JP2001098183A - Reactive dye composition and method for dyeing fiber material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a blue reactive dye capable of uniformly and fast dyeing a nitrogen-containing fiber material or a fiber material containing a nitrogen- containing fiber in a deep color. SOLUTION: This reactive dye composition comprises a dioxazine-based compound represented by formula (I) [T1 and T2 denote each chlorine atom or the like; A1 and A2 denote each an alkoxy or the like; R denotes hydrogen or the like; and X1 and X2 denote each the formula N(R1)-W1-SO2-CH=CH2 (R1 denotes hydrogen or the like; and W1 denotes an alkylene, phenylene or the like) or the like] or its salt and an azo-based compound represented by formula (IV) (R3, R4, R5 and R6 denotes each hydrogen or the like; and R1' and R2' denote each SO2-CH=CH2 or the like) or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue reactive dye capable of dyeing a nitrogen-containing fiber material or a fiber material containing a nitrogen-containing fiber with good reproducibility, uniformly, darkly, and fast.

[0002]

2. Description of the Related Art Conventionally, when dyeing a nitrogen-containing fiber material or a fiber material containing nitrogen-containing fibers, a chromium dye has been used. However, in recent years, there has been a tendency to reduce the use of chromium dyes from the viewpoint of safety and environmental impact, and reactive dyes have been used as substitutes. As a reactive dye for dyeing a nitrogen-containing fiber material and a fiber material containing nitrogen-containing fibers in blue, anthraquinone compounds and azo compounds are known.

[0003]

However, even when dyeing a nitrogen-containing fiber material or a fiber material containing a nitrogen-containing fiber using these blue reactive dyes, the exhaustion property, the fixation rate,
Dyeing performance such as reproducibility of dyeing, leveling property, build-up property, washability, etc. is not at a satisfactory level, light fastness, sweat fastness, potting fastness, wet rub fastness, washing fastness,
There is a problem that various fastnesses such as water fastness cannot be sufficiently satisfied. In addition, when the dyeing bath is set to an acidic condition at the time of dyeing, aggregation of the dye occurs, which becomes a specification on the dyed material or causes a decrease in leveling property. . for that reason,
There is a demand for the development of a blue reactive dye which can sufficiently satisfy each dyeing performance and each fastness.

[0004]

Under these circumstances, the present inventors have conducted intensive studies to find a blue reactive dye that can solve these problems, and as a result, have found that a specific dioxazine compound and a specific azo compound have been studied. A reactive dye composition containing
The inventors have found that the dyeing performance and the fastness are excellent and that the reactive dye does not agglomerate at the time of dyeing, thereby completing the present invention.

That is, the present invention is characterized by containing a dioxazine compound represented by the following general formula (I) or a salt thereof, and an azo compound represented by the following general formula (IV) or a salt thereof. It provides a reactive dye composition.

[0006]

Embedded image (I)

[Wherein T₁ And T_Two Are independent of each other
Hydrogen atom, chlorine atom, bromine atom, lower alkyl group, lower
Having an alkoxy group or a non-fiber-reactive substituent
A preferred aryloxy group is A₁ And A_Two Is hydrogen field
Atom, chlorine atom, bromine atom, lower alkyl group, lower alcohol
R represents a hydrogen atom or a non-oxy group or a carboxyl group;
Lower alkyl group optionally having a fiber-reactive substituent
To X₁Is a fluorine atom, chlorine atom, bromine atom, lower alkyl
Oxy groups, non-fiber-reactive substituents
Amino group or the following general formula (II) -N (R₁) -W₁ -SO_Two-Z₁ (II) ｛where R₁Represents a hydrogen atom or a non-fiber-reactive substituent
An alkyl group which may be₁ Is non-fiber reactive
Optionally substituted alkylene group, non-fiber reaction
Phenylene group or non-fiber which may have hydrophilic substituent
A naphthylene group which may have a reactive substituent is represented by Z
₁ Is -CH = CH_Two Or -CH_TwoCH_Two Z₁’
(Z₁′ Is a group which is eliminated by the action of an alkali)
Represents A fiber-reactive group represented by｝ is represented by X_TwoIs fluorine
Atom, chlorine atom, bromine atom, hydroxyl group, lower alcohol
Amino groups which may have a xy group or a non-fiber-reactive substituent
Amino, wherein the nitrogen atom is a ring member of an N-heterocyclic ring
Or a group represented by the following general formula (III) -N (R_Two) -W_Two -SO_Two-Z_Two (III) ｛where R_Two Is a hydrogen atom or a non-fiber-reactive substituent
An alkyl group optionally having_Two Is a non-fiber reaction
Alkylene group which may have a functional substituent,
A phenylene group or a non-fiber
A naphthylene group which may have a fiber-reactive substituent,
Z_Two Is -CH = CH_Two Or -CH _Two CH_Two Z
_Two'(Z_Two'Is a group which is eliminated by the action of an alkali)
Represents Represents a fiber-reactive group represented by｝. Where X
₁And X_TwoAt least one of the above formulas (II) and (I)
It is a fiber-reactive group represented by the general formula (III). ];

[0008]

Embedded image (IV)

[Wherein R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a carboxyl group or a sulfo group. R ₁ ′ and R ₂ ′ are each independently of the general formula —SO ₂ Z ₃中 wherein Z ₃ is —CH
＝ CH ₂ or —CH ₂ CH ₂ Z ₃ ′ (Z ₃ ′ is a group which is eliminated by the action of an alkali). Fiber-reactive group represented by}, in the general formula -A-SO ₂ Z ₄ {wherein, Z ₄ is -CH =
CH ₂ or —CH ₂ CH ₂ Z ₄ ′ (Z ₄ ′ is a group capable of leaving by the action of an alkali), and A represents —CH ₂ CH
_{2 -, - CH 2 CH 2} CH 2 -, - represents a group represented by - CONHCH ₂ CH ₂ - or _{-CH 2 CH 2 OCH 2 CH 2} . A fiber-reactive group represented by｝, a general formula (V)

[0010]

Embedded image (V)

In the formula, R ₇ represents a hydrogen atom or a lower alkyl group which may be substituted with a non-fiber-reactive group, and X ₃ represents a fluorine atom, chlorine atom or a non-fiber-reactive group. Represents a good amino group. W ₃ is an alkylene group,
Represents a phenylene group or a naphthylene group, each of which may have a non-fiber-reactive substituent. L
Is hydrogen atom or a general formula -SO ₂ Z ₅ (wherein, Z ₅ is -
CH = CH ₂ or a general formula —CH ₂ CH ₂ Z ₅ ′, wherein Z ₅ ′ represents a group which is eliminated by the action of an alkali. ) A fiber-reactive group represented by the formula (VI)

[0012]

Embedded image (VI)

Represents a fiber-reactive group, a hydrogen atom, a lower alkyl group, a lower alkoxy group, a carboxyl group or a sulfo group. However, at least one of R ₁ ′ and R ₂ ′ is a fiber-reactive group represented by the general formula —SO ₂ Z ₃ , the general formula —A—SO ₂ Z ₄ , the general formula (V) and the general formula (VI) Represents any of ｝: The present invention also provides a method for dyeing a nitrogen-containing fiber material or a fiber material containing nitrogen-containing fibers, characterized by using the above reactive dye composition. Hereinafter, the present invention will be described in detail.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The dioxazine compound used in the present invention is represented by the general formula (I), wherein T ₁ and T ₂ are each independently a hydrogen atom, a chlorine atom,
Bromine atom, lower alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, methoxy, ethoxy, n-propoxy,
Represents a lower alkoxy group such as isopropoxy, or an aryloxy group which may have a non-fiber-reactive substituent such as phenoxy and p-methylphenoxy. Preferably, T ₁ and T ₂ are chlorine atoms.

A ₁ and A ₂ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a lower alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, methoxy, ethoxy; , N-propoxy, isopropoxy and the like or a lower alkoxy group or a carboxyl group. A ₁ and A ₂ are preferably a methyl group, an ethyl group, an n-propyl group, a methoxy group, an ethoxy group, and an n-propoxy group.

R represents a hydrogen atom or a lower alkyl group which may have a non-fiber-reactive substituent. Examples of the lower alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-
An unsubstituted alkyl group such as butyl and, hydroxy, cyano, alkoxy (C _1-4), halogen (chlorine, bromine, etc.), carbamoyl, carboxy, alkoxy (C _1-4) carbonyl, alkyl (C _{1 -4)} Examples of the above-mentioned alkyl group substituted with a non-fiber-reactive group such as carbonyloxy, sulfo and sulfamoyl include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and 3-hydroxypropyl. -Hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxyethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3- Methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl,
4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl,
4-carboxybutyl, 1,2-dicarboxyethyl,
Carbamoylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-carbamoylethyl
Methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl,
4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl , Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like. R
Is preferably a hydrogen atom or an ethyl group.

X ₁ represents fluorine, chlorine, bromine, a lower alkoxy group, an amino group which may have a non-fiber-reactive substituent, or a group represented by the above formula (II). In the general formula (II), R ₁ represents a hydrogen atom or a lower alkyl group which may have a non-fiber-reactive substituent, and the alkyl groups are the same as those described above for R. And the like. Examples of the lower alkoxy group represented by X ₁ include the same groups as those exemplified for T ₁ and T ₂ . Examples of the non-fiber-reactive group that is a substituent of the amino group include, for example, a lower alkyl group, a phenyl group which may be substituted with chlorine, bromine, methoxy, ethoxy, methyl, ethyl, carboxy or sulfo. can give.

W ₁ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a non-fiber-reactive substituent. Examples of the alkylene group which may have a substituent include, for example,-(CH _{2
) 2 -, - (CH 2} ) 3 -, - CH (CH 3) CH
_{In addition to 2-} and the like, an alkylene group in which a carbon-carbon bond may be interrupted by a hetero atom such as-(CH ₂ ) ₂ O (CH ₂ ) _2- can be given.

The phenylene group optionally having a non-fiber-reactive substituent or the naphthylene group optionally having a non-fiber-reactive substituent represented by W ₁ is preferably methyl, ethyl A phenylene group optionally substituted with one or two substituents selected from the group consisting of methoxy, ethoxy, chloro, bromo and sulfo, or a naphthylene group optionally substituted with one or two sulfo groups. For example,

[0020]

Embedded image

[0021]

Embedded image

(In the formula, an asterisk means a bond leading to a nitrogen atom.)

[0023]

Embedded image

Is preferred.

Z ₁ represents —CH ＝ CH ₂ or the formula —CH ₂
'I represent, Z _1' CH ₂ Z ₁ represents a group removable by the action of an alkali. Examples of such Z ₁ ′ include fluoro, chloro, bromo, sulfate, thiosulfate, phosphate, acetyloxy and the like, and sulfate is particularly preferred.

In the general formula (I), X ₂ represents a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a lower alkoxy group, a non-fiber-reactive amino group optionally having a substituent, a nitrogen atom Represents an amino group which is a ring member of an N-heterocyclic ring, or a group represented by the general formula (III).
Examples of the lower alkoxy group include the same as those described for A ₁ and A ₂ . General formula (III)
In the group represented by, R ₂ represents a hydrogen atom or a lower alkyl group which may have the same substituent as those described above for R. W ₂ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a non-fiber-reactive substituent; specifically, the same groups as those described for W ₁ , and the like. Can be mentioned. Z ₂ is −
CH = CH ₂ or a general formula —CH ₂ CH ₂ Z ₂ ′;
₂ 'Z _1' represents a group capable of leaving by the action of the same alkali as those mentioned.

The amino group which may have a non-fiber-reactive substituent in X ₂ includes, for example, lower alkyl, C _5-7 cycloalkyl, C _7-12 aralkyl,
_Examples thereof include an amino group which may be substituted with a substituent such as _6-10 aryl and a heterocyclic group.

[0028] In a non-fiber-reactive substituent in such an amino group, an alkyl group may be branched be linear, also may be one be of low molecular weight polymer, preferably, A ₁ and a similar C 1 -C 4 alkyl group and those mentioned a _{2. Examples of} C _5-7 cycloalkylcycloalkyl include cyclopentyl and cyclohexyl groups, examples of C _7-12 aralkyl include benzyl and phenethyl, and examples of C _6-10 aryl include phenyl and naphthyl. it can. Examples of the heterocyclic group include furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole, benzoxazole and the like.

The non-fiber-reactive substituent in the amino group may further include fluoro, chloro, bromo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, acylamino (lower alkylcarbonylamino, benzoylamino, etc.), ureido, hydroxy, carboxy, sulfomethyl, sulfo, and may be substituted by a ₁ and those mentioned a ₂ and the same C 1 -C 4 alkyl and alkoxy groups.

Specific examples of the amino group which may have a non-fiber-reactive substituent represented by X ₂ include, for example, amino, methylamino, hydroxymethylamino, β-chloromethylamino, β-cyanoethyl Amino, 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-sulfoethylamino, etc., optionally substituted with one substituted or unsubstituted alkyl,

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

Anilino, 2-, 3- or 4-toluidino, xylidino, 2-, 3- or 4-chloroanilino, 2-, 3- or 4-anisidino, 2-, 3- or 4-ethylanilino, 2 -, 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) arylamino 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.

The amino group in which the nitrogen atom in X ₂ is a ring member of an N-heterocyclic ring is not particularly limited, but is preferably a 6-membered N-heterocyclic ring compound. May contain nitrogen, oxygen and sulfur.

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

The amino group which may have a non-fiber-reactive substituent at X _2, or, as an amino group nitrogen atom is a ring member of the N- heterocyclic ring is preferably an 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-sulfoanilino, 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-disulfonaphthyl- (2)-
Amino, 3,6,8-trisulfonaphthyl- (2) -amino, N-ethyl-N-phenylamino, N-ethyl-
2-methylanilino, N-ethyl-4-methylanilino, N-ethyl-3-sulfoanilino, N-ethyl-4
-Sulfoanilino, pyridyl- (2) -amino, morpholino, piperidino and piperazino.

The dioxazine compound used in the present invention can be produced by a known method, for example, according to the method described in JP-A-3-770, and is represented by the general formula (I). Is not particularly limited as long as the compound is represented by the general formula (VII):

[0039]

Embedded image (VII)

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

The azo compound used in the present invention is represented by the following general formula (IV).
R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a carboxyl group or a sulfo group. Examples of the lower alkyl group and lower alkoxy group include the same groups as those exemplified for A ₁ and A ₂ . In the formula, R ₁ ′ and R ₂ ′ are, independently of each other, a fiber represented by the general formula —SO ₂ Z ₃ , the general formula —A—SO ₂ Z ₄ , the general formula (V) or the formula (VI) Represents a reactive group, or a hydrogen atom, a lower alkyl group, a lower alkoxy group, a carboxyl group or a sulfo group.
However, at least one of R ₁ ′ and R ₂ ′ is represented by the above-mentioned general formula —SO ₂ Z ₃ , general formula —A—SO ₂ Z ₄ , general formula (V)
And any of the fiber-reactive groups represented by formula (VI).

In the general formula of the fiber-reactive group for R ₁ ′ and R ₂ ′, Z ₃ represents —CH ＝ CH ₂ or —CH ₂ C
The group represented by H ₂ Z ₃ ′, Z ₄ represents —CH ＝ CH ₂ or a group represented by the general formula —CH ₂ CH ₂ Z ₄ ′, and such Z ₃ ′ and Z ₄ ′ independently of one another Z ₁ ′ represents a group which is eliminated by the action of an alkali in the same manner as exemplified above. A is-
CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CONHCH ₂
Represents a group represented by CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ —. In the general formula (V), X ₃ represents the same halogen atom as exemplified in X ₁ , or has the same non-fiber-reactive substituent as exemplified in X _2. Represents an optionally substituted amino group. R ₇ represents a hydrogen atom or a lower alkyl group which may be substituted with a non-fiber-reactive group;
Examples of the lower alkyl include the same groups as those exemplified above for R.

Further, in the general formula (V), W ₃ represents an alkylene group, a phenylene group or a naphthylene group, each of which may have a non-fiber-reactive substituent.
Examples of the alkylene group, phenylene group or naphthylene group include the same groups as those exemplified for W ₁ . L is a hydrogen atom or a general formula -S
O ₂ Z ₅ (wherein Z ₅ is —CH = CH ₂ or a general formula —C
H ₂ CH ₂ Z ₅ ′, wherein Z ₅ ′ represents a group capable of leaving by the action of an alkali. ), And examples of Z ₅ ′ include the same groups as those exemplified for Z ₁ ′.

Lower alkyl groups for R ₁ ′ and R ₂ ′,
Examples of the lower alkoxy group include the same groups as those exemplified for A ₁ and A ₂ .

The azo compound used in the present invention can be prepared by known methods, for example, as described in JP-A-6-287463 and JP-A-56-12838.
It can be manufactured according to the method described in No. 0 publication,
There is no particular limitation as long as it is represented by the general formula (V), but preferably the compound represented by the general formula (VIII)

[0046]

Embedded image (VIII)

(Wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₁ ′ and R ₂ ′ have the above-mentioned meanings) or a salt thereof, or a general formula (IX)

[0048]

Embedded image (IX)

(Wherein X ₃ , R ₇ , W ₃ and Z ₅ have the above-mentioned meanings), and more preferably an azo compound represented by the general formula (X)

[0050]

Embedded image (X)

(Wherein X ₃ , Z ₃ , Z ₅ , W ₃ and R ₇ have the above-mentioned meanings) or
General formula (XI)

[0052]

Embedded image (XI)

(Wherein, R ₇ and Z ₅ have the same meanings as described above).

Dioxazine compound used in the present invention
(I) and the azo compound (IV) may be in the form of a free acid, a salt thereof, or a mixture thereof. Preferably, it is in the form of an alkali metal salt or an alkaline earth metal salt, and particularly preferably in the form of a sodium salt, a potassium salt or a lithium salt. Also,
The reactive dye composition of the present invention may contain two or more oxazine compounds represented by the general formula (I) or two or more azo compounds represented by the general formula (IV). Good.

In the reactive dye composition of the present invention, the content ratio of each compound is not particularly limited, but in the composition containing the dioxazine compound (I) and the azo compound (IV), the content of the dioxazine compound (I) Azo compounds (IV)
Of dioxazine compound (I) per 100 parts by weight of
Those containing up to 99 parts by weight are preferred.

The reactive dye composition of the present invention can be obtained by mixing the dioxazine compound (I) and the azo compound (IV), but the mixing method is not particularly limited. They may be mixed 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. As such other dyes, for example, CIReactive Yellow 145, C.I.
I. Reactive Red 222, CI Reactive Red 223, CI
Reactive Red 195 and CI Reactive Blue 221 are preferred, but there is no particular limitation, and the reactive group is a sulfatoethylsulfone group, a vinylsulfone group, a monochlorotriazine group, a monofluorotriazine group, a mononicotinic acid triazine group, a dichlorotriazine group, or difluoro. A dye having at least one of a monochloropyrimidine group, an α-bromoacrylamide group, and a trichloropyrimidine group, and a known dye can be used. Known dyes include, for example, or Sumifi
x, Sumifix Supra, Remazol, Realan, Levafix, Pro
cion, Cibacron, Basilen, Drimarene, Drimalan, Kaya
Cion, Kayacelon React, Lanasol and other commercially available dyes, and furthermore, JP-A-50-178, JP-A-56-9483, JP-A-56-15481, JP-A-56-118976. No., JP-A-56-128380
JP-A-57-2365, JP-A-57-89679
JP-A-57-143360, JP-A-59-154
No. 51, JP-A-58-191755, JP-A-59-9
No. 6174, JP-A-59-161463, JP-A-60-161
No.-6754, JP-A-60-123559, JP-A-6-123559
0-229957, JP-A-60-260654, JP-A-61-126175, JP-A-61-155469.
JP-A-61-225256, JP-A-63-779
No. 74, JP-A-63-225664, JP-A-1-18
5370, JP-A-3-770, JP-A-5-2473
66, dyes described in JP-A-6-287463, CIReactive Blue 19, CIReactive
Dyes represented by Blue 49 are exemplified.

The reactive dye composition of the present invention may optionally contain
Inorganic salts such as anhydrous sodium sulfate and salt, dispersants such as β-sodium naphthalenesulfonate / formalin condensate, sodium methylnaphthalenesulfonate / formalin condensate, acetylaminonaphthol compounds, and dusts such as di-2-ethylhexyl terephthalate Anti-scattering agent, sodium acetate,
It may contain a pH buffer such as sodium phosphate, a water softener such as polyphosphate, a known dyeing aid, and other dyes.

The reactive dye composition 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.

The present invention also provides a method for dyeing a nitrogen-containing fiber material or a fiber material containing nitrogen-containing fiber, characterized by using such a reactive dye composition. Such a nitrogen-containing fiber material is not particularly limited, and examples thereof include natural or synthetic nitrogen-containing fibers such as wool, silk, 6-nylon, 6,61-nylon and polyurethane, and mixed products thereof. . Examples of the mixed product include wool / polyester, mixed wool / acrylic products, and the like. As the shape of the fiber material used in the method of the present invention,
It includes a wide range of materials such as cotton-like loose materials, tops, threads, and cloths. The reactive dye composition of the present invention can be applied to various known dyeing methods. For example, the dyeing of a nitrogen-containing fiber material is first carried out in an acidic or weakly acidic state at 60-1.
A method is exemplified in which the dye is exhausted to the fiber at a temperature of 20 ° C., and then the dyeing bath is changed to alkaline for dyeing to fix the dye. When dyeing the combined nitrogen fiber material, the acid used to make the dyeing bath acidic or weakly acidic includes, for example, acetic acid, ammonium acetate, sulfuric acid, formic acid, and ammonium sulfate, but the acid is not limited thereto. When dyeing the combined nitrogen fiber material, a leveling assistant can be added to the dye bath. It is preferably a leveling aid comprising anionic, cationic, nonionic and amphoteric surfactants and mixtures thereof or a mixture of these leveling aids. Particularly preferred leveling aids are nonionic and amphoteric surfactants. When dyeing the nitrogen-containing fiber material, various salts, particularly alkali metal salts, for example, sodium sulfate, can be further added to the dyeing bath as an auxiliary.

When dyeing the nitrogen-containing fiber material, other additives such as a wool protecting agent, a wetting agent and an antifoaming agent can be added to the dyeing bath. When dyeing a nitrogen-containing fiber material, the pH is adjusted when the dye bath is changed to alkaline after the dye is exhausted to the fiber in an acidic or weakly acidic state,
The reaction is carried out using an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, ammonia, hexamethylenetetramine, guanidine or a salt thereof. Particularly preferred pH adjusters are ammonia, sodium hydrogencarbonate, sodium carbonate, hexane. Methylenetetramine and guanidine carbonate. Subsequently, the dyed product is sufficiently washed with water, and then washed with acetic acid or formic acid to neutralize the residual alkali. Then, it is washed with water and dried.

[0062]

The reactive dye composition of the present invention does not cause agglomeration of the dye when dyeing a nitrogen-containing fiber material, exhibits high exhaustion and fixability, and provides reproducibility of dyeing, level dyeing and washing. A dyed product having excellent fastness, high build-up property, and excellent in various fastnesses, particularly, light fastness, sweat fastness, potting fastness, wet rub fastness, washing fastness, and water fastness.

[0063]

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 10 parts of a worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 parts of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
Formula (1) in the form of the free acid

[0065]

Embedded image (1)

In the form of free acid in the form of 0.25 part of a dye of formula (2)

[0067]

Embedded image (2)

Each of 0.38 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. Thereafter, the temperature of the dyeing bath is increased at a rate of 1 ° C./min for 10 minutes.
The temperature was raised to 0 ° C. and maintained at the same temperature for 60 minutes. Thereafter, the water was drained, 400 parts of softened water was added, the temperature was raised to 80 ° C, and 25%
About 0.4 part of an aqueous ammonia solution was added to adjust the pH to 8.5 and maintained for 20 minutes. Subsequently, the dyed product was sufficiently washed with water, neutralized with acetic acid, washed with water, and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Also,
The coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 2 10 parts of the worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
Formula (3) in the form of the free acid

[0070]

Embedded image (3)

In the form of 0.03 part of the dye represented by the formula (4)

[0072]

Embedded image (4)

0.59 parts of the dye represented by the formula (1) were added in the form of aqueous solutions. The temperature of the dyeing bath was raised to 100 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. Then drain,
400 parts of softened water was added, the temperature was raised to 80 ° C., and about 2 parts of sodium hydrogen carbonate was added to adjust the pH to 8.7.
Hold for 0 minutes. Next, the dyed product was sufficiently washed with water, neutralized with acetic acid, further washed with water and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 3 10 parts of the worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 parts of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
Formula (5) in the form of the free acid

[0075]

Embedded image (5)

0.14 part of the dye represented by the formula (6) in the form of the free acid

[0077]

Embedded image (6)

Each of 0.12 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 100 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. Then drain,
400 parts of softened water was added and the temperature was raised to 60 ° C., about 0.8 parts of sodium carbonate was added to adjust the pH to 10, and in that state,
Hold for minutes. Then, the dyed product was sufficiently washed with water, neutralized with acetic acid, washed with water, and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment and the residual cleaning solution after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 4 10 parts of the worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 parts of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
Formula (7) in the form of the free acid

[0080]

Embedded image (7)

0.18 parts of the dye of the formula (1) and 0.42 parts of the dye of the formula (2) in the form of the free acid were each added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 100 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. Then drain,
400 parts of softened water was added, the temperature was raised to 80 ° C., about 0.4 parts of a 25% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added,
The pH was adjusted to 9.0 and kept there for 20 minutes. Subsequently, the dyed product was sufficiently washed with water, neutralized with formic acid, washed with water, and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 5 10 parts of the worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 parts of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
Formula (8) in the form of the free acid

[0083]

Embedded image (8)

0.15 part of the dye represented by the formula (9)

[0085]

Embedded image (9)

Each of 0.15 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 105 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. Then drain,
400 parts of softened water was added and the temperature was raised to 60 ° C., and about 0.8 parts of sodium carbonate and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 9.5.
And kept in that state for 20 minutes. Next, the dyed product was sufficiently washed with water, neutralized with formic acid, washed with water, and dried.
As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 6 10 parts of wool surge were mixed with 400 parts of softened water, 0.2 part of acetic acid,
The dyeing liquor was treated in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant at 50 ° C. for 15 minutes with stirring. Then 0.32 parts of the dye of the formula (8) in the form of the free acid and of the formula (10) in the form of the free acid

[0088]

Embedded image (10)

Each of 0.28 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 105 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. After draining, 400 parts of softened water was added and the temperature was raised to 60 ° C., and about 0.8 part of sodium carbonate and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 9.5, and the state was maintained for 20 minutes. Next, the dyed product was sufficiently washed with water, neutralized with formic acid, washed with water, and dried. As a result, a uniform dark blue dyeing product having no spots was obtained.
The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 7 10 parts of wool surge were mixed with 400 parts of softened water, 0.2 parts of acetic acid,
The dyeing liquor was treated in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant at 50 ° C. for 15 minutes with stirring. Then, in the form of the free acid, the formula (11)

[0091]

Embedded image (11)

0.3 part of the dye of the formula (9) and 0.3 part of the dye of the formula (9) in the form of the free acid were each added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 100 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. After draining, 400 parts of softened water was added, the temperature was raised to 60 ° C., and about 0.4 part of a 25% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 8.5. In that state, it was held for 20 minutes. Then, after thoroughly washing the dyed material with water, neutralized with formic acid, washed with water,
Dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 8 10 parts of wool surge were mixed with 400 parts of softened water, 0.2 parts of acetic acid,
The dyeing liquor was treated in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant at 50 ° C. for 15 minutes with stirring. Then the formula (12) in the form of the free acid

[0094]

Embedded image

In the form of 0.24 parts of a dye of the formula (13)

[0096]

Embedded image (13)

The temperature of the dyeing bath was raised at a rate of 1 ° C./min to 100 ° C. and kept at the same temperature for 60 minutes. Thereafter, the water was drained, 400 parts of softened water was added, the temperature was raised to 60 ° C., and about 0.4 part of a 25% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 8.5. Held. Then
After sufficiently washing the dyed product with water, it was neutralized with formic acid, washed with water and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 9 10 parts of wool surge were mixed with 400 parts of softened water, 0.2 part of acetic acid,
The dyeing liquor was treated in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant at 50 ° C. for 15 minutes with stirring. Then the formula (14) in the form of the free acid

[0099]

Embedded image (14)

In the form of free acid, 0.49 part of the dye of the formula (15)

[0101]

Embedded image (15)

Each of 0.11 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. The temperature of the dyeing bath was raised at a rate of 1 ° C./min to 100 ° C. and kept at the same temperature for 60 minutes. After draining, 400 parts of softened water was added, the temperature was raised to 60 ° C., and about 0.8 part of sodium carbonate and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 9.5, and the state was maintained for 20 minutes. Next, the dyed product was sufficiently washed with water, neutralized with formic acid, washed with water, and dried. As a result, a uniform stain-free blue dyed product was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 10 10 parts of a wool top were mixed with 400 parts of softened water, 0.2 part of acetic acid,
The dyeing liquor was treated in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant at 50 ° C. for 15 minutes with stirring. Then the formula (16) in the form of the free acid

[0104]

Embedded image (16)

0.15 parts of a dye of the formula (17) in the form of the free acid

[0106]

Embedded image (17)

Each of 0.17 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 105 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. Then drain,
400 parts of softened water was added and the temperature was raised to 60 ° C., about 0.4 parts of a 25% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added, and p
H was adjusted to 8.5 and kept there for 20 minutes. Then, after thoroughly washing the dyed material with water, neutralized with formic acid, washed with water,
Dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 11 10 parts of a wool top were mixed with 400 parts of softened water and 0.2 parts of acetic acid.
The dyeing liquor was treated at 50 ° C. for 15 minutes in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant while stirring. The dyes of formula (7) in free acid form are then added.
Formula (18) in the form of 42 parts and the free acid

[0109]

Embedded image (18)

Each of 0.18 parts of the dyes represented by the following formulas was added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 100 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. Then drain,
400 parts of softened water was added and the temperature was raised to 60 ° C., and about 0.8 parts of sodium carbonate and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 9.5.
And kept in that state for 20 minutes. Next, the dyed product was sufficiently washed with water, neutralized with formic acid, washed with water, and dried.
As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 12 10 parts of the worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
0.35 part of the dye of the formula (11) in the form of the free acid and 0.025 part of the dye of the formula (18) in the form of the free acid were each added in the form of an aqueous solution. The temperature of the dyeing bath was raised to 105 ° C. at a rate of 1 ° C./min and kept at the same temperature for 60 minutes. After draining, 400 parts of softened water was added, the temperature was raised to 60 ° C., and about 2 parts of sodium hydrogen carbonate was added to adjust the pH to 8.7, and the state was maintained for 20 minutes. Next, the dyed product was sufficiently washed with water, neutralized with formic acid, washed with water, and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 13 10 parts of wool surge were mixed with 400 parts of softened water, 0.2 parts of acetic acid,
The dyeing liquor was treated in a bath containing 2 parts of anhydrous sodium sulfate and 0.3 part of amphoteric surfactant at 50 ° C. for 15 minutes with stirring. The formula (19) in the form of the free acid is then

[0113]

Embedded image (19)

0.2 part of the dye represented by the formula (1) and 0.1 part of the dye represented by the formula (18) in the form of the free acid were each added in the form of an aqueous solution. The temperature of the dyeing bath was raised at a rate of 1 ° C./min to 100 ° C. and kept at the same temperature for 60 minutes. Thereafter, the water was drained, 400 parts of softened water was added, the temperature was raised to 60 ° C., and about 0.4 part of a 5% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 8.5. Held. Then
After sufficiently washing the dyed product with water, it was neutralized with formic acid, washed with water and dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 14 10 parts of the worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 parts of amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
0.4 part of the dye of the formula (11) in the form of the free acid and 0.3 part of the dye of the formula (10) in the form of the free acid were each added in the form of an aqueous solution. Dye bath temperature at 1 ° C / min 10
The temperature was raised to 0 ° C. and maintained at the same temperature for 60 minutes. afterwards,
After draining, 400 parts of softened water was added, the temperature was raised to 60 ° C., about 0.4 parts of a 5% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 8.5, and the state was maintained for 20 minutes. . Then, after thoroughly washing the dyed material with water, neutralized with formic acid,
After washing with water, it was dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

Example 15 10 parts of a worsted yarn were placed in a bath containing 400 parts of softened water, 0.2 parts of acetic acid, 2 parts of anhydrous sodium sulfate and 0.3 part of an amphoteric surfactant while stirring the dyeing liquor at 50 ° C. For 15 minutes. Then
0.21 part of the dye of the formula (16) in the form of the free acid and 0.35 part of the dye of the formula (9) in the form of the free acid were each added in the form of an aqueous solution. Dye bath temperature at 1 ° C / min 10
The temperature was raised to 0 ° C. and maintained at the same temperature for 60 minutes. afterwards,
After draining, 400 parts of softened water was added, the temperature was raised to 60 ° C., about 0.4 parts of a 5% aqueous ammonia solution and 12 parts of anhydrous sodium sulfate were added to adjust the pH to 8.5, and the state was maintained for 20 minutes. . Then, after thoroughly washing the dyed material with water, neutralized with formic acid,
After washing with water, it was dried. As a result, a uniform dark blue dyeing product having no spots was obtained. The light fastness and wet fastness of the obtained dyed product were good. Further, the coloring degree of the residual bath in the acid dyeing of the present dye composition, the residual bath in the alkali treatment, and the residual washing liquid after the dyeing was small, and the dye composition was excellent in exhaustion / fixing property and detergency.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masahide Ikeo 3-1-198 Kasuganaka, Konohana-ku, Osaka-shi F-term (reference) in Sumika Dye-Tech Co., Ltd. 4H056 JA06 JA11 JB01 JB02 JB03 JB04 JC01 JD03 JD13 JD25 JE03 4H057 AA01 AA02 BA07 BA22 BA24 DA01 DA21 GA07 HA05 HA06 JA10 JB02

Claims (6)

[Claims] 1. A dioxazine represented by the following general formula (I)
Or a salt thereof, and represented by the following general formula (IV)
Characterized by containing an azo compound or a salt thereof
Reactive dye composition. Embedded image(I) [where T₁And T_Two Are independently hydrogen and chlorine
Atom, bromine atom, lower alkyl group, lower alkoxy group
Or an aryl optionally having a non-fiber-reactive substituent
An oxy group represented by A₁ And A_Two Is hydrogen atom, chlorine atom, odor
Elemental atom, lower alkyl group, lower alkoxy group or
R is a hydrogen atom or a non-fiber-reactive substituent.
A lower alkyl group which may have a group,₁Is fluorine
Atom, chlorine atom, bromine atom, lower alkoxy group, non-fiber
An amino group which may have a reactive substituent or
General formula (II) -N (R₁) -W₁ -SO_Two-Z₁ (II) ｛where R₁Represents a hydrogen atom or a non-fiber-reactive substituent
A lower alkyl group which may be present,₁ Is non-fiber anti
Alkylene group which may have a reactive substituent, non-fiber
A phenylene group which may have a reactive substituent or
Naphthylene group optionally having a fiber-reactive substituent
To Z₁ Is -CH = CH_Two Or -CH_Two CH_Two
 Z₁’(Z₁’Is a group that leaves under the action of an alkali)
Represents a group. A fiber-reactive group represented by｝ is represented by X_TwoIs
Nitrogen, chlorine, bromine, hydroxyl, lower
It may have an alkoxy group or a non-fiber-reactive substituent.
Amino groups and nitrogen atoms are ring members of an N-heterocyclic ring.
A amino group or the following general formula (III) -N (R_Two) -W_Two -SO_Two-Z_Two (III) ｛where R_Two Is a hydrogen atom or a non-fiber-reactive substituent
An alkyl group optionally having_Two Is a non-fiber reaction
Alkylene group which may have a functional substituent,
A phenylene group or a non-fiber
A naphthylene group which may have a fiber-reactive substituent,
Z_Two Is -CH = CH_Two Or -CH _Two CH_Two Z
_Two'(Z_Two'Is a group which is eliminated by the action of an alkali)
Represents Represents a fiber-reactive group represented by｝. Where X
₁And X_TwoAt least one of the above formulas (II) and (I)
It is a fiber-reactive group represented by the general formula (III). ];(IV) [wherein, R_Three, R_Four, R_FiveAnd R₆Are independent of each other
, Lower alkyl group, lower alkoxy group, carboxyl
Represents a group or a sulfo group. R₁'And R_Two'Are independent of each other
Has the general formula -SO_TwoZ_Three｛Where Z_ThreeIs -CH = CH_Two 
Or -CH_Two CH_Two Z_Three'(Z_Three'Is the action of alkali
Represents a group which is eliminated by Fiber-reactive groups represented by｝
General formula -A-SO_TwoZ_Four｛Where Z_FourIs -CH = CH_Two Also
Is -CH_TwoCH_Two Z_Four'(Z_Four'Is desorbed by the action of alkali
A represents -CH_TwoCH_Two-, -CH_TwoC
H_TwoCH_Two-, -CONHCH_TwoCH_Two-Or -CH_TwoC
H_TwoOCH_TwoCH_TwoRepresents a group represented by-. Indicated by｝
Fiber reactive group, general formula (V)(V) ｛where R₇Is replaced by a hydrogen atom or a non-fiber reactive group
May be a lower alkyl group represented by X_ThreeIs a fluorine atom, chlorine
Amines optionally substituted with atoms or non-fiber reactive groups
A group represented by W_ThreeRepresents an alkylene group or a phenylene group.
Or naphthylene groups, all of which are non-fiber
It may have a responsive substituent. L is a hydrogen atom or
Is the general formula -SO_TwoZ_Five(Where Z_FiveIs -CH = CH_TwoOr one
General formula -CH _TwoCH_TwoZ_Five’Where Z_Five’Is an arca
Represents a group which is eliminated by the action of r. )｝
Responsive group, formula (VI)Fiber-reactive group represented by (VI), hydrogen atom, lower alkyl
Group, lower alkoxy group, carboxyl group or sulfo group
Represents a group. Where R₁’And R_Two’
Is the general formula -SO_TwoZ_Three, General formula -A-SO_TwoZ_Four, General formula
Any of the fiber-reactive groups represented by (V) and general formula (VI)
Indicates ｝ 2. A dioxazine compound represented by the general formula (I) per 100 parts by weight of the dioxazine compound represented by the general formula (I) or a salt thereof and an azo compound represented by the general formula (IV) or a salt thereof: The reactive dye composition according to claim 1, wherein the composition contains 1 to 99 parts by weight of the system compound. 3. A dioxazine compound represented by the general formula (I) or a salt thereof, which is represented by the following general formula (VII): (VII) The reactive dye composition according to claim 1 or 2, which is a compound represented by the formula ( ₁ ) wherein X ₁ , R ₂ and Z ₂ have the meanings described in claim 1 or a salt thereof. 4. An azo compound represented by the general formula (IV) or a salt thereof, which is represented by the general formula (VIII): (VIII) (wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₁ ′ and R ₂ ′ have the meanings described in claim 1) or a salt thereof, or a general formula (IX) Embedded image (IX) wherein X ₃ , R ₇ , W ₃ and Z ₅ are as defined in claim 1, or a salt thereof.
A reactive dye composition according to any one of claims 1 to 3. 5. An azo compound represented by the general formula (IV) or a salt thereof, which is represented by the general formula (X): (X) wherein X ₃ , Z ₃ , Z ₅ , R ₇ and W ₃ have the meanings described in claim 1, or a salt thereof, or a compound of the general formula (XI): (XI) (wherein, R ₇ and Z ₅ represent the meaning described in claim 1)
The reactive dye composition according to claim 1, which is a compound represented by the formula: 6. A method for dyeing a nitrogen-containing fiber material or a fiber material containing a nitrogen-containing fiber, characterized by using the reactive dye composition according to any one of claims 1 to 5.