JPH07113753B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically to a silver halide using a stable color developing solution with improved storage stability. The present invention relates to a method for processing a color photographic light-sensitive material.

Background of the Invention Generally, 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, which is a compound widely used as a preservative of a developing agent in a black and white developer,
The amount used in the color developer 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 performed by an automatic processor while replenishing the replenisher according to the processing amount of the light-sensitive material, but replenishment of the replenisher inevitably causes a large amount of overflow. Because of its occurrence and disposal, this method has become a major economic and pollution problem. 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 is lowered, which also affects the photographic characteristics.

As a technique for improving these drawbacks, Japanese Patent Application No. 58-103839
Japanese Patent Application No. 59-64378, etc., there is a technique for improving the preservability by further using a cerium salt or a manganese salt in a system using the above conventional sulfite and hydroxylamine as a preservative. Is known,
In recent years, the color developing solution has been tending to be replenished more and more for economic reasons and pollution reasons. As a result, the residence time of the developing solution is becoming longer and longer, and the developing solution is often subjected to severer air oxidation. This is becoming more and more difficult to supplement with conventional technology. further,
As the replenishment rate decreases, the amount of photosensitive material processed per unit volume increases, which increases the amount of metal salts such as calcium and magnesium eluted and accumulated from the photosensitive material. The actual situation is that the amount of accumulated bleach-fixing solution and the like is also increasing.

Furthermore, the photographic light-sensitive material was exposed to 30 ° C
Since the processing has been performed under the above high temperature, problems such as coloring of the developer due to high temperature oxidation have become more remarkable. Also, due to the recent compact lab, the transport speed of the automatic developing machine has been slowed down, which makes the transfer time of the photosensitive material from the color developing solution to the next step of bleaching solution or bleach-fixing solution long. Tends to become. Under such circumstances, when the above-mentioned cerium salt or manganese salt technology is used for the color developing solution, the oxidation of the developing solution is promoted by air during this transition time, and the color is developed under this condition. It has been found that when the light-sensitive material after development enters a bleaching solution or a bleach-fixing solution, magenta stain is generated in the light-sensitive material.

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a method for 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.

[Structure of Invention] As a result of various studies by the present inventors, the purpose of the present invention is to
After imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In a method for processing a silver halide color photographic light-sensitive material, which is subjected to processing including at least a color development step, at least one of the silver halide emulsion layers contains silver chloride containing at least 80 mol% of silver halide grains. A color developer containing an emulsion, containing a magenta coupler represented by the following general formula [M] in at least one of the silver halide emulsion layers, and used in the color developing step is represented by the following general formula [I]: Containing at least one compound selected from the group consisting of a manganese salt and a cerium salt, and further having a sulfite concentration of 4 in the color developer.
The inventors of the present invention have found that what can be achieved when the amount is × 10 ^-3 mol / l or less, and thus can achieve the present invention.

General formula [I] (In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom, and neither R ₁ nor R ₂ is a hydrogen atom.
R ₁ and R ₂ may form a ring. ) General formula [M] (In the formula, Ar is a phenyl group and includes a substituted phenyl group. Y is an N-hydroxyalkyl-substituted-p-phenylenediamine derivative, which is released when a dye is formed by coupling with an oxidant of a color developing agent. R represents an acylamino group, anilino group or ureido group.) Of the compounds represented by the general formula [I] of the present invention, for example,
It is known that N, N-diethylhydroxylamine is used as a preservative for a black and white developing agent in a color developer to which a black and white developing agent is added.

Usually, black-and-white developing agents such as hydroquinone, hydroquinone monosulfonic acid, phenidone, and para-aminophenol are relatively stable when used as a black-and-white developing agent in a black-and-white developing solution, and sulfite should be used as a preservative. However, it is known that the storage stability thereof is extremely poor when it is added to the color developing solution to cause a cross-oxidation reaction with the color developing agent. To maintain the black and white developing agent added to the color developer,
Hydroxylamine has little effect.

As a preservative for black and white developing agents added to color developers
As an example of using N, N-diethylhydroxylamine, it is known to be used with phenidone in a so-called external color development method of developing a color photographic light-sensitive material by a reversal method using a color developer containing a coupler. There is. The role of phenidone in this case is to increase the development speed of the external photosensitive material having poor developability and to increase the density of the 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, that is, destroying the coupler. Tokusho
45-22198).

As a preservative for black and white developing agents added to color developers
Other examples of using compounds of the present invention, such as N, N-diethylhydroxylamine, in internal color developers are:
A technique for preserving the phenidone derivative added to the color developing solution (see JP-A-53-32035), and a technique for preserving the phenidone derivative together with hydroquinones (JP-A-53-32035).
52-153437).

As described above, the compound of the present invention is conventionally known to be used as a preservative for a black and white developing agent added to a color developing solution, but a preservative for a color developing agent in a normal color developing solution is used. Is not known as.

In recent years, in the industry, a technique capable of rapid processing of silver halide color photographic light-sensitive materials, and having excellent processing stability and stable photographic characteristics is desired,
In particular, a method for processing a silver halide color photographic light-sensitive material that can be processed rapidly is desired.

In other words, silver halide color photographic light-sensitive materials are run by an automatic processor provided in each laboratory. Users are required to return it, and nowadays, it is even required to return it from the reception desk within a few hours, and there is an urgent need for development of technology that can be processed rapidly.

Regarding the rapid processing of silver halide color photographic light-sensitive materials, the prior arts are examined. [1] Technology by improvement of silver halide color photographic light-sensitive material, [2] Technology by physical means during development processing, [3] Development processing Techniques for improving the composition of the treatment liquid used for.

Among the rapid processing techniques of the above [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-58-95345, JP-A-58-95345). Nos. 60-19140 and JP-A-58-95736) give particularly excellent speed-up performance. However,
When such a high silver chloride-containing light-sensitive material is used, hydroxylamine, which is usually used as a preservative for a color base in a color developing solution, causes a silver development reaction due to its reducing power, which results in an insufficient dye concentration. There is a drawback that becomes. However, when hydroxylamine is not used, the storability of the color developing solution is significantly deteriorated. There is a trade-off relationship. Also, cerium salts and manganese salts remarkably maintain the color developing agent in the presence of hydroxylamine, but when the decomposition speed of hydroxylamine itself is accelerated and the hydroxylamine disappears, its retentivity rapidly increases. It turns out that it will deteriorate. The present inventors have made various investigations, and when using a monoalkylhydroxylamine or dialkylhydroxylamine in combination with a cerium salt and / or a manganese salt, the above-mentioned problems can be solved at the same time. It has been found that can also be improved. Therefore, another object of the present invention is to increase the period for maintaining the homeostasis, and further improve the magenta stain to improve the homeostasis, and it is less likely that a silver development reaction occurs in the high silver chloride light-sensitive material, It is intended to provide a color developing solution for a silver halide color photographic light-sensitive material that enables rapid processing and a method for processing a silver halide color photographic light-sensitive material using the solution.

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

R ₁ and R ₂ each represent an alkyl group or a hydrogen atom that is not a hydrogen atom at the same time, but the alkyl groups represented by R ₁ and R ₂ may be the same or different, and each of them is an alkyl group having 1 to 3 carbon atoms. Are preferred, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. The alkyl group of R ₁ and R ₂ also includes those having a substituent, and examples of the substituent include an amino group, an alkoxy group (for example, a methoxy group, etc.), a sulfonic acid group, a carboxylic acid group, a hydroxyl group, and the like. Is, for example, US Pat.
Hydroxylamines described in 287,125, 3,293,034, 3,287,124 and the like can be mentioned.

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

Preferred specific 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-toluenesulfonate, oxalate, phosphate and acetate.

Among the compounds represented by the above general formula [I], (I-1) and (I-2) are preferably used from the viewpoint of the effect of the object of the present invention.

The concentration of the compound of the present invention in the color developing solution is the same as that of hydroxylamine usually used as a preservative, for example, 0.1 g / l to 50 g / l is preferably used, and more preferably 1 g / 1 to 30 g. / l, more preferably 3g / l ~ 20g
/ l.

The manganese salt and the cerium salt according to the present invention are compounds that release manganese ions or cerium ions when dissolved in a developing solution, and are preferably used below, but are not limited thereto. .

Manganese chloride Manganese sulphate Manganese sulphite Manganese bromide Manganese nitrate Manganese nitrate Potassium permanganate Manganese acetate Manganese oxalate Manganese citrate Ethylenediaminetetraacetic acid Manganese cerium sulfate Cerium nitrate Cerium carbonate Cerium phosphate Cerium cerium Cerium oxalate These The manganese salt and the cerium salt are preferably used in the form of respective ions (manganese ion and cerium ion) in the range of 0.1 mg to 100 mg per color developer, more preferably 0.3 mg to 20 mg, especially 0.5 mg. -10 mg is particularly preferably used from the viewpoint of the effects of the present invention.

Normally, 8x10 of sulfite is used as a preservative in the color developer.
It is used in the range of ⁻³ mol / l to 4 × 10 ⁻² mol / l, but the color developer according to the present invention has a sulfite concentration of color developer 1.
When it is used in an amount of 4 × 10 ^-3 mol or less per unit, it is possible to suppress a decrease in color density, which is considered to be caused by dissolution physical development of a high silver chloride-containing photosensitive material, and an extremely small decrease in preserving ability. Therefore, it is possible to provide a color developing solution which enables rapid processing using a high silver chloride-containing light-sensitive material or a processing method of a silver halide color photograph using the solution, and therefore, in the present invention, a sulfite salt in the color developing solution is provided. Concentration is 4
× 10 ⁻³ mol / l or less is preferably used. Further, it is 0 to 2 × 10 ^-3 mol / l that more effectively exerts this effect.

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

As a color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because the effect of the object of the present invention is satisfactorily achieved and fogging is small.

The p-phenylenediamine compound having a water-soluble group is
Compared with para-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, not only does it have the advantage of not contaminating the light-sensitive material and being less prone to skin rash, In the invention, the object of the present invention can be efficiently achieved by combining with the compound represented by the above general formula [I].

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble _{group, - (CH 2) n-} CH 2 O
H,-(CH ₂ ) _m -NHSO _2- (CH ₂ ) _n -CH ₃ ,-(CH ₂ ) mO- (CH ₂ ) n-CH ₃ ,-(CH ₂ CH ₂ O) nCmH2m + 1 (m and n Each represents an integer of 0 or more), —COOH group, —SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the invention are shown below.

Illustrative color developing agent Among the color-developing agents exemplified above, the occurrence of fogging is small, and therefore, the one preferable for use in the invention is Exemplified 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 salt such as hydrochloride, sulfate, p-toluenesulfonate.

The color developing agent having a water-soluble group used in the present invention is
Usually, it is preferably used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developer, but from the viewpoint of rapid processing, it is 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per color developer. Is more preferable.

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,
4-hydroxymethyl-4-methyl-1-phenyl-3
-It may be used in combination with pyrazolidone or metol.

Further, instead of using the color developing agent as 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 JP-A-58.
No. 65429, No. 58-24137, etc. are used, and specifically, for example, 2 ', 4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4'- (2,4,6-triisopropyl)
Benzenesulfonamido-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 phenylamine, 4-dihexylamino-4 '-(2,4,6-
Triisopropylbenzenesulfonamide) diphenylamine, 4-n-hexyloxy-3'-methyl-4 '
-(2,4,6-Triisopropylbenzenesulfonamide) 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 can be mentioned.

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

The color developing solution according to the present invention includes the following general formula [BI]
To the compound represented by [B-IV],
It is more preferably used in the present invention because it has the effect of more favorably achieving the object and effects of the present invention, and also has the effect of improving bleaching fog that occurs when bleaching or bleach-fixing is performed immediately after color development.

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 , —COOR ₁₆ , Alternatively, it represents a phenyl group. Also, R ₁₅ , R ₁₆ , R ₁₇ and R
₁₈ represents 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, —OR ₁₅ , —COOR ₁₆ , Alternatively, it represents a phenyl group.

Examples of the alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include a methyl group, an ethyl group, an iso-propyl group, and n.
-Propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group and the like, and R ₁₅ , R ₁₆ , R ₁₇ and R
_The alkyl group represented by ₁₈ has the same meaning as described above, 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.

The following are typical examples of the chelating agent of the present invention, but the chelating agent is not limited to these.

(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 (BI-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-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, as a compound particularly preferably used in the present invention, 1,2-dihydroxybenzene-3,5-disulfone is used. Examples of the acid include alkali metal salts such as sodium salt and potassium salt.

In the present invention, the above general formulas [BI] and [B-II]
The compound represented by can be used in the range of 5 mg to 20 g per color developer, preferably 10 mg to 10 g, and more preferably 20 mg to 3 g, to obtain good results.

General formula [B-III] General formula [B-IV] (In the general formulas [B-III] and [B-IV], L is an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -OL ₈
-OL ₈ - or -L ₉ -ZL ₉ - represent. Where Z is N-L
₁₀ -R ₄₀ , N-R ₄₂ or Represents

L _{1 to} L ₁₃ each represent an alkylene group.

R _{33 to} R ₄₃ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof).
Represents However, at least two of R _{33 to} R ₃₆ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least 2 of R _{37 to} R _39.
One is a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). ) In the general formulas [B-III] and [B-IV], the alkylene group represented by L, the cycloalkylene group and the phenylene group, and the alkylene group represented by L _{1 to} L ₁₃ include those having a substituent.

Next, preferable specific exemplary compounds of the compounds represented by the general formulas [B-III] and [B-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-Diaminopropane 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 tetra acetic acid Acetic acid [B-III-11] Ethylenediaminetetrapropionic acid [B-III-12] Phenylenediaminetetraacetic acid [B-III-13] Ethylenediaminetetraacetic acid disodium salt [B-III-14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) ) Salt [B-III-15] Ethylenediaminetetraacetic acid tetrasodium salt [B-III-16] Diethylenetria Minpentaacetic 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] Ethylenediaminetetramethylenephosphonic acid [B-III-20] Cyclohexanediaminetetraacetic acid sodium salt [B -III-21] Diethylenetriamine pentamethylenephosphonic acid [B-III-22] Cyclohexanediaminetetramethylenephosphonic acid [B-IV-1] Nitrilotriacetic acid [B-IV-2] Iminodiacetic acid [B-IV-3] Nitrilotriopropion Acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-5] Iminodimethylenephosphonic acid [B-IV-6] Trisodium nitrilotriacetic acid trisodium salt These general formulas [B-III] or [B-IV] [B-III-1] among the compounds represented by , [B-III-2], [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 preferably used in the range of 0.1 to 20 g per color developing solution, and particularly 0.3 to 5 g in view of the object of the present invention.
The range of is particularly preferably used.

The compounds represented by the general formulas [BI] to [B-IV] may be used alone or in combination.
Furthermore, other chelating agents such as oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid are combined. You may use it.

In the present invention, it is preferable to use a triazyl stilbene-based fluorescent whitening 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, methoxyhetoxy, etc.), an aryloxy group (eg, phenoxy, p-sulfophenoxy etc.), alkyl group (eg methyl, ethyl etc.), aryl group (eg phenyl, methoxyphenyl etc.), amino group, alkylamino group (eg methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino). , Β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, N-
(Β-sulfoethyl) -N′-methylamino, N- (β
-Hydroxyethyl-N'-methylamino, etc.), arylamino 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 is a hydrogen atom,
Represents sodium, potassium, ammonium or lithium.

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

The triazyl stilbene-based whitening agent represented by the general formula [III] is, for example, “Fluorescent Whitening Agent” edited by Chemical Industry Association (Showa 51).
It can be synthesized by the usual method described on page 8.

These triazyl stilbene whitening agents are preferably used in the range of 0.2 to 6 g, and particularly preferably 0.4 to 3 g, per 1 color developer used in the present invention.

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

As the alkaline agent other than the carbonate, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination, The effect of the present invention, that is, the precipitation is not generated, and it can be used in combination within a range of maintaining the pH stabilizing effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

Inorganic and organic antifoggants can be added if necessary.

Further, a development accelerator can be used if necessary.
US Pat. Nos. 2,648,604 and 3,67 as development accelerators.
1,247, 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. 2,531,832,
No. 2,950,970, No. 2,577,127, and Japanese Patent Publication No. 44-9
Polyethylene glycol and its derivatives described in Japanese Patent No. 504, and nonionic compounds such as polythioethers are included. Further, benzyl alcohol, phenethyl alcohol described in U.S. 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 for poorly soluble organic solvents typified by benzyl alcohol, by using the color developing solution for a long period of time, tar easily occurs particularly in running processing in a low replenishment system, and the generation of such tar is Depending on the proximity of the processed paper to the photosensitive material, it may even cause a serious failure that significantly impairs its commercial value.

In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome to use a stirring device to adjust the color developing solution itself, but also the use of such a stirring device results in poor solubility. Therefore, there is a limit to the effect of promoting development.

Furthermore, poorly soluble organic solvents have a large pollution load value such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since there are problems such as requiring labor and cost, it is preferable to reduce or eliminate the use amount as much as possible.

Further, the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, 44-9509 described each publication The compound 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-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multi-layer effect accelerator can be used.

Each component of the color developing solution can be prepared by sequentially adding and stirring to constant 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 in a concentrated aqueous solution, or in a solid state prepared in advance in a small container is added to water and prepared by stirring to prepare a color developing solution of the present invention. Obtainable.

In the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 13.0.

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the quicker the processing can be performed in a shorter time, which is preferable, but it is preferable that the temperature is not so high from the viewpoint of image storage stability, and the temperature is preferably 33 ° C. or higher and 45 ° C. or lower.

The color development time is generally about 3 minutes and 30 seconds, but it is preferably within 2 minutes from the viewpoint of speeding up.
Further, it is preferable to carry out in the range of 30 seconds to 1 minute 30 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 by contact with a carrier impregnated with the processing solution, or a developing method using a viscous processing solution. You can As the processing step, substantially, color development-bleach-fixing-washing (or stabilizing) is preferably used, and in the bleach-fixing step, the bleaching step and the fixing step may be separately provided.

The bleaching agent that 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 preferred organic acid used for forming such a metal 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] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyletherdiaminetetraacetic acid [10] Glycoletherdiaminetetraacetic 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 These bleaching agents are 5 to 450 g / l, Preferably 20-250g
Use with / l. 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. In addition, a bleach-fixing solution comprising a composition containing a small amount of a halide such as ethylenediaminetetraacetic acid iron (III) complex bleach and the above silver halide fixing agent such as ammonium bromide, or conversely, a halogenating agent such as ammonium bromide. A bleach-fixing solution having a composition containing a large amount of silver added, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a large amount of a halide such as ammonium bromide are also used. be able to. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium bromide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 20 g to 250 g / l are used.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as 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 kinds. 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 includes JP-A-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 9.5, the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or lower and 3 ° C. or higher, preferably 5 ° C. higher than the processing solution temperature in the color developing tank
Although it is used at a lower temperature, it is preferably used at 55 ° C or lower while suppressing evaporation and the like.

The halide grains used in the silver halide color photographic light-sensitive material applicable to the present invention are silver chloride, silver bromide, silver iodide,
Although any of silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures thereof can be used, those particularly preferably used from the viewpoint of rapid processability are particularly preferable. A silver halide grain containing at least 80 mol% of silver chloride, preferably 90 mol% or more, more preferably 95 mol% or more.

In a silver halide color photographic light-sensitive material composed of a silver halide emulsion containing such silver halide grains, the dye concentration is remarkably reduced due to hydroxylamine.
The color developer of the present invention is applied particularly advantageously.

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. The silver bromide content 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% or less. Such a silver halide grain substantially consisting of silver chloride according to the present invention contains 80% by weight or more of all the silver halide grains in the silver halide emulsion layer in which the silver halide grain is contained. It is preferable that the content is 100%, more preferably 100%.

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal, or another crystal, and any ratio of [100] plane to [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 have a layered structure (core / shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-17).
No. 0070) can also be used.

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

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

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

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

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

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

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent No. 929.080 and US Pat.
1,658, 2,493,748, 2,503,776, 2,5
No. 19,001, No. 2,912,329, No. 3,656,959, No. 3,
672,897, 3,694,217, 4,025,349, and
4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030
No. 52-24844 and the like. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
72,908, No. 2,739,149, No. 2,945,763, cyanine dyes such as those described in British Patent No. 505,979,
Typical examples thereof include merocyanine dyes and complex cyanine dyes. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.Nos. 2,269,234, 2,270,378, and 2,442,71.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in No. 0, No. 2,454,629, No. 2,776,280 and the like. Furthermore, U.S. Pat.Nos. 2,213,995 and 2,493,748
No. 2,519,001, West German Patent No. 929,080, and the like, a cyanine dye, a merocyanine dye, or a complex cyanine dye can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

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

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

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

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

Further, as a combination of thiacarbocyanine with other carbocyanine, for example, Japanese Patent Publication Nos. 43-4932 and 43-4932
No. 4933, No. 45-26470, No. 46-18107, No. 47-8741,
JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and a styryl dye can be advantageously used.

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

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

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 584,60.
No. 9, No. 1,277,429, JP-A No. 48-85130, No. 49-996.
No. 20, No. 49-114420, No. 49-129537, No. 52-108
No. 115, No. 59-25845, No. 59-111640, No. 59-111
641, U.S. Patent No. 2,274,782, No. 2,533,472, No. 2,956,079, No. 3,125,448, No. 3,148,187,
No. 3,177,078, No. 3,247,127, No. 3,260,601
No. 3, No. 3,540,887, No. 3,575,704, No. 3,653,90
No. 5, No. 3,718,472, No. 4,071,312, No. 4,070,3
Those described in No. 52 can be mentioned.

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

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

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 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, an acylamino group, and a phenyl group represented by Ar is 2 It may have one 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,
A butyl group, a t-butyl group, a t-pentyl group and the like are preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable.

Alkoxy group: methoxy group, ethoxy group, butoxy group,
sec-butoxy group, iso-pentyloxy group, etc.,
Particularly, an alkoxy group having 1 to 5 carbon atoms is preferable.

Aryloxy group: a phenoxy group, a β-naphthoxy group and the like, but this aryl portion may further have the same substituent as the phenyl group represented by Ar.

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

Carbamoyl group: Alkylcarbamoyl group such as carbamoyl group and dimethylalbamoyl group Sulfamoyl group: Alkylsulfamoyl group such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group and ethylsulfamoyl group sulfonyl group: methanesulfonyl Group, ethanesulfonyl group, butanesulfonyl group, etc., alkylsulfonyl group, arylsulfonyl group, sulfonamide group: methanesulfonamide group, toluenesulfonamide group, etc., alkylsulfonamide group, arylsulfonamide group, etc. Acylamino group: acetamino group, pivaloylamino group , Benzamide group, etc. are particularly preferably halogen atoms, with chlorine being most preferred.

Y: N-hydroxyalkyl-substituted-p-phenylenediamine derivative Represents a group that 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,
It represents a group of atoms required to form a 5- or 6-membered ring with an atom selected from sulfur atoms. ) Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc.Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy Group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-
Octylphenylthio group, 2,5-dihexyloxyphenylthio group, etc.Alkylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonylmethylthio group,
Phenoxyethylthio group, etc. Pyrazolyl group, imidazolyl group, triazole group, tetrazolyl group, etc. When R: R is an acylamino group, examples thereof include acetamide group, isobutylamino group, benzamide group, 3- [α
-(2,4-di-tert-amylphenoxy) butylamide] benzamide group, 3- [α- (2,4-di-tert-amylphenoxy) acetamido] benzamide group, 3-
[Α- (3-pentadecylphenoxy) butyramide]
Benzamide group, α- (2,4-di-tert-amylphenoxy) butyramide group, α- (3-pentadecylphenoxy) butyramide group, hexadecanamide group, isostearoylamino group, 3- (3-octadecenyl group Succinimide) benzamide group or pivaloylamino group, etc., and when R is an anilino group, examples thereof include 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) tetradecanamido) 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 an ureido group, examples thereof include 3-
{(2,4-di-tert-aminophenoxy) acetamide}
Examples thereof include a phenylureido group, a phenylureido group, a methylureido group, an octadecylureido group, a 3-tetradecanamidophenylureido group and an N, N-dioctylureido group. 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 formula [I].

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

Specific examples are 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 sec-butoxy group and iso-pentyloxy group is preferable.

Alkyl group: methyl group, ethyl group, iso-propyl group,
An alkyl group having 1 to 5 carbon atoms such as a butyl group, a t-butyl group and a 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 is 1 or 2
Represents When n is 2, R ₁ may be the same or different. The group capable of substituting on the benzene ring represented by R ₁ includes
Halogen atom, R ′, R ″ and R may be the same or different,
It represents a hydrogen atom or an alkyl group, an alkenyl group or an aryl group, each of which may have a substituent. Of these, R′CONH−, R′SO ₂ NH−, Is.

Specific examples of the magenta coupler are shown below, but the magenta coupler is not limited thereto.

Examples of R in the above formula include the following.

M-1 -NHCOC ₁₃ H ₂₇ M-2 -NHCOC ₁₄ H ₂₉ Examples of Y 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, and more preferably 0.01 mol per mol of silver halide.
~ 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].

Examples of cyan couplers include ordinary phenol compounds and naphthol compounds, for example, U.S. Patents 2,369,929 and 2,4.
34,272, 2,474,293, 2,895,826, 3,253,92
No. 4, No. 3,034,892, No. 3,311,476, No. 3,386,301,
3,419,390, 3,458,315, 3,476,563, 3,5
Those described in No. 31,383 and the like 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 a pyrazolone-based magenta coupler, U.S. Pat.
No. 8, No. 3,062,653, No. 3,127,269, No. 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
84,514, 3,888,680, JP-A-49-29639, 49-11
No. 1631, No. 49-129538, No. 50-13041, Japanese Patent Publication No. 53-4716
No. 7, No. 54-10491, No. 55-30615; pyrazolotriazole-based magenta couplers include couplers described in US Pat. No. 1,247,493 and Belgian patent 792,525, which are diffusion resistant As the colored magenta coupler of, a compound in which an arylazo substituent is generally used at the coupling position of a colorless magenta coupler is used, for example, U.S. Patents 2,801,171 and 2,983,608,
3,005,712, 3,684,514, British Patent 937,621,
Examples thereof include compounds described in JP-A-49-123625 and JP-A-49-31448.

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

As the photographic yellow coupler, an open-chain 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. Patents 2,875,057 and 3,265,506.
No., No. 3,664,841, No. 3,408,194, No. 3,277,155,
No. 3,447,928, No. 3,415,652, Japanese Patent Publication No. 49-13576, JP-A No. 48-29432, No. 48-68834, No. 49-10736, No. 49-1
22335, 50-28834, 50-132926 and the like, together with the synthetic method.

The amount of the above diffusion-resistant coupler used in the present invention is generally from 0.05 to 1 mol per mol of silver in the photosensitive silver halide emulsion layer.
2.0 mol.

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 that releases a development inhibitor upon development is also included in the present invention.
297,445, 3,379,529, West German patent application (OLS) 2,41
7,914, JP-A Nos. 52-15271, 53-9116, and 59-12383.
No. 8, No. 59-127038, etc. are mentioned.

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 inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. , U.S. Patent 3,227,5
54, 4,095,984, 4,149,886, etc.

The above-mentioned DIR coupler has a property that upon coupling reaction with an oxidant 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. Patent Nos. 3,652,345, 3,928,041, and 3,958,993.
No. 3,961,959, No. 4,052,213, JP-A-53-110529
No. 54-13333, No. 55-161237 and the like, when a coupling reaction with an oxidant of a color developing agent, a development inhibitor is released but a compound which does not form a dye is also included. Be done.

Furthermore, JP-A Nos. 54-145135, 56-114946 and
When reacted with an oxidant of a color developing agent as described in 57-154234, the mother nucleus forms a dye or a colorless compound, on the other hand, the detached timing group undergoes an intramolecular nucleophilic substitution reaction or an elimination reaction. The so-called timing DIR compounds, which are compounds that release development inhibitors, are also included in the present invention.

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

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, antifoggant, stabilizer, ultraviolet absorber, described in Research Disclosure Magazine 17643,
A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloid used for preparing the emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, a protein such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

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

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

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . 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 depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

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

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

More specifically, the present invention can 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 reduced.

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

[Example 1] On a polyethylene-laminated paper support, the following layers were sequentially coated on the support side to prepare a comparative photosensitive material sample.

Layer 1 ... 1.3 g / m ² of gelatin, 0.34 g / m ² (in terms of silver, the same applies below) of a blue-sensitive silver chlorobromide emulsion (97 mol% as AgCl), and
1.0 × 10 ^-3 dissolved in 0.64 g / 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 gelatin, 0.22 g / m ² green sensitive silver chlorobromide emulsion (98 mol% as AgCl) and 1.3 × 10 ^-3 mol g dissolved in 0.23 g / m ² dioctyl phthalate. A layer containing the following magenta coupler (M'-1) of / m ² .

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

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

Layer containing a layer 6 ... 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 7 ... Layer containing 0.45 g / m ² of gelatin.

As a hardening agent, sodium 2,4-dichloro-6-hydroxy-S-triazine was added to layers 2, 4 and 7 so that the amount was 0.013 g per 1 g of gelatin.

A comparative color paper was prepared as described above. Similarly, the magenta coupler (M'-1) was changed to a magenta coupler as shown in Table 1 below to prepare and use a sample of the present invention and 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 development processing.

 Processing process Processing temperature Processing time [1] Color development 38 ℃ 45 seconds [2] Bleach fixing 38 ℃ 45 seconds [3] Wash with water 30 ℃ 100 seconds [4] Dry 60-80 ℃ 70 seconds Color developer and bleach fixing The following liquid was used.

[Color developer] Potassium chloride 2.0 g Potassium sulfite 0.2 g Hydroxylamines (described in Table 1) Metal salt (described in Table 1) Chelating agent (Exemplified compound example (B-I-2)) 0.5 g Color developing agent ( Exemplified compound example (A-1)) 5.3g Potassium carbonate 30g Add water to make 1 and add pH 1 with potassium hydroxide and 50% sulfuric acid.
Adjust to 0.15.

[Bleach fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Add 1 to the total amount of carbonic acid. Adjust to pH 7.20 with potassium or glacial acetic acid.

The above color developing solution was used at 38 ° C and the opening ratio was 140 cm ² (1
The above color developing solution was placed in a glass container having an air contact area of 140 cm ² ) and stored for 3 weeks. The color developing solution after 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-fix solution.

Using the Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.), measure the magenta density (stain) of the unexposed area and the yellow density of the highest density area with the slowest developability of the sample after development processing. did.

The results are summarized in Table 1.

As is clear from Table 1 above, the compound represented by the general formula [I] and the metal salt (manganese salt and / or
(Or cerium salt) in a color developing solution, and when the magenta coupler represented by the general formula [M] is used in the light-sensitive material, the generation of magenta stain is small and the color developing time is as short as 45 seconds. It can be seen that a sufficient yellow density can be obtained regardless of time. However, when any one of these elements is lacking, either effect becomes insufficient. The use of metal salts outside the scope of the invention likewise gives unsatisfactory results.

[Example 2] Color developing agent (A- in the color developing solution used in Example 1)
When 1) was changed to (B-1) or (B-2) below, and a similar experiment was conducted, the magenta stain in the unexposed area deteriorated by 0.02. Similarly, the color developing agent (A-1) of Example 1 was used as the exemplified compounds (A-2) and (A-
When the same experiment as in Example 1 was carried out by changing each of 4) and (A-15), almost the same result was obtained.

[Example 3] The silver halide composition of the blue-sensitive layer in the silver halide color light-sensitive material used in Example 1 and Experiment No. 11 was changed as shown in Table 2 below, and otherwise the same as in Example 1. The same experiment. The results are summarized in Table 2.

As is clear from Table 3, when the silver halide composition of the silver halide color photographic light-sensitive material is 80 mol% or more of silver chloride, the yellow dye concentration becomes almost sufficient, but the silver chloride content is lower than this. In this case, it can be seen that a sufficient dye concentration cannot be obtained.

Further, when it is 90 mol% or more, a better dye concentration is obtained,
Further, it is found that when it is 95 mol% or more, it becomes particularly good. With respect to this effect, when the silver halide compositions of the red-sensitive layer and the green-sensitive layer were changed in the same manner, the same results were obtained for the cyan dye concentration and the magenta dye concentration. Especially, the silver chloride content of all silver halide emulsion layers is 80 mol% or more, particularly 90 mol% or more.
It has been found that at mol% and above, especially above 95 mol%, all layers give preferred dye densities and give perfect black.

Example 4 The exemplary compound (A′-) was added to the color developing solution used in Example 1.
2), (A'-4) and (A'-9) (all are triazyl stilbene optical brighteners) were added in an amount of 2 g / l, and the same experiment as in Example 1 was carried out except that magenta was used. Occurrence of stain is 0.01 to 0.02, that is, 20% to 40
% Has also decreased.

Example 5 The color developer used in Experiment No. 11 of Example 1 was mixed with 1 ppm of copper ion and 0.3 ml / l of a bleach-fixing solution, and the other examples were used.
The same experiment was performed.

However, in the color developing solution, the exemplified compounds (B-I-2), (b-I-3) (B-III-2), and
(B-IV-1) and 2-phosphonobutane-1, for comparison,
2,4-tricarboxylic acid, tetrapolyphosphoric acid 1g /
l added.

First, the appearance (yellowness) of the color developing solution was observed, and the results are shown in Table 3. However, the appearance of the liquid was evaluated according to the following four grades.

++ Significant yellow coloring ++ Yellow coloring + Slight yellow coloring − No yellow coloring As is clear from Table 3 above, general formulas (BI) to (B-
When the compound represented by IV) is used in combination with the developing solution of the present invention, the decomposition amount of the color developing agent is small and the degree of coloring is further improved even under extremely severe conditions such as the mixing of heavy metal ions. Is understood. Furthermore, it is also effective against M stain when heavy metal ions are mixed. However, this effect is hardly obtained with chelating agents other than the general formulas (BI) to (B-IV).

[Example 6] Using the color paper sample prepared in Example 1, the concentration of potassium sulfite in the color developer before storage used in Experiment No. 11 of Example 1 was changed as shown in Table 4 below. A development process was performed according to the processing steps of Example 1. The yellow dye density (highest density part) of the processed sample was measured.

As is clear from Table 4 above, a sufficient yellow density was obtained when the sulfite concentration in the color developer according to the present invention was 1.6 × 10 ^-2 mol / l or less, and particularly 4 × 10 ^-3 mol / l. Particularly good yellow dye density can be obtained when
It turns out that it is suitable for rapid processing.

[Example 7] The amount of cerium ion added to the color developer No. 11 used in Example 1 was 0 to 400 mg / l as shown in Table 5 below.
The same experiment as in Example 1 was conducted by changing the range.

The results are summarized in Table 5.

From Table 5 above, when the metal salt according to the present invention is present in an ionic form of 0.1 to 100 mg / l, the decomposition and coloring degree (tar property) of the color developing solution are good, and the magenta stain is also good. I understand.

Especially good at 0.3-20 mg / l, especially 0.5-10 mg
It turns out that it is particularly good with / l.

Continuation of the front page (56) Reference JP-A-60-31139 (JP, A) JP-A-59-228251 (JP, A) JP-A-60-205541 (JP, A) JP-A-58-85864 (JP , A) JP 58-136032 (JP, A) JP 58-209734 (JP, A) JP 53-32035 (JP, A) JP 57-185434 (JP, A)

Claims (1)

[Claims] 1. A halogen which is subjected to a treatment including at least a color developing step after imagewise exposing a silver halide color photographic light-sensitive material having a silver halide emulsion layer having at least one silver halide emulsion layer on a support. In the method for processing a silver halide color photographic light-sensitive material, at least one of the silver halide emulsion layers comprises a silver halide emulsion containing at least 80 mol% of silver chloride and silver halide grains.
Further, at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [M],
The color developing solution used in the color developing step contains a compound represented by the following general formula [I] and at least one compound selected from a manganese salt and a cerium salt, and further, the sulfite concentration in the color developing solution is 4 x 10 ^-3 mol
A method for processing a silver halide color photographic light-sensitive material, characterized in that it is less than or equal to 1 / l. 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 [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 is released when a dye is formed by coupling with an oxidant of a color developing agent. R represents an acylamino group, an anilino group or a ureido group.)