JPH0651473A - Treatment for silver halide color photographic sensitive material and photographic bleaching and fixing composition - Google Patents

Abstract

PURPOSE:To obtain a treating method excellent in desilvering property and color reproducing property with little bleaching fog by using a specified bleaching agent and a fixing agent. CONSTITUTION:The bleaching agent used in the desilvering process is a metal chelate compd. of a compd. expressed by formula I. The fixing agent is a compd. expressed by formula III or the like. In formula, Y1 is a nonmetal group necessary to form an aromatic hydrocarbon group or heterocyclic group, R1 is substituent, n is an integer 0-4, X1 is hydrogen atom or -L1-A2, X2 is L2-A3, or compd. expressed by formula II. X3 is hydrogen atom or -L4-A4, L1 to L4 are alkylene groups or arylene groups, W is a bivalent conncecting group, A1-A5 are hydrogen atoms, carboxylic acid or its salt, etc., Q1 is a nonmetal group necessary to form a five- or six-member heteroring. La1 is a single bond, bivalent aliphatic group, aromatic hydrocarbon group or combination of these, Ra1 is a carboxylic acid or salt, sulfonic acid, or its salt, etc., q is an integer 1-3, Ma1 is a hydrogen atom or cation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material and a processing composition. More specifically, it has less bleaching fog and is excellent in desilvering property, recoloring property and liquid stability. The present invention also relates to a method of processing a silver halide color photographic light-sensitive material and a processing composition.

[0002]

2. Description of the Related Art Generally, the processing of a silver halide color photographic light-sensitive material comprises a color development step and a desilvering step. In the desilvering process, the developed silver generated in the color development process is oxidized (bleached) into a silver salt by a bleaching agent having an oxidizing action, and further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. Be done (fixed). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step.
For details of these processing steps, see "The Theory of Photographic Process," 4th Edition, by James.
s, “The Theoryof Photographic Process” 4'th edi
tion) (1977). The above processing steps are generally performed by an automatic processor. In recent years, in particular, a small automatic developing machine called a minilab has been installed in stores, and a rapid processing service has been spreading to customers. Against this background, there has been a strong demand in recent years for a particularly rapid processing step, and a drastic speed-up of the desilvering step, the bleaching step, the fixing step or the bleach-fixing step is also desired. Furthermore, since the treatment has been carried out at various places, the problem of treatment waste liquid is increasing,
Studies are underway to reduce the amount of replenishment in order to reduce processing waste liquid.

In the fixing step of the desilvering step, thiosulfate is usually used as a fixing agent. However, this thiosulfate is insufficient from the viewpoint of speeding up. Further, since this thiosulfate undergoes oxidative deterioration and is sulfided and precipitates, sulfite is added in most cases as an antioxidant preservative. The oxidative deterioration of the thiosulfate becomes more remarkable when the oxidant in the bleaching bath in the case of having a bleaching bath as a prebath is brought into the fixing bath, or when the oxidizing agent such as the bleach-fixing bath and the fixing agent coexist.
As low replenishment progresses further, improvement in liquid stability is further desired. In response to this demand, the means of increasing the amount of sulfite as a preservative has a large problem of solubility of sulfite and precipitation of Glauber's salt when the sulfite is oxidized, and is sufficiently solved. Not not.

The ethylenediaminetetraacetic acid ferric iron complex salt conventionally used as a bleaching agent in the above-mentioned bleaching bath has a fundamental defect that its oxidizing power is weak, and improvements such as the use of a bleaching accelerator have been added. However, the goal of rapid bleaching has not been achieved yet. Further, if the pH of the bleaching solution is lowered to increase the oxidizing power, the color recoloring property deteriorates. Although red blood salts, iron chloride, bromate, etc. are known as bleaching agents that achieve rapid bleaching, red blood salts handle iron corrosion such as metal corrosion due to environmental conservation problems. Due to the above inconvenience, etc., and due to the problem of liquid instability in bromate, it cannot be widely used. Therefore, there has been a demand for a bleaching agent that is easy to handle and that achieves rapid bleaching without causing problems in discharging the waste liquid. Recently, a ferric complex of 1,3-diaminopropanetetraacetic acid has been disclosed as a bleaching agent satisfying such conditions. However, when this bleaching agent is used, not only the above-mentioned problems become prominent but also bleaching fog occurs due to bleaching, which is not sufficiently satisfactory. On the other hand, in the processing of color photographic paper, the bleaching agent and the fixing agent are used in the same bath as the bleach-fixing bath, and the bleaching agent used here is usually ferric ethylenediaminetetraacetic acid complex salt. However, from the viewpoint of speeding up, the use of ethylenediaminetetraacetic acid ferric complex salt as this bleaching agent is not sufficient for the recent demand for speeding up, and means for further speeding up is required. On the other hand, it has been proposed to use an oxidant such as the above-mentioned ferric complex of 1,3-diaminopropanetetraacetic acid having a high oxidizing power in a bleach-fixing bath. It is not practically sufficient because the bleaching fog described above is large even in the bath, and the thiosulfate is further oxidized and deteriorated due to the use of the bleach-fixing bath. This problem has become a fatal defect as the replenishment rate has been lowered in recent years. Therefore, there has been a strong demand for development of a bleaching agent and a fixing agent for solving the above problems, and a processing composition and a processing method using the same.

[0005]

Therefore, the first aspect of the present invention
It is an object of the present invention to provide a processing composition excellent in desilvering property and a processing method using the same. A second object of the present invention is to provide a processing composition which has less bleaching fog and is excellent in color recovery and a processing method using the same. A third object of the present invention is to provide a bath having fixing ability and a treating composition having improved liquid stability of the bath thereafter, and a treating method using the same.

[0006]

The above objects have been achieved by the following processing method and processing composition. (1) In a processing method in which a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is subjected to color development processing and desilvering processing, the bleaching agent in the desilvering processing is A halogenated compound which is a metal chelate compound of the compound represented by formula (I), wherein the fixing agent is a compound represented by the following general formula (A), (B), (C) or (D). Processing method of silver color photographic light-sensitive material. General formula (I)

[0007]

[Chemical 6]

(In the formula, Y ₁ represents a nonmetallic atom group necessary for forming an aromatic hydrocarbon group or a heterocyclic group. R ₁ represents a substituent. N represents an integer of 0 to 4. When n represents an integer of 2 to 4, R _{1 s} may be the same or different, and X ₁ represents a hydrogen atom or -L ₁ -A ₂ .
X ₂ is -L ₂ -A ₃ or

[0009]

[Chemical 7]

Represents X ₃ is a hydrogen atom or -L ₄ -A
Represents ₄ . L ₁ , L ₂ , L ₃ and L ₄ each represent an alkylene group or an arylene group. W ₁ represents a divalent linking group. A _{1 to} A ₅ are each a hydrogen atom, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, a hydroxy group, a hydroxyalkyl group,
Carbamoyl group, acylamino group, sulfonamide group,
It represents a sulfamoyl group, an alkoxy group, an alkylthio group or an amino group. However, at least 1 of A _{1 to} A ₅
Represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, or a hydroxy group, and when X ₂ is -L ₂ -A ₃ , A ₁ is not a hydrogen atom. General formula (A)

[0011]

[Chemical 8]

In the formula, Q _a1 represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring.
L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. R _a1 represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium salt. q represents an integer of 1 to 3, M _a1 represents a hydrogen atom or a cation. General formula (B)

[0013]

[Chemical 9]

In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ^- is -O ^- ,-.
Represents S ^- or -N ^- R _b1 . R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Formula (C) L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _{C3 In the} formula, L _C1 and L _C3 may be the same or different and each is an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Represents a cyclic group, and L _C2 represents a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic linking group, or a linking group combining them. A
_C1 and A _C2 are respectively -S-, _-O- , -NR _C20- ,
-CO -, - it represents a or group composed of a combination of them - SO _2. r represents an integer of 1 to 10. However, L _C1 and L
_C3 at least one -SO ₃ M _C1, -PO ₃ M
_{C2 M C3, -NR C1 (R} C2), - N + R C3 (R C4)
^{_{(R C5) · X C1 -}} , -SO 2 NR C6 (R C7), - NR C8
_{SO 2 R C9, -CONR C10 (} R C11), - NR C12 C
_{OR C13, -SO 2 R C14,} -PO (-NR C15 (R
_C16 )) ₂ , -NR _C17 CONR _C18 ( _RC19 ), -C
It is assumed to be substituted with OOM _C4 or a heterocyclic group.
M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. M _C1 ~ M _C20
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. Provided that at least one of A _C1 and A _C2 represent -S-. General formula (D)

[0015]

[Chemical 10]

In the formula, X _d and Y _d are an aliphatic group, an aromatic hydrocarbon group, a heterocyclic group, -N (R _d1 ) R _d2 , -N (R _d3 ).
N (R _d4) R _d5, represent -OR _d6, or -SR _d7.
Incidentally, X _d and Y _d may form a ring, but they do not undergo enolization. However, at least one of X _d and Y _d is substituted with at least one of a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium group, and a hydroxyl group. . R _d1 , R _d2 , R _d3 , R _d4 and R _d5 represent a hydrogen atom, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group, and R _d6 and R _d7 represent a hydrogen atom, a cation, an aliphatic group, an aromatic group. It represents a group hydrocarbon group or a heterocyclic group. (2) Represented by at least one metal chelate compound of the compound represented by the general formula (I) as a bleaching agent and represented by the general formula (A), (B), (C) or (D) as a fixing agent. A photographic bleach-fixing composition containing at least one compound.

In the present specification, the aliphatic group, aromatic hydrocarbon group and heterocyclic group are as follows unless otherwise specified. An aliphatic group is a substituted or unsubstituted,
It represents a linear, branched or cyclic alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group. The divalent aliphatic group is a divalent group of these aliphatic groups, and is a substituted or unsubstituted linear, branched or cyclic alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene. Represents a group. Examples of the aliphatic group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, 2-hydroxypropyl group, hexyl group, octyl group, vinyl group, propenyl group, butenyl group, benzyl group and phenethyl group. To be The aromatic hydrocarbon group is a substituted or unsubstituted,
It represents an aryl group which may be monocyclic or may be condensed with an aromatic ring or a heterocycle. What is a divalent aromatic hydrocarbon group?
It represents a substituted or unsubstituted arylene group which may be monocyclic or may be condensed with an aromatic ring or a heterocycle. Examples of the aromatic hydrocarbon group include a phenyl group, a 2-chlorophenyl group, a 3-methoxyphenyl group and a naphthyl group. The heterocyclic group means a nitrogen atom as a hetero atom,
3 to 3 having at least one oxygen atom or sulfur atom
It represents a 10-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic ring, which may be further condensed with an aromatic ring or a heterocycle. Examples of the heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a quinoxaline ring, a tetrazole ring, a thiazole ring and an oxazole ring.

Further, each group in the present specification may be substituted unless otherwise specified, and examples of the substituent which they may have include an alkyl group, an aralkyl group, an alkenyl group and an alkynyl group. , Alkoxy group, aryl group, amino group, acylamino group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, acyl group, hydroxy group , Halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, nitro group, hydroxamic acid group, heterocyclic group and the like.
In the specification of the present application, examples of the bath having a bleaching ability include a bleaching bath and a bleach-fixing bath. Examples of the bath having fixing ability include a fixing bath and a bleach-fixing bath. As the processing steps using these baths, various steps such as bleach-> fixing, bleach-fixing, bleach-> bleach-fixing, fixing-> bleach-fixing, bleach->bleach-fixing-> fixing can be performed. The bleaching bath, fixing bath, and bleach-fixing bath may be composed of a plurality of baths. The intermediate step is not usually used here, but a step such as washing with water may be included if necessary. As the bleach-fixing composition in the present invention, a bleach-fixing solution is generally used, but it means a replenishing solution, a supply kit (solution or sticky agent) and the like.

The compound represented by formula (I) is described in detail below. In the formula, Y ₁ represents a nonmetallic atom group necessary for forming an aromatic hydrocarbon group or a heterocyclic group. The aromatic hydrocarbon group or heterocyclic group for Y ₁ is monovalent when A ₁ is a hydrogen atom and divalent when A ₁ is a group other than the hydrogen atom in the definition. The aromatic hydrocarbon group formed by Y ₁ is preferably an aromatic hydrocarbon group having 5 to 20 carbon atoms and may be a monocyclic ring or may be condensed with an aromatic ring or a heterocyclic ring. Rings are preferred. Examples of the aromatic hydrocarbon group formed by Y ₁ include a phenyl group (phenylene group when divalent), a naphthyl group (naphthylene group when divalent) and the like. The heterocyclic group formed by Y ₁ is preferably a 5- to 6-membered monocyclic unsaturated heterocyclic group containing at least one nitrogen atom as a hetero atom. Examples of the preferable heterocycle include an imidazole ring, a pyrazole ring, a pyridine ring, and the like, and in the case of a divalent ring, an imidazole ring, a pyrazole ring, a pyridine ring, and the like, which are divalent with adjacent carbon atoms are preferable. . In the present invention, Y ₁ particularly preferably forms a phenylene group.

Examples of the substituent of R ₁ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an amino group, an acylamino group, a sulfonamide group, a ureido group, a urethane group and an aryloxy group. , Sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, acyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy Group, nitro group, hydroxamic acid group, heterocyclic group and the like. When it has a carbon atom, the substituent preferably has 1 to 10 total carbon atoms (hereinafter referred to as C number), and more preferably 1 to 4 carbon atoms. In the present invention, X ₁ is preferably -L ₁ -A ₂ . Preferably -L ₄ -A ₄ as X _3. A _{1 to} A ₅ are each a hydrogen atom, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, a hydroxyl group, a hydroxyalkyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, an alkoxy group. Represents an alkylthio group or an amino group. However, A
_At least one of _{1 to} A ₅ represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, or a hydroxyl group, and X ₂ represents -L ₂
When -A _3, do not A ₁ is a hydrogen atom.

Examples of the salts of carboxylic acid, sulfonic acid and phosphonic acid in A _{1 to} A ₅ include sodium salt, potassium salt, ammonium salt and calcium salt. The carbamoyl group, the acylamino group, the sulfonamide group, the sulfamoyl group, the alkoxy group, the alkylthio group and the amino group in A _{1 to} A ₅ may have a substituent, and as the substituent, those mentioned as R ₁ can be applied. . The carbamoyl group and sulfamoyl group in A _{1 to} A ₅ are preferably unsubstituted or substituted with an alkyl group, an aryl group or a heterocyclic group, and when having a substituent, a C number of 10 or less, more preferably C The number is 4 or less. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl and N- (4-sulfophenyl) carbamoyl. Examples of the sulfamoyl group include sulfamoyl and N-methylsulfamoyl. The sulfonamide group in A _{1 to} A ₅ is preferably an unsubstituted alkylsulfonamide group or an alkylsulfonamide group substituted with a substituent (preferably a carboxy group, a hydroxy group, a halogen atom), and more preferably, A C number of 1 to 5, more preferably a C number of 1 to 3. Examples of the alkylsulfonamide group include methanesulfonamide and trifluoromethanesulfonamide.

The acylamino group in A _{1 to} A ₅ is substituted with an unsubstituted alkylacylamino group or a substituent (preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a carboxy group or a hydroxy group). And an alkylacylamino group are more preferable, and a C number of 1 is more preferable.
An alkylacylamino group having 10 to 10 carbon atoms, an arylacylamino group having 6 to 10 C atoms, and a heterocyclic acylamino group having 1 to 10 C atoms, and more preferably an alkylacylamino group having 1 to 5 C atoms. Examples of the acylamino group include acetylamino, benzoylamino, t-butanamide, trifluoroacetylamino and the like. The alkoxy group and the alkylthio group in A _{1 to} A ₅ are preferably those having a C number of 1 to 10, and more preferably those having a C number of 1 to 5, and examples thereof include methoxy, ethoxy, and atylthio. The amino group in A _{1 to} A ₅ is an unsubstituted amino group, an unsubstituted alkylamino group or an alkylamino group substituted with a substituent (preferably a carboxy group, a hydroxy group, a phosphono group or a sulfo group). Preferably, the C number is 0 to 10, and more preferably the C number is 1 to 6.
belongs to. A ₁ is carboxylic acid or a salt thereof, or an alkylthio group or an alkoxy group substituted with a carboxylic acid or a salt thereof (ie, —Z ₁ -L ₅ —CO
OM (Z ₁ represents an oxygen atom or a sulfur atom, L ₅ represents an alkylene group, M represents a hydrogen atom or a cation), and a carboxylic acid or a salt thereof is most preferable. As A _{2 to} A ₅ , a carboxylic acid or a salt thereof, a phosphonic acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyalkyl group is more preferable, and a carboxylic acid or a salt thereof is most preferable.

The alkylene group in L _{1 to} L ₄ may be linear, branched or cyclic, and is substituted with a substituent such as those mentioned for R (preferably a carboxylic acid or its salt, a hydroxy group or a halogen atom). Good. It is preferably one having a C number of 1 to 10, more preferably a methylene group or an ethylene group. The arylene group in L _{1 to} L ₄ may be a monocyclic ring or may be condensed with an aromatic ring or a heterocyclic ring, and may have a substituent such as those described for R (preferably an alkyl group, an acylamino group or an alkylsulfone). Amido group, alkoxy group, sulfamoyl group, carbamoyl group, alkylthio group, sulfo group, phosphono group, acyl group, alkoxycarbonyl group, nitro group, carboxy group, hydroxy group, halogen atom, hydroxamic acid group)
May be replaced with. W ₁ is preferably a divalent linking group containing an alkylene group, an alkenylene group, an arylene group, a divalent heterocyclic group and / or a group consisting of a combination thereof. More preferably, it is represented by the general formula (W). General formula (W)

[0024]

[Chemical 11]

(In the formula, W ₂ , W ₃ and W ₅ each represent an alkylene group, and W ₄ represents

[0026]

[Chemical 12]

Represents Y ₁ ′, R ₁ ′ and n ′ have the same meanings as Y ₁ , R ₁ and n in formula (I). c represents an integer of 0 to 3, and d and e are 0 respectively.
Or represents 1. X ₁ is -O-, -S- or -N (R ₃ ).
Represents-. R ₃ represents a hydrogen atom, an alkyl group (eg, methyl, carboxymethyl, hydroxymethyl) or an aryl group (eg, phenyl, 4-sulfophenyl). ) As W ₁ , those in which c is 0 are preferable, and d and e
Is more preferably 0. The C number of W ₁ is preferably 1 to 20, more preferably 2 to 10, and particularly preferably 2 to 5. Examples of W ₁ include the following.

[0028]

[Chemical 13]

The general formula (I) is preferably the general formula (I-
a) and (Ib).

[0030]

[Chemical 14]

(Wherein L ₁ , L ₂ , L ₃ , L ₄ , W ₁ ,
R ₁ and n have the same meaning as in general formula (I). M's may be the same or different from each other and represent a hydrogen atom or a cation. ) Specific examples of the compound represented by formula (I) are shown below.

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

The central metal used in the metal chelate compound of the present invention is, for example, Fe (III), Mn (III), Co (II).
I), Rh (II), Rh (III), Au (III), Au (II), Ce (I
V) and so on. Fe (III) is preferred. The metal chelate compound of the present invention can be synthesized by reacting the compound represented by the general formula (I) with a metal salt. The compound represented by the general formula (I), which serves as a ligand in the metal chelate compound of the present invention, may be, for example, a commercially available one, or may be, for example, “Journal of the American Chemical S”.
ociety), 80, 800 (1958) and the like, and can be obtained by synthesis. For example, it can be synthesized by reacting an anthranilic acid derivative with a halogen-substituted carboxylic acid derivative, or by substituting a halogen atom of a halogen-substituted aromatic derivative with a diamine derivative and then reacting it with a halogen-substituted alkylcarboxylic acid. Examples of the metal salt reacted with the compound represented by the general formula (I) include ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the like. Examples include ferric oxide.

Synthesis Example 1 1- (1) Synthesis of Compound (1) Anthranilic acid 20.0 g (0.146 mol), water 20 ml
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, the sodium hydroxide aqueous solution was added dropwise so that the reaction solution maintained a pH of 7 to 9.) After heating and stirring for 20 hours, the temperature was returned to room temperature and concentrated hydrochloric acid 45.
6 g (0.450 mol) was added. The precipitated crystals were filtered off and washed with water. Transfer the crystals to a beaker and add 300 ml of water.
After adding, the pH was adjusted to 1.6 to 1.7 with concentrated hydrochloric acid. 1
After stirring for an hour, the solid was collected by filtration and washed well with water. By recrystallizing from water, 12.5 hydrate of the compound (1) was obtained as a white solid (32.5 g, 0.125 mol). Yield 86
%. Melting point 214-216 [deg.] C (decomposition). 1- (2) Synthesis of ferric iron complex salt of compound (1) 46.4 g (0.17) of compound (1) synthesized in 1- (1)
9 mol) was suspended in 46 ml of water, and 29% ammonia water 1
0.5 g (0.179 mol) was added and dissolved. The pH at this time was 4.6. After adding 72 ml of an aqueous solution containing 72.3 g (0.179 mol) of iron nitrate (III) nonahydrate, 1N HNO ₃ aqueous solution was added to adjust the pH to 2.9. The precipitated crystals were collected by filtration, washed with water and acetone, and dried to obtain 65.8 g (0.166 mol) of a ferric complex salt of compound (1) as a yellow solid. Yield 93%. Melting point ≧ 130 ° C. (decomposition).

Synthesis Example 2 2- (1) Synthesis of Compound I-18 10.3 g (4.15 × 10 ^-2 mo) of o-iodobenzoic acid
l) and 10.3 g (7.45 × 10 ^-2 mol) of potassium carbonate are suspended in 97 g (1.61 mol) of ethylenediamine and 4
Heated to reflux for hours. 30 ml of water was added to the reaction solution, which was then transferred to an eggplant flask and the solvent was distilled off under reduced pressure. 40 ml of water was added, transferred to a beaker and adjusted to pH 9 with concentrated hydrochloric acid. The resulting precipitate was collected by filtration, placed in a beaker, added with 200 ml of water and adjusted to pH 1 with concentrated hydrochloric acid. The generated precipitate was collected by filtration, washed with water and dried under reduced pressure to give 4.9 g (2.26 × 10 ^-2) of N-aminoethylanthranilic acid monohydrochloride as gray crystals.
mol) was obtained. Yield 54%. 4.9 g of N-aminoethylanthranilic acid monohydrochloride (2.26 × 1) synthesized above
0 ^-2 mol), chloroacetic acid 10.0 g (1.06 x 10 ^-1 mo)
l) suspended in 30 ml of water, 55 ml of 5N sodium hydroxide
(0.275 mol) was gradually added to maintain the pH at 9-11.
The mixture was stirred at an inner temperature of 60 ° C for 5 hours and at 90 ° C for 3 hours. After cooling, the reaction solution was transferred to a beaker and adjusted to pH 1 with concentrated hydrochloric acid. The precipitate formed is filtered off, placed again in a beaker and washed with water 10
0 ml was added. After adjusting to pH 4 by adding 5N sodium hydroxide, it was filtered and adjusted to pH 1.6 with concentrated hydrochloric acid. The resulting precipitate was collected by filtration, washed with water and then dried under reduced pressure.
2.8 g (7.90 × 10 ⁻³ mo) of white crystals (I-18)
l) Got it. Yield 35%. Melting point 222-224 [deg.] C (decomposition).

The metal chelate compound of the present invention may be isolated as a metal chelate compound, or may be a compound represented by the general formula (I) and a metal salt such as ferric sulfate or ferric chloride. An iron salt, a ferric nitrate salt, a ferric phosphate salt, etc. may be used by reacting in a solution. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more with respect to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30. The metal chelate compound of the present invention is added to the processing solution 1 having the bleaching ability as described above.
It is effective to contain 0.05 to 1 mol per liter, and more preferably 0.1 to 0.5 mol per liter of the treatment liquid. Further, a small amount may be contained in the fixing solution or an intermediate bath between the color developing step and the desilvering step. The metal chelate compound of the present invention is used as the bleaching agent, but known bleaching agents may be used in combination to the extent that the effects of the present invention are not impaired (preferably 1/10 or less in molar ratio). Examples of bleaching agents that can be used in combination are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Examples thereof include aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid, or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes.

Next, the compounds represented by the general formulas (A), (B), (C) and (D) which are the fixing agents used in the present invention will be described in detail. In the general formula (A), Q _a1 is preferably a non-atom which is necessary for forming a 5- or 6-membered heterocycle composed of at least one atom of carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom. Represents a group of metal atoms. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle include a tetrazole ring, a triazole ring, an imidazole ring, a thiadiazole ring, an oxadiazole ring, a selenadiazole ring, an oxazole ring, a thiazole ring, a benzoxazole ring, a benzthiazole ring, a benzimidazole ring, a pyrimidine ring, and triazain. Examples thereof include a den ring, a tetraazaindene ring and a pentaazaindene ring. R _a1 is carboxylic acid or a salt thereof (eg sodium salt, potassium salt, ammonium salt, calcium salt), sulfonic acid or a salt thereof (eg sodium salt, potassium salt, ammonium salt,
Magnesium salt, calcium salt), phosphonic acid or salts thereof (eg sodium salt, potassium salt, ammonium salt), substituted or unsubstituted amino group (eg unsubstituted amino, dimethylamino, diethylamino, methylamino, bismethoxyethylamino) Represents a substituted or unsubstituted ammonium group (eg, trimethylammonium, triethylammonium, dimethylbenzylammonium). L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. L _a1 is preferably an alkylene group having 1 to 10 carbon atoms (eg, methylene, ethylene, propylene, butylene, isopropylene, 2-hydroxypropylene, hexylene, octylene), an alkenylene group having 2 to 10 carbon atoms (eg, vinylene, propenylene, Butenylene), aralkylene group having 7 to 12 carbon atoms (for example, phenethylene), arylene group having 6 to 12 carbon atoms (for example, phenylene, 2-chlorophenylene, 3-methoxyphenylene, naphthylene), heterocyclic group having 1 to 10 carbon atoms. It may be a divalent one (for example, pyridyl, thienyl, furyl, triazolyl, imidazolyl), a single bond and a group in which these groups are arbitrarily combined, or -CO- or -SO.
_{2 -, - NR 202 -,} - O- or -S- and may be one arbitrarily combined. Here, R ₂₀₂ is a hydrogen atom and has 1 carbon atom
Represents an alkyl group having 6 to 6 (eg, methyl, ethyl, butyl, hexyl), an aralkyl group having 7 to 10 carbon atoms (eg, benzyl, phenethyl), and an aryl group having 6 to 10 carbon atoms (eg, phenyl, 4-methylphenyl). .

M _a1 is a hydrogen atom or a cation (for example,
And an alkali metal atom such as sodium atom and potassium atom, an alkaline earth metal atom such as magnesium atom and calcium atom, an ammonium group, and an ammonium group such as triethylammonium group). Further, the heterocycle represented by the general formula (A) and R _a1 are a nitro group, a halogen atom (eg, chlorine atom, bromine atom), a mercapto group, a cyano group, and a substituted or unsubstituted alkyl group (eg, methyl, ethyl, Propyl, t-butyl,
Cyanoethyl), aryl groups (eg phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl,
3,4-dichlorophenyl, naphthyl), alkenyl group (eg allyl), aralkyl group (eg benzyl, 4
-Methylbenzyl, phenethyl), a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl), a carbamoyl group (for example, unsubstituted carbamoyl, methylcarbamoyl, phenylcarbamoyl),
Sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide group (eg, acetamide, benzamide), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), acyloxy Group (eg acetyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy), ureido group (eg unsubstituted ureido, methylureido, ethylureido, phenylureido), acyl group (eg acetyl, benzoyl), oxycarbonyl group (Eg methoxycarbonyl, phenoxycarbonyl), oxycarbonylamino group (eg methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarboxyl) Boniruamino), it may be substituted with hydroxyl group and the like.

Q represents an integer of 1 to 3, but when q represents 2 or 3, each R _a1 may be the same or different. In general formula (A), Q _a1 preferably represents a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a triazaindene ring, a tetraazaindene ring, a pentaazaindene ring, and R _a1 represents a carboxylic acid or a carboxylic acid thereof. It represents an alkyl group having 1 to 6 carbon atoms, which is substituted with one or two groups selected from a salt, a sulfonic acid or a salt thereof, and q represents 1 or 2. Among the compounds represented by the general formula (A), more preferable compounds include the compounds represented by the general formula (A-1). General formula (A-1)

[0043]

[Chemical 19]

In the formula, M _a1 and R _a1 have the same _{meanings as} in the general formula (A). T and U represent C—R _a2 or N, and R _a2 represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamido group, a sulfonamide group or a ureido group. Or R _a1 . However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A). Next, general formula (A-1) will be described in detail. T and U represent C—R _a2 or N, and R _a2 is a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom), a hydroxy group, a nitro group, an alkyl group (eg methyl, ethyl, methoxyethyl, n-butyl). , 2-ethylhexyl), alkenyl groups (eg allyl), aralkyl groups (eg benzyl, 4-methylbenzyl, phenethyl, 4-methoxybenzyl), aryl groups (eg phenyl, naphthyl, 4-methanesulfonamidophenyl, 4) -Methylphenyl), carbonamido group (eg, acetylamino, benzoylamino, methoxypropionylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), ureido group (eg, unsubstituted) Ureido, Methyl Ureido, Fe Ruureido), or represents a R _a1. However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A).
In the general formula (A-1), preferably T = U = N or T =
U = C-R _a2 , wherein R _a2 is a hydrogen atom and has 1 to 4 carbon atoms.
R _a1 represents an alkyl group having 1 to 4 carbon atoms substituted with one or two groups selected from a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof. Specific examples of the compound represented by formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[0045]

[Chemical 20]

[0046]

[Chemical 21]

The compound of the general formula (A) used in the present invention is a Berichte der Deutschen Chemischen Ge
sellschaft) 28, 77 (1895), JP-A-60-6
No. 1749, No. 60-147735, Berichte der Germany Chen Hemitschen Gesellschaft (Beri
chte der Deutschen Chemischen Gesellschaft) 22,
568 (1889), 29, 2483 (1896),
Journal of Chemical Society (J. Che
m.Soc.) 1932, 1806, Journal of the
American Chemical Society (J. Am. Chem. So
c.) 71, 4000 (1949), Advances in Heterocyclic Chemistry (Advances in H)
eterocyclic Chemistry) 9, 165 (1968), Organic Synthesis IV, 569
(1963), Journal of the American Chemical Society (J. Am. Chem. Soc.) 45, 23.
90 (1923), Chemische Berichte
richte) 9, 465 (1876).

Next, the general formula (B) will be described in detail. In the general formula (B), Q _b1 is composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom.
Or a 6-membered mesoionic ring, wherein X _b1 ⁻ is —O ⁻ ,
-S ^- or -N ^- represents a R _b1. R _b1 represents an aliphatic group, an aromatic hydrocarbon group, or a heterocyclic group. The mesoionic compound represented by the general formula (B) of the present invention refers to W. Bake
r and W. D. Ollis has a quarterly review (Ouart.R
ev.) 11, 15 (1957), Advanced in
Heterocyclic Chemistry (Advances in Heter
ocyclic Chemistry) 19, 1 (1976), which is a group of compounds defined as “5- or 6-membered heterocyclic compound,
A compound that cannot be satisfactorily represented by one covalent bond structure or polar structure, and in which the ring has a partial positive charge in a compound having a π-electron sextuple associated with all atoms constituting the ring, "Balances the same negative charge on the exocyclic atom or group." The mesoionic ring represented by Q _b1 includes an imidazolium ring, a pyrazolium ring, an oxazolium ring, a thiazolium ring, a triazolium ring, a tetrazolium ring, a thiadiazolium ring, an oxadiazolium ring, a thiatriazolium ring, and an oxatriazolium ring. And so on.

R _b1 is a substituted or unsubstituted aliphatic group (eg, methyl, ethyl, n-propyl, n-butyl, isopropyl, n-octyl, carboxymethyl, dimethylaminoethyl, cyclohexyl, 4-methylcyclohexyl, cyclopentyl, Propenyl, 2-methylpropenyl, propargyl, butynyl, 1-methylpropargyl, benzyl, 4-methoxybenzyl), a substituted or unsubstituted aromatic group (for example, phenyl, naphthyl, 4-methylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-methoxybenzyl) Ethoxycarbonylphenyl) and a substituted or unsubstituted heterocyclic group (eg pyridyl, imidazolyl, morpholino, triazolyl, tetrazolyl, thienyl). Further, the mesoionic ring represented by M may be substituted with the substituent described in formula (A). Further, the compound represented by the general formula (B) may form a salt (for example, acetate, nitrate, salicylate, hydrochloride, iodate, bromate). In the general formula (B), preferably X _b1 ⁻ represents —S ⁻ . Among the mesoionic compounds of the general formula (B) used in the present invention, the following general formula (B-1) is more preferable. General formula (B-1)

[0050]

[Chemical formula 22]

In the formula, X _b2 represents N or C—R _b3 ,
Y _b1 represents O, S, N or N—R _b4 , and Z ₃₀₁ represents N, N—R _b5 or C—R _b6 . R _b2 , R _b3 , R
_b4 , R _b5 and R _b6 are an aliphatic group, an aromatic group, a heterocyclic group,
It represents an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an acyl group or a carbamoyl group. However, R _b3 and R _b6 may be hydrogen atoms. R _b2 and R _b3 , R _b2 and R _b5 , R _b2
And R _b6 , R _b4 and R _b5, and R _b4 and R _b6 may form a ring. The compound represented by formula (B-1) will be described in detail. Aliphatic group, aromatic group, heterocyclic group, amino group, acylamino group, sulfonamide group, ureido group, sulfamoylamino group, acyl group and carbamoyl of R _b2 , R _b3 , R _b4 , R _b5 and R _b6 The group may be substituted. In the general formula (B-1), preferably X _b2 is N or C.
Represents —R _b3 , Y _b1 represents N—R _b4 or S, O, Z _b1 represents N or C—R _b6 , and R _b2 , R _b3 or R _b6 represents a substituted or unsubstituted alkyl group, substituted Alternatively, it represents an unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group.
However, R _b3 and R _b6 may be hydrogen atoms. R
_b4 is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. In formula (B-1), more preferably X _b2 represents N, Y _b1 represents N—R _b4 , and Z _b1 represents C—R _b6 . R _b2 and R _b4 represent an alkyl group having 1 to 6 carbon atoms, and R _b6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. However, it is more preferable that at least one alkyl group of R _b2 , R _b4 and R _b6 is substituted with at least one carboxylic acid group, sulfonic acid group, amino group or phosphono group. Specific examples of the compound represented by formula (B) of the present invention are shown below, but the present invention is not limited thereto.

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

The compounds represented by the general formula (B) of the present invention are disclosed in JP-A-1-201659 and JP-A-4-14375.
It can be synthesized by the method described in No. 5 or the like. Next, general formula (C) will be described in detail. L _C1 and L _C3 are substituted or unsubstituted aliphatic groups having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl, benzyl, phenethyl, vinyl, propenyl,
1-methyl vinyl), substituted or unsubstituted carbon number 6 to
12 aromatic groups (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl) or substituted or unsubstituted heterocyclic groups having 1 to 10 carbon atoms (eg, pyridyl, furyl, thienyl, imidazolyl), L _C2 is a substituted or unsubstituted divalent aliphatic group having 1 to 12 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methylethylene, 1-hydroxytrimethylene, 1 , 2-Xylylene), a substituted or unsubstituted divalent aromatic group having 6 to 12 carbon atoms (for example, phenylene, naphthylene), a substituted or unsubstituted divalent heterocyclic linking group having 1 to 10 carbon atoms ( For example

[0056]

[Chemical formula 26]

A _C1 and B _C1 are --S--, --O--, --NR
_{C20 -, - CO -, -} CS -, - SO 2 - or they represent any combination groups, the groups in any combination example _{-CONR C21 -, - NR C22 CO} -, - NR
_C23 CONR _C24- , -COO-, _-OCO- , -SO
_{2 NR C25 -, - NR C26} SO 2 -, - NR C27 CON
R _C28- and the like. r represents an integer of 1 to 10. However, at least one of L _C1 and L _C3 is —SO ₃
M _C1 , -PO ₃ M _C2 M _C3 , -NR _C1 (R _C2 ) (hydrochloride,
It may also be in the form of a salt such as acetate, for example, unsubstituted amino, methylamino, dimethylamino, N-methyl-N-hydroxyethylamino, N-ethyl-N-carboxyethylamino), -N ⁺ R _C3 (R _{C4 ) (R C5) · X C1} - ( e.g., trimethylammonio chloride), - SO ₂ NR _C6
(R _C7) (e.g., unsubstituted sulfamoyl, _{dimethylsulfamoyl), - NR C8 SO 2 R} C9 ( e.g., methanesulfonamido, benzenesulfonamide), - CON
R _C10 (R _C11 ) (eg, unsubstituted carbamoyl, N-
Methylcarbamoyl, N, N-bis (hydroxyethyl) carbamoyl), -NR _C12 COR _C13 (for example,
Formamide, acetamide, 4-methyl-benzoylamino), - SO ₂ R ₁₄ (e.g., methanesulfonyl, 4
-Chlorophenylsulfonyl), -PO (-NR
_{C1 5} (R _{C16) 2} (e.g., unsubstituted phosphonamido, tetramethyl phosphonic amide), - NR _C17 CONR _C18
(R _C19 ) (eg, unsubstituted ureido, N, N-dimethylureido), heterocyclic group (eg, pyridyl, imidazolyl, thienyl, tetrahydrofuranyl) -COOM _C4
Be replaced with.

M _C1 , M _C2 , M _C3 and M _C4 are hydrogen atoms or counter cations (eg, alkali metal atoms such as sodium atom and potassium atom, magnesium atom, alkaline earth metal atoms such as calcium atom, ammonium). , Ammonium groups such as triethylammonium)
Represents R _{C1 to} R _C28 are a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, benzyl, phenethyl, vinyl, propenyl, 1-methylvinyl),
Represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl), and X ⁻ represents a counter anion (eg, halogen ion such as chlorine ion, bromide ion). , Nitrate ion,
Sulfate ion, acetate ion, p-toluenesulfonate ion). When each of L _C1 , L _C2 , L _C3 , and R _{C1 to} R _C28 has a substituent, the substituent has 1 to 10 carbon atoms.
4 lower alkyl groups (eg methyl, ethyl), aryl groups having 6 to 10 carbon atoms (eg phenyl, 4-methylphenyl), aralkyl groups having 7 to 10 carbon atoms (benzyl), 2 to 4 carbon atoms Alkenyl group (eg, propenyl), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group), halogen atom (eg, chlorine atom, bromine atom), cyano group, nitro group, carboxylic acid group (of salt) Form may be used), a hydroxy group and the like.
When r is 2 or more, A _C1 and L _C2 may be any combination of the groups mentioned above. Also, at least one of A _C1 and B _C1
Represents -S-.

In general formula (C), preferably at least one of L _C1 and L _C3 is --SO ₃ M _C1 , --PO ₃ M _C2 M _C3 ,-
NR _C1 ( _RC2 ), -N ⁺ _RC3 ( _RC4 ) ( _RC5 )
X _C1 ^-, carbon atoms substituted by a heterocyclic group -COOM _C4. 1 to
6 represents an alkyl group, and L _C2 represents an alkylene group having 1 to 6 carbon atoms. A _C1 and B _C1 represent —S—, —O— or —NR _C20 —, and R _C1 , R _C2 , R _C3 , R _C4 and R _C5.
And R _C20 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 6. General formula (C)
And more preferably L _C1 and L _C3 are —SO ₃ M _C1 , —P.
An alkyl group having 1 to 4 carbon atoms substituted with O ₃ M _C2 M _C3 —COOM _C4 , wherein A _C1 and B _C1 represent —S—, and r
Represents an integer of 1 to 3. Hereinafter, the general formula (C) of the present invention will be described.
Specific examples of the compound are shown below, but the present invention is not limited thereto.

[0060]

[Chemical 27]

[0061]

[Chemical 28]

The compounds represented by the above general formula (C) of the present invention are disclosed in JP-A-2-44355 and European Patent Publication 458.
It can be synthesized by the method described in No. 277 or the like. Next, general formula (D) will be described in detail. In the general formula (D),
Examples of the aliphatic group, aromatic group and heterocyclic group represented by X _d , Y _d , R _d1 , R _d2 , R _d3 , R _d4 , R _d5 , R _d6 and R _d7 are the following. . That is, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl, sulfoethyl, aminoethyl, dimethylaminoethyl, phosphonopropyl, carboxymethyl, hydroxyethyl). A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms (eg, vinyl, propenyl, 1-methylvinyl), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenethyl, 3-carboxy) (Phenylmethyl, 4-sulfophenylethyl), a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, phenyl, naphthyl, 4-carboxyphenyl, 3-sulfophenyl), substituted or unsubstituted 1 to carbon atoms 10 heterocyclic groups (eg pyridyl, free Represents thienyl, imidazolyl, pyrrolyl, pyrazolyl, pyrimidinyl, quinolyl, piperidyl, a 5 or 6-membered rings are preferred), such as pyrrolidyl.

The alkyl group, alkenyl group, aralkyl group, aryl group and heterocyclic group may be substituted. Examples of the substituent include an alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group. Base,
Examples thereof include an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a halogen atom, a cyano group and a nitro group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. In the general formula (D), X _d and Y _d may form a ring, but they do not undergo enolization. As the ring formed by X _d and Y _d ,
For example, imidazoline-2-thione ring, imidazolidine-
2-thione ring, thiazoline-2-thione ring, thiazolidine-2-thione ring, oxazoline-2-thione ring, oxazolidine-2-thione ring, pyrrolidine-2-thione ring, or condensed benzo thereof. .

However, in the general formula (D), X _d and Y
_At least one of _d is carboxylic acid or a salt thereof (eg, alkali metal salt, ammonium salt), sulfonic acid or a salt thereof (eg, alkali metal salt, ammonium salt), phosphonic acid or a salt thereof (eg, alkali metal salt). , Ammonium salts), amino groups (eg unsubstituted amino, dimethylamino, methylamino, dimethylamino hydrochloride) or ammonium (eg trimethylammonium, dimethylbenzylammonium),
It is assumed that it is substituted with at least one of the hydroxyl groups.
In the general formula (D), the cations represented by R _d6 and R _d7 are
Represents a hydrogen atom, an alkali metal, ammonium and the like. In the general formula (D), preferably in the present invention, X _d and Y _d
Preferably does not form a ring. X _d and Y _d are
Preferably, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an alkyl group having 1 to 10 carbon atoms substituted with at least one or two groups selected from an amino group, an ammonium group, and a hydroxyl group. ,
Heterocyclic group having 1 to 10 carbon atoms, -N (R having 0 to 10 carbon atoms
_d1 ) R _d2 , -N (R _d3 ) N (R _d4 ) R having 0 to 10 carbon atoms
_d5 represents —OR _d6 having 0 to 10 carbon atoms. R _d1 , R _d2 , R
_d3 , R _d4 , R _d5 and R _d6 represent a hydrogen atom or an alkyl group. In the general formula (D), more preferably X _d and Y _d are alkyl groups having 1 to 6 carbon atoms and substituted with at least one or two groups selected from carboxylic acids or salts thereof, sulfonic acids or salts thereof. , -N (R _d1 ) R having 0 to 6 carbon atoms
_d2, -N 0 to 6 carbon atoms _{(R d3) N (R d4} ) R d5, represents an -OR _d6 0-6 carbon atoms. R _d1 , R _d2 , R _d3 , R _d4 ,
R _d5 and R _d6 represent a hydrogen atom or an alkyl group. Specific examples of the compound represented by formula (D) of the present invention are shown below, but the present invention is not limited thereto.

[0065]

[Chemical 29]

[0066]

[Chemical 30]

[0067]

[Chemical 31]

[0068]

[Chemical 32]

The compound represented by the general formula (D) of the present invention can be prepared by a known method, for example, Journal of Organics.
Chemistry (J. Org. Chem.) 24, 470
-473 (1959), Journal of Heterocyclic Chemistry (J. Heterocycle.
Chem. ) 4,605-609 (1967), "Pharmaceutical magazine" 82, 36-45 (1962), Japanese Patent Publication No. 39-26.
203, JP-A-63-229449, OLS-2,
It can be synthesized with reference to 043,944. The amount of the compounds of the general formulas (A) to (D) of the present invention used in the fixing bath or the bleach-fixing bath is appropriately 1 × 10 ⁻⁵ to 10 mol / liter, and 1 × 10 ^{−3 to} 3 mol. / Liter is preferred.
Here, when the halogen composition of the silver halide emulsion in the light-sensitive material to be processed is silver iodobromide (iodine ≧ 2 mol% or more), it is preferably used at 0.5 to 2 mol / liter, and the halogen composition is Is silver bromide, silver chlorobromide or high silver chloride (silver chloride ≧ 80 mol% or more), it is preferably used at 0.3 to 1 mol / liter. It may be added directly to the tank liquid, or may be supplied in the state of being added to the replenisher liquid. It may also be brought in from the previous bath. In the present invention, a known fixing agent other than the compound of the present invention is used as the fixing agent in a range in which the effect of the present invention is exhibited (for example, 1 by molar ratio).
/ 10 or less). Examples of the fixing agent include thiosulfates, thiocyanates, and iodide salts containing a large amount of thioureas.

Of the compounds of the general formulas (A) to (D), the general formulas (A) and (B) are preferable, and the general formulas (A-1) and (B-1) are more preferable. When the bleaching agent and the fixing agent of the present invention are used in combination in a bleach-fixing solution, the object of the present invention can be more remarkably exhibited. A rehalogenating agent such as ammonium bromide, potassium bromide, sodium bromide, ammonium chloride, potassium chloride or sodium chloride can be used in the processing solution having a bleaching ability of the present invention. The concentration of the rehalogenating agent is preferably 1.8 mol / liter or less, more preferably 0.05 mol / liter or more and 1.6 mol / liter or less. The treatment liquid having a bleaching ability of the present invention includes, in addition, ammonium nitrate,
Known additives such as pH buffers such as potassium nitrate, sodium nitrate and ammonium sulfate, and metal corrosion inhibitors can be added. Further, as a preservative for the bleach-fixing solution, a sulfite salt, a bisulfite salt, a carbonyl bisulfite adduct, or a sulfinic acid compound may be added. In order to improve stability, aminopolycarboxylic acids and organic phosphonic acid-based chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and N, N, N ', N'-
Ethylenediaminetetraphosphonic acid) is preferable. The bleach-fix bath contains various fluorescent whitening agents,
An antifoaming agent, a surfactant, polyvinylpyrrolidone, methanol and the like can be contained.

In the present invention, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain substantially no ammonium ion. The phrase "substantially free of ammonium ions" refers to a state in which the concentration of ammonium ions in the treatment liquid is 10 mmol / liter or less. The content is preferably 3 mmol / liter or less, and more preferably no content. Ammonium ions are required to be reduced from the viewpoint of recent global environmental protection. In order to reduce the ammonium ion concentration in the range of the present invention, an alkali metal ion or an alkaline earth metal ion is preferable as an alternative cation species, an alkali metal ion is particularly preferable, and a lithium ion, a sodium ion, or a potassium ion is particularly preferable. However, specifically, sodium salts and potassium salts of an organic acid ferric iron complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having a bleaching ability, sodium bromide, potassium nitrate, Examples thereof include sodium nitrate. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferable.

The pH of these bleaching solutions or bleach-fixing solutions is
It is usually 4.5 to 8, but preferably 5.0 to 6.8. The pH of the fixing solution is 2-10, preferably 4-9. A known organic acid can be used to adjust the treatment solution having a bleaching ability of the present invention within the above pH range. In the present invention, a pK is added to a processing solution having a bleaching ability.
It is preferable that the organic acid having a of 2.0 to 5.5 be contained in an amount of 0.1 mol / l to 1.2 mol / l. PKa in the present invention represents the logarithm of the reciprocal of the acid dissociation constant,
The ionic strength is 0.1 mol / liter, and the value obtained at 25 ° C. is shown. Preferred specific examples of the pKa of 2.0 to 5.5 are formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid. , Pivalic acid, aminobutyric acid, valeric acid, isovaleric acid and other aliphatic monobasic acids; amino acid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine; benzoin Acids and mono-substituted benzoic acids such as chloro and hydroxy, aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, Aliphatic dibasic acids such as adipic acid; aspartic acid, glutamic acid, cystine, ascorbi Amino acid based dibasic acid such as an acid; phthalic acid, and terephthalic acid, aromatic dibasic acids; can enumerate various organic acids such as polybasic acids such as citric acid. In the present invention, of these, a monobasic acid having a carboxy group is preferable, and acetic acid, glycolic acid and lactic acid are preferably used, and acetic acid and glycolic acid are particularly preferable.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications. U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, RD No. 17129 (197).
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; U.S. Pat. No. 3,706,56.
The thiourea derivative described in JP-A No. 1-58;
Iodide salt described in No. 5; West German Patent No. 2,748,430
Compounds described in Japanese Patent Publication No. Sho 45-
The polyamine compound described in No. 8836; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
Especially US Pat. No. 3,893,858, West German Patent No. 1,
Compounds described in JP-A No. 290,812 and JP-A No. 53-95630 are preferable. Further, US Pat. No. 4,552,83
The compounds described in No. 4 are also preferable. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. When the bleaching accelerator is used in the bleaching solution or the bleach-fixing solution, the addition amount is appropriately 1 × 10 ⁻³ to 1 mol / liter, and preferably 1 × 10 ^{−2 to} 0.2 mol / liter.
The treatment temperature of each bath is not particularly limited, but is preferably 25 to 50 ° C, particularly preferably 35 to 45 ° C. In the present invention, the replenishing amount of the bleaching solution is 1 per photosensitive material.
Although it is set to 50 to 1000 ml per m ² , it is preferably 60 to 600 ml. The bleach-fixing solution and the replenishing amount of the fixing solution are 800 ml / in the case of a color light-sensitive material for photographing (for example, coating silver amount 4 to 12 g / m ² ).
m ² or less is preferable, and in the case of color photographic paper, 60 ml /
It is preferably m ² or less.

From the viewpoint of shortening the desilvering processing time, it is preferable that the stirring of each processing solution in the desilvering step is strengthened as much as possible. As a stirring means, JP-A-62-18346
No. 0 and No. 62-183461, etc., and in the case of a means for colliding jet streams, the time until collision should be within 15 seconds after the photosensitive material is introduced into the processing solution. Is preferred. In the present invention, the crossover time from the color developing solution to the bleach-fixing solution (the aerial time until the photosensitive material comes out of the color developing solution and enters the bleaching solution) is to improve the bleaching fog and the adhesion of stains on the surface of the photosensitive material. In 10
It is preferably within seconds. The processing liquid having the bleaching ability of the present invention is
It is particularly preferable to carry out aeration during the treatment. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak Company's Z-121, Eusing Process C-41 3rd edition (1982), BL-1 to BL
-The items described on page 2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice thereof is JP-A-3-338.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of Japanese Patent No. 47 can be used as they are. In particular, a jet stirring method is preferred in which a processing solution having a bleaching ability is sprayed onto the emulsion surface of the light-sensitive material.

The silver halide color photographic light-sensitive material of the present invention need only have one light-sensitive silver halide emulsion layer on the support, and the light-sensitive silver halide emulsion layer may have a blue color sensitivity, Examples thereof include green-sensitive and red-sensitive silver halide emulsion layers. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is typically provided on a support.
And a silver halide color photographic light-sensitive material, wherein the light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light and red light. Is generally a unit photosensitive layer arrangement,
A red color-sensitive layer, a green color-sensitive layer and a blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the light-sensitive silver halide emulsion layers and as the uppermost layer and the lowermost layer. The intermediate layer may contain a coupler, a DIR compound and the like, and may also contain a color mixing inhibitor as commonly used.

Color light-sensitive materials applicable to the processing of the present invention include color negative films, color reversal films,
Examples include color paper, color reversal paper, color negative film for movies, color positive film for movies, and the like. For example, JP-A-3-33847 and 3-2936.
No. 62, No. 4-130432, etc. Further, the type of silver halide used in the support of the light-sensitive material according to the present invention; coating method; silver halide emulsion layer, surface protective layer, etc. (eg, silver iodobromide, silver iodochlorobromide, silver bromide). ,
Silver chlorobromide, silver chloride), its particle shape (for example, cube, plate, sphere), its particle size, its variation rate, its crystal structure (for example, core / shell structure, multiphase structure, homogeneous phase structure), Its manufacturing method (eg, single jet method, double jet method), binder (eg, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener, emulsion sedimentation agent, size stabilizer , Anti-adhesive agent, stabilizer, anti-staining agent, dye image stabilizer, anti-staining agent,
Chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, nucleating agents, couplers (for example, pivaloyl acetanilide type or benzoyl acetanilide type yellow couplers, 5
-Pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, D
IR coupler, bleaching accelerator releasing coupler, competitive coupler, colored coupler), coupler dispersion method (for example, oil-in-water dispersion method using a high boiling point solvent), plasticizer, antistatic agent, lubricant, coating aid, Surface active agent, whitening agent, formalin scavenger, light scattering agent, matting agent, light absorbing agent,
There are no particular restrictions on UV absorbers, filter dyes, irradiation dyes, development improvers, matting agents, preservatives (eg 2-phenoxyethanol), anti-vibration agents, etc. For example, Product Licensing Magazine (Product Lice
nsing) 92, 107-110 (December 1971)
And Research Disclosure Magazine
losure, RD) No. 17643 (December 1978), RD Magazine No. 18716 (1979 11)
Month), RD magazine No. 307105 (November 1989), etc. can be referred to.

The silver halide in the silver halide emulsion of the light-sensitive material of the present invention may be of any composition, for example, silver iodobromide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, Examples thereof include silver bromide and silver chloride. When the photosensitive material is a color negative film or a color reversal film,
The preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0.1 to 30 mol% of silver iodide. Particularly preferred is about 2
It is silver iodobromide or silver iodochlorobromide containing silver iodide in an amount of from about 25 to about 25 mol%. When the light-sensitive material is a color photographic paper, the silver halide contained in the photographic emulsion layer is preferably silver chlorobromide or silver chloride containing substantially no silver iodide. it can. The phrase "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.
Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride can be used. This ratio can take a wide range depending on the purpose, but the silver chloride ratio is 2
Those having a mol% or more can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. An emulsion of substantially pure silver chloride having a silver chloride content of 98 to 99.9 mol% is also preferably used for the purpose of reducing the replenishment amount of the developing solution. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μ or less or large grains having a projected area diameter of up to about 10 μ, and may be a polydisperse emulsion or a monodisperse emulsion.

Various color couplers can be used in the color light-sensitive material applicable to the processing according to the present invention, and specific examples thereof are RD No. 17643, VII-C.
G, the same No. 307105, the patents described in VII-C to G, JP-A-62-215272, JP-A-3-33847, and JP-A-2-3144.
It is described in European Patent Publication Nos. 447969A and 482552A. Examples of yellow couplers include US Pat.
3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-1073
9, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,
No. 649, No. 5,118,599, European Patent No. 249,473A,
No. 0,447,969, JP-A-63-23145, and 63-123047.
And those described in JP-A Nos. 1-250944 and 1-213648 can be used in combination unless the effects of the present invention are impaired. Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, Japanese Patent Application No. 3-179004, European Patent Publication No. 0447969. No. 3-203545 and an acylacetamide yellow coupler characterized by an acyl group described in Japanese Patent No.
And the general formula (Cp-
2) Yellow coupler.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,6 are preferred.
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (6 June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
Those described in US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and International Publication WO88 / 04795 are more preferable. Particularly preferred magenta couplers are pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-139544. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers. Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, and
4,228,233, 4,296,200, 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication 3,329,729
U.S. Pat.Nos. 0,121,365A, 0,249,453A, U.S. Patents 3,446,622, 4,333,999, 4,77.
No. 5,616, No. 4,451,559, No. 4,427,767, No.
4,690,889, 4,254, 212, 4,296,199,
Those described in JP-A-61-42658 and the like are preferable. Further, JP-A 64-553, 64-554, 64-555, 64-5
Pyrazoloazole couplers described in 56, European Patent Publication No. 0,488,248, pyrrolotriazole couplers described in 0,491,197, pyrroloimidazole couplers described in European Patent Publication 0,456,226A, JP-A-64-46753. Pyrazolopyrimidine couplers described, U.S. Pat.
672, imidazole couplers described in JP-A-2-33144, cyclic active methylene type cyan couplers described in JP-A-64-32260, JP-A-1-83658, JP-A-2-262655 and JP-A-2-262655.
The couplers described in 85851 and 3-48243 can also be used. Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and
No. 4,367,282, No. 4,409,320, No. 4,576, 910
, British Patent 2,102,137, European Patent 341,188A and the like. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat.No. 4,366,237 and British Patent No.
Those described in 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR releasing a development inhibitor
The couplers include the patents described in RD magazine No. 17643, VII to F, JP-A-57-151944, JP-A-57-154234 and JP-A-57-154234.
60-184248, 63-37346, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, there is described in British Patent No. 2,097,140.
No. 2,131,188, JP-A-59-157638, 59-17084.
Those described in No. 0 are preferable. Other couplers that can be used in the color photographic elements of the present invention include U.S. Pat.
Competitive couplers described in US Pat.
472, 4,338,393, 4,310,618, etc., multiequivalent couplers, DIR redox compound releasing couplers, DIR, JP, 60-185950, 62-24252, etc.
Coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that undergoes color restoration after separation described in European Patent 173,302A, RD No. 11449, No. 242.
41, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No.4,553,477, couplers releasing leuco dyes described in JP-A-63-75747, Examples thereof include couplers releasing a fluorescent dye described in US Pat. No. 4,774,181. Suitable supports which can be used in the present invention are described, for example, in Research Disclosure (RD) No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column. The color photographic light-sensitive material described above is
D No. 17643, pages 28-29, and No. 1871.
The development can be carried out by a usual method described in the left column to the right column of 615 of 615. The color developing solution used for developing the light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples thereof include sulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include agents or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) s may be used. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , Chelating agents represented by auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids (for example, Ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic 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), 4,4′-diamino-2 A fluorescent whitening agent such as a 2'-disulfostilbene compound, various surfactants such as an alkylsulfonic acid, an arylsulfonic acid, an aliphatic carboxylic acid and an aromatic carboxylic acid may be added.

However, it is preferable that benzyl alcohol is not substantially contained from the viewpoints of pollution, solution preparation and prevention of color contamination. Here, "substantially" means 2 ml or less (more preferably not including it) per liter of color developing solution. When the reversal process is performed, black and white development is usually performed before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and 1-phenyl-3.
Known black-and-white developing agents such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. In particular, when using a so-called high silver chloride light-sensitive material, the bromine ion in the color developing solution is made low and the chloride ion is made relatively large so that the photographic property and the processability are excellent and the fluctuation of the photographic property is suppressed. It is particularly preferable because it can be obtained. In such a case, the replenishing amount can be reduced to about 20 ml per square meter of the light-sensitive material in which overflow in the color developing bath is substantially eliminated. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The processing temperature of the color developing solution of the present invention is 20 to 20.
It is preferably 30 to 45 ° C. at 50 ° C. The processing time is
The time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. The photographic emulsion layer after color development is usually bleached. The bleaching treatment is carried out at the same time as the fixing treatment (bleach-fixing treatment), but in order to further speed up the treatment, a bleach-fixing treatment after the bleaching treatment may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Soc.
iety of Motion Picture and Television Engineers
Volume 64, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by a method disclosed in JP-A-62-2.
The method of reducing Ca ion and Mg ion described in No. 88838 can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents 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 the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used. In addition, following the water washing treatment, there may be a case where a further stabilizing treatment is performed, and as an example, it is used as a final bath of a color light-sensitive material for photographing.
A stabilizing bath containing a dye stabilizer represented by formalin, hexamethylenetetramine, hexahydrotriazine and N-methylol compounds can be mentioned. Formaldehyde is used as a stabilizer, but N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, azolylmethylamine derivative and the like are preferable from the viewpoint of work environment safety. Among them, N-methylolazoles such as N-methylol-1,2,4-triazole and N-methylolpyrazole, and azolyl such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine Methylamine and its derivatives are preferable because they have high image stability, and particularly triazoles such as 1,2,4-triazole,
Combined use of its derivatives such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine (Japanese Patent Application No.
No. 159918) is preferable because of high image stability and low formaldehyde vapor pressure. If necessary, ammonium compounds, metal compounds such as Bi and Al, fluorescent whitening agents, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents can be used in this stabilizing bath. Agents (preferably silicon-based) can also be added. As the water used in the washing step or the stabilizing step, tap water, water deionized to a Ca ion or Mg ion concentration of 5 mg / liter or less by ion exchange resin, water sterilized by halogen, ultraviolet germicidal lamp, etc. Is preferably used.

The replenishing amount of the above-mentioned washing and / or stabilizing solution is 1 to 50 of the amount carried from the previous bath per unit area of the light-sensitive material.
Times, preferably 2 to 30 times, more preferably 2 to 15 times. The overflow solution accompanying this replenishment can be reused in the desilvering process and other processes. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. Further, for saving silver in the light-sensitive material, West German Patent No. 2,226,770 or US Patent No. 3,674,4
Treatment using cobalt intensification or hydrogen peroxide intensification described in No. 99 may be performed. One example of a silver halide color light-sensitive material is one using direct positive type silver halide. Processing using this photosensitive material will be described below. After the imagewise exposure of the silver halide color photographic light-sensitive material, after the fog treatment with light or a nucleating agent, or while performing the treatment, a pH of 1 containing an aromatic primary amine color developing agent is included.
It is also preferable to directly form a positive color image by color development, bleaching and fixing treatment with a surface developing solution of 1.5 or less. The pH of this developer is more preferably in the range of 11.0 to 10.0.

The fogging treatment in the present invention is carried out by developing in the presence of a so-called "light fogging method" for giving a second exposure to the entire surface of the photosensitive layer and a "chemical fogging method" in the presence of a nucleating agent. Either of the methods may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed. Regarding the light fogging method, the above-mentioned Japanese Patent Application No. 61-
No. 253716, page 47, line 4 to page 49, line 5, and the nucleating agent that can be used in the present invention is described on page 49, line 6 to page 67, line 2, particularly It is preferable to use the compounds represented by the general formulas [N-1] and [N-2]. Specific examples of these are as described in No. 56 of the same specification.
[NI-1] to [NI-10] described on pages 58 to 58 and [N-II-1] to [N] described on pages 63 to 66 of the same specification.
-II-12] is preferred. Regarding the nucleation accelerator that can be used in the present invention, the same specification, page 68, line 11 to page 71, 3
It is described in the line, and as a concrete example of this,
Use of (A-1) to (A-13) described on pages 9 to 70 is preferable.

[0087]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A multi-layer color light-sensitive material A having the following composition was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The coating amount is g for silver halide and colloidal silver.
/ M ² units of silver, for couplers, additives and gelatin the amounts in g / m ² units and for sensitizing dyes the moles per mole of silver halide in the same layer. It is shown by the number.

First layer: antihalation layer Black colloidal silver 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 HBS-1 0.30 HBS-2 1.2 × 10 ^-2 second layer: intermediate layer fine silver iodobromide (AgI 1.0 mol%, sphere equivalent diameter O.O7myuemu) silver coverage 0.15 gelatin ^{1.00 ExC-4 6.0 × 10 -2} Cpd-3 2.0 × 10 - ² 3rd layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A Silver coating amount 0.42 Silver iodobromide emulsion B Silver coating amount 0.40 Gelatin 1.90 ExS-1 6.8 × 10 ^-4 mol ExS-2 2.2 × 10 ^-4 Mol ExS-3 6.0 x 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 x 10 ^-2 ExC-4 2.3 x 10 ^-2 HBS-1 0.32

Fourth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Silver Iodobromide Emulsion C Silver Coating Weight 0.85 Gelatin 0.91 ExS-1 4.5 × 10 ⁻⁴ Mol ExS-2 1.5 × 10 ⁻⁴ Mol ExS-3 4.5 × 10 ^{− 5} mols ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 HBS-1 0.10 Fifth layer: high-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D Silver coating amount 1.50 Gelatin 1.20 ExS-1 3.0 × 10 ^-4 mol ExS-2 9.0 × 10 ^-5 mol ExS-3 3.0 × 10 ^-5 mol ExC-2 8.5 × 10 ^-2 ExC-5 3.6 × 10 ^-2 ExC -6 1.0 x 10 ^-2 ExC-7 3.7 x 10 ^-2 HBS-1 0.12 HBS-2 0.12 Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 x 10 ^-2 HBS-1 8.0 x 10 ^-2

Seventh layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion E Silver coating amount 0.28 Silver iodobromide emulsion F Silver coating amount 0.16 Gelatin 1.20 ExS-4 7.5 × 10 ^-4 mol ExS-5 3.0 × 10 ^-4 mol ExS-6 1.5x10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5x10 ^-2 HBS-1 0.20 HBS-3 3.0x10 ^-2 Eighth layer: Medium-speed green emulsion layer iodobromide emulsion G silver laydown 0.57 gelatin 0.45 ExS-4 5.2 × 10 ^-4 mol ExS-5 2.1 × 10 ^-4 mol ExS-6 1.1 × 10 ^-4 mol ExM-1 0.12 ExM-2 7.1 × 10 - ³ ExM-3 3.5 x 10 ^-2 HBS-1 0.15 HBS-3 1.0 x 10 ^-2

9th layer: Intermediate layer Gelatin 0.50 HBS-1 2.0 × 10 ^-2 10th layer: High sensitivity green emulsion layer Silver iodobromide emulsion H Silver coating amount 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ^-4 mol ExS-5 1.2 × 10 ^-4 mol ExS-6 1.2 × 10 ^-4 mol ExM-4 5.8 × 10 ^-2 ExM-6 5.0 × 10 ^-3 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 HBS-1 0.25 11th layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

Twelfth layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10 Thirteenth layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I 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 HBS-1 0.15 14th layer: Medium speed blue emulsion layer Silver iodobromide emulsion J Silver coating amount 0.19 Gelatin 0.35 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.22 HBS-1 7.0 x 10 ^-2

Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent spherical diameter O.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer: High-sensitivity blue-sensitive emulsion layer Iodobromide Silver emulsion K Silver coating amount 1.55 Gelatin 1.00 ExS-8 2.2 × 10 ^-4 mol ExY-1 0.21 HBS-1 7.0 × 10 ^-2 17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 HBS- 1 1.0 x 10 ^-2 HBS-2 1.0 x 10 ^-2

Eighteenth layer: Second protective layer Fine silver chloride (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 In addition to the above, 1,2-benzisothiazolin-3-one (relative to gelatin) was added to the sample thus prepared. 20 on average
0 ppm), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Further, B-4 to B-6, W-2, W-3, F-1 to F-15, iron salt, lead salt, gold salt, platinum salt, iridium salt, rhodium salt and palladium salt are contained. There is.

[0095]

[Table 1]

In Table 1, (1) Each emulsion was reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. There is. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0097]

[Chemical 33]

[0098]

[Chemical 34]

[0099]

[Chemical 35]

[0100]

[Chemical 36]

[0101]

[Chemical 37]

[0102]

[Chemical 38]

[0103]

[Chemical Formula 39]

[0104]

[Chemical 40]

[0105]

[Chemical 41]

[0106]

[Chemical 42]

[0107]

[Chemical 43]

[0108]

[Chemical 44]

[0109]

[Chemical formula 45]

[0110]

[Chemical formula 46]

After cutting the sample prepared as described above, imagewise exposure was performed, and the replenishing amount of the bleach-fixing solution was doubled in the tank volume in the following processing steps using a negative-development machine. Was continuously processed (running test). In addition, after that, a sample exposed to white light was prepared and subjected to the same processing steps. Treatment process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 38.0 ℃ 3 minutes 05 seconds 600 ml 17 Bleach fixing 38.0 ℃ 50 seconds -5 Bleach fixing 38.0 ℃ 50 seconds 400 ml 5 Water washing 38.0 ℃ 30 seconds 900 ml 3 Stability 38.0 ℃ 20 sec -3 Stability 38.0 ℃ 20 sec 560 ml 3 Dry 80 ℃ 60 sec * Replenishment amount per 1 m ^{2 of} light-sensitive material The bleach-fixing solution and stabilizing solution are countercurrent flow to kara. The amount of developing solution brought into the bleach-fixing process and the amount of bleach-fixing solution brought into the washing process were 65 ml and 50 ml, respectively, per 1 m ² of the light-sensitive material. The crossover time is 6 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 Starter replenisher Diethylenetriaminepentaacetic acid 2.0 g 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 g 3.3 g Sodium sulfite 3.9 g 5.1 g Potassium carbonate 37.5 g 39.0 g Potassium bromide 1.4 g 0.4 g Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 g 3.3 g 2-methyl-4- [N-ethyl-N- (β-hydro 4.5 g 6.0 g xyethyl) amino] aniline sulphate Water was added to 1000 ml 1000 ml pH (25 ℃) 10.05 10.05

Bleach-fixing solution Start solution Replenishing solution Fixing agent (See Table 2) 1.3 mol 1.9 mol Ammonium sulfite 40 g 100 g (Used only when the fixing agent is ammonium thiosulfate) Bleaching agent (See Table 2) 0.15 mol 0.23 mol Chelating agent ( The same kind of bleach) 0.05 mol 0.08 mol Sodium bromide 80 g 120 g Acetic acid 40 g 60 g Water is added 1000 ml 1000 ml pH (25 ° C) (prepared with acetic acid and sodium hydroxide) 5.8 5.6 Rinse water Cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and anion exchange resin (the same Amberlite IRA-40 manufactured by OH type strong base).
0) 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 diisocyanurate 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 Starting solution, replenishing solution Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1 , 4-Bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH (25 ° C) (prepared with acetic acid and sodium hydroxide) 8.5 [Evaluation of desilvering performance] After running processing The residual white amount of the processed white exposed sample was measured using a fluorescent X-ray analyzer. [Evaluation of Bleach Fog] The minimum density (Dmin) of magenta was measured for a sample (imagewise exposed sample) just before the end of the running process, using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd. [Evaluation of Recoloring Property] After the density of the above sample was measured, it was immersed in CN-16N2 (bleaching solution) manufactured by Fuji Photo Film Co., Ltd. at 35 ° C. for 4 minutes, and the density was measured again, and the cyan density became 2.2. The density before reprocessing of the points is shown by the coloring rate. Color development rate (%) = [(density of D _R 2.2 point before rebleaching)
/2.2]×100 [Evaluation of solution stability] The bleach-fix solution after running was visually inspected for precipitation. The evaluation was decided based on the following criteria. No precipitation: ◯, a small amount of precipitation: Δ, a large amount of precipitation: × The results are shown in Table 2.

[0115]

[Table 2]

As can be seen from Table 2, according to the present invention,
It can be seen that good results can be obtained in any of the desilvering property, the bleaching fog, the color recoloring property and the stability of the bleach-fixing solution. Example 2 Using the sample of Example 1, continuous processing (running test) was performed in the following processing steps until the replenishing amount of the bleaching solution became twice the tank volume. In addition, after that, a sample exposed to white light was prepared and subjected to the same processing steps. Treatment process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 38.0 ℃ 3 minutes 05 seconds 600 ml 17 Bleach 38.0 ℃ 1 minute 200 ml 5 Settlement 38.0 ℃ 1 minute 10 seconds 400 ml 5 Water wash 38.0 ℃ 30 seconds 900 ml 3 Stability 38.0 ℃ 20 sec -3 Stability 38.0 ℃ 20 sec 560 ml 3 Dry 80 ℃ 60 sec * Replenishment amount per 1 m ^{2 of} light-sensitive material Stabilizer is a countercurrent flow to kara. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 1 m of the light-sensitive material.
65 ml, 50 ml and 50 ml per ² respectively. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Bleach below,
The composition of the fixer is shown. The other liquid compositions are the same as in Example 1.

Bleaching solution Starter solution Replenishing solution Bleaching agent (see Table 3) 0.33 mol 0.5 mol Sodium bromide 80g 120g Sodium nitrate 15g 25g Hydroxyacetic acid 50g 75g Acetic acid 40g 60g Add water 1 liter 1 liter pH [with sodium hydroxide Adjustment] 4.3 4.0 Fixing solution Start solution Replenishing solution Fixing agent (see Table 3) 1.3 mol 1.9 mol Ammonium sulfite 40 g 100 g (Used only when the fixing agent is ammonium thiosulfate) Imidazole 17 g 26 g Ethylenediaminetetraacetic acid 13 g 20 g Add water to adjust pH [ Adjustment with Sodium Hydroxide and Acetic Acid] 7.0 7.4 The same evaluations as in Example 1 were carried out with respect to desilvering performance, bleaching fog, recoloring property and stability of fixing solution. The results are shown in Table 3.

[0118]

[Table 3]

As can be seen from Table 3, according to the present invention,
It can be seen that good results are obtained in all of desilvering property, bleaching fog, color recoloring property and stability of fixing solution. Example 3 In Example 1, No. 11 bleach was added to compound I-2,
I-3, I-4, I-9, I-16, I-18, I-1
9, I-21, I-26, I-38, I-40, I-4
Example 1 in place of the Fe (III) salt of 1, I-43, respectively.
The same test was performed. As a result, similar to Example 1, good results were obtained. Example 4 In Example 1, the fixing agent No. 11 was changed to A-1, A-.
4, A-10, A-12, A-13, B-1, B-4,
The same test as in Example 1 was performed by substituting C-1, C-2, C-5, C-6, D-2, and D-21, respectively. As a result, similar to Example 1, good results were obtained. Example 5 A sample prepared in the same manner as the multilayer color photographic paper sample 103 of Example 1 of JP-A-4-145433 was cut, then imagewise exposed and bleach-fixed in the following processing steps using a paper processor. Continuous treatment (running test) was performed until the replenishment amount of the liquid became twice the tank volume. Also, after that,
A sample exposed to white light was prepared and subjected to the same processing steps.

Treatment process Temperature Time Replenisher ^* Tank capacity (liter) Color development 39 ° C. 45 seconds 70 ml 20 Bleach fixing 35 ° C. 30 seconds 60 ml ^** 20 rinse 35 ° C. 20 seconds −10 Rinse 35 ° C. 20 seconds −10 Rinse 35 ° C 20 seconds 360ml 10 Dry 80 ° C 60 seconds (Rinse → 3 tank countercurrent method) * Replenishment amount per 1m ^{2 of} light-sensitive material ** In addition to the above 60ml, light-sensitive material 1m ² from rinse
120 ml per volume of color developer tank liquid replenisher water 700 ml 700 ml diethylenetriaminepentaacetic acid 0.4 g 0.4 g N, N, N-trimethylenephosphonic acid 4.0 g 4.0 g 1-hydroxyethylidene-1,1- Diphosphonic acid 0.4 g 0.4 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4B manufactured by Sumitomo Chemical) 1 0.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g N, N-bis (sulfoethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Aminoaniline sulfate 5.0 g 11.5 g Water was added to 1000 ml 1000 ml pH (25 ° C) 10.10 11.10

Bleach-fixing solution Tank solution Replenishing solution Water 500 ml 100 ml Fixing agent (see Table 4) 0.5 mol 1.25 mol Ammonium sulfite 40 g 100 g (Used only when the fixing agent is ammonium thiosulfate) Bleaching agent (see Table 4) 0.15 mol 0.37 mol Chelating agent (same as bleach) 0.02 mol 0.04 mol Sodium bromide 40 g 75 g Nitric acid (67%) 30 g 65 g Water is added 1000 ml 1000 ml pH (25 ° C) (adjusted with acetic acid and sodium hydroxide) 5.8 5 .6 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3 ppm or less) This sample was also evaluated in the same manner as in Example 1.
The results are shown in Table 4.

[0122]

[Table 4]

As can be seen from Table 4, according to the present invention,
It can be seen that good results can be obtained in any of the desilvering property, the bleaching fog, the color recoloring property and the stability of the bleach-fixing solution. Example 6 A sample prepared in the same manner as Sample No. 1 of Example 1 of JP-A-2-90145 was cut and processed, and a W-G-R three-color separation filter was attached to the front surface of the wedge, and exposure was performed. After the application, the sample was subjected to continuous imagewise exposure using an automatic processor by the method described below until the cumulative replenishment amount of the bleach-fixing solution became three times the capacity of the mother liquor tank (running test). Then, it processed. Processing process Time Temperature Mother liquor tank capacity Replenishment amount Color development 135 seconds 38 ° C 15 liters 300 ml / m ² Bleach fixing 30 〃 33 〃 3 〃 300 〃 Water wash (1) 40 〃 33 〃 3 〃 − Water wash (2) 40 〃 33 〃 3 〃 320 〃 Dry 30 〃 80 〃 Rinsing water is replenished in the washing bath (2) and then the washing bath (2)
The so-called countercurrent replenishment system was used in which the overflow liquid of (1) was introduced into the washing bath (1). At this time, the amount of the bleach-fixing solution brought from the bleach-fixing bath with the light-sensitive material to the washing bath (1) was 35 ml / m.
^2, the magnification of the washing water replenishment rate for the amount of carryover of the bleach-fixing solution was 9.1 times. The composition of each treatment liquid was as follows.

Color developer Mother liquor Replenisher Ethylenediaminetetrakismethylenephosphonic acid 1.5 g 1.5 g Diethylene glycol 10 ml 10 ml Benzyl alcohol 12.0 ml 14.4 ml Potassium bromide 0.70 g-g Benzotriazole 0.003 g 0.004 g Sodium sulfite 2.4 g 2.9 g Glucose 2.5 g 3.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 4.8 g triethanolamine 6.0 g 7.2 g N-methyl-N- (β-methanesulfonamide 6.0 g 7.2 g ethyl) -3-methyl-4- Aminoaniline Sulfate Potassium carbonate 30.0 g 25.0 g Optical brightener (WHITEX-4, Sumitomo Chemical Co., Ltd.) 1.0 g 1.2 g Water added 1000 ml 1000 ml pH (25 ° C) 10.25 10.80

Bleach-fixing solution Mother liquor, replenishing solution Fixing agent (see Table 5) 0.9 mol Ammonium sulfite 0.2 mol (used only when the fixing agent is ammonium thiosulfate) Bleaching agent (see Table 5) 0.18 mol Chelate Agent (the same as the bleaching agent) 0.01 mol Sodium nitrate 10 g Sodium p-toluenesulfinate 20 g 5-Mercapto-1,3,4-triazole 0.5 g Water is added to 1000 ml pH (25 ° C) ( 6.20 Washing water Tap water is used as H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strong base anion exchange resin (Amberlite IRA-). 40
0) 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 diisocyanurate 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. The same evaluation as in Example 1 was performed on this sample. The results are shown in Table 5.

[0126]

[Table 5]

As can be seen from Table 5, according to the present invention,
It can be seen that good results can be obtained in any of the desilvering property, the bleaching fog, the color recoloring property and the stability of the bleach-fixing solution. Example 7 JP-A-4-147133 A sample prepared in the same manner as the sample 121 of Example 1 was cut, exposed imagewise, and then replenished with a bleaching solution in the following processing steps using a cine type automatic developing machine. Quantity
Continuous treatment (running test) was performed until the tank capacity was doubled. After that, a sample exposed to white light was prepared and processed in the same processing step. Processing time Temperature Replenishment amount ^* Tank capacity (min) (° C) (liter) (liter) Black and white development 6 38 1.5 12 1st water wash 1 38 7.5 4 Inversion 1 38 1.1 4 Color development 4 38 2.0 12 Adjustment 2 38 1.1 4 Bleaching 3 38 1.3 12 Settling 2 38 1.3 12 Second washing (1) 1 38-4 Second washing (2) 1 38 7. 5 4 Stability 1 38 1.1 4 Drying 250 * Replenishment amount per 1 m ² of light-sensitive material The overflow solution of the second washing (2) was introduced into the second washing (1) bath.

The composition of each processing solution was as follows. (Black-and-white developer) Starter Replenisher Unit (g) Nitrilo-N, N, N-trimethylenephospho 2.0 2.0 Acid 5 sodium salt Diethylenetriamine pentaacetic acid 5 sodium salt 3.0 3.0 Potassium sulfite 30 30 Hydroquinone potassium monosulfonate 20 20 Potassium carbonate 33 33 1-Phenyl-4-methyl-4-hydroxy 2.0 2.0 Methyl-3-pyrazolidone Potassium bromide 2.5 0.9 Potassium thiocyanate 1.2 1.2 Potassium iodide 2.0 mg 2.0 mg Water added 1.0 liter 1.0 liter pH (25 ° C) 9.60 9.70 The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Reversal Solution) Common for Start Solution / Replenisher Unit (g) Nitrilo-N, N, N-trimethylenephospho 2.0 acid ・ 5 sodium salt stannous chloride ・ dihydrate 1.0 p− Aminophenol 0.1 Sodium hydroxide 8.0 Glacial acetic acid 1.5 ml Water added 1.0 liter Ammonium sulfite 20 Water added 1.0 liter pH (25 ° C) 6.60 pH is acetic acid or ammonia water It was adjusted. (Color developer) Start solution Replenisher Unit (g) Nitrilo-N, N, N-trimethylenephospho 2.0 2.0 acid, 5 sodium salt Diethylenetriamine pentaacetic acid 5 sodium salt 2.0 2.0 Sodium sulfite 7.0 7.0 3 potassium phosphate 12 Aqueous salt 36 36 Potassium bromide 1.0-Potassium iodide 90 mg-Sodium hydroxide 3.0 3.0 Citrazinate 1.5 1.5 N-Ethyl- (β-methanesulfonamide 10.5 10.5 tyl) -3-methyl-4-aminoaniline Sulfate 3 , 6-dithiaoctane-1,8-diol 3.5 3.5 Water was added to 1.0 liter 1.0 liter pH (25 ° C) 11.90 12.05 pH was adjusted with hydrochloric acid or potassium hydroxide.

(Adjusting Solution) Common for Starting Solution / Replenishing Solution Unit (g) Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ 8.0 dihydrate sodium sulfite 12 2-mercapto-1,3,4-triazole 0.5 pH ( 25 ° C.) 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. Bleaching solution Start / replenisher common unit (g) Bleaching agent (see Table 6) 0.3 mol Chelating agent (similar to bleaching agent) 0.01 mol Sodium bromide 120 g Sodium nitrate 25 g Hydroxyacetic acid 40 g Acetic acid 30 g Water 1 liter pH [adjusted with sodium hydroxide and acetic acid] 4.2 Fixer common to starter / replenisher (g) Fixer (see Table 6) 1.2 mol Sodium bisulfite 15 g Used only in the case of ammonium sulfate) Imidazole 17 g Ethylenediaminetetraacetic acid 13 g Water was added to adjust pH [adjusted with sodium hydroxide and acetic acid] 6.0 Stabilizing solution The same stabilizing solution as in Example 2 was used. The same evaluation as in Example 1 was performed on this sample. The results are shown in Table 6.

[0131]

[Table 6]

As can be seen from Table 6, according to the present invention,
It can be seen that good results can be obtained in any of desilvering property, bleaching fog, color recoloring property and stability of the fixing solution.

[0133]

According to the method of the present invention, a method of processing a silver halide color photographic light-sensitive material which is excellent in desilvering property, color reversion property and less in bleaching fog can be carried out. Further, the stability of the processing solution having fixing ability can be improved, and the precipitation can be greatly reduced. Further, it is possible to reduce ammonium ions which are not preferable from the viewpoint of environmental protection.

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

[Procedure amendment]

[Submission date] May 31, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] In the formula, Y ₁ represents a non-metal atom group necessary for forming an aromatic hydrocarbon group or a heterocyclic group. R ₁ represents a substituent.
n represents an integer of 0 to 4. When n represents an integer of 2 to 4, R ₁ may be the same or different. X
₁ represents a hydrogen atom or -L ₁ -A ₂ . X ₂ is -L _2-
A ₃ or

[Chemical 2] Represents X ₃ represents a hydrogen atom, or -L ₄ -A _4. L
₁ , L ₂ , L ₃ and L ₄ each represent an alkylene group or an arylene group. W ₁ represents a divalent linking group. A ₁ ~
A ₅ is a hydrogen atom, a carboxylic acid or a salt thereof,
It represents a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, a hydroxy group, a hydroxyalkyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, an alkoxy group, an alkylthio group or an amino group. However, at least one of A _{1 to} A ₅ represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, or a hydroxy group, and when X ₂ is -L ₂ -A ₃ , A ₁ is never a hydrogen atom. General formula (A)

[Chemical 3] In the formula, Q _a1 represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. R _a1 represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium salt. q represents an integer of 1 to 3, M _a1 represents a hydrogen atom or a cation. General formula (B)

[Chemical 4] In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ^— represents —O ^— , —S ^— or —N.
^- representing the R _b1. R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Formula (C) L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _{C3 In the} formula, L _C1 and L _C3 may be the same or different and each is an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Represents a cyclic group, and L _C2 represents a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic linking group, or a linking group combining them. A
_C1 and A _C2 are respectively -S-, _-O- , -NR _C20- ,
-CO -, - it represents a or group composed of a combination of them - SO _2. r represents an integer of 1 to 10. However, L _C1 and L
_C3 at least one -SO ₃ M _C1, -PO ₃ M
_{C2 M C3, -NR C1 (R} C2), - N + R C3 (R C4)
^{_{(R C5) · X C1 -}} , -SO 2 NR C6 (R C7), - NR C8
_{SO 2 R C9, -CONR C10 (} R C11), - NR C12 C
_{OR C13, -SO 2 R C14,} -PO (-NR C15 (R
_C16 )) ₂ , -NR _C17 CONR _C18 ( _RC19 ), -C
It is assumed to be substituted with OOM _C4 or a heterocyclic group.
M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. R _{C1 to} R _C20
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. Provided that at least one of A _C1 and A _C2 represent -S-. General formula (D)

[Chemical 5]Where X_dAnd Y_dIs an aliphatic group, aromatic hydrocarbon group, compound
Substrate, -N (R_d1) R_d2, -N (R_d3) N (R_d4) R
_d5, -OR_d6, Or-SR_d7Represents Incidentally, X _dAnd Y_d
May form a ring but does not enolize.
However, X_dAnd Y_dAt least one of them is carvone
Acid or salt thereof, sulfonic acid or salt thereof, phospho
Acid or salt thereof, amino group or ammonium group,
It is assumed that it is substituted with at least one of the hydroxyl groups.
R_d1, R_d2, R_d3, R_d4And R_d5Is hydrogen atom, aliphatic
A group, an aromatic hydrocarbon group or a heterocyclic group, R_d6And R
_d7Is a hydrogen atom, cation, aliphatic group, aromatic hydrocarbon group
Or represents a heterocyclic group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

2. Description of the Related Art Generally, the processing of a silver halide color photographic light-sensitive material comprises a color development step and a desilvering step. In the desilvering process, the developed silver generated in the color development process is oxidized (bleached) into a silver salt by a bleaching agent having an oxidizing action, and further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. Be done (fixed). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step.
For details of these processing steps, see "The Theory of Photographic Process," 4th Edition, by James.
s, “The Theoryof Photographic Process” 4'th edi
tion) (1977). The above processing steps are generally performed by an automatic processor. In recent years, in particular, a small automatic developing machine called a minilab has been installed in stores, and a rapid processing service has been spreading to customers. Against this background, there has been a strong demand in recent years for a particularly rapid processing step, and a drastic speed-up of the desilvering step, the bleaching step, the fixing step or the bleach-fixing step is also desired. Furthermore, since the treatment has been carried out at various places, the problem of treatment waste liquid is increasing,
Studies are underway to reduce the amount of replenishment to reduce the amount of processing waste liquid.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

The ethylenediaminetetraacetic acid ferric iron complex salt conventionally used as a bleaching agent for the bleaching bath described above has a fundamental defect that its oxidizing power is weak, and improvements such as the use of a bleaching accelerator have been added. Nevertheless, it has not reached the goal of rapid bleaching. Further, if the pH of the bleaching solution is lowered and the oxidative power is increased, the color reversion property deteriorates. Although red blood salts, iron chloride, bromate, etc. are known as bleaching agents that achieve rapid bleaching, red blood salts handle iron corrosion such as metal corrosion due to environmental conservation problems. Due to the above inconvenience, etc., and due to the problem of liquid instability in bromate, it cannot be widely used.
Therefore, there has been a demand for a bleaching agent that is easy to handle and that achieves rapid bleaching without causing problems in discharging the waste liquid. Recently, a ferric complex of 1,3-diaminopropanetetraacetic acid has been disclosed as a bleaching agent satisfying such conditions. However, when this bleaching agent is used, not only the above-mentioned problems become prominent but also bleaching fog occurs due to bleaching, which is not sufficiently satisfactory. On the other hand, in the processing of color photographic paper, the bleaching agent and the fixing agent are used in the same bath as the bleach-fixing bath, and the bleaching agent used here is usually ferric ethylenediaminetetraacetic acid complex salt. However, from the viewpoint of speeding up, the use of ethylenediaminetetraacetic acid ferric complex salt as this bleaching agent is not sufficient for the recent demand for speeding up, and means for further speeding up is required. On the other hand, it has been proposed to use an oxidant such as the above-mentioned ferric complex of 1,3-diaminopropanetetraacetic acid having a high oxidizing power in a bleach-fixing bath. It is not practically sufficient because the bleaching fog described above is large even in the bath, and the thiosulfate is further oxidized and deteriorated due to the use of the bleach-fixing bath. This problem has become a fatal defect as the replenishment rate has been lowered in recent years. Therefore, there has been a strong demand for development of a bleaching agent and a fixing agent for solving the above problems, and a processing composition and a processing method using the same.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ^- is -O ^- ,-.
Represents S ^- or -N ^- R _b1 . R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Formula (C) L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _{C3 In the} formula, L _C1 and L _C3 may be the same or different and each is an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Represents a cyclic group, and L _C2 represents a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic linking group, or a linking group combining them. A
_C1 and A _C2 are respectively -S-, _-O- , -NR _C20- ,
-CO -, - it represents a or group composed of a combination of them - SO _2. r represents an integer of 1 to 10. However, L _C1 and L
_C3 at least one -SO ₃ M _C1, -PO ₃ M
_{C2 M C3, -NR C1 (R} C2), - N + R C3 (R C4)
^{_{(R C5) · X C1 -}} , -SO 2 NR C6 (R C7), - NR C8
_{SO 2 R C9, -CONR C10 (} R C11), - NR C12 C
_{OR C13, -SO 2 R C14,} -PO (-NR C15 (R
_C16 )) ₂ , -NR _C17 CONR _C18 ( _RC19 ), -C
It is assumed to be substituted with OOM _C4 or a heterocyclic group.
M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. R _{C1 to} R _C20
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. Provided that at least one of A _C1 and A _C2 represent -S-. General formula (D)

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

The acylamino group in A _{1 to} A ₅ is substituted with an unsubstituted alkylacylamino group or a substituent (preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a carboxy group or a hydroxy group). And an alkylacylamino group are more preferable, and a C number of 1 is more preferable.
An alkylacylamino group having 10 to 10 carbon atoms, an arylacylamino group having 6 to 10 C atoms, and a heterocyclic acylamino group having 1 to 10 C atoms, and more preferably an alkylacylamino group having 1 to 5 C atoms. Examples of the acylamino group include acetylamino, benzoylamino, t-butanamide, trifluoroacetylamino and the like. The alkoxy group and alkylthio group in A _{1 to} A ₅ are preferably those having a C number of 1 to 10, and more preferably those having a C number of 1 to 5, and examples thereof include methoxy, ethoxy, and methylthio. The amino group in A _{1 to} A ₅ is an unsubstituted amino group, an unsubstituted alkylamino group or an alkylamino group substituted with a substituent (preferably a carboxy group, a hydroxy group, a phosphono group or a sulfo group). Preferably, the C number is 1 to 10, more preferably the C number is 1 to 6.
belongs to. A ₁ is carboxylic acid or a salt thereof, or an alkylthio group or an alkoxy group substituted with a carboxylic acid or a salt thereof (ie, —Z ₁ -L ₅ —CO
OM (Z ₁ represents an oxygen atom or a sulfur atom, L ₅ represents an alkylene group, M represents a hydrogen atom or a cation), and a carboxylic acid or a salt thereof is most preferable. As A _{2 to} A ₅ , a carboxylic acid or a salt thereof, a phosphonic acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyalkyl group is more preferable, and a carboxylic acid or a salt thereof is most preferable.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

The alkylene group in L _{1 to} L ₄ may be linear, branched or cyclic, and is substituted with the substituents described for R ₁ (preferably carboxylic acid or its salt, hydroxy group, halogen atom). May be. It is preferably one having a C number of 1 to 10, more preferably a methylene group or an ethylene group. The arylene group in L _{1 to} L ₄ may be a monocycle or may be further condensed with an aromatic ring or a heterocycle, and may have a substituent such as those described for R ₁ (preferably an alkyl group, an acylamino group or an alkyl group). (Sulfonamide group, alkoxy group, sulfamoyl group, carbamoyl group, alkylthio group, sulfo group, phosphono group, acyl group, alkoxycarbonyl group, nitro group, carboxy group, hydroxy group, halogen atom, hydroxamic acid group)
May be replaced with. W ₁ is preferably a divalent linking group containing an alkylene group, an alkenylene group, an arylene group, a divalent heterocyclic group and / or a group consisting of a combination thereof. More preferably, it is represented by the general formula (W). General formula (W)

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

[0030]

[Chemical 14]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

[Chemical 17]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

Synthesis Example 1 1- (1) Synthesis of Compound (I-1) Anthranilic acid 20.0 g (0.146 mol), water 20 ml
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, the sodium hydroxide aqueous solution was added dropwise so that the reaction solution maintained a pH of 7 to 9.) After heating and stirring for 20 hours, the temperature was returned to room temperature and concentrated hydrochloric acid 45.
6 g (0.450 mol) was added. The precipitated crystals were filtered off and washed with water. Transfer the crystals to a beaker and add 300 ml of water.
After adding, the pH was adjusted to 1.6 to 1.7 with concentrated hydrochloric acid. 1
After stirring for an hour, the solid was collected by filtration and washed well with water. By recrystallizing from water, 32.5 g (0.125 mol) of 1/3 hydrate of compound (I-1) was obtained as a white solid. Yield 86
%. Melting point 214-216 [deg.] C (decomposition). 1- (2) Synthesis of ferric iron complex salt of compound (I-1) 46.4 g (0.1) of compound (I-1) synthesized in 1- (1)
79 mol) was suspended in 46 ml of water, and 29% ammonia water 1
0.5 g (0.179 mol) was added and dissolved. The pH at this time was 4.6. After adding 72 ml of an aqueous solution containing 72.3 g (0.179 mol) of iron nitrate (III) nonahydrate, 1N HNO ₃ aqueous solution was added to adjust the pH to 2.9. The precipitated crystals were collected by filtration, washed with water and acetone, and dried to give the compound (I-
65.8 g (0.166 mol) of the ferric complex salt of 1) was obtained. Yield 93%. Melting point ≧ 130 ° C. (decomposition).

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

M _a1 is a hydrogen atom or a cation (for example,
And an alkali metal atom such as sodium atom and potassium atom, an alkaline earth metal atom such as magnesium atom and calcium atom, an ammonium group, and an ammonium group such as triethylammonium group). Further, the heterocycle represented by the general formula (A) and L _a1 are a nitro group, a halogen atom (eg, chlorine atom, bromine atom), a mercapto group, a cyano group, and a substituted or unsubstituted alkyl group (eg, methyl, ethyl, Propyl, t-butyl,
Cyanoethyl), aryl groups (eg phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl,
3,4-dichlorophenyl, naphthyl), alkenyl group (eg allyl), aralkyl group (eg benzyl, 4
-Methylbenzyl, phenethyl), a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl), a carbamoyl group (for example, unsubstituted carbamoyl, methylcarbamoyl, phenylcarbamoyl),
Sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide group (eg, acetamide, benzamide), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), acyloxy Group (eg acetyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy), ureido group (eg unsubstituted ureido, methylureido, ethylureido, phenylureido), acyl group (eg acetyl, benzoyl), oxycarbonyl group (Eg methoxycarbonyl, phenoxycarbonyl), oxycarbonylamino group (eg methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarboxyl) Boniruamino), it may be substituted with hydroxyl group and the like.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Q represents an integer of 1 to 3, but when q represents 2 or 3, each R _a1 may be the same or different. In general formula (A), Q _a1 preferably represents a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a triazaindene ring, a tetraazaindene ring, a pentaazaindene ring, and L _a1 -R _a1 represents a carvone. It represents an alkyl group having 1 to 6 carbon atoms, which is substituted with one or two groups selected from an acid or a salt thereof, a sulfonic acid or a salt thereof, and q represents 1 or 2. Among the compounds represented by the general formula (A), more preferable compounds include the compounds represented by the general formula (A-1). General formula (A-1)

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

[Chemical 19]

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

In the formula, M _a1 and R _a1 have the same _{meanings as} in the general formula (A). T and U represent C—R _a2 or N, and R _a2 represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamido group, a sulfonamide group or a ureido group. Or R _a1 . However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A). Next, general formula (A-1) will be described in detail. T and U represent C—R _a2 or N, and R _a2 is a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom), a hydroxy group, a nitro group, an alkyl group (eg methyl, ethyl, methoxyethyl, n-butyl). , 2-ethylhexyl), alkenyl groups (eg allyl), aralkyl groups (eg benzyl, 4-methylbenzyl, phenethyl, 4-methoxybenzyl), aryl groups (eg phenyl, naphthyl, 4-methanesulfonamidophenyl, 4) -Methylphenyl), carbonamido group (eg, acetylamino, benzoylamino, methoxypropionylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), ureido group (eg, unsubstituted) Ureido, Methyl Ureido, Fe Ruureido), or represents a R _a1. However, when R _a2 represents R _a1 , it may be the same as or different from R _{a1 in the} general formula (A).
In the general formula (A-1), preferably T = U = N or T =
U = C-R _a2 , wherein R _a2 is a hydrogen atom and has 1 to 4 carbon atoms.
Wherein L _a1 -R _a1 represents an alkyl group having 1 to 4 carbon atoms and substituted with one or two groups selected from carboxylic acid or a salt thereof, sulfonic acid or a salt thereof. Specific examples of the compound represented by formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Where X_b2Is N or C-R_b3Represents,
Y_b1Is O, S, N or NR_b4Represents Z_b1Is N,
N-R_b5Or CR_b6Represents R_b2, R_b3, R_b4,
R_b5And R_b6Is an aliphatic group, aromatic group, heterocyclic group,
Group, acylamino group, sulfonamide group, ureido
Group, sulfamoylamino group, acyl group or carbamo
Represents an yl group. However, R_b3And R_b6Is a hydrogen atom
It may be. Also, R_b2And R_b3, R_b2And R_b5, R_b2When
R_b6, R_b4And R_b5And R_b4And R_b6May form a ring
Yes. For details on the compound represented by the above general formula (B-1)
I will explain in detail. R_b2, R_b3, R_b4, R_b5And R_b6Fat
Aliphatic group, aromatic group, heterocyclic group, amino group, acylamino
Group, sulfonamide group, ureido group, sulfamoyl group
The mino, acyl and carbamoyl groups are substituted
Good. In formula (B-1), preferably X_b2Is N, C-
R_b3Represents Y_b1Is NR_b4Or S or O,
Z_b1Is N or C-R_b6And R_b2, R_b3Or R
_b6Is a substituted or unsubstituted alkyl group, substituted or unsubstituted
Substituted alkenyl group, substituted or unsubstituted alkynyl
Represents a group or a substituted or unsubstituted heterocyclic group. However
R_b3And R_b6May be a hydrogen atom. R
_b4Is a substituted or unsubstituted alkyl group, substituted or
Unsubstituted alkenyl group, substituted or unsubstituted alkynyl
Group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted
Substituted amino groups are preferred. From general formula (B-1),
Preferably X_b2Represents N, Y_b1Is NR_b4Represents
Then Z_b1Is CR_b6Represents R_b2And R_b4Is the carbon number
Represents an alkyl group of 1 to 6, R_b6Is hydrogen atom or charcoal
It represents an alkyl group having a prime number of 1 to 6. However, R_b2, R_b4Oh
And R_b6At least one of the alkyl groups is at least
Also one carboxylic acid group, sulfonic acid group, amino group, phosphine
Those substituted with a hono group are more preferable. Book below
Specific examples of the compound of the general formula (B) of the invention are shown below.
Is not limited to this.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

A_C1And A_C2Is -S-, -O-, -NR
_C20-, -CO-, -SO₂-Or any combination of them
The combined groups are represented, and examples of groups arbitrarily combined are:
CONR_C21-, -NR_C22CO-, -NR_C23CON
R_C24-, -COO-, -OCO-, -SO₂NR_C25
-, -NR_C26SO₂-, -NR_C27CONR_C28-Etc
Can be given. r represents an integer of 1 to 10. However,
L_C1And L_C3At least one of -SO₃M_C1, -PO
₃M_C2M_C3, -NR_C1(R_C2) (Hydrochloride, acetate, etc.
It may be in the form of a salt, for example, unsubstituted amino, methylamino,
Dimethylamino, N-methyl-N-hydroxyethyl
Mino, N-ethyl-N-carboxyethylamino),-
N⁺R_C3(R_C4) (R_C5) ・ X _C1 ^-(For example, Trimethy
Luan monio chloride), -SO₂NR_C6(R_C7) (Example
For example, unsubstituted sulfamoyl, dimethylsulfamoy
Le), -NR_C8SO₂R_C9(For example, methanesulfone
Amide, benzenesulfonamide), -CONR_C10(R
_C11) (Eg, unsubstituted carbamoyl, N-methylcalcyl)
Vamoyl, N, N-bis (hydroxyethyl) carbamo
Ill), -NR_C12COR_C13(For example, formami
De, acetamide, 4-methylbenzoylamino),-
SO₂R_c14(For example, methanesulfonyl, 4-chloro
Phenylsulfonyl), -PO (-NR
_C15(R_C16))₂(For example, an unsubstituted phosphonamide,
Tetramethylphosphonamide), -NR_C17CONR
_C18(R_C19) (Eg, unsubstituted ureido, N, N-di)
Methylureido), heterocyclic groups (eg pyridyl, imine
Dazolyl, thienyl, tetrahydrofuranyl) -COO
M_C4Be replaced with.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

M _C1 , M _C2 , M _C3 and M _C4 are hydrogen atoms or counter cations (eg, alkali metal atoms such as sodium atom and potassium atom, magnesium atom, alkaline earth metal atoms such as calcium atom, ammonium). , Ammonium groups such as triethylammonium)
Represents R _{C1 to} R _C28 are a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, benzyl, phenethyl, vinyl, propenyl, 1-methylvinyl),
Represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl), and X ⁻ represents a counter anion (eg, halogen ion such as chlorine ion, bromide ion). , Nitrate ion,
Sulfate ion, acetate ion, p-toluenesulfonate ion). When each of L _C1 , L _C2 , L _C3 , and R _{C1 to} R _C28 has a substituent, the substituent has 1 to 10 carbon atoms.
4 lower alkyl groups (eg methyl, ethyl), aryl groups having 6 to 10 carbon atoms (eg phenyl, 4-methylphenyl), aralkyl groups having 7 to 10 carbon atoms (benzyl), 2 to 4 carbon atoms Alkenyl group (eg, propenyl), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group), halogen atom (eg, chlorine atom, bromine atom), cyano group, nitro group, carboxylic acid group (of salt) Form may be used), a hydroxy group and the like.
When r is 2 or more, A _C1 and L _C2 may be any combination of the groups mentioned above. Also, at least one of A _C1 and A _C2
Represents -S-.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

In general formula (C), preferably at least one of L _C1 and L _C3 is --SO ₃ M _C1 , --PO ₃ M _C2 M _C3 ,-
NR _C1 ( _RC2 ), -N ⁺ _RC3 ( _RC4 ) ( _RC5 )
X _C1 ^-, carbon atoms substituted by a heterocyclic group -COOM _C4. 1 to
6 represents an alkyl group, and L _C2 represents an alkylene group having 1 to 6 carbon atoms. A _C1 and A _C2 represent -S-, -O- or -NR _C20- , and R _C1 , R _C2 , R _C3 , R _C4 and R _C5.
And R _C20 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 6. General formula (C)
And more preferably L _C1 and L _C3 are —SO ₃ M _C1 , —P.
O ₃ M _C2 M _C3 —COOM _C4 is an alkyl group having 1 to 4 carbon atoms, wherein A _C1 and A _C2 represent —S—, and r
Represents an integer of 1 to 3. Hereinafter, the general formula (C) of the present invention will be described.
Specific examples of the compound are shown below, but the present invention is not limited thereto.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

In the present invention, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain substantially no ammonium ion. The phrase "substantially free of ammonium ions" refers to a state in which the concentration of ammonium ions in the treatment liquid is 10 mmol / liter or less. The content is preferably 3 mmol / liter or less, and more preferably no content. Ammonium ions are required to be reduced from the viewpoint of recent global environmental protection. In order to reduce the ammonium ion concentration to the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, particularly alkali metal ions are preferable, and lithium ion, sodium ion, and potassium ion are particularly preferable. However, specifically, sodium salts and potassium salts of an organic acid ferric iron complex as a bleaching agent, potassium bromide as a rehalogenating agent in a treatment liquid having a bleaching ability, sodium bromide, potassium nitrate, Examples thereof include sodium nitrate. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferable.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0100

[Correction method] Change

[Correction content]

[0100]

[Chemical 36]

[Procedure amendment 20]

[Document name to be amended] Statement

[Name of item to be corrected] 0119

[Correction method] Change

[Correction content]

As can be seen from Table 3, according to the present invention,
It can be seen that good results are obtained in all of desilvering property, bleaching fog, color recoloring property and stability of fixing solution. Example 3 In Example 1, No. 10 bleach was added to compound I-2,
I-3, I-4, I-9, I-18, I-19, I-2
1, I-26, I-38, I-40, I-41, I-4
The same test as in Example 1 was conducted by substituting the Fe (III) salt of No. 3 for each. As a result, similar to Example 1, good results were obtained. Example 4 In Example 1, the fixing agent No. 10 was changed to A-1, A-
4, A-10, A-12, A-13, B-1, C-1,
The same test as in Example 1 was conducted by substituting C-2, C-5, C-6, D-2, and D-21, respectively. As a result, similar to Example 1, good results were obtained. Example 5 A sample prepared in the same manner as the multilayer color photographic paper sample 103 of Example 1 of JP-A-4-145433 was cut, then imagewise exposed and bleach-fixed in the following processing steps using a paper processor. Continuous treatment (running test) was performed until the replenishment amount of the liquid became twice the tank volume. Also, after that,
A sample exposed to white light was prepared and subjected to the same processing steps.

Claims (2)

[Claims] 1. In a processing method of color-developing and desilvering a silver halide color photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, a bleaching agent in the desilvering treatment is used. A metal chelate compound of a compound represented by the following general formula (I), wherein the fixing agent is a compound represented by the following general formula (A), (B), (C) or (D). A method for processing a silver halide color photographic light-sensitive material. General formula (I) In the formula, Y ₁ represents a non-metal atom group necessary for forming an aromatic hydrocarbon group or a heterocyclic group. R ₁ represents a substituent.
n represents an integer of 0 to 4. When n represents an integer of 2 to 4, R ₁ may be the same or different. X
₁ represents a hydrogen atom or -L ₁ -A ₂ . X ₂ is -L _2-
A ₃ or [Chemical formula 2] Represents X ₃ represents a hydrogen atom, or -L ₄ -A _4. L
₁ , L ₂ , L ₃ and L ₄ each represent an alkylene group or an arylene group. W ₁ represents a divalent linking group. A ₁ ~
A ₅ is a hydrogen atom, a carboxylic acid or a salt thereof,
It represents a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, a hydroxy group, a hydroxyalkyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, an alkoxy group, an alkylthio group or an amino group. However, at least one of A _{1 to} A ₅ represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, or a hydroxy group, and when X ₂ is -L ₂ -A ₃ , A ₁ is never a hydrogen atom. General formula (A) In the formula, Q _a1 represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. The heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. L _a1 represents a single bond, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a connecting group in which these are combined. R _a1 represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium salt. q represents an integer of 1 to 3, M _a1 represents a hydrogen atom or a cation. General formula (B): In the formula, Q _b1 represents a 5- or 6-membered mesoionic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X _b1 ^— represents —O ^— , —S ^— or —N.
^- representing the R _b1. R _b1 represents an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Formula (C) L _C1- (A _C1 -L _C2 ) _r -A _C2 -L _{C3 In the} formula, L _C1 and L _C3 may be the same or different and each is an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. Represents a cyclic group, and L _C2 represents a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic linking group, or a linking group combining them. A
_C1 and A _C2 are respectively -S-, _-O- , -NR _C20- ,
-CO -, - it represents a or group composed of a combination of them - SO _2. r represents an integer of 1 to 10. However, L _C1 and L
_C3 at least one -SO ₃ M _C1, -PO ₃ M
_{C2 M C3, -NR C1 (R} C2), - N + R C3 (R C4)
^{_{(R C5) · X C1 -}} , -SO 2 NR C6 (R C7), - NR C8
_{SO 2 R C9, -CONR C10 (} R C11), - NR C12 C
_{OR C13, -SO 2 R C14,} -PO (-NR C15 (R
_C16 )) ₂ , -NR _C17 CONR _C18 ( _RC19 ), -C
It is assumed to be substituted with OOM _C4 or a heterocyclic group.
M _C1 , M _C2 , M _C3 and M _C4 may be the same or different and each represents a hydrogen atom or a counter cation. M _C1 ~ M _C20
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic hydrocarbon group, and X _C1 ⁻ represents a counter anion. Provided that at least one of A _C1 and A _C2 represent -S-. General formula (D) In the formula, X _d and Y _d are an aliphatic group, an aromatic hydrocarbon group, a heterocyclic group, —N (R _d1 ) R _d2 , —N (R _d3 ) N (R _d4 ) R
represents _d5 , -OR _d6 , or -SR _d7 . Note that X _d and Y _d
May form a ring but does not enolize.
However, at least one of X _d and Y _d is a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium group,
It is assumed that it is substituted with at least one of the hydroxyl groups.
R _d1 , R _d2 , R _d3 , R _d4 and R _d5 represent a hydrogen atom, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group, and R _d6 and R _d6
d7 represents a hydrogen atom, a cation, an aliphatic group, an aromatic hydrocarbon group or a heterocyclic group. 2. As a bleaching agent, at least one metal chelate compound of the compound represented by the general formula (I) according to claim 1 and as a fixing agent, the general formulas (A) and (B) according to claim 1. A bleach-fixing composition for photographic use, containing at least one compound represented by (C) or (D).