JPH06100804B2 - 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, since sulfite sulfonates the oxide of the color developing agent generated in the color developing reaction process, it inhibits the coupling reaction between the oxide of the color developing agent and the coupler, and in particular, a coupler having a slow coupling and coupling reaction is used. 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, JP-A-59-228251
JP-A No. 60-205541 and the like, there is a technique for improving the preservability by further using a cerium salt or a manganese salt in a system using the above-mentioned conventional sulfite and hydroxylamine as a preservative. Although it has been known, in recent years there has been a tendency for the color developing solution to be replenished more and more due to economic reasons and pollution reasons. As a result, the residence time of the developing solution is becoming longer and longer. Oxidation is becoming more frequent, 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, the photographic light-sensitive material was exposed to 30 ° C
Processing has been performed under the above high temperature, and troubles such as coloring of the developing solution due to high temperature oxidation have become more serious.When the light-sensitive material is processed with such a color developing solution, the upper layer In a color paper, a cyan coloring layer is generally provided on the upper layer, and cyan stain is generated on the color paper due to ammonia or the like generated in the developing solution due to the decomposition of hydroxylamine.

SUMMARY OF THE INVENTION The first object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material capable of obtaining stable photographic characteristics even when a color developer is subjected to a low replenishing processing. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which generation of stain is improved even when heavy metal ions are mixed.

Other objects of the invention will become apparent below.

[Structure of Invention] As a result of various studies by the present inventors, the purpose of the present invention is to
After imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In a method for processing a silver halide color photographic light-sensitive material, which is subjected to processing including at least a color developing step, a cyan coupler represented by the following general formula [C-1] and a general formula [C -2], a color developer containing one cyan coupler selected from the group consisting of cyan couplers represented by the following general formula [I] is selected from compounds represented by the following general formula [I] and manganese salts and cerium salts. And a halogen developer containing at least one compound selected from the group consisting of manganese salts and cerium salts, wherein the color developing solution used in the color developing step contains at least one cyan coupler It has been found that this is achieved by the processing method of silver halide color photographic light-sensitive material.

General formula [I] (In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom, and neither R ₁ nor R ₂ is a hydrogen atom.
R ₁ and R ₂ may form a ring. ) General formula [C-1] General formula [C-2] In the formula, Y is -COR ₄ , -SO ₂ R ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ is an alkyl group, an alkenyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group, R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₄ and R ₅ are bonded to each other to form a 5- or 6-membered ring. May be formed. R ₃ represents a ballast group, and Z represents a hydrogen atom or a group capable of splitting off by coupling with an oxidation product of an aromatic primary amine color developing agent.

[Specific Structure of the Invention] Of the compounds represented by the general formula [I] of the present invention, for example,
It is known that N, N-diethylhydroxylamine is used as a preservative for a black and white developing agent in a color developer to which a black and white developing agent is added.

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

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

In addition, for example, in a magenta color developing solution containing no phenidone, N, N-diethylhydroxylamine is known to have a bad influence on the storability of the external color developing solution, that is, destroying the coupler. Tokusho
45-22198).

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

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

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

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

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

Among the rapid processing techniques of the above [I], a technique of using a silver halide photographic light-sensitive material containing silver halide grains having a high concentration of silver chloride (for example, JP-A-58-95345, JP-A-58-95345). Nos. 60-19140 and JP-A-58-95736) give particularly excellent speed-up performance. However,
When such a high silver chloride-containing light-sensitive material is used, hydroxylamine, which is usually used as a preservative for a color base in a color developing solution, causes a silver development reaction due to its reducing power, which results in an insufficient dye concentration. There is a drawback that becomes. However, when hydroxylamine is not used, the storability of the color developing solution is significantly deteriorated. There is a trade-off relationship. Also, cerium salts and manganese salts remarkably maintain the color developing agent in the presence of hydroxylamine, but when the decomposition speed of hydroxylamine itself is accelerated and the hydroxylamine disappears, its retentivity rapidly increases. It turns out that it will deteriorate. In various studies, the present inventors have found that the above problems can be solved at the same time when a monoalkylhydroxylamine or dialkylhydroxylamine is used in combination with a cerium salt and / or a manganese salt. Formula [C-1] or [C-
It has been found that the use of the specific cyan coupler represented by [2] can also improve the cyan stain under more severe conditions. Therefore, another object of the present invention is to use a manganese salt and / or a cerium salt in a color developing solution together with a specific cyan coupler for a silver halide color photographic light-sensitive material to maintain the preservability. And a color developing solution for a silver halide color photographic light-sensitive material and a solution for improving the preservability, which makes it difficult for a high silver chloride light-sensitive material to undergo a silver development reaction and enables rapid processing. It is intended to provide a method for processing the used silver halide color photographic light-sensitive material.

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

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

Preferred specific exemplary compounds represented by the general formula [I] are shown below.

These compounds of the present invention may be used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate.

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

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

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

Manganese chloride Manganese 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 per color developer, more preferably 0.3 mg to 20 mg, especially 0.5 mg. From the viewpoint of the effect of the present invention, -10 mg is particularly preferably used.

Usually, sulfite is used as a preservative in the color developing solution, but the sulfite concentration in the color developing solution according to the present invention is
When it is used in an amount of 1.6 × 10 ^-2 mol or less per color developing solution, it is possible to suppress a decrease in color density, which is considered to be caused by dissolution physical development of a high silver chloride-containing photosensitive material, and also a decrease in preserving ability. Since it is extremely slight, it is possible to provide a color developing solution which enables rapid processing using a high silver chloride-containing light-sensitive material or a processing method of a silver halide color photograph using the solution. A sulfite concentration of 1.6 × 10 ^-2 mol / l or less is preferably used. Furthermore, this effect is better exhibited by 4 ×
It is 10 ^-3 mol / l or less.

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

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

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

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble group, - (CH ₂₎ nC
H ₂ OH,-(CH ₂ ) -NHSO _2- (CH ₂ ) -CH ₃ ,-(CH ₂ ) mO-
_{(CH 2) n-CH 3} , - (CH 2 CH 2 O) nCmH2m + 1 (. M and n each represent an integer of 0 or more each) -COOH group, and as -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, Exemplified No. (A-1) is preferable for use in the present invention because it causes less fogging.
The compounds represented by (A-2), (A-3), (A-4), (A-6), (A-7) and (A-15), particularly preferably (A-
1).

The color developing agent is usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, or the like.

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

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

Further, instead of using the color developing agent as a color developing solution, a color developing agent can be added to the light-sensitive material, and the color developing agent used in that case includes a dye precursor. A typical dye precursor is JP-A-58.
No. 65429, No. 58-24137, etc. are used, and specifically, for example, 2 ', 4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4'- (2,4,6-triisopropyl)
Benzenesulfonamido-2-methyl-4-N- (2-
Methanesulfonamidoethyl) ethylaminodiphenylamine, 2'-methanesulfonamido-4 '-(2,4,6
-Triisopropyl) benzenesulfonamide-4-
(Hydroxytrisethoxy) diphenylamine, 4-
N- (2-methanesulfonamidoethyl) ethylamino-2-methyl-2 ', 4'-bis (2,4,6-triisoprovir) benzenesulfonamide diphenylamine, 2,
4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2 '
-Methanesulfonamide-4 '-(2,4,6-triisopropyl) benzenesulfonamide diphenylamine, 4
-Methoxy-2'-methanesulfonamide-4 '-(2,
4,6-Triisopropyl) benzenesulfonamide diphenylamine, 4-dihexylamino-4 '-(2,4,6
-Triisopropylbenzenesulfonamide) diphenylamine, 4-n-hexyloxy-3'-methyl-
4 '-(2,4,6-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 the compound represented by the following general formula [D], not only the effects of the present invention are more favorably exhibited, but also against the air oxidation of the color developing solution. It is more preferably used because it shows an improving 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) diisopropanolamine, (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) - amino-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 includes the following general formula [BI]
To the compound represented by [B-IV],
It is more preferably used in the present invention because it has the effect of more favorably achieving the object and effects of the present invention, and also has the effect of improving bleaching fog that occurs when bleaching or bleach-fixing is performed immediately after color development.

General formula [BI] General formula [B-II] In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₁₅ , —COOR ₁₆ , Alternatively, it represents a phenyl group. 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 , Alternatively, it represents a phenyl group.

The alkyl groups represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include those having a substituent, for example, a methyl group, an ethyl group, is
o-propyl group, n-propyl group, t-butyl group, n-
Butyl group, hydroxymethyl group, hydroxyethyl group,
Examples include methylcarboxylic acid group, benzyl group, and R
_The alkyl group represented by ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ has the same meaning as described above, and further includes an octyl group and the like.

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

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

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (B-I-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1,2,3- Trihydroxybenzene-5-carboxylic acid (BI-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (BI-5) 1,2,3-trihydroxybenzene-5-carboxy -N
-Butyl ester (BI-6) 5-t-butyl-1,2,3 trihydroxybenzene (B-II-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (B-II-2) 2 , 3,8-Trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (B-II-4) 2,3-dihydroxy-8-isopropyl-naphthalene ( B-II-5) 2,3-Dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, as a compound particularly preferably used in the present invention, 1,2-dihydroxybenzene-3,5-disulfonic acid And it can also be used as an alkali metal salt such as sodium salt or potassium salt.

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

General formula [B-III] General formula [B-IV] (In the general formulas [B-III] and [B-IV], L represents an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -O-
Represent or _{-L 9 -ZL 9 - L 8 -OL} 8. Where Z is NL ₁₀ -R ₄₀ , NR ₄₂ or Represents

L _{1 to} L ₁₃ each represent an alkyl 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-Diaminopropanetetraacetic acid [B-III-8] 1,3-Diaminopropan-2-ol-tetraacetic acid [B-III-9] Ethyl ether diamine tetraacetic acid [B-III-10] Glycol ether diamine tetraacetic acid [B-III-10] B-III-11] Ethylenediaminetetrapropionic acid [B-III-12] Phenylenediaminetetraacetic acid [B-III-13] Ethylenediaminetetraacetic acid disodium salt [B-III-14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [B-III-15] Ethylenediaminetetraacetic acid tetrasodium salt [B-III-16] Diethylenetria Minpentaacetic acid pentasodium salt [B-III-17] ethylenediamine-N- (β-hydroxyethyl) -N,
N ', N'-Triacetic acid sodium salt [B-III-18] Propylenediaminetetraacetic acid sodium salt [B-III-19] Ethylenediaminetetramethylenephosphonic acid [B-III-20] Cyclohexanediaminetetraacetic acid sodium salt [B -III-21] Diethylenetriamine pentamethylenephosphonic acid [B-III-22] Cyclohexanediaminetetramethylenephosphonic acid [B-IV-1] Nitrilotriacetic acid [B-IV-2] Iminodiacetic acid [B-IV-3] Nitrilotriopropion Acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-5] Iminodimethylenephosphonic acid [B-IV-6] Trisodium nitrilotriacetic acid trisodium salt These general formulas [B-III] or [B-IV] Among the compounds represented by the following, as a compound preferably used in the present invention, [B-III- ], [B-III-2],
[B-III-5], [B-III-8], [B-III-1
9], [B-IV-1] and [B-IV-4]. Furthermore, these general formulas [B-III] or [B-IV]
The compound represented by the formula (1) is preferably used in the range of 0.1 to 20 g per color developing solution, and particularly from the viewpoint of the object of the present invention.
A range of 0.3-5 g 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.), alkyl group (eg methyl, ethyl etc.), aryl group (eg phenyl, methoxyphenyl etc.), amino group, alkylamino group (eg methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, N
-(Β-sulfoethyl) -N'-methylamino, N-
(Β-hydroxyethyl-N′-methylamino, etc.), arylamino group (eg, anilino, o-, m-, p-sulfoanilino, o-, m-, p-chloroanilino, o
-, M-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

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

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

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

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

As the alkaline agent, for example, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination. , The above effect of the present invention, that is, no precipitation occurs,
It can be used in combination within a range that maintains the pH stabilizing effect.
Further, for the purpose of preparation, or for the purpose of increasing ionic strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate,
Various salts such as borate can be used.

Inorganic and organic antifoggants can be added if necessary.

Further, a development accelerator can be used if necessary.
US Pat. Nos. 2,648,604 and 3,67 as development accelerators.
1,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.No. 2,533,990, No. 2,531,832,
No. 2,950,970, No. 2,577,127, and Japanese Patent Publication No. 44-9
Polyethylene glycol and its derivatives described in Japanese Patent No. 504, and nonionic compounds such as polythioethers are included. Further, benzyl alcohol, phenel alcohol described in US Pat. No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like can be mentioned.

In the above, particularly for a poorly soluble organic solvent represented by benzyl alcohol, tar is liable to be generated particularly in a running process in a low replenishment system by using a color developing solution for a long time, and the generation of such tar is However, depending on the proximity of the paper to be treated, 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, there is no need for troublesome things such as requiring a stirring device to adjust the color developing solution itself. Therefore, there is a limit to the effect of promoting development.

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

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

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

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

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

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

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

The color development time is generally about 3 minutes and 30 seconds, but it is preferably within 2 minutes from the viewpoint of speeding up.
Further, it is preferable to carry out in the range of 30 seconds to 1 minute 30 seconds.

The color developing solution according to the present invention can be applied to various processing methods such as a spray method in which the processing solution is atomized, a web method by contact with a carrier impregnated with the processing solution, or a developing method using a viscous processing solution. You can As the processing step, substantially, color development-bleach-fixing-washing (or stabilizing) is preferably used, and in the bleach-fixing step, the bleaching step and the fixing step may be separately provided.

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

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

The silver halide emulsion containing silver halide grains consisting of 80 mol% or more of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. Silver bromide is 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and when silver iodide is present, 1 mol% or less, preferably 0.5 mol% or less. Such a silver halide grain substantially consisting of silver chloride according to the present invention contains 80% by weight or more of all the silver halide grains in the silver halide emulsion layer in which the silver halide grain is contained. It is preferable that the content is 100%, more preferably 100%.

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal, or another crystal, and any ratio of [100] plane to [111] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside or may have a layered structure (core / shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-17).
No. 0070) can also be used.

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

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

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

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

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

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

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

These sensitizing dyes may be used alone or in combination.

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

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

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

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

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

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

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

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Oxonol dye,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 584,60.
No. 9, No. 1,277,429, JP-A No. 48-85130, No. 49-996.
No. 20, No. 49-114420, No. 49-129537, No. 52-108
No. 115, No. 59-25845, No. 59-111640, No. 59-111
641, U.S. Patent No. 2,274,782, No. 2,533,472, No. 2,956,079, No. 3,125,448, No. 3,148,187,
No. 3,177,078, No. 3,247,127, No. 3,260,601
No. 3, No. 3,540,887, No. 3,575,704, No. 3,653,905
No. 3, No. 3,718,472, No. 4,071,312, No. 4,070,35
The items described in No. 2 can be mentioned.

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

Next, the general formula [C-1] or [C used in the present invention is used.
The cyan coupler represented by -2] will be described. In the general formulas [C-1] and [C-2], Y is-
COR ₄ , It is a group represented by -CONHCOR ₄ or -CONHSO ₂ R ₄ . Here, R ₄ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (eg, an allyl group, Heptadecenyl group, etc.), cycloalkyl group, preferably a 5- to 7-membered ring (eg cyclohexyl etc.), aryl group (eg phenyl group, tolyl group, naphthyl group etc.), heterocyclic group, preferably nitrogen atom, oxygen atom Alternatively, it represents a 5- to 6-membered heterocyclic group containing 1 to 4 sulfur atoms (eg, furyl group, thienyl group, benzothiazolyl group, etc.).

R ₅ represents a hydrogen atom or a group represented by R ₄ . R ₄ and
R ₅ may combine with each other to form a 5- to 6-membered heterocycle containing a nitrogen atom. In addition, arbitrary substituents can be introduced into R ₂ and R ₃ , for example, an alkyl group having 1 to 10 carbon atoms (for example, ethyl, i-propyl, i-butyl, t-).
Butyl, t-octyl, etc.), aryl group (eg, phenyl, naphthyl, etc.), halogen atom (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide group (eg, methanesulfonamide, butanesulfonamide, p-toluenesulfone) Amide etc.), sulfamoyl group (eg methylsulfamoyl, phenylsulfamoyl etc.), sulfonyl group (eg methanesulfonyl, p-toluenesulfonyl etc.), fluorosulfonyl, carbamoyl group (eg dimethylcarbamoyl, phenylcarbamoyl etc.), oxy Examples include carbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (eg, acetyl, benzoyl, etc.), heterocyclic group (eg, pyridyl group, virazolyl group, etc.), alkoxy group, aryloxy group, acyloxy group, etc. Rukoto can.

In the general formulas [C-1] and [C-2], R ₃ is diffusion resistant to the cyan couplers represented by the general formulas [C-1] and [C-2] and the cyan dye formed from the cyan coupler. Represents a ballast group necessary for imparting
Preferred is an alkyl group having 4 to 30 carbon atoms, an aryl group or a heterocyclic group. For example, a linear or branched alkyl group (for example, t-butyl, n-octyl, t-octyl,
n-dodecyl etc.), alkenyl group, cycloalkyl group,
A 5-membered or 6-membered heterocyclic group and the like can be mentioned.

In formulas [C-1] and [C-2], Z represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidation product of a color developing agent. For example, halogen atom (eg chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, sulfonyloxy group, alkylthio group, arylthio group, heterocycle Thio group, sulfonamide group and the like, further specific examples are U.S. Pat.No. 3,741,563, JP-A-47-37425,
JP-B-48-36894, JP-A-50-10135, 50-117422
No. 50, No. 50-130441, No. 51-108841, No. 50-120343,
52-18315, 53-105226, 54-14736, 54-48
No. 237, No. 55-32071, No. 55-65957, No. 56-1938, No.
56-12643, 56-27147, 59-146050, 59-1669
No. 56, No. 60-24547, No. 60-35731, and No. 60-37557.

In the present invention, the following general formulas [C-3] and [C-4]
Alternatively, a cyan coupler represented by [C-5] is more preferable.

General formula [C-3] General formula [C-4] General formula [C-5] In the general formula [C-3], R ₃₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent is -SO.
₂ R ₃₇ , halogen atom (eg fluorine, bromine, chlorine etc.),
-CF ₃ , -NO ₂ , -CN, -COR ₃₇ , -COOR ₃₇ , -SO ₂ OR ₃₇ , -OR ₃₇ , -OCOR ₃₇ , At least one substituent selected from is included.

Here, R ₃₇ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group such as methyl, ethyl, tert-butyl, dodecyl, etc.), an alkenyl group, preferably 2 carbon atoms.
To 20 alkenyl groups (eg, allyl group, heptadecenyl group, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (eg, cyclohexyl group, etc.), aryl groups (eg, phenyl group, tolyl group, naphthyl group, etc.) , R ₃₈ is a hydrogen atom or a group represented by R ₃₇ .

A preferred compound of the phenolic cyan coupler represented by the general formula [C-3] is a compound in which R ₃₇ is a substituted or unsubstituted phenyl group, and cyano, nitro, -SO ₂ R ₃₉ (as a substituent for the phenyl group). R ₃₉ is an alkyl group), a halogen atom,
A compound such as trifluoromethyl.

In the general formulas [C-4] and [C-5], R ₃₅ , R ₃₆
Is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg methyl, ethyl, tert-butyl, dodecyl etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (eg allyl, oleyl etc.), cyclo Alkyl group, preferably 5 to 7-membered ring group (eg cyclohexyl etc.), aryl group (eg phenyl group, tolyl group, naphthyl group etc.), heterocyclic group (nitrogen atom, oxygen atom or sulfur atom 1 to 4) Preferred are 5- to 6-membered heterocycles including, for example, a furyl group, a thienyl group, a benzothiazolyl group and the like).

The above R ₃₇ , R ₃₈ and the general formulas [C-4] and [C-5]
Any substituent can be further introduced into R ₃₅ and R ₃₆ of, and specifically, general formulas [C-1] and [C-2]
Is a substituent that can be introduced into R ₄ or R ₅ . As the substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable.

In general formulas [C-3], [C-4] and [C-5], Z and R ₃ have the same meanings as in general formulas [C-1] and [C-2], respectively. A preferred example of the ballast group represented by R ₃ is a group represented by the following general formula [C-6].

General formula [C-6] In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, l represents 0 or 1, and when K is 2 or more, two or more R _{41 s} are the same. R ₄₀ may be different, represents a linear or branched C 1-20 linear or branched, and substituted alkylene group such as an aryl group, R ₄₁ represents a monovalent group, preferably a hydrogen atom, a halogen atom ( For example, chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.). Group), aryl group (eg phenyl group), heterocyclic group (preferably nitrogen-containing heterocyclic group), alkoxy group, preferably linear or branched alkoxy group having 1 to 20 carbon atoms (eg methoxy, ethoxy). t-butyloxy, octyloxy, decyloxy, dodecyloxy and other groups), aryloxy group (eg phenoxy group), hydroxy, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (eg acetoxy group, benzoyloxy group) ), Carboxy, an alkyloxycarbonyl group, preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms, an aryloxycarbonyl group, preferably phenoxycarbonyl,
An alkylthio group, preferably 1 to 20 carbon atoms, an acyl group,
Preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably 1 to 20 carbon atoms
A linear or branched alkylcarboxamide, benzenecarboxamide or sulfonamide group, preferably having 1 to 1 carbon atoms.
20 linear or branched alkylsulfonamide group or benzenesulfonamide group, carbamoyl group, preferably C 1-20 linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group, sulfamoyl group, preferably carbon number It represents a linear or branched alkylaminosulfonyl group of 1 to 20 or a phenylaminosulfonyl group.

Next, specific compound examples of the cyan coupler represented by the general formula [C-1] or [C-2] will be shown, but the cyan coupler is not limited thereto.

[Compound example]

These cyan couplers can be synthesized by various methods, for example, U.S. Patents 2,772,162 and 3,758,308.
No. 3, No. 3,880,661, No. 4,124,396, No. 3,222,176,
British patents 975,773, 8,011,693, 8,011,694
No. 47-21139, No. 50-112038, No. 55-163537
No. 56, No. 56-29235, No. 55-99341, No. 56-116030, No. 5
2-69329, 56-55945, 56-80045, 50-134644
No., British Patent 1,011,940, U.S. Patent 3,446,622
No. 3,996,253, JP-A-56-65134, 57-204543.
No. 57, No. 57-54444, No. 57-204545, No. 56-131312
No. 56, No. 56-131313, No. 56-131314, No. 56-131309,
56-131311, 57-149791, 56-130459, JP-A-59-146050, 166956, 60-24547, 60-3573.
No. 1, 60-37557 and the like can be used for the synthesis.

In the present invention, the cyan coupler represented by the general formula [C-1] or [C-2] can be used in combination with a conventionally known cyan coupler within the range not deviating from the object of the present invention. In addition, general formulas [C-1] and [C-
The cyan coupler [2] can also be used in combination.

When the cyan coupler according to the present invention represented by the general formula [C-1] or [C-2] is contained in the silver halide emulsion layer, it is usually about 0.005 to 2 per mol of silver halide.
It is used in a molar amount, preferably 0.01 to 1 mol.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As a pyrazolone-based magenta coupler, US Pat.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
84,514, 3,888,680, JP-A-49-29639, 49-11
No. 1631, No. 49-129538, No. 50-13041, Japanese Patent Publication No. 53-4716
Nos. 7, 54-10491 and 55-30615; pyrazolotriazole-based magenta couplers include couplers described in US Pat. No. 1,247,493 and Belgium Patent 792,525, and have diffusion resistance As the colored magenta coupler, a compound having an arylazo substitution at the coupling position of a colorless magenta coupler is generally used, for example, U.S. Pat.Nos. 2,801,171 and 2,983,608.
No. 3,005,712, No. 3,684,514, British Patent 937,621
And the compounds described in JP-A-49-123625 and JP-A-49-31448.

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

As the photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used. Further, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction is also advantageously used. Examples of these are U.S. Patents 2,875,057 and 3,265,506.
No., No. 3,664,841, No. 3,408,194, No. 3,277,155,
No. 3,447,928, No. 3,415,652, Japanese Patent Publication No. 49-13576, JP-A No. 48-29432, No. 48-68834, No. 49-10736, No. 49-1
22335, 50-28834, 50-132926 and the like, together with the synthetic method.

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

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

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

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

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. , U.S. Patent 3,227,5
54, 4,095,984, 4,149,886, etc.

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

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

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

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

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggant, stabilizer, ultraviolet absorber, described in Research Disclosure Magazine 17643,
A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

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

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

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

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers.

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

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

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

[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 ... 1.3 g / m ² gelatin, 0.35 g / m ² (silver equivalent, the same applies below) blue-sensitive silver chlorobromide emulsion (96 mol% as AgCl), and
1.1 x 10 ^-3 dissolved in 0.64 g / m ² dioctyl phthalate
A layer containing the following yellow coupler (Y-1) in mol g / m ² .

Layer 2 ... an intermediate layer consisting of 0.53 g / m ² of gelatin.

Layer 3 ... 1.3 g / m ² gelatin, 0.24 g / m ² green sensitive silver chlorobromide emulsion (98 mol% as AgCl) and 1.3 × 10 ⁻³ mol g dissolved in 0.3 g / m ² dioctyl phthalate. / m ² A layer containing the following magenta coupler (M-1).

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

Layer 5 ... 1.2 g / m ² gelatin, 0.21 g / m ² red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride) and 1.3 × 10 ^-3 mol dissolved in 0.2 g / m ² dibutyl phthalate. A layer containing g / m ² of the following comparative cyan coupler (C′-1).

Layer 6 ... A layer containing 1.3 g / m ² of gelatin and 0.32 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) dissolved in 0.24 g / m ² of dioctyl phthalate.

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

As a hardener, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to layers 2, 4 and 7 so that the amount was 0.012 g per 1 g of gelatin.

A comparative color paper was prepared as described above. In the same manner, the cyan coupler (C'-1) was used as shown in Table 1 below.
The cyan couplers as shown in (4) were changed to prepare and use the samples of the present invention and the experimental samples as the comparative samples.

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

The following color developing solution and bleach-fixing solution were used.

[Color developer] [Bleaching fixer] The above color developing solution was heated at 38 ° C. and the opening ratio was 160 cm ² (1
The above color developing solution was placed in a glass container having an air contact area of 160 cm ² ) and stored for 3 weeks. The color developing solution after storage was used for development processing.

The sample after the development treatment was measured for the cyan density of the unexposed area and the yellow density of the highest density area with the slowest developability by using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.).

The results are summarized in Table 1.

As is clear from Table 1 above, the compound represented by the general formula [I] and the metal salt (manganese salt and / or
(Or cerium salt) in a color developer and when the cyan coupler represented by the general formula [C-1] or [C-2] is used in the light-sensitive material, the generation of cyan stain is small for the first time, and It can be seen that a sufficient yellow density can be obtained despite the short color development time of 50 seconds. However, when any one of these elements is lacking, either effect becomes insufficient. Similarly, when a metal salt other than the present invention is used, the effect is insufficient.

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

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

[Example 5] To the color developers used in Example 1 and Experiment No. 11, 12 g / l of the exemplified compounds (D-3) and (D-7) were added, and the same experiment as in Example 1 was conducted. As a result, the coloring degree of the color developing solution was further improved, and the cyan stain was further 0.01%.
To a lesser extent.

Example 6 The color developing solution used in Example 1 and Experiment No. 11 was mixed with 1 ppm of copper ion and 0.3 ml / l of a bleach-fixing solution, and the other examples were used.
The same experiment was performed.

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

As is clear from Table 3 above, general formulas (BI) to (B-
When the compound represented by IV) is used in combination with the color developing solution of the present invention, the decomposition amount of the color developing agent is small and the degree of coloring is further improved even under extremely severe conditions such as the mixing of heavy metal ions. I understand. Furthermore, it is also effective against cyan 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. Particularly good yellow dye density can be obtained when
It turns out that it is suitable for rapid processing.

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

The results are summarized in Table 5.

From Table 5 above, it is found that when the metal salt according to the present invention is present in the form of ions in the range of 0.1 to 100 mg / l, the decomposition and coloration degree (tar property) of the color developing solution are good, and the cyan stain is also good. I understand.

Especially good at 0.3-20 mg / l, especially 0.5-10 mg
It turns out to be particularly good with / l.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material which is subjected to a process including at least a color developing step after imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. In the processing method,
At least one of the silver halide emulsion layers has a cyan coupler represented by the following general formula [C-1] and a general formula [C-1]
-2], a color developer containing at least one cyan coupler selected from the group consisting of cyan couplers represented by the following general formula [I] and a manganese salt and a cerium salt are used. A method of processing a silver halide color photographic light-sensitive material, which comprises at least one compound selected. General formula [I] (In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom, and neither R ₁ nor R ₂ is a hydrogen atom.
R ₁ and R ₂ may form a ring. ) General formula [C-1] General formula [C-2] In the formula, Y is -COR ₄ , -SO ₂ R ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ is an alkyl group, an alkenyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group, R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₄ and R ₅ are bonded to each other to form a 5- or 6-membered ring. May be formed. R ₃ represents a ballast group, and Z represents a hydrogen atom or a group capable of splitting off by coupling with an oxidation product of an aromatic primary amine color developing agent.