JPH11199792A - Reactive dye mixture and dyeing or printing method using the same - Google Patents

Abstract

[PROBLEMS] To provide a blue reactive dye mixture suitable for dyeing or printing cellulosic fiber materials and the like. A reactive dye mixture containing a dioxazine compound represented by the following formula (I) or the like. ｛A1, A2, T1 and T2 represent hydrogen or halogen,
R represents hydrogen or alkyl; X1 and X2 are halogen, alkoxy, hydroxy or the following formula (II) -N (R1) -W1-SO2-Z1 (II) (wherein, R1 is hydrogen, W1 is alkylene , Phenylene, etc., and Z1 represents vinylsulfone, β-sulfatoethylsulfone, etc.), and at least one of X1 and X2 represents a halogen or a group represented by the above formula (II). . ｝

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reactive dye mixture, and more particularly to a blue reactive dye mixture containing a plurality of dioxazine compounds suitable for dyeing or printing cellulosic fiber materials and the like.

[0002]

2. Description of the Related Art As a blue reactive dye mixture for dyeing a cellulosic fiber material, for example, a composition comprising a dioxazine compound and an anthraquinone compound (JP-A-5-247369) or an anthraquinone compound and copper Compositions comprising a formazan-based compound (JP-A-2-99564, JP-A-1-103668) and the like are known.

[0003]

However, even if the above-mentioned known composition is used for dyeing or printing cellulosic fiber materials, the dyeing performance (clear hue, reproducibility of dyeing, leveling property, build-up property) can be improved. And fastness), various fastnesses (fastness to chlorinated water, fastness to running chlorine, fastness to light, fastness to sweat and sunlight, fastness to NOx gas, etc.), and stability of the obtained dyed products over time. However, there is a problem that such dyes are not always satisfactory, and the development of reactive dyes having excellent dyeing performance, various fastnesses and stability over time is desired.
In addition, the coloring amount of the dyeing wastewater when using the above-described known composition has a problem that it is larger than the amount required in accordance with increasing interest in environmental issues in recent years, and the effective dyeing rate is high. There is a strong demand for the development of reactive dyes.

[0004]

The present inventors have conducted intensive studies to find a reactive dye mixture that can solve these problems in dyeing and printing, and as a result, have found that a specific combination of a plurality of dioxazine compounds is obtained. The present invention has been completed by finding that the reactive dye mixture achieves the above object.

That is, the present invention provides a) a dioxazine compound represented by the following general formula (I) in the form of a free acid; and b) a dioxazine compound represented by the following general formula (IV) in the form of a free acid: In the form of a compound and a free acid, the following general formula (X
A reactive dye mixture containing at least one compound selected from the group consisting of dioxazine compounds represented by I), and a method for dyeing or printing a cellulosic fiber material characterized by using the mixture. Is what you do.

[0006]

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(I)

Wherein T ₁ and T ₂ are independently of each other:
A hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or an aryloxy group which may have a substituent; A ₁ and A ₂ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, Represents a lower alkoxy group or a carboxyl group, R represents a hydrogen atom or a lower alkyl group which may have a substituent, X ₁ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group An optionally substituted amino group or the following general formula (II) —N (R ₁ ) —W ₁ —SO ₂ —Z ₁ (II) wherein R ₁ represents a hydrogen atom or a substituent Represents an alkyl group which may be possessed, and W ₁ may have a substituent, or may have an alkylene group or a substituent in which the carbon chain may be interrupted by a hetero atom. Phenylene group or substituent Represents an naphthylene group optionally having, Z ₁
It represents a group is -CH = CH ₂ or _{-CH 2 CH 2 Z 1 '(} Z 1' represents. A group capable of leaving by the action of an alkali) represented by. And X ₂ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, an amino group which may have a substituent or the following general formula (III) -N (R ₂ ) —W ₂ —SO ₂ —Z ₂ (III) In the formula, R ₂ represents a hydrogen atom or an alkyl group which may have a substituent, and W ₂ represents a group having a substituent. And an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group optionally having a substituent or a naphthylene group optionally having a substituent, Z ₂
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 2 '(} Z 2' represents a group capable of leaving by the action of an alkali.). Represents a group represented by｝. However, at least one of X ₁ and X ₂ is one selected from the group consisting of a halogen atom, a group represented by the formula (II) and a group represented by the formula (III). ]

[0009]

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(IV)

Wherein T ₃ and T ₄ are independently of each other:
Represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or an aryloxy group which may have a substituent, and Y ₁ is represented by the following general formula (V)

[0012]

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(V)

In the formula, W ₃ represents an alkylene group which may have a substituent, a phenylene group which may have a substituent or a naphthylene group which may have a substituent;
₃ , a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group, an amino group which may have a non-fiber-reactive substituent or the following general formula (VI) —N (R ₃ ) —W ₄ —SO ₂ —Z ₃ (VI) (wherein R ₃ represents a hydrogen atom or an alkyl group which may have a substituent, and W ₄ represents a substituent Or an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group optionally having a substituent or a naphthylene group optionally having a substituent. , Z ₃
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 3 '(} Z 3' represents a group capable of leaving by the action of an alkali.). X ₄ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group, or a non-fiber-reactive substituent. also an amino group or a group represented by the general formula _{(VII) -N (R 4)} -W 5 -SO 2 -Z 4 (VII) ( wherein, R ₄ which may have a hydrogen atom or a substituent alkyl W ₅ may have a substituent, and may have an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group which may have a substituent, or a substituent. It represents an naphthylene group which may have, Z ₄
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 4 '(} Z 4' represents a group capable of leaving by the action of an alkali.). ). Represents a group represented by｝, and represents Y
₂ is the following general formula (VIII)

[0015]

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(VIII)

In the formula, W ₆ represents an alkylene group which may have a substituent, a phenylene group which may have a substituent or a naphthylene group which may have a substituent;
₅ is a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group, an amino group which may have a non-fiber-reactive substituent or the following general formula (IX) —N (R ₅ ) —W ₇ —SO ₂ —Z ₅ (IX) (wherein, R ₅ represents a hydrogen atom or an alkyl group which may have a substituent, and W ₇ represents a substituent Or an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group optionally having a substituent or a naphthylene group optionally having a substituent. , Z ₅
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 5 '(} Z 5' represents a group capable of leaving by the action of an alkali.). X ₆ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group, or a non-fiber-reactive substituent. An amino group or a compound represented by the following general formula (X) —N (R ₆ ) —W ₈ —SO ₂ —Z ₆ (X) wherein R ₆ is a hydrogen atom or an alkyl which may have a substituent W ₈ may have a substituent, and may have an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group which may have a substituent, or a substituent. It represents an naphthylene group which may have, Z ₆
It represents a group is -CH = CH ₂ or _{-CH 2 CH 2 Z 6 '(} Z 6' represents. A group capable of leaving by the action of an alkali) represented by. ) Represents a group represented by｝. Provided that at least one of X ₃ , X ₄ , X ₅ and X ₆ is a pyridinium-based fiber-reactive group, a halogen atom, a group represented by the formula (VI), a group represented by the formula (VII), IX) and one selected from the group consisting of a group represented by formula (X). ]

[0018]

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(XI)

Wherein T ₅ and T ₆ are independently of each other:
Represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or an aryloxy group which may have a substituent, and Z ₇ represents —CH ＝ CH ₂ or —CH ₂ CH
₂ Z ₇ ′ represents a group represented by Z ₇ ′ (Z ₇ ′ represents a group which is eliminated by the action of an alkali), and Z ₈ represents —CH ＝ CH ₂ or —CH ₂ CH ₂ Z ₈ ′ (Z ₈ ′ Y ₃ and Y ₄ independently of each other in the form of a free acid are represented by the following general formula (XII) or (XIII) -NH _{(CH 2) n NHCO (CH} 2) n COOH (XII) -NH (CH 2) n OSO 3 H (XIII) { wherein, n represents an integer of 1-4. Represents｝. Hereinafter, the present invention will be described in detail.

[0021]

DETAILED DESCRIPTION OF THE INVENTION The general formula (I) used in the present invention
In the dioxazine compound represented by, R represents a hydrogen atom or a lower alkyl group which may have a substituent. Examples of the lower alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as isobutyl and sec-butyl. Examples of the substituent include hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl. As these substituted lower alkyl groups, specifically, for example, 2-hydroxyethyl,
2-hydroxypropyl, 3-hydroxypropyl, 3
-Hydroxybutyl, 4-hydroxybutyl, 2,3-
Dihydroxypropyl, 3,4-dihydroxybutyl,
Cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxyethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,
-Ethoxypropyl, 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxy Ethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonyl Ethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl,
3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-ethylcarbonyloxypropyl, -Methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl and 4-sulfo Famoyl butyl and the like. R is preferably a hydrogen atom or a methyl group.

T ₁ and T ₂ are each independently a hydrogen atom,
Halogen atom such as chloro or bromo, methyl, ethyl, n
Linear or branched carbon atoms such as -propyl, isopropyl, n-butyl, isobutyl and sec-butyl;
-4 lower alkyl groups, straight-chain or branched lower alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy and isopropoxy, or phenoxy, p-methoxyphenyloxy and p-methylphenoxy Represents an optionally substituted aryloxy group. T ₁ and T ₂ are preferably chloro.

A ₁ and A ₂ each independently represent a hydrogen atom,
Halogen atom such as chloro or bromo, methyl, ethyl, n
Linear or branched carbon atoms such as -propyl, isopropyl, n-butyl, isobutyl and sec-butyl;
Represents a lower or higher alkyl group having 1 to 4 carbon atoms, such as a lower alkyl group having 1 to 4 carbon atoms, a methoxy, ethoxy, n-propoxy and isopropoxy, or a carboxyl group. A ₁ and A ₂ are, independently of each other, preferably a methyl group, an ethyl group, an n-propyl group, a methoxy group, an ethoxy group or an n-propoxy group.

X ₁ is a halogen atom such as fluoro, chloro and bromo, a lower alkoxy group which may have a substituent, a hydroxyl group, an amino group which may have a substituent, In the formula (II), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent, and represents an alkyl group which may have a substituent. Specific examples include the same groups as those described above for the group R.

W ₁ represents an alkylene group, a phenylene group or a naphthylene group, all of which may have a substituent. Examples of the substituent of the alkylene group include sulfo, alkoxy, and halogen.
The alkylene group which may have a substituent, for _{example, - (CH 2) 2 -} , - (CH 2) 3 - and -CH (CH
₃ ) In addition to CH ₂ — and the like, an alkylene group whose carbon chain may be interrupted by a hetero atom such as oxygen, and the like, such as represented by the following formula — (CH ₂ ) ₂ O (CH ₂ ) ₂ —, are exemplified. Can be

The optionally substituted phenylene group or unsubstituted naphthylene group represented by W ₁ is preferably, for example, methyl, ethyl,
Examples include a phenylene group which may be substituted with one or two substituents selected from the group consisting of methoxy, ethoxy, chloro, bromo and sulfo, and a naphthylene group which may be substituted with one sulfo group. Examples of these are, for example,

[0027]

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[0028]

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(In the formula, the bond indicated by an asterisk means a bond leading to a nitrogen atom.) And the like.
Among them

[0030]

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And the like are preferred.

Z ₁ represents —CH ＝ CH ₂ or a general formula —CH
₂ CH ₂ Z ₁ ′ represents a fiber-reactive group represented by the formula:
Z ₁ ′ represents a group capable of leaving by the action of an alkali. Examples of such Z ₁ ′ include halogen atoms such as fluoro, chloro, and bromo, sulfate, thiosulfate, and the like.
Phosphate and acetyloxy can be exemplified, and sulfate is particularly preferred.

In the general formula (I), X ₂ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, an amino group which may have a substituent or the above-mentioned formula (I) Represents a group represented by III). Examples of such a halogen atom, a lower alkoxy group which may have a substituent and a hydroxyl group include those similar to those exemplified for X ₁ . In the group represented by the general formula (III), R ₂ represents a hydrogen atom or an alkyl group which may have a substituent, and examples of the alkyl group include the same groups as those described for R. . W ₂ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a substituent, and specific examples include the same groups as those described for W ₁ . Z ₂ represents —CH ＝ CH ₂ or a general formula —
Represents CH ₂ CH ₂ Z ₂ ′, wherein Z ₂ ′ represents a group capable of leaving under the action of an alkali similar to those mentioned for Z ₁ ′.

The optionally substituted amino group in X ₁ and X ₂ may be, for example, an alkyl group, a cycloalkyl, an aralkyl, an aryl, a heterocyclic group or the like. Good amino groups and amino groups in which the amino nitrogen atom is a ring member of an N-heterocyclic ring are included.

In the substituent on the amino group,
The alkyl group may be linear or branched, but preferably has ₁ to 4 carbon atoms similar to those mentioned for A ₁ and A _2.
Alkyl groups. Examples of cycloalkyl include a cyclohexyl group and the like, examples of aralkyl include benzyl and phenethyl, and examples of aryl include phenyl and naphthyl. Examples of the heterocyclic group include furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole.

The amino group in which the amino nitrogen atom is a ring member of an N-heterocyclic ring is preferably a 6-membered N-heterocyclic ring compound, which further has nitrogen as a hetero atom.
It may contain oxygen and sulfur.

Further, the substituent in the amino group and the amino group in which the amino nitrogen atom is a ring member of the N-heterocyclic ring may further include fluoro, chloro, bromo, nitro,
Cyano, trifluoromethyl, sulfamoyl, carbamoyl, acylamino, ureido, hydroxy, carboxy, other substituents such as sulfomethyl and sulfo, for example, the same carbon atom and those exemplified in A ₁ and A ₂ are 1-4
And may be substituted with alkyl and alkoxy.

Specific examples of the optionally substituted amino group represented by X ₁ and X ₂ include, for example, amino; methylamino, hydroxymethylamino, ethylamino,
n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, β
-Methoxyethylamino, β-ethoxyethylamino,
γ-methoxypropylamino, β-hydroxyethylamino, β-sulfatoethylamino, γ-hydroxypropylamino, N-β-sulfoethyl-N-methylamino, β-carboxyethylamino, β-chloromethylamino, β-cyanoethyl Monoalkyl-substituted aminos such as amino and β-sulfoethylamino;

N, N-dimethylamino, N, N-dihydroxymethylamino, N, N-diethylamino, N, N
N, N-dialkylamino such as -di-β-hydroxyethylamino; cycloalkylamino such as cyclohexylamino; aralkylamino such as benzylamino and phenethylamino;

Anilino, 2-, 3- or 4-toluidino, xylidino, 2-, 3- or 4-chloroanilino, 2-, 3- or 4-anisidino, 2-, 3- or 4-ethylanilino, -, 3- or 4-sulfoanilino, 2,4- or 2,5-disulfoanilino,
Sulfomethylanilino, N-sulfomethylanilino, 3
-Or 4-carboxyanilino, 2-carboxy-5
-Sulfoanilino, 2-carboxy-4-sulfoanilino, 2-methoxy-5-sulfoanilino, 2-methyl-
5-sulfoanilino, 2-methyl-4-sulfoanilino, 2-methoxy-4-sulfoanilino, 3-methoxy-4-sulfoanilino, 2,4-dimethoxyanilino,
2,4-dimethoxy-5-sulfoanilino, 2-, 3-,
4-, 5-, 6-, 7- or 8-sulfonaphthyl-
(1) -amino, 1-, 5-, 6-, 7- or 8-sulfonaphthyl- (2) -amino, 5,7-, 6,8-,
4,8-, 4,7-, 3,8-, 4,6-, 3,7- or 3,6-disulfonaphthyl- (1) -amino, 3,
6,8-trisulfonaphthyl- (1) -amino, 4,
6,8-trisulfonaphthyl- (1) -amino, 6-sulfonaphthyl- (2) -amino, 4,8-disulfonaphthyl- (2) -amino, 3,6,8-trisulfonaphthyl- ( 2) aryl-substituted aminos such as -amino, 4,6,8-trisulfonaphthyl- (2) -amino;

N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-propyl-N-phenylamino, N-propyl-N-phenylamino, N-butyl-N-phenylamino, N- β-cyanoethyl-N
-Phenylamino, N-ethyl-2-methylanilino,
Mixed substituted amino such as N-ethyl-4-methylanilino, N-ethyl-3-sulfoanilino, N-ethyl-4-sulfoanilino;

Fural- (2) -amino, thiophenyl-
(2) -amino, pyrazole- (2) -amino, pyridyl- (2) -amino, pyrimidyl- (2) -amino, quinolyl- (2) -amino, benzimidazole- (2)
And amino groups substituted with a heterocyclic group such as -amino, benzothiazole- (2) -amino and benzoxazole- (2) -amino.

When the amino nitrogen atom in X ₁ and X ₂ is N-
Specific examples of the amino group that is a ring member of the heterocyclic ring include, for example, morpholino, piperidino, piperazino, nicotinic acid, and the like.

The amino group which may have a substituent in X ₁ and X ₂ is preferably amino, methylamino, hydroxymethylamino, ethylamino, β-hydroxyethylamino, β-carboxyethylamino,
β-sulfoethylamino, N, N-di-β-hydroxyethylamino, N-methyl-N-phenylamino, N
-Β-sulfoethyl-N-methylamino, cyclohexylamino, anilino, toluidino, xylidino, 2-,
3- or 4-chloroanilino, 2-, 3- or 4-anisidino, 2-, 3- or 4-sulphoanilino, 2-, 3- or 4-ethylanilino, phenetidino, 2,4- and 2,5 -Disulfoanilino, 2-
Methoxy-5-sulfoanilino, 2-methyl-5-sulfoanilino, 3,6-disulfonaphthyl- (1) -amino, 3,6,8, -trisulfonaphthyl- (1) -amino, 4,8-di Sulfonaphthyl- (2) -amino, 3,
6,8-trisulfonaphthyl- (2) -amino, N-
Ethyl-N-phenylamino, N-ethyl-2-methylanilino, N-ethyl-4-methylanilino, N-ethyl-3-sulfoianilino, N-ethyl-4-sulfoianilino, pyridyl- (2) -amino, morpholino, piperidino And piperazino.

The dioxazine compound represented by the general formula (II) used in the present invention has the following formula:

[0046]

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[0047] _{(wherein, A 1, A 2, T} 1, T 2 and R are each as defined above.) Triphenedioxazine represented by dioxazine compounds and formula _{H-X 1 H-X 2} ( wherein Wherein X ₂ and X ₁ each have the above-mentioned meaning.)
It can be produced by condensing with 4,6-trihalogeno-s-triazine, respectively. Temporary conditions in this condensation are preferably at a temperature of -10 ° C to 40 ° C and pH 2-9, and secondary conditions are preferably at a temperature of 0 ° C to 70 ° C and pH 2-9. When performing tertiary condensation, preferably at a temperature of 10 ° C.
To 100 ° C. and pH 2-7. In addition, the above-mentioned triphenedioxazine compound is, for example, the following formula

[0048]

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(Wherein T ₁ and T ₂ have the above-mentioned meanings,
T ₃ and T ₄ represent a halogen atom. ) Represented by the following formula:

[0050]

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(Wherein R and A ₁ have the same meanings as described above), and a compound represented by the following formula:

[0052]

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(In the formula, A ₂ has the meaning described above.)
Condensed with a diaminobenzene disulfonic acid compound represented by the following formula

[0054]

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(Wherein T ₁ , T ₂ , R, A ₁ and A ₂ have the same meaning as described above), and the obtained compound is optionally oxidized. The compound can be produced by cyclization in the presence of an agent.

Preferred dioxazine compounds of the general formula (I) include, for example, those of the general formula (XIV)

[0057]

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(XIV)

(Wherein X ₂ , R ₁ and Z ₁ have the above-mentioned meanings).

In the dioxazine compound represented by the general formula (IV) used in the present invention, T3 and T4 each independently have a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a substituent. And specific examples thereof include, for example, those exemplified for T1 and T2 above.

In the formula, Y 1 represents the above general formula (V), wherein W ₃ represents an alkylene group, a phenylene group or a naphthylene group, even if any of these has a substituent. More specifically, the same groups as those described for W ₁ can be exemplified.

In the general formula (V), X_ThreeIs halo
Gen atom, lower alkoxy optionally having substituent (s)
Groups, hydroxyl groups, pyridinium-based fiber-reactive groups,
An amino group which may have a non-fiber-reactive substituent or
Represents a group represented by the general formula (VI). Such haloge
Atom, a lower alkoxy group which may have a substituent,
Hydroxyl group and optionally substituted amino group
As X ₁The same as those listed in
Can be mentioned.

In the group represented by the general formula (VI), R ₃
Represents a hydrogen atom or an alkyl group which may have a substituent, and examples of the alkyl group include the same groups as those described for R. W ₄ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a substituent, and specific examples include the same groups as those described for W ₁ . Z ₃ represents —CH ＝ CH ₂ or a general formula —CH ₂ CH ₂ Z ₃ ′, and Z ₃ ′ is Z ₁ ′
Represents a group which is eliminated by the action of an alkali in the same manner as described above.

In the general formula (V), X_FourIs halo
Gen atom, lower alkoxy optionally having substituent (s)
Groups, hydroxyl groups, pyridinium-based fiber-reactive groups,
An amino group which may have a non-fiber-reactive substituent or
Represents a group represented by the general formula (VII). Such halo
Gen atom, lower alkoxy optionally having substituent (s)
Group, hydroxyl group and amino group which may have a substituent.
Each of the groups is represented by X ₁Similar to the ones listed in
And the like.

In the group represented by the general formula (VII), R ₄
Represents a hydrogen atom or an alkyl group which may have a substituent, and examples of the alkyl group include the same groups as those described for R. W ₅ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a substituent, and specific examples include the same groups as those described for W ₁ . Z ₄ represents —CH ＝ CH ₂ or a general formula —CH ₂ CH ₂ Z ₄ ′, wherein Z ₄ ′ is Z ₄ ′
Represents a group which is eliminated by the action of an alkali in the same manner as described above.

In the formula, Y 2 is a group represented by the general formula (VIII)
In the formula, W ₆ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a substituent, and specifically, the same groups as those described for W ₁ And the like.

In the general formula (VIII), X ₅ is a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group,
It represents an amino group which may have a non-fiber-reactive substituent or a group represented by the formula (IX). Examples of such a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group and an amino group which may have a substituent include those similar to those exemplified for X ₁ and the like. Comes out.

In the group represented by the general formula (IX), R ₅
Represents a hydrogen atom or an alkyl group which may have a substituent, and examples of the alkyl group include the same groups as those described for R. W ₇ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a substituent, and specific examples include the same groups as those described for W ₁ . Z ₅ is -CH =
CH ₂ or formula -CH ₂ CH ₂ Z ₅ 'represent, Z _5'
Represents a group capable of leaving by the action of an alkali similar to those exemplified for Z ₁ ′.

In the general formula (VIII), X₆Ha
Rogen atom, lower alkoxy optionally having substituent (s)
Groups, hydroxyl groups, pyridinium-based fiber-reactive groups,
An amino group which may have a non-fiber-reactive substituent or
Represents a group represented by the general formula (X). Such haloge
Atom, a lower alkoxy group which may have a substituent,
Hydroxyl group and optionally substituted amino group
As X ₁The same as those listed in
Can be mentioned.

In the group represented by the general formula (X), R ₆
Represents a hydrogen atom or an alkyl group which may have a substituent, and examples of the alkyl group include the same groups as those described for R. W ₈ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a substituent, and specific examples include the same groups as those described for W ₁ . Z ₆ represents —CH ＝ CH ₂ or a general formula —CH ₂ CH ₂ Z ₆ ′, and Z ₆ ′ is Z ₁ ′
Represents a group which is eliminated by the action of an alkali in the same manner as described above.

The dioxazine compound represented by the general formula (IV) used in the present invention can be produced by a known method, for example, according to the method described in JP-A-62-048768. ) Is not particularly limited, but is preferably represented by the general formula (XV)

[0072]

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(XV)

(Wherein X ₄ , X ₆ , W ₃ and W ₆ have the above-mentioned meanings).

In the dioxazine compound represented by the general formula (XI) used in the present invention, T5 and T6 each independently have a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a substituent. And specific examples thereof include, for example, those exemplified for T1 and T2 above.

Z ₇ represents —CH ＝ CH ₂ or a general formula —CH
₂ CH ₂ Z ₇ ′, wherein Z ₇ ′ represents a group capable of leaving by the action of an alkali similar to those mentioned for Z ₁ ′. Also, Z
₈ represents —CH ＝ CH ₂ or a general formula —CH ₂ CH ₂ Z ₈ ′, and Z ₈ ′ represents a group which is eliminated by the action of an alkali similar to those mentioned for Z ₁ ′.

Y ₃ and Y ₄ are each independently of the formula (XII) or (XIII) —NH (CH ₂ ) _n NHCO (CH ₂ ) _n COOH (XII) —NH (CH ₂ ) _n represents OSO ₃ H (XIII), where n is preferably 2 or 3.

The dioxazine compound represented by the general formula (XI) used in the present invention can be produced according to a known method, and is not particularly limited as long as it is a compound represented by the general formula (XI). General formula (XVI)

[0079]

Embedded image

(XVI)

A dioxazine compound represented by

Formula (XVII)

[0083]

Embedded image

(XVII)

And the like.

Dioxazine compound used in the present invention
(I), the dioxazine compound (IV) and the dioxazine compound (XI) may be in the form of a free acid, a salt thereof, or a mixture thereof. Preferably, it contains an alkali metal salt and an alkaline earth metal salt, and particularly preferably contains a sodium salt, a potassium salt or a lithium salt. Further, the reactive dye mixture of the present invention, the compound of the above (I),
It is sufficient that the reactive dye mixture of the present invention contains at least one of the compounds (IV) and (XI). Further, the reactive dye mixture of the present invention contains two or more dioxazine compounds represented by the general formula (I). And may contain two or more kinds of dioxazine compounds represented by the general formula (IV), and may contain two or more kinds of dioxazine compounds represented by the general formula (XI).

The content of each compound in the reactive dye mixture of the present invention is preferably from 10 to 90% by weight of the compound (I).
And at least one compound in the compound (IV) and the compound (XI) accounts for 10 to 90% by weight. In particular, when the dioxazine compound (I) and the dioxazine compound (IV) are contained and the dioxazine compound (XI) is not contained, the dioxazine compound (I) is added to the total weight of the dioxazine compound (I) and the dioxazine compound (IV). Is preferably a mixture containing 40 to 90% by weight. When the dioxazine compound (I) and the dioxazine compound (XI) are contained and the dioxazine compound (IV) is not contained, the dioxazine compound (I) is added to the total weight of the dioxazine compound (I) and the dioxazine compound (XI). 10 to 80% by weight
Preferably, the mixture is a mixture containing. Furthermore, when containing three kinds of compounds of dioxazine compound (I), dioxazine compound (IV) and dioxazine compound (XI),
Dioxazine compound (I), dioxazine compound (IV)
And 10 to 80% by weight of the dioxazine compound (I) and 10 to 70% by weight of the dioxazine compound (IV), based on the total weight of the dioxazine compound (XI),
Further, a mixture containing 10 to 70% by weight of the dioxazine compound (XI) is preferable.

The reactive dye mixture of the present invention can be obtained by mixing dioxazine compound (I), dioxazine compound (IV) and dioxazine compound (XI) in the above-mentioned combination, but the mixing method is not particularly limited. For example, they may be mixed in advance before being used for dyeing, or may be mixed in a dyeing bath.

The dye mixture of the present invention may be used by mixing with other dyes, if necessary, in order to obtain a desired hue, as long as the characteristics of the present invention are not impaired. Such other dyes are not particularly limited, and include, for example, a sulfo-ethyl sulfone group, a vinyl sulfone group, a monochlorotriazine group, a monofluorotriazine group, a triazine mononicotinic acid group, a dichlorotriazine group, and a difluoromonochloropyrimidine as a reactive group. A dye having at least one of a group and at least one of trichloropyrimidine groups and a known dye can be used. Known dyes include, for example, or Sumifix, Sumifix Supr
a, Remazol, Levafix, Procion, Cibacron, Basilen, D
Dyes which are commercially available under crown names such as rimarene, Kayacion, and Kayaceleon React are exemplified.

The reactive dye mixture of the present invention may be optionally used
Inorganic salts such as anhydrous sodium sulfate and salt, dispersants, dust scattering inhibitors, pH stabilizers, water softeners such as polyphosphate, etc.
Known dyeing auxiliaries and the like can be contained.

The reactive dye mixture of the present invention is not particularly limited in its form, and may be in a known form.
It may be in the form of powder, granule, or liquid.

In the method for dyeing and printing the cellulosic fiber material of the present invention, the cellulosic fiber material to be dyed is not particularly limited, and examples thereof include cotton, linen, hemp, jute, ramie fiber, In addition to natural, refined or regenerated cellulose fibers such as viscose human silk and Bemberg, fiber materials containing cellulosic fibers, that is, cotton / polyester blends, cotton / nylon blends, and cotton / wool blends are also exemplified. You.

The dyeing and printing method in the present invention may be any method using the above-mentioned reactive dye mixture.
There is no particular limitation. For example, in the exhaust dyeing method, a known inorganic neutral salt such as anhydrous sodium sulfate or sodium chloride, and a method of dyeing using a known acid binder such as sodium carbonate, sodium bicarbonate, caustic soda or sodium tertiary phosphate, alone or in combination, are used. Although exemplified, the dyeing aid is not limited to these. The amount of the inorganic neutral salt or acid binder used at this time is not limited, but is preferably at least 1 g per liter,
Although 100 g or more may be used per liter, in the present invention, for example, a small amount of use of 50 g or less per liter can sufficiently dye. In addition, these inorganic neutral salts and acid binders may be charged into the dyeing bath at once, or may be divided and charged by a conventional method. Further, other dyeing assistants such as leveling agents, slow dyeing agents and bath softeners may be used in combination by, for example, a known method, but the dyeing assistants are not particularly limited to these. The dyeing temperature in the exhaust dyeing method is usually from 40 to 90 ° C., preferably from 40 to 8 ° C.
0 ° C. In the cold batch-up dyeing method, after padding using a known inorganic neutral salt such as anhydrous sodium sulfate and sodium chloride, and a known acid binder such as caustic soda and sodium silicate, the pad is left in a closed packaging material at a constant temperature. A method for dyeing is exemplified. In the continuous dyeing method, a known acid binder such as sodium carbonate or sodium bicarbonate is mixed with a dye padding solution, and padding is performed by a known method, followed by a one-bath padding method of dyeing by dry heat or steaming. A two-bath padding method in which a known inorganic neutral salt such as sodium sulfate and sodium salt and a known acid binder such as caustic soda and sodium silicate are padded and dyed by dry heat or steaming by a known method, and the like are exemplified.
In the printing method, a printing paste containing a known acid binder such as sodium bicarbonate is printed, followed by a one-phase printing method of printing by dry heat or steaming, and a printing paste after printing. And a two-phase printing method in which the material is put into a high-temperature solution at 90 ° C. or higher containing an inorganic neutral salt such as sodium chloride and a known acid binder such as caustic soda or silicate soda for printing. .

[0094]

EFFECT OF THE INVENTION By using the mixture of the present invention, it is possible to obtain a dyed or printed product having a clear hue, high build-up properties, and excellent various fastnesses and stability over time. Further, the method of the present invention is excellent in reproducibility of dyeing, leveling property and washability, and also excellent in effective dyeing rate.

[0095]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 100 kg of a knitted cotton fabric was set in a wind dyeing apparatus, the bath ratio was 1:15, and the water temperature was 56 ° C. In the form of the free acid, the formula
(1)

[0097]

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(1)

520 parts of a dye represented by the following formula, in the form of a free acid,
Equation (2)

[0100]

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(2)

280 parts of the dye represented by the following formula, and 200 parts of a sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde having a degree of sulfonation of 110% and an average degree of condensation of 1.8 were sufficiently mixed. 3 kg of the resulting dye mixture were dissolved by a known method. Thereafter, the mixture was put into the bath, and the water temperature was kept at 56 ° C. Then, anhydrous sodium sulfate 5
After putting 0 kg into the bath in a known manner, at this temperature 20 kg
The knitted fabric is then treated for one minute with sodium carbonate 1 in a known manner.
5 kg were put into the bath. Next, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The dyed product was further washed and finished in a conventional manner. The obtained dyed product was uniform and clear blue. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of the dyed product, and the stability over time of the dyed product were all good.

Example 2 100 kg of a knitted cotton fabric was set in a wind dyeing apparatus, the bath ratio was 1:15, and the water temperature was 60 ° C. In the form of the free acid, the formula
(3)

[0104]

Embedded image

(3)

In the form of a free acid, 350 parts of a dye represented by the following formula (4)

[0107]

Embedded image

(4)

In the form of a free acid, 200 parts of the dye represented by the formula (5)

[0110]

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(5)

450 parts of the dye represented by the formula (1) were sufficiently mixed.
After dissolving 6 kg of the obtained dye mixture by a known method,
It was thrown into the above bath and the water temperature was kept at 60 ° C. Thereafter, 150 kg of anhydrous sodium sulfate was put into the bath by a known method, the cotton knitted fabric was treated at this temperature for 20 minutes, and 30 kg of sodium carbonate was put into the bath by a known method. Then, at the same temperature, 60
The cotton knit was treated for a minute and the dyeing was completed. The dyed product was washed and finished in a conventional manner. The resulting dyed product was uniform, clear, dark blue with no spots. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of this dyed product, and stability over time of the dyed product were all good.

Example 3 In the form of the free acid, 250 parts of the dye represented by the formula (3) was added to the dye of the formula (6) in the form of the free acid.

[0114]

Embedded image

(6)

Is mixed thoroughly with 750 parts of the dye represented by the formula (1).
20 g of the obtained reactive dye mixture was dissolved in hot water and further cooled to 25 ° C. Immediately after adding 1 g of sodium alginate, 10 g of sodium metanitrobenzenesulfonate and 20 g of sodium hydrogencarbonate to the dye solution, and further adding water to make the total volume 1 L at 25 ° C., the solution was used as a padding solution to prepare wood. The cotton fabric was padded. The padded cotton fabric is dried at 120 ° C. for 2 minutes and then at 100 ° C.
For 5 minutes to fix the dye. The resulting dyed product was uniform dark blue. In addition, the light resistance of this dyed product, sweat sunlight, chlorinated water, running water chlorine and washing fastness,
In addition, the stability over time of the dyed product was good.

Example 4 100 kg of cheese-like cotton yarn was set in a cheese dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 65 ° C. In the form of the free acid,
Equation (7)

[0118]

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(7)

In the form of 5.6 kg of the dye represented by the formula (8)

[0121]

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(8)

1.4 kg of the dye represented by the above formula was thoroughly mixed.
After 7 kg of the obtained dye mixture was dissolved by a known method, it was poured into a bath, and the water temperature was maintained at 65 ° C. Then, salt 50
kg in the bath in a known manner, the yarn is treated at this temperature for 30 minutes and then sodium tertiary phosphate 1 in a known manner.
0 kg was put into the bath. The yarn was then treated at this temperature for 60 minutes to complete the dyeing. The dyed yarn was washed and finished in a conventional manner. The obtained dyed yarn had no difference in density between the inner and outer layers of the cheese and was uniform and dark blue. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of this dyed product, and stability over time of the dyed product were all good.

Example 5 In the free acid form, 500 parts of the dye represented by the formula (7) were added to the free acid form of the formula (9)

[0125]

Embedded image

(9)

500 parts of the dye shown in the above was added and mixed well. Using the obtained dye mixture, a printing paste having the following formulation was prepared. Dye composition 80 g Urea 50 g Sodium alginate 550 g Hot water 300 g Sodium bicarbonate 20 g Total 1000 g The obtained printing paste is printed on a 40th cotton broad by a usual method and then steamed at 100 ° C. for 5 minutes. Was done. Then, washing with water, washing with hot water, soaping, washing with hot water, washing with water, and drying were completed. The resulting cotton broad was a uniform dark blue color. Further, the light resistance, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of the printed matter, and the stability over time of the printed matter were all good.

Example 6 100 kg of cotton knitted fabric was set in a jet dyeing apparatus, and the bath ratio was set to 1:
15. The water temperature was adjusted to 60 ° C. 3.0 kg of the dye of the formula (7) in the form of the pre-dissolved free acid, 4.0 kg of the dye of the formula (5) in the form of the pre-dissolved free acid, and
1.0 kg of the dyestuff of the formula (9) in the form of the pre-dissolved free acid was introduced into the bath in a known manner. Further, after 150 kg of anhydrous sodium sulfate was put into the bath in two portions by a known method, the knitted fabric was treated at this temperature for 20 minutes, and 30 kg of sodium carbonate was divided into three portions by a known method into the bath. I put it in. Next, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The dyed product was washed and finished in a conventional manner. The resulting dyed product was uniform dark blue without spots. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of this dyed product, and stability over time of the dyed product were all good.

Example 7 240 parts of the dye of the formula (1) in the form of the free acid, 240 parts of the dye of the formula (4) in the form of the free acid and the compound of the formula (6) in the form of the free acid 520 parts of the indicated dye were thoroughly mixed. 30 g of the obtained reactive dye composition was dissolved in hot water and further cooled to 25 ° C. 15 ml of a 32.5% aqueous solution of caustic soda and water glass 150 °
g was added in a known manner, and water was further added to bring the total amount to 25.
Immediately after the temperature was adjusted to 1 L at 0 ° C, the cotton fabric was padded using this solution as a padding solution. The padded cotton fabric was rolled up, closed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, and the dyed product was washed and dried in a conventional manner to finish. The resulting dyed product was uniform dark blue. The obtained dyed product had good light fastness, sweat and sunlight, chlorinated water, running water chlorine, washing fastness, and stability over time of the dyed product.

Example 8 50 kg of cheese-like cotton yarn was set in a cheese dyeing apparatus, and the bath ratio was 1:10 and the water temperature was 58 ° C. Formula (1) in the form of the free acid
Are sufficiently mixed with 150 parts of the dye represented by the formula (2) in the form of free acid and 150 parts of the dye represented by the formula (8) in the form of free acid. 5k of the resulting dye mixture
g and Remazol Yellow3R-SN (DyStar product) 1k
g and Sumifix Brilliant Red 3BF 150% gran.
(Sumitomo Chemical Co., Ltd.) After dissolving 3 kg by a known method, it was thrown into a bath, and the water temperature was kept at 58 ° C. Then anhydrous sodium sulfate 4
After putting 0 kg into the bath in a known manner, at this temperature 30 kg
The yarn was treated for 5 minutes and 5 kg of sodium tertiary phosphate was charged into the bath by a known method. The yarn is then treated at this temperature for 60 minutes,
Staining was terminated. The obtained dyed yarn was washed and finished in a conventional manner. The obtained dyed yarn was uniform, dull and dark purple with no difference in density between the inner and outer layers of the cheese. The obtained dyed product had good light fastness, sweat and sunlight, chlorinated water, running water chlorine, washing fastness, and stability over time of the dyed product.

Example 9 In the form of the free acid, the compound of the formula (10)

[0132]

Embedded image

(10)

850 parts of the dye represented by the formula (11)

[0135]

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(11)

150 parts of the dye represented by the formula (1) were sufficiently mixed.
30 g of the obtained reactive dye mixture was dissolved in hot water and further cooled to 25 ° C. Immediately after adding 1 g of sodium alginate, 10 g of sodium metanitrobenzenesulfonate and 20 g of sodium hydrogencarbonate to this dye solution, and further adding water to make the total volume 1 L at 25 ° C., the cotton fabric was used by using this solution as a padding solution. Pagged. The padded cotton fabric is dried at 120 ° C for 2 minutes and then at 100 ° C for 5 minutes.
The dye was fixed by steaming for minutes. The obtained dyed product was a uniform blue color. Further, the lightfastness, sweat and sunlight, chlorinated water, running water chlorine and various fastnesses of washing of the dyed product and the stability over time of the dyed product were all good.

Example 10 400 parts of the dye of the formula (10) in the form of the free acid, and the compound of the formula (12) in the form of the free acid

[0139]

Embedded image

(12)

100 parts of the dye of the formula (11) and 500 parts of the dye of the formula (11) in the form of the free acid were thoroughly mixed. Dissolve 50 g of the obtained reactive dye mixture with hot water,
It was further cooled to 25 ° C. Anhydrous sodium sulfate 30
g and 32.5% aqueous solution of caustic soda were added, and water was further added to bring the total volume to 1 L at 25 ° C. Immediately after that, this liquid was used as a padding liquid to pad cotton fabric.
The padded cotton fabric was wound up, sealed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, and the dyed product was washed by a conventional method and dried to finish. The resulting dyed product was uniform dark blue. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of this dyed product, and stability over time of the dyed product were all good.

Example 11 100 kg of a knitted fabric made of rayon fiber was set in a low bath ratio type jet dyeing apparatus, and the bath ratio was 1: 6 and the water temperature was 65 ° C.
In the form of the free acid, 340 parts of the dye represented by the formula (10) and in the form of the free acid, the compound of the formula (13)

[0143]

Embedded image

(13)

660 parts of the dye represented by the formula (1) were thoroughly mixed.
After dissolving 6 kg of the obtained dye mixture by a known method, it was thrown into a bath, and the water temperature was kept at 65 ° C. Then, after 40 kg of anhydrous sodium sulfate was put into the bath by a known method, the knitted fabric was treated at this temperature for 20 minutes, and 6 kg of sodium carbonate was put into the bath by a known method. Next, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The dyed product was washed and finished in a conventional manner. The resulting dyed product was a uniform dark blue color with no spots. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of this dyed product, and stability over time of the dyed product were all good.

Reference Example 1 1,4-phenylenediamine-2,6-disulfonic acid 80
50 parts and 1,4-phenylenediamine-2-methoxy-
6550 parts of 5-sulfonic acid were dissolved in water. Next, 7380 parts of chloranil was added, the pH was adjusted to 4-8 at room temperature, and the mixture was stirred until the reaction was completed. Thereafter, salting out was performed, and the crystals were separated and dried. 70 of the resulting dianilide compound
00 parts was added to 450,000 parts of 3-30% fuming sulfuric acid at 0-15 ° C and stirred at 15-40 ° C until the reaction was completed. The reaction mixture was poured into ice water, the precipitated crystals were separated by filtration, water was added to the obtained cake, and the pH was adjusted to 3-pH with a sodium hydroxide solution.
Adjusted to 6. Next, salting out was performed using sodium chloride, and the precipitated crystals were separated by filtration. 6320 parts of the obtained triphenedioxazine compound is dissolved in 150,000 parts of water (λmax is 600
nm), at a temperature of 5-30 ° C, 19 parts of cyanuric chloride are added,
The reaction was terminated while maintaining the pH at 2-7 with a sodium carbonate solution. Next, 1-aminobenzene-4-sulfonic acid was added and reacted at 10-50 ° C. The obtained compound is dissolved in water, 1-aminobenzene-4-β-sulfateethylsulfone is added, and while maintaining the pH at 2-5, 50
The temperature was raised to -70 ° C to cause a reaction. Cool to room temperature, then add potassium chloride, isolate the precipitated crystals,
A dioxazine compound represented by the following formula (15) was obtained in the form of a free acid.

[0147]

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(15)

Example 12 200 kg of a mixed knitted fabric composed of 50% of cotton fibers and 50% of polyester fibers was set in a high-pressure liquid jet dyeing apparatus, the bath ratio was set to 1:10, the water temperature was set to 80 ° C., and then acetic acid was used. P
H was set to 5. Formula (14) previously dispersed sufficiently in water

[0150]

Embedded image

2.0 kg of a disperse dye represented by the formula below and 2 kg of a dispersant Sumipon TF (manufactured by Sumitomo Chemical Co., Ltd.) were put into a bath, and
Thereafter, the temperature was raised to 130 ° C. in 40 minutes, and the polyester side was dyed at this temperature for 40 minutes. Subsequently, the dyeing liquor was drained and then supplied with water, the bath ratio being 1:10 and the water temperature being 60 ° C.
In the form of the free acid, 500 parts of a reactive dye of the formula (4)
Dioxazine compound represented by the formula (15) (Reference Example 1
500 parts). After dissolving 2.4 kg of the obtained dye mixture by a known method, the mixture was poured into the bath, and the water temperature was maintained at 60 ° C. Then, anhydrous sodium sulfate 8
After putting 0 kg into the bath in a known manner, at this temperature 20 kg
The knit was treated for 30 minutes and 30 kg of sodium carbonate was put into the bath by a known method. Next, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The dyed product was washed and finished in a conventional manner. The resulting dyed product was a uniform dark blue color with no spots. Further, the light fastness, sweat and sunlight, chlorinated water, running water chlorine and washing fastness of this dyed product, and stability over time of the dyed product were all good. The compositions of the dioxazine reactive dye mixtures in Examples 1 to 12 are shown in Table 1 below.

Examples 13 to 20 Using the reactive dye mixtures shown in Table 2 below, dyeing was carried out in the same manner as in Example 1 to obtain uniform, spot-free, dark-colored dyeings. The obtained dyed product was excellent in stability over time, and was excellent in light fastness, fastness to sweat and sunlight, fastness to chlorinated water, fastness to running water chlorine, and fastness to washing. Furthermore, all of the obtained dyed products had good washability, and the coloring amount of dyeing wastewater was small. The expressions (16) to (24) in Table 2 are used.
Have the following structures in the form of the free acids, respectively.

[0153]

Embedded image

(16)

[0155]

Embedded image

(17)

[0157]

Embedded image

(18)

[0159]

Embedded image

(19)

[0161]

Embedded image

(20)

[0163]

Embedded image

(21)

[0165]

Embedded image

(22)

[0167]

Embedded image

(23)

[0169]

Embedded image

(24)

[0171]

[Table 1]

[0172]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06P 3/66 D06P 3/66 B

Claims (9)

[Claims] 1. A) In the form of a free acid, the following general formula (I)
A) a dioxazine compound represented by the following general formula (IV) in the form of a free acid and a dioxazine compound represented by the following general formula (IV):
A reactive dye mixture comprising at least one dioxazine compound selected from the group consisting of the dioxazine compounds represented by I). Embedded image (I) wherein, T ₁ and T _2, independently of one another, represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or an optionally substituted aryloxy group, A ₁ and a _2, independently of one another, a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a carboxyl group, R represents a hydrogen atom or an optionally substituted lower alkyl group, X ₁ is halogen atom, an optionally substituted lower alkoxy group, a hydroxyl group, an optionally substituted amino group or a group represented by the general formula _{(II) -N (R 1)} -W 1 -SO 2 - Z ₁ (II) In the formula, R ₁ represents a hydrogen atom or an alkyl group which may have a substituent, W ₁ may have a substituent, and the carbon chain is a hetero atom. An alkylene group which may be interrupted, Represents an naphthylene group optionally also have a phenylene group or a substituted group optionally having substituent, Z ₁
Is -CH = CH ₂ or - CH ₂ CH ₂ Z ₁ '
(Z ₁ 'represents a group which is eliminated by the action of an alkali.) And X ₂ represents a halogen atom, a lower alkoxy group which may have a substituent,
During hydroxyl group, an amino group or a group represented by the general formula may have a substituent _{(III) -N (R 2)} -W 2 -SO 2 -Z 2 (III) { wherein, R ₂ is a hydrogen atom or a substituent Represents an alkyl group which may have a group, W ₂ may have a substituent, or an alkylene group whose carbon chain may be interrupted by a hetero atom, or a substituent. also represents an naphthylene group optionally having a phenylene group or a substituent, Z ₂
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 2 '(} Z 2' represents a group capable of leaving by the action of an alkali.). Represents a group represented by｝. However, at least one of X ₁ and X ₂ is one selected from the group consisting of a halogen atom, a group represented by the formula (II) and a group represented by the formula (III). [Chemical formula 2] (IV) wherein T ₃ and T ₄ independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or an aryloxy group which may have a substituent;
₁ is the following general formula (V): In (V) {wherein, W ₃ represents a substituent alkylene group which may have a which may have a substituent phenylene group or an optionally substituted naphthylene group, X ₃ Is a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group,
Non fiber-reactive optionally substituted amino group or a group represented by the general formula _{(VI) -N (R 3)} -W 4 -SO 2 -Z 3 (VI) ( wherein, R ₃ is a hydrogen atom Or an alkyl group which may have a substituent, W ₄ may have a substituent, or an alkylene group in which a carbon chain may be interrupted by a hetero atom, or a substituent. have a phenylene group or a substituted group optionally represents an naphthylene group, Z ₃
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 3 '(} Z 3' represents a group capable of leaving by the action of an alkali.). X ₄ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group, or a non-fiber-reactive substituent. An optionally substituted amino group or the following general formula (VII) -N (R ₄ ) -W ₅ -SO ₂ -Z ₄ (VII) (wherein R ₄ is a hydrogen atom or an alkyl which may have a substituent) W ₅ may have a substituent, and may have an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group which may have a substituent, or a substituent. It represents an naphthylene group which may have, Z ₄
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 4 '(} Z 4' represents a group capable of leaving by the action of an alkali.). ) Represents a group represented by｝, and represents a group represented by Y ₂
Is represented by the following general formula (VIII): In (VIII) {wherein, W ₆ represents a substituent alkylene group which may have a which may have a substituent phenylene group or an optionally substituted naphthylene group, X ₅ Is a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group,
In a non-fiber-reactive optionally substituted amino group or a group represented by the general formula _{(IX) -N (R 5)} -W 7 -SO 2 -Z 5 (IX) ( wherein, R ₅ is a hydrogen atom Or an alkyl group which may have a substituent, W ₇ may have a substituent, or an alkylene group in which a carbon chain may be interrupted by a hetero atom, or a substituent. have a phenylene group or a substituted group optionally represents an naphthylene group, Z ₅
Represents a group is represented by -CH = CH ₂ or _{-CH 2 CH 2 Z 5 '(} Z 5' represents a group capable of leaving by the action of an alkali.). X ₆ represents a halogen atom, a lower alkoxy group which may have a substituent, a hydroxyl group, a pyridinium-based fiber-reactive group, or a non-fiber-reactive substituent. An amino group or a compound represented by the following general formula (X) —N (R ₆ ) —W ₈ —SO ₂ —Z ₆ (X) wherein R ₆ is a hydrogen atom or an alkyl which may have a substituent W ₈ may have a substituent, and may have an alkylene group whose carbon chain may be interrupted by a hetero atom, a phenylene group which may have a substituent, or a substituent. It represents an naphthylene group which may have, Z ₆
It represents a group is -CH = CH ₂ or _{-CH 2 CH 2 Z 6 '(} Z 6' represents. A group capable of leaving by the action of an alkali) represented by. ) Represents a group represented by｝. Provided that at least one of X ₃ , X ₄ , X ₅ and X ₆ is a pyridinium-based fiber-reactive group, a halogen atom, a compound represented by the formula (VI)
, A group represented by the formula (VII), a group represented by the formula (IX) and a group represented by the formula (X). [Chemical formula 5] (XI) wherein T ₅ and T ₆ independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or an aryloxy group which may have a substituent;
₇ -CH = CH ₂ or -CH ₂ CH ₂ Z ₇ is '(. Z _7' is representative of a group removable by the action of an alkali) represents a group represented by, Z ₈ is -CH = CH ₂ or - CH ₂ CH ₂ Z ₈ ′
(Z ₈ ′ represents a group capable of leaving under the action of an alkali). Y ₃ and Y ₄ independently of each other when represented in the form of a free acid, represented by the following general formula (XII) or _{(XIII) -NH (CH 2)} n NHCO (CH 2) n COOH (XII) -NH (CH 2) n OSO 3 H (XIII) { wherein, n represents an integer of 1-4. Represents a group represented by｝. ] 2. The dioxazine compound represented by the general formula (I) is represented by the following general formula (XIV): The reactive dye mixture according to claim 1, which is a compound represented by the formula (XIV) (wherein X ₂ , R ₁ and Z ₁ have the meanings described in claim 1). 3. A dioxazine compound represented by the general formula (IV), wherein the dioxazine compound is represented by the following general formula (XV): (XV) (wherein X ₄ , X ₆ , W ₃ and W ₆ have the meanings described in claim 1).
9. The reactive dye mixture according to item 1. 4. The dioxazine compound represented by the general formula (XI) is a compound represented by the formula (XVI): The reactive dye mixture according to any one of claims 1 to 3, which is a compound represented by the formula (XVI): 5. The dioxazine compound represented by the general formula (XI) is represented by the formula (XVII): The reactive dye mixture according to any one of claims 1 to 3, which is a compound represented by the formula (XVII). 6. A dioxazine compound represented by the general formula (I) and a dioxazine compound represented by the general formula (IV), wherein the dioxazine compound represented by the general formula (I) is a dioxazine compound represented by the general formula (I) 10 to 9 based on the total weight of the compound and the dioxazine compound represented by the general formula (IV)
The reactive dye mixture according to any one of claims 1 to 3, which is contained at 0% by weight. 7. A dioxazine compound represented by the general formula (I) comprising a dioxazine compound represented by the general formula (I) and a dioxazine compound represented by the general formula (XI), wherein the dioxazine compound represented by the general formula (I) is 10 to 8 based on the total weight of the compound and the dioxazine compound represented by the general formula (XI)
6. The reactive dye mixture according to claim 1, comprising 0% by weight. 8. A dioxazine compound represented by the general formula (I), a dioxazine compound represented by the general formula (IV) and a dioxazine compound represented by the general formula (XI), wherein the total weight of these three compounds is On the other hand, the dioxazine compound represented by the general formula (I) is 10 to 80% by weight, and the dioxazine compound represented by the general formula (IV) is 10 to 70% by weight.
The reactive dye mixture according to any one of claims 1 to 5, wherein the dioxazine compound represented by the general formula (XI) is contained in an amount of 10 to 70% by weight. 9. A method for dyeing or printing a cellulosic fiber material using the reactive dye mixture according to claim 1.