JP2001335719A - Reactive dye mixture and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a reactive dye mixture for three primary colors, useful for dyeing cellulose fibers. SOLUTION: The reactive dye mixture contains a dye of formula (I) (wherein (m) and (n) are each 0 or 1; R1, R2 and R3 are each H, or the like; B1 and B2 are each an optionally substituted phenylene; and Y1 and Y2 are each SO2 CH=CH2, or the like), a dye of formula (II) (wherein (p) is 0 to 3; R4 is H, or the like; R5 is a halogeno, or the like; R7 is a halogeno, an alkyl, ureido, or the like; R8 is H; R9 is H, an alkyl, or the like; B3 is an optionally substituted phenylene; and Y3 is SO2CH=CH2, or the like), and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive dye useful for dyeing a cellulosic fiber material and the like, and its application to the fiber material.

[0002]

BACKGROUND OF THE INVENTION Due to their excellent dye properties, reactive dyes are frequently used for dyeing and printing fiber materials, especially cellulosic fibers. In dyeing fiber materials using reactive dyes, yellow, red and blue reactive dyes can be used as three primary colors, or those three primary color dyes can be used in combination, or a plurality of dyes can be appropriately combined for each of the three primary colors. Dyeing or printing methods are known to be useful.

[0003]

With respect to the reactive dyes used for the three primary colors, (i) each dye has good peel-off properties, levelness, dyeing temperature dependency and bath ratio dependency, and the reproducibility of dyeing is high. (Ii) the dyeing speeds of the three primary colors are equal, the dyeing temperature dependency is excellent, and these speeds and dependencies are uniform, and the compatibility is good; (iii) the three primary color dyes It is preferable to have excellent fastnesses such as fastness to light, combined fastness to sweat and sunlight, washing fastness, fastness to chlorine, etc., and to have the same level of fastness. In particular, regarding the levelness and reproducibility of dyeing of item (i),
With the diversification of the types and forms of the materials, the automation of factories, and the simplification of operations by shortening the dyeing time, there is a strong demand for a reactive dye mixture having better leveling properties and good dye reproducibility. In the case where the build-up properties of the three primary color dyes are different from each other and the dyeing properties do not match when dyeing using the respective dyes alone and when appropriately dyeing, a computer color matching system that has been frequently used in recent years Color matching becomes difficult,
If the dyeing speeds and the dyeing temperature dependencies of the three primary color dyes in item i) are different from each other, the reproducibility of dyeing such as the problem of uniform dyeing in which spotting occurs during dyeing and the occurrence of color differences between dyeing lots A problem of failure occurs. In addition, when the fastness levels of the three primary color dyes in the item (iii) are not uniform, discoloration is conspicuous in some or all of light fastness, sweat fastness, washing fastness, and chlorine fastness, which is favorable. Problems such as difficulty in obtaining a dyed product arise. On the other hand, dyeing using a reactive dye for each color or for the three primary colors, especially in the case of dyeing with a high dyeing concentration, requires a large amount of inorganic neutral salt, but the addition of a large amount of inorganic neutral salt is enormous. Since time and labor are required, the operability of the dyeing operation is significantly reduced. Also, addition of a large amount of inorganic neutral salt increases the content of inorganic neutral salt in dyeing wastewater, and is not preferable in view of environmental problems. Therefore,
There is a strong need for a reactive dye mixture that can provide high density dyeings with the addition of small amounts of inorganic neutral salts. In addition, due to the increasing interest in environmental issues in recent years, the rules for the coloring load of the dyeing wastewater also tend to be strict, and a reactive dye mixture having a high fixation rate and a low degree of coloring of the dyeing wastewater is strongly desired.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems in dyeing and printing a reactive dye mixture for each color or using three primary color dyes.
The present invention has been completed by finding that a specific mixture achieves this purpose.

That is, the present invention relates to a monoazo dye compound having a free acid form represented by the general formula (I) and a monoazo dye compound having a free acid form represented by the general formulas (II), (IV), (VI), (VIII) and (VIII). A reactive dye mixture containing at least one selected from the group consisting of five dye compounds represented by (X), and a method for dyeing or printing a fiber material using the mixture.

[0006]

Embedded image (I)

[Wherein m and n are independently 0 or 1
Wherein R ₁ and R ₂ independently represent a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl group, R ₃ represents a hydrogen atom or a methyl group, and B ₁ and B ₂ represent each other To C
_A phenylene group which may be substituted with one or two substituents selected from the group consisting of a ₁ to ₄ alkyl group, a ₁ to ₄ alkoxy group, a sulfo group and a halogen atom;
Represents a naphthylene group which may be substituted by two sulfo groups, and Y ₁ represents a group —SO ₂ CH ＝ CH ₂ or a group —SO ₂ CH ₂ C
H ₂ Z ₁ , where Y ₂ is a group —SO ₂ CH ＝ CH ₂ or a group —S
O ₂ CH ₂ CH ₂ Z ₂ , wherein Z ₁ and Z ₂ independently represent a group which is eliminated by the action of an alkali. ]

[0008]

Embedded image (II)

[Wherein p represents 0, 1, 2 or 3;
₄ represents a hydrogen atom or a C ₁ -C ₄ alkyl group which may be substituted; R ₅ represents a halogen atom, a phenylamino group which may be substituted by a non-fiber reactive group, or a compound represented by the general formula (III):

[0010]

Embedded image (III)

Wherein R ₆ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl group, and U ₁ represents an optionally substituted phenylene, an optionally substituted naphthylene group or an optionally substituted Represents an optionally substituted C ₂ -C ₆ alkylene group, and Y ₄ represents a group —SO ₂ CH ＝ CH ₂ or a group —SO ₂ CH
₂ CH ₂ Z ₄ , wherein Z ₄ represents a group which is eliminated by the action of an alkali. Represents a group represented by｝. R ₇ is a halogen atom, C ₁
-C ₄ alkyl group, ureido group, optionally substituted C ₁ -C ₄ alkylcarbonylamino group, optionally substituted C ₂ -C ₄ alkenylcarbonylamino group or optionally substituted phenylcarbonylamino Represents a group,
R ₈ represents a hydrogen atom, but R ₇ and R ₈ may together form a benzene ring, and the ring may be substituted with a sulfo group. R ₉ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group or a sulfo group, and B ₃ represents a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a sulfo group and a halogen atom. A phenylene group which may be substituted by one or two substituents selected from the group of atoms, or 1
Represents a naphthylene group which may be substituted by two sulfo groups, and Y ₃ represents a group —SO ₂ CH ＝ CH ₂ or a group —SO ₂ CH ₂ C
Represents H ₂ Z _3, Z ₃ represents a group capable of leaving by the action of an alkali. ]

[0012]

Embedded image (IV)

[Wherein R_TenAnd R₁₂Are hydrogen independently of each other
Atom or optionally substituted C₁~ C _FourTable of alkyl
Then R₁₃Is a hydrogen atom, optionally substituted C₁~ C_FourA
Alkyl group, nitro group, sulfo group or -SO_TwoC_TwoH_FourCl
And Me represents a metal ion having an atomic number of 27 to 29.
Then B_FiveIs C₁~ C_FourAlkyl group, C₁~ C_FourAlkoxy
Group, a sulfo group and a halogen atom.
Is phenylene which may be substituted by two substituents
Group or naph which may be substituted with one sulfo group
Represents a tylene group, Y_FiveIs the group -SO_TwoCH = CH_TwoOr group-
SO_TwoCH_TwoCH_TwoZ_FiveAnd Z_FiveIs removed by the action of alkali.
Represents a leaving group;₁₁Is a halogen atom, a non-fiber reactive group
An optionally substituted phenylamino group or a general formula
(V)

[0014]

Embedded image (V)

｛R ₁₄ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl group, and U ₂ represents an optionally substituted phenylene group, an optionally substituted naphthylene group or an optionally substituted Represents a C _{2 to} C ₆ alkylene group, and Y ₆ represents a group —SO ₂ CH ＝ CH ₂ or a group —SO ₂ CH ₂ C
Represents H ₂ Z _6, Z ₆ represents a group capable of leaving by the action of an alkali. Represents a group represented by｝. ]

[0016]

Embedded image (VI)

Wherein q represents 0, 1 or 2, R ₁₅ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl, B ₆ represents a C ₁ -C ₄ alkyl group, _A phenylene group which may be substituted by one or two substituents selected from the group consisting of a _{1 to} C ₄ alkoxy group, a sulfo group and a halogen atom, or a naphthylene group which may be substituted by one sulfo group And Y ₇ represents a group —SO ₂ CH ＝ CH ₂ or a group —
SO ₂ CH ₂ CH ₂ Z ₇ , Z ₇ represents a group capable of leaving by the action of an alkali, and R ₁₆ represents a halogen atom, a phenylamino group optionally substituted with a non-fiber reactive group, or a compound represented by the general formula (VI
I)

[0018]

Embedded image (VII)

｛R ₁₇ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl, and U ₃ represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted C ₂ -C ₆ alkylene, Y ₈ represents a group -SO ₂ CH = CH ₂ or the group _{-SO 2 CH 2 CH 2 Z 8} , Z 8 represents a group capable of leaving by the action of an alkali. Represents a group represented by｝. ]

[0020]

Embedded image (VIII)

Wherein R ₁₈ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl, and U ₄ represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted Represents an optionally substituted C ₂ -C ₆ alkylene,
Y ₉ represents a group —SO ₂ CH ＝ CH ₂ or a group —SO ₂ CH ₂ CH ₂ Z
_And Y ₁₀ represents a group —SO ₂ CH ＝ CH ₂ or a group —SO ₂ C
H ₂ CH ₂ Z ₁₀ , Z ₉ and Z ₁₀ each independently represent a group capable of leaving by the action of an alkali, R ₁₉ represents a halogen atom,
A phenylamino group which may be substituted with a non-fiber reactive group or a compound of the general formula (IX)

[0022]

Embedded image (IX)

｛R ₂₀ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl, and U ₅ represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted C ₂ -C ₆ alkylene, Y ₁₁ represents a group -SO ₂ CH = CH ₂ or the group _{-SO 2 CH 2 CH 2 Z 11} , Z 11 represents a group capable of leaving by the action of an alkali. Represents a group represented by｝. ]

[0024]

Embedded image (X)

Wherein W 1 and W 2 are independently of each other hydrogen
Atom, halogen atom, C₁~ C_FourAlkyl group, C₁~ C_FourA
Aryloxy optionally having a alkoxy group or a substituent
X 1 and X 2 are each independently a hydrogen atom,
Halogen atom, C₁~ C_FourAlkyl group, C₁~ C_FourAlkoki
R represents a carboxyl group or a carboxyl group;_{twenty one}And R_{twenty three}Is hydrogen field
C or an optionally substituted C₁~ C_FourTable showing alkyl groups
Then B₇Is C₁~ C_FourAlkyl group, C₁~ C_FourAlkoxy
Group, a sulfo group and a halogen atom.
Is phenylene which may be substituted by two substituents
Group or naph which may be substituted with one sulfo group
Represents a tylene group, Y₁₂Is the group -SO_TwoCH = CH_Two Or group-
SO_TwoCH_TwoCH_TwoZ₁₂And Z₁₂Is the action of alkali
Represents a leaving group;_{twenty two}Is a halogen atom, non-fiber reactive group
Optionally substituted phenylamino group, non-fiber reaction
An alkylamino group optionally substituted with a group or a general formula
(X)

[0026]

Embedded image (XI)

｛R ₂₄ represents a hydrogen atom or an optionally substituted C ₁ -C ₄ alkyl, and U ₆ represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted C ₂ -C ₆ alkylene, Y ₁₃ represents a group -SO ₂ CH = CH ₂ or the group _{-SO 2 CH 2 CH 2 Z 13} , Z 13 represents a group capable of leaving by the action of an alkali. Represents a group represented by｝. Hereinafter, the present invention will be described in detail.

[0028]

DETAILED DESCRIPTION OF THE INVENTION The general formulas (I), (II) and (I)
V), (V), (VI), (VII), (VIII),
In (IX) and (X), R₁, R_Two, R_Four, R₆, R
_Ten, R₁₂, R₁₄ , R_Fifteen, R₁₇, R₁₈, R₂₀, R_{twenty one}, R_{twenty three}
And R_{twenty four}Represents a hydroxyl group, a cyano group, an alkoxy group
Group, carboxy group, carbamoyl group, alkoxycarbo
Nyl group, alkylcarbonyloxy group, sulfo group, sulf
Substituted with a substituent such as a famoyl group or a halogen atom
May be C₁~ C_FourAlkyl group or hydrogen atom
You. Such an optionally substituted C₁~ C_FourAlkyl group
Specific examples include methyl, ethyl, n-propyl, is
o-propyl, n-butyl, iso-butyl, sec-
Butyl, 2-hydroxyethyl, 2-hydroxypropyl
, 3-hydroxypropyl, 2-hydroxybutyl,
3-hydroxybutyl, 4-hydroxybutyl, 2,3
-Dihydroxypropyl, 3,4-dihydroxybuty
, Cyanomethyl, 2-cyanoethyl, 3-cyanopro
Pill, 4-cyanobutyl, methoxymethyl, ethoxyme
Chill, 2-methoxyethyl, 2-ethoxyethyl, 3-
Methoxypropyl, 3-ethoxypropyl, 2-hydro
Xy-3-methoxypropyl, carboxymethyl, 2-
Carboxyethyl, 3-carboxypropyl, 4-cal
Boxybutyl, 1,2-dicarboxyethyl, carbamo
Ilmethyl, 2-carbamoylethyl, 3-carbamoy
Propyl, 4-carbamoylbutyl, methoxycarbo
Nylmethyl, ethoxycarbonylmethyl, 2-methoxy
Carbonylethyl, 2-ethoxycarbonylethyl, 3
-Methoxycarbonylpropyl, 3-ethoxycarbonyl
Propyl, 4-methoxycarbonylbutyl, 4-ethoxy
Xycarbonylbutyl, methylcarbonyloxymethyl
, Ethylcarbonyloxymethyl, 2-methylcarbo
Nyloxyethyl, 2-ethylcarbonyloxyethyl
, 3-methylcarbonyloxypropyl, 3-ethyl
Carbonyloxypropyl, 4-methylcarbonyloxy
Cibutyl, 4-ethylcarbonyloxybutyl, sulfo
Methyl, 2-sulfoethyl, 3-sulfopropyl, 4-
Sulfobutyl, sulfamoylmethyl, 2-sulfamo
Ilethyl, 3-sulfamoylpropyl, 4-sulf
Amoylbutyl, chloromethyl, bromomethyl, 2-c
Loroethyl, 2-bromoethyl, 3-chloropropyl,
3-bromopropyl, 4-chlorobutyl, 4-bromobut
Chill and the like can be mentioned.

R₁, R_Two, R_Four, R₆, R_Ten, R₁₂, R₁₄,
R_Fifteen, R₁₇, R₁₈, R₂₀, R_{twenty one}, R _{twenty three}And R_{twenty four}As
Is preferably a hydrogen atom, a methyl group or an ethyl group,
Atoms are particularly preferred.

In the general formula (I), R ₃ represents a hydrogen atom or a methyl group. As R ₃ , a hydrogen atom is particularly preferred. In the general formula (I), m and n independently represent 0 or 1. In particular, m is preferably 0,
n is preferably 1.

Formulas (I), (II), (IV) and (VI)
And (X), B ₁ , B ₂ , B ₃ , B ₅ , B ₆ and B ₇
1 or 2 which is selected from the group of C ₁ -C ₄ alkyl group (the alkyl group may be substituted by C ₁ -C ₄ alkoxy), C ₁ -C ₄ alkoxy group, a sulfo group and a halogen atom Represents a phenylene group which may be substituted by a substituent, or a naphthylene group which may be substituted by one sulfo group. Examples of the substituent of the phenylene group include, for example, methyl, ethyl, n-propyl, iso-
Propyl, n-butyl, iso-butyl, sec-butyl, methoxy, ethoxy, n-propoxy group, iso-
Propoxy group, n-butoxy group, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,
-Methoxybutyl, 4-ethoxybutyl, sulfo, chloro, bromo and the like.

B ₁ , B ₂ , B ₃ , B ₅ , B ₆ and B ₇ are each substituted with an unsubstituted phenylene group or one or two substituents selected from the group consisting of methyl, methoxy and sulfo. Phenylene is preferred, and unsubstituted phenylene is particularly preferred.

Formulas (I), (II), (III),
(IV), (V), (VI), (VII), (VII
In I), (IX), (X) and (XI), Y₁, Y
_Two, Y_Three, Y_Four, Y_Five, Y₆, Y₇, Y₈, Y₉, Y_Ten, Y₁₁,
Y₁₂And Y₁₃Is a group -SO_TwoCH = CH_TwoRepresents or
Is a group -SO_TwoCH_TwoCH_TwoZ₁, -SO_TwoCH_Two
CH_TwoZ_Two, -SO_TwoCH_TwoCH_TwoZ_Three, -SO_TwoCH_TwoCH_Two
Z_Four, -SO_TwoCH_TwoCH_TwoZ_Five, -SO_TwoCH_TwoCH_TwoZ₆,
-SO_TwoCH_TwoCH_TwoZ₇, -SO_TwoCH_TwoCH_TwoZ₈, -SO
_TwoCH_TwoCH_TwoZ₉, -SO_TwoCH_TwoCH_TwoZ_Ten, -SO_TwoCH
_TwoCH_TwoZ₁₁, -SO_TwoCH_TwoCH_TwoZ₁₂And -SO_TwoCH_Two
CH_TwoZ₁₃(Z₁, Z_Two, Z_Three, Z_Four, Z_Five, Z₆, Z₇,
Z₈, Z₉, Z_Ten, Z₁₁, Z₁₂And Z₁₃Are al
A group which is eliminated by the action of potassium). Z₁, Z_Two, Z_Three,
Z_Four, Z_Five, Z₆, Z₇, Z₈, Z₉, Z_Ten, Z₁₁, Z₁₂as well as
Z₁₃Are, for example, a sulfate group, a thiosulfate ester
Ter group, phosphate group, acetate group and halogeno
Or 1 or 2 consisting of the group of carboxy and carbamoyl
A pyridinio group which may be substituted with
I can do it. Z₁, Z_Two, Z_Three, Z_Four, Z_Five, Z₆, Z
₇, Z₈, Z₉, Z_Ten, Z₁₁, Z₁₂And Z₁₃As the sulfur
Acid ester groups are preferred. Y₁, Y_Two, Y_Three, Y_Four, Y_Five,
Y₆, Y₇, Y₈, Y₉, Y_Ten, Y₁₁, Y₁₂And Y₁₃Preferred
A specific example is -SO_TwoCH = CH_TwoOr -SO_Two
CH_TwoCH_TwoOSO_ThreeH, -SO_TwoCH
_TwoCH_TwoOSO_ThreeH is particularly preferred.

In the general formula (II), when R ₇ is an optionally substituted C ₁ -C ₄ alkylcarbonylamino or an optionally substituted C ₂ -C ₄ alkenylcarbonylamino, Alkenyl substituents include sulfo, carboxy, halogen atoms and the like. When R ₇ is an optionally substituted phenylcarbonylamino, examples of the substituent of the phenyl include a sulfo, carboxy, methyl, and halogen atom. Preferred R ₇ is methyl or ureido, or an amino group substituted with acetyl, propionyl, maleinyl, succinyl or benzoyl, or R ₇ and R ₈ together form a benzene ring, and And the same ring is substituted with one sulfo.
C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy represented by R ₉ is linear or branched, and the alkyl or alkoxy may have a substituent such as chloro or hydroxy. , Preferably unsubstituted, and particularly preferably methyl and methoxy. The best combination of R ₇ , R ₈ and R ₉ is when R ₈ and R ₉ are hydrogen and R ₇ is ureido or acetylamino, or
R ₇ is methyl, R ₈ is a hydrogen atom, and R ₉
Is methoxy.

In the general formula (II), p is 0, 1, 2,
Or 3 is represented. p is preferably 2 or 3, and particularly preferably 3.

In the general formula (IV), R ₁₃ is a hydrogen atom,
An optionally substituted C ₁ -C ₄ alkyl group, nitro group,
It represents a sulfo group or -SO2C2H4Cl, and particularly preferably a hydrogen atom.

Among the metal ions of atomic numbers 27 to 29 represented by Me in the general formula (IV), a preferred metal ion is copper ion.

Formulas (III), (V), (VII) and (VII)
In I), (IX) and (XI), U1, U2, U3,
When U4, U5 and U6 are phenylene which may be substituted, the phenylene which may be substituted includes C1 to C4 alkyl groups such as methyl group and ethyl group, and C1 to C4 groups such as methoxy and ethoxy. C4 alkoxy group, C
1-C4 alkoxy C1-C4 alkyl group, chlorine, phenylene which may be substituted by one or two substituents selected from the group of halogen such as bromine and sulfo group,
Examples of the substituent of the phenylene include methyl, ethyl, n-propyl, iso-propyl, n-butyl and i.
so-butyl, sec-butyl, methoxy, ethoxy,
n-propoxy group, iso-propoxy group, n-butoxy group, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,
Examples thereof include 3-ethoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, sulfo, chloro, and bromo.

As the optionally substituted phenylene represented by U1, U2, U3, U4, U5 and U6, unsubstituted phenylene or one or two phenylenes selected from the group consisting of methyl, methoxy and sulfo Phenylene substituted by a substituent is preferred, and unsubstituted phenylene is particularly preferred.

Formulas (III), (V), (VII) and (VII
In I), (IX) and (XI), U1, U2, U3,
When U4, U5 and U6 are optionally substituted naphthylene, these optionally substituted naphthylene preferably include naphthylene optionally substituted with one sulfo group.

Formulas (III), (V), (VII) and (VII)
In I), (IX) and (XI), U1, U2, U3,
U4, U5 and U6 are optionally substituted C2 to C6
When it is alkylene, these optionally substituted C2-C6 alkylene includes, for example,-(CH2) 2
C2-C4 alkylene groups such as-,-(CH2) 3- and -CH (CH3) CH2- are preferred.

In the general formula (VI), q is 0, 1 or 2
Represents As q, 1 or 2 is preferable, and 1 is particularly preferable.

Formulas (II), (IV), (VI) and (VIII)
And (X), R ₅ , R ₁₁ , R ₁₆ , R ₁₉ and R ₂₂
Is a phenylamino group which may be substituted with a non-fiber reactive group, the amino compound forming an optionally substituted phenylamino group includes, for example, 1-
Aminobenzene, 1-amino-2-, -3- or -4-
Methylbenzene, 1-amino-2,4-, -3,4- or -3,5-dimethylbenzene, 1-amino-2-, -3
-Or -4-ethylbenzene, 1-amino-2-, -3
-Or -4-methoxybenzene, 1-amino-2-,-
3- or -4-ethoxybenzene, 1-amino-2-,
-3- or -4-chlorobenzene, 1-amino-2-,
-3- or -4-bromobenzene, 1-amino-2-,
-3- or -4-fluorobenzene, 3- or 4-aminophenylmethanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 3- or 4-methylaminobenzenesulfonic acid, 3- or 4- Ethylaminobenzenesulfonic acid, 5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,3- or -1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid,
4-amino-5-methylbenzene-1,2-disulfonic acid, 2-, 3- or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid , 4-amino-2-hydroxybenzenesulfonic acid, 5-amino-2-ethoxybenzenesulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or -4-
Methylbenzene, 1-ethylamino-3- or -4-methylbenzene, 1-methylamino-2-, -3- or-
4-chlorobenzene, 1-ethylamino-2-, -3-
Or -4-chlorobenzene, 1- (2-hydroxyethyl) amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5 -Dimethoxybenzene, 2-, 3- or 4-aminophenol, 1-amino-3- or -4-acetylaminobenzene, 2,4- or 2,5-diaminobenzenesulfonic acid, and 1-aminobenzene- 3- or -4- (β-hydroxyethylsulfone) and the like.

R ₅ , R ₁₁ , R ₁₆ and R ₁₉ include fluoro, chloro and 1-aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-2 -, -3- or -4-ethylbenzene, 2-3
-Or 4-aminobenzenesulfonic acid, 2-, 3- or 4-aminobenzoic acid, residues of N-methylaminobenzene and N-ethylaminobenzene are preferred, and fluoro, chloro and 1-amino- Particularly preferred are residues of 2-ethylbenzene, 3-aminobenzenesulfonic acid and 2-aminobenzoic acid.

Examples of the alkylamino group which may be substituted with the non-fiber reactive group represented by R ₂₂ in the general formula (X) include, for example, methylamino, hydroxymethylamino, ethylamino, n-propylamino, isopropyl Amino, n-butylamino, isobutylamino, sec
-Butylamino, β-methoxyethylamino, β-ethoxyethylamino, γ-methoxypropylamino, β-
Hydroxyethylamino, β-sulfo-ethylamino, γ-hydroxypropylamino, N-β-sulfoethyl-N-methylamino, β-carboxyethylamino, β-chloromethylamino, β-cyanoethylamino, β-sulfoethylamino, Examples thereof include N, N-dimethylamino, N, N-dihydroxymethylamino, N, N-diethylamino, N, N-di-β-hydroxyethylamino, cycloalkylamino, benzylamino, and morpholino.

Preferred R ₂₂ include fluoro and chloro, 1-aminobenzene, 1-amino-2-ethylbenzene, 2-, 3- or 4-aminobenzenesulfonic acid, 1-amino-2-, -3- Or the residue of 4-methoxybenzene, 2-, 3- or 4-aminobenzoic acid, N-methylaminobenzene and N-ethylaminobenzene,
Amino, hydroxymethylamino, N, N-di-β-hydroxyethylamino, β-sulfoethylamino, β-
Carboxyethylamino and morpholino, with fluoro, chloro, amino and β-sulfoethylamino being particularly preferred.

In the general formula (X), W1 and W2 are each independently a hydrogen atom, a halogen atom such as chloro or bromo, methyl, ethyl, n-propyl, isopropyl, n
Linear or branched alkyl groups having 1 to 4 carbon atoms, such as -butyl, isobutyl and sec-butyl, methoxy,
Linear or branched alkoxy groups having 1 to 4 carbon atoms such as ethoxy, n-propoxy and isopropoxy, or phenoxy, p-methoxyphenyloxy and p-
Represents an aryloxy group which may have a substituent such as methylphenoxy. W1 and W2 are preferably each independently a hydrogen atom, chloro, methyl, ethyl, methoxy, or ethoxy, and chloro is particularly preferable.

In the general formula (X), X ₁ and X ₂ each independently represent a hydrogen atom, a halogen atom such as chloro or bromo, methyl, ethyl, n-propyl, isopropyl, n
Linear or branched alkyl groups having 1 to 4 carbon atoms, such as -butyl, isobutyl and sec-butyl, methoxy,
It represents a linear or branched C1-C4 alkoxy or carboxyl group such as ethoxy, n-propoxy and isopropoxy. X ₁ and X ₂ are preferably each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a methoxy group, an ethoxy group, or an n-propoxy group, and a methoxy group or an ethoxy group is particularly preferable.

The dye compound represented by the formula (I) can be produced according to a known method, for example, the method described in JP-A-63-101458, and the dye compound represented by the formula (II)
Can be produced according to a known method, for example, the method described in JP-A-63-225664. The dye compound represented by the general formula (IV) can be produced by a known method. For example, it can be produced according to the method described in JP-B-3-10669, and the dye compound represented by the general formula (VI) can be produced by a known method, for example,
It can be produced according to the method described in JP-A-56-128380. The dye compound represented by the general formula (VIII) can be produced by a known method, for example, JP-A-6-28746.
No. 3 and JP-A-56-128380. The dye compound represented by the general formula (X) can be produced by a known method, for example, a method described in JP-A-9-2.
It can be produced according to the method described in JP-A-02788.

Formulas (I), (II), (IV), (VI),
The dye compounds (VIII) and (X) are present in the form of the free acid or in the form of a salt thereof, particularly preferably an alkali metal and alkaline earth metal salt, particularly preferably a sodium salt, a potassium salt and a lithium salt. .

The method for preparing the reactive dye mixture of the present invention is not particularly limited, and the dye compounds may be mixed and then dyed, or the dye compounds may be mixed in a dye bath when dyeing. Is also good.

The reactive dye mixture of the present invention has the general formula (I)
And a monoazo dye compound represented by formula (II) or (I
V), (VI), (VIII) and one or more selected from the group of five dye compounds represented by (X), preferably a monoazo dye represented by the general formula (I) 99-1% by weight of the compound is represented by the general formula (II), (IV),
It contains 1 to 99% by weight of one or more compounds selected from the dye compound group represented by (VI), (VIII) and (X). More preferably, 80 to 20% by weight of at least one of the monoazo dye compounds represented by the general formula (I) and the monoazo dye compound represented by the general formulas (II), (IV), (VI), (VIII) and (X) 20 to 80% by weight of one or more compounds selected from the dye compound group.

The reactive dye mixture of the present invention may be optionally used
Inorganic salts such as sodium sulfate and sodium salt, β-sodium naphthalene sulfonate / formalin condensate, methyl naphthalene sulfonate / formalin condensate, dispersants such as acetylaminonaphthol compounds, and dust dispersion such as di-2-ethylhexyl terephthalate It may contain a known dyeing aid such as an inhibitor, a pH buffer such as sodium acetate and sodium phosphate, a water softener such as polyphosphate, and other dyes.

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

The reactive dye mixture of the present invention is useful for dyeing or printing fiber materials, especially cellulosic fiber materials and fiber materials containing the same. Although the cellulosic fiber material is not particularly limited, natural or regenerated cellulosic fibers such as cotton, linen, hemp, jude, ramie fibers, viscose human silk, Bemberg (registered trademark) and the like, and hybrid products thereof are exemplified. You. Examples of the fiber material containing cellulosic fibers include cotton / polyester, cotton / nylon, and cotton / acrylic mixed products.

The dyeing and printing method of the present invention is not particularly limited. In the exhaust dyeing method, for example, one or more inorganic neutral salts such as anhydrous sodium sulfate and salt, and sodium carbonate,
A method of dyeing using one or more acid binders such as sodium bicarbonate, caustic soda and sodium tertiary phosphate is exemplified. For the above inorganic neutral salts and acid binders, 1 g per liter of dyeing bath
It is preferable to use the above. The charging of the inorganic neutral salt or the acid binding agent into the dye bath may be performed at once or may be performed separately. Also, other dyeing assistants such as leveling agents, slow dyeing agents, bath softeners and the like may be used in combination. The dyeing temperature is usually 4
It is 0-90 degreeC, Preferably it is 50-90 degreeC.

In the cold batch-up dyeing method, padding is carried out using an inorganic neutral salt such as anhydrous sodium sulfate and sodium chloride, or an acid binder such as caustic soda and sodium silicate, and then the padding is carried out in a sealed packaging material.
A method of dyeing by leaving at a temperature of 90 ° C., preferably 10 to 40 ° C. is exemplified. In the continuous dyeing method, for example, an acid binder such as sodium carbonate, sodium bicarbonate, and caustic soda is mixed with a dye padding solution, padding is performed by a known method, and a one-bath padding method of dyeing by dry heat or steaming, and after dye padding. And a two-bath padding method in which an inorganic neutral salt such as anhydrous sodium sulfate or sodium salt, or an acid binder such as caustic soda or sodium silicate is padded and dried or steamed for dyeing. The printing method includes, for example, a one-phase printing method in which a printing paste containing an acid binder such as sodium carbonate and sodium bicarbonate is printed, followed by drying and steaming for printing, and after printing the printing paste, anhydrous sodium sulfate and salt. And a two-phase printing method in which an inorganic neutral salt of the above and an acid binder solution such as caustic soda and sodium silicate are put into a high temperature of 80 ° C. or higher to perform printing. At this time, a leveling agent, a slow dyeing agent, a softening agent in the bath and the like may be used in combination.

Acid binders suitable for fixing the reactive dye mixtures according to the invention on cellulose fibers include alkali metals or alkaline earth metals and inorganic or organic acids or compounds which release alkalis under heating. It is a water-soluble basic salt. For example, hydroxides of alkali metals and alkali metal salts of inorganic or organic acids of weak to moderate strength are exemplified, and soda salts and potassium salts are particularly preferred. Examples of the acid binder include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

[0059]

The reactive dye mixture of the present invention has good compatibility, leveling property, reproducibility and build-up property in dyeing and printing of fiber materials, and fastness to sweat-sunlight combined action. Dyeings and prints having good fastnesses such as fastness to chlorine, fastness to oxidizing gas and the like. In particular, in exhaust dyeing, the dyeing temperature dependency and bath ratio dependency are small and excellent in reproducibility, and even at high dyeing concentration, sufficient color yield can be obtained by addition of a small amount of neutral inorganic salt, and the fixation rate is high, The coloring load of dyeing wastewater is small.

[0060]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples.
The present invention is not limited to these examples. In the examples,% and parts represent% by weight and parts by weight unless otherwise specified.

Example 1 The form of the free acid is represented by the following formula (1)

[0062]

Embedded image (1)

39 parts of the dye represented by the following formula (2)

[0064]

Embedded image (2)

17 parts of the dye represented by the following formula (3)

[0066]

Embedded image (3) 24 parts of the dye represented by the following formula (4)

[0067]

Embedded image (4)

13 parts of a dye represented by the following formula (5)

[0069]

Embedded image By mixing 7 parts of the dye represented by (5), a brown reactive dye mixture is obtained. 0.26 part of this dye mixture and 4 parts of anhydrous sodium sulfate are charged by a known method into a dyeing apparatus (bath ratio 1:10, bath temperature 70 ° C.) in which 10 parts of a knitted fabric made of cotton fiber are set. The knitted fabric is treated at 70 ° C. for about 20 minutes after charging, then 2 parts of sodium carbonate are poured into the bath, and the knitted fabric is dyed and washed at this temperature for 60 minutes.
A uniform, dark scarlet red dyeing with good washing and perspiration fastness without spots is obtained. Also, the reproducibility of the above dyeing is good.

Example 2 The form of the free acid is represented by the following formula (6)

[0071]

Embedded image (6)

25 parts of the dye represented by the above formula, 13 parts of the dye represented by the above formula (2), 33 parts of the dye represented by the above formula (3), 19 parts of the dye represented by the above formula (4), ) Are mixed to obtain a navy dye mixture. 0.36 parts of this mixture and 4 parts of anhydrous sodium sulfate were introduced into a dyeing apparatus (bath ratio 1:10, bath temperature 80 ° C.) in which 10 parts of a knitted fabric made of cotton fiber were set as in Example 1. After the pouring, the knitted fabric is treated at 80 ° C. for about 20 minutes, and then caustic soda of 38 ° B. (7.5 ml for 100 g of anhydrous sodium sulfate) is poured into the bath. Dyeing and washing gives a uniform dark scarlet red dyeing with good washing and perspiration fastness and without spots. Also, the reproducibility of the above dyeing is good.

Example 3 The form of the free acid is represented by the following formula (7)

[0074]

Embedded image (7)

17 parts of the dye represented by the formula (2), 51 parts of the dye represented by the formula (3), 17 parts of the dye represented by the formula (4), 10 parts of the dye represented by the formula (4), Is mixed with 5 parts of the dyestuff of the formula (1) to give a carkey-colored reactive dyestuff mixture. 30 parts of this mixture and 400 parts of sodium chloride are charged by a known method into a cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) in which 1,000 parts of a yarn made of cotton fiber are set.
After treating at 80 ° C. for 20 minutes, 200 parts of sodium carbonate is put into the bath, and then dyed and washed at this temperature for 60 minutes, and the washing and sweat fastness are good, and there is no concentration difference between the inner and outer layers of cheese. A uniform scarlet red dyed yarn is obtained. or,
The reproducibility of this cheese dyeing is also good.

Example 4 17 parts of the dye represented by the above formula (6) in the form of the free acid, and the following formula (8) in the form of the free acid

[0077]

Embedded image (8)

39 parts of the dye represented by the formula (11), 11 parts of the dye represented by the above formula (3), 27 parts of the dye represented by the above formula (5), and the form of the free acid is represented by the following formula (9)

[0079]

Embedded image (9)

By mixing 6 parts of the dye represented by the formula (1), a brown reactive dye mixture is obtained. 0.26 parts of the above composition and 4 parts of anhydrous sodium sulfate are put into a dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) in which 10 parts of a rayon knit are set, and knitting is performed at 80 ° C. for 20 minutes. After adding 2 parts of sodium carbonate, dyeing and washing at this temperature for 60 minutes gives a uniform scarlet red color without spots, and a dyeing with good washing and fastness to sweat and sunlight. Also, the reproducibility is good even if the above dyeing is repeated.

Example 5 10 parts of a rayon knit were set in a dyeing apparatus,
The bath ratio was 1:10 and the water temperature was 70 ° C. 25 parts of the dye represented by the above formula (6) and the form of the free acid are represented by the following formula (10)

[0082]

Embedded image (Ten)

13 parts of the dye represented by the formula (3), 16 parts of the dye represented by the formula (3), 38 parts of the dye represented by the formula (5), and 8 parts of the dye represented by the formula (9) are sufficiently mixed. To obtain a dye mixture. After charging 0.36 part of this mixture and 4 parts of anhydrous sodium sulfate in a bath, the knitted fabric is treated at the temperature at the time of charging for 20 minutes, and 2 parts of sodium carbonate is charged. Next, the knitted fabric is treated at the above temperature for 60 minutes, and after finishing the dyeing, the fabric is washed and finished in a conventional manner. The resulting stain is uniform scarlet red with no spots. Washing and perspiration fastness of this dyed product are both good. In addition, even if the above-mentioned dyeing is repeatedly performed, the reproducibility of the dyeing is good in any case.

Example 6 17 parts of the dye represented by the above formula (1), 51 parts of the dye represented by the above formula (2), 8 parts of the dye represented by the above formula (3), and the dye represented by the above formula (5) 20 parts, the form of the free acid is the following formula (1
1)

[0085]

Embedded image (11)

When 4 parts of the dye represented by the formula (1) are mixed, a brown reactive dye mixture is obtained. After dissolving 200 parts of this mixture with hot water, the mixture was cooled to 25 ° C., and sodium alginate 1 was added.
, 10 parts of sodium metanitrobenzenesulfonate, and 20 parts of sodium hydrogencarbonate, and further, water was added to make the total amount 1000 parts at 25 ° C. Using this solution as a padding liquid, padding a cotton fabric, After drying at 120 ° C. for 2 minutes and then steaming at 100 ° C. for 5 minutes to fix the dyestuff, a dyeing is obtained which is uniform dark blue and has good washing and sweat fastness. Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 7 0.5 part of the reactive dye mixture obtained in Example 3 was
Dissolve in 00 parts of water, add 20 parts of sodium sulfate, and add 1 cotton
Add 0 parts and raise the temperature to 70 ° C. 3 after reaching 70 ° C
After a lapse of 0 minutes, 4 parts of sodium carbonate was added, and the mixture was dyed at the same temperature for 1 hour. Next, washing and soaping are performed. The amount of coloring of the dyeing wastewater at the time of washing and soaping is small, and a dyed product excellent in various fastnesses such as washing fastness of uniform and dark color can be obtained.

Example 8 Instead of 0.26 parts of the reactive dye mixture, 0.5 part of the reactive dye mixture and the sodium salt of the condensate of methylnaphthalenesulfonic acid and formaldehyde (degree of sulfonation 11
Dyeing is carried out in the same manner as in Example 1 except that 0.06 parts of 0% and an average degree of polymerization of 1.8) are used. The dyeings obtained have the same quality as the dyeings obtained in Example 1.

Example 9 Dyeing is carried out in the same manner as in Example 1, except that instead of 0.26 parts of the reactive dye mixture obtained in Example 1, 0.5 parts of the reactive dye mixture are used. The dyed product obtained using 0.5 part of the reactive dye mixture is sufficiently thicker than that of Example 1 using 0.26 part, and the build-up property of the used dye mixture is good.

Example 10 Using the reactive dye mixture obtained in Example 1, a color paste having the following composition is prepared.

Color paste composition Reactive dye mixture 5 parts Urea 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance (water) 13 parts Total 100 parts

This color paste is printed on mercerized cotton broad, intermediately dried, steamed at 100 ° C. for 5 minutes, washed with hot water, soaped, washed with hot water, and dried.
Finish. The resulting prints are uniform and dark in color and have good fastnesses.

Example 11 30 parts of the reactive dye mixture obtained in Example 1 are dissolved in hot water and cooled to 25 ° C. To this dye solution, 15 parts of a 32.5% aqueous solution of caustic soda and 50 °
And water at 25 ° C. to make a total amount of 1000 parts.
Immediately after the mixing, the cotton fabric is padded using this solution as a padding solution. The padded cotton fabric is rolled up, closed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, washed by a conventional method, and dried to finish. The dyeings obtained are uniform and dark in color and have good fastnesses.

Continued on the front page (72) Inventor Minoru Uchiyama 3-1-198 Kasuganaka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. F-term (reference) 4H056 FA01 JA02 JA06 JA12 JA14 JB03 JC05 JD03 JD08 JD20 JD23 4H057 AA01 AA02 BA07 BA22 BA24 DA01 DA24 GA04 GA07

Claims (14)

[Claims] (1) a monoacid represented by the general formula (I)
The azo dye compound and the form of the free acid are represented by the general formula (II) or (I
Five dyes represented by (V), (VI), (VIII) and (X)
Reaction comprising at least one selected from the group of compounds
Dye mixture. Embedded image(I) [wherein, m and n independently represent 0 or 1;₁
And R_TwoAre independently hydrogen atoms or substituted
Good C₁~ C_FourRepresents an alkyl group of_ThreeIs a hydrogen atom or
Represents a methyl group;₁And B_TwoAre independently of each other C₁~ C_Fourof
Alkyl group, C₁~ C_FourAn alkoxy group, a sulfo group and
One or two substituents selected from the group of
Phenylene group which may be substituted or
Represents a naphthylene group which may be substituted with a sulfo group,
Y₁Is the group -SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ
₁And Y_TwoIs the group -SO_TwoCH = CH_TwoOr group -SO_TwoC
H_TwoCH_TwoZ_TwoAnd Z₁And Z_TwoAre independent of each other
Represents a group which is eliminated by the action of r. ](II) wherein p represents 0, 1, 2 or 3;_FourIs a hydrogen atom
Or optionally substituted C₁~ C_FourRepresents an alkyl group,
R_FiveIs substituted with a halogen atom or a non-fiber reactive group.
Good phenylamino group or general formula (III)(III) Ｒ where R₆Is a hydrogen atom or an optionally substituted C₁
~ C_FourRepresents an alkyl group;₁Is an optional
Phenylene group, naphthylene group which may be substituted or substituted
C which may be replaced_Two~ C₆Represents an alkylene group, Y_Four
Is the group -SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ_FourTo
Represents, Z_FourRepresents a group capable of leaving by the action of an alkali. }so
Represents the group shown. R₇Is a halogen atom, C₁~ C_FourAl
A kill group, a ureido group, an optionally substituted C₁~ C_FourA
Alkylcarbonylamino group, optionally substituted C_Two
~ C_FourAlkenylcarbonylamino group or substituted
Represents a phenylcarbonylamino group which may be₈Is water
Represents an element atom,₇And R₈Together form a benzene ring
And the ring is substituted with a sulfo group.
You may. R₉Is a hydrogen atom, C₁~ C_FourAlkyl group, C₁~
C_FourRepresents an alkoxy group or a sulfo group;_ThreeIs C₁~ C_FourA
Alkyl group, C₁~ C_FourAlkoxy, sulfo and halogen
One or two substituents selected from the group of
Optionally substituted phenylene group or one sulfo
A naphthylene group which may be substituted with_ThreeIs
Group-SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ_ThreeThe table
Then Z_ThreeRepresents a group capable of leaving by the action of an alkali. ](IV) [wherein, R_TenAnd R₁₂Are independently hydrogen atoms or substituted
C that may be₁~ C _FourRepresents alkyl, R₁₃Is hydrogen
Atom, optionally substituted C₁~ C_FourAlkyl group, nitro
B, a sulfo group or -SO2C2H4Cl;
Represents a metal ion having an atomic number of 27 to 29;_FiveIs C₁~
C_FourAlkyl group, C₁~ C_FourAlkoxy group, sulfo group and
One or two substituents selected from the group of halogen atoms
A more substituted phenylene group, or one
Represents a naphthylene group which may be substituted with a sulfo group,
Y_FiveIs the group -SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ
_FiveAnd Z_FiveRepresents a group capable of leaving under the action of an alkali;
₁₁May be substituted with a halogen atom or a non-fiber reactive group.
Phenylamino group or the general formula (V)(V) ｛R₁₄Is a hydrogen atom or an optionally substituted C₁~ C_FourA
Represents a alkyl group,_TwoIs an optionally substituted phenyle
Group, an optionally substituted naphthylene group or a substituted
May be C_Two~ C₆Represents an alkylene group, Y₆Is the group
SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ₆Represents
Z₆Represents a group capable of leaving by the action of an alkali. Indicated by｝
Represents a group. ](VI) wherein q represents 0, 1 or 2;_FifteenIs a hydrogen atom or
Optionally substituted C₁~ C_FourRepresents alkyl, B₆Is
C₁~ C_FourAlkyl group, C₁~ C_FourAlkoxy group, sulfo group
And one or two substitutions selected from the group consisting of
A phenylene group which may be substituted by a group, or 1
The naphthylene group which may be substituted with
Then Y₇Is the group -SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoC
H_TwoZ₇And Z₇Represents a group that is eliminated by the action of an alkali.
Then R₁₆Is substituted with a halogen atom or a non-fiber reactive group.
A phenylamino group or a compound of the general formula (VII)(VII) ｛R₁₇Is a hydrogen atom or an optionally substituted C₁~ C_FourA
Stands for quill, U_ThreeIs an optionally substituted phenyle
, Optionally substituted naphthylene or substituted
May be C_Two~ C₆Represents alkylene, Y₈Is the group -SO_TwoC
H = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ₈And Z₈Is
It represents a group that is eliminated by the action of lukari. The group represented by｝
You. Embedded image(VIII) [wherein, R₁₈Is a hydrogen atom or an optionally substituted C₁~
C_FourRepresents alkyl, U_FourIs an optionally substituted phenyl
Len, optionally substituted naphthylene or substituted
May be C_Two~ C₆Represents alkylene, Y₉Is the group -SO_Two
CH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ₉And Y_Ten
Is the group -SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ_Ten
And Z₉And Z_TenAre independent of each other by the action of alkali
Represents a leaving group;₁₉Is a halogen atom, non-fiber reactive group
A phenylamino group or a general formula
(IX)(IX) ｛R₂₀Is a hydrogen atom or an optionally substituted C₁~ C_FourA
Stands for quill, U_FiveIs an optionally substituted phenyle
, Optionally substituted naphthylene or substituted
May be C_Two~ C₆Represents alkylene, Y₁₁Is the group -SO_Two
CH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ₁₁And Z₁₁
Represents a group capable of leaving by the action of an alkali. Group represented by｝
Represents ](X) wherein W1 and W2 are each independently a hydrogen atom, a halogeno
Atom, C₁~ C_FourAlkyl group, C₁~ C_FourAlkoxy group or
Represents an aryloxy group which may have a substituent,
X1 and X2 each independently represent a hydrogen atom, a halogen atom,
Child, C₁~ C_FourAlkyl group, C₁~ C_FourAlkoxy group or
Represents a ruboxyl group;_{twenty one}And R_{twenty three}Is a hydrogen atom or substitution
C that may be₁~ C_FourRepresents alkyl, B₇Is C₁~
C_FourAlkyl group, C₁~ C_FourAlkoxy group, sulfo group and
One or two substituents selected from the group of halogen atoms
A more substituted phenylene group, or one
Represents a naphthylene group which may be substituted with a sulfo group,
Y₁₂Is the group -SO_TwoCH = CH_TwoOr group -SO_TwoCH_TwoCH_Two
Z₁₂And Z₁₂Represents a group that is eliminated by the action of an alkali.
Then R_{twenty two}Is substituted with a halogen atom or a non-fiber reactive group.
May be substituted with a phenylamino group, a non-fiber reactive group
Optionally an alkylamino group or a compound of the general formula (XI)(XI) ｛R_{twenty four}Is a hydrogen atom or an optionally substituted C₁~ C_FourA
Stands for quill, U₆Is an optionally substituted phenyle
, Optionally substituted naphthylene or substituted
May be C_Two~ C₆Represents alkylene, Y₁₃Is the group -SO_Two
CH = CH_TwoOr group -SO_TwoCH_TwoCH_TwoZ₁₃And Z₁₃
Represents a group capable of leaving by the action of an alkali. Group represented by｝
Represents ] 2. The mixture according to claim 1, wherein R ₁ and R ₂ in the formula (I) are each independently a hydrogen atom, a methyl group or an ethyl group, and R ₃ is a hydrogen atom. 3. B ₁ and B ₂ in the formula (I) are each independently substituted by one or two substituents selected from the group consisting of an unsubstituted phenylene group and a methyl group and a methoxy group. 3. The mixture according to claim 1, which is a phenylene group. 4. The mixture according to claim 1, wherein m in formula (I) is 0 and n is 1. 5. A dye compound represented by the formula (II):
The mixture according to any one of claims 1 to 4, wherein p in the formula is 2 or 3, R ₇ is ureido or acetylamino, and R ₈ and R ₉ are hydrogen atoms. 6. A dye compound represented by the formula (II):
B ₃ in the formula is an unsubstituted phenylene group, or
2. A phenylene group substituted by one or two substituents selected from the group consisting of a methyl group and a methoxy group.
A mixture according to any one of claims 1 to 5. 7. A dye compound represented by the formula (IV):
In the formula, R ₁₁ is chloro or fluoro, R ₁₃ is a hydrogen atom, and B ₅ is an unsubstituted phenylene group or one or two substituents selected from the group consisting of a methyl group and a methoxy group. The mixture according to any one of claims 1 to 6, which is a substituted phenylene group. 8. A dye compound represented by the formula (VI):
In the formula, R ₁₆ is chloro or fluoro, and B ₆ is an unsubstituted phenylene group or a phenylene group substituted by one or two substituents selected from the group consisting of a methyl group and a methoxy group. Item 8. The mixture according to any one of Items 1 to 7. 9. A dye compound represented by the formula (VI):
In the formula, R ₁₆ is a group represented by the general formula (VII), and U ₃ and B ₆ are each independently selected from the group consisting of an unsubstituted phenylene group, a methyl group and a methoxy group The mixture according to any one of claims 1 to 7, which is a phenylene group substituted with two substituents. Comprises 10. A dye compound represented by the formula (VIII), may be U ₄ substitutions in the equation is C ₂ -C
₆ alkylene, mixtures of any of claims 1 to 9 R ₁₉ is chloro, fluoro or non-fiber-reactive phenyl amino group optionally substituted with a group. 11. A dye compound represented by the formula (VIII), wherein R ₁₉ is a group represented by the general formula (IX), and U ₄ and U ₅ are each independently a non-substituted phenylene group. Or the phenylene group substituted by one or two substituents selected from the group consisting of a methyl group and a methoxy group. 12. A dye compound represented by the formula (X):
The mixture according to any one of claims 1 to 11, wherein W1 and W2 in the formula are chloro, X1 is a hydrogen atom, and X2 is a C1 to C4 alkoxy group. 13. A dye compound represented by the formula (X):
B ₇ in the formula is an unsubstituted phenylene group or a phenylene group substituted by one or two substituents selected from the group consisting of a methyl group and a methoxy group.
13. The mixture according to any of 12. 14. A method for dyeing or printing a fiber material, comprising using the mixture according to claim 1.