JP2002069864A - Dyeing method of mixed fiber of cellulosic fiber and polyamide fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for dyeing a mixed article of cellulose fiber and polyamide fiber, in which both fibers are dyed in similar hues and which gives a dyed material having excellent fastnesses. SOLUTION: A reactive dye mixture comprising a dye of the formula (I) or the like and a dye of the formula (III) or the like is used. Embedded image (I) (III) [wherein, m and n are 0 or 1, p is 0 to 3, R ₁ ,
R ₂ , R ₃ , R ₁₀ , R ₁₄ , R ₁₅ are hydrogen, etc., R ₁₁ , R ₁₃ are halogen, etc., B ₁ , B ₂ , B ₄ are substituted phenylene, etc., Y ₁ ,
Y ₂ and Y ₃ represent vinyl or the like. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing mixed fibers of cellulosic fibers and polyamide fibers.

[0002]

2. Description of the Related Art When dyeing mixed fibers of cellulosic fibers and polyamide fibers, a method of dyeing both cellulosic fibers and polyamide fibers with a reactive dye is used. Dyeing with a mixture of a plurality of reactive dyes having different hues is also performed. However, when dyeing a mixed fiber of cellulosic fiber and polyamide fiber using a mixture of a plurality of reactive dyes, the balance between the dyeing ability of each reactive dye on cellulose fiber and the dyeing property on polyamide fiber is not approximate. In addition, there is a problem that cellulose-based fibers and polyamide-based fibers are dyed in different hues, and a uniform dyed product cannot be obtained. Accordingly, there is a need for a mixture of a plurality of reactive dyes having a similar balance between the dyeing properties for cellulosic fibers and the dyeing properties for polyamide fibers. When dyeing the mixed fiber using a mixture of a plurality of reactive dyes, (i) the build-up properties of each reactive dye, the leveling property, the dyeing temperature dependency, the bath ratio dependency, and the like are good. , That the reproducibility of the dyeing is excellent, (ii) the dyeing speed of each reactive dye is equal, the dyeing temperature dependency and the bath ratio dependency are uniform, and the compatibility is good, (iii) Conditions such as the light fastness of each reactive dye, the combined fastness with sweat and sunlight, the fastness to washing, the fastness to chlorine, etc., and the level of these fastnesses are uniform. It is desirable to satisfy In particular, regarding the leveling property and reproducibility of dyeing of item (i), the diversification of fiber material types and forms has been progressing in recent years, and the simplification of operations by automation of factories and shortening of dyeing time. Along with the progress of dyeing, there is a strong demand for a reactive dye mixture having better levelness and good reproducibility of dyeing. For example, if the build-up properties of the respective reactive dyes are different from each other, or if the dyeing properties do not match when dyeing using each reactive dye alone and when appropriately dyeing in combination, computer color matching that has been frequently used in recent years If the color matching by the system becomes difficult, and the dyeing speeds of the respective reactive dyes in the above item (ii) and the dyeing temperature dependence are different from each other, spot dyeing occurs during dyeing, resulting in poor levelness. As a result, there arises a problem that color reproducibility becomes poor as a result of producing a color difference between dyeing lots. Further, when the fastness levels of the respective reactive dyes in the item (iii) are not uniform, discoloration is conspicuous in at least one of light fastness, sweat fastness, washing fastness and chlorine fastness, and good dyeing is performed. There is also a problem that a product cannot be obtained.

[0003]

The present inventors have made intensive studies to solve the above problems, and as a result, have found that a specific reactive dye mixture achieves this object, and have completed the present invention.

That is, the present invention relates to the compounds represented by the general formulas (I) and (II)
One or more selected from the group of azo reactive dyes represented by
A reactive dye mixture containing at least one selected from the group of reactive dyes represented by the general formulas (III), (V), (VII), (IX) and (XI). An object of the present invention is to provide a method for dyeing a mixed fiber of a cellulosic fiber and a polyamide fiber.

[0005]

Embedded image (I)

[Wherein m and n are the same or different from each other and represent 0 or 1, R ₁ and R ₂ are the same or different from each other and may be hydrogen or optionally substituted C ₁ -C ₄
R ₃ represents hydrogen or methyl; B ₁
And B ₂ are the same or different from each other, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo and one or two phenylene which may optionally be substituted with a substituent selected from the group consisting of halogen Or naphthylene which may be substituted by one sulfo group, wherein Y ₁ is -CH = C
H ₂ or —CH ₂ CH ₂ Z ₁ , where Y ₂ is —CH ＝ CH ₂
Or represents _{-CH 2 CH 2 Z 2, Z} 1 and Z ₂ are the same or different from each other, represents a group capable of leaving by the action of an alkali. ]

[0007]

Embedded image (II)

[Wherein, R_FourAnd R_FiveAre the same as each other or
Differently represents hydrogen or methyl;₇And R₈Is
Identical or different, even if they are hydrogen or substituted
Good C ₁~ C_FourRepresents an alkyl of₆And R₉Is halogen
And B_ThreeIs optionally substituted C_Two~ C₆Archire
Represents ]

[0009]

Embedded image (III)

[Wherein p represents 0, 1, 2 or 3;
_TenIs hydrogen or optionally substituted C ₁~ C_FourAlkyl
Represents, R₁₁Is substituted with halogen, non-fiber reactive groups
Phenylamino or general formula (IV)

[0011]

Embedded image (IV)

In the formula, R₁₂Is hydrogen or substituted
Good C₁~ C_FourRepresents alkyl, U₁Has been replaced
Phenylene, optionally substituted naphthylene or
Is optionally substituted C_Two~ C₆Represents alkylene, Y
_FourIs -CH = CH_TwoOr -CH_TwoCH_TwoZ_FourAnd Z_FourIs
It represents a group that is eliminated by the action of lukari. The group represented by｝
You. R₁₃Is halogen, C₁~ C_FourAlkyl, ureido, place
C which may be replaced₁~ C_FourAlkylcarbonylamido
No, optionally substituted C_Two~ C_FourAlkenylcarboni
Amino or optionally substituted phenylcarboni
Represents ruamino, R₁₄Represents hydrogen, but R₁₃And R₁₄Haichi
May form a benzene ring, and the ring is
It may be substituted by sulfo. R_FifteenIs hydrogen, C ₁~ C_Four
Alkyl, C₁~ C_FourRepresents alkoxy or sulfo, B_Four
Is C₁~ C_FourAlkyl, C₁~ C_FourAlkoxy, sulfo and
By one or two substituents selected from the group of halogen
Optionally substituted phenylene or one sulfene
Represents naphthylene which may be substituted by e,_ThreeIs-
CH = CH_TwoOr -CH_TwoCH_TwoZ_ThreeAnd Z_ThreeIs al
It represents a group that is eliminated by the action of potassium. ]

[0013]

Embedded image (V)

[0014] [wherein, R ₁₆ and R ₁₈ are the same or different from each other, represent hydrogen or substituted C ₁ optionally -C ₄ alkyl, R ₁₉ is hydrogen, optionally C ₁ substituted
-C ₄ alkyl, nitro, sulfo or -SO ₂ C ₂ H ₄ Cl
And Me represents a metal ion having an atomic number of 27 to 29, and B ₅ is substituted with one or two substituents selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, and halogen. Phenylene, or 1
Represents naphthylene which may be substituted with
Y ₅ represents -CH = CH ₂ or _{-CH 2 CH 2 Z 5, Z} 5
Represents a group capable of leaving by the action of an alkali, and R ₁₇ represents a halogen, phenylamino optionally substituted with a non-fiber reactive group, or a compound represented by the general formula (VI):

[0015]

Embedded image (VI)

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

[0017]

Embedded image (VII)

Wherein q represents 0, 1 or 2;_{twenty one}
Is hydrogen or optionally substituted C₁~ C_FourTable showing alkyl
Then B₆Is C₁~ C_FourAlkyl, C₁~ C_FourAlkoxy,
1 or 2 substitutions selected from the group of ruho and halogen
Phenylene optionally substituted by a group, or 1
Represents naphthylene which may be substituted with
Y ₇Is -CH = CH_TwoOr -CH_TwoCH_TwoZ₇And Z₇
Represents a group capable of leaving under the action of an alkali;_{twenty two}Is haloge
Phenylamine, which may be substituted with a non-fiber reactive group
No or general formula (VIII)

[0019]

Embedded image (VIII)

｛R ₂₃ represents hydrogen 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 to} C ₆ alkylene; Y ₈ represents —CH ＝ CH ₂ or —CH ₂ CH ₂ Z ₈ , and Z ₈ represents a group capable of leaving by the action of an alkali. Represents a group represented by｝. ]

[0021]

Embedded image (IX)

[Wherein R_{twenty four}Is hydrogen or substituted
Good C₁~ C_FourRepresents alkyl, U_FourHas been replaced
Phenylene, naphthylene which may be substituted
Or optionally substituted C_Two~ C₆Represents alkylene,
Y₉Is -CH = CH_TwoOr -CH _TwoCH_TwoZ₉And Y
_TenIs -CH = CH_TwoOr -CH_TwoCH_TwoZ_TenAnd Z₉
And Z_TenAre the same or different from each other,
Represents a group which is eliminated by _{twenty five}Is halogen, non-fiber reactive group
Optionally substituted phenylamino or a general formula
(X)

[0023]

Embedded image (X)

｛R ₂₆ represents hydrogen 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 It represents ₂ -C ₆ alkylene, Y ₁₁ represents -CH = CH ₂ or _{-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｝. ]

[0025]

Embedded image (XI)

Wherein W ₁ and W ₂ are the same or different from each other and are hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄
X ₁ and X ₂ are the same or different from each other, and represent hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ , or C ₄ alkoxy or aryloxy optionally having substituent (s).
Represents alkoxy or carboxyl, and R ₂₇ and R ₂₉ are
The same or different from each other, and represents hydrogen or an optionally substituted C ₁ -C ₄ alkyl, and B ₇ is 1 or selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo and halogen Phenylene which may be substituted by two substituents, or naphthylene which may be substituted by one sulfo, Y ₁₂ represents -CH = CH ₂ or -CH ₂ CH ₂ Z ₁₂ ; Z ₁₂ represents a group capable of leaving under the action of an alkali; R ₂₈ represents halogen, phenylamino optionally substituted with a non-fiber reactive group, alkylamino optionally substituted with a non-fiber reactive group, or a compound represented by the general formula ( XII)

[0027]

Embedded image (XII)

｛R ₃₀ represents hydrogen 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 to} C ₆ alkylene; Y ₁₃ represents —CH ＝ CH ₂ or —CH ₂ CH ₂ Z ₁₃ , and 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.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The above formulas (I), (II) and (II)
I), (IV), (V), (VI), (VII), (VII
I), (IX), (X), (XI) and (XII)
R₁, R_Two, R ₇, R₈, R_Ten, R₁₂, R₁₆, R₁₈, R
₁₉, R₂₀, R_{twenty one}, R_{twenty three}, R_{twenty four}, R₂₆, R₂₇, R₂₉And R
₃₀C indicated by₁~ C_FourExamples of the alkyl substituent include:
For example, hydroxy, cyano, C₁~ C_FourAlkoxy, carbo
Xy, carbamoyl, alkoxy (C₁~ C_Four) Carboni
, Alkyl (C₁~ C_Four) Carbonyloxy, sulfo,
And sulfamoyl and halogen. Also,
C₁~ C_FourExamples of the halogen as an alkyl substituent include, for example,
For example, chlorine, bromine and the like can be mentioned. Have been replaced
May be C₁~ C_FourSpecific examples of alkyl include methyl,
Ethyl, n-propyl, iso-propyl, n-butyl
, Iso-butyl, sec-butyl, 2-hydroxy
Ethyl, 2-hydroxypropyl, 3-hydroxypro
Pill, 2-hydroxybutyl, 3-hydroxybutyl,
4-hydroxybutyl, 2,3-dihydroxypropyl
3,4-dihydroxybutyl, cyanomethyl, 2-
Cyanoethyl, 3-cyanopropyl, 4-cyanobuty
Methoxymethyl, ethoxymethyl, 2-methoxyethyl
Chill, 2-ethoxyethyl, 3-methoxypropyl, 3
-Ethoxypropyl, 2-hydroxy-3-methoxyprop
Ropyl, carboxymethyl, 2-carboxyethyl, 3
-Carboxypropyl, 4-carboxybutyl, 1,2
-Dicarboxyethyl, carbamoylmethyl, 2-cal
Bamoylethyl, 3-carbamoylpropyl, 4-cal
Bamoylbutyl, methoxycarbonylmethyl, ethoxy
Carbonylmethyl, 2-methoxycarbonylethyl, 2
-Ethoxycarbonylethyl, 3-methoxycarbonyl
Propyl, 3-ethoxycarbonylpropyl, 4-meth
Xoxycarbonylbutyl, 4-ethoxycarbonylbuty
, Methylcarbonyloxymethyl, ethylcarbonyl
Oxymethyl, 2-methylcarbonyloxyethyl, 2
-Ethylcarbonyloxyethyl, 3-methylcarbonyl
Ruoxypropyl, 3-ethylcarbonyloxypropyl
4-methylcarbonyloxybutyl, 4-ethylca
Rubonyloxybutyl, sulfomethyl, 2-sulfoethyl
, 3-sulfopropyl, 4-sulfobutyl, sulfa
Moylmethyl, 2-sulfamoylethyl, 3-sulf
Amoylpropyl, 4-sulfamoylbutyl, chloro
Methyl, bromomethyl, 2-chloroethyl, 2-bromo
Ethyl, 3-chloropropyl, 3-bromopropyl, 4
-Chlorobutyl, 4-bromobutyl and the like.
Wear.

R₁, R_Two, R₇, R₈, R_Ten, R₁₂, R₁₆,
R₁₈, R₁₉, R₂₀, R_{twenty one}, R_{twenty three}, R _{twenty four}, R₂₆, R₂₇, R
₂₉And R₃₀Is preferably hydrogen, methyl or ethyl
And hydrogen is particularly preferred.

R ₃ , R ₄ and R ₅ in the formulas (I) and (II) represent hydrogen or methyl, preferably hydrogen.
Further, m and n in the formula (I) are the same or different from each other and represent 0 or 1, and m is preferably 0,
n is preferably 1.

In formulas (I), (III), (V), (VII) and (XI), B ₁ , B ₂ , B ₄ , B ₅ , B ₆ and B ₇ are
₁ -C ₄ alkyl (the alkyl may be substituted by C ₁ -C ₄ alkoxy), optionally substituted by 1 or 2 substituents selected from C ₁ -C ₄ alkoxy, sulfo and a group of halogens Represents phenylene which may be substituted or naphthylene which may be substituted by one sulfo. Specific examples of the substituent of the phenylene include methyl, ethyl,
n-propyl, iso-propyl, n-butyl, iso
-Butyl, sec-butyl, methoxy, ethoxy, n-
Propoxy, iso-propoxy, n-butoxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2
-Ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, sulfo, chloro and bromo. B ₁ , B ₂ , B ₄ , B ₅ , B ₆ and B _{7 each} represent an unsubstituted phenylene group or phenylene substituted by one or two substituents selected from the group consisting of methyl, methoxy and sulfo Are preferable, and unsubstituted phenylene is particularly preferable.

Formulas (I), (III), (IV), (V),
(VI), (VII), (VIII), (IX), (X), (X
Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y in I) and (XII)
_{6, Y 7, Y 8,} Y 9, Y 10, Y 11, Y 12 and Y ₁₃ are, -C
H = CH ₂ , or each represents —CH ₂ CH ₂ Z ₁ ,
_{-CH 2 CH 2 Z 2, -CH} 2 CH 2 Z 3, -CH 2 CH
_{2 Z 4, -CH 2 CH 2} Z 5, -CH 2 CH 2 Z 6, -CH 2 C
_{H 2 Z 7, -CH 2 CH} 2 Z 8, -CH 2 CH 2 Z 9, -CH 2
_{CH 2 Z 10, -CH 2 CH} 2 Z 11, represents a -CH ₂ CH ₂ Z ₁₂ and _{-CH 2 CH 2 Z 13, Z} 1, Z 2, Z 3, Z 4, Z 5,
Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ each represent a group which is eliminated by the action of an alkali. The above Z _1-
Z ₁₃ is, for example, a sulfate group, a thiosulfate group, a phosphate group, an acetate group, a halogeno, or a pyridinio which may be substituted with one or two substituents selected from the group consisting of carboxy and carbamoyl. And the like. As Z _{1 to} Z ₁₃ , a sulfate group is preferable. Preferred specific examples of the above Y _{1 to} Y ₁₃ include —CH ＝ CH ₂ or —CH ₂ CH ₂ OSO ₃ H
And —CH ₂ CH ₂ OSO ₃ H is particularly preferable.

When R ₆ and R ₉ in the formula (II) are halogen, the halogen is preferably fluoro or chloro.

When B ₃ in the formula (II) is an optionally substituted C ₂ -C ₆ alkylene, the optionally substituted C ₂ -C ₆ alkylene is-(CH 2) 3
-,-(CH2) 4-,-(CH2) 5-, -CH (CH
3) -CH2-, -CH (CH3)-(CH2) 2- or -CH2-CH (CH3)-(CH2) 3- are preferred.

R in the formula (III)₁₃Has been replaced
Good C₁~ C_FourAlkylcarbonylamino or substituted
May be C_Two~ C_FourAlkenylcarbonylamino
In these cases, these alkyl or alkenyl substituents
Include sulfo, carboxy and halogen.
You. Also, R₁₃May be substituted phenylcarboni
When the amino group is ruamino, the substituent of the phenyl is
Such as ruho, carboxy, methyl and halogen
You. Preferred R₁₃Is methyl or ureido, or
Cetyl, propionyl, maleinyl, succinyl or
Amino substituted with nzoyl, or R ₁₃When
R₁₄Together form a benzene ring, and
One in which one sulfo is substituted. R_FifteenIndicated by
C₁~ C_FourAlkyl or C₁~ C_FourAlkoxy is straight chain or
Is branched, and the alkyl or alkoxy is chloro or
May have a substituent such as hydroxy. R_Fifteen
Is C₁~ C_FourAlkyl or C₁~ C_FourPlaces that are alkoxy
If preferred, R_FifteenIs unsubstituted methyl and methoxy
You. R₁₃, R₁₄And R_FifteenThe best combination of is R₁₄as well as
R_FifteenIs hydrogen and R₁₃Is ureido or acetyl
If it is amino, or R₁₃Is methyl and R
₁₄Is hydrogen and R_FifteenIs methoxy
You.

In the formula (III), p is 0, 1, 2, or 3.
And 2 or 3 is preferable, and 3 is particularly preferable.

In the formula (V), R ₁₉ is hydrogen, optionally substituted C ₁ -C ₄ alkyl, nitro, sulfo or —S
O ₂ C ₂ H ₄ Cl is represented, but hydrogen is particularly preferred. Expression (V)
Among the metal ions of atomic numbers 27 to 29 represented by Me, preferred metal ions are copper ions.

Formulas (IV), (VI), (VIII), (IX),
When U ₁ , U ₂ , U ₃ , U ₄ , U ₅ and U _{6 in} (X) and (XII) are phenylene which may be substituted, the phenylene may be a C ₁ -C ₄ alkyl ( One or two selected from the group consisting of methyl, ethyl, etc., C ₁ -C ₄ alkoxy (methoxy, ethoxy, etc.), C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl, halogen (chlorine, bromine, etc.) and sulfo And phenylene which may be substituted by the substituent (i). Specific examples of the phenylene substituent include methyl, ethyl, n-propyl, iso-propyl, n-
Butyl, iso-butyl, sec-butyl, methoxy,
Ethoxy, n-propoxy, iso-propoxy, n-
Butoxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 4-methoxybutyl,
Ethoxybutyl, sulfo, chloro, bromo and the like can be mentioned. Examples of the optionally substituted phenylene represented by the above U _{1 to} U ₆ include unsubstituted phenylene or phenylene substituted by one or two substituents selected from the group consisting of methyl, methoxy and sulfo. Preferably, unsubstituted phenylene is particularly preferred.

Formulas (IV), (VI), (VIII) and (I
X), (X) and (XII) U ₁ , U ₂ , U ₃ , U ₄ ,
When U ₅ and U ₆ are optionally substituted naphthylene, the optionally substituted naphthylene preferably includes naphthylene which may be substituted with one sulfo. Formulas (IV), (VI), (VI
II), (IX), U 1 in (X) and (XII), U _2, U
₃ , U ₄ , U ₅ and U ₆ are optionally substituted C 2 -C 6
When it is an alkylene, these optionally substituted C ₂ -C ₆ alkylene includes, for example,-(CH 2) 2
-,-(CH2) 3- and -CH (CH3) -CH2-
C ₂ -C ₄ alkylene and the like are preferable.

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

Formulas (III), (V), (VII), (IX)
And R ₁₁ , R ₁₇ , R ₂₂ , R ₂₅ and R ₂₈ in (XI)
Is phenylamino which may be substituted with a non-fiber reactive group, examples of the amino compound forming phenylamino which may be substituted include 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-ethyl Aminobenzenesulfonic 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-methyl Amino-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).

R ₁₁ , R ₁₇ , R ₂₂ and R ₂₅ include fluoro and chloro, 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, N-methylaminobenzene and N
A residue of -ethylaminobenzene is preferred, and fluoro, chloro, and 1-amino-2-ethylbenzene, 3
Particularly preferred are residues of -aminobenzenesulfonic acid and 2-aminobenzoic acid.

When R ₂₈ in the general formula (XI) represents an alkylamino which may be substituted by a non-fiber reactive group, examples of the optionally substituted alkylamino include methylamino, hydroxymethylamino, Ethylamino, n-propylamino, isopropylamino, n-
Butylamino, isobutylamino, sec-butylamino, β-methoxyethylamino, β-ethoxyethylamino, γ-methoxypropylamino, β-hydroxyethylamino, β-sulfatoethylamino, γ-hydroxypropylamino, N-β -Sulfoethyl-N-
Methylamino, β-carboxyethylamino, β-chloromethylamino, β-cyanoethylamino, β-sulfoethylamino, N, N-dimethylamino, N, N-dihydroxymethylamino, N, N-diethylamino, N, N
Examples thereof include N-di-β-hydroxyethylamino, cycloalkylamino, benzylamino, morpholino, and the like.

Preferred R ₂₈ is fluoro, chloro, 1-
Aminobenzene, 1-amino-2-ethylbenzene, 2
-, 3- or 4-aminobenzenesulfonic acid, 1-amino-2-, -3- or -4-methoxybenzene, 2-,
Residues of 3- or 4-aminobenzoic acid, N-methylaminobenzene and N-ethylaminobenzene, and amino, hydroxymethylamino, N, N-di-β-hydroxyethylamino, β-sulfoethylamino, β-carboxyethylamino and morpholino, with fluoro, chloro, amino and β-sulfoethylamino being particularly preferred.

W ₁ and W ₂ in the general formula (XI) are the same or different from each other and are hydrogen, halogen such as chloro or bromo, methyl, ethyl, n-propyl, isopropyl, n
Straight-chain or branched alkyl having 1 to 4 carbon atoms such as -butyl, isobutyl and sec-butyl, straight-chain or branched alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy and isopropoxy; Or,
Represents an optionally substituted aryloxy group such as phenoxy, p-methoxyphenyloxy and p-methylphenoxy. W ₁ and W ₂ are preferably the same or different from each other and are hydrogen, chloro, methyl, ethyl, methoxy, ethoxy, and chloro is particularly preferable.

X ₁ and X ₂ in the general formula (XI) are the same or different from each other and are hydrogen, halogen such as chloro or bromo, methyl, ethyl, n-propyl, isopropyl, n
Straight-chain or branched alkyl having 1 to 4 carbon atoms such as -butyl, isobutyl and sec-butyl, straight-chain or branched alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy and isopropoxy, or Represents carboxyl. X ₁ and X ₂ are preferably the same or different from each other and are hydrogen, methyl, ethyl, n-propyl,
Methoxy, ethoxy, n-propoxy, with methoxy or ethoxy being particularly preferred.

The azo reactive dye represented by the general formula (I) is
It can be produced according to a known method, for example, the method described in JP-A-63-101458, and has a compound represented by the general formula (I
The azo reactive dye represented by I) can be produced by a known method, for example,
It can be produced according to the method described in JP-A-7-504949. The reactive dye represented by the general formula (III) can be produced by a known method, for example, JP-A-63-225664.
The reactive dye represented by the general formula (V) can be produced according to a known method, for example, a method described in JP-B-3-10669. The reactive dye represented by the general formula (VII) can be prepared by a known method, for example, JP-A-56-12838.
No. 0, can be manufactured according to the method described in
The reactive dye represented by the formula (IX) can be prepared by a known method, for example, as described in JP-A-6-287463 and JP-A-56-12.
The reactive dye represented by formula (XI) can be produced according to a known method, for example, a method described in JP-A-9-202788. Can be manufactured. General formula (I), (I
The reactive dyes of I), (III), (V), (VII), (IX) and (XI) are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts Are preferable, and a sodium salt, a potassium salt, and a lithium salt are particularly preferable. The method for preparing the reactive dye mixture used in the present invention is not particularly limited, and may be dyed after mixing each reactive dye, or may be mixed in a dye bath when dyeing each reactive dye. Good.

The reactive dye mixture used in the present invention comprises at least one selected from the group of azo reactive dyes represented by formulas (I) and (II) and formulas (III), (V), (VII),
(IX) and one or more selected from the group of reactive dyes represented by (XI), and preferably one or more of the azo reactive dyes represented by formulas (I) and (II). 99-1% by weight and the formulas (III), (V), (VII) and (I
X) and one or more 1-99% by weight selected from the group of reactive dyes represented by (XI). More preferably, 80-20% by weight of one or more of the azo reactive dyes of formulas (I) and (II),
(V), (VII), (IX) and one or more selected from the reactive dyes represented by (XI).

The reactive dye mixture used in the present invention may be, if necessary, an inorganic salt such as sodium sulfate or sodium chloride, β-naphthalenesulfonic acid sodium / formalin condensate, methylnaphthalenesulfonic acid sodium / formalin condensate, acetylaminonaphthol Dispersing agents such as compounds, dust scattering inhibitors such as di-2-ethylhexyl terephthalate, sodium acetate, pH buffering agents such as sodium phosphate, known dyeing assistants such as hard water softeners such as polyphosphate, Other reactive dyes and the like can be contained. The reactive dye mixture used in the present invention is not particularly limited in its form. For example, it may be in the form of powder, granule, or liquid.

The method of the present invention is useful for dyeing a mixed fiber material of a cellulosic fiber and a polyamide fiber. The cellulosic fiber is not particularly limited, and examples thereof include natural, regenerated or purified cellulose fibers such as cotton, linen, hemp, jude, ramie fiber, viscose silk, Bemberg (registered trademark), and Tencel. Examples of the polyamide fiber include wool, 6-nylon, 6,6-nylon, angora, silk and the like.

The method of the present invention is applicable to various dyeings, and is not particularly limited. In the exhaust dyeing method, for example, dyeing is performed using one or more inorganic neutral salts such as anhydrous sodium sulfate and sodium chloride, and one or more acid binders such as sodium carbonate, sodium bicarbonate, caustic soda, and sodium tertiary phosphate. A method is illustrated. For the above inorganic neutral salts and acid binders,
It is preferable to use 1 g or more per liter of the dyeing bath. 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 leveling agents,
Dyeing assistants such as slow dyes and bath softeners may be used in combination. The temperature of the exhaust dyeing is preferably from 40 to 90 ° C, more preferably from 50 to 70 ° C. In the cold batch-up dyeing method, after padding using an inorganic neutral salt such as anhydrous sodium sulfate and sodium chloride, or an acid binder such as caustic soda or sodium silicate, in a closed packaging material, preferably 0 to 90 ° C., more preferably A method of dyeing by leaving it at a temperature of 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.

Suitable acid binders for fixing the reactive dye mixture used according to the invention on the fibers include alkali metals or alkaline earth metals and inorganic or organic acids or compounds which release alkalis under heating. Is a water-soluble basic salt of Examples of the water-soluble basic salt include a hydroxide of an alkali metal and an alkali metal salt of an inorganic or organic acid having a weak to moderate strength, and a soda salt and a potassium salt are particularly preferable. Examples of the water-soluble basic salt include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate and sodium trichloroacetate.

In the method of the present invention, a dye-proofing agent for polyamide fibers may be used, and commercially available products and the like are used.
Examples of the method of using the anti-dyeing agent include a method of performing an anti-dyeing treatment before dyeing, a method of adding an anti-dyeing agent at the same time as the dyeing, and the like.

[0055]

According to the method of the present invention, cellulose fibers and polyamide fibers can be dyed to approximate colors in the dyeing of mixed fibers of cellulose fibers and polyamide fibers. Good reproducibility, reproducibility and build-up properties. In addition, dyed products having various fastnesses, such as fastness to the combined action of sweat and sunlight, fastness to chlorine and fastness to oxidizing gas, can be obtained. In particular,
In exhaust dyeing, the dyeing temperature dependency and bath ratio dependency are small, and the reproducibility of dyeing is excellent.

[0056]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples,% 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)

[0058]

Embedded image (1)

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

[0060]

Embedded image (2)

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

[0062]

Embedded image (3)

10 parts of the dye represented by the following formula (4)

[0064]

Embedded image (4)

15 parts of the dye represented by the following formula (5)

[0066]

Embedded image (5)

By mixing 15 parts of the dye represented by the formula (1), a brown reactive dye mixture is obtained. 0.26 parts of this dye mixture, the anti-dyeing agent [Tasegal PWR (Bay
er)] 0.2 parts and anhydrous sodium sulfate 7 parts with cotton fiber 50
1 consisting of 50% wool and 50% shrink-proof wool fibers
Dyeing apparatus with 0 parts set (bath ratio 1:10, bath temperature 6
0 ° C.) by a known method, and at about 60 ° C.
The knit is treated for 2 minutes, then 2 parts of sodium carbonate are poured into the bath, and the knit is dyed and washed at this temperature for 60 minutes, and the cotton and wool fibers are dyed to similar hues, spotless. A uniform dark brown dyeing is obtained. The dyeing described above has good reproducibility and good washing fastness and light fastness.

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

[0069]

Embedded image (6)

16 parts of the dye represented by the above formula (2), 20 parts of the dye represented by the above formula (3), 37 parts of the dye represented by the above formula (5), free acid form Is the following formula (7)

[0071]

Embedded image (7)

By mixing 10 parts of the dye represented by the formula (1), a gray dye mixture is obtained. 0.36 part of this mixture and 6 parts of anhydrous sodium sulfate were previously heated at 100 ° C. in 100 parts of water containing 0.05 part of acetic acid and 0.5 part of a stain-proofing agent [Uniton MW (manufactured by Morita Chemical)]. A dyeing apparatus (10: 1 bath ratio) set with 10 parts of a knitted fabric composed of 50% cotton fibers subjected to a dye-proof treatment for 30 minutes and 50% wool fibers subjected to a shrink-proof treatment.
0, bath temperature is 60 ° C).
The knit is treated for a minute, then 0.3 parts of caustic soda at 38 ° Baud are poured into the bath and the knit is dyed and washed at this temperature for a further 50 minutes. A uniform, dark gray dyeing without spots is obtained, in which cotton and wool fibers are dyed to similar hues. The dyeing described above has good reproducibility and good washing fastness and light fastness.

Example 3 The form of the free acid is represented by the following formula (8)

[0074]

Embedded image (8)

14 parts of a dye represented by the following formula (9)

[0076]

Embedded image (9)

When 46 parts of the dye represented by the above formula, 10 parts of the dye represented by the above formula (3), 15 parts of the dye represented by the above formula (4) and 15 parts of the dye represented by the above formula (5) are mixed, A colored reactive dye mixture is obtained. 30 parts of this mixture, 20 anti-staining agents [Tasegal PWR (manufactured by Bayer)]
In a cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.), in which 100 parts of yarn and 500 parts of sodium sulfate are set with 1000 parts of a yarn consisting of 40% cotton fiber and 60% shrink-proof wool fiber. Charged and treated at 60 ° C. for 20 minutes, sodium carbonate 2
When 100 parts were put into the bath and then dyed and washed at this temperature for 60 minutes, the cotton fiber and the wool fiber were dyed to similar hues, and had a uniform dark gray color with no difference in concentration between the inner and outer layers of the cheese. A dye is obtained. The dyeing described above has good reproducibility and good washing fastness and light fastness.

Example 4 20 parts of the dye represented by the above formula (6), 5 parts of the dye represented by the above formula (2), 5 parts of the dye represented by the above formula (5) and the form of the free acid were represented by the following formula (10) )

[0079]

Embedded image (10)

By mixing 70 parts of the dye represented by the formula (1), a dark blue reactive dye mixture is obtained. In advance, 0.05 parts of acetic acid and an anti-staining agent [Sunresist NR100L (manufactured by Nichika Chemical)]
Dyeing apparatus (bath ratio: 1) containing 10 parts of a knitted fabric consisting of 45% rayon and 55% shrink-proofed wool fiber in 100 parts of water containing 0.5 part at 100 ° C. for 30 minutes. 10, in a bath temperature of 70 ° C.), 0.1 part of the above composition and 4 parts of anhydrous sodium sulfate are added, and the knitted fabric is treated at 70 ° C. for 20 minutes. Dyeing and washing give a uniform, dark blue dyeing with rayon and wool fibers dyed to similar hues and without spots. The dyeing described above has good reproducibility and good washing fastness and light fastness.

Example 5 30 parts of the reactive dye mixture obtained in Example 2 are dissolved in hot water and then cooled to 25.degree. 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 it is used as a padding liquid, the cotton fiber 50
And a woven fabric consisting of 50% wool fiber. The padded woven fabric is wound up, closed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, and then washed and dried by a conventional method. The dyed product obtained is of a uniform and dark color having similar hues of cotton fiber and wool fiber, and its fastnesses are good.

Example 6 40 parts of the dye represented by the above formula (6), 20 parts of the dye represented by the above formula (2), 10 parts of the dye represented by the above formula (3), and the dye represented by the above formula (5) Mixing 30 parts gives a brown reactive dye mixture. After dissolving 200 parts of this mixture with hot water, the mixture was cooled to 25 ° C., and 1 part of sodium alginate,
10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium hydrogen carbonate are added, and water is further added to make a total amount of 1000 parts at 25 ° C. Using this solution as a padding solution, 60% of cotton fiber and 40% of wool fiber are used. And the fabric is dried at 120 ° C. for 2 minutes and then
When the dye is fixed by steaming at 5 ° C for 5 minutes, the cotton and wool fibers are dyed in similar hues, are uniform dark brown without spots, and have good washing and perspiration fastness. can get. Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 7 When 80 parts of the dye represented by the above formula (8), 15 parts of the dye represented by the above formula (9) and 5 parts of the dye represented by the above formula (3) are mixed, a scarlet red reactive dye mixture is obtained. Is obtained. Cotton fiber 45
% In a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 parts of a knitted fabric consisting of 55% by weight and nylon fiber are set, 0.6 parts of the above composition, a dyeing inhibitor [Tasegal P]
WR (manufactured by Bayer)] and 0.2 parts of anhydrous sodium sulfate were added, and the knitted fabric was treated at 60 ° C. for 20 minutes.
After charging the part, dyeing and washing at this temperature for 60 minutes,
A uniform, dark scarlet red dyeing is obtained, with cotton fibers and nylon fibers dyed to similar hues, without spots. The reproducibility of the above dyeing is good, and the washing fastness and light fastness are also good.

Example 8 The form of the free acid is represented by the following formula (11)

[0085]

Embedded image (11)

14 parts of the dye represented by the following formula (12)

[0087]

Embedded image (12)

When 46 parts of the dye represented by the above formula, 10 parts of the dye represented by the above formula (3), 15 parts of the dye represented by the above formula (4) and 15 parts of the dye represented by the above formula (5) are mixed, A color dye mixture is obtained. A cheese dyeing machine (bath) in which 7 parts of this mixture, 20 parts of a dye-proofing agent [Tasegal PWR (manufactured by Bayer)] and 500 parts of sodium sulfate are set, and 1000 parts of a yarn composed of 40% cotton fiber and 60% shrink-proof wool fiber are set. The ratio was 1:10, and the bath temperature was 60 ° C.), and the mixture was treated at 60 ° C. for 20 minutes.
0 parts were put in the bath, and then dyed and washed at this temperature for 60 minutes. When the cotton fiber and the wool fiber were dyed to similar hues, a uniform dark olive color with no density difference between the inner and outer layers of the cheese. A dye is obtained. The reproducibility of the above dyeing is good, and the washing fastness and light fastness are also good.

Example 9 16 parts of the dye represented by the above formula (6), 16 parts of the dye represented by the above formula (2), 20 parts of the dye represented by the above formula (3), and the dye represented by the above formula (5) By mixing 37 parts and 10 parts of the dye represented by the formula (7), a gray reactive dye mixture is obtained. Beforehand, 0.05 parts of acetic acid and a dyeing resist [Unit
on MW (manufactured by Moribun Chemical)] Water 10 containing 0.5 part
Rayon 4 treated in 100 parts at 0 ° C for 30 minutes
In a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 parts of a knitted fabric composed of 5% and 55% of Angora fibers were set, 0.2 part of the above composition and 7 parts of anhydrous sodium sulfate were charged, 6
The knitted fabric is treated at 0 ° C. for 20 minutes, 2 parts of sodium carbonate are added, and then dyed and washed at this temperature for 60 minutes to give a uniform, dark gray color without rayon and angora fibers dyed to similar hues. A dye is obtained. The reproducibility of the above dyeing is good, and the washing fastness and light fastness are also good.

Example 10 50 parts of the dye represented by the above formula (1), 4 parts of the dye represented by the above formula (2), 10 parts of the dye represented by the above formula (3), and the dye represented by the above formula (10) Mixing 36 parts gives a brown dye mixture. As in Example 1, 0.4 part of this mixture and 8 parts of anhydrous sodium sulfate were dyed with 10 parts of a knitted fabric consisting of 50% cotton fiber and 50% shrink-proof wool fiber (bath ratio: 1). 10, the bath temperature is 60 ° C), and the knitting is treated at 60 ° C for about 20 minutes after the charging.
Next, after adding 2 parts of sodium carbonate, 50
Dyeing and washing the knitted fabric for a minute gives a uniform, dark brown dyeing with cotton fibers and wool fibers dyed to similar hues. The reproducibility of the above dyeing is good, and the washing fastness and light fastness are also good.

Example 11 20 parts of the dye represented by the above formula (6), 5 parts of the dye represented by the above formula (2), 5 parts of the dye represented by the above formula (3), and the dye represented by the above formula (5) By mixing 5 parts and 65 parts of the dye represented by the above formula (7), a dark blue dye mixture is obtained.
0.4 parts of this mixture and 8 parts of anhydrous sodium sulfate were used, as in Example 1, with 50% cotton fibers and 50% shrink-proof wool fibers.
Into a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 parts of a knitted fabric are set, treat the knitted fabric at 60 ° C. for about 20 minutes, and then add 2 parts of sodium carbonate. Further, when the knitted fabric was dyed and washed at this temperature for 50 minutes, cotton fibers and wool fibers were dyed to similar hues.
A uniform dark blue dyeing without spots is obtained. Further, the reproducibility of the above dyeing is good, and the fastness to washing and light fastness are also good.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06P 1/384 D06P 1/384 3/82 3/82 C D 3/87 3/87 D

Claims (14)

[Claims] An azo compound represented by the general formula (I) or (II)
At least one selected from the group of dyes, and a compound represented by the general formula (III):
Reactive dyes represented by (V), (VII), (IX) and (XI)
A reactive dye mixture containing at least one selected from the group consisting of
Cellulosic fiber and poly, characterized by using a compound
A method for dyeing mixed fibers of amide fibers. Embedded image(I) wherein m and n are the same or different from each other, and
Represents 1 and R₁And R_TwoAre the same or different
Or hydrogen or optionally substituted C₁~ C_FourThe alkyl of
And R_ThreeRepresents hydrogen or methyl;₁And B
_TwoAre the same or different from each other;₁~ C_FourArchi
Le, C₁~ C_FourA group of alkoxy, sulfo and halogen
Substituted by one or two substituents selected from
Phenylene, or substituted with one sulfo group
Represents naphthylene which may be₁Is -CH = CH_TwoMa
Or -CH_TwoCH_TwoZ₁And Y_TwoIs -CH = CH_TwoAlso
Is -CH_TwoCH_TwoZ_TwoAnd Z₁And Z_TwoAre identical to each other
Or, unlike the above, the
You. ](II) [wherein, R_FourAnd R_FiveAre the same or different from each other,
Represents hydrogen or methyl;₇And R₈Are the same or
Is different from hydrogen or optionally substituted C ₁~ C_Four
Represents an alkyl of₆And R₉Represents halogen, B_Three
Is optionally substituted C_Two~ C₆Represents alkylene. ](III) wherein p represents 0, 1, 2 or 3;_TenIs hydrogen or
Optionally substituted C ₁~ C_FourRepresents alkyl, R₁₁Is
Phenyl which may be substituted with halogen or non-fiber reactive groups
Ruamino or general formula (IV)(IV) Ｒ where R₁₂Is hydrogen or optionally substituted C₁~
C_FourRepresents alkyl, U₁Is an optionally substituted phenyl
Len, optionally substituted naphthylene or substituted
May be C_Two~ C₆Represents alkylene, Y_FourIs -CH =
CH_TwoOr -CH_TwoCH_TwoZ_FourAnd Z_FourIs made of alkali
Represents a group which is eliminated by use. Represents a group represented by｝. R₁₃Is
Halogen, C₁~ C_FourAlkyl, ureido, substituted
May be C₁~ C_FourAlkylcarbonylamino, substituted
May be C_Two~ C_FourAlkenylcarbonylamino or
Represents an optionally substituted phenylcarbonylamino
Then R₁₄Represents hydrogen, but R₁₃And R₁₄Are together
May form a benzene ring, and the ring is substituted with sulfo
It may be. R_FifteenIs hydrogen, C ₁~ C_FourAlkyl, C
₁~ C_FourRepresents alkoxy or sulfo, B_FourIs C₁~ C_FourA
Luquil, C₁~ C_FourGroup of alkoxy, sulfo and halogen
Substituted by one or two substituents selected from
Phenylene, or substituted with one sulfo
Represents naphthylene which may be_ThreeIs -CH = CH_TwoMa
Or -CH_TwoCH_TwoZ_ThreeAnd Z_ThreeIs removed by the action of alkali.
Represents a leaving group. ](V) [wherein, R₁₆And R₁₈Are the same or different from each other,
Hydrogen or optionally substituted C₁~ C_FourTable showing alkyl
Then R₁₉Is hydrogen, optionally substituted C₁~ C_FourArchi
, Nitro, sulfo or -SO_TwoC_TwoH_FourCl, M
e represents a metal ion having an atomic number of 27 to 29;_FiveIs C₁
~ C_FourAlkyl, C₁~ C_FourAlkoxy, sulfo and halo
Substituted by one or two substituents selected from the group of
Phenylene, or one sulfo
Represents an optionally substituted naphthylene;_FiveIs -CH
= CH_TwoOr -CH_TwoCH_TwoZ_FiveAnd Z_FiveIs alkaline
Represents a group leaving by the action of₁₇Is halogen, non-fiber anti
Phenylamino optionally substituted with a reactive group or a general formula
(VI)(VI) ｛R₂₀Is hydrogen or optionally substituted C₁~ C_FourAl
Represents a kill, U_TwoIs phenylene which may be substituted,
Optionally substituted naphthylene or substituted
Good C_Two~ C₆Represents alkylene, Y₆Is -CH = CH_Two
Or -CH_TwoCH_TwoZ₆And Z₆Is the action of alkali
Represents a leaving group. Represents a group represented by｝. ](VII) wherein q represents 0, 1 or 2;_{twenty one}Is hydrogen or
C which may be replaced₁~ C_FourRepresents alkyl, B₆Is C₁
~ C_FourAlkyl, C₁~ C_FourAlkoxy, sulfo and halo
Substituted by one or two substituents selected from the group of
Phenylene, or one sulfo
Represents an optionally substituted naphthylene; ₇Is -CH
= CH_TwoOr -CH_TwoCH_TwoZ₇And Z₇Is alkaline
Represents a group leaving by the action of_{twenty two}Is halogen, non-fiber anti
Phenylamino optionally substituted with a reactive group or general
Formula (VIII)(VIII) ｛R_{twenty three}Is hydrogen or optionally substituted C₁~ C_FourAl
Represents a kill, U_ThreeIs phenylene which may be substituted,
Optionally substituted naphthylene or substituted
Good C_Two~ C₆Represents alkylene, Y₈Is -CH = CH_Two
Or -CH_TwoCH_TwoZ₈And Z₈Is the action of alkali
Represents a leaving group. Represents a group represented by｝. ](IX) [wherein, R_{twenty four}Is hydrogen or optionally substituted C₁~ C
_FourRepresents alkyl, U_FourIs an optionally substituted phenyle
, Optionally substituted naphthylene or substituted
May be C_Two~ C₆Represents alkylene, Y₉Is -CH =
CH_TwoOr -CH _TwoCH_TwoZ₉And Y_TenIs -CH = C
H_TwoOr -CH_TwoCH_TwoZ_TenAnd Z₉And Z_TenIs
Groups which are the same or different and which are eliminated by the action of alkali
And R _{twenty five}Are substituted with halogen, non-fiber reactive groups
Phenylamino or a compound of the general formula (X)(X) ｛R₂₆Is hydrogen or optionally substituted C₁~ C_FourAl
Represents a kill, U_FiveIs phenylene which may be substituted,
Optionally substituted naphthylene or substituted
Good C_Two~ C₆Represents alkylene, Y₁₁Is -CH = CH
_TwoOr -CH_TwoCH_TwoZ₁₁And Z₁₁Is made of alkali
Represents a group which is eliminated by use. Represents a group represented by｝. [Image Omitted](XI) [where W₁And W_TwoAre the same or different from each other,
Element, halogen, C₁~ C_FourAlkyl, C₁~ C_FourAlkoxy
Or an aryloxy which may have a substituent
Then X₁And X_TwoAre the same or different from each other,
Element, halogen, C₁~ C_FourAlkyl, C₁~ C_FourAlkoxy
Or carboxyl, R₂₇And R₂₉Are identical to each other
Or differently, hydrogen or optionally substituted C₁
~ C_FourRepresents alkyl, B₇Is C₁~ C_FourAlkyl, C₁~
C_FourSelected from the group of alkoxy, sulfo and halogen
Fe which may be substituted by one or two substituents
May be substituted with nylene or one sulfo
Represents naphthylene, Y₁₂Is -CH = CH_TwoOr -CH_Two
CH_TwoZ₁₂And Z₁₂Is a group that leaves under the action of an alkali
And R₂₈Are substituted with halogen, non-fiber reactive groups
Phenylamino, which may be substituted with non-fiber reactive groups
Alkylamino or a compound of the general formula (XII)(XII) ｛R₃₀Is hydrogen or optionally substituted C₁~ C_FourAl
Represents a kill, U₆Is phenylene which may be substituted,
Optionally substituted naphthylene or substituted
Good C_Two~ C₆Represents alkylene, Y₁₃Is -CH = CH
_TwoOr -CH_TwoCH_TwoZ₁₃And Z₁₃Is made of alkali
Represents a group which is eliminated by use. Represents a group represented by｝. ] 2. R ₁ and R ₂ in the formula (I) are the same or different from each other and are hydrogen, methyl or ethyl,
The method of claim 1 R ₃ is hydrogen. 3. B ₁ and B ₂ in the formula (I) are the same or different from each other and are unsubstituted phenylene or phenylene substituted by one or two substituents selected from the group consisting of methyl and methoxy. The method according to claim 1 or 2, wherein 4. The method according to claim 1, wherein m in formula (I) is 0 and n is 1. 5. R ₄ , R ₅ , R ₇ and R ₈ in the formula (II)
Is hydrogen, and R ₆ and R ₉ are fluorine.
The method according to any of the above. 6. A reactive dye represented by the formula (III):
The method according to any one of claims 1 to 5, wherein p in the formula is 2 or 3, R ₁₃ is ureido or acetylamino, and R ₁₄ and R ₁₅ are hydrogen. 7. A reactive dye represented by the formula (III):
The method according to any one of claims 1 to 6, wherein B ₄ in the formula is unsubstituted phenylene or phenylene substituted by one or two substituents selected from the group consisting of methyl and methoxy. 8. A reactive dye represented by the formula (V), wherein R ₁₇ is chloro or fluoro, R ₁₉ is hydrogen and B ₅ is unsubstituted phenylene or methyl and methoxy. The method according to any one of claims 1 to 7, which is phenylene substituted by one or two substituents selected from the group. 9. A reactive dye represented by the formula (VII):
In the formula, R ₂₂ is chloro or fluoro, and B ₆ is unsubstituted phenylene or phenylene substituted by one or two substituents selected from the group consisting of methyl and methoxy. The method according to any of the above. 10. A reactive dye represented by the formula (VII), wherein R ₂₂ is a group represented by the general formula (VIII) and U ₃ is unsubstituted phenylene or methyl and methoxy. The method according to any one of claims 1 to 8, which is phenylene substituted by one or two substituents selected from the group consisting of: 11. A reactive dye represented by the formula (IX):
11. The method according to claim 1, wherein U ₄ in the same formula is an optionally substituted C ₂ -C ₆ alkylene, and R ₂₅ is phenylamino optionally substituted with a chloro, fluoro or non-fiber reactive group. The method described in Crab. 12. A reactive dye represented by the formula (IX):
R ₂₅ in the formula is a group represented by the general formula (X),
U ₅ is unsubstituted phenylene, or The method according to claim 1 is phenylene which is substituted by 1 or 2 substituents selected from the group consisting of methyl and methoxy. 13. A reactive dye represented by the formula (XI):
A W ₁ and W ₂ in the equation is chloro, X ₁ is hydrogen, and, according to claim 1 X ₂ is a C ₁ -C ₄ alkoxy
The method according to any one of claims 12 to 12. 14. A reactive dye represented by the formula (XI):
The B ₇ in the formula is an unsubstituted phenylene, or method according to any one of claims 1 to 13 is phenylene substituted by 1 or 2 substituents selected from the group consisting of methyl and methoxy.