JP2002121415A - Reactive dye mixture and application thereof to fiber material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a navy-blue reactive dye useful for dyeing cellulose fiber or the like. SOLUTION: This dye mixture contains a bisazo dye compound of formula (I) and an azo dye compound of formula (II) [R1, R2, R12, R13, R14 and R15 are each hydrogen; U1 and U2 are each a specific vinyl sulfone-based group reactive with a fiber; X1 to X5 are each chloro or the like; T1 and T2 are each a specific group unreactive with the fiber; one of W1 and W2 is amino and the other is hydroxy; one of two (*) marks in [] is a bond to -U1 or -U2 and the other is the bond to -T1 or -T2].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dark blue reactive dye mixture useful for dyeing or printing cellulosic fiber materials and the like.
And its application to fiber materials.

[0002]

2. Description of the Related Art A dark blue reactive dye used for dyeing and printing cellulosic fiber materials and the like is disclosed in, for example,
No. 78458 and JP-A-57-198757.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found that in dyeing fiber materials and the like,
Good dyeability at low salt concentration, reproducibility of dyeing, leveling property, dyeing performance (build-up property, effective dyeing rate and wash-off property, etc.) and dye solubility are good, and various fastnesses (chlorine resistance) Resistance, light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance and washing resistance to peroxide)
As a result of diligent studies to develop a reactive dye that gives an excellent dark blue dyed product, it has two triazine rings, and one of the rings has one vinyl sulfone-based compound via a divalent linking group. A bisazo dye compound having a fiber reactive group,
A specific mixture comprising three triazine rings, an azo dye compound having a vinylsulfone-based fiber reactive group on one end of the triazine ring, and a non-fiber-reactive group on the other end of the triazine ring. Have achieved the above object, and have completed the present invention.

That is, according to the present invention, the form of the free acid is represented by the following formula (I):
And a reactive dye mixture comprising a bisazo dye compound represented by the formula (1) and an azo dye compound having a free acid form represented by the following formula (II), and dyeing or printing a fiber material using the reactive dye mixture: It provides a method.

[0005]

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[Wherein R ¹ and R ² are the same or different and each represents hydrogen or an optionally substituted alkyl;
¹ is the following formula (1a), (1b) or (1c)

[0007]

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Wherein R ³ represents hydrogen or an optionally substituted alkyl; R ⁴ and R ⁵ are the same or different and are hydrogen, optionally substituted alkyl or optionally substituted phenyl; A ¹ represents an optionally substituted phenylene or an optionally substituted naphthylene, A ² represents an optionally substituted alkylene,
Q ¹ represents -O-, -S- or -NR ^6- , R ⁶ is hydrogen, optionally substituted alkyl or optionally substituted phenyl, and r and s are the same or different , 2, 3 or 4, wherein Z ¹ , Z ² and Z ³ are the same or different and represent a vinylsulfone-based reactive group represented by the following formula (2a) or (2b).

[0009]

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Wherein Y ¹ and Y ² are the same or different and represent —CH ＝ CH ₂ or —CH ₂ CH ₂ L, L is a group capable of leaving by the action of an alkali, and R ⁷ is Represents hydrogen or alkyl which may be substituted, and m is an integer of 1 to 6. ]> Represents a fiber-reactive group. X ¹ and X ²
Are the same or different and are fluoro, chloro, or optionally substituted pyridinio, and T ¹ is a group represented by the following formula (3
a), (3b) or (3c)

[0011]

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Wherein R ⁸ represents hydrogen or an optionally substituted alkyl, and R ⁹ represents an optionally substituted alkyl, an optionally substituted cyano, or a group having 1 carbon atom.
1 or 2 selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylic acid ester, amino, acylamino and alkyl (1 to 4 carbon atoms) amino A phenyl which may be substituted by a substituent,
¹⁰ represents hydrogen, optionally substituted alkyl or optionally substituted phenyl, and Q ² represents -CH _2- , -O
—, —S—, —SO ₂ — or —NR ¹¹ —, wherein R ¹¹ represents hydrogen or an optionally substituted alkyl, and n is 1, 2 or 3. Represents a non-fiber-reactive group represented by｝. However, two * marks shown in [] indicate that one is -U
A bond between the ¹ and the other represents a bond with -T ^1. ]

[0013]

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Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are
The same or different, and represents hydrogen or an alkyl which may be substituted, and U ² represents a fiber-reactive group represented by the formula (1a), (1b) or (1c), wherein U ¹ and U ² May be the same or different.
X ³ , X ⁴ and X ⁵ are the same or different and are fluoro,
Chloro, or optionally substituted pyridinio,
T ² represents a non-fiber-reactive group represented by the formula (3a), (3b) or (3c), and T ¹ and T ² may be the same or different. One of W ¹ and W ² is amino, and the other is hydroxy. However, two * marks shown in [] indicate that one is -U
A bond of ^2, the other represents a bond with -T ^2. Hereinafter, the present invention will be described in detail.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a bifunctional compound represented by formula (I)
Suazo dye compounds and azo dye compounds of formula (II)
A reactive dye mixture comprising:¹, R^Two, R
¹², R¹³, R ¹⁴And R^FifteenAre the same or different and are hydrogen
Or an optionally substituted alkyl,
The kill is preferably one having 1 to 4 carbon atoms.
Examples of the substituent of phenyl include hydroxy, cyano, and charcoal.
Alkoxy having 1 to 4 carbon atoms, hydroxya having 1 to 4 carbon atoms
Lucoxy, halogeno, carbamoyl, carboxy, al
Coxy (carbon number 1-4) carbonyl, alkyl (carbon number
1-4) carbonyloxy, sulfo and sulfamoyl
And the like. The above alkyl, the alkyl
Alkoxy having 1 to 4 carbon atoms as a substituent,
Coxy (1-4 carbon) carbonyl and alkyl (carbon
Formulas 1 to 4) The carbonyloxy may be linear,
It may be branched.

Specific examples of the optionally substituted alkyl represented by R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ include, for example, methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, sec-butyl, tert-
Butyl, 2-hydroxyethyl, 2- (2-hydroxyethoxy) ethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 1-hydroxy Methyl-1-methylethyl, 1,1
-Di (hydroxymethyl) ethyl, 1,1-di (hydroxymethyl) -2-hydroxyethyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl,
-Cyanopropyl, methoxymethyl, 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, carbamoylmethyl, 2
Carbamoylethyl, 3-carbamoylpropyl, 4
Carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl,
-Methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, -Methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-
Sulfamoylpropyl, 4-sulfamoylbutyl and the like can be mentioned.

R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are preferably hydrogen, methyl or ethyl, more preferably hydrogen.

In the dye compound used in the present invention,
U ¹ and U ² in formulas (I) and (II) are the same or different from each other, and are represented by formula (1a), (1b) or (1c)
Represents a fiber-reactive group represented by R ³ represents hydrogen or optionally substituted alkyl; R ⁴ and R ⁵ represent hydrogen, optionally substituted alkyl or optionally substituted phenyl, but R ³ , R ⁴ and R ⁵ Examples of the alkyl represented by R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ and R
^{The same} ones as exemplified in ¹⁵ can be mentioned. Also, R ⁴
And the substituent of phenyl represented by R ⁵ include, for example, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, halogeno, hydroxy, sulfo, cyano and the like. R ³ , R ⁴ and R ⁵ are preferably hydrogen, methyl or ethyl.

U ¹ and U ² in formulas (I) and (II)
Is a group represented by the formula (1a), A ¹ represents phenylene which may be substituted or naphthylene which may be substituted. Examples of the phenylene which may be substituted include, for example, carbon Examples thereof include phenylene which may be substituted with one or two substituents selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, and halogeno. Preferred phenylene which may be substituted includes phenylene which may be substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo. Specific examples of such phenylene include, for example,

[0020]

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[Wherein the symbol # represents a bond connected to -NR ^3- (R ³ has the above-mentioned meaning). And the like. Preferred optionally substituted phenylene represented by A ¹ is phenylene optionally substituted by one or two groups selected from methyl and methoxy.

The optionally substituted naphthylene represented by A ¹ in the formula (1a) includes, for example, one having 1 carbon atom
And alkyls having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, and naphthylene which may be substituted with one or two substituents selected from the group of halogeno. The optionally substituted naphthylene represented by A ¹ is preferably a naphthylene optionally substituted by one or two sulfo. Specific examples of such naphthylene include, for example,

[0023]

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[In this formula, the symbol # represents a bond connected to —NR ³ — (R ³ has the above-mentioned meaning). And the like.

A ¹ is preferably phenylene which may be substituted with one or two groups selected from methyl and methoxy, and unsubstituted phenylene is particularly preferred.

A ² in the formula (1b) represents an alkylene which may be substituted, and the alkylene includes alkyl having 1 to 4 carbon atoms, halogeno, hydroxy,
Sulfo, cyano, alkoxy having 1 to 4 carbon atoms, 1 carbon atom
And alkoxycarbonyl having 1 to 4 carbon atoms, alkylcarbonyloxy having 1 to 4 carbon atoms, and alkylene having 2 to 4 carbon atoms which may be substituted with a substituent selected from the group consisting of carbamoyl. The optionally substituted alkylene represented by A ² preferably includes unsubstituted alkylene having 2 to 4 carbon atoms, and among them, ethylene and trimethylene are particularly preferred.

Q in equation (1c)¹Is -O-, -S-
Or -NR⁶-Represents R⁶Is hydrogen, may be substituted
Represents an alkyl or an optionally substituted phenyl
Is R ⁶And optionally substituted alkyl represented by
For example, R¹, R^Two, R^{1 Two}, R¹³, R¹⁴And R
^FifteenAlkyl having 1 to 4 carbon atoms and the like as exemplified in
Can be mentioned. Also, R⁶Is replaced by
As phenyl which may be substituted, for example,
And optionally phenyl. R⁶Is
Preferably, it is a hydrogen atom, methyl or ethyl.

R and s in the formula (1c) are the same or different, and are 2, 3 or 4. In the group represented by the formula (1c), Q ¹ is —O—, and r and s are
Same or different, preferably it has 2 or 3, the following _{** - CH 2 CH 2 -O-} CH 2 CH 2 - ** - CH 2 CH 2 -O-CH 2 CH 2 CH 2 - ** —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ — ** — CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ — [In the formula, ** indicates —NR ⁵ — (R ⁵ is (Having the above meaning). ] Group are more _{preferable, ** - CH 2 CH 2 -O} -CH 2 CH 2 - is particularly preferred.

U ¹ and U ² in formulas (I) and (II)
The fiber-reactive group represented by the formula (1a) or (1)
The group represented by b) is preferred, and the group represented by formula (1a) is particularly preferred.

U ¹ and U ² in formulas (I) and (II)
Is a group represented by the formula (1a), it is preferable that A ¹ is phenylene which may be substituted and R ³ is hydrogen, methyl or ethyl. When U ¹ and U ² are groups represented by the formula (1b), it is preferable that A ² is ethylene or trimethylene and R ⁴ is hydrogen, methyl or ethyl.

Z in the formulas (1a), (1b) and (1c)
¹ , Z ² and Z ³ each represent a vinyl sulfone-based reactive group represented by the formula (2a) or (2b), and Y ¹ and Y ² represent —SO
₂ CH = CH ₂ or —SO ₂ CH ₂ CH ₂ L (L is a group which is eliminated by the action of an alkali);
Examples thereof include groups such as sulfate, thiosulfate, phosphate, acetate, and halogeno. Among them, a sulfate group and chloro are preferable.
Z ¹ , Z ² and Z ³ are preferably -CH = CH ₂ , -CH ₂
CH ₂ Cl, etc., or -CH ₂ CH ₂ OSO ₃ H can be mentioned, in particular -CH = CH ₂ and -CH ₂ CH ₂ OSO ₃ H
Is preferred.

M in the formula (2b) is an integer of 1 to 6,
R ⁷ represents hydrogen or an alkyl which may be substituted, and examples of the alkyl which may be substituted include those exemplified above for R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ Alkyl having 1 to 4 carbon atoms and the like can be mentioned. As the group represented by the formula (2b), those in which R ⁷ is hydrogen and m is 2 or 3 are particularly preferable. As the groups represented by Z ¹ , Z ² and Z ³ , groups represented by the formula (2a) are particularly preferred.

X ¹ , X ² , X in formulas (I) and (II)
³ , X ⁴ and X ⁵ are the same or different and represent fluoro, chloro or optionally substituted pyridinio, and as the optionally substituted pyridinio, for example,
Pyridinio, 2-, 3- or 4-carboxypyridinio, 2-, 3- or 4-carbamoylpyridinio, 3-
Examples thereof include sulfopyridinio, 4- (2-sulfoethyl) pyridinio, 3- (2-hydroxyethyl) pyridinio, 4-chloropyridinio, 3-methylpyridinio, and 3,5-dicarboxypyridinio. In particular,
3- or 4-carboxypyridinio is preferred. X above
^{As the} groups represented by ¹ , X ² , X ³ , X ⁴ and X ⁵ , fluoro and chloro are particularly preferred.

T ¹ and T in the formulas (I) and (II)
² represents a non-fiber-reactive group represented by the formula (3a), (3b) or (3c). R ⁸ in the formula (3a) represents hydrogen or an optionally substituted alkyl, and the alkyl is preferably a linear or branched one having 1 to 4 carbon atoms.

Examples of the optionally substituted alkyl include, for example, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, sulfamoyl, carbamoyl, hydroxy, halogeno (chloro, bromo, etc.), cyano, carboxylate and sulfone. 1 selected from the group of acid esters
Or 1 carbon atom which may be substituted by two substituents
To 4 alkyl and the like. Specific examples of the optionally substituted alkyl represented by R ⁸ include the same groups as those exemplified for R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ . it can. As the optionally substituted alkyl, preferably, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2-sulfoethyl, 2-methoxyethyl, 2-carboxy Ethyl, 2-carbamoylethyl, 2-sulfamoylethyl and the like are exemplified.

R in equation (3a)⁹Is replaced
Optionally substituted alkyl, optionally substituted cyano, or
Is an alkyl having 1 to 4 carbons, an alkoxy having 1 to 4 carbons
Si, carboxy, halogeno, hydroxy, cyano, cal
Bamoyl, carboxylate, amino, acylamino
And alkylamino (1 to 4 carbon atoms)
Phenyl which may be substituted by one or two substituents
Represents R⁹Optionally substituted alkyl represented by
Specific examples of R¹, R ^Two, R¹², R¹³, R¹⁴
And R^FifteenList the same groups as those exemplified in
And preferably methyl, ethyl, n-propyl
, Isopropyl, n-butyl, isobutyl, sec-butyl
Tyl, tert-butyl, 2-hydroxyethyl, 2- (2
-Hydroxyethoxy) ethyl, 1-hydroxymethyl
-1-methylethyl, 1,1-di (hydroxymethyl)
Ethyl, 1,1-di (hydroxymethyl) -2-hydro
Xyethyl, 2-sulfoethyl, 2-methoxyethyl,
2-carboxyethyl, 2-carbamoylethyl and 2
-Sulfamoylethyl and the like.

An alkyl having 1 to 4 carbon atoms represented by R ⁹ ,
C1-C4 alkoxy, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylate, amino, acylamino [preferably alkyl (C1-C4) carbonylamino] and alkyl (C1-C4) amino The phenyl which may be substituted by one or two substituents selected from the group of preferably includes phenyl, 2-, 3- or 4-methylphenyl, 2
-, 3- or 4-methoxyphenyl, 2-, 3- or 4
-Ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isopropylphenyl, 2-,
3- or 4-carboxyphenyl, 2-, 3- or 4-
Carbamoylphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-hydroxyphenyl, 2-carboxy-4-acetylaminophenyl, 2-methoxy-5-methylphenyl, 2,4-dimethoxyphenyl,
And 2,5-dimethoxyphenyl.

The formula as (3a) is, R ⁸ is hydrogen, a methyl or ethyl, if R ⁹ is an optionally cyano be also alkyl or substituted optionally substituted are preferable, among them R ⁸ is Particularly preferred is hydrogen, wherein R ⁹ is optionally substituted alkyl or optionally substituted cyano.

R ¹⁰ in the formula (3c) represents hydrogen, an optionally substituted alkyl or an optionally substituted phenyl, and the optionally substituted alkyl includes R ¹ , R ² , Examples of the same optionally substituted alkyl as those exemplified for R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are mentioned. Examples of the optionally substituted phenyl represented by R ¹⁰ include, for example, alkyl having 1 to 4 carbons and 1 carbon
~ 4 alkoxy, sulfo, carboxy, halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, carboxylate, 2-hydroxyethylsulfonyl,
Amino, acylamino [preferably, alkyl (1 to 4 carbon atoms) carbonylamino] and alkyl (1 to 4 carbon atoms)
4) Phenyl and the like which may be substituted by one or two substituents selected from the group of amino can be mentioned. The above-mentioned optionally substituted phenyl is preferably phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3-
Or 4-ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isopropylphenyl,
2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-carbamoylphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-sulfophenyl, 2
-, 3- or 4-hydroxyphenyl, 2-sulfo-4
-Methoxyphenyl, 2-sulfo-4-acetylaminophenyl, 2-carboxy-4-acetylaminophenyl, 2-methoxy-5-methylphenyl, 2,4-dimethoxyphenyl, and 2,5-dimethoxyphenyl No.

As R ¹⁰ , hydrogen or alkyl having 1 to 4 carbon atoms is preferable, and methyl or ethyl is particularly preferable.

T ¹ and T ² in the formulas (I) and (II)
Is a group represented by the formula (3a), examples of the amine compound represented by the formula HNR ⁸ R ⁹ used to form this group include the following.

A) The following aromatic amines: 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-propylbenzene, 1-amino-2-, -3-
Or -4-isopropylbenzene, 1-amino-2-,
-3- or -4-chlorobenzene, 1-amino-2-,
-3- or -4-bromobenzene, 1-amino-2-,
-3- or -4-fluorobenzene, 1-amino-2,
4- or -2,5-dimethoxybenzene, 1-amino-
2-methoxy-5-methylbenzene, 2-, 3- or 4
-Aminobenzoic acid, 2-, 3- or 4-carbamoylaniline, 1-amino-2-carboxy-4-acetylaminobenzene, 5-aminobenzene-1,3-dicarboxylic 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 -methylaminobenzoic acid, 1-amino-2-methoxy-5-methylbenzene,
1-amino-2,5-dimethoxybenzene, 2-, 3-
Or 4-aminophenol and 1-amino-3- or -4-acetylaminobenzene.

B) Cyanamide.

C) The following aliphatic amines: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-
Butylamine, tert-butylamine, dimethylamine,
Diethylamine, methylethylamine, allylamine,
2-chloroethylamine, 2-methoxyethylamine,
2-aminoethanol, 2- (2-aminoethoxy) ethanol, 2-methylaminoethanol, bis (2-hydroxyethyl) amine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3 -Propanediol, 2-amino-2-hydroxymethyl-1,3
-Propanediol, 2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid amide, 2-aminoethanesulfonic acid, amino Methanesulfonic acid, (2-methylamino) ethanesulfonic acid amide, (2-methylamino) ethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid,
Methylaminoacetic acid, 3-aminopropionic acid, 3-aminopropionic amide, 3-methylaminopropionic acid, 3-methylaminopropionic amide,? -Aminocaproic acid, benzylamine, 2-, 3- or 4-sulfobenzyl Amine, 2-, 3- or 4-chlorobenzylamine, 2-, 3- or 4-methylbenzylamine, N
-Methylbenzylamine, 1-phenylethylamine,
2-phenylethylamine, 1-phenyl-2-propylamine.

As the amines of the above a), b) and c), preferably, for example, 1-aminobenzene, N-methylaminobenzene, N-ethylaminobenzene, 1-amino-2-, -3- or- 4-chlorobenzene, 1-methylamino-2-, -3- or -4-chlorobenzene,
1-ethylamino-2-, -3- or -4-chlorobenzene, 1-amino-2-, -3- or -4-methylbenzene, 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-propylbenzene , 1-amino-2-, -3- or -4-isopropylbenzene, 2-, 3- or 4-aminophenol, 2-, 3- or 4-aminobenzoic acid, 2-, 3- or 4-carbamoyl Aniline, 1-amino-2,4- or -2,5-dimethoxybenzene, 1-amino-2-carboxy-4-acetylaminobenzene, 1-amino-
2-methoxy-5-methylbenzene, cyanamide, methylamine, ethylamine, dimethylamine, isobutylamine, sec-butylamine, tert-butylamine, diethylamine, methylethylamine, 2-amino-2-
Methylpropanol, 2-amino-2-methyl-1,3
-Propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-aminoethanesulfonic acid, (2-methylamino) ethanesulfonic acid, 2-
Examples thereof include methylaminoethanol, bis (2-hydroxyethyl) amine, 2-sulfamoylethylamine, 2-carbamoylethylamine, aminoacetic acid, methylaminoacetic acid, and 3-aminopropionic acid. Among them, 1-aminobenzene, N-methylaminobenzene, N-ethylaminobenzene, 1-amino-2-, -3- or -4-ethylbenzene, 2-, 3-
Or 4-aminobenzoic acid, cyanamide, methylamine,
Ethylamine, dimethylamine, tert-butylamine,
2-amino-2-methylpropanol, 2-amino-2
-Methyl-1,3-propanediol, 2-amino-2
-Hydroxymethyl-1,3-propanediol, 2-
Aminoethanesulfonic acid, (2-methylamino) ethanesulfonic acid, 2-methylaminoethanol, bis (2-
Hydroxyethyl) amine and aminoacetic acid and the like are particularly preferred.

T ¹ and T ² in the formulas (I) and (II)
Is a group represented by the formula (3c), the compound represented by HOR ¹⁰ used to form this group includes:
For example, the following can be mentioned.

D) The following phenols: phenol, 1
-Hydroxy-2-, -3- or -4-methylbenzene, 1-hydroxy-3,4- or -3,5-dimethylbenzene, 1-hydroxy-2-, -3- or -4-ethylbenzene, 1 -Hydroxy-2-, -3- or -4
-Methoxybenzene, 1-hydroxy-2-, -3- or -4-ethoxybenzene, 1-hydroxy-2-,-
3- or 4-chlorobenzene, 3- or 4-hydroxyphenylmethanesulfonic acid, 3- or 4-hydroxybenzenesulfonic acid, 5-hydroxybenzene-1,3
-Disulfonic acid, 2-hydroxybenzene-1,4-disulfonic acid, 4-hydroxybenzene-1,2-disulfonic acid, 4-hydroxy-5-methylbenzene-1,2
-Disulfonic acid, 3- or 4-hydroxybenzoic acid, 5
-Hydroxybenzene-1,3-dicarboxylic acid, and
5-hydroxy-2-ethoxybenzenesulfonic acid.

E) The following aliphatic alcohols: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol,
2-ethoxyethanol, 3-methoxypropanol,
3-ethoxypropanol, 2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2
-Cyanoethanol, 2-sulfateethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol, 4-methylbenzyl alcohol, 2-, 3- or 4
-Sulfobenzyl alcohol, 2-phenylethanol and 1-phenyl-2-propanol.

Q ² in the formula (3b) is -CH ₂ -,-
O -, - S -, - SO 2 - or -NR ¹¹ - (R ¹¹ is an alkyl group which may optionally be hydrogen or substituted) represents, n represents 1,
2 or 3, but as the alkyl represented by R ¹¹ ,
Those having 1 to 4 carbon atoms are preferable, and examples of the substituent of the alkyl include halogeno (chloro, bromo, etc.) and alkoxy having 1 to 4 carbon atoms. The R ^11, hydrogen is exemplified alkyl such as C1-4 straight-chain or branched carbon, particularly hydrogen, methyl and ethyl are preferred. Equation (3
Examples of the group represented by b) include a residue derived from pyrrolidine, piperidine, piperazine, n-alkylpiperazine, morpholine, and the like. Among them, n is a 2, and, Q is -O- or -CH ₂
-, That is, morpholino or piperidino is particularly preferred. The groups represented by T ¹ and T ² include those represented by the formula (3)
a) or (3c) is particularly preferred.

The bisazo dye compound (I) and the azo dye compound (II) used in the present invention may be in the form of a free acid, a salt thereof, or a mixture thereof. You may. It is preferably in the form of an alkali metal salt, an alkaline earth metal salt and a mixture containing them, and particularly preferably a sodium salt, a potassium salt, a lithium salt and a mixture containing them.

The method for producing the bisazo dye compound (I) is not particularly limited, but it can be produced, for example, as follows. First, among the above dye compounds (I), X ¹
And X ² is chloro or fluoro, for example,
The form of the free acid is the following formula (4)

[0052]

Embedded image [Wherein T ¹ has the above-mentioned meaning. And a compound represented by the following formula (5):

[0053]

Embedded image

[Wherein, R ¹ has the meaning described above. And a 2,4,6-trihalogeno compound represented by the formula:
By condensing s-triazine according to a known method, the following formula (6)

[0055]

Embedded image

[Wherein R ¹ and T ¹ represent the same meaning as above;
X ¹ a represents fluoro or chloro. ] Can be obtained. On the other hand, the following equation (7)

[0057]

Embedded image Wherein U ¹ has the meaning described above. And a compound represented by the following formula (8):

[0058]

Embedded image

Wherein R ² has the meaning described above. And a 2,4,6-trihalogeno compound represented by the formula:
By condensing s-triazine according to a known method, the following formula (9)

[0060]

Embedded image

[Wherein R ² and U ¹ have the same meaning as described above, and X ²
a represents fluoro or chloro. ] Can be obtained.

Each of the amine compounds represented by the above formulas (6) and (9) is diazotized in accordance with a conventional method, and the resulting diazotized product is converted into a free acid form of the following formula (10)

[0063]

Embedded image

Is coupled with the 1-amino-8-naphthol compound at a temperature of -10 ° C. to 30 ° C. while adjusting the pH to 0 to 4. Then, the former diazotized product is added to the obtained coupling reaction product. At pH 0 to 40 ° C.
By coupling while adjusting to 8, a compound represented by the following formula (11) can be obtained.

[0065]

Embedded image

[0066] ^{wherein, R 1, R 2, T} 1 and U ¹ represent the meaning of the, X ¹ a, X ² a represents a fluoro or chloro. ] Can be obtained.

The bisazo dye compound (I) can also be produced as follows. First, the compounds represented by the above formulas (5) and (7) and 2,4,6-trihalogeno-s-triazine whose free acid forms are condensed according to a known method to give the following formula (12)

[0068]

Embedded image

[Wherein, R ¹ and U ¹ have the same meaning as described above, and X ¹
a represents fluoro or chloro. Is obtained.

Separately, the amine compounds represented by the formulas (4) and (8) and 2,4,6-trihalogeno-s-triazine are condensed according to a known method to give the following formula (1)
3)

[0071]

Embedded image

[Wherein R ² and T ¹ have the same meaning as described above, and X ²
a represents fluoro or chloro. Is obtained.

The amine compounds represented by the above formulas (12) and (13) are each diazotized according to a conventional method, and the latter diazotized compound is first converted to a 1-amino-8-formula represented by the above formula (10).
A naphthol compound, at a temperature of -10 ° C to 30 ° C and a pH of 0
And then coupling the resulting product with the former diazotized product at 0 ° C to 40 ° C and a pH of 2
By coupling while adjusting to 8, a compound represented by the following formula (14) can be obtained.

[0074]

Embedded image

[0075] ^{wherein, R 1, R 2, T} 1 and U ¹ are as defined above, X ¹ a and X ² a represents a fluoro or chloro. ]
Can be obtained.

Further, among the bisazo dye compounds (I),
X ¹ and X ² which are optionally substituted pyridinio may be, for example, a compound having a free acid form of the above formula (11) synthesized in the same manner as described above, The corresponding pyridine compound is heated at a temperature of 10 ° C to 100 ° C.
To give a compound of the following formula (15).

[0077]

Embedded image

[0078] wherein the meaning of R ^1, R ^2, T ¹ and U ¹ is the, X ¹ b, X ² b denote an pyridinio substituted. ]

The method for producing the azo dye compound (II) is not particularly limited, but for example, it can be produced as follows. First, among the azo dye compounds (II), X ³ and X ⁴
And those in which X ⁵ is chloro or fluoro, for example, when the free acid form is the following formula (16)

[0080]

Embedded image Wherein U ² has the meaning described above. And a compound represented by the following formula (17):

[0081]

Embedded image

[Wherein, R ¹² and R ¹³ have the above-mentioned meanings. And a diamine compound represented by the following formula (8):

[0083]

Embedded image

[Wherein, R ¹⁴ has the meaning described above. And a 2,4,6-trihalogeno compound represented by the formula:
By condensing s-triazine according to a known method, the following formula (19)

[0085]

Embedded image

[0086] ^{wherein, R 12, R 13, R} 14 and U ¹ represents the meaning of the, X ³ a and X ⁴ a represents a fluoro or chloro. ] Can be obtained. In the above condensation, the condensation with 2,4,6-trihalogeno-s-triazine is performed twice.

Separately, the following formula (20)

[0088]

Embedded image [Wherein T ² has the above-mentioned meaning. And a compound represented by the following formula (21):

[0089]

Embedded image

[Wherein, R ¹⁵ has the meaning described above. And a 2,4,6-trihalogeno compound represented by the formula:
By condensing s-triazine according to a known method, the following formula (22)

[0091]

Embedded image

Wherein R ¹⁵ and T ² have the same meaning as described above, and X ⁵
a represents fluoro or chloro. ] Can be obtained.

Each of the amine compounds represented by the general formulas (19) and (22) is diazotized according to a conventional method, and the former diazotized product is converted into the free acid form by the following formula (2)
3)

[0094]

Embedded image

And coupling with the 1-amino-8-naphthol compound at a temperature of -10 ° C. to 30 ° C. while adjusting the pH to 0 to 4, and then adding the latter diazotized product to the obtained coupling reaction product. At pH 0 to 40 ° C.
By coupling while adjusting to に 8, the following formula (24) is obtained.

[0096]

Embedded image

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , U ² and T ² represent the same meaning as above, and X ³ a, X ⁴ a and X ⁵ a represent fluoro or chloro. Or a salt thereof.

In the method for obtaining the compound represented by the general formula (24), the coupling order of the diazotized compounds derived from the amine compounds represented by the general formulas (19) and (22) is changed, whereby the following formula is obtained. (25)

Embedded image

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , U ² ,
T ² , X ³ a, X ⁴ a and X ⁵ a represent the above-mentioned meaning. Or a salt thereof.

Further, among the bisazo compounds (II) of the present invention, those wherein X ³ , X ⁴ and X ⁵ are chloro or fluoro can be produced, for example, as follows. First, the form of the free acid is represented by the formulas (17), (18) and (2).
The compound of formula (0) is converted to 2,4,6-trihalogeno-s
-Condensation according to a known method with triazine to give the following formula (26)

[0101]

Embedded image

[Wherein R ¹² , R ¹³ , R ¹⁴ and T ² represent the same meaning as above, and X ³ a and X ⁴ a represent fluoro or chloro. ] Can be obtained.

Separately, each of the compounds represented by the general formulas (16) and (21) is condensed with 2,4,6-trihalogeno-s-triazine according to a known method to give a compound represented by the following formula (27)

[0104]

Embedded image

Wherein R ¹⁵ and U ² have the same meaning as defined above, and X ⁵
a represents fluoro or chloro. ] Can be obtained.

The amine compounds represented by the formulas (26) and (27) are each diazotized according to a conventional method, and the former diazotized product is represented by the general formula (23) in the form of a free acid. The resulting 1-amino-8-naphthol compound is coupled at a temperature of -10 ° C to 30 ° C while adjusting the pH to 0-4, and then the obtained product is combined with the former diazotized product at 0 ° C to 40 ° C. By coupling while adjusting the pH to 2 to 8, the following formula (28) is obtained.

[0107]

Embedded image

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , U ² ,
T ² , X ³ a, X ⁴ a and X ⁵ a represent the above-mentioned meaning. Or a salt thereof.

In the method for obtaining the compound represented by the general formula (28), the coupling order of the diazotized compounds derived from the amine compounds represented by the general formulas (26) and (27) is changed to obtain the following compound (29)

[0110]

Embedded image

[Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , U ² ,
T ² , X ³ a, X ⁴ a and X ⁵ a represent the above-mentioned meaning. Or a salt thereof.

Further, among the bisazo compounds (II) of the present invention, those in which X ³ a, X ⁴ a and X ⁵ a are optionally substituted pyridinio are, for example, those whose free acid forms The compound represented by (24) is synthesized in the same manner as described above, and the pyridine compound corresponding to the optionally substituted pyridinio is reacted at a temperature of 10 ° C to 100 ° C under a condition of pH 2 to 9 to obtain the following compound. The compound represented by the formula (30) can be obtained.

[0113]

Embedded image

[Wherein, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , U ² and T ² have the same meanings as above, and X ³ b, X ⁴ b and X ⁵ b each represent an optionally substituted pyridinio. Represent. ]

In the above-mentioned production method, the order and reaction conditions of the condensation reaction with 2,4,6-trihalogeno-s-triazine are not particularly limited. For example, the first condensation reaction is carried out at a temperature of -10 ° C. The reaction was carried out under the conditions of 40 ° C. and pH 1 to 10.
It can be carried out under the conditions of pH 2 and pH 2-11.

In the dye compounds (I) and (II), the groups represented by Y ¹ and Y ² in the formulas (2a) and (2b) are —CH ₂ CH ₂ L, wherein L is a sulfate ester And a dye compound which is an ester group such as a phosphoric acid ester, for example, is converted into the ester group by an esterification reaction of a precursor compound having a β-hydroxyethylsulfonyl group obtained after the condensation reaction with sulfuric acid or phosphoric acid. Thus, the dye compounds of the formulas (I) and (II) can be obtained.
As the 2,4,6-trihalogeno-s-triazine, cyanuric chloride or cyanuric fluoride is preferable.

As the 1-amino-8-naphthol compound represented by the formulas (10) and (23), H acid and K acid are preferable, and H acid is particularly preferable.

The reactive dye mixture of the present invention contains a bisazo dye compound (I) and an azo dye compound (II). After synthesizing the bisazo dye compound (I) and the dye compound (II), they are mixed. It may be prepared by mixing in a dye bath at the time of dyeing. Further, the mixed form may be a solid such as a powder or a granule, an aqueous solution, or a combination thereof.

The reactive dye mixture of the present invention preferably has a ratio of the azo dye compound (II) of 1 to 50 parts by weight, more preferably 100 parts by weight of the bisazo dye compound (I), more preferably bisazo dye compound (II). The ratio of the azo dye compound (II) is 1 to 20 parts by weight per 100 parts by weight of the dye compound (I).

The dye mixture of the present invention is useful, for example, as a reactive dye for dyeing or printing a fiber material. The fiber material is not particularly limited as long as it contains a hydroxy group and / or a carbonamide group. For example, natural or regenerated cellulose fiber material, natural or synthetic polyamide fiber material, polyurethane fiber material, leather, and And the like.

Examples of natural cellulose fiber materials include cotton and other plant fibers such as linen,
Hemp, jute and ramie fibers can be mentioned.
As the regenerated cellulose fiber material, for example, rayon, polynosic, cupra fiber, and trade name "Tencel",
"Toughcell", "Modal", "Certima" and the like can be mentioned. Specific examples of the natural or synthetic polyamide fiber material include wool, other animal hair, silk, polyamide-6,6, polyamide-6, polyamide-11, polyamide-4, and the like. Examples of the blended material containing these include a blended material of these fiber materials and a blended material of these fiber materials and synthetic fibers such as polyester, nylon, and acrylic.

The reactive dye mixture of the present invention can be dyed or printed on a fiber material, especially on the above-exemplified fiber materials by a method depending on the physicochemical properties. Specifically, for example, a method of dyeing or printing on the above-mentioned fiber material by a method such as an exhaust dyeing method, a cold batch-up method, a continuous dyeing method, or a printing method can be exemplified. For example, when exhaustion dyeing on cellulose fiber material, sodium carbonate,
In the presence of an acid binder such as tertiary sodium phosphate, sodium bicarbonate, and caustic soda, a neutral salt such as sodium sulfate and sodium chloride is added, if necessary, and if necessary, a solubilizing agent, a penetrant, or a leveling agent. And the like, and dyeing at a temperature of about 30 to 100 ° C. is exemplified. Here, the addition of the acid binder, the neutral salt, and the like may be performed all at once, or may be performed in a divided manner by a conventional method. When dyeing on cellulose fiber by the cold batch-up method, after padding using neutral salts such as sodium sulfate and sodium chloride, and an acid binder such as caustic soda and sodium silicate, the mixture is placed in a closed packaging material at a constant temperature. An example of a method in which the treatment is performed by leaving the material to stand is exemplified. In the case of dyeing on a cellulose fiber by a continuous dyeing method, padding is performed at room temperature or at an elevated temperature by a known method in the presence of an acid binder such as sodium carbonate or sodium bicarbonate, followed by steaming or dry heat treatment. Phase padding method, or after immersing the fiber in a padding solution in which the compound of the present invention is dissolved, neutral salts such as sodium sulfate and salt,
Further, a two-phase padding method in which an acid binder such as caustic soda or sodium silicate is padded and treated by steaming or heat drying is used.

In the case of printing on cellulose fibers, printing is performed in one phase with a printing paste containing a binder such as baking soda and then steaming at a high temperature of 80 ° C. or higher, or in two phases. For example, printing with a neutral or weakly acidic printing paste and passing it through an electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and then treating by steaming or drying. A method and the like are exemplified. Here, the printing paste may contain a sizing agent such as sodium alginate or starch ether and / or an emulsifier, and if necessary, a printing aid such as urea and / or a dispersant. May be.

When the reactive dye mixture of the present invention is dyed or printed on cellulose fiber, the acid binder used is not particularly limited. For example, an alkali metal hydroxide, an alkali metal or an alkaline earth metal and an inorganic or alkaline Examples thereof include a water-soluble basic salt with an organic acid and a compound that releases an alkali under heating. In particular, mention may be made of alkali metal hydroxides and alkali metal salts of inorganic acids or organic acids of weak to moderate strength, of which sodium or potassium hydroxides, sodium salts and potassium salts are preferred. Specific examples of such an acid binder include sodium carbonate, tertiary sodium phosphate, sodium bicarbonate, caustic soda, sodium carbonate, sodium silicate, and sodium bicarbonate. Sodium diphosphate,
Sodium trichloroacetate and the like can also be mentioned.

In the case of exhaustion dyeing on synthetic or natural polyamide fibers or polyurethane fibers, acidic to
Examples of the method include a method in which the compound of the present invention is exhausted in a weakly acidic dyeing bath while controlling the pH value, and then the pH is changed to a neutral to alkaline pH value at a temperature of about 60 to 120 ° C. If necessary, a leveling agent such as cyanuric chloride and 3
A leveling agent such as a condensation product of a double molar amount of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or an addition product of, for example, stearylamine and ethylene oxide may be used.

The reactive dye mixture of the present invention or a salt thereof is excellent in reproducibility, particularly when dyeing or printing a cellulose fiber material, has good leveling properties and wash-off properties, and has high build-up properties. It has good dye solubility and high effective dyeing rate. Also, there is an advantage that dyeing can be performed at a low salt concentration. Furthermore, by using the reactive dye mixture of the present invention, various fastnesses, especially chlorine resistance, light resistance, sweat resistance, sweat and sun resistance, acid hydrolysis resistance, alkali resistance, washing resistance and peroxidation resistance Dyeings and prints with good washability are obtained.

The reactive dye mixture of the present invention can 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. The dye used in combination is not particularly limited as long as it is a reactive dye.For example, as a reactive group, a sulfatoethyl sulfone group, a vinyl sulfone group, a monochlorotriazine group,
A dye having at least one of monofluorotriazine group, mononicotinic acid triazine group, dichlorotriazine group, difluoromonochloropyrimidine group, and trichloropyrimidine group, or Sum
ifix, Sumfix Supra, Sumif
ix HF, Remazol, Levafix, Pro
Cion, Cibacron, Basilen, Dri
marene, Kaaacion, Kaacelon
Dyes commercially available under the titles such as React and the like, and further, JP-A-50-178, JP-A-51-17538, JP-A-56-948
No. 3, JP-A-56-15481, JP-A-56-118976, JP-A-56
-128380, JP-A-57-2365, JP-A-57-89679, JP-A-57-143360, JP-A-58-191755, JP-A-59-15451
No., JP-A-59-96174, JP-A-59-161463, JP-A-60-161
No. 6754, JP-A-60-123559, JP-A-60-229957, JP-A-60-260654, JP-A-61-126175, JP-A-61-15546
No. 9, JP-A-61-225256, JP-A-63-77974, JP-A-63
-225664, JP-A-1-185370, JP-A-3-770, JP-A
And dyes described in JP-A-5-247366 and JP-A-6-287463. I. Reactive Blue 19,
C. I. Dyes represented by Reactive Black 5 are exemplified.

[0128]

The reactive dye mixture of the present invention is useful, for example, as a reactive dye for cellulose fiber materials, and is particularly excellent in dye solubility such as solubility in water, build-up property and leveling property. Further, according to the method of the present invention, dark blue dyeings and prints excellent in various fastnesses can be obtained with good reproducibility.

[0129]

The present invention will be described in more detail with reference to the following examples. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

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

[0131]

Embedded image

And the free acid form is represented by the following formula (B):

[0133]

Embedded image

A reactive dye mixture is obtained by thoroughly mixing with 20 parts of the dye compound represented by the formula (1). This mixture 0.1, 0.3
And 0.6 parts each were dissolved in 200 parts of water.
And 10 parts of cotton, and the temperature was raised to 60 ° C.
Then, after dyeing for 1 hour, washing with water, soaping, washing with water and drying are performed. At the time of washing and soaping, the amount of coloring in the dyeing wastewater is slight, and the resulting dyed products are all uniform and dark blue in color. The dyed product obtained using 0.6 part of the reactive dye mixture is sufficiently darker than the dyed product obtained using 0.3 part, and the dyed product obtained using 0.3 part of the reactive dye mixture is obtained. Is sufficiently darker than the dyed product obtained using 0.1 part, and the build-up property of this reactive dye mixture is good. Furthermore, the solubility of the dye mixture in water is good. The exhaustion properties, fixation rate and levelness of the reactive dye mixture are excellent,
The resulting dyed product has good fastnesses such as light fastness, sweat fastness, sweat and sun fastness, chlorine fastness, hydrolysis fastness, alkali fastness, washing fastness and peroxide washing fastness.

Example 2 Dyeing is carried out in the same manner as in Example 1 except that the amount of sodium sulfate used is changed from 10 parts to 4 parts. The dyeings obtained each have the same quality as the dyeings obtained in Example 1.

Example 3 Example 1 except that the dyeing temperature was changed from 60 ° C. to 70 ° C.
Dyeing is carried out according to 2. The dyeings obtained have the same quality as the dyeings obtained in Examples 1 and 2, respectively.

Example 4 To each of 0.1, 0.3 and 0.6 parts of the reactive dye mixture,
Dyeing is carried out according to Examples 1 to 3, except that 0.06 part of a sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde having a degree of sulfonation of 110% and an average degree of polymerization of 1.8 is added. The obtained dyeings have the same quality as the dyeings obtained in Examples 1 to 3, respectively.

Example 5 Using the reactive dye mixture described 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%) original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance (water) 13 parts Total 100 parts

This color paste is printed on a mercerized cotton broad, and after intermediate drying, steaming is performed at 100 ° C. for 5 minutes, followed by washing with hot water, soaping, washing with hot water and drying. The resulting print is uniform and dark blue, has good build-up properties, and has good fastness and storage stability.

Example 6 30 parts of the reactive dye mixture described in Example 1 were 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 °
0 parts were added, and water was further added at 25 ° C. to bring the total amount to 100 parts.
Immediately after reducing the amount to 0 parts, 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 25 ° C. for 20 hours, washed by a conventional method, and dried to finish. The resulting dyed product is uniform and dark blue, has good build-up properties, and has good fastness and storage stability.

Example 7 20 parts of the reactive dye mixture described in Example 1 are dissolved in hot water and cooled to 25 ° C. To this dye solution was added 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate, and water was added at 25 ° C. to make the total amount 1000 parts. Padding. The cotton fabric after padding is dried at 120 ° C. for 2 minutes, and then steamed at 100 ° C. for 5 minutes to fix the dye. The resulting dyed product is uniform and dark blue, has good build-up properties, and has good fastness and storage stability.

Example 8 In each of the reactive dye mixtures described in Examples 1 to 7, each of the dye compounds represented by the above formulas (A) and (B) was replaced with the second column A, B in Tables 1 to 9 below. Change to the described compound,
And, except for changing to the composition ratio described in the third column, Examples 1 to
Dyeing is performed according to 7. The obtained dyeings have the same quality as the dyeings obtained in Examples 1 to 7, respectively.

[0143]

[Table 1]

[0144]

[Table 2]

[0145]

[Table 3]

[0146]

[Table 4]

[0147]

[Table 5]

[0148]

[Table 6]

[0149]

[Table 7]

[0150]

[Table 8]

[0151]

[Table 9]

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshiharu Toishi 3-1-198 Kasuganaka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. F-term (reference) 4H056 FA01 JA06 JB02 JB03 JE03 JE04 4H057 AA02 BA07 BA24 DA01 EA01

Claims (11)

[Claims] A reactive dye mixture comprising a bisazo dye compound having a free acid form represented by the following formula (I) and an azo dye compound having a free acid form represented by the following formula (II). Embedded image [Wherein, R ¹ and R ² are the same or different and represent hydrogen or an optionally substituted alkyl, and U ¹ represents the following formula (1a), (1b) or (1c)] Wherein R ³ represents hydrogen or an optionally substituted alkyl; R ⁴ and R ⁵ are the same or different and represent hydrogen, an optionally substituted alkyl or an optionally substituted phenyl , A ¹ represents an optionally substituted phenylene or an optionally substituted naphthylene, A ² represents an optionally substituted alkylene, Q ¹ represents -O-,
Represents -S- or -NR ^6- , wherein R ⁶ is hydrogen, optionally substituted alkyl or optionally substituted phenyl, and r and s are the same or different and are 2, 3 or 4 And Z ¹ , Z ² and Z ³ are the same or different and represent a vinylsulfone-based reactive group represented by the following formula (2a) or (2b). Embedded image Wherein Y ¹ and Y ² are the same or different, and —CH−C
H ₂ or —CH ₂ CH ₂ L is represented, L is a group capable of leaving by the action of an alkali, R ⁷ is hydrogen or an optionally substituted alkyl, and m is an integer of 1 to 6. ]> Represents a fiber-reactive group. X ¹ and X ² are the same or different and are fluoro, chloro, or optionally substituted pyridinio, and T ¹ is a group represented by the following formula (3a), (3b) or (3c): In the formula, R ⁸ represents hydrogen or an optionally substituted alkyl; R ⁹ represents an optionally substituted alkyl, an optionally substituted cyano, or an alkyl having 1 to 4 carbons, 1-4 alkoxy, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylate, amino, acylamino and alkyl (C 1
-4) phenyl which may be substituted by one or two substituents selected from the group of amino, wherein R ¹⁰ is hydrogen,
Represents an optionally substituted alkyl or an optionally substituted phenyl, and Q ² represents -CH _2- , -O-, -S-,
Represents —SO ₂ — or —NR ¹¹ —, wherein R ¹¹ represents hydrogen or an optionally substituted alkyl, and n is 1, 2 or 3. Represents a non-fiber-reactive group represented by｝. However,
[] Two asterisks shown in, one is a bond between -U ^1, the other represents a bond with -T ^1. [Chemical formula 5] [Wherein, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are the same or different and represent hydrogen or an optionally substituted alkyl,
U ² represents a fiber-reactive group represented by the formula (1a), (1b) or (1c), and U ¹ and U ² may be the same or different. X ³ , X ⁴ and X
⁵ is the same or different and is fluoro, chloro, or optionally substituted pyridinio, and T ² represents a non-fiber-reactive group represented by the above formula (3a), (3b) or (3c) However, T ¹ and T ² may be the same as each other,
They may be different. One of W ¹ and W ² is amino, and the other is hydroxy. However, []
Two asterisks shown within, one is a bond with -U ^2, the other represents a bond with -T ^2. ] 2. The ratio of the dye compound represented by the formula (II) is
The mixture according to claim 1, wherein the amount is 1 to 50 parts by weight based on 100 parts by weight of the bisazo dye compound represented by the formula (I). 3. R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ and R
3. The mixture according to claim 1, wherein ¹⁵ is hydrogen. 4. The mixture according to claim ¹ , wherein X ¹ , X ² , X ³ , X ⁴ and X ⁵ are the same or different and are fluoro or chloro. 5. The mixture according to claim ¹ , wherein X ¹ , X ² , X ³ , X ⁴ and X ⁵ are an optionally substituted pyridinio. 6. The method according to claim 1, wherein U ¹ in the formula (I) and U ² in the formula (II) are a fiber-reactive group represented by the formula (1a) or (1b). mixture. 7. The mixture according to claim ¹ , wherein U ¹ in formula (I) and U ² in formula (II) are the same as each other. 8. The mixture according to claim 6, wherein Z ¹ and Z ² are groups represented by the formula (2a). 9. The mixture according to claim 1, wherein T ¹ and T ² are non-fiber-reactive groups represented by the formula (3a). 10. The mixture according to claim 1, wherein T ¹ in the formula (I) and T ² in the formula (II) are the same as each other. 11. A method for dyeing or printing a fiber material, comprising using the mixture according to claim 1.