JPH0833644B2 - 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. 58-10383.
A technique for improving preservability by further using a cerium salt or a manganese salt in a system using the above-mentioned conventional sulfite salt and hydroxylamine as a preservative as disclosed in Japanese Patent Application No. 9 and Japanese Patent Application No. 59-64378. However, in recent years, the color developer tends to be replenished more and more due to economical reasons and pollution reasons, and the residence time of the developer is becoming longer and longer. Air oxidation is becoming more common, and it is becoming more and more difficult to compensate with conventional techniques. Furthermore, the amount of the light-sensitive material processed per unit volume increases with the reduction of the replenishment amount, which increases the amount of metal salts such as calcium and magnesium eluted and accumulated from the light-sensitive material, and also as a bleaching agent. The actual situation is that the amount of accumulated bleach-fixer containing iron complex salts is increasing.

Furthermore, with the speeding up of processing, 30
Since processing is performed at a high temperature of ℃ or more, troubles such as coloring of a developing solution 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 technique of cerium salt or manganese salt as described above is used for a color developing solution, air oxidizes the developing solution during this transition time, and under this condition, color developing It has been found that when the light-sensitive material of the solution enters a bleaching solution or a bleach-fixing solution, a problem occurs that magenta stains are 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 performance even when the color developer is replenished at a low level. A second object is to provide a processing method of a silver halide color photographic light-sensitive material in which a magenta stain generated in a bleaching solution or a bleach-fixing solution is improved in a low speed automatic processor.

Other objects of the invention will become apparent below.

[Structure of the Invention] As a result of various studies conducted by the present inventors, the above-mentioned object of the present invention was that after imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. In the method for processing a silver halide color photographic light-sensitive material, which is subjected to processing including at least a color development step, the halogenated grains in the silver halide emulsion layer are at least silver chloride.
The color developer containing 80 mol% or more of the silver halide emulsion layer contains a magenta coupler represented by the following general formula [I] in at least one of the silver halide emulsion layers, and the color developing solution used in the color developing step has the following general formula [ The present invention has been completed by finding out what can be achieved when the compound represented by A] and at least one compound selected from a manganese salt and a cerium salt are contained.

General formula [I] (In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by the Z may have a substituent.

X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ) General formula [A] (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. ) Among the compounds represented by the general formula [A] of the present invention, for example, N, N-diethylhydroxylamine is used as a preservative of a black and white developing agent in a color developer containing a black and white developing agent. It has been known.

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 developer, and sulfite should be used as a preservative. However, when added to the color developing solution, a cross oxidation reaction with the color developing agent occurs,
It is known that its storage stability is extremely poor. Hydroxylamine has almost no effect on the preservation of the black and white developing agent added to the color developing solution.

An example of using N, N-diethylhydroxylamine as a preservative of a black and white developing agent added to a color developer is to develop a color photographic light-sensitive material by a reversal method using a color developer containing a coupler. It is known to be used with phenidone in the so-called external color method. 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.

Further, in a magenta color developing solution containing no such phenidone, N, N-diethylhydroxylamine is
It is known that destruction of the coupler rather adversely affects the storage stability of the external color developer (see Japanese Patent Publication No. 45-22198).

Another example of using a 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, in an internal color developing solution, in a color developing solution. A technique for preserving the added phenidone derivative (see JP-A-53-32035) and a technique for retaining the phenidone derivative together with hydroquinones (see JP-A-52-153437) can also be mentioned. .

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, there has been a demand in the art for a technique capable of rapid processing of a silver halide color photographic light-sensitive material, and moreover, having excellent processing stability and obtaining stable photographic characteristics. A method of processing a silver halide color photographic light-sensitive material is desired.

In other words, silver halide color photographic light-sensitive materials are lined with an automatic developing machine 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 color bases 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 disadvantage that it becomes a thing. 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, further improve the magenta stain, improve the homeostasis, less likely to develop silver development reaction 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.

In the general formula [A], R ₁ and R ₂ each represent an alkyl group or a hydrogen atom which is not a hydrogen atom at the same time.
The alkyl groups represented by R ₁ and R ₂ may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group of R ₁ and R ₂ also includes those having a substituent, and R ₁ and R ₂ may be bonded to form a ring,
For example, a heterocycle such as piperidine or morpholine may be formed.

Specific compounds of the hydroxyamine compound represented by the general formula [A] are described in US Pat. Nos. 3,287,125 and 3,293,0.
No. 34, No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention are usually free amines, hydrochlorides, sulfates, p-toluenesulfonates, oxalates,
It is used in the form of phosphate, acetate, etc.

The concentration of the compound represented by the general formula [A] of the present invention in the color developer is usually 0.1 g / l to 50 g / l, preferably 1 g / l to 3
It is 0 g / l, and more preferably 3 g / l to 20 g / l.

The compound represented by the general formula [A] of the present invention is used in a conventional color developing solution for a silver halide color photographic light-sensitive material in place of hydroxylamine sulfate which has been widely used as a preservative. However, among the compounds of the present invention, for example, N, N-diethylhydroxylamine is known to be used as a preservative for a black-and-white developing agent in a color developing solution to which a black-and-white developing agent is added. In a so-called external color developing method in which a color photographic light-sensitive material is developed by a reversal method using a color developing solution containing a coupler, there is a technique used together with phenidone. (Japanese Patent Publication Sho 45
-22198).

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

Manganese chloride Manganese sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese nitrate Potassium permancanate Manganese acetate Manganese oxalate Manganese citrate Ethylenediaminetetraacetic acid Manganese cerium sulfate Cerium nitrate Cerium carbonate Cerium phosphate Cerium acetate 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, more preferably 0.3 mg to 20 mg, per color developer.
In particular, from 0.5 mg to 10 mg in view of the effect of the object of the present invention,
It is preferably used.

Normally, 8x of sulfite is used as a preservative in the color developer.
It is used in the range of 10 ⁻³ mol / l to 4 × 10 ⁻² mol / l, and is used in the color developer according to the present invention with a sulfite concentration of 4 × 10 ⁻³ mol or less per color developer. In this case, it is possible to suppress the decrease in color density, which is considered to be caused by the dissolution physical development of the high silver chloride-containing photosensitive material, and the deterioration of the preserving ability is extremely small. In the present invention, the concentration of sulfite in the color developing solution is 4 because it is possible to provide a color developing solution or a processing method for silver halide color photography using the solution.
× 10 ⁻³ mol / l or less is preferably used. Further, it is 0 to 2 × 10 ⁻³ mol / l or less that this effect is exhibited more effectively.

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 it exhibits the desired effects of the present invention and generates little fog.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the light-sensitive material and the skin than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage of being less prone to fogging, but in particular, the object of the present invention can be efficiently achieved by combining it with the compound represented by the general formula [A] in the present invention.

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 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) nCmH2m + 1 ( m and n each represent 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 ones which are preferably used in the present invention because of low occurrence of fog are exemplified by 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 preferably used in the range of 1 × 10 ⁻² to 2 × 10 ⁻¹ mol per 1 color developing solution, but from the viewpoint of rapid processing, color development is performed. The range of 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liquid is more preferable.

Further, the color developing agents are used alone or in combination of two or more, and if desired, they are used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. May be.

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-SHO
58-65429, those described in paragraphs 58-24137 etc. are used,
Specifically, for example, 2 ', 4'-bismethanesulfonamido-4-diethylaminodiphenylamine, 2'-methanesulfonamido-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) benzenesulfonamidodiphenylamine, 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.

When the color developing solution according to the present invention contains a compound represented by the following general formula [D], it not only exerts the effect of the present invention more favorably but also has an effect on air oxidation of the color developing solution. It is more preferably used to show an improvement effect.

General formula [D] (In the formula, R ₂₁ represents a hydroxyalkyl group having 2 to 6 carbon atoms, R _21
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 In the above formula, n ₁ is an integer X ′ and Z ′ of ₁ to 6 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-ami 2- (hydroxymethyl) -1,
3-propanediol.

These compounds represented by the general formula [D] are preferably used in the range of 3 g to 100 g, more preferably 6 g to 50 g, per 1 color developing solution in terms of the effect of the present invention.

The color developing solution according to the present invention has the following general formula [BI]
To the compound represented by [B-IV], the effects of the present invention can be better achieved, and after color development,
It is more preferably used in the present invention because it also has an effect of improving bleaching fog that occurs when bleaching or bleach-fixing treatment is carried out immediately.

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 , Or, it represents a phenyl group. 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, —OR ₁₅ , —COOR ₁₆ , Or, it represents a phenyl group.

Examples of the alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include a methiki group, an ethyl group, an iso-propyl group,
Examples thereof include n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, and the alkyl represented by R ₁₅ , R ₁₆ , R ₁₇ and R _18. The group has the same meaning as above,
Furthermore, an octyl group etc. can be mentioned.

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.

(BI-1) 4-isopropyl-1,2-dihydroxybenzene (BI-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (BI-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-
Examples thereof include disulfonic acid, which can also be used as an alkali metal salt such as sodium salt and potassium salt.

In the present invention, the above general formulas [BI] and [BI]
The compound represented by the formula [I] is 5 mg to 20 g per color developing solution.
Can be used in the range of, preferably 10mg ~ 10g,
More preferably, good results are obtained by adding 20 mg to 3 g.

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. Wherein 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] diethylenetriamine pen Acetate pentasodium salt [B-III-17] ethylenediamine-N-(beta-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] Nitrilotripropion 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], [B-III-1] and [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, methoxyethoxy etc.), an aryloxy group (eg phenoxy, p -Sulfophenoxy etc.), an alkyl group (eg methyl, ethyl group), an aryl group (eg phenyl, methoxyphenyl group), an amino group, an 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 and the like), arylamino groups (eg, anilino, o-, m-, p-sulfoanilino, o-, m-, p-chloroanilino, o
-, M-, p-triidino, 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 not limited to these.

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

These triazylstilbene-based brighteners are preferably used in the range of 0.2 to 6 g, more preferably 0.4 to 3 g, per color developing solution 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. U.S. Pat.Nos. 2,648,604 and
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, Second 2,531,832
No. 2,950,970, No. 2,577,127, and Shokoku Sho
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, etc. described in JP-A-44-9504 are included. Further, benzyl alcohol, phenethyl alcohol, and acetylene glycol, methyl ethyl ketone, which are described in US Pat. No. 2,304,925,
Examples thereof include cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines.

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 (a so-called DIR coupler), a development inhibitor releasing compound, or the like can be added.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

Each component of the color developer is added to a certain amount of water in order,
It can be prepared by stirring. 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
The higher the temperature is from 50 ° C. to 50 ° C., the faster the rapid processing is possible, which is preferable. However, the image storage stability is preferably not so high, and the temperature is preferably from 33 ° C. to 45 ° C.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but it is preferably within 2 minutes for speeding up, and more preferably in the range of 30 seconds to 1 minute and 30 seconds.

The color developing solution according to the present invention may be applied to various processing methods such as a spray method of a processing solution, a web method by contact with a carrier impregnated with the processing solution, or a developing method using a viscous processing solution. it 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
A metal ion such as iron, cobalt, or copper is coordinated 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 a 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 20-25
Use at 0g / 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. Also,
A bleach-fixing solution comprising a composition containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and the above-mentioned silver halide fixing agent and a small amount of a halide such as ammonium bromide, or conversely a large amount of a halide such as ammonium bromide. It is also possible to use a bleach-fixing solution having a composition added to the above, and 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. . As the halide, hydrogen chlorides in addition to ammonium bromide,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

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-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffering agents such as 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-B-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910.
Various bleaching accelerators described in JP-B Nos. 45-8836, 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 p
Used at H5.0 or higher and pH9.5 or lower, preferably pH6.0 or higher
Used below 8.5, and further stated the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or less and 3 ° C. or more, preferably 5 ° C., higher than the temperature of the processing solution in the color developing tank.
Although it is used at a lower temperature, it is desirably used at a temperature of 55 ° C. or less 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, silver chlorobromide, silver chloroiodide, silver iodobromide, chloroiodobromide. Any of silver and a mixture thereof can be used, but particularly preferably used from the viewpoint of rapid processability is a silver halide grain containing at least 80 mol% of silver chloride, The content is preferably 90 mol% or more, 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 dye concentration due to hydroxylamine is remarkably lowered, so that the color developing solution of the present invention is particularly advantageously applied.

The silver halide emulsion containing silver halide grains composed 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%
It is preferably 5 mol% or less, more preferably 1 mol% or less, and preferably 0.5 mol% or less when silver iodide is present. Such a silver halide grain substantially consisting of silver chloride according to the present invention contains 80% or more by mol% of all 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 grains used in the present invention may be a normal crystal, a twin crystal or any other 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 be 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 (JP-A-58-113934, Japanese Patent Application No.
0070) can also be used.

The silver halide grains used in the present invention may be obtained by any of the preparation methods such as an acid method, a neutral method, and an ammonia method.

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

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

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as primary sensitizers.
Tin salts, thiourea dioxide, polyamines, etc .; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 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 (of these Certain compounds act as sensitizers or fog inhibitors depending on the amount of the sensitizers, etc.) alone or in combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and selenium). Chemical sensitization in combination with a sensitizer).

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

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

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include, for example, West German Patent No. 929,080 and U.S. Pat.
31,658, 2,493,748, 2,503,776, 2,
No. 519,001, No. 2,912,392, No. 3,656,959, No.
No. 3,672,897, No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-140
Examples thereof include those described in No. 30, No. 52-24844, etc. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Cyanine dyes, merocyanine dyes or composite cyanine dyes described in 2,072,908, 2,739,149, 2,945,763 and British Patent No. 505,979 can be mentioned as typical examples. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Patent Nos. 2,269,234, 2,270,378, and 2,44.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in No. 2,710, No. 2,454,629, No. 2,776,280 and the like. Further, U.S. Pat.Nos. 2,213,995 and 2,49
Cyanine dyes, merocyanine dyes or complex cyanine dyes as described in 3,748, No. 2,519,001, West German Patent No. 929,080, etc. 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 optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

Representative examples of particularly preferred spectral sensitization methods include, for example, Japanese Patent Publication No. 43-4936 (JP-B-43-4936) relating to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
Nos. 43-22884, 45-18433, 47-37443, 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.

Examples of a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine include, for example, JP-B-45-25831, JP-B-47-11114, and JP-B-47-11114.
-25379, 48-38406, 48-38407, 54-34535
No., 55-1569, JP-A-50-33220, 50-38526,
51-107127, 51-115820, 51-135528, 52-
No. 104916, No. 52-104917 and the like.

Further, as for the combination of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
JP-A-57-1483 and merocyanine include, for example, JP-B-48-38408, JP-A-48-41204, and JP-A-50-406.
No. 62, JP-A-56-25728, JP-A-58-10753, JP-A-58-91445
No. 59-116645 and No. 50-33828.

Further, examples of combinations of thiacarbocyanine with other carbocyanines include, for example, Japanese Examined Patent Publication Nos. 43-4932 and 4
3-4933, 45-26470, 46-18107, 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 styryl dyes 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 used in an amount of 2 per mol of silver in the emulsion layer.
It is preferable to use x10 ^{-3 to} 5 x 10 ^-1 mol, and more preferably 1 x 10 ^-2 to 1 x 10 ^-1 mol.

Next, the magenta coupler of the general formula [I] according to the present invention will be described in detail.

General formula [I] In the magenta coupler represented by, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent which can be eliminated by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and the alkynyl group have 2 to 32 carbon atoms.
, A cycloalkyl group and a cycloalkenyl group are preferably those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkyl group, alkenyl group and alkynyl group may be linear or branched.

Further, these alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group are substituents [for example, aryl, cyano, halogen atom, heterocycle,
In addition to cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl and the like which are substituted through a carbonyl group, further via a hetero atom Those specifically substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfa Moylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, those substituted via a nitrogen atom such as ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl,
Those substituted through a sulfur atom such as sulfinyl and sulfamoyl, those substituted through a phosphorus atom such as phosphonyl, and the like}].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4 ′-{α- [4 ″ (p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino} phenylpropyl group, 3- {4 ′-[α-
(2 ″, 4 ″ -di-t-amylphenoxy) butanamido] phenyl} -propyl group, 4- [α- (o-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group, cyclopentyl group, cyclohexyl group Etc.

The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a 4-tetradecanamidophenyl group, a hexadecyloxyphenyl group,
4 ′-[α- (4 ″ -t-butylphenoxy) tetradecanamide] phenyl group and the like can be mentioned.

The heterocyclic group represented by R is preferably a 5- to 7-membered heterocyclic group, which may be substituted or may be condensed. Specific examples include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

Examples of the acyl group represented by R include an acetyl group,
Phenylacetyl group, dodecanoyl group, α-2,4-di-
Examples thereof include an alkylcarbonyl group such as a t-amylphenoxybutanoyl group, an arylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R include an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, and a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and an m-pentadecylphenylsulfinyl group. .

The phosphonyl group represented by R is an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group,
And an arylphosphonyl group such as a phenylphosphonyl group.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include an N-methylcarbamoyl group, an N, N-dibutylcarbamoyl group and an N- (2-pentagroup. And decyloctylethyl) carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl group.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-propylsulfamoyl group, N, N-diethylsulfamoyl group and N- ( 2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group and the like can be mentioned.

Examples of the spiro compound residue represented by R include spiro [3.3] heptan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include bicyclo [2.2.1] heptan-1-yl and tricyclo [3.3.
1.1 ^3,7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

The alkoxy group represented by R may be further substituted with the above-mentioned substituents for the alkyl group, for example, methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, 2-dodecyl. Examples thereof include an oxyethoxy group and a phenethyloxyethoxy group.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted by the substituents or atoms described above for the aryl group. For example, a phenoxy group, pt-butylphenoxy And m-pentadecylphenoxy group.

The heterocyclic oxy group represented by R is preferably a 5- to 7-membered heterocyclic ring, and the heterocyclic ring may further have a substituent, for example, 3,4,5,6-tetrahydropyrani Ru-2-oxy group, 1-phenyltetrazole-
A 5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group or the like, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group and an arylcarbonyloxy group, and may further have a substituent, specifically, an acetyloxy group and an α-chloroacetyloxy group. And a benzoyloxy group.

The carbamoyloxy group represented by R is an alkyl group,
An aryl group or the like may be substituted, and examples thereof include an N-ethylcarbamoyloxy group, an N, N-diethylcarbamoyloxy group, and an N-phenylcarbamoyloxy group.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include an ethylamino group, anilino group, m-chloroanilino group and 3-pentadecyloxycarbonylanilino group. Two
-Chloro-5-hexadecanamidanilino group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group) and the like, and may further have a substituent.
Examples thereof include an ethylpropanamide group, an N-phenylacetamide group, a dodecane amide group, a 2,4-di-t-amylphenoxyacetamide group and an α-3-t-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, and may further have a substituent. Specific examples thereof include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, for example, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutar And imide groups.

The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-ethylureido group, N-methyl-N-decylureido group and N-phenylureido group. , Np-tolylureido group and the like.

The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N, N-dibutylsulfamoylamino group and N-methylsulfamoyl. Examples thereof include an amino group and an N-phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by R may further have a substituent, and examples thereof include a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, and an octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R is
It may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group,
Examples include octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group and benzyloxycarbonyl group.

The aryloxycarbonyl group represented by R may further have a substituent, and examples thereof include a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group and a m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group, a p-methoxyphenylthio group, a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, −
Examples thereof include a carboxyphenylthio group and a p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a condensed ring;
It may have a substituent. Examples include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the substituent capable of leaving by the reaction with the oxidation product of the color developing agent represented by X include, for example, a halogen atom (chlorine atom,
And a group substituted through a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom in addition to a bromine atom and a fluorine atom.

Examples of the group substituted through a carbon atom include a carboxyl group, for example, a compound represented by the general formula (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) , A hydroxymethyl group and a triphenylmethyl group.

Examples of the group substituted through an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, and an alkoxyoxalyloxy group Is mentioned.

The alkoxy group may further have a substituent, and examples thereof include an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group, and a p-chlorobenzyloxy group.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent.
Specifically, a phenoxy group, a 3-methylphenoxy group, 3
-Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4- [α- (3'-pentadecylphenoxy) butanamide] phenoxy group, hexadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-Methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, and may be a condensed ring or may have a substituent. Specific examples include a 1-phenyltetrazolyloxy group and a 2-benzothiazolyloxy group.

Examples of the acyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group, and an arylcarbonyloxy group such as a benzoyloxy group.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group and the like.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituted through a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group and a benzylthio group.

Examples of the arylthio group include phenylthio, 4-methanesulfonamidophenylthio, 4-dodecylphenethylthio, 4-nonafluoropentanamidophenethylthio, 4-carboxyphenylthio, and 2-ethoxy-5-t-butyl. A phenylthio group and the like.

Examples of the heterocyclic thio group include 1-phenyl-1,
Examples thereof include a 2,3,4-tetrazolyl-5-thio group and a 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

As the group substituted through the nitrogen atom, for example, a general formula The items shown in are listed. Here, R ₄ ′ and R ₅ ′ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R ₄ ′ and R ₅ ′ may combine to form a heterocyclic ring. However, neither R ₄ ′ nor R ₅ ′ is a hydrogen atom.

The alkyl group may be linear or branched, and preferably,
It has 1 to 22 carbon atoms. The alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group and a sulfonamide. Group, imino group,
Acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group,
A halogen atom is mentioned. Specific examples of the alkyl group include an ethyl group, an octyl group, a 2-ethylhexyl group, and a 2-chloroethyl group.

The aryl group represented by R ₄ ′ or R ₅ ′ is preferably a carbon number of 6 to 32, especially a phenyl group or a naphthyl group, and the aryl group may have a substituent,
The substituents to the alkyl group represented by R ₄ ′ or R ₅ ′ and the alkyl group are exemplified. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R ₄ ′ or R ₅ ′ is preferably a 5- to 6-membered heterocyclic group, and may be a condensed ring or may have a substituent. Specific examples include a 2-furyl group, a 2-quinolyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group,
A 2-pyridyl group and the like.

As the sulfamoyl group represented by R ₄ ′ or R ₅ ′,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-
Examples thereof include diarylsulfamoyl groups, and these alkyl groups and aryl groups may have the substituents described for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include, for example, N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and Np-tolylsulfamoyl group.

As the carbamoyl group represented by R ₄ ′ or R ₅ ′,
-Alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group and the like, and these alkyl groups and aryl groups are the substituents mentioned for the alkyl group and aryl group. May have. Specific examples of the carbamoyl group include, for example, N, N-diethylcarbamoyl group, N
-Methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, Np-
And a tolylcarbamoyl group.

Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the aryl group, and the heterocyclic group have a substituent. It may be. Specific examples of the acyl group include a hexafluorobutanoyl group, a 2,3,4,5,6-pentafluorobenzoyl group, an acetyl group, a benzoyl group, a naphthyl group, a 2-furylcarbonyl group, and the like. .

Examples of the sulfonyl group represented by R ₄ ′ or R ₅ ′ include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent.Specific examples include ethanesulfonyl. Group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group and the like.

The aryloxycarbonyl group represented by R ₄ ′ or R ₅ ′ may have the substituent described for the aryl group as a substituent, and specific examples include a phenoxycarbonyl group.

An alkoxycarbonyl group represented by R ₄ ′ or R ₅ ′
You may have the substituent mentioned about the said alkyl group,
Specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group and the like.

The heterocycle formed by combining R ₄ ′ and R ₅ ′ is 5
~ 6-membered, preferably saturated or unsaturated,
Further, it may or may not have aromaticity, and may be a condensed ring. Examples of the hetero ring include an N-phthalimido group, an N-succinimide group, a 4-N-urazolyl group, a 1-N-hydantoinyl group, a 3-N-2,4-dioxooxazolidinyl group, N-1,1-dioxo-3-
(2H) -oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-
Pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1
-Indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1- (1,2,4
-Triazolyl) group, 1- (1,2,3-triazolyl)
Group, 1- (1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3,4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-1H-pyridone group , A phthalazine group, a 2-oxo-1-piperidinyl group, and the like, and these heterocyclic groups are an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an acyl group, a sulfonyl group, an alkylamino group, an arylamino group, Substituted with an acylamino group, sulfoneamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imide group, nitro group, cyano group, carboxyl group, halogen atom, etc. May be.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described for R above. Is mentioned.

Further, the general formula [I] and the general formulas [I-1] to [I
-7] Substituent on the heterocycle (eg, R, R _{1 to} R ₈ )
But Part (where R ″, X and Z ″ are R in the general formula [I],
Synonymous with X and Z. A), a so-called bis type coupler is formed, which is of course included in the present invention. Also, Z, Z ′,
The ring formed by Z ″ and Z ₁ described later may be condensed with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [V], R ₅ and R ₆ are In the general formula [VI], R ₇ and R ₈ may combine with each other to form a ring (for example, a 5- to 7-membered cycloalkene or benzene).

What is represented by the general formula [I] is more specifically represented by, for example, the following general formulas [I-1] to [I-6].

General formula [I-1] General formula [I-2] General formula [I-3] General formula [I-4] General formula [I-5] General formula [I-6] In the general formulas [I-1] to [I-6], R _{1 to} R ₆ and X have the same meanings as R and X.

Among the general formulas [I], those represented by the following general formula [I-7] are preferable.

General formula [I-7] In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the formula [I].

Among the magenta couplers represented by the above general formulas [I-1] to [I-6], the most preferable one is the general formula [I-1].
It is a magenta coupler represented by.

Regarding the substituents on the heterocycle in the general formulas [I-1] to [I-7], R in the general formula [I] is
However, in the general formulas [I-1] to [I-7], it is preferable that R ₁ satisfies the following condition 1, and it is more preferable that R ₁ satisfies the following conditions 1 and 2, and particularly preferable. This is a case where the following conditions 1, 2 and 3 are satisfied.

Condition 1 A root atom directly connected to a heterocyclic ring is a carbon atom.

Condition 2 One or no hydrogen atom is bonded to the carbon atom.

Condition 3 All the bonds between the carbon atom and the adjacent atom are single bonds.

The most preferred as substituents R and R ₁ on the heterocyclic, those represented by the following general formula [IX].

General formula [IX] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group. , Phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group , An acylamino group, a sulfonamide group, an imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms.

And two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may combine to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), Further, R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

The group represented by R _{9 to} R ₁₁ may have a substituent, R
Specific examples of the groups represented by _{9 to} R ₁₁ and the substituents that the groups may have include the specific examples of the groups represented by R in the aforementioned general formula [I] and the substituents.

Also, for example, a ring formed by the combination of R ₉ and R ₁₀ and R _{9 to} R ₁₁
Specific examples of the bridged hydrocarbon compound residue formed by
Cycloalkyl, cycloalkenyl represented by R in
Specific examples of the heterocyclic group bridged hydrocarbon compound residue and its substituents are given.

Among the general formula [IX], it is preferable that (i) when two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ is, for example, R ₁₁ is a hydrogen atom. And when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is 2 of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group.

Here, the alkyl, the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include the alkyl represented by R in the general formula [I], the cycloalkyl and the substituent thereof. Specific examples of the group include:

In addition, the synthesis of the above-mentioned coupler
Chemical Society (Journal of the Chemical So
ciety), Perkin I (1977), 2047-2052,
U.S. Pat.No. 3,725,067, JP-A-59-99437 and JP-A-58-
The synthesis was carried out with reference to No. 42045 and the like.

The coupler of the present invention usually contains 1 × per mol of silver halide.
It can be used in the range of 10 ^-3 mol to 5 × 10 ^-1 mol, preferably 1 × 10 ^-2 mol to 5 × 10 ^-1 mol.

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

Ordinary phenolic compounds as cyan couplers,
Naphthol compounds, such as U.S. Pat.
2,434,272, 2,474,293, 2,895,826, 3,25
3,924, 3,034,892, 3,311,476, 3,386,301
No. 3,419,390, 3,458,315, 3,476,563,
Those described in No. 3,531,383 etc. can be used. The method for synthesizing these compounds is also described in the publication.

Examples of the magenta coupler for photography include pyrazolone-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. Patent Nos. 2,600,788, 3,062,653, and 3,
127,269, 3,311,476, 3,419,391, 3,519,4
No. 29, No. 3,558,318, No. 3,684,514, No. 3,888,680
No. 49-29639, 49-111631, 49-129538
No. 50, No. 50-13041, Japanese Patent Publication No. 53-47167, No. 54-10491,
Compounds described in JP-A-55-30615; as the diffusion-resistant colored magenta coupler, a compound in which an arylazo-substituted coupling position of a colorless magenta coupler is generally used, for example, US Pat. No. 2,801,171,
The compounds described in JP-A-2,983,608, JP-A-3,005,712, JP-A-3,684,514, British Patent 937,621, JP-A-49-123625 and JP-A-49-31448 may be mentioned.

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 a photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler which is generally widely used,
A pivaloylacetanilide type yellow coupler 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 diffusion-resistant coupler used in the present invention is generally 0.05 to 0.05 mol per mol of silver in the photosensitive silver halide emulsion layer.
~ 2.0 moles.

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

Further, in addition to the DIR compound, compounds that release a development inhibitor upon development are also included in the present invention.
3,297,445, 3,379,529, West German patent application (OLS) 2,4
17,914, JP-A Nos. 52-15271, 53-9116, and 59-1238
38, 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 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 3,22
7,554, 4,095,984, 4,149,886, etc.

The above-mentioned DIR coupler forms a dye when the mother nucleus of the coupler reacts with the oxidation product of the color developing agent,
On the other hand, it has the property of releasing a development inhibitor. In the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, 3,958,99
3, 3,961,959, 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, when reacted with an oxidant of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234, the mother nucleus forms a dye or a colorless compound. On the other hand, the present invention also includes a so-called timing DIR compound in which the released timing group is a compound that releases a development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction.

JP-A-58-160954 and JP-A-58-162949, the timing group as described above is present in a coupler nucleus which generates a completely diffusible dye when reacted with an oxidized form of a color developing agent. It also includes the 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, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure No. 17643 , 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.

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

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,79
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1 and 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 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 various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are appropriately used as constituent layers. It can be used in combination. 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, as a silver halide color photographic light-sensitive material,
If the photosensitive material contains a coupler and is processed by a so-called internal development method, color paper, color negative film, color positive film, slide color reversal film, movie color reversal film, TV color reversal film. It can be applied to any silver halide color photographic light-sensitive material such as reverse color paper.

[Specific effects of the invention] As described above, according to the present invention, a color developing solution that is excellent in storage stability and gives stable photographic characteristics even when low replenishment processing or rapid processing is used. It was possible to provide a method for processing a silver halide color photographic light sensitive material.

More specifically, the present invention can provide a processing method of a silver halide color photographic light-sensitive material in which magenta stain generated in a bleaching solution or a bleach-fixing solution in a constant 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 from the support side to prepare a comparative photosensitive material sample.

Layer 1 ... 1.32 g / m ² of gelatin, 3.34 g / m ² (silver equivalent, the same applies below) of a blue-sensitive silver chlorobromide emulsion (96 mol% as AgCl), and
1.20 × 10 ^-3 dissolved in 0.62 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 0.56 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 0.2 × 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: 1.1 g / m ² gelatin, 0.21 g / m ² red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride) and 0.26 g / m ² 1.1 × 10 ^-3 mol dissolved in 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 (manufactured by Ciba-Geigy UV absorber).

Layer 7 ... Layer containing 0.43 g / m ² of gelatin.

As a hardener, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to layers 2, 4 and 7,
Each of them was added to 0.015 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 experimental samples as samples of the present invention and comparative samples.

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] Water washing 30 ℃ 100 seconds [4] Dry 60-80 ℃ 70 seconds Color developing solution and bleach-fix The following liquid was used.

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, after the color development processing, the color pH sample was developed with a transit time of 8 seconds before entering the bleach-fixing solution.

The sample after the current processing is measured with the Sakura Densitometer PDA-65 (manufactured by Konishi Roku Photo Co., Ltd.) to measure the magenta density (stain) of the unexposed area and the yellow density of the highest density area with the slowest developability. did.

 The results are summarized in Table 1.

As is clear from Table 1, the compound represented by the general formula [A] and the metal salt (manganese salt and / or cerium salt) according to the present invention are used in a color developing solution, and the general formula is used in a light-sensitive material. When using the magenta coupler represented by [I], the occurrence of magenta stain is small for the first time,
It is also clear that a sufficient yellow density can be obtained despite the short color development time of 45 seconds.
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 2, 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, it can be seen that when it is 90 mol% or more, a better dye concentration is obtained, and when it is 95 mol% or more, it is 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. In particular, when the silver chloride content of all the silver halide emulsion layers is 80 mol% or more, particularly 90 mol% or more, and particularly 95 mol% or more, all the layers give a preferable dye concentration and a completely black color is obtained. understood.

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 To the color developer used in Experiment No. 11 of Example 1, 12 g / l of the exemplified compounds (D-3) and (D-7) were added,
When the same experiment as in Example 1 was carried out, the coloring degree of the color developing solution was further improved, and the magenta stain was further improved.
It decreased by about 0.01.

Example 6 The same experiment as in Example 1 was carried out except that 1 ppm of copper ion and 0.3 mg / l of bleach-fix solution were mixed in the color developer used in Experiment No. 11 of Example 1.

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

First, the appearance of the color developer (yellowness) 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 coloration ++ Yellow coloration + Slightly yellow coloration − No yellow coloration As is clear from Table 3 above, general formulas (BI) to (B
-When the compound represented by the formula (IV) is used in combination with the developing solution of the present invention, the amount of color developing agent decomposed is small and the degree of coloring is further improved even under extremely severe conditions such as the mixing of heavy metal ions. I understand. 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 7] 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. It can be seen that a particularly good yellow dye density can be obtained when it is 1 or less, and that it is suitable for rapid processing.

[Example 8] The amount of cerium ions added to the color developer No. 11 used in Example 1 was 0 to 400 mg / m as shown in Table 5 below.
The same experiment as in Example 1 was conducted by changing the range of l.

 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
It turns out that it is particularly good at mg / l.

 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-59-228251 (JP, A) JP-A-60-205541 (JP, A) JP-A-57-185434 (JP, A) JP-A-56- 94349 (JP, A) JP-A-60-19140 (JP, A) US Patent 3746544 (US, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material which is subjected to imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and then at least a color development step. In the processing method of
The halogenated grains of the silver halide emulsion layer contain at least 80 mol% of silver chloride, and at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [I], and A color developing solution used in the color developing step contains a compound represented by the following general formula [A] and at least one compound selected from a manganese salt and a cerium salt. A silver halide color photographic light-sensitive material. Processing method. General formula [I] (In the formula, Z represents a non-metal group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X is a hydrogen atom or an oxidized product of a color developing agent. And R represents a hydrogen atom or a substituent.) General formula [A] (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.
In addition, the ring of R ₁ and R ₂ may be formed. )