JPH0827518B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, the processing stability and color contamination are improved, and the fluctuation of the maximum density of cyan dye is small. The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

BACKGROUND OF THE INVENTION The processing of a silver halide color photographic light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilizing treatment, and the like are added as additional treatment steps.

In color development, the exposed silver halide is reduced to silver and at the same time oxidized primary aromatic amine color developing agent represented by p-phenylenediamine developing agent reacts with a coupler to form a dye. To do. In this process, halogen ions generated by reduction of silver halide are eluted and accumulated in the developer. Separately, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic light-sensitive material as soluble silver salts with a fixing agent. There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

In the color developer, the development inhibitor is accumulated by developing the silver halide color photographic light-sensitive material as described above, while the color-developing agent, benzyl alcohol, etc. are consumed, or accumulated in the photographic light-sensitive material and taken out. As a result, the concentration of those components decreases. Therefore, in a development processing method in which a large amount of silver halide color photographic light-sensitive material is continuously processed by an automatic developing machine or the like, the components of the color developing solution are kept in a certain concentration range in order to avoid a change in development finish characteristics due to a change in component concentration. We need a way to keep it. As such means, a method is usually employed in which a replenisher for replenishing deficient components and diluting unnecessary increased components is replenished. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method is a serious problem in terms of economy and pollution. Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a developer by an ion exchange resin method or an electrodialysis method, a concentrated low replenishment method, or a method of adding a regenerant to the overflow solution and using it again as a replenisher. Etc. have been proposed. Of these, the concentrated low replenishment method is extremely suitable for small-scale laboratories such as mini-labs because it requires no new equipment and is easy to manage.

On the other hand, in an ordinary color developing solution, in order to prevent oxidation of an aromatic primary amine color developing agent typified by a p-phenylenediamine developing agent, a sulfite or a sulfite and a hydroxylamine are used as a preservative. And a water-soluble salt thereof are added.

If these sulfites were added alone to the developer,
It is already known that effective preservation can be obtained by adding hydroxylamine as a water-soluble salt because the storage stability is not always sufficient.

However, hydroxylamine salts are decomposed by catalysis by trace amounts of coexisting metal ions, especially iron ions, and not only reduce the preservative effect, but also generate ammonia when decomposed. It is known that fogging and stains are formed on the surface, and abnormalities in photographic characteristics, particularly hardening of the shoulder portion, occur, thereby deteriorating the processing stability.

When metal ions, especially iron ions, are mixed in the color developing solution, a ferric salt of an organic acid is usually used as a bleaching agent in the color developing solution by a splash, a transport leader, a hanger for suspending a belt or a film. This is caused by so-called back contamination in which the bleaching solution and the bleach-fixing solution that are used are brought in.

In order to prevent these unfavorable effects of metal ions, techniques for incorporating various metal chelating agents have been proposed and put into practical use. For example, a technique in which a lithium salt is used in combination with a hydroxyalkylidene-diphosphonic acid sequestering agent described in U.S. Patent No. 3,839,045, a polyhydroxy compound and a metal aminopolycarboxylate described in U.S. Patent No. 3,746,544 Techniques using ion sequestering agents in combination, such as techniques using polyhydroxy compounds and aminopolyphosphonic acid sequestering agents described in U.S. Pat.No.4,264,716, can also be mentioned. At present, such problems have not been solved.

The loss of process stability due to such hydroxylamine salts is exacerbated at low replenishment processing. That is, in the low replenishment process, not only the accumulated metal ions increase, but also the renewal rate of the developer decreases, so that the stagnation time of the developer in the processing tank significantly increases. For this reason, the above-mentioned problems of generation of fog due to the decomposition of the hydroxylamine salt and hardening of the shoulder portion become more remarkable. In addition, under such circumstances, it was revealed that the conventional multi-replenishment treatment had almost no effect, for example, the acceleration of decomposition of the hydroxylamine salt by trace metals contained in the reagent, particularly copper ions. It has been found that it is difficult to detoxify this copper ion by using a conventional chelating agent.

Therefore, the present inventors have completed the present invention as a result of various studies on a preservative having a high preservative ability without the drawback of the hydroxylamine salt such that the processing stability is lowered.

As a result of further studies on the use technology of the specific preservative used in the present invention, it was found that the maximum concentration of the cyan dye is easily affected by the concentration fluctuation of the specific preservative used in the present invention. That is, when the concentration of the specific preservative used in the present invention increases, the maximum concentration of the cyan dye tends to decrease. The reason for affecting the maximum density of the cyan dye is not always clear and cannot be explained by simple inhibition of coupling or suppression of silver development, but it is considered that the balance between silver development and coupling is likely to be lost.

[Object of the Invention] Accordingly, a first object of the present invention is to have excellent stability over time of a color developing solution such as preservability, increase fog in a dye image,
It is an object of the present invention to provide a processing method of a silver halide color photographic light-sensitive material which is excellent in processing stability with little fluctuation in photographic performance such as high contrast of shoulders.

A second object of the present invention is not only little change in photographic performance such as stability of color developing solution over time such as preservability, increase of fog in dye image, and increased contrast of shoulder, but also maximum cyan dye. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material having a small density fluctuation.

[Construction of the Invention] The above-mentioned object of the present invention is to carry out a treatment including at least a color development 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 method for processing a silver halide color photographic light-sensitive material, at least one of the silver halide emulsion layers contains at least one cyan coupler represented by the following general formulas [C-1] and [C-2], The color developing solution used in the color developing step comprises a compound represented by the following general formula [I] and the following general formula [IV]:
It was achieved by a method for processing a silver halide color photographic light-sensitive material, which contains at least one compound selected from the compounds represented by [V], [VI] and [VII].

General formula [I] (In the formula, R ₁ has 1 carbon atom substituted with an alkoxy group.
Represents an alkyl group having 1 to 5 carbon atoms, and R ₂ has 1 carbon atom substituted with an alkyl group having 1 to 5 carbon atoms or an alkoxy group.
Represents an alkyl group of ~ 5. According to a preferred embodiment of the present invention, at least one of the silver halide emulsion layers has the following general formula [C-
1] and at least one cyan coupler selected from the cyan couplers represented by [C-2].

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 represents an alkyl group, an alkenyl group, a cycloalkyl group, 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, R ₄ and R ₅ may combine with each other to form a 5- or 6-membered ring), and R ₃ represents a ballast group, Z
Represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine type color developing agent.

Further, the color developing solution used in the color developing step contains at least one compound selected from compounds represented by the following general formulas [II] and [III].

General formula [II] General formula [III] (In the general formulas [II] and [III], L is an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -O-L ₈
- or -L ₉ -Z-L ₉ - represent. Wherein Z is, N-L ₁₀ -R _18, N-R ₂₀ or Represents

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

R _{11 to} R ₂₁ 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 _{11 to} R ₁₄ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least 2 of R _{15 to} R ₁₇
One is a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). [Specific Configuration of the Invention] In the color developer used in the processing method of the present invention, the compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention) is used as a preservative.

In the general formula [I], R ₁ represents an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and the like. Examples of the alkyl group having 1 to 5 carbon atoms with which the alkoxy group is substituted include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group and a pentyl group, and an alkyl group other than the methyl group. The substitution position of the alkoxy group substituted by is arbitrary.
Further, at least one alkoxy group may be substituted.

In the general formula [I], R ₂ is 1 to 5 carbon atoms substituted with an alkyl or alkoxy group having 1 to 5 carbon atoms.
5 represents an alkyl group having 5 carbon atoms, and the alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group represented by R ₂ represents the same group as the group represented by R ₁ and has 1 carbon atom.
Examples of the alkyl group of to 5 include those having an alkoxy group as a substituent in the group represented by R ₁ .

Hereinafter, specific examples of the compound of the present invention used in the treatment method of the present invention will be illustrated, but the present invention is not limited thereto.

Exemplified compound 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 compounds of the present invention may be used alone or in combination of two or more, and the addition amount may be any amount as long as the object of the present invention can be effectively achieved.
The amount is preferably 0.001 to 60 mol, more preferably 0.005 to 40 mol.

Incidentally, some of the compounds of the present invention are known as black-and-white developing agents. For example, in JP-A-61-43742, it is possible to use a dicarboxylic acid salt as a developer in a diffusion transfer processing composition. Has been described.

However, the use of the compounds of the present invention in a color developer not only acts as a good preservative, but it also catalyzes metal ions such as hydroxylamine sulfate, which has been widely used as a preservative in the past. The fact that the decomposition reaction described above hardly occurs was not known at all.

Furthermore, as compared with N, N-dialkylhydroxylamine such as N, N-diethylhydroxylamine, N, N-dimethylhydroxylamine having a similar structure, the compound of the present invention is -It has an advantage that there is almost no unpleasant amine odor peculiar to dialkylhydroxylamines, and also has a great advantage in practical use. Furthermore, N, N−
The compound of the present invention has no problem in this respect as compared with the problem that the dialkylhydroxylamines cause the color developing solution to be colored yellow and dye the photosensitive material.

The method of processing a silver halide color photographic light-sensitive material of the present invention is characterized in that the compound of the present invention is contained in a color developing solution. However, when the concentration of the compound of the present invention is increased, a cyan dye Since the maximum density tends to decrease, at least one of the silver halide emulsion layers of the silver halide color photographic light-sensitive material applicable to the present invention has the following general formulas [C-1] and [C-2]. ] It is preferable to contain at least one cyan coupler selected from the cyan couplers shown below.

The cyan coupler represented by the general formula [C-1] or [C-2], which is preferably used in the invention, will be described.

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 represents an alkyl group, an alkenyl group, a cycloalkyl group, 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, R ₄ and R ₅ may combine with each other to form a 5- or 6-membered ring), and R ₃ represents a ballast group, Z
Represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent.

In the general formulas [C-1] and [C-2], Y
Is -COR ₄ , -SO ₂ R 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, a 5- to 6-membered heterocyclic group containing 1 to 4 sulfur atoms (for example, a furyl group, a thienyl group,
Benzothiazolyl group). R ₅ is a hydrogen atom or
It represents a group represented by R ₄ . R ₄ and R ₅ may combine with each other to form a 5-membered to 6-membered heterocycle containing a nitrogen atom. Incidentally, any substituent can be introduced into R ₂ and R ₃ ,
For example, an alkyl group having 1 to 10 carbon atoms (eg ethyl, i-
Propyl, i-butyl, t-butyl, t-octyl etc.), aryl groups (eg phenyl, naphthyl etc.), halogen atoms (fluorine, chlorine, bromine etc.), cyano, nitro, sulfonamide groups (eg methanesulfonamide,
Butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl, carbamoyl group (eg, dimethyl). Sulfamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (eg, acetyl, benzoyl, etc.), heterocyclic group (eg, pyridyl group, pyrazolyl group, etc.), alkoxy group, aryloxy Group, acyloxy group and the like.

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. Examples thereof include linear or branched alkyl groups (for example, t-butyl, n-octyl, t-octyl, n-dodecyl etc.), alkenyl groups, cycloalkyl groups, 5-membered or 6-membered heterocyclic groups.

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] or [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 (for example, 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 1 to 20 carbon atoms.
An alkyl group of (for example, methyl, ethyl, tert-butyl,
Each group such as dodecyl), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (for example, an allyl group, a heptadecenyl group, etc.), a cycloalkyl group, preferably a 5- to 7-membered ring group (for example, a cycloalkoxyl group, etc.) Represents an aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), R ₃₈
Is a hydrogen atom or a group represented by R ₃₇ above.

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 is used as a substituent for the phenyl group.
Nitro, -SO ₂ R ₃₉ (R ₃₉ is an alkyl group), a halogen atom, compounds as are 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.), A cycloalkyl group, preferably a 5- to 7-membered ring group (eg cyclohexyl), an aryl group (eg phenyl group, tolyl group, naphthyl group etc.), a heterocyclic group (nitrogen atom, oxygen atom or sulfur atom) And a 5- to 6-membered heterocyclic ring, including, for example, a furyl group, a thienyl group, a benzothiazolyl group and the like.

The aforementioned R ₃₇ , R ₃₈ and the general formulas [C-4] and [C-
5], R ₃₅ and R ₃₆ in 5] can be further introduced with arbitrary substituents. Specifically, specific 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 the general formulas [C-3], [C-4] and [C-5], Z and R ₃ are the general formulas [C-1] and [C-2], respectively.
Has the same meaning as. 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]

The cyan coupler represented by the general formula [C-1] or [C-2] can be synthesized by various methods. For example, U.S. Pat. Nos. 2,772,162 and 3,758,308,
No. 3,880,661, No. 4,124,396, No. 3,222,176
No., British Patent Nos. 975,773, 8,011,693, and 8,01
1,694, JP-A-47-21139, 50-112038, 55-163
No. 537, No. 56-29235, No. 55-99341, No. 56-116030,
52-69329, 56-55945, 56-80045, 50-134
644, British Patent 1,011,940, U.S. Patent 3,44
0,622, 3,996,253, JP-A-56-65134, 57-2
04543, 57-204544, 57-204545, Japanese Patent Application No. 56-13
1312, 56-131313, 56-131314, 56-131309
No. 56, No. 56-131311, No. 57-149791, No. 56-130459,
JP-A-59-146050, 166956, 60-24547, 60-
It can be synthesized by the synthetic method described in 35731, 60-37557 and the like.

When the cyan coupler of 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.

The color developer used in the present invention preferably further contains at least one compound selected from the compounds represented by the following general formulas [II] and [III].

General formula [II] General formula [III] (In the general formulas [II] and [III], L is an alkylene group, a cycloalkylene group, a phenylene group, -L ₈ -O-L ₈
- or -L ₉ -Z-L ₉ - represent. Wherein Z is, N-L ₁₀ -R _18, N-R ₂₀ or Represents

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

R _{11 to} R ₂₁ 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 _{11 to} R ₁₄ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least 2 of R _{15 to} R ₁₇
One is a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). ) In the general formulas [II] and [III], 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, preferred specific exemplary compounds of the compounds represented by the general formulas [II] and [III] are shown below.

[Exemplified compound] [II-1] Ethylenediaminetetraacetic acid [II-2] Diethylenetriaminepentaacetic acid [II-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid [II-4 ] Propylenediaminetetraacetic acid [II-5] Triethylenetetraminehexaacetic acid [II-6] Cyclohexanediaminetetraacetic acid [II-7] 1,2-Diaminopropanetetraacetic acid [II-8] 1,3-Diaminopropane-2 -All-Tetraacetic acid [II-9] Ethyletherdiaminetetraacetic acid [II-10] Glycoletherdiaminetetraacetic acid [II-11] Ethylenediaminetetrapropionic acid [II-12] Phenylenediaminetetraacetic acid [II-13] Ethylenediaminetetraacetic acid Acetic acid disodium salt [II-14] ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [II-15] ethylenediaminetetra Acetic acid tetrasodium salt [II-16] Diethylenetriamine pentaacetic acid pentasodium salt [II-17] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid sodium salt [II-18] Propylenediamine Tetraacetic acid sodium salt [II-19] Ethylenediaminetetramethylenephosphonic acid [II-20] Cyclohexanediaminetetraacetic acid sodium salt [II-21] Diethylenetriaminepentamethylenephosphonic acid [II-22] Cyclohexanediaminetetramethylenephosphonic acid [III-1 ] Nitrilotriacetic acid [III-2] Iminodiacetic acid [III-3] Nitrilotripropionic acid [III-4] Nitrilotrimethylenephosphonic acid [III-5] Iminodimethylenephosphonic acid [III-6] Nitrilotriacetic acid trisodium salt Among these chelating agents represented by the general formula [II] or [III], compounds (II-1), (II-2) and (II) which are particularly preferably used from the viewpoint of the effects of the present invention are particularly preferable.
-5), (II-8), (II-19), (III-1) and (III-4)
Is mentioned.

The amount of the chelating agent represented by the general formula [II] or [III] to be added is preferably in the range of 0.1 to 20 g per 1 color developing solution, and is preferably 0.3 in view of the object of the present invention.
A range of 1010 g is particularly preferably used.

The color developing solution used in the present invention further includes a compound represented by the following general formula [IV], a compound represented by the general formula [V], a compound represented by the general formula [VI] and a general formula [VI
It is preferable to use at least one compound selected from the compounds represented by the formula [I] together.

General formula [IV] General formula [V] In the formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ and R ₅₆ are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a carbon number of 1 to
An alkyl group of 7, -OR ₅₇ , -COOR ₅₈ , Or a phenyl group. Also, R ₅₇ , R ₅₈ , R ₅₉ and R ₆₀
Are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₅₁ and R ₅₂ represent -OH or a hydrogen atom, R ₅₃ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OH ₅₇ , -COO.
R ₅₈ , Or, it represents a phenyl group.

Examples of the alkyl group represented by R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ and R ₅₆ include a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, a t-butyl group, an n- Butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group and the like, and also R ₅₇ , R ₅₈ ,
The alkyl group represented by R ₅₉ and R ₆₀ has the same meaning as described above, and further includes an octyl group and the like.

The phenyl group represented by R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ and R ₅₆ is a phenyl group, a 2-hydroxyphenyl group,
4-aminophenyl group etc. are mentioned.

Typical specific examples of the compounds represented by the general formulas [IV] and [V] are shown below, but the invention is not limited thereto.

(IV-1) 4-isopropyl-1,2-dihydroxybenzene (IV-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (IV-3) 1,2,3-trihydroxybenzene-5- Carboxylic acid (IV-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (IV-5) 1,2,3-trihydroxybenzene-5-carboxy-n-butyl ester (IV-6) 5-t-butyl-1,2,3-trihydroxybenzene (IV-7) 1,2-dihydroxybenzene-3,4,5-trisulfonic acid (IV-8) 1,2-dihydroxybenzene-3, 5,6-Trisulfonic acid (V-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (V-2) 2,3,8-Trihydroxynaphthalene-6-sulfonic acid (V-3) 2,3 -Dihydroxynaphthalene-6-carboxylic acid (V-4) 2,3-dihydroxy-8-isopropyl-naphthalene (V-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 compounds represented by the general formulas [IV] and [V] can be used in a range of 5 mg to 20 g, preferably 10 mg to 10 g, more preferably 2 mg per developer.
Good results are obtained with the addition of 0 mg to 3 g.

General formula [VI] (Represented in the general formula _{[VI], R 61, R} 62 and R ₆₃ are each a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt) or a phosphoric acid group (including salts thereof). However R _61, R ₆₂
And at least one of R ₆₃ is a hydroxyl group, and R ₆₁ , R
Only one of ₆₂ and R ₆₃ is a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof).
n ₁ , n ₂ and n ₃ each represent an integer of 1 to 3. ) In the general formula [VI], R ₆₁ , R ₆₂ and R ₆₃ are each a hydrogen atom, a hydroxyl group or a carboxylic acid group (including salts thereof).
Or a phosphate group (including a salt thereof), and examples of the salt of a carboxylic acid group and a phosphate group include salts of an alkali metal atom and salts of an alkaline earth metal atom, and preferably sodium, potassium, and the like. And the like. Further, at least one of R ₆₁ , R ₆₂ and R ₆₃ is a hydroxyl group, and any one of R ₆₁ , R ₆₂ and R ₆₃
Only one is a carboxylic acid group (including its salt) or a phosphoric acid group (including its salt). R ₆₁ , R ₆₂ and R ₆₃ are preferably selected from a hydroxyl group, a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof).
n ₁ , n ₂ and n ₃ each represent an integer of 1 to 3.

Hereinafter, typical specific examples of the compound represented by the general formula [VI] will be described, but the invention is not limited thereto.

General formula [VII] In the general formula [VII], R ₇₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₇₂ and R ₇₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, and a benzyl group. Or expression In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.

Of the compounds represented by the general formula [VII], the compound represented by the following general formula [VIIa] is preferably used.

R ₇₁ is preferably a hydroxyalkyl group having 2 to 4 carbon atoms, and R ₇₂ and R ₇₃ are preferably alkyl groups having 1 to 4 carbon atoms or hydroxyalkyl groups having 2 to 4 carbon atoms.

Preferred specific examples of the compound represented by the general formula [VII] are as follows.

Ethanolamine, diethanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-
Dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propanol, 3-dimethylamino-1-propanol, isopropylaminoethanol,
3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, ethylenediaminetetraisopropanol, benzyldiethanolamine, 2-
Amino-2- (hydroxymethyl) -1,3-propanediol.

These compounds represented by the above general formulas [VI] and [VII] are preferably used in the range of 3 g to 100 g, and more preferably in the range of 6 g to 50 g, per 1 color developer from the viewpoint of the effect of the object of the present invention. Used in.

General formula [VIII] (In the formula, R ₈₁ represents an alkylene group having 1 to 6 carbon atoms, R ₈₂ represents an alkyl group, and n represents an integer of 500 to 20,000.) 1 to 8 carbon atoms represented by R ₈₁ . The alkylene group of 6 may be linear or branched, and preferably has 2 to 4 carbon atoms.
And an alkylene group such as ethylene group, propylene group, butene group, isobutene group, dimethylethylene group and ethylethylene group. The alkyl group represented by R ₈₂ is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and the like, and a group having a substituent (for example, a hydroxyl group) is also included. . n represents the number of repeating units in the polymer chain,
Represents an integer of 500 to 20,000, preferably 500 to 2,000
Is an integer. Most preferred for the purposes of the present invention are poly (ethyleneimines) in which R ₈₁ is an ethylene group.

Specific examples of the poly (alkyleneimine) represented by the general formula [VIII] are shown below, but the invention is not limited thereto.

Exemplified compound The poly (alkyleneimine) can be used in the color developing solution in any amount that can achieve the object of the present invention, but generally 0.1 to 500 g per 1 color developing solution is preferable,
It is more preferably used in the range of 0.5 g to 300 g.

The compound of the present invention represented by the above general formula [I] may be used in combination with other preservatives. Examples of the preservatives that can be used in combination include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like. And bisulfite adducts of aldehydes or ketones such as bisulfite adduct of formaldehyde and bisulfite adduct of glutaraldehyde.

As the color developing agent used in the color developing solution of the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used in order to reduce coloring and color contamination.

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, by combining with the compound represented by the general formula [I] in the present invention, the object of the present invention can be efficiently achieved.

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- (C
_{H 2) n -CH 3, -} (CH 2 CH 2 O) n C m H 2m + 1 (m and n each represent an integer of 0 or more), -. COOH group, -SO ₃ H group and the like It is mentioned as a thing.

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 preferable for use in the present invention because of less coloring and color contamination are 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.

In the present invention, when a triazylstilbene-based fluorescent whitening agent represented by the following general formula [IX] is used for the color developing solution according to the present invention, gamma of a cyan dye is stabilized, and color contamination is further reduced, which is preferable.

General formula [IX] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ each represent 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 groups (eg, methyl, ethyl, etc.), aryl groups (eg, phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (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-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-based whitening agent represented by the general formula [IX] 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 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, for example, sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination And can be used. 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 others described in U.S. Pat.No. 2,304,925, acetylene glycol, methyl ethyl ketone,
Examples thereof include cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines.

In the above, particularly for poorly water-soluble organic solvents typified by benzyl alcohol, tar is liable to be generated particularly in a running process in a low replenishment system due to long-term use of a color developing solution, and such tar is generated. Adheres to the paper to be treated,
It may even cause a serious failure that significantly impairs its commercial value.

In addition, poorly soluble organic solvents have poor solubility in water, which not only complicates the necessity of using a stirrer for preparing the color developing solution itself, but also reduces the dissolution rate by using such a stirrer. Due to the badness, the development promoting effect has a limit.

Furthermore, poorly soluble organic solvents have a large pollution load value such as biochemical oxygen demand (BOD), and it is not necessary to dispose of them in sewers or rivers. Since it has problems such as requiring labor and cost of
It is preferable to reduce or eliminate the amount used.

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

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

In the present invention, the processing temperature for color development is 30 ° C.
As described above, the higher the temperature is 50 ° C. or lower, the faster 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.

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.

In the present invention, any system using a color developing solution containing the compound of the present invention represented by the general formula [I] can be applied. For example, a single bath treatment and other various methods such as treatment Various processing methods such as a spray method in which the liquid is sprayed, a web method by contact with a carrier impregnated with the processing liquid, and a developing method using a viscous processing liquid can be used, but the processing step is substantially coloration. It consists of steps of development, bleach-fix, washing with water or a stabilization process instead of this.

In the bleach-fixing step, a bleaching step and a fixing step may be separately provided, or a bleach-fixing bath in which bleaching and fixing are performed in a single bath may be used.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is a metal complex salt of an organic acid. The complex salt is obtained by coordinating a metal ion such as iron, cobalt or copper with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes 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] Ethyl Etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are preferably 5-450 g / l. Is 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 halide such as ammonium bromide. It is also possible to use a bleach-fixing solution having a composition added in a large amount, 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. it can. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, 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 such that they can be dissolved at 5 g / l or more, but generally 70 g to 250 g / l.

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, ammonium hydroxide and the like 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 hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or stabilizers such as nitroalcohols and nitrates,
An organic solvent such as methanol, dimethylsulfamide, dimethylsulfoxide or the like may be appropriately contained.

The bleach-fixing solution used in the present invention includes JP-A-46-280, JP-B-48-8506, and JP-A-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, with a further preferred pH of 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.

In the present invention, subsequent to the color development and bleach-fixing steps, washing with water or an alternative stabilizing treatment with washing is performed.

Hereinafter, the washing stabilizing solution applicable to the present invention will be described.

The pH of the washing alternative stabilizer applicable to the present invention is preferably in the range of 5.5 to 10.0, and more preferably pH 6.3 to 9.5.
And particularly preferably pH 7.0 to 9.0. As the pH adjusting agent that can be contained in the washing-substitute stabilizing solution applicable to the present invention, any commonly known alkali agent or acid agent can be used.

The treatment temperature of the stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ℃ ~ 45 ℃ is good. The processing time is also preferably shorter from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes,
The time is most preferably 1 minute to 3 minutes. In the case of the multiple tank stabilization treatment, it is preferable that the treatment is performed in a shorter time in the former tank and the treatment time is longer in the latter tank. In particular, it is desirable to sequentially perform the treatments with a treatment time that is 20% to 50% longer than that in the previous tank. No water washing treatment is required after the stabilization treatment applicable to the present invention, but rinsing by small amount of water washing and surface washing in an extremely short time can be arbitrarily performed as necessary.

In the case of using a multi-tank countercurrent method, it is preferable to supply a post-bath bath and overflow from a pre-bath, when a stabilizing treatment step applicable to the present invention is supplied in a stabilizing treatment step using a multi-tank countercurrent method. Of course, it can also be processed in a single tank. As a method of adding the above compound, the compound and other additives are added to a stabilization tank as a concentrated solution, or the above-mentioned compound and other additives are added to a stabilization tank to be replaced with a water washing alternative stabilizing solution. Although there are various methods such as a method of supplying the liquid, the liquid may be added by any method.

As described above, in the present invention, the treatment with the water-washing alternative stabilizing solution refers to a treatment for stabilizing treatment in which the stabilizing treatment is carried out immediately after the treatment with the bleach-fixing solution and substantially no washing treatment is carried out. The treatment liquid used for is called a water-washing substitute stabilizer, and the treatment tank is called a stabilizing bath or a stabilizing tank.

The stabilization tank in the stabilization treatment applicable to the present invention is 1 to
When the number of tanks is five, the effect of the present invention is large, particularly preferably one to three tanks, and preferably at most nine tanks or less.

The crystal of the silver halide grain 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.

In addition, 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 allyl thiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salts and thiodioxide. Urea, polyamines and the like; noble metal sensitizers such as gold sensitizers, specifically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride and the like, or ruthenium, palladium, platinum, Sensitizers of water-soluble salts such as rhodium and iridium, specifically, ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or fog suppression depending on the amount thereof). Acting alone or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer). Combination of agents, together like a gold sensitizer and a selenium sensitizer) may be chemically sensitized with.

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 929,080 and U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in No. 3,694,217, No. 4,025,349, No. 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. Patents 1,939,201, 2,072,908, and 2,739,149.
Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes such as those described in U.S. Pat. No. 2,945,763 and British Patent 505,979. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent Nos. 2,269,234 and 2,270,3
Representative examples thereof include cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in Nos. 78, 2,443,710, 2,454,629, and 2,776,280. Furthermore, U.S. Patent No. 2,213,995,
Cyanine dyes, merocyanine dyes, or complex cyanine dyes such as those described in U.S. Pat.

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.

A typical example of a particularly preferable spectral sensitization method is, for example, 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.

Further, as a combination of carbocyanine having a benzimidazole nucleus and other cyanine, or merocyanine, for example, JP-B-45-25831, JP-A-47-11114,
47-25379, 48-38406, 48-38407, 54-345
No. 35, No. 55-1569, JP-A No. 50-33220, No. 50-38526
No. 51, No. 51-107127, No. 51-115820, No. 51-135528,
52-104916, 52-104917, etc.

Further, as a combination of benzoxazolocarbocyanine (oxa-carbocyanine) and another 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, 48-41204 and 50-4.
0662, JP-A-56-25728, 58-10753, 58-91445
No. 59-116645 and No. 50-33828.

Further, as a combination of thiacarbocyanine and other carbocyanine, for example, Japanese Patent Publication No. 43-4932,
43-4933, 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 a styryl dye can be advantageously used.

To add these sensitizing dyes to the silver halide emulsion according to the present invention, as a dye solution, for example, methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in Japanese Patent Publication No. 50-40659 is used. 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 are British Patent 584,609.
No. 1,277,429, JP-A-48-85130, 49-99620
No. 49, No. 114420, No. 49-129537, No. 52-108115,
59-25845, 59-111640, 59-111641, US Patents 2,274,782, 2,533,472, 2,956,079, 3,1
25,448, 3,148,187, 3,177,078, 3,247,12
No. 7, No. 3,260,601, No. 3,540,887, No. 3,575,704,
3,653,905, 3,718,472, 4,071,312, 4,0
The thing described in 70,352 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.

The silver halide emulsion layers according to the present invention may each contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the above-mentioned coupler which can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and diffusible dye-releasing couplers and the like can be used in combination with these couplers.

Among the photographic couplers used in the present invention, the cyan coupler is the above-mentioned cyan coupler.

As the photographic magenta coupler, a pyrazolone-based compound, a pyrazolinobenzimidazole-based compound, an indazolone-based compound or the like is used. As a pyrazolone-based magenta coupler, U.S. Pat.Nos. 2,600,788, 3,062,653, and 3,127,
No. 269, No. 3,311,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,318, No. 3,684,514, No. 3,888,680,
JP-A-49-29639, 49-111631, 49-129538,
50-13041, Japanese Patent Publication No. 53-47167, 54-10491, 55-3
As the compound described in No. 0615, the diffusion-resistant colored magenta coupler, a compound in which an arylazo substitution is generally used at the coupling position of a colorless magenta coupler is used, for example, U.S. Pat.
3,608, 3,005,712, 3,684,514, British patent 93
The compounds described in JP-A No. 7,621 and JP-A Nos. 49-123625 and 49-31448 can 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.

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. Includes bound timing DIR compounds.

The amount of the DIR compound contained in the photosensitive material is preferably in the range of 1 × 10 ⁻⁴ mol to 10 × 10 ⁻³ 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, the stability of the color developer such as preservability is excellent over time, and fluctuations in photographic performance such as fog in the dye image and high contrast of the shoulder portion occur. A method for processing a silver halide color photographic light-sensitive material excellent in processing stability can be provided.

Further, according to the present invention, there can be provided a processing method of a silver halide color photographic light-sensitive material in which the maximum variation of the cyan dye concentration is small.

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 to these.

[Example 1] Color developer Nos. 1 to 6 having the following compositions were prepared.

(Color developer) Ferric ion 4ppm, copper ion 2ppm in the above color developer
(FeCl ₃ , CuSO ₄ · 6H ₂ O are respectively dissolved and added) and added at 33 ° C in a glass container with an opening ratio of 150 cm ² / l (air contact area for a color developer of 1 is 150 cm ² ). The concentration of the color developing agent in the color developing solution was analyzed by the cerium sulfate method while storing, and the number of days until the concentration of the color developing agent became 0 was determined as the life of the color developing solution.

 The results are also shown in Table 1.

As is clear from the results in Table 1, one of the conventional preservatives
In a color developer using hydroxylamine sulfate, the life of the color developer when metal ions are mixed is short. On the other hand, the life of each of the color developing solutions using the compound of the present invention is greatly extended.

Example 2 A silver halide light-sensitive material was prepared by sequentially coating the following layers on a polyethylene-supported paper support from the support side.

Gelatin layer ^{1 ...... 1.20g / m 2, 0.40g} / m 2 ( in terms of silver, hereinafter the same) blue-sensitive silver halide emulsion (AgBr: AgCl = 4: 9
6) and 1.0 dissolved in 0.55 g / m ² of dioctyl phthalate
A layer containing the following yellow coupler (YR) in an amount of × 10 ^-3 mol g / m ² .

Layer 2: an intermediate layer made of 0.70 g / m ² gelatin.

Layer 3 ...... 1.20g / m ² of gelatin, 0.22 g / m ² green-sensitive silver halide emulsion (AgBr: AgCl = 3: 97 ) 1.0 dissolved in dioctyl phthalate and 0.30g / m ² × 10 ^-3 A layer containing mol g / m ² of the following magenta coupler (MR).

Layer 4: An intermediate layer made of 0.70 g / m ² of gelatin.

Layer 5 ...... 1.20g / m ² of gelatin, of 0.28 g / m ² red-sensitive silver halide emulsion (AgBr: AgCl = 4: 96 ) and 0.25 g / m ² of 1.75 × dissolved in dibutyl phthalate ^10-3 A layer containing the moles of g / m ^{2 of} an exemplary cyan coupler (C-76).

Layer 6 A layer containing 0.32 g / m ² of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) dissolved in 1.0 g / m ² of gelatin and 0.25 g / m ² of dioctyl phthalate.

Layer 7: Layer containing 0.48 g / m ² of gelatin. As a hardening agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to layers 2, 4 and 7 so that the amount was 0.017 g per 1 g of gelatin.

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

Processing step Processing temperature Processing time (1) Color development 35 ° C 45 seconds (2) Bleaching and fixing 35 ° C 45 seconds (3) Rinse 30 ° C 90 seconds (4) Dry 60-80 ° C 60 seconds No. 7 to 13 having the following composition
belongs to.

(Color developer) The bleach-fix solution used had the following composition.

[Bleaching fixer] The sample after the treatment was measured for the reflection density of the cyan dye using an optical densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.),
The minimum reflection density of the magenta dye was measured while creating a sensitometric curve. Next, the reflection density of cyan dye
The slope (gamma value) from the density point of 0.8 to the density point of reflection density 1.8 was calculated.

The same metal ions as in Example 1 were added to the color developing solution after the processing, and stored at 35 ° C. for one week. Repeat the same process after storage to measure the minimum reflection density of magenta dye,
The cyan gamma value was calculated.

The difference in the minimum reflection density of the magenta dye before and after storage and the difference in the cyan gamma value were determined and are shown in Table 2.

As is clear from Table 2, in the case of processing with the color developing solution using hydroxylamine sulfate which is one of the conventional preservatives, the fog density of magenta and the gamma of cyan after storage are remarkably increased. . On the other hand, it can be seen that all the products treated with the color developing solution using the compound of the present invention as a preservative are good.

[Example 3] In the color developer No. 12 of Example 2, the chelating agent V-
When exactly the same color developing solution was used except that 2 was not added and the same experiment as in Example 2 was repeated, magenta fog further increased by 0.02 and cyan gamma further increased by +0.2. Further, color developing solutions No. 14 to 19 in which the chelating agent of the color developing solution No. 12 of Example 2 was changed as shown in Table 3 were prepared, and the same experiment as in Example 2 was repeated, but almost the same was carried out. Similar results to the example were obtained.

[Example 4] In the color developer No. 12 of Example 2, the exemplified compounds (A'-2), (A'-4) and (A'-9) (all triazyl stilbene optical brighteners) were added. When 2 g / l was added to each and the same experiment as in Example 2 was carried out, the increase in cyan gamma was further improved by 0.05.

Example 5 A sample used in Example 2 and a sample in which the cyan coupler of the sample was replaced with the following cyan coupler C-R were used in Example 2.
It processed by the same process as.

The maximum concentration of cyan dye in the sample after treatment is shown in Table 4. However, here, the preservative and the addition amount in the color developing solution are as described in Table 4.

As is clear from Table 4, with respect to the variation of the maximum concentration of the cyan dye with respect to the cyan coupler (CR) with respect to the quantitative change of the compound of the present invention, the exemplified cyan coupler (C-76) was used.
It can be seen that the variation of maximum cyan dye density is extremely small in the case of using. Also, an example cyan coupler (C-76)
Instead of, the exemplified cyan couplers (C-1) and (C-
Similar experiments were conducted with samples using 3), (C-19), (C-58), etc., but good results were obtained in which the fluctuation of the maximum density of the cyan dye was extremely small.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Ishikawa 1 Sakura-cho, Hino-shi, Tokyo Inside Konishi Roku Photo Industrial Co., Ltd. (56) References JP 59-197037 (JP, A) JP 63- 5341 (JP, A) US Patent 3293034 (US, A)

Claims (2)

[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 cyan couplers represented by the following general formulas [C-1] and [C-2] is contained in at least one of the silver halide emulsion layers, and a color developing solution used in the color developing step is At least one selected from the compounds represented by the following general formula [I] and the compounds represented by the following general formulas [IV], [V], [VI] and [VII]:
A method of processing a silver halide color photographic light-sensitive material, characterized by containing various compounds. General formula [C-1] General formula [C-2] (In the formula, Y is -COR ₄ , -CONHCOR ₄ or -CONHSO ₂ R ₄ (R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group. Or represents a heterocyclic group, R ₄
And R ₅ may combine with each other to form a 5- or 6-membered ring. And R ₃ represents a ballast group, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine type color developing agent. However, the coupler except for. ) General formula [I] (In the formula, R ₁ has 1 to 1 carbon atoms substituted with an alkoxy group.
5 represents an alkyl group having 5 carbon atoms, and R ₂ has 1 to 5 carbon atoms substituted with an alkyl group having 1 to 5 carbon atoms or an alkoxy group.
Represents an alkyl group of general formula [IV] General formula [V] (In the formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R _55, and R ₅₆ are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a carbon atom number of 1 to 1.
An alkyl group of 7, -OR ₅₇ , -COOR ₅₈ , Or represents a phenyl group. Also, R ₅₇ , R ₅₈ , R ₅₉ and R
₆₀ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₅₁ and R ₅₂ represent —OH or a hydrogen atom, R ₅₃ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅₇ , —COOR ₅₈ , Or represents a phenyl group. ) General formula [VI] (In the general formula [VI], R ₆₁ , R ₆₂ and R ₆₃ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof. However, R ₆₁ At least one of R ₆₂ and R ₆₃ is a hydroxyl group, and R ₆₁ and R ₆₃
Only one of ₆₂ and R ₆₃ is a carboxylic acid group (including a salt thereof) or a phosphoric acid group (including a salt thereof).
n ₁ , n ₂ and n ₃ each represent an integer of 1 to 3. ) General formula [VII] (In the general formula [VII], R ₇₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₇₂ and R ₇₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, Benzyl group or formula In the above formula, n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. ) 2. The color developing solution used in the color developing step contains at least one compound selected from the compounds represented by the following general formulas [II] and [III]. The method for processing a silver halide color photographic light-sensitive material as described in 1) above. General formula [II] General formula [III] (In the general formulas [II] and [III], L is an alkylene group,
Cycloalkylene group, a phenylene group, -L ₈ -O-L ₈ -O
-L ₈ - or -L ₉ -Z-L ₉ - represents a. Where Z is Represents L _{1 to} L ₁₃ each represent an alkylene group. R ₁₁ or R ₂₁
Each represents a hydrogen atom, a hydroxyl group, a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof). However, at least two of R _{11 to} R ₁₄ are a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof),
At least two of R _{15 to} R ₁₇ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof).
Is. )