JPH05127330A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable color development without causing deposition in a developing soln. or causing uneven color development and scratch even in the case of continuous processing by using the developing soln. in combination with specified compds. CONSTITUTION:A color developing soln. contg. at least one kind of compd. represented by formula I and at least one kind of compd. represented by formula II is used. In the formula I, each of R1-R6 is H, alkyl, aryl, aralkyl, halogen, hydroxy, amino, alkoxy, carboxy, sulfo, phosphono, nitro, cyano, a heterocyclic group, carbamoyl, etc., each of (k), (m) and (n) is an integer of 0-3 and L is an org. divalent group. In the formula II, each of R<1> and R2 is H, alkyl, alkenyl, aryl or a hetero arom. group.

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 which does not cause precipitation in a color developing solution and has little photographic processing waste solution. Furthermore, the present invention relates to a processing method in which scratches and uneven coloring are not generated even during continuous processing.

[0002]

2. Description of the Related Art In recent years, reduction of waste liquid for photographic processing 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 have the effect of preventing the precipitation of crystals, but the effect is insufficient, and in the low replenishment processing and the rapid processing using the high silver chloride sensitive material, crystals are not formed in the processing tank or rack of the automatic processor. A new problem was found that not only does it deposit and contaminate the rack, but it also has a serious adverse effect on photographic properties, such as scratches and uneven coloring.

[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 processing method in which scratches and uneven coloring are not generated on the surface of paper even after continuous processing.

[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 for 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 , R ₄ , R ₅ and R ₆ 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, Alkoxy group, carboxy group, sulfo group, phosphono group, nitro group, cyano group, heterocyclic group, carbamoyl group, sulfamoyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group or ureido group. R ₁ and R ₂ or R ₃ and R ₄ may be combined to form a condensed ring, and k, m and n may be the same or different and each represents an integer of 0 to 3. L is Represents an organic divalent group.)

General formula (II)

[Chemical 4] (In the formula, R ¹ and R ² are each independently a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group or a heteroaromatic group, and R ¹ and R ² may be connected to each other to form a hetero ring together with a nitrogen atom. However, R ¹ and R ² are not hydrogen atoms at the same time. )

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) will be described in detail. In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
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, carbonyl 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 or R ₃ and R ₄ may be the same or different, and R ₁ and R ₂ or R ₃ and R ₄
May be linked together to form a condensed ring. An alkyl group, an aryl group, an aralkyl group, an amino group, an alkoxy group, a heterocyclic group (which is a 5- or 6-membered ring substituent containing at least one nitrogen atom, and optionally containing a carbon atom, a sulfur atom or an oxygen atom, For example, pyridyl group, pyrimidinyl group, tetrazolyl group, morpholino group, piperazinyl group, pyrrolidinyl group), carbamoyl group, sulfamoyl group, acyl group, acylamino group, alkylsulfonylamino group,
The arylsulfonylamino group and the alkoxycarbonyl group may be further substituted with a substituent, and the substituent is the same as the substituents mentioned for R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R _6. .. R ₁ , R ₂ , R ₃ , and R ₄ are preferably hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 15 carbon atoms, substituted or unsubstituted aryl groups having 6 to 15 carbon atoms, and total carbon atoms. It is a substituted or unsubstituted aralkyl group having a number of 7 to 15, and particularly preferably an alkyl group having a total of 1 to 10 carbon atoms substituted with an alkylsulfonylamino group, a hydroxy group or a ureido group.
R ₃ , R ₄ , R ₅ , and R ₆ 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,
A substituted or unsubstituted aralkyl group and heterocyclic group having a total of 7 to 15 carbon atoms are preferable. Particularly preferably a hydrogen atom,
It is a substituted or unsubstituted alkyl group having a total of 1 to 10 carbon atoms. k, m and n may be the same or different and preferably each represent an integer of 0 or 1. L represents an organic divalent group, specifically, an alkylene group, an arylene group, -CO
-, - NH -, - SO 2 - is an organic divalent group formed by singly or in combination.

Specific examples of the compound of the present invention include the following compounds, but the present invention is not limited thereto.

[0010]

[Chemical 5]

[0011]

[Chemical 6]

[0012]

[Chemical 7]

For the synthesis of the above compounds, see Chemical A
It can be synthesized by the method described in bstracts, Volume 76, page 102, 128782t. In the present invention, the color developing composition may be a solution or a powder. The amount of the compound represented by formula (I) of the present invention added to the color developer is 0.001 per 1 liter of the developer.
It is in the range of g to 10 g. Preferably 0.005
It is in the range of g to 5 g. More preferably, 0.0
It is in the range of 05 g to 2 g. Two or more compounds represented by formula (I) can be used in combination. These compounds may be added directly when the color developing composition is prepared, or may be a method in which a concentrated solution is prepared in advance and a necessary amount is added.

Next, the compound represented by formula (II) of the present invention will be described in more detail. In the general formula (II), R
^The alkyl group and alkenyl group represented by ¹ and R ² may be linear, branched or cyclic. As a substituent of the alkyl group, alkenyl group or aryl group represented by R ¹ or R ² , a halogen atom (F, Cl, Br, etc.), an aryl group (phenyl group, p-chlorophenyl group, etc.), an alkyl group (methyl group) , Ethyl group, isopropyl group, etc.),
Alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfone) Amido group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, naphthamide group, etc.), ureido Groups (methylureido group, phenylureido group, etc.), alkoxycarbonylamino groups (methoxycarbonylamino group, etc.), allyloxycarbonylamino groups (phenoxycarbonylamino group, etc.), alkoxycarbonyl groups (methoxy Rubonyl group), aryloxycarbonyl group (phenoxycarbonyl group), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (methylthio group, etc.) ),
Examples thereof include an arylthio group (such as a phenylthio group), a hydroxyamino group, and a heterocyclic group (such as a morpholyl group and a pyridyl group). Here, R ¹ and R ² may be the same or different from each other, and the substituents of R ¹ and R ² may be the same or different.

The heteroaromatic groups represented by R ¹ and R ² include pyrrole, pyrazole, imidazole, 1,2,4.
-Triazole, tetrazole, benzimidazole,
Benzoxazole, benzthiazole, 1,2,4-
Thiadiazole, pyridine, pyrimidine, triazine (s-triazine, 1,2,4-triazine), indazole, purine, quinoline, isoquinoline, quinazoline, pyrimidine, isoxazole, oxazole, thiazole, selenazole, tetraazaindene, s-triazolo [1. , 5-a] pyrimidine, s-triazolo (1,5-b) pyridazine, pentaazaindene, s-
Triazolo (1,5-b) [1,2,4] triazine,
Examples thereof include s-triazolo (5,1-d) -us-triazine and triazaindene (imidazolo [4,5-b] pyridine etc.). A substituent may be further substituted on the heteroaromatic group. As the substituent, an alkyl group,
It is the same as the substituents mentioned for the alkenyl group and the aryl group. Examples of the nitrogen-containing heterocycle formed by connecting R ¹ and R ² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group and a benztriazole group. In the general formula (I),
The case where R ¹ and R ² are an alkyl group or an alkenyl group is preferable, and the number of carbon atoms is preferably 1 to 10, particularly preferably 1 to 5. Preferred substituents for R ¹ and R ² are hydroxy, alkoxy, alkyl or aryl sulfonyl, amide, carboxy, cyano, sulfo, nitro and amino groups.

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 Chemica 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) 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added to 200 ml of an aqueous solution of 20 g of hydroxylamine hydrochloride, 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 matter was filtered off, 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) 7.2 g of hydroxylamine hydrochloride and 18.0 g of phosphorous acid
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 per 1 liter of the replenishing solution. Is about 2
A concentration of 1 millimolar to 45 millimolar, more preferably about 23 millimolar to 40 millimolar. Even at such a high concentration, 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 should contain substantially no sulfite ion in order to suppress fluctuations in photographic characteristics due to continuous processing. 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 further contains hydroxylamine in order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine. It is more preferable not to do this (the term "substantially free from" means a hydroxylamine concentration of 5.0 x 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 oxidation of a color developing agent due to air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyl 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.
No. 63, No. 63-55151, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-.
43138, 63-146041, 63-44.
657, 63-46656, and 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.
No. 340, JP-A Nos. 1-186939 and 1-1875.
Amines as described in JP-A-57-57, JP-A-54-35
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 development, which is not preferable for achieving the object of the present invention that the concentration 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 added to the color developer 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 /
When it is more than liter, development is delayed and the maximum density and sensitivity are lowered. When it is less than 3.0 × 10 ^-5 mol / liter, fog cannot be sufficiently prevented.

Here, chlorine ions and bromine ions 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 process, chlorine ions and bromine ions may be supplied together from the emulsion,
It may be supplied from 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, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in a high pH range of pH 9.0 or higher, 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 not causing (fog 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-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned. The amount of the buffer added to the color developing solution 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. Sho 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019 and the thioether compounds represented by US Pat. No. 3,813,247, and JP-A Nos. 52-49829 and 50-49.
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
0074, JP-A-56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,329, U.S. Pat. Nos. 2,494,903 and 3,128,182.
Nos. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, U.S. 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
No. 23883 and U.S. Pat. No. 3,532,501, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added if 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. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid and polyalkyleneimine 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.
In 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 and 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,
Persulfate, hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid treatment 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, 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, ferric ammonium sulfate, ferric phosphate 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, ferric aminopolycarboxylic acid 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 bleaching accelerators in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, it is described in U.S. 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 kinds 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 or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

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,
A thioether compound such as 8-octanediol and a water-soluble silver halide solvent agent 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 preferably contains a sulfite ion-releasing compound such as bisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are converted to sulphite ions and the amount is about 0.0
The content is preferably 2 to 0.05 mol / liter, and 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 and the like may be added, and benzenesulfinic acid is also effective. Furthermore, a buffer for the bleach-fixing solution and fixing solution,
A fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added if necessary.

In the present invention, it is general to carry out washing and / or stabilizing treatment after desilvering treatment such as fixing or bleach-fixing. The replenishment amount in the water washing step or the stabilizing step is preferably 3 to 50 times, more preferably 3 to 30 times, as much as the carry-in amount 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 by a multi-stage countercurrent system to flow into the bleach-fixing bath of the preceding bath and replenishing the bleach-fixing bath with a concentrated solution. 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 is 2 in the multi-stage countercurrent system.
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 in the residence time of water in the tank, Bacteria propagate and the suspended matter generated adheres 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. Also, the isothiazolone compounds and siabendazoles described in JP-A-57-8542, and JP-A-61-1201.
Chlorinated bactericides such as sodium chlorinated isocyanurate described in No. 45, benzotriazole, copper ion described in JP-A No. 61-267761, 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)
Year), and the fungicide described in can be used. Further, in the wash water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

It is also 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 typified by formalin, a buffering agent for adjusting a 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 and the like 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 rinsing solution is also used as a washing or 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. 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 photographic material. Is the following patent publication,
In particular, European Patent EP 0,355,660 A2 (Japanese Patent Application No.
No. -107011) is 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, among the 4-equivalent couplers of coupler (42) listed as a specific example) Is a divalent equivalent 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 (especially color paper).

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of improving the sharpness of an image or the like, and it is described in European Patent EP 0,337,490A2, Nos. 27-27.
A dye which can be decolorized by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 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, the compound (F) and // which chemically bond 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 an oxidized 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. Are preferable, for example, in order to prevent stain generation and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage after processing.

Further, the light-sensitive material of the present invention has a mildewproofing agent as described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. 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-based support for a 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 further 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 U.S. Pat. No. 4,880,726. As a result, the light color mixture is removed, and the 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 fifth layer coating solution 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 size emulsion.
Mol, and 1.1 × 10 ⁻⁴ mol was added to a 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. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, 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 in 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]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large-sized emulsion and 1.0 × 10 ^-5 mol 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 × 10 ⁻³ mol was added per mol of silver halide.

[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 per mol of silver halide, respectively. × 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. Numbers represent 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 side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)]

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion having average grain size of 0.88 μm and small size emulsion of 0.70 μm (silver mole ratio). Coefficients of variation of size distribution are 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide is locally contained in a part of grain surface in each size emulsion. 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

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

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of a large size emulsion having an average grain size of 0.55 μm and a small size emulsion of 0.39 μm (Ag mole ratio). Coefficients of variation of size distribution are 0.10 and 0.08, respectively. In each size emulsion, AgBr 0.8 mol% was locally contained in 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

Fourth layer (UV absorbing layer) Gelatin 1.41 UV absorbing agent (UV-1) 0.47 Anti-color mixing agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm (Ag mole ratio). Coefficients of variation of size distribution are 0.09 and 0.11, respectively. In each size emulsion, AgBr 0.6 mol% was locally contained in 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

Sixth layer (UV absorbing layer) Gelatin 0.48 UV absorbing agent (UV-1) 0.16 Anti-color mixing agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protecting layer) Gelatin 1.10 Polyvinyl alcohol Acrylic modified copolymer (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 38.0 ℃ 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 to 35 ° C 20 seconds 250 5 Dry 70 to 80 ° C 60 seconds ^* Replenishment amount was 3 tanks counter current from rinsing to 1 m ² of light-sensitive material. The composition of each treatment liquid is as follows.

[Color developer] Tank liquid Replenisher Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 6.0 g-Potassium carbonate 25 g 25 g Organic preservative (compound of general formula (II), see Table 11) 20 mmol 30 mmol 4-amino-3-methyl-N-ethyl-N- [β- ( Methanesulfonamido) ethyl] -aniline sulphate 5.0g 9.5g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 3.0g Additive (compound of general formula (I), see Table 11) 0.05g 0.05 Water Add 1000ml 1000ml pH (25 ℃) 10.10 10.90

[Bleach-fixing solution] (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water In addition 1000 ml pH (25 ° C) 6.0

[Rinse solution] (The same tank solution and replenisher solution) 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 light source: 3200 °) for the coated sample.
K) was used to give a uniform gray exposure. 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 uniformly exposed sample was processed, and the density was measured in the direction (transverse direction) perpendicular to the direction of processing. The difference between the maximum value and the minimum value of the density value at that time was calculated and used for evaluation of color unevenness. Further, the degree of occurrence of scratches in the above sample was visually evaluated. ◯: No scratch was generated Δ: Scratch was confirmed with a magnifying glass X: Scratch was confirmed with the naked eye Further, the replenisher for the color developing solution immediately after the above preparation was filled in each container and allowed to stand in a thermostatic chamber at 0 ° C. . After the passage of time, the presence or absence of precipitates was confirmed and evaluated. ◯: No precipitates △: Slight precipitates were generated ×: Precipitates were generated on the entire bottom surface

[0100]

[Table 11]

[0101]

[Chemical formula 24]

As is clear from Table 11, 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 a low temperature (No. 1 to 8). Further, when a conventional compound is used for preventing crystallization, the crystallization, or uneven coloring or scratches tends to be improved, but the effect is insufficient (No. 2, 3, 4, 5). , 6, 7,
8). Further, when the compound of the general formula (I) of the present invention is used as an additive, precipitation tends to be prevented, but uneven coloring and scratches are not improved (No. 7, 8). 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 coloring unevenness and scratches during continuous treatment are significantly improved (No. .9-12).

[0103]

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 uneven coloring is caused even in continuous processing. It is possible to perform color development processing without scratches. Among them, 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 the direction of color development processing of high silver chloride type print photographic light-sensitive materials.

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

[Procedure amendment]

[Submission date] June 15, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ 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, Alkoxy group, carboxy group, sulfo group, phosphono group, nitro group, cyano group, heterocyclic group, carbamoyl group, sulfamoyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group or ureido group. R ₁ and R ₂ or R ₃ and R ₄ may be linked to form a condensed ring, and k, m and n may be the same or different and each represents an integer of 0 to 3. L is Represents an organic divalent group.) General formula (II)

[Chemical 2] (In the formula, R ¹ and R ² are each independently a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, or a heteroaromatic group, and R ¹ and R ² may be linked to each other to form a hetero ring together with a nitrogen atom. However, R ¹ and R ²
Are not hydrogen atoms at the same time. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction content]

General formula (I)

[Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ 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, Alkoxy group, carboxy group, sulfo group, phosphono group, nitro group, cyano group, heterocyclic group, carbamoyl group, sulfamoyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group or ureido group. R ₁ and R ₂ or R ₃ and R ₄ may be linked to form a condensed ring, and k, m and n may be the same or different and each represents an integer of 0 to 3. L is Represents an organic divalent group.)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Hiroshi Fujimoto, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. 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, 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 , R ₄ , R ₅ and R ₆ 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, Alkoxy group, carboxy group, sulfo group, phosphono group, nitro group, cyano group, heterocyclic group, carbamoyl group, sulfamoyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group or ureido group. R ₁ and R ₂ or R ₃ and R ₄ may be combined to form a condensed ring, and k, m and n may be the same or different and each represents an integer of 0 to 3. L is Represents an organic divalent group.) General formula (II): (In the formula, R ¹ and R ² are each independently a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, or a heteroaromatic group, and R ¹ and R ² may be linked together to form a heterocycle together with a nitrogen atom. However, R ¹ and R ²
Are not hydrogen atoms at the same time. )