JPH08166663A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enable exhibition of stable photographic characteristics even in the case of a low replenishing rate of a color developing solution by incorporating a specified magenta coupler in a silver halide emulsion layer and a specified compound in the color developing solution. CONSTITUTION: At least one of the silver halide emulsion layers contains the magenta coupler represented by formula I and the color developing solution contains at least one of the compounds represented by formulae II and III and a manganese and cerium salt. In formulae I-III, Ar is a phenyl group; Y is a group to be released by coupling with the oxidation product of the color developing agent of an n-hydroxyalkylated p-phenylenediamine when a dye is formed; R is an acylamino or anilino group or the like; each of R1 and R2 is an alkyl group or an H atom; R21 is a 2-6 C hydroxyalkyl group or the like; and each of R22 and R23 is an H atom or 1-6 alkyl group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material using a stable color developing solution having improved storage stability. .

[0002]

BACKGROUND OF THE INVENTION In general, a silver halide color photographic light-sensitive material is exposed and then processed with a color developing solution containing a color developing agent. Aromatic primary amines are usually used as color developing agents, but aromatic primary amine color developing agents are generally very easily oxidized, and oxygen in the air is high in a highly alkaline solution such as a color developing solution. Easily oxidized by.

Therefore, sulfite is generally used for the purpose of preserving the aromatic primary amine color developing agent. Sulfite is generally in the form of a sulfite or bisulfite of an alkali metal such as sodium or potassium, and is a compound widely used as a preservative of a developing agent in a black and white developing solution. In liquid, the amount used is extremely limited. That is, sulfite sulfonates the oxide of the color developing agent generated in the color developing reaction process, and thus inhibits the coupling reaction between the oxide of the color developing agent and the coupler, and particularly uses a coupler having a slow coupling reaction. To reduce the color density of the silver halide emulsion layer.
Therefore, the sulfite concentration in the color developer is usually kept low. The low concentration of sulfite causes the color developing agent to be gradually oxidized in the presence of sulfite, but these problems are addressed by the use of hydroxylamine as described in U.S. Pat.No. 3,746,544. Be improved.

On the other hand, in color photographic processing, continuous processing is usually carried out by an automatic developing machine while replenishing the replenishing solution according to the processing amount of the light-sensitive material. This method has become a major economic and pollution problem because of the large amount of overflow and disposal. Therefore, in recent years, in order to reduce the overflow, a so-called concentrated low replenishment process in which the amount of the replenisher is reduced and a small amount of the concentrated replenisher is replenished is becoming popular. In such a processing method, since the residence time of the color developing solution in the processing tank of the automatic developing machine becomes long, the oxidation of the color developing agent progresses further. This tendency can be improved by increasing the sulfite concentration in the color developing solution, but such a method results in a significant decrease in dye concentration as described above. Further, hydroxylamine effectively suppresses the progress of the oxidation of the color developing agent that occurs when the sulfite concentration is low as described above, but since it is rapidly oxidized when the sulfite is lost, increasing the amount of hydroxylamine has almost no effect. Not only that, but rather, there is a drawback that fog occurs in the light-sensitive material due to ammonia generated by the decomposition of hydroxylamine. Furthermore, the generated ammonia volatilizes into the air, which causes a phenomenon in which the pH of the color developing solution itself drops.
This also affects the photographic characteristics.

As a technique for improving these drawbacks, a system using the above-mentioned conventional sulfite and hydroxylamine as a preservative is disclosed in JP-A-59-228251 and JP-A-60-205541. Further, a technique for improving the storage stability by using a cerium salt or a manganese salt has been known, but in recent years, the color developing solution tends to be more and more replenished due to economical reasons and pollution reasons. As a result, the residence time of the developer is becoming longer and longer,
Developers are often subjected to more severe air oxidation, and with conventional techniques, it is becoming more and more difficult to compensate.

Further, as the replenishment rate is lowered, the amount of the light-sensitive material processed per unit volume increases, which increases the amount of metal salts such as calcium and magnesium eluted and accumulated from the light-sensitive material, and further bleaching. The actual situation is that the amount of bleach-fixer mixed with iron complex salt is increasing.

Further, with the rapid processing, photographic light-sensitive materials have been processed at a high temperature of 30 ° C. or higher, and troubles such as coloring of a developing solution due to high-temperature oxidation have become more remarkable. ing.

Further, due to the recent minilabization, the transporting speed of the automatic developing machine has been slowed down. As a result, the light-sensitive material passes from the color developing solution to the bleaching solution or bleach-fixing solution which is the next step. Time tends to be long.

Under such circumstances, when the above-mentioned technique of cerium salt or manganese salt is used for a color developing solution, the oxidation of the developing solution is promoted by air during this transition time, It has been found that when the light-sensitive material after color development enters the bleaching solution or the bleach-fixing solution, magenta stain is generated in the light-sensitive material.

[0010]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a method of processing a silver halide color photographic light-sensitive material which provides stable photographic characteristics even when the color developer is replenished at a low level. A second object is to provide a method for processing a silver halide color photographic light-sensitive material in which magenta stain generated in a bleaching solution or a bleach-fixing solution in a low speed automatic processor is improved.

Other objects of the invention will become apparent below.

[0012]

As a result of various studies, the inventors of the present invention have found that the object of the present invention is, after imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, A method for processing a silver halide color photographic light-sensitive material, which comprises at least a color development step, wherein at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [M], and A silver halide color in which the color developer used in the step contains at least a compound represented by the following general formula [I] and a compound represented by the following general formula [D], and at least one compound selected from a manganese salt and a cerium salt. It has been found to be achieved by the processing method of the photographic light-sensitive material.

General formula [M] (In the formula, Ar is a phenyl group and includes a substituted phenyl group. Y is a N-hydroxyalkyl-substituted-p-phenylenediamine derivative, which leaves when a dye is formed by coupling with an oxidant of a coloring agent. R represents an acylamino group, anilino group or ureido group.) General formula [I] (In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom, and both R ₁ and R ₂ are not hydrogen atoms. R ₁ and R ₂ may form a ring. .) General formula [D] (Wherein, R ₂₁ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula X'and Z'represent a hydrogen atom and a carbon number of 1 to 1, respectively.
6 represents an alkyl group having 6 or a hydroxyalkyl group having 2 to 6 carbon atoms. Among the compounds represented by the general formula [I] of the present invention, for example, N, N-diethylhydroxylamine is known to be used as a preservative of a black and white developing agent in a color developing solution containing a black and white developing agent. ing.

Hydroquinone, which is usually a black and white developing agent,
Hydroquinone monosulfonic acid, phenidone, para-aminophenol, etc. are relatively stable when used as a black-and-white developing agent in a black-and-white developer, and are sufficiently preserved by using sulfite as a preservative. It is known that when added to a color developing solution, a cross-oxidation reaction with a color developing agent occurs and the storage stability thereof is extremely poor. Hydroxylamine has little effect on the preservation of the black-and-white main agent added to the color developer.

As an example of using N, N-diethylhydroxylamine as a preservative of a black and white developing agent added to a color developing solution, a color developing solution containing a coupler is used and a color photographic light-sensitive material is prepared by a reversal method. Is known to be used with phenidone in the so-called external color development method. The role of Phenidone in this case is
This is to increase the developing speed of an external photosensitive material having poor developability and to increase the density of a dye image.

In addition, for example, in a magenta color developing solution containing no phenidone, N, N-diethylhydroxylamine is known to have a bad influence on the storability of the external color developing solution by destroying the coupler. (See Japanese Patent Publication No. 45-22198).

Another example of using the compound of the present invention such as N, N-diethylhydroxylamine as a preservative of a black and white developing agent added to a color developing solution is a color developing solution in an internal color developing solution. The phenidone derivative added to the liquid and the preservation technique (see JP-A-53-32035) and the technique of retaining the phenidone derivative together with hydroquinones (see JP-A-52-153437) be able to.

As mentioned above, the compounds of the present invention have hitherto been
It is known to be used as a preservative of a black and white developing agent added to a color developing solution, but it is not known as a preservative of a color developing agent in an ordinary color developing solution.

In recent years, there has been a demand in the art for a technique capable of rapidly processing a silver halide color photographic light-sensitive material and obtaining stable photographic characteristics with excellent processing stability. There is a demand for a method of processing a silver halide color photographic light-sensitive material that can be processed.

That is, the silver halide color photographic light-sensitive material is subjected to running processing by an automatic developing machine provided in each laboratory. It is required to develop and return it to the user, and in recent years, it has even been required to return it within a few hours from reception, and there is an urgent need for the development of technology capable of quicker processing.

[0021] Regarding the rapid processing of silver halide color photographic light-sensitive materials, the prior arts are as follows: [I] Technology by improvement of silver halide color photographic light-sensitive material, [II] Technology by physical means during development processing, [III] ] It is roughly classified into a technique by improving the composition of a processing solution used for development processing.

Among the rapid processing techniques of [I], a technique of using a silver halide photographic light-sensitive material containing silver halide grains having a high concentration of silver chloride (for example, JP-A-58-9).
5345, JP-A-60-19140, JP-A-58-95736, etc.) give particularly excellent speed-up performance. However, when such a high silver chloride-containing photosensitive material is used,
Hydroxylamine, which is usually used as a preservative for a color developing agent in a color developing solution, has a drawback that it causes a silver developing reaction due to its reducing power, resulting in an insufficient dye concentration. However, when hydroxylamine is not used, the storability of the color developing solution is significantly deteriorated. There is a trade-off relationship.

Further, the cerium salt and the manganese salt remarkably maintain the color developing agent in the presence of hydroxylamine, but the decomposition speed of hydroxylamine itself is accelerated, and when the hydroxylamine disappears, the retention is rapidly maintained. It was found that homeostasis deteriorates.

In various investigations by the present inventors, the above problems can be solved simultaneously when a monoalkylhydroxylamine or dialkylhydroxylamine is used in combination with a cerium salt and / or a manganese salt. It has been found that the magenta stain can be improved.

Therefore, another object of the present invention is to extend the period for maintaining the homeostasis, and further improve the magenta stain to improve the homeostasis, and then subject the high silver chloride light-sensitive material to a silver development reaction. (EN) It is intended to provide a color developing solution for silver halide color photographic light-sensitive materials which is less likely to occur and enables rapid processing, and a method for processing silver halide color photographic light-sensitive materials using the solution.

Next, the general formula [I] will be described in detail.

In the general formula [I], R ₁ and R ₂ each represent an alkyl group or a hydrogen atom which is not a hydrogen atom at the same time, and the alkyl groups represented by R ₁ and R ₂ may be the same or different. Each of them is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.

The alkyl groups of R ₁ and R ₂ include those having a substituent, and examples of the substituent include an amino group, an alkoxy group (eg, methoxy group), a sulfonic acid group, a carboxylic acid group, a hydroxyl group and the like. For these, for example, U.S. Pat.Nos. 3,287,125, 3,293,034, and 3,28
Examples thereof include hydroxylamines described in No. 7,124.

R ₁ and R ₂ may combine with each other to form a ring, for example, a heterocycle such as piperidine or morpholine.

Preferred exemplary compounds represented by the general formula [I] are shown below. These compounds of the present invention may be used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonic acid group, oxalate, phosphate and acetate.

Among the compounds represented by the above general formula [I], (I-1) and (I-2) are preferable for achieving the object of the present invention and producing the effect.

The concentration of the compound of the general formula [I] of the present invention in the color developer is usually used as a preservative.

The manganese salt and the cerium salt according to the present invention are compounds that release manganese ion or cerium ion when dissolved in a developing solution. The following compounds are preferable, but the present invention is not limited to these. Not a thing.

Manganese chloride Manganese sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese nitrate Potassium permanganate Manganese acetate Manganese oxalate Manganese citrate Ethylenediamine manganese tetraacetate Cerium sulfate Cerium nitrate Cerium carbonate Cerium phosphate Cerium acetate Cerium citrate Cerium acid These manganese salts and cerium salts are in the form of ions (manganese ion and It is preferable to use within the range, more preferably 0.3
It is preferably contained in an amount of mg to 20 mg, particularly 0.5 mg to 10 mg.

[0035] It is possible to suppress the decrease in color density, which is thought to be caused by the dissolution physical development of the light-sensitive material, and the deterioration of the preserving ability is very slight, so that it is possible to perform the rapid processing by using the light-sensitive material containing high silver chloride. It is possible to provide a color developing solution or a method for processing a silver halide color photograph using the solution. Therefore, in the present invention, the sub-component in the color developer is

Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.

As the color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group achieves the object of the present invention, exhibits excellent effects, and causes fog. It is preferably used because it is small.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material than the para-phenylenediamine-based compound having no water-soluble group, such as N, N-diethyl-p-phenylenediamine. As for the skin, not only has the advantage that the skin is less prone to rash, but the object of the present invention can be efficiently achieved especially by combining with the compound represented by the above general formula [I] in the present invention.

The water-soluble group has at least one amino group on the p-phenylenediamine compound or on the benzene nucleus.
And one having a specific water-soluble group,
_{- (CH 2) n-CH} 2 OH, - (CH 2) m-NHSO
_{2 - (CH 2) n-} CH 3, - (CH 2) m O- (CH 2)
_{n-CH 3, - (CH} 2 CH 2 O) nCm H 2m + 1 (m
And n each represent an integer of 0 or more. ), -COO
H group, and as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the present invention are shown below. Illustrative color developing agent Among the color-developing agents exemplified above, since the occurrence of fogging is small, it is preferable to use in the present invention No. (A-
1), (A-2), (A-3), (A-4), (A-
6), (A-7) and (A-15), and particularly preferably (A-1).

The color-developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

[0042] The enclosure is more preferred.

The color developing agents may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone or 4-hydroxymethyl-4-methyl-1-.
You may use together with phenyl-3-pyrazolidone, methol, etc.

Further, instead of using the above color developing agent in a color developing solution, a color developing agent can be added to the light-sensitive material, and the color developing agent used in that case includes a dye precursor.

A typical dye precursor is disclosed in JP-A-58-654.
Nos. 29 and 58-24137 are used, and specifically, for example, 2 ', 4'-bismethanesulfonamide-
4-Diethylaminodiphenylamine, 2'-methanesulfonamide-4 '-(2,4,6-triisopropyl) benzenesulfonamide-2-methyl-4-N-
(2-Methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4'-
(2,4,6-Triisopropyl) benzenesulfonamide-4- (hydroxytrisethoxy) diphenylamine, 4-N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis ( 2, 4,
6-triisopropyl) benzenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4
-N, N-diethylaminodiphenylamine, 4-n-
Hexyloxy-2'-methanesulfonamide-4'-
(2,4,6-Triisopropyl) benzenesulfonamide diphenylamine, 4-methoxy-2'-methanesulfonamide-4 '-(2,4,6-triisopropyl) benzenesulfonamide diphenylamine, 4-dihexylamino-4 ′-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine, 4-n
-Hexyloxy-3'-methyl-4 '-(2,4,6
-Triisopropylbenzenesulfonamido) diphenylamine, 4-N, N-diethylamino-4 '-(2,
4,6-triisopropylbenzenesulfonamide) diphenylamine, 4-N, N-dimethylamino-2-phenylsulfonyl-4 '-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine, and the like.

The amount of the dye precursor added to the light-sensitive material is 0.5 to 22 mg per 100 cm ² of the light-sensitive material.
Is preferable, and more preferably 4 to 12 mg.

The color developing solution according to the present invention contains a compound represented by the following general formula [D].

General formula [D] (Wherein, R ₂₁ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula X ′ and Z ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. Preferred specific examples of the compound represented by the general formula [D] are as follows.

(D-1) ethanolamine, (D-2)
Diethanolamine, (D-3) triethanolamine, (D-4) di-isopropanolamine, (D-
5) 2-methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol,
(D-9) 1-diethylamino-2-propanol,
(D-10) 3-diethylamino-1-propanol,
(D-11) 3-dimethylamino-1-propanol,
(D-12) Isopropylaminoethanol, (D-13)
3-amino-1-propanol, (D-14) 2-amino-2-methyl-1,3-propanediol, (D-15)
Ethylenediaminetetraisopropanol, (D-16)
Benzyldiethanolamine, (D-17) 2-amino-
2- (hydroxymethyl) -1,3-propanediol.

The compound represented by the general formula [D] is a color developing solution in view of the objects and effects of the present invention. Used in the range of up to 50 g.

When the color developer according to the present invention contains the compounds represented by the following general formulas [BI] to [B-IV], the object of the present invention can be achieved and the effects can be improved. In addition, since it has an effect of improving bleaching fog that occurs when bleaching or bleach-fixing is performed immediately after color development, it is more preferably used in the present invention.

General formula [BI] General formula [B-II] In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₁₅ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₁₂ represents —OH or a hydrogen atom, R ₁₁ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, Examples of the alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include methyl group, ethyl group, iSO-propyl group, n-propyl group, t-butyl group, n-butyl group and hydroxymethyl. Group, hydroxyethyl group, methylcarboxylic acid group, benzylic acid group and the like.

The alkyl groups represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are the above R ₁₁ , R ₁₂ , R ₁₃ and R _14.
It has the same meaning as the alkyl group represented by and further includes an octyl group and the like.

Examples of the phenyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Typical examples of the chelating agent of the present invention are shown below, but the present invention is not limited thereto. (B-I-1) 4-Isopropyl-1,2-dihydroxybenzene (B-I-2) 1,2-dihydroxybenzene-3,5
-Disulfonic acid (B-I-3) 1,2,3-trihydroxybenzene-
5-carboxylic acid (BI-4) 1,2,3-trihydroxybenzene-
5-Carboxymethyl ester (BI-5) 1,2,3-trihydroxybenzene-
5-Carboxy-n-butyl ester (B-I-6) 5-t-butyl-1,2,3 trihydroxybenzene (B-II-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (B -II-2) 2,3,8-trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2,3-dihydroxynaphthalene-6-
Carboxylic acid (B-II-4) 2.3-dihydroxy-8-isopropyl-naphthalene (B-II-5) 2,3-dihydroxy-5-chloro-naphthalene-6-sulfonic acid Among the above compounds, in the present invention, Particularly preferably used compounds are 1,2-dihydroxybenzene-3,
5-disulfonic acid can be used, and it can be used also as an alkali metal salt such as sodium salt and potassium salt.

In the present invention, the compounds represented by the general formulas [BI] and [B-II] are Is 10 mg to 10 g, more preferably 20 mg to 3 g
Good results are obtained by adding.

General formula [B-III] General formula [B-IV] (Formula [B-III] and [B-IV] in, L is an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -
O-L ₈ -O-L ₈ or -L ₉ -Z-L ₉ - represent. Where Z is L _{1 to} L ₁₃ each represent an alkylene group. R ₃₃ ~ R
₄₃ represents a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt), respectively. However, at least two of R _{33 to} R ₃₆ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof), and at least two of R _{37 to} R ₃₉ are a carboxylic acid group (including a salt thereof). It is an acid group (including its salt) or a phosphonic acid group (including its salt). ) In the general formulas [B-III] and [B-IV], an alkylene group represented by L, a cycloalkylene group and a phenylene group, and an alkylene group represented by L _{1 to} L ₁₃ may have a substituent. Including.

Next, these general formulas [B-III] and [B
Preferred examples of the compound represented by formula [IV] are shown below.

[Exemplified Compound] [B-III-1] Ethylenediaminetetraacetic acid [B-III-2] Diethylenetriaminepentaacetic acid [B-III-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid [B-III-4] propylenediaminetetraacetic acid [B-III-5] triethylenetetraminehexaacetic acid [B-III-6] cyclohexanediaminetetraacetic acid [B-III-7] 1,2- Diamine propane tetraacetic acid [B-III-8] 1,3-diaminopropan-2-ol tetraacetic acid [B-III-9] ethyl ether diamine tetraacetic acid [B-III-10] glycol ether diamine tetraacetic acid [B- III-11] ethyleneamine tetrapropionic acid [B-III-12] phenylenediamine tetraacetic acid [B-III-13] ethylenediami Tetraacetic acid disodium salt [B-III-14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [B-III-15] Ethylenediaminetetraacetic acid tetrasodium salt [B-III-16] Diethylenetriamine pentaacetic acid pentasodium salt [B- III-17] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid sodium salt [B-III-18] Propylenediaminetetraacetic acid sodium salt [B-III-19] Ethylenediaminetetramethylene Phosphonic acid [B-III-20] Cyclohexanediaminetetraacetic acid sodium salt [B-III-21] Diethylenetriamine pentamethylenesulfonic acid [B-III-22] Cyclohexanediaminetetramethylenephosphonic acid [B-IV-1] Nitrilotriacetic acid B-IV-2 ] Iminodiacetic acid [B-IV-3] Nitrilotripropionic acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-5] Iminodimethylenephosphonic acid [B-IV-6] Nitrilotriacetic acid trisodium salt These general Among the compounds represented by the formula [B-III] or [B-IV], as the compounds particularly preferably used in the present invention, [B-III-1], [B-III-2] and [B
-III-5], [B-III-8], [B-III-19],
[B-IV-1] and [B-IV-4] are mentioned.

Further, the compound represented by the general formula [B-III] or [B-IV] is a color developing agent. From the standpoint of clarity, the range of 0.3 to 5 g is particularly preferably used.

The compounds represented by the above general formulas [BI] to [B-IV] may be used alone or in combination.

Furthermore, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2,
Other chelating agents such as phosphonocarboxylic acid such as 4-tricarboxylic acid and polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

In the present invention, it is preferable to use a triazyl stilbene-based optical brightening agent represented by the following general formula [III] in the color developing solution according to the present invention because fogging is further reduced.

General formula [III] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (eg methoxy, ethoxy, methoxyethoxy, etc.),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
An aryl group (eg, phenyl, methoxyphenyl, etc.),
Amino group, alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β
-Hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino,
N- (β-hydroxyethyl-N′-methylamino and the like), arylamino groups (for example, anilino, o-, m
-, P-sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-
Carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-p-aminoanilino, o-, m-, p-anidino, etc.).

M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned, but the invention is not limited thereto. The triazyl stilbene-based whitening agent represented by the general formula [III] is, for example, “Fluorescent Whitening Agent” edited by Chemical Industry Association (Showa 5
It can be synthesized by the usual method described on page 8).

[0067] It is preferably used in the range of 0.2 to 6 g, and particularly preferably in the range of 0.4 to 3 g.

The color developer of the present invention may contain the following developer components in addition to the above components.

As an alkaline agent other than the above-mentioned carbonates, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. alone or In combination, the above-mentioned effect of the present invention, that is, no precipitation occurs,
It can be used in combination within the range of maintaining the pH stabilizing effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate, etc. are used for the necessity of preparation or for the purpose of increasing ionic strength. can do.

If necessary, inorganic and organic antifoggants can be added.

If necessary, a development accelerator can also be used. US Pat. No. 2,648,604 as a development accelerator
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. No. 2,533,990, No. 2,532,832, No. 2,950,970, No. 2,577,127
And polyethylene glycol and its derivatives described in JP-B-44-9504, and nonionic compounds such as polythioethers.

Further, benzyl alcohol, phenethyl alcohol described in US Pat. No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like can be mentioned.

In the above, particularly with respect to the poorly soluble organic solvent represented by benzyl alcohol, tar is liable to be generated particularly in the running process in the low replenishment system due to the long-term use of the color developing solution. Occurrence depends on the proximity to the paper to be processed
It may even cause a serious failure that significantly impairs its commercial value.

Further, since the poorly soluble organic solvent has poor solubility in water, not only is it troublesome that a stirring device is required for adjusting the color developing solution itself, but the dissolution of the poorly soluble organic solvent is also caused by using such a stirring device. Due to the poor rate, the effect of promoting development is limited.

Further, the poorly soluble organic solvent has a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. However, since there are problems such as requiring a great deal of labor and cost, it is preferable to reduce or eliminate the amount used.

Further, in the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509. The compounds described in each publication can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminiphenol hexalphate (methol), phenidone, N, N'-diethyl-p.
-Aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride, etc. are known. No. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds, and the like can be added, if necessary.

In addition, various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

Each component of the above color developing solution can be adjusted by sequentially adding and stirring to a certain amount of water. In this case, a component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Also, more generally, a plurality of components, each of which can coexist stably, are prepared in a concentrated aqueous solution, or in a solid state, which is prepared in advance in a small container in water and prepared by stirring to prepare a color developing solution of the present invention. Obtainable.

In the present invention, the above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH of the color developer is 9.
Used in 5 to 13.0.

In the present invention, the higher the processing temperature for color development is 30 ° C. or more and 50 ° C. or less, the quicker the processing can be carried out in a short time, which is preferable, but the one which is not so high in terms of image storage stability. It is good, and it is preferable to treat at 33 ° C. or higher and 45 ° C. or lower. Conventionally, the color development time is generally about 3 minutes and 30 seconds.
The time is preferably within 30 minutes, and further 30 seconds to 1 minute 30
It is preferable to carry out in the range of seconds.

The color developing solution according to the present invention can be applied to various processing methods such as a spray method in which the processing solution is atomized, a web method in which a carrier impregnated with the processing solution is brought into contact, or a developing method using a viscous processing solution. Can be applied.

The processing steps are essentially color development-bleach-fixing-
Washing (or stabilization) with water is preferably used, and the bleach-fixing step may be provided separately from the bleaching step and the fixing step.

The bleaching agent which can be used in the bleaching solution or the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid.
The complex salt is obtained by coordinating a metal ion such as iron, cobalt or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid.

The most preferable organic acid used for forming such a metal complex salt of an organic acid includes polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ′, N′-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine Citric acid (or tartaric acid) [9] Ethyl Etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-Triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt Used in. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied.

Further, iron (III) ethylenediaminetetraacetate
A bleach-fixing solution containing a complex salt bleaching agent and a composition containing a small amount of a halide such as ammonium bromide in addition to the above silver halide fixing agent, or conversely, a bleaching composition containing a large amount of a halide such as ammonium bromide. A fixing solution, or a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide can be used.

As the above-mentioned halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. are also used. can do.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate. sodium thiosulfate,
Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether.

[0090]

The bleach-fixing solution contains various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. Can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention is disclosed in JP-A-46 / 46.
-280, Japanese Patent Publication Nos. 45-8506, 46-556, Belgian Patent No. 770,910, Japanese Patent Publication Nos. 45-8836, 53-9854, JP-A-5
Various bleaching accelerators described in 4-71634 and 49-42349 can be added.

The pH of the bleach-fixing solution is used at 4.0 or higher, but it is generally used at pH 5.0 or higher and pH 9.5 or lower, preferably pH 6.0 or higher and pH 9.5 or lower, and most preferably pH. Is processed at 6.5 or more and 8.5 or less.

The processing temperature is 80 ° C. or lower and the temperature is 3 ° C. or higher, preferably 5 ° C. or lower than the temperature of the processing solution in the color developing tank, but it is preferably 55 ° C. or lower to prevent evaporation and the like. .

The halogenated grains used in the silver halide color photographic light-sensitive material applicable to the present invention are silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, Although any of silver chloroiodobromide and a mixture thereof can be used, particularly preferably used from the viewpoint of rapid processability, silver chloride is at least 80 mol%.
A silver halide grain containing the above, preferably 9
The content is 0 mol% or more, and more preferably 95 mol% or more.

In a silver halide color photographic light-sensitive material comprising a silver halide emulsion containing such silver halide grains, the color developer of the present invention is particularly advantageously applied because the dye concentration is remarkably lowered due to hydroxylamine. To be done.

The silver halide emulsion containing silver halide grains consisting of 80 mol% or more of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride, In this case, silver bromide is 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and when silver iodide is present, 1 mol% or less, preferably 0.5 mol%. It is the following.

The silver halide grains substantially consisting of silver chloride according to the present invention as described above are 80% by weight of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. % Or more, and more preferably 100%.

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal or other crystal.
Any ratio of the plane to the [111] plane can be used.

Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core / shell type) having different inside and outside. Good. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain.

Further, tabular silver halide grains (JP-A-58)
-113934, Japanese Patent Application No. 59-170070) can also be used.

The silver halide grains used in the present invention are:
It may be obtained by any of the acid method, the neutral method and the ammonia method.

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

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

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

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before this chemical ripening,
At least one kind of a nitrogen-containing heterocyclic compound having at least one kind of hydroxytetrazaindene and a mercapto group may be contained during the aging or after the aging.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × with respect to 1 mol of silver halide in order to impart photosensitivity to a desired light-sensitive wavelength region.
Optical sensitization may be carried out by adding 10 ⁻³ mol.

Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion include, for example, West German Patent No. 929,080, US Patent Nos. 2,231,658, 2,493,748, and 2,50.
No. 3,776, No. 2,519,001, No. 2,912,329, No.
3,656,959, 3,672,897, 3,694,217,
No. 4,025,349, No. 4,046,572, British Patent No. 1,2
42,588, Japanese Examined Patent Publication No. 44-14030, No. 52-24844 and the like can be mentioned.

Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, US Pat. Nos. 1,939,201, 2,072,908, 2,739,149 and 2,945,763.
Nos. 5,051,979 and the like, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical ones.

Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, US Pat. No. 2,269,234 can be used.
No. 2,270,378, 2,442,710, 2,45
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in 4,629 and 2,776,280.

Furthermore, US Pat. Nos. 2,213,995 and
2,493,748, 2,519,001, West German patent 929,080
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in JP-A No. 1994-187 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone,
Also, these may be used in combination.

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

As a particularly preferable spectral sensitization method, a typical one is, for example, a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
43-4936, 43-22884, 45-18433, 47-37443
No. 48-28293, No. 49-6209, No. 53-12375, JP-A No. 52-23931, No. 52-51932, No. 54-80118, and No. 58-153.
Methods described in No. 926, No. 59-116646, No. 59-116647 and the like can be mentioned.

The combination of a carbocyanine having a benzimidazole nucleus with another cyanine or merocyanine is described in, for example, Japanese Patent Publication Nos. 45-25831 and 47-111.
No. 14, No. 47-25379, No. 48-38406, No. 48-38407, No.
54-34535, 55-1569, JP-A-50-33220, 50-38
526, 51-107127, 51-115820, 51-135528
No. 52-104916, No. 52-104917, etc.

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

The combination of thiacarbocyanine with other carbocyanines is described in, for example, JP-B-43-4.
No. 932, No. 43-4933, No. 45-26470, No. 46-18107, No.
47-8741 and JP-A-59-114533.

Further, the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorine described in JP-B-50-40659 can be prepared in advance. It is used by dissolving it in a hydrophilic organic solvent such as carboxylic alcohol.

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

A dye (AI dye) which is water-soluble or decolorizes with a color developing solution can be added to the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention. As the AI dye, an oxonol dye, Hemioxonol dyes, merocyanine dyes and azo dyes are included. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

Examples of AI dyes that can be used include British Patents 584,609 and 1,277,429, JP-A-48-85130,
No. 49-99620, No. 49-114420, No. 49-129537,
No. 52-108115, No. 59-25845, No. 59-111640,
No. 59-111641, U.S. Pat.Nos. 2,274,782, 2,53
No. 3,472, No. 2,956,079, No. 3,125,448, No. 3
3,148,187, 3,177,078, 3,247,127,
No. 3,260,601 No. 3,540,887, No. 3,575,704
No. 3,653,905, No. 3,718,472, No. 4,071,
Examples thereof include those described in No. 312 and No. 4,070,352.

Generally, these AI dyes are preferably used in an amount of 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mol, per mol of silver in the emulsion layer. To use.

The magenta coupler represented by the general formula [M] will be described in detail below.

The magenta dye-forming coupler used in the present invention can be represented by the following general formula [M].

General formula [M] Ar: a phenyl group, especially a substituted phenyl group.

The substituent is a halogen atom, an alkyl atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamide group or an acylamino group, and Ar is Ar. The phenyl group represented may have two or more substituents.

Specific examples of the substituent will be given below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: methyl group, ethyl group, iso-propyl group, butyl group, t-butyl group, t-pentyl group, etc., but especially alkyl having 1 to 5 carbon atoms Groups are preferred.

Alkoxy group: methoxy group, ethoxy group,
A butoxy group, a sec-butoxy group, an iso-pentyloxy group and the like are preferable, and an alkoxy group having 1 to 5 carbon atoms is particularly preferable.

Aryloxy group: a phenoxy group, a β-naphthoxy group, etc., and this Arule part further contains Ar.
The phenyl group represented by may have the same substituents.

Alkoxycarbonyl group: A carbonyl group having an alkoxy group as described above, preferably an alkyl moiety such as methoxycarbonyl group and pentyloxycarbonyl group having 1 to 5 carbon atoms.

Carbamoyl group: Alkylcarbamoyl group such as carbamoyl group and dimethylcarbamoyl group Sulfamoyl group: Alkylsulfamoyl group such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group and ethylsulfamoyl group sulfonyl group: Alkylsulfonyl group such as methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, arylsulfonyl group Sulfonamide group: Alkylsulfonamide group such as methanesulfonamide group, toluenesulfonamide group, arylsulfonamide group, etc. Acylamino group: acetamino group, A pivaloylamino group, a benzamide group and the like are particularly preferable as a halogen atom, and among these, chlorine is most preferable.

Y: N-hydroxyalkyl-substituted-p-phenylenediamine derivative Represents a group which is released when a dye is formed by coupling with an oxidized product of a color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z is a nitrogen atom, a carbon atom, an oxygen atom, a nitrogen atom,
Represents the group of atoms required to form a 5- or 6-membered ring with atoms selected from sulfur atoms. ) Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradexcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group Groups, etc. Acyloxy groups: acetoxy groups, myristoyloxy groups, benzoyloxy groups, etc. Arylthio groups: phenylthio groups, 2-butoxy-5-
Octylphenylthio group, 2,5-dihexyloxyphenylthio group, 2,5-dihexyloxyphenylthio group, etc. Alkylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonyl A methylthio group,
Phenoxyethylthio group, etc. : Pyrazolyl group, imidazolyl group, triazole group, tetrazolyl group, etc. R: When R is an acylamino group, examples thereof include acetamide group, isobutylamino group, benzamide group, 3-
[Α- (2,4-di-tert-amylphenoxy) butyramide] benzamide group, 3- [α- (2,4-di-te
rt-Amylphenoxy) acetamide] benzamide group, 3- [α- (3-pentadecylphenoxy) butylamide] benzamide group, α- (2,4-di-tert-amylphenoxy) butylamide group, α- (3-penta Decylphenoxy) butylamide group, hexadecanamide group, isostearoylamino group, 3- (3-octadecenylsuccinimide) benzamide group or pivaloylamino group, and the like, when R is an anilino group, examples thereof include an anilino group, 2-chloroanilino group, 2,4-dichloroanilino group, 2,5-dichloroanilino group, 2,
4,5-trichloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5- (3-octadecenylsuccinimide) anilino group, 2-chloro-5- [α- ( 3-tert-butyl-4-hydroxy) tetradecanoamido] anilino group, 2-chloro-5-tetradecyloxycarbonylanilino group, 2-chloro-5
-(N-tetradecylsulfamoyl) anilino group,
2,4-dichloro-5-tetradecyloxyanilino group, 2-chloro-5- (tetradecyloxycarbonylamino) anilino group, 2-chloro-5-octadecylthioanilino group or 2-chloro-5- ( N-tetradecylcarbamoyl) anilino group and the like, and when R is a ureido group, examples thereof include 3-{(2,4-di-tert-aminophenoxy) acetamido} phenylureido group, phenylureido group, methylureido group. Group, octadecylureido group, 3-tetradecanamidophenylureido group, N, N-dioctylureido group and the like.

Among the compounds represented by the general formula [I], a particularly preferred compound is represented by the general formula [II].

General formula [II] In the formula, Y and Ar have the same meanings as in the general formula [I].

X: represents a halogen atom, an alkoxy group or an alkyl group.

Specific examples will be given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: methoxy group, ethoxy group, butoxy group,
An alkoxy group having 1 to 5 carbon atoms such as a sec-butoxy group and an iso-pentyloxy group is preferable.

Alkyl group: methyl group, ethyl group, iso
An alkyl group having 1 to 5 carbon atoms such as -propyl group, butyl group, t-butyl group, t-pentyl group is preferable. A halogen atom is particularly preferable, and chlorine is particularly preferable.

R ₁ : represents a group capable of substituting on the benzene ring, and n represents 1 or 2. When n is 2, R ₁ may be the same or different. As the group capable of substituting on the benzene ring represented by R ₁ , a halogen atom, R ', R ", Are the same or different and each represents a hydrogen atom or an alkyl group, an alkenyl group or an aryl group which may have a substituent. Among these, preferably Is.

Specific examples of magenta couplers are shown below, but the magenta couplers are not limited to these. Examples of R in the above formula include the following. These magenta couplers of the present invention are disclosed in JP-A-56-38043.
It can be easily synthesized according to the method described in Nos. 57-14837, 57-204036 and 58-14833.

The addition amount of the magenta coupler of the present invention is preferably 0.005 to 2 mol per mol of silver halide,
More preferably, it is 0.01 to 1 mol.

In the present invention, the following photographic couplers can be used in addition to the magenta coupler represented by the general formula [M].

As the cyan coupler, usual phenol compounds and naphthol compounds, for example, US Pat.
9,929, 2,434,272, 2,474,293, 2,895,
No. 826, No. 3,253,924, No. 3,034,892, No. 3,311,47
No. 6, No. 3,386,301, No. 3,419,390, No. 3,458,315
Nos. 3,476,563, 3,531,383, etc. can be used. The method for synthesizing these compounds is also described in the publication.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds, which can be used in combination with the magenta coupler of the present invention.

As the pyrazolone magenta coupler,
U.S. Patents 2,600,788 3,062,653, 3,127,269
Issue 3, Issue 3,311,476, Issue 3,419,391, Issue 3,519,429
Issue 3,58,318, 3,684,514, 3,888,680
No. 49-29639, 49-111631, 49-129538
No. 50-13041, Japanese Patent Publication No. 53-47167, 54-10491
And 55-30615.

As the pyrazolotriazole type magenta coupler, US Pat. No. 1,247,493 and Belgian patent 792,52 are mentioned.
The couplers described in No. 5 are mentioned.

As the diffusion-resistant colored magenta coupler, a compound in which the coupling position of a colorless magenta coupler is substituted with arylazo is generally used. For example, US Pat. Nos. 2,801,171, 2,983,608 and 3,005,7 are used.
12, 3,684,514, British Patent 937,621, JP-A-49
-123625, the compound described in 49-31448 are mentioned.

Further, a colored magenta coupler of the type described in US Pat. No. 3,419,391, in which the dye flows out into the processing solution upon reaction with the oxidized product of the developing agent, can also be used.

As the photographic yellow coupler, a closed ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used. Further, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. Examples of these are U.S. Pat.
3,265,506, 3,664,841, 3,408,194, and
3,277,155, 3,447,928, 3,415,652, JP-B-49-13576, JP-A-48-29432, 48-68834, 49
-10736, 49-122335, 50-28834, 50-132926
, Etc. together with the synthesis method.

The amount of the above diffusion-resistant coupler used in the present invention is generally 0.05 to 2.0 mol per mol of silver in the photosensitive silver halide emulsion.

In the present invention, a DIR compound is preferably used in addition to the above diffusion resistant coupler.

Further, in addition to the DIR compound, a compound which releases a development inhibitor upon development is also included in the present invention. For example, US Pat. Nos. 3,297,445 and 3,379,529, West German Patent Application (OLS) 2,417,914, and Japanese Patent Laid-Open No. Sho 52-52. -15271, 53
-9116, 59-123838, 59-127038 and the like.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitor action when released from the active site is introduced into the active site of the coupler. British Patent 935,454
U.S. Patents 3,227,554, 4,095,984, 4,14
It is described in No. 9,886.

The above-mentioned DIR coupler has a property that upon coupling reaction with an oxidized product of a color developing agent, the mother nucleus of the coupler forms a dye, while releasing a development inhibitor. Further, in the present invention, U.S. Patents 3,652,345 and 3,928,0
41, 3,958,993, 3,961,959, 4,052,213
Release agent is released when it undergoes a coupling reaction with an oxidant of a color developing agent as described in JP-A Nos. 53-110529, 54-13333 and 55-161237. Also included are compounds that do not form pigments.

Furthermore, JP-A-54-145135 and JP-A-56-11.
When reacted with an oxidant of a color developing agent as described in 4946 and 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Alternatively, a so-called timing DIR compound, which is a compound that releases a development inhibitor by an elimination reaction, is also included in the present invention.

Further, as described above in the coupler mother nucleus which forms a completely diffusible dye when reacted with an oxidant of a color developing agent described in JP-A-58-160954 and JP-A-58-162949. It also includes a timing DIR compound to which a timing group is attached.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image browning inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. , Plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloid used for preparing an emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and other polymer, albumin,
Examples include proteins such as casein, hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole, polyacrylamide, and other single or copolymer synthetic hydrophilic polymers. It

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

Various coating methods such as dipping coating, air doctor coating, curtain coating and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. The method described in US Pat. Nos. 2,761,791 and 2,941,898
A simultaneous coating method of more than one layer can also be used.

In the present invention, the coating positions of various emulsion layers can be arbitrarily determined. For example, in the case of a full-color photographic paper light-sensitive material, an arrangement of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order from the support side is preferred. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers.

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

In the method for processing a silver halide color photographic light-sensitive material of the present invention, any silver halide color photographic light-sensitive material can be used as long as it is a light-sensitive material which is processed by a so-called internal development method containing a coupler in the light-sensitive material. , Color paper, color negative film, color positive film, slide color reversal film, movie color reversal film,
It can be applied to any silver halide color photographic light-sensitive material such as a color reversal film for TV and a color reversal paper.

[0171]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but embodiments of the present invention are not limited to these.

[Example 1] On a polyethylene-laminated paper support, the following layers were sequentially coated from the support side to prepare comparative light-sensitive material samples.

Layer 1 ... 1.3 g / m ² of gelatin,
0.34 g / m ² (in terms of silver, the same applies hereinafter) of a blue-sensitive silver chlorobromide emulsion (97 mol% as AgCl) and 0.64 g /
1.0 × 10 ⁻³ dissolved in m ² dioctyl phthalate
A layer containing the following yellow coupler (Y-1) in mol g / m ² .

Layer 2: an intermediate layer consisting of 0.51 g / m ² of gelatin.

Layer 3 ... 1.3 g / m ² of gelatin,
The following magenta couplers of 0.22 g / m ² green-sensitive silver chlorobromide emulsion (98 mol% as AgCl) and 0.23 g / 1.3 × dissolved in dioctyl phthalate m ² 10 ^-3 mol g / m ² A layer containing (M'-1).

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

Layer 5: 1.2 g / m ² gelatin,
Red-sensitive silver chlorobromide emulsion of 0.21 g / m ² (98 mol% as silver chloride) and 1.2 × 10 ⁻³ mol g / m ² of the following cyan dissolved in 0.25 g / m ² of dibutyl phthalate: A layer containing a coupler (C-1).

[0178] layer 6 containing ··· 1.1g / m ² of gelatin and 0.28 g / m ² of Tinuvin 328 of dioctyl phthalate were dissolved in a 0.34 g / m ² (Ciba-Geigy UV absorber) Layer to do.

Layer 7--A layer containing 0.45 g / m ² of gelatin.

As a hardening agent, 2,4-dichloro-
Layer 6 of sodium 6-hydroxy-S-triazine
0.017 g per 1 g of gelatin was added to each of Nos. 7 and 7. A comparative color paper was prepared as described above. Similarly, a magenta coupler (M'-1) described above was changed to a magenta coupler as shown in Table 1 below to prepare an experimental sample as a comparative sample.

Next, these samples were subjected to wedge-shaped exposure by a conventional method and then subjected to the following developing treatment.

Processing step Processing temperature Processing time [1] Color development 38 ° C. 45 seconds [2] Bleach fixing 38 ° C. 45 seconds [3] Water washing 30 ° C. 100 seconds [4] Dry 60-80 ° C. 70 seconds Color developing solution The following bleach-fixing solutions were used.

[Color developer] Potassium chloride 2.0 g Potassium sulfite 0.2 g Hydroxylamines (shown in Table 1) Metal salt (shown in Table 1) Chelating agent (Exemplary compound example (B-I-2)) 0 0.5 g Color developing agent (Exemplified compound example (A-1)) 5.3 g Potassium carbonate 30 g To adjust.

[Bleach-fixing solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml adjust.

[0185] The image solution was placed in a glass container having an air contact area of 140 cm ² ) and stored for 3 weeks, and the color developing solution after the storage was used for development processing.

However, the color paper samples were developed after the color development process with a transit time of 8 seconds before entering the bleach-fixing solution.

After the development processing, the sample is subjected to a Sakura photoelectric densitometer PD.
A-65 (manufactured by Konica Corporation) was used to measure the magenta density (stain) of the unexposed area and the yellow density of the highest density area with the slowest developability.

The coloring degree of the color developing solution was evaluated by first observing the appearance (yellow coloring degree) of the color developing solution, and then observing the following four levels.

++ Marked yellow coloration ++ Colored yellow color + Some yellow coloration-No yellow coloration The results are summarized in Table 1.

[0190] As is clear from Table 1 above, the compound represented by the general formula [I], the compound represented by the general formula [D], and the metal salt (manganese salt and / or cerium salt) according to the present invention
Is used as a color developing solution and the magenta coupler represented by the general formula [M] is used in the light-sensitive material, less magenta stain is generated and the color developing time is 4
It can be seen that a sufficient yellow density can be obtained despite the short time of 5 seconds, and the coloring degree of the developer is small.

[0191]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a color developing solution which is excellent in the storage stability of the color developing solution and gives stable photographic characteristics even when low replenishment processing or rapid processing is carried out. A processing method of the used silver halide color photographic light-sensitive material can be provided.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material which is subjected to a process including at least a color developing step after imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. In the processing method,
At least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [M], and the color developing solution used in the color developing step is at least a compound represented by the following general formula [I] and A method of processing a silver halide color photographic light-sensitive material comprising a compound represented by the general formula [D] and at least one compound selected from a manganese salt and a cerium salt. General formula [M] (In the formula, Ar is a phenyl group and includes a substituted phenyl group. Y is a N-hydroxyalkyl-substituted-p-phenylenediamine derivative, which leaves when a dye is formed by coupling with an oxidant of a coloring agent. R represents an acylamino group, anilino group or ureido group.) General formula [I] (In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom, and both R ₁ and R ₂ are not hydrogen atoms. R ₁ and R ₂ may form a ring. .) General formula [D] (Wherein, R ₂₁ is a hydroxyalkyl group having 2 to 6 carbon atoms,
R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula X ′ and Z ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. )