JPH05197107A - Processing method for silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide the processing method rarely causing defective desilvering and defective recoloring even when the processing with little waste liquid is applied to a photographing silver halide color photosensitive material. CONSTITUTION:In the method processing a silver halide color photosensitive material having a silver halide emulsion layer containing at least silver iodide of 0.5mol.% or above with an automatic developing machine, a color developer contains an aromatic primary amine color developing agent and a hydroxylamine derivative, the concentration of sulfite is set to 25mmol/l or below, the replenishment quantity of the color developer is set to 60-300ml for the photosensitive material of 1m<2>, the concentration of the bleaching agent contained in the processing liquid having a bleaching capability after color development is set to 3-120mmol/l, and the replenishment quantity of the processing liquid is set to 0.01-5 times the drag-in quantity by the photosensitive material from the color developer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide color photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material) by using an automatic processor, and more specifically, to reduce the discharge of processing waste liquid. The present invention relates to a processing method in which desilvering failure and color restoration failure are less likely to occur even if the replenishment amount during processing is significantly reduced.

[0002]

2. Description of the Related Art Photosensitive materials for photographing have been required to have high sensitivity and high image quality for the purpose of use. Using silver iodide as a silver halide is an effective means for increasing the sensitivity, but the iodide ion generated from silver iodide has a relatively bad influence on the desilvering property. When many additives are used for imparting various functions such as a light-sensitive material, the desilvering property is obviously deteriorated. Generally, a light-sensitive material is processed by using an automatic processor. The automatic developing machine is composed of a color developing bath for color development, a bleaching bath for bleaching, a fixing bath for fixing, a bleach-fixing bath for bleach-fixing, a washing bath for washing, and a stabilizing bath for stabilizing treatment. ing. Although a means for scraping off the processing solution adhering to the processed photosensitive material with a squeegee is provided between these processing baths, it cannot be completely removed. ,
The reality is that they will be brought to the next bath.

On the other hand, when a photosensitive material is processed by an automatic processor, each processing solution is replenished with a replenishing solution in order to keep the amount of processing solution components stable. Therefore, a processing waste liquid corresponding to the replenishment amount is generated. From the viewpoint of environmental protection, the reduction of processing waste liquid is an important issue, but if the replenishment amount of processing liquid is reduced to reduce the waste liquid discharge, the above iodide will be added to the processing liquid in the color developing solution and the desilvering process. Accumulation of ions and eluted additives increases, and desilvering failure becomes a serious problem. For example, if the replenishing amount of the color developing solution is reduced, the accumulation of oxidative deterioration products of the color developing agent is increased, and if the replenishing amount of the subsequent desilvering bath is reduced, the color developing solution is brought into the desilvering bath. The components of the color developing solution containing deterioration products increase. Not only are these liable to cause desilvering defects, but also color restoration defects are likely to occur. Furthermore, aminopolycarboxylic acid ferric iron complex salts such as ethylenediaminetetraacetic acid ferric iron complex salt used as a bleaching agent in the desilvering bath are poor in biodegradability, and it is preferable that the amount used is small in view of environmental protection. The above desilvering failure and color recovery failure are more likely to occur when the concentration of the bleaching agent is lower.

On the other hand, various desilvering accelerators have been studied as a desilvering acceleration technique. For example, US Pat. No. 3,893,858, West German Patent 1,290,81
2, No. 2,059,988, JP-A-53-3273.
No. 6, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53
-95631, No. 53-104232, No. 53-1
No. 24424, No. 53-141623, No. 53-28
426, Research Disclosure No. 1712
No. 9 (July 1978), etc., and compounds having a mercapto group or a disulfide group; JP-A-50-140.
No. 129, a thiazolidine derivative; JP-B-45-8
No. 506, JP-A Nos. 52-20832 and 53-327.
35, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16235; West German Patent 96.
6,410, 2,748,430; polyoxyethylene compounds; JP-B-45-8836; polyamine compounds; and others, JP-A-49-40943.
49-59644, 53-94927, 54
-35727, 55-26506, 58-16
Use of compounds described in 3940; bromide ion, etc. has been studied. However, when the replenishment of the color developer and the desilvering bath are made low at the same time, sufficient acceleration cannot be obtained, and there is almost no improvement effect on the color restoration failure.

[0005]

When a silver halide emulsion containing silver iodide is used to obtain the sensitivity required for photographing and the replenishment amount of the processing solution is remarkably reduced in order to reduce processing waste solution. As described above, as the accumulation of iodide ions and the additive eluted from the light-sensitive material increases, desilvering failure tends to occur. Further, the color developing solution needs to use a preservative for the purpose of preventing oxidation, but when the most commonly used hydroxylamine or sulfite to date is used, the desilvering bath of these preservatives is used. It was found that when brought in, defective color restoration is likely to occur. In particular, when the replenishment of the color developer is made low, it is generally necessary to increase the concentration of the preservative to improve the stability, but of course, the carry-in amount to the post-bath is also increased, and the color restoration is more and more defective. Is a problem. This is probably because the concentration of the ferrous salt in the desilvering bath increases and the concentration of the ferric salt required for bleaching decreases as the color developer components decompose in the desilvering bath. However, this also causes defective desilvering.

Therefore, an object of the present invention is to prevent defective desilvering even when a photographic light-sensitive material using a silver halide emulsion containing silver iodide is processed with a low discharge using an automatic processor. Another object of the present invention is to provide a method for processing a light-sensitive material that can obtain good photographic performance with extremely few color restoration defects.

[0007]

The object of the present invention can be achieved by the following method. An automatic developing machine comprising a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing at least 0.5 mol% silver iodide and a color developing bath followed by a processing bath having a bleaching ability. In the method of processing by using, the color developing solution in the color developing bath contains an aromatic primary amine color developing agent and a hydroxylamine derivative, and the concentration of sulfite is 25 mmo.
1 / liter or less, the replenishing amount of the color developing solution is 60 to 300 ml per 1 m ^{2 of the} light-sensitive material, and the concentration of the bleaching agent contained in the processing solution of the processing bath having the bleaching ability is 3 to 1
20 mmol / liter, and the replenishment amount of the processing solution is
The carry-in amount of the photosensitive material from the color developing solution is 0.0
A method of processing a silver halide color photographic light-sensitive material, which is 1 to 5 times.

The effect of the present invention is exhibited when the replenishment amount of the color developing solution and the replenishing amount of the desilvering bath are both reduced. Here, the replenishment amount of the desilvering bath means the amount of the component added to keep the components of the processing solution constant. Therefore, in the case of replenishment that is generally carried out, the volume is used, and in the case where, for example, the overflow solution of the desilvering bath is collected and necessary components are added as additives and then reused as a replenisher, The liquid that is replenished directly to the silver bath contains not only new components but also deteriorated components that have already been used.
Therefore, the amount of the component added to keep the amount and concentration of the treatment liquid constant is the amount of the regenerant and water. As a result of research conducted by the present inventors, it has been found that when hydroxylamine or sulfite, which has been conventionally used as a preservative for a color developing solution, is brought into a bath having a bleaching ability, it causes defective color restoration and defective desilvering. However, it should be noted that adjusting the concentration of sulfite significantly reduces these problems when derivatives other than hydroxylamine are used. It was unexpected that it would be effective only when low-emission treatment was performed so as to reduce the replenishment amount of the active bath.

The present invention will be described in detail below. The hydroxylamine derivative of the present invention is preferably a compound represented by the following general formula (A). General formula (A)

[0010]

[Chemical 4]

In the formula, R ¹ represents a hydrogen atom, an alkyl group or an unsaturated heterocyclic group, R ² represents an alkyl group or an unsaturated heterocyclic group, and R ¹ and R ² are linked to each other to form a nitrogen atom. And may form a heterocycle together with. In the general formula (A), the alkyl group represented by R ¹ and R ² may be linear, branched or cyclic. The alkyl group represented by R ¹ and R ² may have a substituent, and these substituents include a halogen atom (F, Cl, Br, etc.), an aryl group (phenyl group, p-chlorophenyl group, etc.). ), Alkyl groups (methyl group, ethyl group, isopropyl group, etc.), alkoxy groups (methoxy group, ethoxy group,
Methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p
-Toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide 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 group (methylureido group, phenylureido group, etc.), alkoxycarbonyl Amino group (methoxycarbonylamino group, etc.), aryloxycarbonylamino group (phenoxycarbonylamino group, etc.),
Alkoxycarbonyl group (methoxycarbonyl group etc.), aryloxycarbonyl group (phenoxycarbonyl group etc.), cyano group, hydroxy group, phosphono group,
Phosphinic acid residue, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (methylthio group, etc.), arylthio group (phenylthio group, etc.), hydroxyamino group,
An ammonio group and a heterocyclic group (a morpholyl group, a pyridyl group, etc.) can be mentioned. 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 unsaturated heterocyclic group represented by R ¹ and R ² is preferably a 4- to 8-membered unsaturated heterocyclic group having at least one nitrogen atom, sulfur atom, or oxygen atom selenium atom as a heteroatom, For example, 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, s-triazolo (5,1-d)-
s-triazine, triazaindene (imidazole [4,
5-b] pyridine etc.) and the like. This unsaturated heterocyclic group may be further substituted with a substituent, and the substituent is the same as the substituent mentioned above for the alkyl group. R ¹
Examples of the nitrogen-containing heterocycle formed by linking with 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 (A), it is preferable that R ¹ and R ² are alkyl groups, and the number of carbon atoms is preferably 1-10, particularly preferably 1-5. Preferred substituents of the alkyl group of R ¹ and R ² are a hydroxy group, an alkoxy group, an alkyl or aryl sulfonyl group, an amide group, a carboxy group, a cyano group, a phosphono group, a phosphinic acid residue, a sulfo group, a carbamoyl group and a sulfamoyl group. Group, nitro group,
An ammonio group and an amino group.

The hydroxylamine derivative represented by the general formula (A) of the present invention is particularly preferably the one represented by the following general formula (AI). General formula (AI)

[0015]

[Chemical 5]

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, preferred examples include methylene, ethylene, trimethylene, and propylene. Examples of the substituent of the alkylene group include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an ammonio group which may be alkyl-substituted, and a carboxy group, a sulfo group, a phosphono group, and a hydroxy group are preferable. Take as an example. 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, and a sulfamoyl group which may be alkyl-substituted. In the above, a carboxy group, a sulfo group, a hydroxy group, a phosphono group, or a carbamoyl group which may be alkyl-substituted may be mentioned as a preferred example.

Preferred examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group and 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 is a hydrogen atom,
It represents 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 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, an alkyl group Examples thereof include a sulfamoyl group which may be substituted. 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. When the compound represented by the general formula (A) has an acid group, the compound represented by the general formula (A) may be an alkali metal (for example, sodium or potassium) salt, and hydrochloric acid. ,
It may form salts with various organic or inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, or ammonium salts. Specific compounds of the compound represented by formula (A) of the present invention are shown below, but the invention is not limited thereto.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Chemical 6]

The compound represented by the general formula (A) can be obtained as a commercial product. Also, US Pat. No. 3,66
1,996, 3,362,961, 3,29
No. 3,034, No. 3,491, 151, No. 3,65
It can be synthesized by the method described in No. 5,764, No. 3,467,711 and the like. In the present invention, the hydroxylamine derivative is from 5.0 × 10 ⁻³ to 1 liter of the color developing solution.
5.0 × 10 ^-1 mol, preferably 3.0 × 10 ^-2 to 1.
It is desirable to add it so as to have a concentration of 0 × 10 ^-1 mol.

In the present invention, the sulfite concentration in the color developer is 25 mmol / liter or less, preferably 20 mmol / liter or less, more preferably 1
It is 0 mmol / liter or less. As sulfite,
Sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite and the like can be mentioned. The sulfite in the color developing solution prevents coloring and tar from being generated due to deterioration of the color developing solution, but as mentioned above, it is easy to cause desilvering failure and color restoration failure when brought into the desilvering bath. Most preferably, it does not contain a sulfite and it is preferable to use a hydroxylamine derivative to improve the preservative property with respect to coloring and generation of tar.

In the present invention, various organic preservatives can be used in addition to the hydroxylamine derivative within the range in which the effects of the present invention are exhibited. 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, organic compounds having a function of preventing oxidation of the color developing agent due to air and the like, among them, hydroxamic acids, hydrazines,
Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines and the like are particularly effective organic preservatives. These are Japanese Patent Application Nos. 61-147823 and 61.
-173595, 61-165621, 61-
188619, 61-197760, 61-1
86561, 61-198987, 61-20
No. 1861, No. 61-186559, No. 61-170
No. 756, No. 61-188742, No. 61-1887
41, US Pat. Nos. 3,615,503 and 2,49
4,903, JP-A-52-143020, JP-B-4
No. 8-30496, and the like.

The aromatic primary amine color developing agent used in the color developing solution is a paraphenylenediamine type,
In particular, N, N-dialkyl-substituted paraphenylenediamine compounds can be used, and many of them have been proposed in the past, and such compounds can be arbitrarily used in the present invention. For example, the N-substituted alkyl group has been devised as N-hydroxyalkyl group and the like, U.S. Pat. No. 2,108,243, British Patent 807,899, European Patent 410,450A2.
U.S. Pat. Nos. 2,193,015, 2,552,240 and 2,566,271 regarding N-sulfonamidoalkyl groups and the like, U.S. Pat. No. 337, JP-A-3-2
46542, 3-246543, N-sulfamoylalkyl groups and the like, U.S. Pat. No. 2,193,015
U.S. Pat. No. 2, regarding N-acylaminoalkyl groups
552,242, 2,592,363, N-4 quaternary ammonium alkyl groups and the like, British Patent No. 539,9
No. 37, the N-alkyl group having a phosphorus atom as a substituent on an alkyl group and the like, British Patent No. 539,395.
U.S. Pat. No. 2,37 with respect to N-acylalkyl groups
4,337, U.S. Pat. No. 2,603,656 concerning N-alkoxyalkyl groups and the like, JP-A-47-11534.
No. 47-11535, Japanese Patent Publication No. 54-16860
No. 58, No. 58-14670, No. 58-23618, N
-UK Patent 811,679 for sulfoalkyl groups
No. 2,716,1 for N-aralkyl radicals
32, etc. Further, as a devised substituent for the benzene nucleus, US Pat.
No. 2,552,240, 2,592,364
U.S. Pat. Nos. 2,350,109 and 2,449,919 regarding the nuclear acylaminosulfonamido group, and U.S. Pat. Nos. 2,552,241 and 2, with respect to the nuclear acylaminoalkylsulfonamidoalkyl group. 566,2
71, 2,592,364, U.S. Pat. Nos. 2,570,116 and 2,575,027 concerning nuclear amino groups.
, No. 2,652,331, and nuclear thiosulfonic acid groups are described in British Patent No. 872,683. Further, regarding the use of an analog of paraphenylenediamine as a color developing agent, US Pat.
739, 2,566,259, U.S. Pat. No. 2,612,500 for N- (p-aminophenyl) hexamethyleneimine, and U.S. Pat. No. 2,707,681 for 9-aminojulolidine. There is a description in the number etc.

The color developing agent particularly preferably used in the present invention is a compound represented by the following general formula (D) or general formula (E). The cause of these developing agents exerting the effect of the present invention is unknown, but it is presumed that the developing agent and its oxidant brought in from the color developing solution have some interaction with the emulsion. General formula (D)

[0028]

[Chemical 7]

In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms. R ₂
Represents an alkylene group having 3 to 6 carbon atoms or a hydroxyalkylene group having 3 to 6 carbon atoms. R ₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. General formula (E)

[0030]

[Chemical 8]

In the formula, R ₄ to R ₁₁ may be the same or different and each is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an amino group, an alkylamino group, an alkoxy group, an amide group or a sulfonamide group. Represents a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group, a sulfonyl group, a carboxy group or a sulfo group. R ₁₂ to R ₁₅ may be the same or different and each is a hydrogen atom, a halogen atom, an amino group, an alkylamino group, a hydroxyl group, an alkyl group, an alkoxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group or Represents a sulfamoylamino group.

The general formula (D) will be described in detail below. In the general formula (D), R ₁ represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms. The alkyl group and the hydroxyalkyl group may be linear or branched. Specific examples thereof include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an n-hexyl group, a neopentyl group, a 3-hydroxypropyl group, and a 4-hydroxy group.
Hydroxybutyl group, 5-hydroxypentyl group, 6-
Hydroxyhexyl group, 4-hydroxypentyl group, 3
-Hydroxybutyl group, 4-hydroxy-4-methylpentyl group, 5,6-dihydroxyhexyl group and the like.

In the general formula (D), R ₂ has 3 to 10 carbon atoms.
It represents an alkylene group having 6 or a hydroxyalkylene group having 3 to 6 carbon atoms. The alkylene group and the hydroxyalkylene group may be linear or branched. Specific examples thereof include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1-methylethylene group, 2-methylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, and 3 -Methyltrimethylene group, 3-methylpentamethylene group, 2-methylpentamethylene group, 2-ethyltrimethylene group, 3-hydroxypentamethylene group and the like.

In the general formula (D), when R ₁ is an alkyl group, it preferably has 1 to 4 carbon atoms. Of these, a methyl group, an ethyl group, and an n-propyl group are preferable, and an ethyl group is most preferable.
When R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is preferably an alkylene group having 3 to 4 carbon atoms, of which a trimethylene group and a tetramethylene group are preferable, and a tetramethylene group is a tetramethylene group. Is most preferred. On the other hand, in the general formula (D), when R ₁ is a hydroxyalkyl group having 3 to 6 carbon atoms, R ₂ preferably has 4 to 6 carbon atoms, and more preferably 5 to 6 carbon atoms. In the general formula (D), R ₁ is preferably an alkyl group having 1 to 4 carbon atoms.

In the general formula (D), R ₃ is a hydrogen atom,
It represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The alkyl group or the alkoxy group may be linear or branched. Specific examples of R ₃ include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group,
Examples thereof include isopropyl group, sec-butyl group, methoxy group, ethoxy group and isopropoxy group. R ₃ is preferably an alkyl group, more preferably a methyl group or an ethyl group, and most preferably a methyl group.

Specific examples of typical developing agents represented by formula (D) in the present invention are shown below, but the developing agents are not limited to these. D-1 4-amino-3-methyl-N-methyl-N-
(3-Hydroxypropyl) aniline D-2 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline D-3 4-amino-3-methyl-N-ethyl-N-
(2-Hydroxypropyl) aniline D-4 4-amino-3-methyl-N-ethyl-N-
(1-Hydroxy-2-propyl) aniline D-5 4-amino-3-ethyl-N-methyl-N-
(3-Hydroxypropyl) aniline D-6 4-amino-3-ethyl-N-ethyl-N-
(3-Hydroxypropyl) aniline D-7 4-amino-3-methyl-N-propyl-N
-(3-hydroxypropyl) aniline

D-8 4-amino-3-propyl-N
-Methyl-N- (3-hydroxypropyl) aniline D-9 4-amino-3-butyl-N-methyl-N-
(3-Hydroxypropyl) aniline D-10 4-amino-3-methyl-N-butyl-N-
(3-Hydroxypropyl) aniline D-11 4-amino-3-methyl-N-propyl-N
-(4-Hydroxybutyl) aniline D-12 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline D-13 4-amino-3-ethyl-N-methyl-N-
(3-Hydroxy-2-methylpropyl) aniline D-14 4-amino-3-ethyl-N-ethyl-N-
(3-Hydroxybutyl) aniline D-15 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxy-2-methylpropyl) aniline D-16 4-amino-3-methyl-N-ethyl-N-
(3-hydroxybutyl) aniline

D-17 4-amino-3-methyl-N-
Ethyl-N- (6-hydroxyhexyl) aniline D-18 4-amino-3-methyl-N, N-bis (4
-Hydroxybutyl) aniline D-19 4-amino-3-ethyl-N, N-bis (3
-Hydroxypropyl) aniline D-20 4-amino-3-methyl-N, N-bis (5
-Hydroxypentyl) aniline D-21 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (6-hydroxyhexyl) aniline D-22 4-amino-3-ethyl-N, N-bis (5
-Hydroxypentyl) aniline D-23 4-amino-3- (1-methyl) ethyl-N
-(4-Hydroxybutyl) -N- (5-hydroxypentyl) aniline D-24 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxypentyl) aniline D-254 -Amino-3-ethyl-N-propyl-N
-(4,5-Dihydroxypentyl) aniline D-26 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (3-hydroxypropyl) aniline D-27 4-amino-3-ethyl- N- (2-hydroxybutyl) -N- (4-hydroxybutyl) aniline D-28 4-amino-3- (1,1-dimethyl) ethyl-N, N-bis (4-hydroxybutyl) aniline

D-29 4-amino-N-ethyl-N-
(3-Hydroxypropyl) aniline D-30 4-amino-3-methoxy-N-ethyl-N
-(4-hydroxybutyl) aniline D-31 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline D-32 4-amino-N- (5-hydroxypentyl) -N- ( 3-hydroxypentyl) aniline D-33 4-amino-N-propyl-N- (4-hydroxybutyl) aniline D-34 4-amino-3- (1-methyl) ethoxy-
N, N-bis (4-hydroxybutyl) aniline D-35 4-amino-N- (5-hydroxypentyl) -N- (6-hydroxyhexyl) aniline D-36 4-amino-3- (1,1) -Dimethyl) ethyl-N-methyl-N- (3-hydroxypropyl) aniline D-37 4-amino-3-methyl-N-hexyl-N
-(5,6-Dihydroxyhexyl) aniline D-38 4-amino-3-butoxy-N-pentyl-
N- (3,4-dihydroxybutyl) aniline Among the compounds represented by the general formula (D), exemplified compounds D-2, D-12 and D-20 are preferable, and exemplified compound D-12 is most preferable.

Next, the general formula (E) will be described in detail. In the general formula (E), R ₄ to R ₁₁ may be the same or different and each is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an amino group, an alkylamino group, an alkoxy group, an amide group or a sulfone. It represents an amide group, a carbamoyl group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group, a sulfonyl group, a carboxyl group or a sulfo group.

The details of R ₄ to R ₁₁ will be described.
The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, which is an alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen. Atom or other oxygen atom, nitrogen atom, may be substituted with a substituent formed by a sulfur atom or a carbon atom, for example, methyl, ethyl, propyl, isopropyl,
t-butyl, hydroxymethyl, methanesulfonamidomethyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-
Methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, n-hexyl, 2-hydroxypropyl, 4-hydroxy. Butyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-
Carbamoylbutyl, 2-carbamoyl-1-methylethyl and 4-nitrobutyl.

The alkylamino group has 1 to 1 carbon atoms.
6, preferably an alkylamino group having 1 to 6 carbon atoms, which is an alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom or other oxygen atom, nitrogen atom, sulfur atom or carbon atom. It may be substituted with a substituent formed, for example,
N, N-dimethylamino, N, N-diethylamino, N
-Butylamino. Alkoxy group has 1 carbon
To 16, preferably an alkoxy group having 1 to 6 carbon atoms, which is an alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom or other oxygen atom, nitrogen atom, sulfur atom or carbon atom. It may be substituted with a substituent formed, for example,
Methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 4-hydroxybutoxy, 2-methanesulfonylethoxy. 1 carbon atom as an amide group
To 16, preferably an amide group having 1 to 6 carbon atoms, which is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other oxygen atom, a nitrogen atom, a sulfur atom or It may be substituted with a substituent formed by a carbon atom, and examples thereof include acetamide, 2-methoxypropionamide, and pentanoylamide.

The sulfonamide group has 1 to 1 carbon atoms.
6, preferably a sulfonamide group having 1 to 6 carbon atoms, which is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other oxygen atom, nitrogen atom, sulfur atom or It may be substituted with a substituent formed by a carbon atom, and examples thereof include methanesulfonamide and benzenesulfonamide. Carbamoyl group has 1 to 1 carbon atoms
6, preferably a carbamoyl group having 1 to 6 carbon atoms, which is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. It may be substituted with a substituent formed by an atom, and examples thereof include carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl and N-butylcarbamoyl. The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 16 carbon atoms, preferably 2 to 6 carbon atoms, which are alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom or other oxygen. Atom, nitrogen atom, may be substituted with a substituent formed by a sulfur atom or a carbon atom, for example, methoxycarbonylamino,
These are ethoxycarbonylamino and butoxycarbonylamino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and these are alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogen atoms or other oxygen atoms. It may be substituted with a substituent formed by a nitrogen atom, a sulfur atom or a carbon atom, and examples thereof include ureido, methylureido and N, N-diethylureido.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably a sulfamoylamino group having 0 to 6 carbon atoms, which are alkyl group, alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom or other oxygen atom, nitrogen atom, It may be substituted with a substituent formed by a sulfur atom or a carbon atom, and examples thereof include sulfamoylamino, dimethylsulfamoylamino and dipropylsulfamoylamino. The sulfonyl group has 1 to 16 carbon atoms,
It is preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, which is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other oxygen atom, a nitrogen atom, It may be substituted with a substituent formed by a sulfur atom or a carbon atom, and examples thereof include methanesulfonyl and ethanesulfonyl.

R ₁₂ to R ₁₅ may be the same or different and each is a hydrogen atom, a halogen atom, an amino group, an alkylamino group, a hydroxyl group, an alkyl group, an alkoxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, It represents an ureido group or a sulfamoylamino group, and the details of each substituent are the same as R ₄ to R ₁₁ . General formula (F) shows a preferable range in general formula (E). General formula (F)

[0046]

[Chemical 9]

In the formula, R ₄ to R ₁₁ and R ₁₃ have the same meanings as in formula (E). In formula (F), R ₄ to R ₁₁ are hydrogen atom, hydroxyl group, alkyl group, unsubstituted amino group, alkylamino group, alkoxy group, amide group, sulfonamide group, carbamoyl group, alkoxycarbonylamino group, ureido. It is preferably a group or a sulfamoylamino group. Also, R ₁₃
Is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group or a ureido group, and among them, a hydrogen atom, an alkyl group or an alkoxy group is preferable, and an alkyl group is more preferable. . The most preferred alkyl group is a lower alkyl group such as methyl and ethyl.

Specific examples of typical developing agents represented by formula (E) in the present invention are shown below, but the developing agents are not limited thereto. E-1 N- (4-aminophenyl) -3-hydroxymethylpyrrolidine E-2 N- (4-amino-3-methylphenyl) -3
-Methanesulfonamide methylpyrrolidine E-3 N- (4-amino-3-methylphenyl) -3
-Pyrrolidine carboxamide E-4 N- (4-aminophenyl) -3-hydroxymethyl-3-methylpyrrolidine E-5 N- (4-amino-3-methoxyphenyl) pyrrolidine E-6 N- (4-amino- 3-ethylphenyl) -3
-Hydroxypyrrolidine E-7 N- (4-aminophenyl) -3-hydroxymethyl-4-methylpyrrolidine E-8 N- (4-amino-3-methoxycarbonylaminophenyl) -2- (2-hydroxyethoxymethyl) ) Pyrrolidine E-9 N- (4-amino-3-methylphenyl) -3
-Hydroxymethylpyrrolidine E-10 N- (4-amino-3-methylphenyl)-
3-hydroxypyrrolidine

E-11 N- [4-amino-3- (2-
Hydroxyethoxy) phenyl] -3- (3,3-dimethylsulfamoylamino) pyrrolidine E-12 N- (4-amino-3-methylphenyl)-
2-Hydroxymethylpyrrolidine E-13 N- (4-amino-3-chlorophenyl)-
3-Methanesulfonamide pyrrolidine E-14 N- (4-amino-2-methylaminophenyl) -3-ethoxypyrrolidine E-15 N- (4-amino-2-hydroxyphenyl) -3-sulfopyrrolidine E-16 N- [4-amino-3- (3,3-dimethylureido) phenyl] -3-methylsulfonylpyrrolidine E-17 N- [4-amino-2- (3-methylureido) phenyl] -3-diethylaminopyrrolidine E-18 N- (3,4-diaminophenyl) -3-cyanopyrrolidine E-19 N- (4-amino-2-acetamidophenyl) -3-fluoropyrrolidine E-20 N- (4-amino-2- Methanesulfonamidophenyl) -3-aminopyrrolidine E-21 N- [4-amino-3- (3,3-dimethylsulfamoyl) Amino) phenyl] -3-ethoxycarbonylaminopyrrolidine

The color developing agent represented by formula (D) or (E) of the present invention is, for example, Journal of the American Chemical Society, Vol. 73, page 3100 (1951), British Patent No. 807. , 899, and can be easily synthesized. Further, the following synthesis examples and methods similar thereto can also be used. The color developing agent represented by formula (D) of the present invention is described in JP-A-4-443. Synthesis Example 1 (Synthesis of Exemplified Compound (E-3))

[0051]

[Chemical 10]

Synthesis of (3-b) 95.1 g of (3-a) and 70 ml of triethylamine were put in 500 ml of toluene, and 39 ml of methanesulfonyl chloride was added dropwise thereto over 30 minutes while stirring under ice cooling. After stirring at room temperature for 30 minutes, insoluble matter was filtered off, and 58 g of potassium t-butoxide was gradually added thereto while stirring the filtrate. After stirring at room temperature for a whole day and night, water was added to the system to separate the toluene layer, washed with water, concentrated and distilled under reduced pressure to obtain 45 g of (3-b) as a fraction of 142 to 155 ° C / 2 mmHg. A colorless liquid solidified upon standing.

Synthesis of (3-c) While stirring 30 ml of concentrated sulfuric acid under ice cooling, there was added (3-c) thereto.
19.5 g of the solid from b) was added slowly. More water 1.0
After adding ml, the mixture was stirred at 50 ° C. for 1 hour and allowed to cool. Pour the system into ice water with stirring to remove sodium hydroxide 3
An aqueous solution of 5 g was further added, and the precipitated crystals were separated by filtration, washed with water and recrystallized from methanol to obtain 16 g of (3-c) as colorless crystals. Synthesis of (3-d) 16 ml of concentrated hydrochloric acid and 13.7 g of (3-c) were added to 60 ml of water.
Then, an aqueous solution of 4.6 g of sodium nitrite was gradually added dropwise thereto with stirring under ice cooling (about 30 minutes). After the dropping, the mixture was stirred for another 30 minutes, and then an aqueous solution of 8.5 g of sodium hydroxide was added, whereby crystals were precipitated in the system. The crystals were separated by filtration, washed with water, and recrystallized from methanol / water (3-
d) 12 g was obtained as green crystals. Synthesis of Exemplified Compound (E-3)

9.5 g of (3-d) and 0.5 g of 10% palladium carbon were added to 70 ml of ethanol, and the mixture was stirred in an autoclave at a hydrogen pressure of 50 kg / cm ² and an internal temperature of 70 ° C. for 3 hours. After filtering off the catalyst, 1.1 ml of concentrated sulfuric acid was added to the filtrate while stirring, and the precipitated crystals were collected by filtration to obtain 8 g of 1/2 sulfate of the target compound (E-3) as light brown crystals. It was Elemental analysis value as C ₁₂ H ₁₈ N ₃ O ₃ S _1/2 (%) C H N S calculated value: 53.72 6.76 15.66 5.97 measured value: 53.45 6.50 15. 66 5.81 Synthesis Example 2 (Synthesis of Exemplified Compound (E-12))

[0055]

[Chemical 11]

Synthesis of (12-b) 20 g of (12-a) and 2-pyrrolidinemethanol 14.
3 g was added together with 20 g of potassium carbonate in 100 ml of dimethylformamide, and the mixture was stirred at 100 ° C. for 2 hours.
After cooling, the system was poured into water, extracted with ethyl acetate, washed with water, concentrated and recrystallized from acetonitrile (12-b) 26.
g was obtained as yellow crystals. Synthesis of Exemplified Compound (E-12) (12-b) 17.7 g and 10% Palladium on carbon 0.9
g was added to 80 ml of ethanol, and the mixture was stirred in an autoclave at a hydrogen pressure of 50 kg / cm ² and an internal temperature of 50 ° C. for 2 hours. The catalyst was filtered while hot, then allowed to cool and the precipitated crystals were collected by filtration to obtain 12 g of the desired exemplary compound (E-12) as light brown crystals.

Since the compound represented by the general formula (D) or (E) is extremely unstable when stored as a free amine, it is generally produced as a salt of an inorganic acid or an organic acid.
It is preferable that the free amine is not stored until it is stored and added to the processing solution. Examples of the inorganic or organic acid for forming the salt of the compound of the general formula (D) or (E) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-disulfonic acid and the like. To be Of these, salts of sulfuric acid and p-toluenesulfonic acid are preferable, and salts of sulfuric acid are most preferable. For example, Exemplified Compound D-12 is obtained as a sulfate, and its melting point is 112 to 114 ° C. (recrystallized from ethanol). The color developing agent represented by the general formula (D) is preferable to the color developing agent represented by the general formula (E). In the present invention, the amount of the color developing agent used is preferably 0.1 g per liter of the color developing solution.
˜20 g, more preferably 1 g to 15 g.

The color developing agent represented by formula (D) or (E) of the present invention is preferably used alone or in combination with another p-phenylenediamine derivative. Representative examples of the compound to be combined are shown below, but the invention is not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino)
Toluene P-3 2-amino-5- (N-ethyl-N-laurylamino) toluene P-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline P-5 2-methyl-4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline P-6 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline P-10 4-amino-3-methyl-N-ethyl-N-
β-ethoxyethylaniline P-11 4-amino-3-methyl-N-ethyl-N-
β-butoxyethylaniline

Of the above-mentioned p-phenylenediamine derivatives, the exemplified compound P- is particularly preferable as the compound to be combined.
5 or P-6. In addition, these p-phenylenediamine derivatives are generally used in salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, naphthalene-1,5-disulfonates. ..
The amount of the color developing agent used in combination is preferably 1/100 to 5 moles per 1 mole of the color developing agent represented by the general formula (D) or (E) of the present invention, unless the effect is impaired. , 1/50 to 1 mol is more preferable.

The color developer of the present invention comprises a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It is common to include a development inhibitor such as a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. If necessary, ethylene glycol, an organic solvent such as diethylene glycol, benzyl alcohol, polyethylene glycol, a quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples. The processing temperature of the color developing solution is 20 to 50 ° C, preferably 30 to 45 ° C.

In the present invention, the replenishing amount of the color developing solution is 60 to 300 ml, preferably 70 to 250 ml per 1 m ² of the light-sensitive material. If the amount is less than 60 ml per 1 m ² of the light-sensitive material, it is difficult to keep the amount of the color developing solution constant because the light-sensitive material is taken out. In the present invention, the color development processing time is preferably 20 seconds to 3 minutes and 30 seconds. This time can be shortened by adjusting the composition of silver halide other than silver iodide, or by increasing the development activity such as raising the pH of the color developing solution or the processing temperature.

Bleaching or bleach-fixing treatment is carried out after the color developing treatment, but a bleach-fixing treatment may be carried out after the bleaching treatment in order to accelerate the processing. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment,
Alternatively, desilvering processing such as bleach-fixing and further fixing processing after bleaching processing, or continuous fixing processing in two tanks after bleaching processing may be carried out by dividing it into three or more solutions, depending on the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other amino acids. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used.

In the present invention, a ferric iron complex salt of an organic acid represented by the following general formula (H) is preferably used as a bleaching agent. General formula (H)

[0064]

[Chemical 12]

In the formula, L ₁ , L ₂ and L ₃ each represent an alkylene group, M ₁ , M ₂ and M ₃ each represent a hydrogen atom or a cation, R represents a substituent, u represents 0,
1, 2, 3 or 4, and k, t, m and n each represent 0 or 1. First, the organic acid represented by the general formula (H) will be described in detail below. The substituent represented by R is an alkyl group (for example, a methyl group or an ethyl group),
Aralkyl group (eg phenylmethyl group), alkenyl group (eg allyl group), alkynyl group, alkoxy group (eg methoxy group, ethoxy group), aryl group (eg phenyl group, p-methylphenyl group), amino group (eg dimethyl group) Amino group), acylamino group (eg acetylamino group), sulfonylamino group (eg methanesulfonylamino group), ureido group, urethane group, aryloxy group (eg phenyloxy group), sulfamoyl group (eg methylsulfamoyl group) A carbamoyl group (for example, a carbamoyl group, a methylcarbamoyl group),
Alkylthio group (methylthio group), arylthio group (eg phenylthio group), sulfonyl group (eg methanesulfonyl group), sulfinyl group (eg methanesulfinyl group), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine atom), Cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl group), acyl group (eg acetyl group, benzoyl group), alkoxycarbonyl group (eg methoxycarbonyl group), acyloxy group (eg acetoxy group) Group), carbonamido group, sulfonamide group, nitro group, hydroxamic acid group and the like. When these substituents have carbon atoms, they preferably have 1 to 4 carbon atoms.

When u is 2 or more, R may be the same or different, and Rs may be linked to each other to form a ring. The alkylene group represented by L ₁ , L ₂ and L ₃ may be linear or branched and preferably has 1 carbon atom.
~ 6. Further, in the general formula, L ₁ , L ₂ and L ₃ may be the same or different. L ₁ and L ₂
And L ₃ may have a substituent, and examples thereof include the substituents mentioned for R. L ₁ , L ₂ and L ₃ are preferably a methylene group or an ethylene group. M ₁ , M ₂
And cations represented by M ₃ include alkali metals (lithium, sodium, potassium, etc.), ammonium (ammonium, tetraethylammonium, etc.),
Examples thereof include pyridinium. Specific examples of the organic acid represented by the general formula (H) for forming the bleaching agent are shown below, but the invention is not limited thereto.

[0067]

[Chemical 13]

[0068]

[Chemical 14]

[0069]

[Chemical 15]

[0070]

[Chemical 16]

Next, typical synthetic examples of the organic acid represented by the general formula (H) are shown below. Synthesis example 1. Synthesis of Compound 1 20.0 g (0.146 mol) anthranilic acid, 20 ml water
In a three-necked flask, stirring well in an ice bath,
29.2 ml of 5N sodium hydroxide aqueous solution (0.146 mo
l) was added. After the anthranilic acid was dissolved, the temperature was returned to room temperature and 52.3 g (0.449 mol) of chloroacetic acid was added. Heat and stir in an oil bath at 60 ° C, and add 5N sodium hydroxide solution 8
5 ml was added dropwise. (However, an aqueous solution of sodium hydroxide was added dropwise so that the reaction solution maintained a pH of 9 to 11.) After stirring with heating for 20 hours, the temperature was returned to room temperature, and 45.6 g of concentrated hydrochloric acid was added.
(0.450 mol) was added. The precipitated crystals were filtered off and washed with water. The crystals were transferred to a beaker, 300 ml of water was added, and the pH was adjusted to 1.6 to 1.7 with concentrated hydrochloric acid. After stirring for 1 hour, the solid was collected by filtration and washed well with water. By recrystallizing from water, 25.7 g (0.
0991 mol) was obtained. Yield 68%, melting point 214-216 ° C (decomposition)

Synthesis Example 2. Synthesis of Compound 11 50.0 g of o-aminothiophenol under nitrogen atmosphere
Dissolve (0.399 mol) in 300 ml of water, 80-85 ℃
Sodium chloroacetate 1 while heating and stirring at
300 g of an aqueous solution of 53 g (1.31 mol) was added dropwise. 9
After heating to 0 to 95 ° C., 52.4 g of sodium hydroxide
100 ml of water (1.31 mol) was slowly added dropwise. After reacting at the same temperature for 5 hours, the mixture was cooled to room temperature and p-ionized with 5N hydrochloric acid.
H was adjusted to about 1.7, and the precipitated solid was collected by filtration and washed with water to give 84.7 g (0.283 mol) of the desired product.
Obtained. The 71% yield structure was identified by NMR spectrum and elemental analysis. Elemental analysis value H% C% N% S% Calculated value 4.38 48.16 4.68 10.71 Actual value 4.46 48.01 4.52 10.53 Other compounds can be similarly synthesized. it can.

In the present invention, the concentration of the bleaching agent in the processing solution having a bleaching ability is 3 to 120 mmol / liter. It is preferably 10 to 100 mmol / liter, more preferably 30 to 100 mmol / liter. Further, a bleaching agent of an inorganic compound may be used in combination with the bleaching agent of the ferric iron complex salt. Examples of bleaching agents of inorganic compounds include hydrogen peroxide, persulfates and bromates. When these inorganic compound bleaching agents are used in combination, the concentration of the above-mentioned ferric organic acid complex salt can be used at a low concentration of about 3 to 10 mmol.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, acetic acid, propionic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. And
In particular, ammonium thiosulfate can be used most widely. Further, it is also preferable to use thiosulfate in combination with thiocyanate, thioether compound, thiourea and the like. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294769.
The sulfinic acid compounds described in No. A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the pH of the bleaching solution or the bleach-fixing solution is usually 3.8 to 8, but preferably 4.0 to 4.0.
5.5, lower pH for faster processing
It can also be processed with. In the present invention, the fixing solution or the bleach-fixing solution has a pKa of 6.0 to adjust the pH.
It is preferable to add a compound of 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / liter. The total time for the desilvering step is preferably 1 minute to 8 minutes, more preferably 1 minute to 5 minutes. The processing temperature of the desilvering process is 25 ° C to 5 ° C.
It is 0 ° C, preferably 35 ° C to 45 ° C.

In the automatic developing machine, the carry-in amount of the photosensitive material from the color developing bath is devised so as to be as small as possible by a roller or a squeegee between the processing baths to the extent that the photosensitive material is not scratched. Usually 50-10
It is about 0 ml / m ² . In the present invention, the replenishing amount to the processing bath (bleaching bath or bleach-fixing bath) having a bleaching ability immediately after the color developing bath is 0.01 to 5 times the carry-in amount of the light-sensitive material from the color developing bath. When the replenishment amount of the processing bath having a bleaching ability is reduced as described above, the color developer component in the bleaching solution or the bleach-fixing solution remarkably increases due to the carry-in. In particular, when the bleaching solution or the bleach-fixing solution is regenerated, the amount of the color developing solution component may be larger than that of the bleaching or bleach-fixing component. The present invention effectively exhibits the effects of the present invention in such a low emission treatment. The replenishment amount is
0.05 of carry-in amount from the photosensitive material from the color developing solution
It is preferably 3 to 3 times, and 0.1 to 2 times.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing step can be set within a wide range depending on the characteristics and application of the light-sensitive material, the temperature of the rinsing water, the number of rinsing tanks (for example, 2 to 4), the replenishment system such as countercurrent and downflow, and various other conditions. .. According to the multi-stage countercurrent method, the amount of washing water can be significantly reduced, but the increase in the residence time of water in the tank causes problems such as bacteria breeding and the produced floating substances adhering to the photosensitive material. In the processing of the light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-28
The method of reducing calcium ion and magnesium ion described in No. 8838 can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as sodium chlorinated isocyanurate described in JP-A-57-8542, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986
Sankyo Publishing, Sanitary Technology Society, "Sterilization, Sterilization, and Antifungal Technology of Microorganisms" (1982), Industrial Technology Association, Japan Society for Antibacterial and Antifungal, Encyclopedia of Antibacterial and Antifungal Agents (1986) A bactericide can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. To be done. Further, the light-sensitive material of the present invention, instead of the above water washing,
It is also possible to treat directly with the stabilizing solution. In such stabilizing treatment, JP-A-57-8543 and JP-A-5-543 have been used.
All the known methods described in JP-A-8-14834 and JP-A-60-220345 can be used.

When further stabilizing treatment is carried out after the water washing treatment, a compound for stabilizing the dye image in the stabilizing solution, such as formalin, hexamethylenetetramine and its derivative, hexahydrotriazine and its derivative, , N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The preferred addition amount of these compounds is Stabilizer 1
Although it is 0.001 to 0.02 mol per liter, it is preferable that the concentration of free formaldehyde in the stabilizing solution is lower, because formaldehyde gas is less scattered. From this point of view, as a dye image stabilizer, Japanese Patent Application No.
N-methylolazoles described in -318644;
Azolylmethylamines described in Japanese Patent Application No. 3-142708 such as N, N′-bis (1,2,4-triazol-1-yl) piperazine are preferable. The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step.

The processing method of the present invention is carried out using an automatic processor. In the present invention, it is preferable that a means for preventing liquid evaporation and air oxidation is provided by reducing the contact area of the treatment tank with air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. Opening ratio = [contact area between processing liquid and air (cm ² )] ÷ [volume of processing liquid (cm ³ )] The above opening ratio is preferably 0.1 cm ⁻¹ or less, more preferably 0 0.001 to 0.05 cm ⁻¹ .
As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
The slit developing treatment method described in JP-A-63-216050 can be used. Reducing the aperture ratio is preferably applied not only in both the color developing process and the black and white developing process but also in the subsequent processes, for example, all the processes such as bleaching, bleach-fixing, fixing, washing, and stabilizing. Further, it is preferable to use a means for suppressing the accumulation of bromide ions in the developing solution.

In the present invention, in order to carry out the processing rapidly, the shorter the in-air time when the photosensitive material moves between the processing solutions, that is, the crossover time, the shorter the better, and it is preferably 10 seconds or less. In order to achieve the short-time crossover as described above, it is preferable to use a cine type automatic developing machine in the present invention, and a leader conveyance system is particularly preferable. Such a system is an automatic processor FP-5 manufactured by Fuji Photo Film Co., Ltd.
It is used in 60B. As a reader and a conveying means for the photosensitive material, there are disclosed in JP-A-60-191257 and 60-1.
91258 and 60-191259 are preferable, and particularly, as a conveying mechanism, Japanese Patent Application Nos. 1-265794, 1-266915, and 1-2.
It is preferable to adopt each method described in No. 66916. Further, in order to shorten the crossover time and prevent the processing solution from being mixed, the structure of the crossover rack preferably has a mixing prevention plate described in Japanese Patent Application No. 1-265795.

In the present invention, it is preferable that the stirring of each treatment liquid is strengthened as much as possible in order to more effectively exhibit the effects of the present invention. Specific methods for strengthening stirring are disclosed in JP-A-62-183460 and JP-A-62-183.
No. 461, that is, a color negative film processor FP-56 manufactured by Fuji Photo Film Co., Ltd.
No. 0B, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, a method in which a rotating means of JP-A-62-183461 is used to enhance a stirring effect, and further a method is provided in the solution. Examples include a method of moving the light-sensitive material (film) while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of causing jetting of the processing liquid to collide is most preferable. Above all, it is preferable that the stirring is strengthened as much as possible in the desilvering step, and it is more preferable to adopt this method for all processing tanks. Since the metal chelate bleaching agent in the bleaching solution and / or the bleach-fixing solution becomes a reducing state with the bleaching treatment, the bleaching solution and / or the bleach-fixing solution should be continuously regenerated in cooperation with the treatment. preferable. Specifically, it is preferable that air is blown into the bleaching solution and / or the bleach-fixing solution by an air pump to reoxidize the reduced metal chelate with oxygen, so-called aeration.
Aeration is disclosed in JP-A-2-176746 and 2
-176747, pore size 300 μm
The following porous nozzle was used to obtain a density of 0.
It is preferable to supply a flow rate of 01 liter or more.

Next, the photosensitive material used in the present invention will be described. The silver halide contained in the silver halide emulsion layer of the light-sensitive material used in the present invention needs to contain 0.5 mol% or more of silver iodide. In addition to this, silver bromide and silver chloride are also included. Can be included. A preferred silver halide is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 0.5 to 30 mol% of silver iodide. Especially preferred is 2 to 2.
It is a silver iodobromide containing 5 mol% of silver iodide. The light-sensitive material in the present invention is not particularly limited in the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a light-sensitive material having a light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. A unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer photosensitive material, the unit photosensitive layers are generally arranged in order from the support side to the red sensitive layer and green. The color-sensitive layer and the blue color-sensitive layer are installed in this order. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. As the plural halogen silver emulsion layers constituting each unit photosensitive layer, a two-layer constitution of a high sensitivity emulsion layer and a low sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the photosensitivity is gradually lowered toward the support.

The emulsion of the present invention is preferably a monodisperse emulsion. In the present invention, the monodisperse emulsion is a coefficient of variation relating to the grain size (sphere equivalent diameter) of silver halide grains.

[0085]

[Equation 1]

Is an emulsion having a grain size distribution of 0.25 or less. That is, when the grain size of each emulsion grain is ri and the number is ni, the average grain size is

[0087]

[Equation 2]

And its standard deviation is

[0089]

[Equation 3]

It is defined as The term "individual grain size" as used in the present invention means a silver halide emulsion.
(TH James) et al., "The Theory of the Photogra Process"
phic Process) 3rd edition, pp. 36-43, published by Macmillan, Inc. (1966), the area projected when micro-imaged by a method well known in the art (usually electron microscopy). Is the diameter equivalent to the projected area. Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle which is equal to the projected area of a silver halide grain as described in the above-mentioned book. Therefore, when the shape of the silver halide grains is other than spherical (for example, cubic, octahedral, tetradecahedral, tabular, potato-like), the average grain size and its deviation can be obtained as described above. The coefficient of variation related to the grain size of silver halide grains is 0.30
The following are preferred. Regarding the light-sensitive material in the present invention,
The details are described in JP-A-3-213853, page 15, lower right column, line 4 to page 20, upper right column, line 5. The present invention can be applied to various light-sensitive materials. Particularly, it is preferably used for a color negative film for general use or movies, and a reversal film for slides or televisions.

[0091]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 On a subbed cellulose triacetate film support,
A light-sensitive material 101 having the following composition was prepared. (Composition of photosensitive layer) The coating amount is the amount of silver expressed in units of g / m ² for silver halides and colloidal silver,
Additives and gelatin in amounts expressed in g / m ^{2 and} sensitizing dyes in the same layer of silver halide 1
It is shown by the number of moles per mole. First layer: antihalation layer Black colloidal silver Coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ⁻² Cpd-2 1.9 × 10 ^-2 Solv-1 0.30 Solv-2 1.2x10 ^-2 Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol% sphere equivalent diameter 0.07 µm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2

Third layer: first red-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular form Grain, diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, sphere equivalent diameter 0.4 μm, sphere equivalent diameter variation coefficient 18% , Tetradecahedral grains) Silver coating amount 0.40 Gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv-1 0.32 Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8 0.5 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0. 85 Gelatin 0.91 ExS-1 3.0 × 10 ⁻⁴ mol ExS-2 1.0 × 10 ⁻⁴ mol ExS-3 3.0 × 10 ⁻⁵ mol ExC-1 0.13 ExC-2 6.2 X10 ^-2 ExC-4 4.0 x10 ^-2 Solv-1 0.10.

Fifth layer: third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, spherical equivalent diameter 1.4 μm, variation coefficient of spherical equivalent diameter 28%, plate-like) Particles, diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ⁻⁴ mol ExS-2 6.0 × 10 ⁻⁵ mol ExS-3 2.0 × 10 ^-5 mol ExC-2 8.5x10 ^-2 ExC-5 7.3x10 ^-2 Solv-1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.00 Cpd-4 8. 0x10 ^-2 Solv-1 8.0x10 ^-2

Seventh Layer: First Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular form Grain, diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter 0.4 μm, variation coefficient of equivalent sphere diameter 18% , Tetradecahedral grains) Silver coating amount 0.16 Gelatin 1.20 ExS-4 5.0 × 10 ⁻⁴ mol ExS-5 2.0 × 10 ⁻⁴ mol ExS-6 1.0 × 10 ⁻⁴ mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5x10 ^-2 Solv-1 0.20 Solv-3 3.0x10 ^-2

Eighth Layer: Second Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 25%, plate-like) Particles, diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ⁻⁴ mol ExS-5 1.4 × 10 ⁻⁴ mol ExS-6 7.0 × 10 ^-5 mol ExM-1 0.12 ExM-2 7.1x10 ^-3 ExM-3 3.5x10 ^-2 Solv-1 0.15 Solv-3 1.0x10 ^-2 9th layer: Intermediate Layer Gelatin 0.50 Solv-1 2.0 × 10 ^-2 10th layer: third green emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, equivalent spherical diameter 1.4 μm) , Variation coefficient of equivalent spherical diameter of 28%, plate-like particles, diameter / thickness ratio of 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 1 ^-4 mol ExS-5 8.0 × 10 ^-5 mol ExS-6 8.0 × 10 ^-5 mol ^{ExM-4 4.5 × 10 -2 ExM} -6 1.0 × 10 -2 ExC-2 4. 5 × 10 ⁻³ Cpd-5 1.0 × 10 ⁻² Solv-1 0.25

11th layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 Solv-1 0.12 12th layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 25%, tabular grains, diameter / thickness ratio 7.0) Silver Coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 ExY-2 2.3 × 10 ^-2 Solv-1 0.15 14th layer: second blue sensation Emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 16%, octahedral grains) Silver coating amount 0.19 Gelatin 0.1. 35 ExS-7 2.0 × 10 ^-4 mol ExY-1 0.22 Solv 1 7.0 × 10 ^-2 15th layer: Intermediate layer fine silver iodobromide (AgI 2 mol%, uniform AgI type, sphere-corresponding diameter 0.13 [mu] m) of silver coating amount 0.20 Gelatin 0.36

Sixteenth Layer: Third Blue Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, sphere equivalent diameter 1.7 μm, variation coefficient of sphere equivalent diameter 28%, plate-like) Grain, diameter / thickness 5.0) Silver coating amount 1.55 Gelatin 1.00 ExS-8 1.5x10 ^-4 mol ExY-1 0.21 Solv-1 7.0x10 ^-2 17th layer: First protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2 Eighteenth layer: Second protective layer Fine particle chlorination Silver (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (diameter 1.5 μm) 2.0 × 10 ^-2 B-2 (diameter 1.5 μm) 0.15 B-3 3.0 × 10 ⁻² W-1 2.0 × 10 ⁻² H-1 0.35 Cpd-7 1.00 This sample contained 1,2-benz. Isothiazolin-3-one (200 ppm on average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 pp)
m), and 2-phenoxyethanol (approx.
00 ppm) was added. Furthermore, B-4, B-5, W
-2, W-3, F-1, F-2, F-3, F-4, F-
5, F-6, F-7, F-8, F-9, F-10, F-
11, F-12, F-13 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

[0098]

[Chemical 17]

[0099]

[Chemical 18]

[0100]

[Chemical 19]

[0101]

[Chemical 20]

[0102]

[Chemical 21]

[0103]

[Chemical formula 22]

[0104]

[Chemical formula 23]

[0105]

[Chemical formula 24]

[0106]

[Chemical 25]

[0107]

[Chemical formula 26]

[0108]

[Chemical 27]

[0109]

[Chemical 28]

[0110]

[Chemical 29]

[0111]

[Chemical 30]

The light-sensitive material 101 thus produced was cut into a width of 35 mm, processed, exposed imagewise, and then color-developed by an automatic processor in which the tank capacity of the color negative processor FP-560B manufactured by Fuji Photo Film Co., Ltd. was modified. The treatment was continuously performed until the cumulative replenishment amount of the liquid became three times the volume of the mother liquor tank. Color developer replenishment amount is 35 mm width of photosensitive material 1
8 ml per m ^2, which corresponds to 229 ml per m ² . The aeration condition of the bleaching solution at this time was such that 200 ml / min was foamed from the piping part having a large number of 0.2 mmφ pores provided at the bottom of the bleaching solution tank.

Treatment process Treatment time Treatment temperature Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.5 ° C 8ml 3l Bleach 3 minutes 15 seconds 38.0 ° C B-1 5ml 1l B-2 17.5ml Fixed 1 minute 40 seconds 38.0 ℃ 30ml 2 liters Washed with water (1) 30 seconds 38.0 ℃ -1 liters Washed with water (2) 30 seconds 38.0 ℃ 30ml 1 liter Stabilized 30 seconds 38.0 ℃ 20ml 1 liter Dry 1 minute 55 ℃ 35mm width per 1m Washing with water from (2) to (1) countercurrent method Note that the amount of color developing solution brought into the bleaching process is 2.5ml per 1m length of the 35mm wide photosensitive material (71ml / m ² ).
Met. The crossover time is 8 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 2.0 2.5 Potassium carbonate 30.0 30.0 Potassium bromide 3.2-Potassium iodide 1.5 mg-hydroxylamine compound (see Table 5) 30mmol 62mmol 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 6.0 10.4 Add water 1000ml 1000ml pH 10.05 10.25

(Bleaching solution B-1) Mother liquor (g) Replenishing solution (g) 1,3-Diaminopropaneferric acid ferric ammonium monohydrate 35.0 (89 mmol) 52.5 Ammonium bromide 84.0 126.0 Ammonium nitrate 17.5 26.3 Ammonia water ( 27%) 38.0 57.0 Acetic acid (90%) 45.7 68.5 Glycolic acid 46.0 69.0 Potassium carbonate 10.0-Add water 1000 ml 1000 ml pH 4.3 4.0

(Bleaching solution B-2) Mother liquor (g) Replenishing solution (g) 1,3-Diaminopropaneferric acid ferric ammonium monohydrate 35.0 (89 mmol) 40.0 Ammonium bromide 84.0 96.0 Ammonium nitrate 17.5 20.0 Ammonia water ( 27%) 38.0 43.4 Acetic acid (90%) 45.7 52.2 Glycolic acid 46.0 52.6 Potassium carbonate 10.0-Add water 1000 ml 1000 ml pH 4.3 4.2

(Fixer) Common mother liquor and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / liter) 260.0 ml Water is added 1000 ml pH 7.0

(Washing water) Common to mother liquor and replenisher tap water was prepared by using H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-type). Four
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium isocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) Unit (g) Start Solution / Replenishing Solution Common p-toluenesulfinic acid 0.1 sodium polyoxyethylene-p-monononyl 0.2 phenyl ether (average degree of polymerization 10) ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 N, N′-bis (1,2,4-triazol-1.0 1-ylmethyl) piperazine Water was added to 1000 ml pH 7.2

After the completion of the above continuous processing, the photosensitive material 101 was processed by sensitizing exposure using a continuous wedge. After the treatment, the amount of residual silver in the highest color density portion was measured by fluorescent X-ray analysis. Further, after the maximum color densities of magenta and cyan were measured, desilvering was performed again using a fresh bleaching solution and a fixing solution, and then the maximum color densities of magenta and cyan were measured again. The change in cyan density with respect to the change in magenta density before and after the desilvering process was calculated again. In other words, if there is an increase in density rather than a change in magenta density, there is a cyan color restoration failure,
If it is not, it can be determined that there is no cyan color restoration defect. The results are shown in Table 5.

[0121]

[Table 5]

As can be seen from Table 5, the color developing process is a low replenishing process, and the bleaching solution replenishing process is carried out from the color developing solution.
When it is doubled, hydroxylamine is almost good although desilvering and recoloring are slightly bad, but also for derivatives other than hydroxylamine, desilvering and recoloring are good. However, this is not a sufficiently low replenishment treatment. On the other hand, when the replenishment of the bleaching solution is twice as much as that brought in from the color developing solution and hydroxylamine desilvering and color restoration are bad at the time of sufficiently low replenishment processing, but the hydroxylamine derivative is as good as 7 times. It can be seen that photographic performance can be obtained.

Example 2 Using the light-sensitive material 101 prepared in Example 1, the same color developer as in Example 1 was used except that the concentration of sodium sulfite in the color developer was changed as shown in Table 6. , (B-
The same bleaching solution as in Example 1 was used except that the concentration of 1,3-diaminopropanetetraferric ammonium ammonium monohydrate as the bleaching agent of 1) was changed as shown in Table 6, and hydroxyl group was used. The same color developer as in Example 1 was used except that the amine compound was also changed as shown in Table 6, and continuous processing was performed in the same manner as in Example 1 to evaluate the desilvering performance and the color restoration failure. However, the replenishing amount of the bleaching solution is 5 m per 1 m width of the light-sensitive material of 35 mm.
l was replenished. The results are shown in Table 6.

[0124]

[Table 6]

From Table 6, when the sulfite concentration is outside the range of the present invention, the desilvering and recoloring properties of the preservatives are poor for both hydroxylamine and its derivatives, and especially for hydroxylamine, sodium sulfite is used. When the concentration increases or the concentration of the bleaching agent decreases (120 mmol / liter or less), it becomes worse. On the other hand, according to the constitution of the present invention, it can be seen that good performance can be obtained in spite of the small replenishment amounts of the color developing solution and the bleaching solution and the low concentration of the bleaching agent.

Example 3 Using the light-sensitive material 101 prepared in Example 1, 1,3-diaminopropanetetraacetic acid ammonium ferric acid monohydrate in the bleaching solution (B-1) was prepared as shown in Table 7. The same treatment as in Example 1 was carried out except that ferric ammonium monohydrate was changed and the hydroxylamine compound was also changed as shown in Table 7. The results are shown in Table 7.

[0127]

[Table 7]

It can be seen from Table 7 that good performance can be obtained according to the constitution of the present invention. It can be seen that the desilvering and recoloring performance is further improved by changing to the ferric iron complex salt of the organic acid represented by the formula (H).

Example 4 301 and 302 were prepared by changing each emulsion of the light-sensitive material 101 of Example 1 as follows. Photosensitive material 301 302 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion Silver iodobromide emulsion (AgI 0.2 mol%) (AgI 0.5 mol%) Fourth layer: Second red-sensitive emulsion layer Silver iodobromide Emulsion Silver iodobromide emulsion (AgI 0.2 mol%) (AgI 0.7 mol%) Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion Silver iodobromide emulsion (AgI 0.4 mol%) (AgI 1.0 mol%) Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion Silver iodobromide emulsion (AgI 0.1 mol%) (AgI 0.5 mol%) Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion Iodobromide Silver emulsion (AgI 0.3 mol%) (AgI 0.8 mol%) 10th layer: third green emulsion layer Silver iodobromide emulsion Silver iodobromide emulsion (AgI 0.4 mol%) (AgI 1.2 mol%) 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion Silver iodobromide emulsion (AgI 0.1 mol%) (AgI 0.6 mol%) 14th layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion Silver iodobromide emulsion (AgI 0.4 mol%) (AgI 0.9 mol%) Other than the above It was prepared in the same manner as in Example 1.

Next, the developing agent 4- (N-ethyl-N-β-hydroxyethylamino) in the color developer of Example 1 was used.
-2-Methylaniline sulfate was changed to the compound represented by the general formula (D) or the general formula (E) as shown in Table 8, and the hydroxylamine compound was also changed as shown in Table 8, and the same was applied, The above-mentioned photosensitive materials 301 and 101 were imagewise exposed and then continuously processed, and evaluated in the same manner as in Example 1. The bleaching solution used was B-1 of Example 1. The results are shown in Table 8.

[0131]

[Table 8]

As can be seen from Table 8, the light-sensitive material 3 used has an AgI mol content of less than 0.5 mol%.
In the case of 01, the influence on desilvering is small and it is better than that of the light-sensitive material 101 regardless of the use of hydroxylamine or a hydroxylamine derivative. However, it was found that they did not have sufficient sensitivity during imagewise exposure. (Target ISO-400) On the other hand, in the case of the photosensitive material 302, when the preservative of the color developer is conventional hydroxylamine, desilvering and deterioration of color restoration tend to appear, but use of the hydroxylamine derivative causes no problem. I understand. Further, in the case of the photosensitive material 101 of Example 1, it is understood that good performance can be obtained according to the constitution of the present invention. It can be seen that particularly when the compound represented by the general formula (D) or (E) of the present invention is used as a color developing agent, the amount of residual silver is small and more excellent desilvering property is obtained.

[0133]

INDUSTRIAL APPLICABILITY The present invention can reduce the replenishment amount of the color developing solution and the processing solution having a bleaching ability, and is environmentally excellent. Further, the concentration of the bleaching agent in the processing solution having bleaching ability can be reduced, which is also environmentally excellent. Even in such an environmentally excellent mode, the light-sensitive material for photographing can be processed without lowering the desilvering property and the color reversion property.

Claims (3)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing at least 0.5 mol% of silver iodide by using an automatic processor. The solution contains an aromatic primary amine color developing agent and a hydroxylamine derivative, the sulfite concentration is 25 mmol / liter or less, and the replenishing amount of the color developing solution is 6 per 1 m ^{2 of the} light-sensitive material.
0 to 300 ml, and the concentration of the bleaching agent contained in the processing solution having bleaching ability after color development is 3 to 120 mm.
A processing method of a silver halide color photographic light-sensitive material, characterized in that the replenishing amount of the processing liquid is 0.01 to 5 times the carry-in amount of the light-sensitive material from the color developing solution. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the bleaching agent is a ferric iron complex salt of an organic acid represented by the following general formula (H). General formula (H) (In the formula, L ₁ , L ₂ and L ₃ each represent an alkylene group, M ₁ , M ₂ and M ₃ each represent a hydrogen atom or a cation, R represents a substituent, and u represents 0, 1, 2 or 3 or 4 and k, t, m and n respectively represent 0 or 1.) 3. A silver halide color photograph according to claim 1, wherein the aromatic primary amine color developing agent is a compound represented by the following general formula (D) or (E). Method of processing photosensitive material. General formula (D) (In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 3 to 6 carbon atoms. R ₂ represents 3 carbon atoms.
Represents an alkylene group having 6 to 6 or a hydroxyalkylene group having 3 to 6 carbon atoms. R ₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. )
General formula (E) (In the formula, R ₄ to R ₁₁ may be the same or different and each is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an amino group, an alkylamino group, an alkoxy group, an amide group, a sulfonamide group or carbamoyl. Represents a group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group, a sulfonyl group, a carboxy group or a sulfo group, R ₁₂ to R ₁₅ may be the same or different, and each is a hydrogen atom, a halogen atom, an amino group, Represents an alkylamino group, a hydroxyl group, an alkyl group, an alkoxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group or a sulfamoylamino group.)