JPH1069043A - Color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain rapid processing aptitude and superior graininess by processing an imagewise exposed silver halide color photographic sensitive material with a developing solution containing a specified color developing agent and then processing it with a processing solution containing a ferric complex salt of a specified compound and having a bleaching power. SOLUTION: The imagewise exposed color photographic sensitive material is developed with the developing solution containing a color developing agent represented by formula I and processed with the processing solution containing the ferric complex salt of the compound represented by formula II, and in formulae I and II, each of R1 -R6 is, independently, an H atom or a substituent; R7 is an alkyl or aryl or heterocyclic group; R8 is a substituent; (m) is 0, 1, 2, or 3; R11 is an H atom or an aliphatic hydrocarbon group or the like; L1 is an alkylene group; R12 is an aliphatic hydrocarbon or aryl group or the like; and each of M1 and M2 is a 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 forming a color image using a silver halide photographic light-sensitive material. The present invention relates to a color image forming method which is low in graininess and excellent in graininess.

[0002]

2. Description of the Related Art In a color image forming method using a silver halide color photographic light-sensitive material, many N, N-dialkylparaphenylenediamine compounds have been known as a color developing agent used in a color developing solution. . In the desilvering step of oxidizing (bleaching) the developed silver generated by color development and converting it to soluble silver and removing it, as a bleaching agent,
A ferric ethylenediaminetetraacetic acid complex salt or a 1,3-diaminopropanetetraacetic acid ferric complex salt is used. A color image is formed by a fixing step using a thiosulfate as a fixing agent, followed by a washing and / or stabilizing step. Recently, various color developing agents have been studied for rapid processing. For example, a tetrahydroquinoline-based compound as a developing agent having low fog and capable of rapid processing is disclosed in
No. 287370. However,
Further improvements have been demanded in terms of achieving both rapid development and bleaching stain and reducing the color density during bleaching.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a color image forming method suitable for rapid processing and excellent in graininess. Another object of the present invention is to provide a color image forming method in which generation of stain after processing and reduction in color density are small.

[0004]

According to the present invention, there is provided an electronic apparatus comprising:
And the silver halide color image forming methods described in (1) to (4). (1) An image-exposed silver halide color photographic material is developed with a developer containing at least one color developing agent represented by the following general formula (D), and then developed by the following general formula (I) ,
A method for forming a color image, comprising processing with a processing solution having at least one bleaching ability, which comprises at least one ferric complex salt of the compound represented by formula (II) or (III). General formula (D)

[0005]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
₆ may be the same or different and each represents a hydrogen atom or a substituent. Where R ₁ and R ₂ , R ₃ and R ₄ and R
_{In the} group consisting of each combination of ₅ and R ₆ , at least one pair is a substituent. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₈ represents a substituent, and m represents an integer of 0 to 3. General formula (I)

[0007]

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In the formula, R ₁₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. L ₁ represents an alkylene group; R ₁₂ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. M ₁ and M ₂ each represent a hydrogen atom or a cation. General formula (II)

[0009]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group hydroxy group or a carboxy group. t and u each represent 0 or 1. w represents a divalent linking group containing a carbon element. Each M _21, M _22, M ₂₃ and M ₂₄ represent a hydrogen atom or a cation. General formula (III)

[0011]

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In the formula, Q represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring. p represents 0 or 1. M
₄ represents a hydrogen atom or a cation. (2) The color image forming method according to (1), wherein the color development processing time is 90 seconds or less. (3) In the above (1), the processing solution having bleaching ability is combined with at least one of the compounds represented by the general formulas (I) and (III) and contains a ferric complex salt thereof. Color image forming method. (4) A color image forming method according to the above (1), wherein the processing solution having bleaching ability contains at least one ferric complex salt of the compound represented by the general formula (II).

The compound used in the present invention will be described in more detail. In the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ in the compound represented by the general formula (D)
R ₇ , R ₈ and m will be described in detail below. R ₁ , R
₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or a substituent. More specifically, R ₁ ,
R ₂ , R ₃ and R ₄ are a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, and a sulfo group. , Alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group , An aryloxycarbonyl group and an acyl group. These are alkyl groups,
It may be substituted with an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom, or another substituent formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom.

Further examples of the substituents of R ₁ , R ₂ , R ₃ and R ₄ are shown below. Examples of the halogen atom include a fluorine atom and a chlorine atom. The alkyl group has 1 to 2 carbon atoms.
5, preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2- Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, hydroxymethyl, 2-carboxylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2, 3-dihydroxypropyl, 3,4-dihydroxybutyl, methanesulfonamidomethyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobuty , 4-carbamoyl-butyl, 2
-Carbamoyl 1-methylethyl, carbamoylaminomethyl, 4-nitrobutyl, 2- (2-hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy)
Ethoxy] ethyl, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl, 2- [2-
(2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethyl, 2- (2-methoxyethoxy) ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl, 2- (2- [2- (2-methoxyethoxy) ethoxy] ethoxy) ethyl, 2- [2- (2-
[2- (2-methoxyethoxy) ethoxy] ethoxy)
Ethoxy] ethyl, 2- (2-ethoxyethoxy) ethyl and 2- [2- (2-butoxyethoxy) ethoxy] ethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the kind of element may be one or more, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl, and pyrazolyl. The alkoxy group is an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, for example, phenoxy, p-methoxyphenoxy, m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms.
-Methoxypropionamide, p-nitrobenzoylamide. The alkylamino group has 1 to 1 carbon atoms.
6, preferably an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino and 2-hydroxyethylamino. The anilino group has 6 to 2 carbon atoms.
Examples of the anilino group 4 include anilino, m-nitroanilino, and N-methylanilino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as ureide, methyl ureide, N, N-diethyl ureide and 2-methanesulfonamidoethyl ureide.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably 0 to 6 carbon atoms, for example, dimethylsulfamoylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino. The alkylthio group has 1 to 1 carbon atoms.
16, preferably an alkylthio group having 1 to 6 carbon atoms, for example, methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, such as phenylthio, 2-carboxyphenylthio, and 4-cyanophenylthio. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
16, preferably an alkoxycarbonylamino group having 2 to 6 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino. The sulfonamide group is a sulfonamide group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as carbamoyl, N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group has 0 to 1 carbon atoms.
6, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl. The sulfonyl group has 1 carbon atom
To 16, preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl and 2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl. The heterocyclic oxy group has 1 to 1 carbon atoms.
5 is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen, nitrogen or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are one. However, the number may be plural, such as 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy and 2-pyridyloxy.

The azo group is an azo group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms.
Hydroxy-4-propanoylphenylazo and 4-sulfophenylazo. The acyloxy group is an acyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group is a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy, and N-phenylcarbamoyloxy. The silyl group is a silyl group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl,
t-butyldimethylsilyl. The silyloxy group is a silyloxy group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, such as phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, and 2,6-dimethoxyphenoxycarbonylamino. The imide group has 4 to 1 carbon atoms
The imide group 6 is, for example, N-succinimide or N-phthalimide. The heterocyclic thio group has 1 to 5 carbon atoms.
Is a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom or sulfur atom, having at least one heteroatom and one kind of element constituting the ring. It may be plural, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group has 1 to 16 carbon atoms,
Preferably it is a C1-C6 sulfinyl group, for example, methanesulfinyl, benzenesulfinyl, and ethanesulfinyl. The phosphonyl group has 2 to 1 carbon atoms.
6, preferably a phosphonyl group having 2 to 6 carbon atoms, for example,
Methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, 2-methylphenoxycarbonyl, and 4-acetamidophenoxycarbonyl. As the acyl group, an acyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl,
4-chlorobenzoyl.

R ₅ and R ₆ represent a hydrogen atom or a substituent. In this case, the substituent represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . However, R ₅ , R ₆
Is a heterocyclic group, it is bonded to a carbon atom constituting the heterocyclic ring of the heterocyclic group. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. For details, see R ₁ ,
It has the same meaning as that described for R ₂ , R ₃ and R ₄ . However, when R ₇ is an alkyl group, among the carbon atoms in R ₇ , the carbon atom directly bonded to the nitrogen atom in the general formula (D) includes a hydrogen atom and a carbon atom other than the two elements. Are not combined. When R ₇ is a heterocyclic group, the nitrogen atom in the general formula (D) to which R ₇ is bonded is connected to a carbon atom constituting the hetero ring of the heterocyclic group. R ₈ represents a substituent. For details, see R ₁ , R ₂ , R
₃ and is synonymous to those described in R _4. m represents an integer of 0 to 3.

Among the compounds represented by the general formula (D),
Compounds represented by the following formulas (DD-1) and (DD-2) are particularly preferred. General formula (DD-1)

[0021]

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Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R
₁₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each of R ₁₁ and R _12, R ₁₃ and R _14, R ₁₅ and R _16, which is at least one of both substituents. R ₁₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₁₈ represents a hydrogen atom or a substituent. General formula (DD-2)

[0023]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆
May be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each of R ₂₁ and R _22, R ₂₃ and R _24, R ₂₅ and R _26, which is at least one of both substituents. R ₉ and R ₂₈ represent a hydrogen atom or a substituent, and n represents an integer of 2 to 8.

In the general formula (DD-1), R ₁₁ , R ₁₂ ,
Preferred combinations of R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ will be described below. R ₁₈ is a hydrogen atom, an alkyl group or an alkoxy group, R ₁₇ is an alkyl group, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Is preferably a combination each of which is a hydrogen atom or an alkyl group. Here, the alkyl group and the alkoxy group include those substituted with another substituent. In this combination,
More preferably, at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group, a carboxyl group , A sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group is preferable. Particularly, it is preferably an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group.

As a more preferred combination, R ₁₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or
And R ₁₇ is an alkyl group having 1 to 6 carbon atoms, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this combination, it is more preferable that at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group. , A carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group. It is particularly preferable that the alkyl group is substituted with a hydroxyl group, a carboxyl group, a ureido group or a sulfonamide group.

More preferably, R ₁₈ is an alkyl group having 1 to 6 carbon atoms, and R ₁₇ is an alkyl group having 1 to 6 carbon atoms.
It is preferable that R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this combination, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈
It is more preferable that at least one of them is an alkyl group substituted with a water-soluble group, and further a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, and a sulfamoyl. It is preferably an alkyl group substituted with an amino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group, particularly an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group. Is preferred.

In a more preferred combination, R ₁₈ is a methyl group and an isopropyl group, and R ₁₇ has 1 carbon atom.
And R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
_{A combination in which 15} and R ₁₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. In this combination, it is more preferable that at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is an alkyl group substituted with a water-soluble group, and further a hydroxyl group, a carboxyl group , A sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkyl group substituted with a sulfonyl group is preferable. Particularly, it is preferably an alkyl group substituted with a hydroxyl group, a carboxyl group, a ureido group, or a sulfonamide group.

In the general formula (DD-2), R ₂₁ , R ₂₂ ,
Preferred combinations of R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₉ and R ₂₈ will be described below. R ₂₈ is a hydrogen atom, an alkyl group or an alkoxy group, R ₉ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are Combinations each being a hydrogen atom or an alkyl group are preferred. Here, the alkyl group, the alkoxy group, the aryl group and the heterocyclic group include those substituted by other substituents. As the substituent, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group is preferable. Particularly, a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are preferred.

Next, specific examples of the representative developing agent represented by the formula (D) in the present invention are shown, but the invention is not limited thereto.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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As a more preferred combination, R ₂₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group having 1 carbon atom.
R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂₁ , R ₂₂ , R ₂₃ ,
R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom or a carbon atom
Combinations of ~ 3 alkyl groups are preferred. Here, the alkyl group and the alkoxy group include those substituted with another substituent. As a substituent, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group,
A sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group is preferred, and a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are particularly preferred.

More preferably, R ₂₈ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
It is preferable that R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Here, the alkyl group includes those substituted with another substituent. As the substituent, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an acylamino group, an amino group, an alkylamino group, a ureido group,
A sulfamoylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group is preferred, and a hydroxyl group, a carboxyl group, a ureido group and a sulfonamide group are particularly preferred.

In a more preferred combination, R ₂₈ is a methyl group and an isopropyl group, R ₉ is a hydrogen atom and a methyl group, and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅
And a combination in which R ₂₆ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, respectively. Here, the alkyl group includes those substituted with another substituent. As the substituent, a hydroxyl group, a carboxyl group, a sulfo group,
Alkoxy, acylamino, amino, alkylamino, ureido, sulfamoylamino, sulfonamide, carbamoyl, sulfamoyl or sulfonyl are preferred, especially hydroxyl, carboxyl, ureido, sulfonamide. Is preferred.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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The compound represented by the general formula (D) is very unstable when stored as a free amine,
In general, it is preferable to produce and store the salt as a salt of an inorganic acid or an organic acid, and then to form a free amine for the first time when the salt is added to the treatment solution. Examples of the inorganic and organic acids that form a salt of the compound of the formula (D) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-
1,5-disulfonic acid and the like can be mentioned. Among these, a salt of sulfuric acid or p-toluenesulfonic acid is preferable, and salt formation as a salt with sulfuric acid is most preferable. The color developing agent of the present invention is, for example, a journal of the
It can be easily synthesized according to the methods described in American Chemical Society 73, 3100 (1951), JP-A-7-287,370, and Japanese Patent Application 8-121,472. .

Next, the compound represented by formula (I) will be described in detail. The number of carbon atoms described below is the number of carbon atoms excluding the substituent. The aliphatic hydrocarbon group represented by R ₁₁ includes a linear, branched or cyclic alkyl group (preferably having 1 to 12, more preferably 1 to 10, and still more preferably 1 to 8), and an alkenyl group (preferably Represents an alkynyl group (preferably having 2 to 12 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 10, more preferably 2 to 7);
It is more preferably 2 to 10, further preferably 2 to 7), and may have a substituent. Examples of the substituent include an aryl group (preferably having 6 to 12 carbon atoms, more preferably having 6 to 10 carbon atoms, particularly preferably having 6 to 8 carbon atoms, and examples thereof include phenyl and p-methylphenyl). Alkoxy group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 6 carbon atoms)
4, for example, methoxy, ethoxy and the like. ), An aryloxy group (preferably having 6 to 1 carbon atoms)
2, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, such as phenyloxy. ), Acyl group (preferably 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 2 carbon atoms)
8, for example, acetyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and particularly preferably having 2 to 2 carbon atoms.
8, for example, methoxycarbonyl and the like. ), An acyloxy group (preferably having 1 to 12 carbon atoms,
More preferably, it has 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as acetoxy. ), An acylamino group (preferably having 1 to 10 carbon atoms,
More preferably 2 to 6 carbon atoms, particularly preferably 2 carbon atoms
To 4, for example, acetylamino and the like. ), A sulfonylamino group (preferably having 1 to 1 carbon atoms)
0, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methanesulfonylamino. ), A sulfamoyl group (preferably having 0 to 10 carbon atoms, more preferably having 0 to 6 carbon atoms, particularly preferably having 0 to 4 carbon atoms, such as sulfamoyl and methylsulfamoyl), and a carbamoyl group ( Preferably 1 to 10 carbon atoms, more preferably 1 carbon atom
To 6, particularly preferably 1 to 4 carbon atoms, such as carbamoyl and methylcarbamoyl. ),
An alkylthio group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, such as methylthio and ethylthio, etc.), and a sulfonyl group (preferably having 1 carbon atom). -8, more preferably 1-6 carbon atoms, particularly preferably 1-4 carbon atoms.
And for example, methanesulfonyl and the like. ), A sulfinyl group (preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 1 carbon atoms)
4, for example, methanesulfinyl and the like. ), A hydroxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxy group, a nitro group, and a heterocyclic group (eg, imidazolyl, pyridyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent of the aliphatic hydrocarbon group represented by R ₁₁ is preferably an alkoxy group, a carboxy group, a hydroxy group, or a sulfo group, and more preferably a carboxy group or a hydroxy group. Preferably the aliphatic hydrocarbon group represented by R ₁₁ is an alkyl group, more preferably a linear alkyl group, more preferably methyl, ethyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl,
1,2-dicarboxyethyl, 1-carboxy-2-hydroxyethyl, 2-carboxy-2-hydroxyethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-
Sulfoethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2- (4-imidazolyl) ethyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl , 2-carbamoyl-1-carboxyethyl, 4-imidazolylmethyl, and particularly preferably methyl, carboxymethyl, 1-carboxyethyl, 2-
Carboxyethyl, 1,2-dicarboxyethyl, 1-
Carboxy-2-hydroxyethyl, 2-carboxy-
2-hydroxyethyl, 2-hydroxyethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl. The aryl group represented by R ₁₁ is preferably a monocyclic or bicyclic aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably 6 carbon atoms.
To 15 phenyl groups, more preferably 6 to 10 phenyl groups. The aryl group represented by R ₁₁ may have a substituent. Examples of the substituent include those exemplified as the substituent of the aliphatic hydrocarbon represented by R ₁₁ and an alkyl group (preferably having 1 carbon atom). To 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, methyl, ethyl and the like.), Alkenyl group (preferably 2 to 8 carbon atoms, more preferably carbon number) 2 to 6, particularly preferably 2 to 4 carbon atoms, for example, vinyl, allyl, etc.), alkynyl group (preferably 2 to 2 carbon atoms)
8, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as propargyl. ) And the like. The preferred substituent of the aryl group represented by R _11, an alkyl group, an alkoxy group, hydroxy group, a sulfo group, more preferably an alkyl group, a carboxy group, hydroxy group. Specific examples of the aryl group represented by R ₁₁ include 2-carboxyphenyl, 2-carboxymethoxyphenyl, and the like. The heterocyclic group represented by R ₁₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, which may be a single ring, It may form a condensed ring with another ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, more preferably a 5- to 6-membered aromatic heterocyclic group containing a nitrogen atom, and further preferably a nitrogen atom having 1 to 2 atoms. And a 5- or 6-membered aromatic heterocyclic group. Specific examples of the heterocyclic group include, for example, pyrrolidinyl, piperidyl, piperazinyl, imidazolyl, pyrazolyl, pyridyl, quinolyl and the like, and preferably imidazolyl and pyridyl. The heterocyclic group represented by R ₁₁ may have a substituent. Examples of the substituent include those exemplified as the substituent of the aliphatic hydrocarbon represented by R ₁₁ and an alkyl group (preferably having a carbon number of 1 to 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methyl, ethyl and the like.), Alkenyl group (preferably 2 to 8 carbon atoms, more preferably carbon 2 to 6, particularly preferably 2 to 4 carbon atoms, for example, vinyl, allyl, etc.), alkynyl group (preferably 2 to 8 carbon atoms, more preferably 2 to 2 carbon atoms)
6, particularly preferably having 2 to 4 carbon atoms, such as propargyl. ) And the like. The substituent of the heterocyclic group represented by R ₁₁ is preferably an alkyl group, an alkoxy group, a hydroxy group, or a sulfo group, and more preferably an alkyl group, a carboxy group, or a hydroxy group. R ₁₁ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom, methyl, ethyl, 1-carboxyethyl, 2-carboxyethyl,
They are hydroxyethyl and 2-carboxy-2-hydroxyethyl, and particularly preferably a hydrogen atom. Examples of R ₁₂ include the groups described for R ₁₁ , and preferred examples include those described for R ₁₁ . The alkylene group represented by L ₁ may be linear, branched or cyclic. Further, it may have a substituent, and examples of the substituent include those exemplified as the substituent of the aliphatic hydrocarbon represented by R ₁₁ , and an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 6, particularly preferably 2 to 2 carbon atoms
4, for example, vinyl, allyl and the like. ), Alkynyl group (preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms)
And, for example, propargyl and the like. ) And the like. The substituent of the alkylene group represented by L ₁ is preferably an aryl group, an alkoxy group, a hydroxy group, a carboxy group, or a sulfo group, and more preferably an aryl group, a carboxy group, or a hydroxy group. The alkylene group represented by L ₁ preferably has 1 to 6 carbon atoms in the alkylene group portion, and more preferably has 1 carbon atom.
To 4, more preferably substituted or unsubstituted methylene or ethylene. Preferred specific examples of the alkylene group include, for example, methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1,2-cyclohexylene,
1-carboxymethylene, carboxymethyltimerene,
Carboxyethylmethylene, hydroxymethylmethylene, 2-hydroxyethylmethylene, carbamoylmethylmethylene, phenylmethylene, benzylmethylene,
-Imidazolylmethylmethylene, 2-methylthioethylmethylene, more preferably methylene, ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethylmethylene, hydroxy Methyl methylene, benzyl methylene,
4-imidazolylmethylmethylene, 2-methylthioethylmethylene, and more preferably methylene, ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethyltimene, hydroxymethylmethylene , Benzylmethylene. The cations represented by M ₁ and M ₂ represent organic or inorganic cations, such as alkali metals (Li ⁺ , Na ⁺ , K ⁺ , Cs ^+, etc.), and alkaline earth metals (Mg ²⁺ , Ca ^2+). ), Ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium,
1,2-ethanediammonium, etc.), pyridinium,
Examples include imidazolium and phosphonium (such as tetrabutylphosphonium). M ₁ and M ₂ are preferably alkali metals and ammonium, and more preferably Na ⁺ , K ⁺ and NH ₄ ⁺ . Among the compounds represented by the general formula (I), a compound represented by the general formula (Ia) is preferable. General formula (Ia)

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(In the formula, L ₁ and M ₁ have the same meanings as those in formula (I), and the preferred ranges are also the same. M _a1 and M _{a2 each} represent M ₂ in formula (I) In formula (Ia), L ₁ is more preferably a substituted or unsubstituted methylene or ethylene, and M ₁ ,
M _a1 and M _a2 are each a hydrogen atom, an alkali metal, or ammonium; more preferably, L ₁ is a substituted or unsubstituted methylene; and M ₁ , M _a1 , and M _a2 are a hydrogen atom or an alkali. A metal or ammonium, and particularly preferably, L ₁ is a substituted or unsubstituted methylene having a total carbon number of 1 to 10 including a substituent,
M ₁ , M _a1 and M _a2 represent a hydrogen atom, Na ⁺ , K ⁺ , NH ₄ ⁺
This is one of the cases. Next, the compound represented by formula (II) will be described in detail. The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are the aliphatic hydrocarbon group represented by R ₁₁ in the general formula (I), the aryl group, It has the same meaning as the heterocyclic group, and the preferred range is also the same. R ₂₁ , R ₂₂ ,
R ₂₃ and R ₂₄ are preferably a hydrogen atom or a hydroxy group, and more preferably a hydrogen atom. t and u are
Each represents 0 or 1, and is preferably 1. The divalent linking group represented by W is preferably represented by the following general formula (W)
Can be represented by Formula ^{(W) - (W 1 -D} ) v - (W 2) w - wherein, W ¹ and W ² may be different even in the same straight-chain or branched having 2 to 8 carbon atoms (E.g., ethylene, propylene, tonomethylene), a C5-C10 cycloalkylene group (e.g., 1,2-cyclohexylene), a C6-C10 arylene group (e.g., o-phenylene), a C7-C7 10, an aralkylene group (eg, o-xylenyl), a divalent nitrogen-containing heterocyclic group,
Or a carbonyl group. The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered heteroatom in which the hetero atom is nitrogen, and is preferably a group connected to W ¹ and W ² at adjacent carbon atoms such as an imidazolyl group. . D is-
Represents O-, -S-, -N ( _Rw )-. R _w represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl) or an aryl group having 6 to 10 carbon atoms (for example, phenyl) which may be substituted by a carboxyl group, a phosphono group, a hydroxy group or a sulfo group. . As W ¹ and W ² , an alkylene group having 2 to 4 carbon atoms is preferable. v represents an integer of 0 to 3, and when v is 2 or 3, W ¹ -D may be the same or different. v is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. w
Represents an integer of 1 to 3, and when w is 2 or 3, W ²
May be the same or different. w is preferably 1 or 2
It is. Examples of W include the following.

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As W, ethylene, propylene, trimethylene and 2,2-dimethyltrimethylene are more preferred, and ethylene and trimethylene are particularly preferred.
M ₂₁ , M ₂₂ , M ₂₃ and M ₂₄ each represent a hydrogen atom or a cation, and these are represented by M ₁ , M ₂ and M 3 in the general formula (I).
Synonymous with ₂ . Among the compounds represented by the general formula (II), those in which R ₂₂ and R ₂₄ are hydrogen atoms, and t and u are preferably 1, and more preferably R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are hydrogen Atom and t and u are 1. General formula (II)
More preferably, R ₂₁ , R ₂₂ ,
R ₂₃ and R ₂₄ are hydrogen atoms, t and u are 1, W is ethylene, M
_{21, M 22, M 23,} M 24 is a hydrogen atom, Na ^+, K ^+, NH
₄ ⁺ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are hydrogen atoms, t and u are 1, W is trimethylene, M ₂₁ ,
M ₂₂ , M ₂₃ and M _{24 each} represent a hydrogen atom, Na ⁺ , K ⁺ , NH ₄ ⁺
It was chosen from When the compound represented by the general formula (I) or (II) has an asymmetric carbon in the molecule, it is preferable that at least one asymmetric carbon is an L-form. Further, in the case of having two or more asymmetric carbons, it is preferable that the asymmetric carbon has a larger L-form structure. Specific examples of the compound represented by the general formula (I) or (II) are shown below, but the present invention is not limited thereto. In addition, compounds described as L in the compounds indicate that the asymmetric carbon portion of the described portion is L-form, and those without description indicate that the compound is a mixture of D and L.

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The above compounds may be those in which the hydrogen atom of the carboxy group has become a cation. In this case, the cation has the same meaning as defined for the cations represented by M ₁ and M ₂ in the general formula (I). The compound represented by the general formula (I) of the present invention is described, for example, in "Journal of Inorganic and Nuclear Chemistry", Vol. 35, p. 523 (1973) (Journal
of Inorganic and Nuclear Chemistry Vol. 35, 52
3 (1973)), Swiss Patent No. 561504, German Patent Nos. 3,912,551 A1 and 3,939,755 A1.
No. 3,939,756 A1, JP-A-5-265159
Nos. 6-59422 (Exemplified Compounds I-42 and I-4)
3, I-46, I-52, and L-53 are described in Synthesis Examples 1, 2, 3, 4, and 6. 6-9
No. 5319 (Exemplified compounds I-8, I-11, I-37,
Synthesis methods of L-forms of I-38 and I-40 are described in Synthesis Examples 2 to 6), JP-A-6-161504, and JP-A-6-1610.
It can be synthesized according to the method described in No. 65 or the like. Compounds represented by the general formula (II) are described in, for example, JP-A-63-19 / 1988.
9295, JP-A-3-173857, "Bulletin of the Chemical Society of Japan", Vol. 46, p. 884 (1973) (Bulletin of Ch.
emical Society of Japan Vol. 46, 844 (197
3)), "Inorganic Chemistry", Vol. 7, 24
05 (1968) (Inorganic Chemistry Vol. 7,
2405 (1968)) (A method for synthesizing L and L forms of Exemplified Compound II-15 is described.).

In the present invention, the compound represented by the general formula (I) or (I
Among the ferric complex salts of the compound represented by I), preferred are ferric complex salts of the compound represented by the general formula (II).

The compound represented by the general formula (I) or (II) is used in a molar ratio of 1.0 or more with respect to iron ions.
This ratio is preferably large when the stability of the metal chelate compound is low, and is usually in the range of 1 to 30.

The ferric complex salt of the compound represented by formula (I) or (II) of the present invention (hereinafter sometimes referred to as the ferric complex salt of the present invention) is a processing solution having a bleaching ability (bleaching solution). Alternatively, the content is preferably 0.005 to 1 mol per liter, more preferably 0.01 to 0.5 mol, and particularly preferably 0.05 to 0.5 mol, per liter. The ferric complex salt of the present invention is used in an amount of 0.005 to 1 liter of the processing solution.
Even when used at a dilute concentration of 0.2 mol, preferably 0.01 to 0.2 mol, more preferably 0.05 to 0.18 mol, excellent performance can be exhibited.

Next, the compound represented by formula (III) will be described in detail. The nitrogen-containing heterocyclic ring formed by Q is a 3- to 10-membered heterocyclic group having a nitrogen atom as a heteroatom, and may be saturated or unsaturated. May further form a condensed ring with another aromatic or heterocyclic ring. The nitrogen-containing heterocyclic ring is preferably a 5- to 6-membered nitrogen-containing unsaturated heterocyclic ring, and more preferably a 5- to 6-membered nitrogen-containing aromatic heterocyclic group. The nitrogen-containing heterocycle is preferably pyridine, pyrazine, pyrimidine, pyridazine, pyrrole, imidazole, pyrazole, thiazole, oxazole, triazole, thiadiazole, triazine, indole, more preferably pyridine, imidazole, pyrazine, and particularly preferably. Is pyridine. The nitrogen-containing heterocyclic ring formed by Q may have a substituent. As the substituent, for example, those mentioned as the substituent which R ₁₁ in formula (I) may have can be applied.

P represents 0 or 1, and is preferably 0. M ₄ has the same meaning as M ₁ and M ₂ in formula (I). Specific examples of the compound represented by the general formula (III) are shown below, but the present invention is not limited thereto.

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The above compounds may be used in the form of an ammonium salt, an alkali metal salt or the like. The compound represented by the above general formula (III) is described in Organic SynthesisC
The compound can be synthesized according to the method described in, for example, Item 3, 3, 740, and the like, or a commercially available product can be used. Among the compounds represented by the general formula (III), preferred are 2-carboxypyridine, 2-carboxypyrazine, 2-carboxyimidazole, 4-carboxyimidazole and derivatives thereof, and particularly preferred is 2-carboxyimidazole.
Carboxypyridine.

The compound represented by the general formula (III) of the present invention is used in an amount of 0.001 to 1 liter of a processing solution having a bleaching ability.
To 0.3 mol, preferably 0.01 to 0.1 mol.
20 mol is more preferable, and 0.05 to 0.15 mol is particularly preferable.

The color developing agent of the present invention can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 4-amino-3-methyl-N, N-diethylaniline P-3 4-amino-3-methyl-N-ethyl-N-
(3-hydroxypropyl) aniline P-4 4-amino-N-ethyl-N- (2-hydroxyethyl) aniline P-5 4-amino-3-methyl-N-ethyl-N-
(2-hydroxyethyl) aniline P-6 4-amino-3-methyl-N-ethyl-N-
(2-methanesulfonamidoethyl) aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4- Amino-3-methyl-N-ethyl-N-
(2-Methoxyethyl) aniline P-10 4-amino-3-methyl-N-ethyl-N-
(4-hydroxybutyl) aniline P-11 4-amino-3-methyl-N-ethyl-N-
(2-butoxyethyl) aniline

As the compound to be combined, particularly preferred among the above-mentioned p-phenylenediamine derivatives are P-3 and P-phenylenediamine derivatives.
5, P-6 or P-10. In addition, these p
-Phenylenediamine derivative and sulfate, hydrochloride, sulfite, p-toluenesulfonate, nitrate, naphthalene-
It is generally used in salts such as the 1,5-disulfonate. In the present invention, the treatment composition may be in a liquid state or a solid state (for example, a powdery state or a granular state). These compounds can be used in combination of two or more depending on the purpose. The amount of the aromatic primary amine developing agent to be used is preferably from 0.001 mol to 1 liter of the color developer.
0.2 mol, more preferably 0.005 mol to 0.1
Is a mole.

In the color developer of the present invention, compounds which directly preserve the aromatic primary amine color developing agent are disclosed in JP-A-63-5341, JP-A-63-106655 or JP-A-4-144446. Various hydroxylamines, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, and phenols described in JP-A-63-44657 and 63-58443. 63-4
Α-Hydroxy ketones and α-amino ketones described in No. 4656, various sugars described in 63-36244 and the like can be contained. Further, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
Monoamines described in JP-A-3-27841 and JP-A-63-25654, JP-A-63-30845, JP-A-63-14
No. 640, No. 63-43139, diamines described in JP-A Nos. 63-21647, 63-26655 and 63-44655, polyamines described in No. 63-44655, and No. 63
Nitroxyl radicals described in JP-A-53551, 63
Alcohols described in JP-A-43140 and JP-A-63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239947 can be used. Other preservatives are disclosed in
Various metals described in Nos. 44148 and 57-53749, salicylic acids described in 59-180588, alkanolamines described in 54-3582, and polyethyleneimines described in 56-94349. And an aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, if necessary.
In particular, when hydroxylamines are used, the above-mentioned alkanolamines and aromatic polyhydroxy compounds are preferably used in combination. Particularly preferred preservatives are disclosed in
These are hydroxylamines represented by the general formula (I) of JP-144446, and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferred. The addition amount of these preservatives is 20 to 200 mmol, preferably 30 to 150 mmol, per liter of the color developer.

Other additives described in JP-A-3-144446 can be used in the color developer of the present invention. For example, carbonic acids, phosphoric acids, boric acids, hydroxybenzoic acids, etc. described in page (9) of the same patent can be used as a buffer for maintaining pH. It is preferable that the pH of the color developer is maintained at 9.0 to 12.5 using these buffers. More preferably, it is 9.5 to 11.5. Examples of the antifoggant include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developer is as high as 20 mmol / L or more, or when processing at a high temperature of 40 ° C. or more, it is preferable that the bromide ion concentration is somewhat high.
It is preferably from 7 mmol / liter to 60 mmol. If necessary, halogen can be removed using an ion-exchange resin or an ion-exchange membrane to control the concentration in a preferable range. As the chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid are preferably used. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N,
N-trimethylene phosphonic acid, ethylenediamine-N,
Compounds represented by N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be used. Preferred chelating agents include compounds having biodegradability. Examples of this are disclosed in JP-A-63-146998, JP-A-63-199295, and JP-A-63-267750.
JP-A-63-267751, JP-A-2-2291
No. 46, JP-A-3-186841, German Patent 3739
610 and EP 468325. Furthermore, development inhibitors such as benzimidazoles, benzothiazoles or mercapto compounds, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers,
A competing coupler, an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, or various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid, if necessary. It may be added.

The replenishment amount of the color developer of the present invention is preferably 550 ml or less per 1 m ^{2 in} the case of a photographic material.
450 ml or less is more preferable, and 400 ml or less, 80
The most preferred is ml or more. By reducing or not including the bromide ion concentration in the replenisher, 300 ml
It can also be: The processing temperature of the color developer is preferably 35 ° C or higher, more preferably 40 ° C or higher and 50 ° C or lower. Processing time of color developer is 3 minutes 15
Seconds or less are preferable, and 30 seconds to 2 minutes 30 seconds are more preferable. It is preferable to prevent evaporation of the liquid and air oxidation. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, more preferably Preferably it is 0.0005-0.01.
As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
A slit developing method described in JP-A-63-216050 can be exemplified. Further, it is preferable that the processing solution in the replenishment tank of the color developer or the processing layer is shielded with a high boiling point organic solvent or a high molecular compound to reduce the contact area with air. Particularly, liquid paraffin, organosiloxane and the like are preferable. Reducing the aperture ratio can be applied not only to both color development and black-and-white development, but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the activity of the developing solution is increased by adding a processing chemical called a regenerating agent, and used again as a processing solution. . In this case, the regeneration rate (the percentage of overflow in the replenisher)
It is preferably at least 50%, particularly preferably at least 70%. As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in Diaion Manual (I) (14th edition of 1986) issued by Mitsubishi Kasei Kogyo. Among the anion exchange resins, JP-A-2-952 and JP-A-1-28115
The resin having the composition described in No. 2 is preferred.

In the present invention, the color-developed photosensitive material is subjected to a desilvering process. The desilvering process referred to here basically comprises a bleaching process and a fixing process, but is constituted by a bleach-fixing process in which these processes are performed simultaneously and a combination of these processes. As the bleaching agent, compounds of the general formulas (I) to (III) can be used. In combination with these compounds, aminopolycarboxylic acid secondary compounds as described in the above-mentioned JP-A-3-144446 (11) are used. Iron salts or salts thereof are preferably used. For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Ferric salts such as glycol ether diamine tetraacetic acid are mentioned. In addition, complex salts such as citric acid, tartaric acid and malic acid can be used as bleaching agents. Among these, iron (III) complex salt of ethylenediaminetetraacetate, and 1,3
Particularly preferred are iron (III) complex salts of aminopolycarboxylic acids including iron (III) complex salt of diaminopropanetetraacetate. These iron (III) aminopolycarboxylic acid complex salts are particularly useful in a bleaching solution and a bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444
No. 94927, No. 54-35727, No. 55-265
Nos. 06 and 58-163940; bromide ions and the like. Among them, a compound having a mercapto group or a disulfide group is preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In the desilvering bath of the present invention, besides the bleaching agent, a rehalogenating agent, a pH buffering agent and known additives described in JP-A-3-144446, page (12), can be used. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pka) of 2
And acetic acid, propionic acid,
Examples include hydroxyacetic acid succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid, adipic acid and the like, with succinic acid, maleic acid and glutaric acid being particularly preferred. The pH of the bleaching solution or the bleach-fixing solution is usually 4.0 to 8.0.
However, in order to speed up the processing, the processing can be performed at a lower pH.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Use is common, especially ammonium thiosulfate being the most widely used. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane Diaminetetraacetic acid, 1,2
-Propylenediaminetetraacetic acid. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred. The fixer and the bleach-fixer have a pKa of 6. for pH adjustment.
It is preferable to contain a compound of 0 to 9.0. For example, it is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / l. The imidazole compound represents imidazole and its derivatives, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom, and the like.
Further, the alkyl group, alkenyl group, and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom, or the like. The preferred total carbon number of the substituents of imidazole is 1 to 6, and the most preferred substituent is a methyl group.

When the replenishment method is employed in the processing of the present invention, the replenishment amount of the fixing solution or the bleach-fixing solution is preferably 100 to 3000 ml per 1 m ² of the light-sensitive material, and more preferably 300 to 1800 ml. Replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher, or by using an overflow solution of the bleaching solution and the fixing solution as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389. You may. In the present invention, the total processing time of the desilvering step comprising a combination of bleaching, bleach-fixing and fixing is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The processing temperature is 30 to 60 ° C, preferably 35 to 60 ° C.
55 ° C.

The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector.

The processing solution having a fixing ability of the present invention can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. The processing solution having the bleaching ability of the present invention can be reused after collecting the overflow solution used for the processing, correcting the composition by adding components, and then reusing it. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied in the form of a powder and also have a low hygroscopicity. Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

After the processing step having a fixing ability, usually,
A water washing process is performed. After processing with a processing solution having fixing ability,
A simple treatment method of performing a stabilization treatment using a stabilizing solution without substantially performing water washing can also be used. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage
e Society of MotionPictureand Television Enginee
rs, vol. 64, pages 248-253 (May 1955). The number of stages is preferably 2 to 4 stages. The replenishing amount is 1 to 50 times, preferably 1 to 30 times, more preferably 1 to 10 times the amount brought in from the previous bath per unit area. Further, as a method of efficiently reducing the replenishment amount, a washing tank or a stabilizing bath is divided by a partition wall,
A so-called multi-chamber rinsing or stabilizing treatment in which the photosensitive material is processed in a liquid without passing through a slit portion of a wiper blade or the like without coming out into the air is preferably used.

According to the above-mentioned multi-stage countercurrent method or multi-room water washing method, the amount of washing water can be greatly reduced. Problems such as adhesion to materials occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, JP
No. -8,542, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Publishing Co., Ltd. "Sterilization, Sterilization, and Mold Prevention Techniques of Microorganisms" edited by the Sanitation Technology Society (1982), Japan Society of Industrial Technology, "The Encyclopedia of Bactericidal and Antifungal Agents" (ed. 1986)
Can be used.

The pH of the washing water and the stabilizing solution in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The temperature and time can also be variously set depending on the characteristics of the photosensitive material, the application, etc., but generally ranges from 15 to 45 ° C. for 20 seconds to 10 minutes, preferably from 25 to 40 ° C. for 30 seconds to 5 minutes. Selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, JP-A-57-8543, JP-A-58-14834, and JP-A-60-2
All known methods described in 20345 can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives thereof, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffers are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. However, the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole described in JP-A-4-270344, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets when the processed photosensitive material is dried. Among them, a nonionic surfactant is preferably used, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

It is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent 345,172A1 can be mentioned.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

The various processing solutions 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 promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

The silver halide color photographic light-sensitive material of the present invention preferably has a specific photographic sensitivity of 320 or more, more preferably 320 or more and 3200 or less.
Here, the specific photographic sensitivity is a sensitivity based on the ISO sensitivity which is an international standard.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, each of which is provided on a support. The number of silver halide emulsion layers and non-photosensitive layers is not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least two color-sensitive layers comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Material, the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to either of red light and red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer and a green light-sensitive layer. A color layer and a blue-sensitive layer are provided in this order. The entire hydrophilic colloid layer including these color-sensitive emulsion layers is called a "photosensitive layer". Preferred maximum spectral sensitivity wavelengths of each layer are, for example, 420 to 480 nm for the blue-sensitive layer and 520 to 5 nm for the green-sensitive layer.
80 nm, and the red-sensitive layer is at 620 to 680 nm. A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer is described in JP-A-61-43748,
Nos. 9-113438, 59-113440, 61
Couplers, DIR compounds and the like described in JP-A-20037 and JP-A-61-20038, and may contain a color mixture inhibitor as usually used. As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-speed emulsion layer and a low-speed emulsion layer. A two-layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, JP-A-62-200350 and JP-A-6-200350
A low-speed emulsion layer on the side away from the support as described in JP-A-2-206541 and JP-A-62-206543;
A high-sensitivity emulsion layer may be provided on the side close to the support. As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /, or BH / BL / GL / GH / RH / RL, or B
They can be installed in the order of H / BL / GH / GL / RL / RH. As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.
Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat.
No. 3,271, No. 4,705,744, No. 4,7
07,436, JP-A-62-160448, JP-A-63-160448
It is preferable to arrange a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, RL described in the specification of JP-A-89850, adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The color light-sensitive material used in the present invention includes
Various known silver halide emulsions can be used.
Preferred emulsions include tabular silver halide emulsions. For example, the aspect ratio is 2 or more. The details thereof are described in JP-A-7-287370, No. 24.
On page 28. Regarding spectral sensitizing dyes, antifoggants, stabilizers and sensitizers used in emulsions such as tabular emulsions, JP-A-7-287370, Nos. 24 and 25,
It is described on page 28.

The emulsion of the present invention may be used alone in the photosensitive emulsion layer, or two or more emulsions having different average grain sizes may be used in combination. When two or more types of emulsions are used, they may be used in different layers, but are preferably used in a mixture with the same photosensitive layer. When two or more kinds of emulsions are used, an emulsion having an average aspect ratio specified in the present invention and an emulsion having an average aspect ratio not used may be used. As mentioned above, the use of a mixture of emulsions provides gradation control, control of graininess from low to high exposure areas,
And the dependence on color development (e.g., from the viewpoints of the dependence on the composition of the developer such as time and color developing agent, sodium sulfite, etc., and the control of pH (dependency), etc.) The emulsion of the present invention is disclosed in JP-A-60-143332. , Id.
The relative standard deviation of the silver iodide content between grains described in No. 2 is particularly preferably 20% or less.

In the present invention, the thickness of the emulsion layer is 25
It means a film thickness measured at 55 ° C. and 55% humidity control (2 days). The film thickness can be measured with a commercially available film thickness meter. The effect of the present invention is greater as the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is reduced, but there is a limit depending on the volume occupied by a binder such as gelatin, a coupler and a dispersing solvent. To 22 μm, more preferably 12 to 20 μm, and particularly preferably 15 to 18 μm.
m.

The swelling ratio of the color photographic light-sensitive material of the present invention in a developer is preferably 2.3 or more from the viewpoint of accelerating the diffusion of the developing agent. More preferably, 2.4 or more 4
It is as follows. Particularly preferably, it is 2.4 or more and 3 or less.
If it is too large, the diffusion distance becomes long, and development may be delayed. In the present invention, the swelling ratio in the developer is a value obtained by dividing the film thickness after swelling in the developer (the thickness of the photographic layer on the side having the photosensitive layer with respect to the support) by the dry film thickness. . The measurement of the swollen film thickness in the developer is described in A. Green and GI
P. Levenso, J. Phot. Sci., 20, 205 (1972)
Can be performed by the method described in (1). That is, 38 ° C. It can be determined from the equilibrium value of the swollen film thickness in the heated developer. As the developer, for example, the formulations described in the examples can be used. The developer A is used for the measurement of the swelling ratio defined in the present invention.

As the 2-equivalent coupler of the red-sensitive layer used in the present invention, known couplers can be used. Specifically, two equivalents of couplers described below can be used. Two-equivalent couplers form one molecule of dye when forming two atoms of image silver by color development. Conventional four-equivalent couplers reduce four silver halides to form one molecule of dye, while two-equivalent couplers reduce two silver halides to form one molecule of dye. Therefore, when a 2-equivalent coupler is used, the amount of silver halide is reduced by half compared to when a 4-equivalent coupler is used to obtain the same color image.
That would be fine.

In the present invention, such a two-equivalent coupler is used in an amount of at least 50 mol%, preferably 75 mol%, of the total red-sensitive layer coupler.
When the content is at least mol%, the coloring speed of the red-sensitive layer can be increased. The two-equivalent cyan coupler used in the present invention includes phenol-based and naphthol-based couplers, and is described in U.S. Pat. Nos. 4,052,212, 4,146,396, and 4,228,233. No. 4,296,200, No. 2,369,929,
Nos. 2,801,171 and 2,772,162
No. 2,895,826, No. 3,772,00
No. 2, No. 3,758,308, No. 4,334,0
11, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A.
No. 249,453A, U.S. Pat.
No. 622, No. 4,333,999, No. 4,77
No. 5,616, No. 4,451,559, No. 4,4
No. 27,767, No. 4,690,889, No. 4,
Preferred are 2-equivalent couplers described in 254,212, 4,296,199 and JP-A-61-42658. Further, Japanese Patent Application Laid-Open Nos. 64-553 and 64-554.
Pyrazoloazole-based couplers described in U.S. Pat. No. 4,818,6 and U.S. Pat. No. 4,818,6.
No. 72 imidazole couplers can also be used. Particularly preferred are U.S. Pat.
52,212, 4,146,396, 4,22
8,233 and 4,296,200 are examples of oxygen atom-elimination type 2-equivalent naphthol couplers.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 2 mol%
Silver iodobromide or silver iodochlorobromide containing from 1 to about 10 mol% of silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having regular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. Even if the grain size of silver halide is about 0.2 μm or less, the projected area diameter is about 10 μm.
Large-sized grains up to and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions usable in the present invention include, for example, Research Disclosure (R)
D) No. 17643 (December 1978), 22-23
Page, "I. Emulsion prepar
nation and types) "and No. 1 of the same.
No. 8716 (November 1979), p. 648; 307
105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montel (P. Glafkides, Chemie et P.).
hisique Photographique, Pa
ul Montel, 1967), Duffin, "Emulsion Chemistry", published by Focal Press (GF Duffi).
n, Photographic Emulsion C
hemistry (Focal Press, 196)
6)), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikman et al.)
al. , Making and Coating P
photographic Emulsion, Foca
1 Press, 1964).

US Pat. Nos. 3,574,628 and 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-13354.
No. 2. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm.
5-20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 17643, ibid. No. 18716 and the same No.
307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat. No. 4,082,553.
No. 626,498, JP-A-59-214852, and JP-A-59-214852, in which a silver halide grain and a colloidal silver are coated with a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. Can be used preferably. The term "silver halide emulsion having a fogged inside or surface of a grain" means a silver halide emulsion which can be uniformly (non-imagewise) developed irrespective of unexposed portions and exposed portions of the photosensitive material.
A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498;
-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. The silver halide having the inside or surface of the grain covered is silver chloride,
Any of silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm.
m is preferred. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains is ± 40% of the average grain size). %).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.5 μm.
2 μm is more preferred. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. The coated silver amount of the light-sensitive material of the present invention is 8.0 g.
/ M ² or less are preferred, 6.0 g / m ² or less is most preferred. Further, it is preferably 0.3 g / m ² or more. In the case of a color light-sensitive material for photography, it is preferably ² g / m ² or more.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 648 page right column page 866 2. Sensitivity enhancer Page 648, right column 3. 3. Spectral sensitizers, pages 23 to 24, right column at page 648 to pages 866 to 868 supersensitizers, right column at page 649 Brightener page 24 page 647 page right column page 868 5. Antifoggants page 24-25 page 649 right column pages 868-870 Stabilizer 6. 6. Light absorber, page 25-26, page 649, right column-page 873, filter dye, page 650, left column, UV absorber 7. Anti-stain agent Page 25, right column, page 650, left column to page 872, right column. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener page 26 page 651 left column pages 874 to 875 10. Binder page 26 page 651 left column pages 873-874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static 27 pages 650 pages right column 876-877 Inhibitors 14. Matting agent 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in JP-A No. 7 or 4,435,503 to the photosensitive material. Nos. 4,740,454 and 4,788,132 in the photosensitive material of the present invention.
It is preferable to contain a mercapto compound described in JP-A-62-18539 and JP-A-1-283551. Compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in JP-A-1-106052. Is preferably contained. The light-sensitive material of the present invention may be added to International Publication WO88 / 047.
No. 94, JP-A No. 1-502912, or dyes described in EP 317,308A, U.S. Pat. No. 4,420,555, and JP-A-1-259358. preferable. Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. supra. 1764
3, VII-CG, and VII-CG. 307105, VII-
It is described in the patents described in C to G. As the yellow coupler, for example, US Pat. No. 3,933,501
No. 4,022,620, No. 4,326,02
No. 4, No. 4,401,752, No. 4,248,9
No. 61, Japanese Patent Publication No. 58-10739, British Patent No. 1,4
Nos. 25,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023,
No. 4,511,649, European Patent No. 249,473
Those described in No. A, etc. are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable. US Pat. Nos. 4,310,619 and 4,351,897
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable. Examples of 4-equivalent cyan couplers that can be used in combination in the present invention include phenol-based and naphthol-based couplers, and are described in U.S. Pat. Nos. 4,052,212 and 4,14.
No. 6,396, No. 4,228,233, No. 4,2
No. 96,200, No. 2,369,929, No. 2,
Nos. 801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,32
No. 9,729, EP 121,365A, No. 2
No. 49,453A; U.S. Pat. No. 3,446,622;
Nos. 4,333,999 and 4,775,616
No. 4,451,559 and 4,427,76
No. 7, No. 4,690,889, No. 4,254, 2
No. 12, No. 4,296,199, JP-A-61-42
No. 658, etc. are preferred. Further, JP-A-64-553, JP-A-64-554, and JP-A-64-554
-555 and 64-556, and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211;
No. 4,367,282, No. 4,409,320
No. 4,576,910; British Patent 2,102,
137 and EP 341 188A.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred. A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing a development inhibitor is described in RD17643, VII-F and No. 307105, Patents described in Sections VII-F, JP-A-57-151944 and JP-A-57-15423.
No. 4, No. 60-184248, No. 63-37346
No. 63-37350, U.S. Pat. No. 4,248,96
Those described in Nos. 2 and 4,782,012 are preferred. As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,097,14
No. 0, No. 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred. Also, Japanese Patent Application Laid-Open Nos. 60-107029 and 60-2
52340, JP-A-1-44940, 1-456
Compounds described in No. 87 which release a fogging agent, a development accelerator, a silver halide solvent, and the like by an oxidation-reduction reaction with an oxidized form of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a leuco dye releasing coupler described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Emitting couplers and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-di-ethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoates (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide),
N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4
-Di-tert-amylphenol), aliphatic carboxylic esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (N, N- Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,54.
1, 230 and the like.

In the color light-sensitive material of the present invention, phenethyl alcohol or JP-A-63-257747, JP-A-63-257747 may be used.
272248 and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, It is preferable to add various preservatives or fungicides such as 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described in, for example, RD. No. No. 17643, page 28, ibid. 18716
No. 647, right column to page 648, left column; 307
105, page 879. As a support,
Preferably, a triacetate support (TAC), a polyester support and the like can be mentioned. In the light-sensitive material of the present invention, the film swelling speed T _1/2 of the entire hydrophilic colloid layer having the emulsion layer is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was adjusted at 25 ° C. and a relative humidity of 55% (2
D) means the film thickness, and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr. Sci. Eng.) By A. Green et al., 1
Vol. 9, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2
Is the saturated film thickness, which is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds.
/ 2 is defined as the time to reach. Film swelling speed T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The photosensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) of m. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of the back layer is preferably 2.5 to 6.0. When the silver halide color photographic light-sensitive material of the present invention is applied to a film unit with a lens described in JP-B-2-32615, JP-B-3-39784 or the like, the effect is more easily exhibited and is effective. .

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The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

Example 1 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Silver iodobromide emulsion G Silver 0.067 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion Silver 0.68 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide E silver 1.42 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.72

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.78 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.89

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E 1.27 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.40

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.08

Twelfth Layer (Medium Speed Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion D 0.38 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F silver 1.02 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Silver iodobromide emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00

15th layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

In order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-3, B-4 to B- 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts.

[0153]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples in JP-A-2-19938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing 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 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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As described above, the multilayer color photosensitive material sample 101
Was exposed to light and processed using an automatic developing machine by the method described below (until the cumulative replenishment amount of the developing solution became three times the tank capacity). (Processing method) Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 10 seconds 38 ° C 20 ml 20 liter Bleaching 2 minutes 30 seconds 38 ° C 25 ml 40 liter Water washing (1) 15 seconds 24 ° C From (2) (1) 10 liter countercurrent piping method Rinse (2) 15 seconds 24 ° C 15 ml 10 liters Fixed 3 minutes 00 seconds 38 ° C 15 ml 30 liters Rinse (3) 30 seconds 24 ° C From (4) ( 3) to 10 liter counter-current piping system Rinse (4) 30 seconds 24 ℃ 1200ml 10 liters Stabilization 30 seconds 38 ℃ 20ml 10 liters drying 4 minutes 20 seconds 55 ℃ * Replenishment amount is 35mm width 1m length Hit

Next, the composition of the processing solution will be described. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.3 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.3 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 39.3 Potassium bromide 1.4 0.25 Potassium iodide 1.5 mg-Hydroxyamine sulfate 2.4 3.2 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate (P-5) 4.5 6.2 Add water and add 1.0 liter 1.0 liter pH (water Adjusted with potassium oxide and sulfuric acid) 10.05 10.15

(Bleaching solution) Tank solution Replenisher Ethylenediaminetetraacetic acid (Comparative compound A) 0.18 mol 0.22 mol Ferric nitrate nonahydrate 0.16 mol 0.20 mol 3-mercapto-1,2,4-triazole 0.03 g 0.08 g Ammonium bromide 140.0 g 160.0 g Ammonium nitrate 30.0 g 35.0 g Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 5.7

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL 320.0 mL Acetic acid (90%) 3.3 4.0 Add water 1.0 L 1.0 L pH ( (Adjust with ammonia water and acetic acid) 6.7 6.8

(Stabilizer) Common to tank liquid / replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2 1,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water and add 1.0 liter pH 8.5

With respect to the multilayer color photosensitive material sample 111 which had been subjected to the above processing, the amount of residual silver in the highest color density portion was measured by X-ray fluorescence analysis. The RMS value at a magenta density of 1.0 was determined by a usual method using a circular aperture of φ48 μm. Next, these photosensitive material samples 111 obtained by processing were measured with green light (G light).
The min values were each read. Next, using the multilayer color photosensitive material sample 111, the increase in stain during storage of the photosensitive material after processing is stored under the following conditions, and the density change before and after storage of Dmin of the uncolored portion is determined from the change in density. I asked. Dark / moist heat conditions: 60 ° C., 70% RH, increase in stain for 25 days (ΔD) = (Dmin after storage) − (Dmin before storage) Next, the developing agent P-5 in the color developer is equimolar. Except that the developing agent for comparison shown in Table 2 or the developing agent of the present invention was used, exactly the same color developing solution was prepared and the same processing was carried out. (At this time, the developing time was adjusted so that the concentration in each processing was 1.0 at the exposure amount giving a concentration of 1.0 of the sample 111.) Then, the comparative compound A in the bleaching solution was equimolar to Table 2 Except that the chelating agent for comparative bleaching or the chelating agent of the present invention was used, the same bleaching solution was prepared and subjected to the same treatment. The obtained sample was evaluated for the amount of residual silver, the granularity, and the stain in exactly the same manner as for the sample 111, and the obtained results are shown in Table 2.

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[Table 2]

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From the results shown in Table 2, it is apparent that the present invention is preferable in that both the residual silver amount and the stain increase are small while improving the graininess as compared with the comparative examples.

Example 2 Color paper sample 1 described in JP-A-4-145433
03 was treated as follows. [Processing process] [Temperature] [Time] Color development 38 ° C 45 seconds Bleaching and fixing 35 ° C 25 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Drying 80 ° C 60 seconds (color developer) Water 600 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 2.0 g Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Fluorescent brightener (WHITEX 4B. 1.0 g diethylhydroxylamine 4.2 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (P-6) 5.0 g Water was added. 1000ml pH (25 ° C) 10.05

(Bleach-fixing solution) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron chloride 0.30 mol Ethylenediaminetetraacetic acid (comparative compound A) 0.33 mol Ammonium bromide 40 g Water was added to 1000 ml pH ( 6.8

(Rinse solution) Deionized water (Calcium and magnesium are each 3 pp.
(m or less) Further, a sample subjected to uniform exposure so that the gray density became 1.5 was processed in the same manner as in Example 1, and the amount of residual silver and stain were measured in the same manner as in Example 1. Further, by treating the sample after the treatment with the bleaching solution of Example 1,
The maximum density of increasing cyan was measured, and the fading of the cyan dye during bleach-fixing was measured. Table 3 shows the obtained results.

[0183]

[Table 3]

From the results shown in Table 3, the sample of the present invention was preferable to the comparative example in that both the amount of residual silver and the increase in stain were small, and the bleach-fix fading of cyan was small.

Claims (4)

[Claims] An image-exposed silver halide color photographic material is developed with a developer containing at least one color developing agent represented by the following general formula (D), and then developed by the following general formula (I) A method for forming a color image, comprising: treating with a processing solution having at least one ferric complex salt of a compound represented by formula (II) or (III) and having bleaching ability. General formula (D) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom or a substituent. However, in the group consisting of each combination of R ₁ and R ₂ , R ₃ and R _4, and R ₅ and R ₆ , at least one pair is a substituent. R ₇ represents an alkyl group, an aryl group or a heterocyclic group. R ₈ represents a substituent, and m represents an integer of 0 to 3. General formula (I) In the formula, R ₁₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. L ₁ represents an alkylene group,
R ₁₂ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. M ₁ and M ₂ each represent a hydrogen atom or a cation. General formula (II) In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group hydroxy group or a carboxy group. t and u each represent 0 or 1. w represents a divalent linking group containing a carbon element. Each M _21, M _22, M ₂₃ and M ₂₄ represent a hydrogen atom or a cation. General formula (III) In the formula, Q represents a group of nonmetal atoms necessary to form a nitrogen-containing heterocyclic ring. p represents 0 or 1. M ₄ represents a hydrogen atom or a cation. 2. A color development processing time according to claim 1, wherein
A color image forming method, which is performed within 0 second. 3. The method according to claim 1, wherein the processing solution having the bleaching ability is combined with at least one of the compounds represented by the general formulas (I) and (III) and contains a ferric complex salt thereof. Characteristic color image forming method. 4. A color image forming method according to claim 1, wherein the processing solution having bleaching ability contains at least one ferric complex salt of the compound represented by the general formula (II).