JPH0527395A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce an amount of replenishing solution of a photographic processing solution and to enhance the low temperature stability of a color developing solution by incorporating 2 kinds of specified compound in the color processing solution. CONSTITUTION:The color developing solution contains at least each one of the compounds represented by formulae I and II, respectively, in which each of R1-R4 is, independently, H, alkyl, aryl, aralkyl, or the like, or R1 may combine with R2 to form a condensed ring; and each of m and n is, independently, 0, 1, 2, or 3; L is optionally substituted alkylene; A is carboxy, sulfo, phosphono, alkylsulfonyl, or the like; R is H or optionally substituted alkyl, thus permitting the replenishing amount of the photographic processing solution to be reduced and low temperature stability of the developing solution to be enhanced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method of a silver halide color photographic light-sensitive material of the present invention, and more particularly to a processing method in which there is no precipitation in a color developing solution and there is little photographic processing waste solution. Furthermore, the present invention relates to a processing method in which the stain does not increase even during continuous processing.

[0002]

2. Description of the Related Art In recent years, reduction of photographic processing waste liquid has become an important issue from the viewpoint of environmental protection. In order to reduce the photographic processing waste liquid, it is known to perform a so-called low replenishment process for reducing the replenishment amount of the process replenisher during continuous processing. In order to reduce the replenishment of the color developing solution, it is generally necessary to increase the concentration of the developing agent or preservative, which is a compound in the color developing replenishing solution and is a consumption component at the time of color development. However, if the color developing solution is made thicker, the developing agent and the like will deposit at a low temperature during storage of the solution, which will cause troubles such as clogging of the replenishing pump and maintenance of stable photographic performance. In order to solve these problems, various crystal precipitation inhibitors have been developed. For example, JP-B-47-20743 describes the use of a homopolymer or copolymer of polyvinyl alcohol or polyvinylpyrrolidone in a color developing solution. Further, JP-B-58-16179 and JP-A-53-69035 describe adding an ethylenically unsaturated polymer and higher fatty acids to a color developer. Certainly, these compounds show the effect of preventing the precipitation of crystals, but the effect is weak, and it was found that when continuous processing was performed, the sample immediately after the development was likely to be contaminated,
It was a big obstacle for practical use. That is, even if various compounds are simply used for preventing precipitation, there is a problem that if the treatment is continued for a long period of time, stains, that is, stains immediately after the treatment or Dmin increase.

[0003]

Therefore, the first aspect of the present invention
It is an object of the invention to provide a processing method in which the replenishment amount of the photographic processing solution is small and the low temperature stability of the color developing solution is excellent. A second object of the present invention is to provide a treatment method which does not increase stains immediately after treatment even when continuous treatment is performed.

[0004]

The above problems can be solved by the following method. That is, in a method of treating a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent after imagewise exposure, the color developing solution is represented by the following general formula ( I)
It can be achieved by a method of processing a silver halide color photographic light-sensitive material characterized by containing at least one compound represented by the following formula and at least one compound represented by the following general formula (II).

General formula (I)

[Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxy group, an amino group, an alkoxy group, a carboxy group, sulfo group, a phosphono group, a nitro group, a cyano group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, an acyl group, an acylamino group, alkylsulfonylamino group, arylsulfonylamino group, and .R ₁ representing the alkoxycarbonyl group or a ureido group R ₂
May be linked to each other to form a condensed ring. m and n may be the same or different and each represents an integer of 0 or 1 to 3. )

General formula (II)

[Chemical 4] (In the formula, L represents an optionally substituted alkylene group, and A
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl substituted, an ammonio group which may be alkyl substituted, a carbamoyl group which may be alkyl substituted, or an alkyl substituted. Represents a good sulfamoyl group or an optionally substituted alkylsulfonyl group, and R represents a hydrogen atom or an optionally substituted alkyl group. )

Further, the method of the present invention is particularly effective when used in a color developing solution having a high concentration such that the concentration of the color developing agent in the color developing solution is 21 ml / liter.

The compound represented by formula (I) of the present invention will be described in more detail. In the formula, R ₁ , R ₂ , R ₃ , and R ₄
May be the same or different, each is a hydrogen atom, an alkyl group,
Aryl group, aralkyl group, halogen atom, hydroxy group, amino group, alkoxy group, carboxy group, sulfo group, phosphono group, nitro group, cyano group, heterocyclic group, carbamoyl group, sulfamoyl group, acyl group, acylamino group, alkyl It represents a sulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, or a ureido group. R ₁ and R ₂ may be the same or different, and R ₁ and R ₂ may be connected to each other to form a condensed ring. An alkyl group, an aryl group, an aralkyl group, an amino group, an alkoxy group, a heterocyclic group (a 5- or 6-membered ring substituent containing at least one nitrogen atom, which may contain a carbon atom, a sulfur atom, or an oxygen atom, For example, pyridyl group, pyrimidinyl group, tetrazolyl group, morpholino group, piperazinyl group,
Represents a pyrrolidinyl group. ), A carbamoyl group, a sulfamoyl group, an acyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, and an alkoxycarbonyl group may be further substituted with a substituent, and the substituents may be R ₁ , R ₂ and R. It is the same as the substituents mentioned in ₃ and R ₄ .

R ₁ and R ₂ are preferably hydrogen atoms,
A substituted or unsubstituted alkyl group having a total of 1 to 15 carbon atoms,
A substituted or unsubstituted aryl group having a total of 6 to 15 carbon atoms and a substituted or unsubstituted aralkyl group having a total of 7 to 15 carbon atoms, particularly preferably a total substituted with an alkylsulfonylamino group, a hydroxy group or a ureido group. It is an alkyl group having 1 to 10 carbon atoms. R ₃ and R ₄ are preferably a hydrogen atom and a total carbon number of 1 to
15 substituted or unsubstituted alkyl groups, total carbon number 6 to
15 substituted or unsubstituted aryl groups, total carbon number 7 to
15 substituted or unsubstituted aralkyl groups and heterocyclic groups are preferable. Particularly preferably hydrogen atom, total carbon number of 1 to 1
0 is a substituted or unsubstituted alkyl group. m and n may be the same or different and each represents an integer of 0 or 1 to 3. These compounds may be salts such as sulfate, hydrochloride, sulfite and p-toluenesulfonate. Examples of the specific compound include, but are not limited to, the following compounds.

[0010]

[Chemical 5]

[0011]

[Chemical 6]

[0012]

[Chemical 7]

Regarding the synthesis of the above compounds, Organic Reac
tions, Volume 7, pages 59-98. (John Wiley & Sons I
nc.). The content of these compounds in the color developing solution is preferably 0.00 per 1 liter of the color developing solution.
It is 1 g to 10 g, more preferably 0.005 to 5 g, and further preferably 0.005 g to 2 g.

Next, the compound represented by the general formula (II) of the present invention will be described in more detail. In the formula, L has 1 to 10 carbon atoms
Represents a linear or branched alkylene group which may be substituted, and preferably has 15 carbon atoms. Specifically, methylene,
Preferred examples include ethylene, propylene and butylene. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group,
It represents an ammonio group which may be alkyl-substituted, and preferred examples thereof include a carboxyl group, a sulfo group, a phosphono group and a hydroxyl group. A is a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an alkyl-substituted amino group, an alkyl-substituted ammonio group, an alkyl-substituted carbamoyl group, or an alkyl-substituted Represents a good sulfamoyl group, a carboxyl group, a sulfo group, a hydroxyl group,
Preferred examples include a phosphono group and a carbamoyl group which may be alkyl-substituted. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group,
A carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be mentioned as particularly preferable examples.

R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. As the substituent, a carboxyl group,
A sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, and a sulfamoyl group which may be alkyl-substituted. Represent. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group and a hydroxyethyl group, and a hydrogen atom and carboxymethyl group. A group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferable examples. L and R may combine to form a ring. Further, these may be alkali metal salts (for example, sodium, potassium, lithium).

The specific compounds of the present invention are described below, but the invention is not limited thereto.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

The compound represented by the general formula (II) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction). West German Patent 1159634
Publication, "Inorganica Chemika Actor" (Inorgai
ca Chimica Acta), 93 (1984) 101-108 and the like, but the specific method is described below. Synthesis Example Synthesis of Exemplified Compound (II-7) To 200 ml of an aqueous solution of 20 g of hydroxylamine hydrochloride, 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added, and the mixture was kept at 60 ° C. and 40 ml of an aqueous solution of 23 g of sodium hydroxide was taken for 1 hour. And slowly added.
Further, the reaction solution was concentrated under reduced pressure for 3 hours at 60 ° C.,
200 ml of concentrated hydrochloric acid was added and heated to 50 ° C. The insoluble material was filtered and 500 ml of methanol was added to the filtrate to obtain the desired product (Exemplified compound (II-7)) as crystals of monosodium salt. Four
1 g (53% yield)

Synthesis of Exemplified Compound (II-11) Hydroxylamine hydrochloride 7.2 g and phosphorous acid 18.0 g
32.6 g of formalin was added to the hydrochloric acid aqueous solution of and heated under reflux for 2 hours. The generated crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified compound (II-11). The content of these compounds in the color developing solution is preferably 0.1 g to 50 per liter of the color developing solution.
g, more preferably 0.2 to 20 g. These compounds may be present in the light-sensitive material and dissolved in the color developing solution to have the above content.

A preferred example of the aromatic primary amine color developing agent used in the present invention is a p-phenylenediamine derivative, and a typical example thereof is N, N-dimethyl-p-.
Phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-N-laurylamino) toluene, 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2 -Methyl-4-
[N-ethyl-N- (β-hydroxyethyl) amino]
Aniline, 4-amino-3-methyl-N-ethyl-N-
[Β (methanesulfonamido) ethyl] -aniline, N
-(2-amino-5-diethylaminophenylethyl)
Methanesulfonamide, N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-
N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, 4-
Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline and the like can be mentioned. Particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline. Further, these p-phenylenediamine derivatives are sulfates,
It may be a salt such as hydrochloride, sulfite or p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is generally about 4 mmol to 50 mmol per liter of the color developing solution, but the amount of the color developing replenishing solution is preferably 1 liter of the replenishing solution. Is about 2
The concentration is 1 millimolar to 45 millimolar, more preferably about 23 millimolar to 40 millimolar. Even at such high concentrations, the method of the present invention is particularly effective.

In carrying out the present invention, in the work environment,
It is preferred to use a color developer which is substantially free of benzyl alcohol. Here, the term "substantially free from" means that the concentration of benzyl alcohol is preferably 21 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably benzyl alcohol is not contained at all.

The color developing solution used in the present invention contains substantially no sulfite ion in order to suppress fluctuations in photographic characteristics associated with continuous processing (substantially no sulfite ion here means a sulfite ion concentration of 3). 0.0 × 10 ⁻³ mol / liter or less) is more preferable. Most preferably, it contains no sulfite ion at all. However, in the present invention, however, a very small amount of sulfite ion used for the antioxidant of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded.

The color developer used in the present invention preferably contains substantially no sulfite ion, but in order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine, it further contains hydroxylamine. It is more preferable not to do so (the term "substantially free of inclusion" means that the hydroxylamine concentration is 5.0 × 10 ^-3 mol / liter or less). Most preferably, it contains no hydroxylamine.

The color developing solution used in the present invention may contain the following organic preservatives. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing the oxidation of a color developing agent due to air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Ketones,
Combined with organic preservatives such as α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. May be. These are disclosed in JP-B-48-30496 and JP-A-52.
143020, 63-4235, 63-30
No. 845, No. 63-21647, No. 63-44655.
63, 53-55131, 63-43140, 63-56654, 63-58346, 63-.
43138, 63-146041, 63-44.
657, 63-44656, U.S. Pat. No. 3,61.
5,503, 2,494,903, JP-A-1-9
7953, 1-186939, 1-18694
No. 0, No. 1-187557, No. 2-306244, etc. Other preservatives include JP-A-57
-44148 and 57-53749, various metals, salicylic acids described in JP-A-59-180588, JP-A-63-239447, and JP-A-63-128.
340, JP-A-1-186939 and 1-1875.
Amines as described in JP-A-57-35,
No. 32 alkanolamines, JP-A-56-94
Polyethyleneimines described in U.S. Pat.
You may use the aromatic polyhydroxy compound etc. of 746,544 etc. as needed.

In the present invention, it is preferable that the color developer contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. Particularly preferably 3.5 × 10 ^-2
˜1 × 10 ⁻¹ mol / liter. When the chlorine ion concentration is more than 1.5 × 10 ⁻¹ to 10 ⁻¹ mol / liter, it has a drawback of delaying the development and is not preferable for achieving the object of the present invention that it is rapid and the maximum concentration is high. Further, if it is less than 3.0 × 10 ^-2 mol / liter, it is not preferable for preventing fog. In the present invention, bromine ions are contained in the color developing solution in an amount of 3.0 × 10 ⁻⁵ mol / liter.
It is preferably contained at 1.0 × 10 ⁻³ mol / liter. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter. Bromine ion concentration is 1 × 10 ^-3 mol /
If it is more than liter, the development is delayed and the maximum density and sensitivity are lowered. If it is less than 3.0 × 10 ^-5 mol / liter, fog cannot be sufficiently prevented.

Here, the chlorine ion and the bromine ion may be added directly to the color developing solution, or may be eluted from the light-sensitive material into the color developing solution during the development processing. When added directly to the color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. Further, it may be supplied from the fluorescent whitening agent added to the color developing solution. As a source of bromide ions,
Examples thereof include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide. When eluted from the light-sensitive material during the development processing, chlorine ions and bromine ions may be supplied together from the emulsion,
It may be supplied from sources other than emulsion.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution contains compounds of other known developing solution components. be able to. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt,
3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, carbonate, phosphate, tetraborate and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH range of pH 9.0 or more, and even if added to a color developing solution, they adversely affect photographic performance. It is preferable to use these buffers, because they have the advantages of being free from (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the color developer is preferably 0.1 mol / liter or more, and particularly 0.1 mol / liter to 0.1.
It is particularly preferably 4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as a calcium or magnesium precipitation preventing agent or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, trans-silohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2
-Hydroxybenzyl) ethylenediamine-N, N'-
Examples thereof include diacetic acid and hydroxyethyliminodiacetic acid. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution.
For example, it is about 0.1 g to 10 g per liter.

If desired, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019, and thioether compounds represented by US Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,29, U.S. Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. The benzyl alcohol is as described above.

In the present invention, any antifoggant can be added, if desired. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine. The color developer applicable to the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g
~ 4 / liter. Further, if necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, polyalkyleneimine and the like may be added.

The processing temperature of the color developer applicable to the present invention is 30 ° to 50 ° C, preferably 39 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Smaller replenishment amount is preferable, but photosensitive material 1 m ²
20 to 600 ml is suitable per unit, preferably 50 ml
-200 ml, more preferably 60-150 ml.
Next, the desilvering process applicable to the present invention will be described.
As the desilvering step, generally, any step such as a bleaching step-fixing step, a fixing step-bleaching fixing step, a bleaching step-bleaching fixing step, a bleaching fixing step may be used.

The bleaching solution, the bleach-fixing solution and the fixing solution applicable to the present invention will be described below. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used, but especially organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids Complex salts such as phosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid,
Persulfates, hydrogen peroxide and the like are preferred.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of ethylene diamine tetraacetic acid, diethylenetriamine pentaacetic acid, 1,3-diaminopropane tetraacetic acid, propylene Examples thereof include diaminotetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid and glycol etherdiaminetetraacetic acid. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride,
Forming a ferric complex salt in a solution by using ferric nitrate, ammonium ferric sulfate, ferric phosphate and the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid and phosphonocarboxylic acid Good. Further, the chelating agent may be used in excess to form the ferric complex salt. Among the ferric complex salts, aminopolycarboxylic acid ferric complex is preferable, and the addition amount thereof is 0.01 to 1.0 mol / liter, preferably 0.05 to 0.50 mol / liter.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, it is described in US Pat. No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978). Compounds having a mercapto group or a disulfide bond, thiourea compounds described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, US Pat. No. 3,706,561 and the like, Alternatively, halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). ) Or iodide (eg, ammonium iodide) or the like. Shelf sand, meta-shelf sodium, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, if necessary.
One or more types of inorganic acids having pH buffering ability such as citric acid, sodium citrate, tartaric acid, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents, surfactants, organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution or the fixing agent used in the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide solvent agents such as thioureas,
These can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution is 3 to.
10 is preferable, and 5-9 is more preferable. In particular, when a high silver chloride emulsion is used in the light-sensitive material, the pH of the bleach-fixing solution is preferably 7.0 or less, more preferably 6.5 or less.

The bleach-fixing solution or fixing solution contains sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) and metas as preservatives. It is preferable to contain a sulfite ion-releasing compound such as bisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are converted to sulphite ion and the amount is about 0.0
The content is preferably 2 to 0.05 mol / liter, more preferably 0.04 to 0.40 mol / liter.

As a preservative for the bleach-fixing solution and the fixing solution,
Sulfite is generally added, but ascorbic acid, carbonyl bisulfite adduct, carbonyl compound or the like may be added, and benzenesulfinic acid is also effective. Furthermore, a buffer for the bleach-fixing solution and the fixing solution,
A fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as necessary.

In the present invention, it is common to carry out washing and / or stabilizing treatment after desilvering treatment such as fixing or bleach-fixing. The amount of replenishment in the washing step or stabilizing step is preferably 3 to 50 times, more preferably 3 to 30 times, the amount carried in from the previous bath per unit area of the light-sensitive material. The replenishment may be performed continuously or intermittently. Washing and /
Alternatively, the liquid used in the stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by reducing the overflow of washing water into a bleach-fixing bath, which is the pre-bath, by supplementing the bleach-fixing bath with a concentrated liquid by reducing the overflow of the washing water by a multi-stage countercurrent system. The amount of rinsing water in the rinsing process varies depending on the characteristics of the photosensitive material (for example, depending on the material used such as coupler) and application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Can be set to a range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage counterflow system is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motio).
n Picture and Television Engineers) Volume 64, p.2
48-253 (May 1955 issue). Normally, the number of stages in the multi-stage countercurrent system is 2
6 is preferable, and 2 to 4 is particularly preferable.

According to the multi-stage countercurrent system, the amount of washing water can be greatly reduced, and, for example, 0.5 liter / m ^{2 of the} light-sensitive material can be used.
The amount of water can be 1 liter or less, and the effect of the present invention is remarkable, but due to the increase of the residence time of water in the tank, Bacteria propagate and the floating substances generated adhere to the photosensitive material. As a solution to such a problem, Japanese Unexamined Patent Publication No.
The method of reducing calcium and magnesium described in JP-A-2-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, and JP-A-61-1201.
Chlorinated germicides such as chlorinated sodium isocyanurate described in JP-B No. 45, benzotriazole described in JP-A No. 61-267761, copper ion and others, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal" (1986) Sankyo Publication, Sanitary Technology Society edited by "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" (1986)
Years), and the fungicides described in. Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin, a buffering agent for adjusting the film pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

Further, a surface active agent, an optical brightening agent and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a water washing step, JP-A-57-8543 and JP-A-58-14834,
All known methods described in JP-A-60-220345 can be used. In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinse solution is also used as a washing solution or a stabilizing solution used after the desilvering process. The pH of the washing step or the stabilizing step is preferably 4 to 10, more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 3
0 seconds.

The present invention can be applied to any photosensitive material. As a silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and a processing method and a processing iodide additive applied for processing the light-sensitive material. Is the following patent publication,
In particular, European Patent EP 0,355,660 A2 (Japanese Patent Application No.
Those described in No. -107011) are preferably used.

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

[0055]

[Table 10]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan couplers described in 3314, 3-hydroxypyridine-based cyan couplers described in European Patent EP 0,333,185A2 (among others, 4-equivalent couplers of couplers (42) listed as specific examples Is a 2-equivalent product with a chlorine leaving group,
Couplers (6) and (9) are particularly preferable) and JP-A-64-3
Cyclic active methylene cyan couplers described in No. 2260 (among others, coupler example 3 listed as a specific example,
The use of (8,34 is particularly preferable) is also preferable.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver iodide of 90 mol% or more, further 95% or more, and particularly 98% or more. The method of the present invention is particularly preferably used for high silver chloride type photosensitive materials for printing (particularly color paper).

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the photosensitive colloid layer for the purpose of improving the sharpness of an image, etc., in EP No. 0,337,490A2, Nos. 27-37.
Dyes which can be decolorized by treatment (among others, oxonol dyes) described on page 76 are added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or the water-resistant resin layer of the support. It is preferable that titanium oxide surface-treated with a dihydric to tetrahydric alcohol (eg, trimethylolethane) is contained in an amount of 12% by weight or more, more preferably 14% by weight or more.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and / or a compound which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (C) which chemically bonds with the oxidation product of the aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent. The support used in the light-sensitive material according to the present invention may be a white polyester support for display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or light illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0063]

EXAMPLES Next, the present invention will be specifically described with reference to Examples. Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form a layer shown below. A multilayer color photographic paper having the constitution was produced. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer Cyan coupler (ExC) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-).
8) 5.0 g, ethyl acetate 50.0 cc and solvent (S
14.0 g of olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion with average grain size 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag molar ratio). Coefficients of variation of grain size distribution are 0.09 and 0.11, respectively, and each size emulsion is AgBr
0.6 mol% was locally contained in a part of the particle surface) was prepared. The red-sensitive sensitizing dye E shown below was added to this emulsion in an amount of 0.9 × 10 ^-4 per mol of silver for a large-sized emulsion.
Mol, and 1.1 × 10 ⁻⁴ mol was added to the small size emulsion. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

The coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, the total amount of Cpd-10 and Cpd-11 in each layer is 2
It was added to a 5.0 mg / m ² and 50.0 mg / m ^2.
The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue-sensitive emulsion layer] Sensitizing dye A

[0066]

[Chemical 8]

And sensitizing dye B

[0068]

[Chemical 9]

(2.0 × 10 ⁻⁴ mol for large size emulsion and 2.5 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] Layer] Sensitizing dye C

[0070]

[Chemical 10]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large-sized emulsion and 5.6 × 10 ^-4 mol for small-sized emulsion) and: Sensitizing dye D

[0072]

[Chemical 11]

(Each mole of silver halide is 7.0 × 10 ^-5 mole for large-sized emulsion and 1.0 × 10 ^-5 mole for small-sized emulsion) [Red-sensitive emulsion layer ] Sensitizing dye E

[0074]

[Chemical 12]

(Per mol of silver halide, 0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion) 2.6 × per mol of silver halide
10 ⁻³ mol was added.

[0076]

[Chemical 13]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, at 8.5 × 10 ⁻ per mol of silver halide. ⁵ mol, 7.7 × 10 ^-4
Mol, 2.5 × 10 ⁻⁴ mol. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ^-4
Mol added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0078]

[Chemical 14]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)]

[0080] First layer (blue sensitive emulsion layer)   Silver chlorobromide emulsion (cubic, large size emulsion with an average grain size of 0.88 μm)     And a 0.70 μm small size emulsion in a 3: 7 mixture (silver molar ratio).     Coefficients of variation of particle size distribution are 0.08 and 0.10, respectively     Both agents contain 0.3 mol% of silver bromide localized on a part of the grain surface.) 0.30   Gelatin 1.22   Yellow Coupler (ExY) 0.82   Color image stabilizer (Cpd-1) 0.19   Solvent (Solv-3) 0.18   Solvent (Solv-7) 0.18   Color image stabilizer (Cpd-7) 0.06

[0081] Second layer (color mixing prevention layer)   Gelatin 0.64   Color mixing inhibitor (Cpd-5) 0.10   Solvent (Solv-1) 0.16   Solvent (Solv-4) 0.08

[0082] Third layer (green sensitive emulsion layer)   Silver chlorobromide emulsion (cubic, large size emulsion with average grain size 0.55 μm)     And a 1: 3 mixture of 0.39 μm small size emulsion (Ag molar ratio).     Coefficients of variation of particle size distribution are 0.10 and 0.08, respectively     Both agents contained 0.8 mol% of AgBr localized on a part of the particle surface) 0.12   Gelatin 1.28   Magenta coupler (ExM) 0.23   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-3) 0.16   Color image stabilizer (Cpd-4) 0.02   Color image stabilizer (Cpd-9) 0.02   Solvent (Solv-2) 0.40

[0083] Fourth layer (UV absorption layer)   Gelatin 1.41   UV absorber (UV-1) 0.47   Color mixing inhibitor (Cpd-5) 0.05   Solvent (Solv-5) 0.24

[0084] Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion (cubic, large size emulsion with an average grain size of 0.58 μm)     And a small size emulsion of 0.45 μm in a 1: 4 mixture (Ag molar ratio).     Coefficients of variation of particle size distribution are 0.09 and 0.11, respectively.     Both agents contained 0.6 mol% of AgBr localized on a part of the particle surface) 0.23   Gelatin 1.04   Cyan coupler (ExC) 0.32   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-4) 0.02   Color image stabilizer (Cpd-6) 0.18   Color image stabilizer (Cpd-7) 0.40   Color image stabilizer (Cpd-8) 0.05   Solvent (Solv-6) 0.14

[0085] Sixth layer (UV absorption layer)   Gelatin 0.48   UV absorber (UV-1) 0.16   Color mixing inhibitor (Cpd-5) 0.02   Solvent (Solv-5) 0.08 Seventh layer (protective layer)   Gelatin 1.10   Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.17   Liquid paraffin 0.03

[0086]

[Chemical 15]

[0087]

[Chemical 16]

[0088]

[Chemical 17]

[0089]

[Chemical 18]

[0090]

[Chemical 19]

[0091]

[Chemical 20]

[0092]

[Chemical 21]

[0093]

[Chemical formula 22]

[0094]

[Chemical formula 23]

First, after subjecting the above sample to imagewise exposure, a continuous processing (using a paper processor using a solution having the following processing steps and processing compositions) until replenishment of twice the tank capacity of color development ( Running test). Process temperature Time Replenishment amount ^* Tank capacity (ml) (liter) Color development 39.5 ℃ 45 seconds 80 5 Bleach fixing 30-35 ℃ 45 seconds 215 8 Rinse 30-35 ℃ 20 seconds -5 Rinse 30-35 ℃ 20 seconds -5 Rinse 30-35 ° C 20 seconds 250 5 Dry 70-80 ° C 60 seconds ^* Replenishment rate was 3 tanks countercurrent from rinsing to 1 m ² of light-sensitive material. The composition of each treatment liquid is as follows.

[0096] [Color developer] Tank solution Replenisher   800 ml water 800 ml   Ethylenediaminetetraacetic acid 3.0 g 3.0 g   1,2-dihydroxybenzene-4,6-sulfonic acid     Sodium 0.5g 0.5g   Potassium bromide 0.015g −   Triethanolamine 8.0g 12.0g   Sodium chloride 4.1 g −   Potassium carbonate 25g 25g   Organic preservatives (compounds of general formula (II), see Table 1) 13.7mmol 27.3mmol   4-Amino-3-methyl-N-ethyl-N- [β-     (Methanesulfonamido) ethyl] -aniline sulfur     Acid salt Table F Table F   Optical brightener (WHITEX 4B, Sumitomo Chemical) 1.0g 3.0g   Additive (compound of general formula (I), see Table F) 0.1 g 0.2 g   Add water 1000ml 1000ml     pH (25 ℃) 10.00 10.80

[0097] [Bleaching fixer] (tank solution and replenisher are the same)   400 ml of water   Ammonium thiosulfate (70%) 100 ml   Sodium sulfite 17g   Ethylenediaminetetraacetic acid iron (III) ammonium 55g   Ethylenediaminetetraacetic acid disodium 5g   40 g of ammonium bromide   Add water 1000ml     pH (25 ° C) 6.0

[Rinse Solution] (The tank solution and the replenisher are the same) Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of the light source of 3200 °) was applied to the coated sample.
K) was used to give a gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 0.1 seconds. At the start and after the running test, the sensitometry was processed, and the minimum density of yellow, magenta and cyan in the white background was measured using a Macbeth densitometer, and the increase in density after the running test was checked. It was The results are shown in Table G. In addition, 1 liter of the replenisher for color developing solution immediately after the above-mentioned preparation was filled in each 1 liter replenisher tank and allowed to stand in a thermostatic chamber at 10 ° C. as shown in Tables F and G. After the passage of time, the presence or absence of precipitates was confirmed and evaluated.
It is shown in Table G with a mark of x when there is a precipitate and a mark of ◯ when there is no precipitate.

[0100]

[Table 11]

[0101]

[Table 12]

[0102]

[Chemical formula 24]

As is clear from Tables F and G, in the low replenishment processing of the color developing solution, the concentration of the developing agent in the replenishing solution is high and crystallization easily occurs at low temperature (Nos. 1 to 4). Further, it can be seen that when a conventional compound is used for preventing crystallization, the crystallization is certainly improved, but the stain during continuous treatment is deteriorated (No. 5, 6, 8, 12, 14, 16, 18). ).
Further, when the compound of the general formula (I) of the present invention is used as an additive, the precipitation is almost completely prevented, but when the comparative compound is used, the stain is hardly improved (No. 7, 15). On the other hand, when the additive of the present invention and the compound of the general formula (II) are used in combination, precipitation is completely prevented and the increase in stain during continuous treatment is significantly improved (No. 9). ~ 11, 13, 17, 1
9). Further, these improving effects are greater as the concentration of the main drug in the replenisher is higher, and it is understood that the present invention is suitable for low replenishment treatment (for example, comparison between No. 8, 10 and No. 18, 19).

[0104]

As in the method of the present invention, by using the compound of the general formula (I) in combination with the compound of the general formula (I), precipitation in a color developing solution does not occur, and continuous processing is performed before and after running. It is possible to perform color development processing with little change in Dmin. Above all, it is effective in increasing the concentration of the replenisher for the color developing solution and reducing the replenishing amount of the color developing solution. It is also effective in a color development processing method for high silver chloride type print photographic light-sensitive materials.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 6, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxy group, an amino group, an alkoxy group, a carboxy group, sulfo group, a phosphono group, a nitro group, a cyano group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, an acyl group, an acylamino group, alkylsulfonylamino group, arylsulfonylamino group, and .R ₁ representing the alkoxycarbonyl group or a ureido group R ₂
May be linked to each other to form a condensed ring. m and n may be the same or different and each represents an integer of 0 or 1 to 3. ) General formula (II)

[Chemical 2] (In the formula, L represents an optionally substituted alkylene group, and A
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl substituted, an ammonio group which may be alkyl substituted, a carbamoyl group which may be alkyl substituted, or an alkyl substituted. Represents a good sulfamoyl group or an optionally substituted alkylsulfonyl group, and R represents a hydrogen atom or an optionally substituted alkyl group. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

General formula (I)

[Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxy group, an amino group, an alkoxy group, a carboxy group, sulfo group, a phosphono group, a nitro group, a cyano group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, an acyl group, an acylamino group, alkylsulfonylamino group, arylsulfonylamino group, and .R ₁ representing the alkoxycarbonyl group or a ureido group R ₂
May be linked to each other to form a condensed ring. m and n may be the same or different and each represents an integer of 0 or 1 to 3. )

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyoshi Morimoto             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd.

Claims (2)

[Claims] 1. A method in which a silver halide color photographic light-sensitive material is imagewise exposed and then treated with a color developing solution containing at least one aromatic primary amine color developing agent, wherein the color developing solution is: A method of processing a silver halide color photographic light-sensitive material comprising at least one compound represented by the general formula (I) and at least one compound represented by the following general formula (II). General formula (I) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxy group, an amino group, an alkoxy group, a carboxy group, sulfo group, a phosphono group, a nitro group, a cyano group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, an acyl group, an acylamino group, alkylsulfonylamino group, arylsulfonylamino group, and .R ₁ representing the alkoxycarbonyl group or a ureido group R ₂
May be linked to each other to form a condensed ring. m and n may be the same or different and each represents an integer of 0 or 1 to 3. ) General formula (II): (In the formula, L represents an optionally substituted alkylene group, and A
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl substituted, an ammonio group which may be alkyl substituted, a carbamoyl group which may be alkyl substituted, or an alkyl substituted. Represents a favorable sulfamoyl group or an optionally substituted alkylsulfonyl group, and R represents a hydrogen atom or an optionally substituted alkyl group. ) 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the replenisher used in the color development contains at least 21 mmol / liter of a color developing agent.