preferable substituents of the alkyl group include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group and the like. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

IV-2 NH ₂ NHCH _{2 4} SO ₃ H IV-3 NH ₂ NHCH _{2 2} OH _{IV-6 NH 2 NHCOCH 3 IV} -7 NH 2 NHCOOC 2 H 5 IV-10 NH ₂ NHCONH ₂ IV-12 NH ₂ NHSO ₃ H IV-14 NH ₂ NHCOCONHNH ₂ IV-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H IV-18 NH ₂ NHCH ₂ CH ₂ COOH The following are preferred as phenols.

General formula (V) In the formula, R ⁴¹ is hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amide group, sulfonamide group, ureido group, alkylthio group, It represents an arylthio group, a nitro group, a cyano group, an amino group, a formyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When R ⁴¹ is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, and the like. When two or more R ^41's are present, they may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. The ring structure is a 5- or 6-membered ring and is composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated.

R ⁴² represents a hydrogen atom or a hydrolyzable group. Further, m and n are integers from 1 to 5, respectively.

In formula (V), preferred R ⁴¹ is an alkyl group, a halogen group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, an amide group, a sulfonamide group, a nitro group, and It is a cyano group. Among them, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and these are more preferably in the ortho position or the para position of the (OR ⁴² ) group. Further, the carbon number of R ⁴¹ is preferably from 1 to 10, particularly preferably from 1 to 6.

Preferred R ⁴² is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Further, when there are two or more (OR ⁴² ) groups, it is more preferable that they are located in the ortho position or the para position with respect to each other.

The following are preferred as α-hydroxyketones and α-aminoketones.

General formula (VI) In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group. And R ⁵¹ and R ⁵² may form a carbocyclic or heterocyclic ring together. X ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In formula (VI), R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and R ⁵²
Is preferably a hydrogen atom or an alkyl group.

Sugars are also preferred organic preservatives.

(Also referred to as carbohydrate) saccharide comprises monosaccharide and polysaccharide, many have the general formula C _n H _2m O _m. Monosaccharides generally refer to aldehydes or ketones of polyhydric alcohols (referred to as aldoses and ketoses, respectively) and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. The polysaccharide refers to a product obtained by dehydrating and condensing two or more of the aforementioned monosaccharides.

Among these sugars, more preferable ones are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferable ones are those corresponding to monosaccharides.

VII-1 D-oxylose VII-2 L-arabinose VII-3 D-ribose VII-4 D-deoxyribose VII-5 D-glucose VII-6 D-galactose VII-7 D-mannose VII-8 glucosamine VII-9 L-sorbose VII-10 D-sorbit (sorbitol) Examples of monoamines include the following.

General formula (VIII) 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 form a nitrogen-containing heterocyclic ring.

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 sulfone group, a carboxyl group, a halogen atom, a nitro group,
Amino groups and the like can be mentioned.

VIII-1 NCH ₂ CH ₂ OH) ₃ VIII-2 H ₂ NCH ₂ CH ₂ OH VIII-3 HNCH ₂ CH ₂ OH) ₂ VIII-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ VIII-11 HNCH ₂ COOH) ₂ VIII-13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ VIII-14 H ₂ N-CCH ₂ OH) ₂ The following diamines are preferred.

General formula (IX) In the formula, R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

R ⁸⁵ represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group or a heterocyclic group.

R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are particularly preferably a hydrogen atom and an alkyl group, and R ⁸⁵ is particularly preferably an alkylene group.

IX-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ IX-4 H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ The following are preferable polyamines.

General formula (X) In the formula, R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ are a hydrogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

R ⁹⁵ , R ⁹⁶ , and R ⁹⁷ represent a divalent organic group, and specifically have the same meaning as R ^{85 in the} general formula (IX).

X ⁹¹ and X ⁹² R represents a linking group composed of —O—, —S—, —CO—, —SO ₂ —, —SO— or a combination of these linking groups;
⁹⁸ has the same ^meaning as R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ . m represents 0 or an integer of 1 or more.

(The upper limit of m is not particularly limited and may be a high molecular weight as long as the compound is water-soluble, but usually m is preferably in the range of 1 to 3) X-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ OCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ X-6 H ₂ NCH ₂ CH ₂ NH _n H n = 500,20,000 The following are preferred as quaternary ammonium salts.

General formula (XI) (Where R¹⁰¹Represents an n-valent organic group, R¹⁰², R¹⁰³as well as
R¹⁰⁴Represents a monovalent organic group. The organic group here is carbon
Represents a group of formula 1 or more, specifically, an alkyl group, an aryl
And a heterocyclic group. R¹⁰², R¹⁰³And R¹⁰⁴Horse
A quaternary ammonium source in which at least two groups are bonded
It may form a heterocycle containing a child. n is one or more integers
A number, X Represents a counter anion. ) R¹⁰², R¹⁰³And R¹⁰⁴Among them, particularly preferred monovalent group is substituted
Or an unsubstituted alkyl group, R¹⁰², R¹⁰³And R¹⁰⁴of
At least one is a hydroxyalkyl group or an alkoxy group
The most preferred case is alkyl group or carboxyalkyl group.
Good. n is preferably an integer of 1 to 3, more preferably
1 or 2.

The following are preferred as nitroxy radicals.

General formula (XII) R ¹¹¹ and R ¹¹² each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, these alkyl group, aryl group or heterocyclic group may have a substituent.
Examples of such a substituent include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably, R ¹¹¹ and R ¹¹² are a substituted or unsubstituted aryl group or a tertiary alkyl group (for example, a t-butyl group).

(Compound example) The following alcohols are preferable.

General formula (XIII) Wherein R ¹²¹ represents a hydroxy-substituted alkyl group;
¹²² represents an unsubstituted alkyl group or the same group as ^R121 . R
¹²³ represents a hydrogen atom or a group similar to ^R122 . X ¹²¹ is a hydroxy group, a carboxyl group, a sulfo group, a nitro group,
It represents an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted amide group, and a sulfonamide group.

In formula (XIII), X ¹²¹ is preferably a hydroxy group, a carboxyl group or a hydroxyalkyl group.

XIII-4 HO-CHCH ₂ OH) ₂ XIII-5 (HO-CH _{2 3} COOH XIII-6 CCH ₂ OH) ₄ XIII-7 (HOCH _{2 3} C-CH ₃ XIII-8 (HOCH _{2 3} C-NHCOCH ₃ The following alcohols are preferable.

General formula (XIV) In the formula, R ¹³¹ , R ¹³² and R ¹³³ each represent a hydrogen atom or an alkyl group, and n represents a positive integer up to 500.

The alkyl group represented by R ¹³¹ , R ¹³² and R ¹³³ preferably has 5 or less carbon atoms, and more preferably 2 or less carbon atoms. R ¹³¹ , R ¹³² and R ¹³³ are very preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

n is preferably a positive integer of 3 or more and 100 or less, and more preferably 3 or more and 30 or less.

XIV-1 HOCH ₂ CH ₂ O ₄ OH XIV-2 CH ₃ OCH ₂ CH ₂ O ₃ OH XIV-3 CH ₃ OCH ₂ CH ₂ O ₂ OCH ₃ XIV-5 HOCH ₂ CH ₂ OCH ₃ XIV-6 C ₂ H ₅ OCH ₂ CH ₂ O ₂ OH XIV-7 HOCH ₂ CH ₂ O _n H Average molecular weight About 300 XIV-8 HOCH ₂ CH ₂ O _n H Average molecular weight About the following are preferred as _{800 XIV-9 HOCH 2 CH 2} O n H average molecular weight of about _{3000 XIV-10 HOCH 2 CH 2} O n H average molecular weight of about 8000 oximes.

General formula (XV) In the formula, R ¹⁴¹ and R ¹⁴² represent a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, respectively. Further, R ¹⁴¹ and R ¹⁴² may be the same or different, and these groups may be connected to each other.

Preferred as R ¹⁴¹ and R ¹⁴² in the general formula (XV) are a halogen group, a hydroxyl group, an alkoxyl group,
Amino group, carboxyl group, sulfo group, phosphonic acid group,
And an alkyl group substituted with a nitro group, and an unsubstituted alkyl group.

The total number of carbon atoms in the general formula (XV) is preferably 30 or less, more preferably 20 or less.

The following are preferable polyamines.

General formula (XVI) In the formula, X ¹⁵¹ and X ¹⁵² represent -CO- or -SO _2- , and R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent a hydrogen atom, an unsubstituted or substituted alkyl group. And R ¹⁵⁷ represent an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group and an unsubstituted or substituted aralkylene group. m ¹ , m ² and n represent 0 or 1.

The following are preferred as _{XVI-6 H 2 NSO 2 NHSO} 2 NH 2 condensed ring amines.

General formula (XVII) 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.

Among the general formulas (XVII), particularly preferred are the compounds represented by the general formulas (1-a) and (1-b).

In the formula, X ¹ represents N or CH. R ¹ and R ² are defined as in the general formula (XVI), R ³ is the same group as R ¹ and R ² , or Represents

In the general formula (1-a), X ¹ is preferably N. The carbon number of R ¹ , R ² , and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (XVII).

In the general formula (1-b), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (1-a) and (1-b), the compound represented by the general formula (1-a) is particularly preferable.

Many compounds of formulas (II) to (XVII) according to the present invention can be easily obtained as commercial products.

Two or more kinds of the organic preservatives may be used in combination. A preferred combination is at least one compound of the general formulas (II) to (VII) and at least one compound of (VIII) and (XVII).

More preferred combined use is at least one of the general formulas (II) and (IV) and at least one of the general formulas (VIII) and (XVII).

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 present 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 methanesulfonamidoethyl) -aniline D-4 is particularly preferably used.

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 about 20 g, and more preferably about 0.5 g to about 10 g per developing solution.

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 developer is 0.1 mol /
It is preferably at least above, and particularly preferably 0.1 mol / to 0.4 mol /.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, 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 salt ・ Diethylenetriamine pentaacetic acid ・ Ethylenediaminetetraacetic acid ・ Triethylenetetramine hexaacetic acid ・ N, N, N-trimethylenephosphonic acid ・ Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid ・ 1, 3-Diamino-2-propanoltetraacetic acid-Transcyclohexanediaminetetraacetic acid-Nitrilotriapropionic acid-1,2-Diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol etherdiaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxy Phenylacetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid If necessary, use two or more of these chelating agents in combination. May be.

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 per unit.

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. 45-9919, and thioether-based compounds represented in U.S. Pat.No. 3,813,247, and JP-A Nos. 52-49829 and 50-15554. p-phenylenediamine compound, JP-A-50-1377
No. 26, Japanese Patent Publication No. 44-30074, JP-A No. 56-156826 and 5
2-43429, quaternary ammonium salts represented by US Pat. Nos. 2,610,122 and 4,119,462, and p-aminophenols described in U.S. Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,909, Japanese Patent Publication No. 41-11431
U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,58.
Amine compounds described in 2,346, etc., JP-B-37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41
-11431, 42-23883 and U.S. Pat.
If necessary, phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added.

In the present invention, in addition to the compound represented by the general formula (I), any antifoggant can be added, if necessary.

As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples thereof include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

Among them, chloride ion in the developer is 3.5 × 10 ^-2 ~
1.5 × 10 ^-1 mol / content and 3.0 × 10 bromide ion
^{-5 to} 1.0 × 10 ^-3 mol / mol is particularly preferable from the viewpoint of reduction in fluctuations in photographic characteristics (especially increase in minimum density and change in sensitivity) due to continuous processing.

The chloride ion and bromide ion may be added directly or may be those eluted from the light-sensitive material into the developer and accumulated.

The color developer used in the present invention preferably contains a fluorescent whitening agent. 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1-4 g /.

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

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

The replenishing amount of the color developing solution of the present invention is 20 m per 1 m ² of the light-sensitive material.
It is 1 to 120 ml, preferably 30 to 100 ml. The replenishing amount referred to here indicates the amount of replenishment of a so-called color developing replenisher, and the amount of an additive or the like for correcting deterioration with time or concentration is outside the replenishing amount of the present invention.

The additive as used herein refers to, for example, water for diluting the concentrate, a preservative that easily deteriorates with time, or an alkaline agent that raises the pH.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
The complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-
95,630, Research Disclosure No. 17,129 (July 1978), etc., compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A No. 50-140,129; described in US Pat. Thiourea derivatives; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamide compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite, sulfinate or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. 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 a coupler), the purpose, 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 the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picturr and T
It can be determined by the method described in elevision 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, calcium ions described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in general, at 15-45 ° C for 20 seconds-10 minutes, preferably at 25-40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in 57-8,543, 58-14,834, 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A Nos. 56-64,339, 57-144,547, and 58.
-115,438 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The method of the present invention can be applied to processing of color paper, color reversal paper, color direct positive paper and the like.

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 consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. From the viewpoint of rapidity, the higher the silver chloride content, the better. The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. This may increase the amount of light absorption in terms of photosensitivity, enhance the adsorption of spectral sensitizing dyes, or reduce the desensitization due to spectral sensitizing dyes, and there are many useful points.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have a phase different from the inside and the surface layer, may have a multiphase structure having a bonding structure, or may have a uniform whole grain. It may consist of phases. 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).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
preparation and dtypes) ”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.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, 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 bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

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

The silver halide emulsion used in the present invention can be introduced with various polyvalent metal ion impurities in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additive used in such a process is 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 patent 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-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,067, 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,
Those described in No. 4,540,654 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.
Preferred are those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, EP 161,626A and the like.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-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. 95,570 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 can also be 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,
Multiequivalent couplers described in JP-A No. 4,310,618, JP-A-60-185.
Examples thereof include DIR redox compound releasing couplers described in No. 950 and the like, and couplers releasing a dye that undergoes color recovery after withdrawal described in European Patent 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 US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the present invention, it is preferable to use the following compounds together with the above-mentioned coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable for preventing stains and other side effects due to color development due to the reaction of the coupler with the residual color developing agent or its oxidant in the film.

Preferred compound (F) is a compound having a second-order reaction rate constant k2 (in trioctyl phosphate at 80 ° C) of 1.0 / mol · sec to 1 × 10 ⁻³ / mol · sec with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the residual aromatic amine-based developing agent is slow, and as a result, the side effect of the residual aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n- X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which reacts with an aromatic amine type developing agent to form a chemical bond, and X represents a group which reacts with an aromatic amine type developing agent and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents an aromatic amine developing agent added to the compound of the general formula (F II). Represents a promoting group. Where R ₁ and X, Y and R ₂
Alternatively, B and B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine-based developing agent, the representative ones are a substitution function and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545, JP-A-62-283338, JP-A-62-158342, and JP-A-63-18439. Those described in the specification such as are preferable.

On the other hand, a more preferred compound (G) that chemically bonds with the oxidation product of the aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and colorless compound is represented by the following general formula (GI ).

General formula (GI) RZ In formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pcarson's nucleophilic ⁿ CH ₃ I value (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) is preferably a group of 5 or more, or a group derived therefrom.

Specific examples of the compound represented by the general formula (GI) are disclosed in European Patent Publication No. 255722, JP-A-62-143048, and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-18439, 63-136724, 6
Those described in 2-214681 and 62-158342 are preferable.

Details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

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 the right column
See page 648, left column.

Example 1 On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having the layer constitutions shown above and below was prepared. 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, and the resulting dispersion is 420 g of a chlorobromide emulsifier (0.7 mol% 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 the gelatin hardening agent for each layer.

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

Blue-sensitive emulsion layer; Anhydro-5-5'-chloro-3,3 '
-Disulfoethylthiacyanine hydroxide green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl -5-methoxy-9,9 '
-(2,2'-Dimethyl-1,3-propano) thiacarbocyanine iodide The following substances were used as stabilizers for each emulsion layer.

(II-52) The following substances were used as the anti-irradiation dye.

[Carboxy-5-hydroxy-4- (3- (3-carboxy-5-oxo-1- (2,5-disulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl-1-pyrazolyl ] Benzene-2,5-disulfonate-disodium 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 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: 70 mol%, cubic average grain size 0.9μ) 0.27 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading agent (Cpd) -1) 0.28 solvent (Solv-3) 0.01 solvent (Solv-4) 0.03 second layer (color mixing prevention layer) gelatin 0.80 anti-fading agent (Cpd-2) 0.055 solvent (Solv-1) 0.03 solvent (Solv-2) 0.015 Third Layer (Green Sensitive Layer) Silver Halide Emulsion (AgBr: 70 mol%, cubic average particle size 0.45μ) 0.28 Gelatin 1.40 Magenta coupler (ExM) 0.67 Anti-fading agent (Cpd-3) 0.23 Anti-fading agent (Cpd) -4) 0.11 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.02 Fourth layer (color mixing prevention layer) Gelatin 1.70 Color mixing inhibitor (Cpd-2) 0.065 UV absorber (UV-1) 0.45 UV absorber ( UV-2) 0.23 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.05 Five layers (red sensitive layer) Silver halide emulsion (AgBr: 2 mol%, cubic average grain size 0.5 μ) 0.19 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd- 1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Sixth layer (UV absorption 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-3-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) color mixture inhibitor 2,5-di- tert-octyl hydridoquinone (Cpd-3) anti-fading agent 1,4-di-tert-amyl-2,5-dioctyloxybenzene (Cpd-4) anti-fading agent 2,2'-methylenebis (4-methyl-6) -Tert-butylphenol) (Cpd-5) p- (p-trienesulfonamide) phenyldodecane (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-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-di-tert) -Butylphenyl) benzotriazole (Solv-1) solvent di (2-ethylhexyl) hetarate (Solv-2) solvent dibutylphthalate The sample obtained as above was designated as A.

Next, samples B to E were prepared in the same manner as sample A, except that the stabilizer I-I-52 was changed as shown in Table 1.

The following experiments were conducted to examine the photographic characteristics of these coated samples.

First, using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) on the above coated sample,
Tonal exposures for sensitometry were provided. The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 1/10 second.

Next, continuous processing (running test) was performed in the following processing steps and the following processing solution compositions until the tank capacity of the color developing solution was doubled. However, the composition of the color developer was changed as shown in Table 2 and a running test was performed for each of them.

Processing temperature Time Replenishment amount Tank capacity Color development 38 ℃ 45 seconds 80ml 8 Bleach-fix 30-36 ℃ 45 seconds 161ml 8 Rinse 30-37 ℃ 20 seconds -4 Rinse 30-37 ℃ 20 seconds -4 Rinse 30-37 ℃ 20 s - 4 rinse 30 to 37 ° C. 30 seconds 200 ml 4 drying 70 to 85 ° C. 60 seconds * (. was a four-tank counter-current system to rinse →) photosensitive material 1m per ² had the following composition of each processing solution is there.

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Glacial acetic acid Add 9 g water to 1000 ml pH (25 ℃) 5.40 Rinse solution (same as tank solution and replenishment amount) Ion-exchanged water (calcium and magnesium are 3ppm or less each) Treat the sensitometry at the start and end of running , The minimum density (Dmin) and maximum density (Dman) of blue (B) and the sensitivity (logE value representing density 0.5) with continuous processing were measured using a Macbeth densitometer, and the result was Shown in the table. In the sensitivity change, + indicates a direction of increasing sensitivity, and-indicates a direction of decreasing sensitivity.

At the same time, the presence or absence of floating matters in the color developing solution at the end of running was visually confirmed, and the results are shown in Table 2.

According to Table 2, when a light-sensitive material containing no compound represented by the general formula (I) is used, or when the color developing solution contains benzyl alcohol, as shown in the processing steps to and, The minimum and maximum densities and sensitivities fluctuate significantly at the start and end of running, and a large amount of suspended matter that is considered to be silver eluted from the light-sensitive material is generated in the color developer at the end of running. It was observed.

When a light-sensitive material containing the compound represented by the general formula (I) according to the present invention is used and a color developing solution containing no benzyl alcohol is used, as shown in the processing steps (1) to (3), a photograph clearly associated with running is obtained. The change in properties was reduced, and the above-mentioned suspended matter was not generated at the end of running.

As described above, according to the present invention, the replenishment amount of the developer can be remarkably reduced without impairing the quickness.

Reference Example-1 A multilayer color photographic paper 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 Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color-stabilizing agent (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g, and this solution was added with 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic average grain size 0.85μ, grain size distribution variation coefficient 0.07, and silver bromide 0.1 mol% localized on a part of the grain surface) contains the following two types of blue-sensitizing compounds. A sensitizing dye was added in an amount of 2.0 × 10 ^-4 mol per mol of silver and then sulfur-sensitized. 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. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener 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.

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 (II-45) was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 5 per mol of silver halide. ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 1
0 ^-4 mol was added.

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

and (Layer Configuration) 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 (ultraviolet)] 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 Color image stabilizer (Cpd-7) 0.03 Solvent (Solv-3) 0.35 Second layer (color mixing inhibitor) 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 (cubic with an average grain size of 0.4μ and a coefficient of variation of 0.07, 1 mol% of silver bromide is one of the grain surfaces) 0.36 Gelatin 1.24 Magenta coupler (ExM) 0.31 Color image stabilizer (Cpd-3) 0.12 Color image stabilizer (Cpd-4) 0.06 Color image stabilizer (Cpd-8) 0.09 Solvent (Solv -2) 0.42 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 with an average grain size of 0.36μ and coefficient of variation of 0.11 and 1.6 mol% of silver bromide localized on a part of the grain surface) 0.21 Gelatin 1.34 Cyan coupler (ExC) 0.34 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.34 Color image stabilizer (Cpd-9) 0.04 Solvent (Solv-6) 0.37 Six layers (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 Acrylic modified co-weight of polyvinyl alcohol Coalescence (Degeneration degree
17%) 0.17 Liquid paraffin 0.03 (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The sample obtained as described above was designated as H.

Then, samples H to N were prepared in the same manner as sample H, except that the stabilizer I-I-42 was changed as shown in Table 3.
The amount added to each emulsion layer was the same as that of Sample H.

After the imagewise exposure of the above sample, continuous processing (running test) was carried out using an automatic developing machine for paper with the following processing steps and processing compositions until the tank capacity of the color developing solution was replenished to twice.

The color developing composition was changed as shown in Table 4.

Step Temperature Time Replenishment rate ^* Tank capacity Color development 38 ° C. 45 seconds 109 ml 4 bleach-fixing 30 to 36 ° C. 45 seconds 215 ml 4 stable 30 to 37 ° C. 20 seconds - 2 stable 30 to 37 ° C. 20 seconds - 2 stable 30 to 37 ° C. 20 seconds 364 ml 2 Dry 70-85 ° C 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material (stabilized → countercurrent flow system) The composition of each processing solution is as follows.

Bleach-fix solution (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Glacial acetic acid 9 g Add water 1000 ml pH (25 ℃) 5.40 Stabilizer (same as tank and replenisher) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one
0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g Copper sulphate 0.005 g Ammonia water (28%) 2.0 ml Add water to 1000 ml pH (25 ° C) 4.0 Note that the chloride ion concentration and bromine ion of the developer are Regarding the concentration, the replenisher concentration was set so that the tank concentration was maintained from the start to the end of the running process.

A gradation exposure for sensitometry was applied to the coated sample using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time is 1/10
The exposure amount was 250 CMS with the exposure time of 2 seconds.

The above-mentioned sensitometry was processed at the start and end of running, and the amount of change in the minimum density (Dmin) of blue (B) and sensitivity (logE value representing a density of 0.5) was measured using a Macbeth densitometer. The results are shown in Table 4. In the change in sensitivity, + represents the direction of increasing the sensitivity and- represents the direction of decreasing the sensitivity.

At the same time, the presence or absence of floating matters in the color developing solution at the end of running was visually confirmed, and the results are shown in Table 4.

According to Table 4, when the light-sensitive materials L to N containing no compound represented by the general formula (I) are used and when the developing solution contains benzyl alcohol, the processing steps are as follows: It was observed that the minimum density and sensitivity varied remarkably between the time and the end, and a large amount of floating substances considered to be eluted silver from the light-sensitive material were generated in the color developer at the end of running.

When the light-sensitive materials H to K containing the compound represented by the general formula (I) in the present invention are processed with a color developing solution containing no benzyl alcohol, the minimum density and sensitivity change due to running as shown in processing steps Was small, and the generation of the above-mentioned suspended matter was significantly prevented, and good results were obtained.

Among the present invention, when the compound of the general formula (II) or (IV) is used for the organic preservative A, the minimum density and photosensitivity change due to running are further smaller, and further the effect of preventing the above-mentioned floating substances is further enhanced, It turns out that it is particularly preferable.

Reference Example-2 In the same manner as Reference Example-1, except that the treatment step II-
Instead of 1, II-2, III-7, IV-15, V-5, VI-
Similarly, favorable results were obtained using No. 1 and VII-5. Also, because of the treatment process, instead of triethanolamine, IX-5, IX-8, X-1, X-3, XI-1,
XII-2, XII-3, XII-10, XIV-8, XV-1, XVI-
The same favorable results were obtained when 1, XVI-6 and XVII-1 were used.

Example 2 A multilayer color photographic paper 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 Yellow coupler (ExY) 19.1g and color image stabilizer (Cpd
-1) To 4.4 g and color image stabilizer (Cpd-7) 0.7 g, ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic average grain size 0.88μ, grain size distribution coefficient of variation 0.08, silver bromide containing 0.2 mol% on the grain surface) was mixed with the following blue-sensitive sensitizing dyes at 2.0 × / mol silver. After addition of 10 ^-4 mol, sulfur-sensitized one 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. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1 as a gelatin hardening agent for each layer
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

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

and 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 (II-45) was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer at 8.5 × per mol of silver halide. 10 ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 1
0 ^-4 mol was added.

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

and (Layer Configuration) 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 (ultraviolet)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing inhibitor) 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 (with cubic average particle size 0.55μ,
(1: 3 mixture (Ag mol) ratio of 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) 0.27 Color image stabilizer (Cpd-3) 0.15 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 0.44μ mixture of 1: 4 (Ag mole ratio), a variation coefficient of particle size distribution of 0.09, 0.11, and AgBr 0.6 mole% 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 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (modified) Every time
17%) 0.17 Liquid paraffin 0.03 (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The sample obtained as described above was designated as O. Then, Samples O to S were prepared in the same manner as Sample O, except that the coating silver amount of each emulsion layer was changed as shown in Table 5. Further, the stabilizer I-I-45 was changed to A-1 of Example-2 to prepare T to X, respectively.

After imagewise exposing the samples O to X, a paper processor was used in the following processing steps to reduce the tank capacity of the color developing machine to 2%.
Continuous processing (running test) was performed until double replenishment.

Treatment process temperature Time Replenishment amount ^* Tank capacity Color development 38 ℃ 45 seconds See Table 6 4 Bleach fixing 30-36 ℃ 45 seconds 61ml 4 Washing with water 30-37 ℃ 30 seconds-2 Washing with water 30-37 ℃ 30s-2 Washing with water 30 〜37 ℃ 30 seconds 364ml 2 Dry 70〜85 ℃ 60 seconds Replenishment amount per 1m ^{2 of} light-sensitive material (wash-to-tank counter-current method. Washing solution for bleach-fixing 122m ² per 1m ^{2 of} sensitive material The composition of each treatment liquid is as follows.

Color developer [Tank liquid] Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 3.0 g Triethanolamine 8.0 g Sodium chloride See Table 6 Potassium bromide See Table 6 Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g Organic preservative A (II-19) 0.03 mol Optical brightener (WHITEX-4 made by Sumitomo Chemical) 1.0 g Water is added to 1000 ml pH (25 ° C) 10.05 Bleach-fix solution [tank solution] Water 400 ml Ammonium thiosulfate (70%) 100 ml Ammonium sulfite 38 g Ammonium ethylenediaminetetraacetate (III) 55 g Ethylenediaminetetraacetic acid disodium 5 g Glacial acetic acid 9 g Water 1000 ml pH ( 25 ° C) 5.40 [Replenisher] 2.5 times the concentration of the tank solution Concentrated solution Washing solution (the tank solution and the replenisher are the same) Ion-exchanged water (calcium and magnesium are 3p each
pm or less) For color developing solution, bleach-fixing solution and washing solution,
Distilled water was added in the amount of evaporated water, and continuous treatment was performed while correcting the evaporation concentration.

A gradation exposure for sensitometry was applied to the coated sample using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time is 1/10
The exposure amount was 250 CMS with the exposure time of 2 seconds.

The above-mentioned sensitometry was processed at the start and end of running, and the amount of change in the minimum density (Dmin) of blue (B) and sensitivity (logE value representing a density of 0.5) was measured using a Macbeth densitometer. The results are shown in Table 6. In the sensitivity change, + indicates a direction of increasing sensitivity, and-indicates a direction of decreasing sensitivity.

At the same time, the presence or absence of floating matters in the color developing solution at the end of running was visually confirmed, and the results are shown in Table 6.

According to Table 6, as shown in the processing steps, ..., the replenishment amount is remarkably reduced by the treatment with the developer of the present invention containing no general formula (I) and the present invention containing benzyl alcohol. However, the change in the minimum concentration and the change in the sensitivity due to running were small, and the effect of preventing the generation of suspended matter was high, and good results were obtained.

In contrast to the present invention, when the compound of the general formula (I) and the developing solution of the present invention are not used, when the replenishment amount is remarkably reduced, the minimum density change and the sensitivity change due to running are remarkable, as shown in the processing steps 1 to Is extremely floating,
It turns out that it does not achieve the object of the invention.

In the processing steps, the fluctuation of photographic characteristics and the generation of floating matters are small, but the replenishment amount is large and the object of the present invention is not achieved.

As shown in (1) to (3) of the processing steps, it is understood that, in the present invention, when the coated silver amount of the light-sensitive material is 0.8 g / m ² , it is preferable in terms of the fluctuation of the photographic characteristics and the prevention of floating matters. More preferably 0.75 g / m ² or less, 0.65 g / m ^2.
It can be seen that m ² or less is particularly preferable.

Further, as shown in the processing steps-, among the present invention, the chloride ion and bromide ion concentrations in the developing solution are respectively 3.5 to 10 ^{-2 to} 1.5 x 10 ^-1 mol /, 3.0 x 10 ^{-5 to} 1.0.
It can be seen that the content of ^{x10 -3} mol / mol is more preferable from the viewpoints of sensitivity change due to running and prevention of the above-mentioned floating substances.

Claims (3)

(57) [Claims] 1. A method of processing a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent, which comprises a high chloride content of 80 mol% or more of silver chloride. A silver halide color photographic light-sensitive material having a silver emulsion in at least one layer and a coating silver amount of 0.8 g / m ² or less is substantially contained in the presence of a compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material, characterized in that a color developer containing no benzyl alcohol is used and the replenishing amount of the color developer is 20 to 120 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. General formula [I] Z-S-M (In the formula, M represents a hydrogen atom, a cation or -S-Z, and Z represents a heterocyclic residue containing at least one nitrogen atom.) 2. The color developer contains chloride ions at 3.5 × 1.
0 ^-2 x 1.5 to 10 ^-1 mol / content, and bromide ion 3.
The treatment method according to claim 1, wherein the content is 0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / mol. 3. The processing method according to claim 2, wherein the color developing solution contains substantially no hydroxylamine.