JPH11199793A - Reactive dye mixture and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a yellow reactive dye mixture which is excellent in fastness to light. laundering, sweat, etc., by mixing a plurality of monoazo compds. having fiber-reactive vinylsulfone groups. SOLUTION: This dye mixture contains at least two monoazo compds. of which the free acid forms are represented by formula I, and the compds. represented by formula II account for 50-100 wt.% of the total wt. of the monoazo compds. Exhaustion dyeing of cellulose fibres, etc., with this dye mixture is conducted in the presence of an acid binder (e.g. sodium carbonate) together with a neutral salt (common salt), a dissolution assistant, penetrant or a level dyeing agent, etc., at 30-100 deg.C. Printing with the dye mixture can be done by printing with a printing paste contg. an acid binder (e.g. sodium bicarbonate) and steaming at 80 deg.C or higher. In the formulas, R1 and R2 are each H, lower alkyl, or the like; R3 is lower alkyl; Y is phenylene; A is phenylene or 2-6C alkylene; n is 2 or 3; m is 1-2; and Z1 and Z2 are each -CH=CH2 or -CH2 CH2 Z (Z is a group separable by the action of an alkali).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reactive dye mixture and its application, and more particularly to a neutral yellow reactive dye mixture.

[0002]

2. Description of the Related Art Various reactive dyes and mixtures thereof have hitherto been known.
Widely used in the field of dyeing or printing fiber materials. For example, as a reactive dye having a vinyl sulfone-based fiber reactive group,

[0003]

Embedded image

[Wherein, R, R1, R2 independently represent hydrogen or a lower alkyl group, X2 represents a phenylene group or a naphthylene group, X1 represents an aliphatic divalent group, Z1 and Z2 independently of one another, -CH = C
Represents H2 or -CH2CH2-Z, Z represents a group capable of leaving by the action of an alkali, and F represents an organic dye residue. ]
(Japanese Unexamined Patent Publication (Kokai) No. 5-32907) are known. However, even if the fiber material is dyed or printed using the known yellow dye, the exhaustion property, the fixing rate, the build-up property, Color value, easy removal of unfixed dye from fiber material, storage stability in dry, wet and solution state, dye reproducibility, solubility in aqueous solvents, compatibility with other reactive dyes Dyeing performance such as dyeing properties, suitability for dyeing in combination dyeing, and suitability for more economical dyeing prescriptions, for example, light fastness, sweat fastness, sweat sunlight fastness, chlorine fastness, acid hydrolysis resistance It does not sufficiently satisfy the current requirements for fastness, alkali fastness, washing fastness, peroxide washing fastness, thermal discoloration, phototropy, and fiber-dye bond stability. For various performance and robustness The development of reactive dye composition of yellow is desired.

[0005]

[Means for Solving the Problems] Under such circumstances,
The present inventors have conducted intensive studies to develop a reactive dye mixture having excellent dyeing performance and fastness as described above, and as a result, a mixture of specific monoazo compounds having a vinyl sulfone-based fiber reactive group has been developed for the above purpose. The present invention has been completed by finding what is achieved. That is, the present invention relates to a compound of the formula (I)

[0006]

Embedded image

(I)

Wherein R1 and R2 are independently of each other:
R 3 represents a hydrogen atom or an optionally substituted lower alkyl group, R 3 represents an optionally substituted lower alkyl group, Y represents an optionally substituted phenylene group, and A represents A phenylene group or
Represents an alkylene group having 2 to 6 carbon atoms which may be substituted, and may have a carbon chain interrupted by a hetero atom;
n represents 2 or 3, m represents 1 or 2, Z
1 and Z2 independently represent -CH = CH2 or -CH2CH2-Z, wherein Z represents a group which leaves under the action of an alkali. A reactive dye mixture comprising two or more of the monoazo compounds represented by the formula (1), and its application to fiber materials. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The monoazo compound used in the mixture of the present invention has the form of a free acid represented by the general formula (I)
Wherein R 1 and R 2 independently represent a hydrogen atom or a lower alkyl group which may be substituted. Specific examples of such a lower alkyl group include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, etc.
Examples of the substituent include a hydroxy group, an alkyloxy group, a halogeno group, a carboxyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, And a sulfo group.

Specific examples of the lower alkyl group which may be substituted in R1 and R2 include methyl, ethyl, n
-Propyl, iso-propyl, n-butyl, iso-
Butyl, sec-butyl, 2-hydroxyethyl, 2-
Hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 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, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonyl Butyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl,
Examples include ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like.

R1 and R2 are, among others, a hydrogen atom,
Methyl or ethyl is preferred.

In the monoazo compound (I) used in the mixture of the present invention, R3 represents a lower alkyl group which may be substituted. Examples of such an alkyl group include those described above for R1 and R2. similar,
Examples thereof include a lower alkyl group having 1 to 4 carbon atoms which may be substituted.

As R3, methyl or ethyl is preferable, and methyl is particularly preferable.

In the monoazo compound (I), Y represents a phenylene group which may be substituted, and the substituent may be a lower alkyl group having 1 to 4 carbon atoms or a lower alkyl group having 1 to 4 carbon atoms.
To 4 lower alkyloxy groups, alkoxyalkyl groups having 2 to 5 carbon atoms, or sulfoalkyl groups, and specifically, methyl, ethyl, n-propyl, iso-propyl, n- Butyl, iso-butyl,
sec-butyl, 2-hydroxyethyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like Can be mentioned.

As Y, phenylene and
Phenylene substituted with methyl or methoxy is preferred.

In the monoazo compound (I), A
Represents a phenylene group which may be substituted or an alkylene group having 2 to 6 carbon atoms which may be substituted and whose carbon chain may be interrupted by a hetero atom. Examples of the phenylene which may be substituted include the same phenylenes which may be substituted as those exemplified in the above Y, and among them, phenylene, and phenylene which is substituted with methyl or methoxy are preferable. Phenylene can be mentioned. Specific examples of the alkylene group having 2 to 6 carbon atoms which may be substituted include ethylene, trimethylene, methylethylene, tetramethylene or -CH2CH2OCH2CH2-, and among them, ethylene or trimethylene is preferable.

In the monoazo compound (I), Z1
And Z2 are, independently of each other, -CH = CH2 or-
CH2CH2-Z, wherein Z represents a group capable of leaving by the action of an alkali, and specifically, Z is, for example, a group such as a sulfate ester, a thiosulfate ester, a phosphate ester, and an acetate ester; Can be mentioned. Among them, a sulfate group and chloro are preferred. Therefore, Z
Preferred examples of 1 and Z2 include —CHＣＨCH
2, —CH 2 CH 2 OSO 3 H, —CH 2 CH 2 Cl, etc., among which —CH 2 CH 2 OSO
3H is particularly preferred.

The monoazo compound (I) may be in the form of a free acid, a salt thereof, or a mixture thereof. Preferred are alkali metal salts, alkaline earth metal salts, and mixtures containing them, with soda salts, potassium salts, lithium salts and mixtures containing them being particularly preferred.

The method for producing the monoazo compound (I) is not particularly limited, but for example, it can be produced as follows. That is, the following general formula (III)

[0020]

Embedded image

(III)

Wherein R3, m and n have the same meaning as described above. And a compound represented by the following general formula (IV)

Wherein R2, A and Z2 have the same meaning as described above. And a compound represented by the following general formula (V)

[0024]

Wherein R1, Y and Z1 have the same meaning as described above. The compound represented by 2,4,6-
Condensed with trichloro-s-triazine or 2,4,6-trifluoro-s-triazine in any order. In the condensation reaction with 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-s-triazine, the order is not particularly limited, and the reaction conditions are not particularly limited. Primary temperature is -10 ° C to 40 ° C and pH is 1 to 9;
PH 4 to 10 at ~ 70 ° C, temperature 10 to 100 for tertiary
Condensate while adjusting the pH to 1 to 8 at ° C.

The method for producing the compound represented by the general formula (III) is not particularly limited.

[0027]

Embedded image

(VI)

[Wherein, n represents the same meaning as described above. A diazotized compound represented by the following general formula (VII):

[0030]

Embedded image

(VII)

[Wherein R3 and m represent the same meaning as described above. By performing diazo coupling with the compound represented by the general formula (III), a compound of the general formula (III) can be obtained.

As the compound represented by the general formula (VI), for example, 2-aminonaphthalene-1,5-, 3,6-,
Examples thereof include 4,8-, 5,7- or 6,8-disulfonic acid, 2-aminonaphthalene-3,6,8 or 4,6,8-trisulfonic acid, and among others, 2-aminonaphthalene -4,8-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-3,
6,8- or 4,6,8-trisulfonic acid is preferred,
Particularly, 2-aminonaphthalene-4,6,8-trisulfonic acid is particularly preferred. As the compound represented by the general formula (VII), preferably, for example, o-methoxyaniline,
o-ethoxyaniline, m-methoxyaniline, m-ethoxyaniline, 2,5-dimethoxyaniline, 2,5
-Diethoxyaniline, among which o
-Methoxyaniline or m-methoxyaniline is particularly preferred.

As the compound represented by the general formula (V), for example,

[0035]

Embedded image

And the like.

The compound represented by the general formula (IV) includes, in addition to the compounds described above as the compound represented by the general formula (V), for example,

H2NCH2CH2SO2CH = CH2 H2NCH2CH2CH2SO2CH = CH2 H2NCH2CH2CH2CH2SO2CH = CH2 H2NCH2CH2SO2CH2CH2OSO3H H2NCH2CH2CH2SO2CH2CH2OSO3
H H2NCH2CH2CH2CH2SO2CH2CH2O
SO3H H2NCH2CH2SO2CH2CH2OCOCH3 H2NCH2CH2CH2SO2CH2CH2OCOC
H3 H2NCH2CH2CH2CH2SO2CH2CH2O
COCH3 H2NCH2CH2SO2CH2CH2Cl H2NCH2CH2CH2SO2CH2CH2Cl H2NCH2CH2CH2CH2SO2CH2CH2C
l H2NCH2CH2OCH2CH2SO2CH = CH2

And the like. Among them,

H2NCH2CH2SO2CH = CH2 H2NCH2CH2CH2SO2CH = CH2 H2NCH2CH2SO2CH2CH2OSO3H H2NCH2CH2CH2SO2CH2CH2OSO3
H H2NCH2CH2SO2CH2CH2OCOCH3 H2NCH2CH2CH2SO2CH2CH2OCOC
H3 H2NCH2CH2SO2CH2CH2Cl H2NCH2CH2CH2SO2CH2CH2Cl

Is preferred. In particular, when the compound represented by the general formula (VI) is 2-aminonaphthalene-4,6,8-trisulfonic acid, these compounds are particularly preferable as the compound represented by the general formula (IV).

Among the monoazo compounds (I), the compounds represented by the general formula (II)

[0043]

Embedded image

(II)

(Where R1, R2, R3, A, Y, Z1
And Z2 have the same meaning as described above). The proportion of each component compound in the reactive dye mixture of the present invention is not particularly limited, but preferably, one or a plurality of monoazo compounds represented by the general formula (II) is added to the total weight of the component compounds. 5 for
0 to 100% by weight, more preferably 75 to 100% by weight.
%, More preferably 90 to 100% by weight.

The proportion of each component compound in the reactive dye mixture of the present invention is not particularly limited, but preferably, among the plurality of monoazo compounds represented by the general formula (II), A is substituted. And the proportion of alkylene groups having 2 to 6 carbon atoms whose carbon chain may be interrupted by a hetero atom is 50 to 100 relative to the total amount of the monoazo compound represented by the general formula (I). %, More preferably 75 to 100%, even more preferably 90 to 90%.
１００100%.

Each compound in the reactive dye mixture of the present invention is
Since it has a vinyl sulfone-based fiber reactive group, the above mixture can be used as a 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 an amide group. For example, natural or regenerated cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, and blends containing these are used. Materials and the like can be mentioned.

As natural cellulose fibers, specifically,
Cotton, Nerin, hemp, jute, ramie fiber and the like can be mentioned. Preferably, it is cotton.

As the regenerated cellulose fiber, specifically,
Rayon, polynosic, cupra fiber, and trade names “Tencel”, “Toughcell”, “Modal”, “Certima” and the like can be mentioned.

Specific examples of natural or synthetic polyamide fibers include wool, silk, polyamide-6,6, polyamide-
6, polyamide-11, polyamide-4 and the like.

Examples of the blended material include, in addition to the blended material of the above fiber materials, 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 the above-mentioned materials, especially on the above-mentioned fibrous materials, by a method depending on physical and chemical properties.

Specifically, there can be mentioned, for example, a method of dyeing or printing the above-mentioned fibers by an exhaust dyeing method, a cold batch-up method, a continuous dyeing method, a printing method, or the like. For example, when dyeing cellulose fibers by the exhaust dyeing method, in the presence of an acid binder such as sodium carbonate, sodium bicarbonate, sodium tertiary phosphate, and caustic soda, if necessary, neutral salt such as sodium sulfate and sodium chloride. And, if necessary, in combination with a solubilizing agent, a penetrant or a leveling agent, and 30 to 1
A method of dyeing at a temperature of about 00 ° C. is exemplified. Here, the addition of the acid binder, the neutral salt, and the like may be performed at once, or may be performed in a divided manner by a conventional method.

In the case of dyeing cellulose fibers by the cold batch-up method, neutral salts such as sodium sulfate and sodium chloride,
Further, a method of padding with an acid binder such as caustic soda or sodium silicate, followed by treatment in a hermetically sealed packaging material at a constant temperature and the like is exemplified.

In the case where cellulose fibers are dyed by a continuous dyeing method, padding is carried out 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, and then steaming or drying heat. After the fiber is immersed in a padding solution in which the compound of the present invention is dissolved, a neutral salt such as sodium sulfate or salt, and an acid binder such as caustic soda or sodium silicate are padded. And a two-phase padding method for treating by steaming or drying.

In the case of printing on cellulose fibers, printing is carried out in one phase with a printing paste containing an acid binder such as baking soda, and then steaming at a high temperature of 80 ° C. or higher. A method of printing with a neutral or weakly acidic printing paste and passing it through an electrolyte-containing alkaline bath, or overpadging with an alkaline electrolyte-containing padding solution, followed by steaming or dry heat treatment, etc. Is exemplified. Here, the printing paste may contain a sizing agent such as sodium alginate and starch ether and / or an emulsifier, and if necessary, a printing aid and / or a dispersant such as urea. May be.

When the reactive dye composition of the present invention is dyed or printed on cellulose fiber, the acid binder used is not particularly limited, and the above-mentioned sodium carbonate, sodium bicarbonate, sodium tertiary phosphate, sodium hydroxide, and sodium silicate are used. Other, caustic potash,
Sodium formate, potassium carbonate, primary or secondary sodium phosphate, sodium trichloroacetate and the like can also be used.

In the case of exhaustion dyeing on synthetic or natural polyamide fiber or polyurethane fiber, acidic to
A method in which the compound of the present invention is exhausted in a weakly acidic dyeing bath while controlling the pH, and then the pH is changed to neutral to alkaline at a temperature of about 60 to 120 ° C. is exemplified. Here, if necessary, a leveling agent or the like, for example, a condensation product of cyanuric chloride and aminobenzenesulfonic acid, a condensation product of cyanuric chloride and aminonaphthalenesulfonic acid, an addition product of stearylamine and ethylene oxide, etc. A leveling agent may be used.

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 a monofluorotriazine group, a mononicotinic acid triazine group, a dichlorotriazine group, a difluoromonochloropyrimidine group, and a trichloropyrimidine group, or Sumifix
, Sumifix Supra, Remazol, Levafix, Procio
n, Cibacron, Basilen, Drimarene, Kayacion, Kay
Dyes that are commercially available under crown names such as acelon React,
Further, JP-A-50-178, JP-A-56-9483, JP-A-5-9
6-15481, JP-A-56-118976, JP-A-56-128380
No., JP-A-57-2365, JP-A-57-89679, JP-A-5
No. 7-143360, JP-A-59-15451, JP-A-58-191755
No., JP-A-59-96174, JP-A-59-161463, JP-A-59-161463
No. 0-6754, JP-A-60-123559, JP-A-60-229957
No., JP-A-60-260654, JP-A-61-126175, JP-A-61-155469, JP-A-61-225256, JP-A-63-779
No. 74, JP-A-63-225664, JP-A-1-185370, JP-A-3-770, JP-A-5-32907, JP-A-5-117538,
JP-A-5-247366, dyes described in JP-A-6-287463, and CIReactive Blue19, CIReacti
Dyes represented by ve Black 5 are exemplified.

[0060]

Industrial Applicability The reactive dye mixture of the present invention has excellent exhaustion properties, high fixation rate, excellent build-up properties and high color value in dyeing and printing treatment of fiber material, and has a non-fixed dye fiber. Easy to wash and remove from materials, good storage stability in dry, wet and solution state, reproducibility, solubility, compatibility with other reactive dyes, dyeing condition in compound dyeing, economical Good suitability for various dyeing formulations, etc., by using this, the overall fastness, for example, fastness to light, fastness to sweat, fastness to sweat and sunlight, fastness to chlorine, fastness to acid hydrolysis, Alkali resistance,
Excellent washing fastness, peroxidation fastness, heat discoloration,
Yellow dyeings and prints with good phototropic properties and good fiber-dye bond stability are obtained. Further, the dyed product and the printed product obtained by using the reactive dye composition of the present invention have a small discoloration at the time of fix processing, resin processing, mercerizing processing, and the like, and discoloration due to contact with a basic substance during storage is also small. small.

[0061]

The present invention will be described below in detail with reference to 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 formula (1)

[0063]

Embedded image

(1)

The compound represented by the formula (2)

[0066]

Embedded image

(2)

Is sufficiently mixed with 10 parts of a compound represented by the following formula:
A reactive dye mixture was obtained. The reactive dye mixture gave a yellow shade on cotton.

Example 2 A reactive dye mixture was obtained according to Example 1, except that the amount of the compound represented by the formula (2) was changed to 100 parts.

Example 3 Instead of the compound of formula (2), the free acid form is
The following equation (3)

[0071]

Embedded image

(3)

A reactive dye mixture was obtained in the same manner as in Examples 1 and 2, except that the compound represented by the formula (1) was used.

Example 4 In place of the compounds represented by the formulas (1), (2) and (3), the compounds shown in the second column of the following table were each mixed at the composition ratio shown in the third column. According to Examples 1 to 3, the respective corresponding reactive dye mixtures are obtained. The color of the dyed product when these mixtures are applied to cotton is yellowish as shown in the fourth column of the table below.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5]

Example 5 0.3 part of the reactive dye mixture obtained in Examples 1 to 4 was dissolved in 200 parts of water, 10 parts of sodium sulfate was added, 10 parts of cotton was added, and the temperature was raised to 60 ° C. Warm up. 30 minutes after the temperature reached 60 ° C., 3 parts of sodium carbonate was added, and the mixture was dyed at the same temperature for 1 hour. Next, washing and soaping are performed. The wash-off property at the time of washing and soaping is good even when any mixture is used, and the coloring amount of the dyeing wastewater is small. The dyeings obtained are all uniform and dark yellow. During dyeing, the solubility is good, the exhaustion properties are excellent, the fixation rate is high, and a high color value is exhibited. The light fastness, sweat resistance, sweat and sunlight resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance of the obtained dyed product are all good, It has good thermochromic properties and phototropic properties.

Example 6 Dyeing is carried out in accordance with Example 5, except that the amount of sodium sulfate used is changed from 10 parts to 6 parts. The resulting dyed product was obtained in Example 5.
Has the same quality as the dyed product obtained in

Example 7 Dyeing is carried out according to Example 5, except that the amount of sodium sulfate is changed from 10 parts to 4 parts. The resulting dyed product was obtained in Example 5.
It has the same quality as the dyed product.

Example 8 Example 5 except that the dyeing temperature was changed from 60 ° C. to 70 ° C.
Dyeing is performed in accordance with Nos. To 7, and the obtained dyed products have the same quality as the dyed products of Examples 5 to 7, respectively.

Example 9 Instead of 0.3 part of the reactive dye mixture, 0.3 part of the reactive dye mixture was used.
Examples 5 to 8 except that a mixture of 0.06 parts of methylnaphthalenesulfonic acid / formaldehyde condensate (sodium salt) having a sulfonation degree of 110% and an average polymerization degree of 1.8 was used. Are performed in accordance with each of the above, but the obtained dyed product has the same quality as each of the dyed products of Examples 5 to 8.

Example 10 The procedure of Example 10 was repeated except that instead of using 0.3 part of the reactive dye mixture containing a plurality of monoazo compounds, 0.1 part or 0.6 part of the reactive dye mixture containing a plurality of monoazo compounds was used. Dyeing is carried out according to each of Examples 5 to 9. The above mixture 0.
The dyed product obtained using 6 parts is sufficiently thicker than those obtained in Examples 5 to 9 using 0.3 part of the same mixture.
The build-up properties of the compounds of Nos. To 4 are all good. Other qualities are the same as those obtained in Examples 5 to 9 regardless of the amount of the mixture used.

Example 11 Using the respective reactive dye mixtures obtained in Examples 1 to 4, a color paste having the following composition is prepared.

[0087] color paste composition reactive dye composition 5 parts of urea 5 parts Sodium alginate (5%) stock paste 50 parts Hot water 25 parts sodium bicarbonate 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, washed with hot water, soaped, washed with hot water, and dried.
Finish. The resulting prints are all uniform and dark yellow, but their light resistance, sweat resistance, sweat and sunlight resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance and peroxidation washing resistance Are all good in fastness, and show good properties in thermochromic property and phototropic property.

Example 12 30 parts of the reactive dye mixtures of Examples 1 to 4 were each dissolved in hot water, and then cooled to 25 ° C.
Immediately after adding 15 parts of a 5% aqueous solution of sodium hydroxide and 150 parts of water glass having a temperature of 50 ° B. to a total amount of 1000 parts by adding water at 25 ° C., the cotton fabric is padded using the liquid as a padding liquid. The padded cotton fabric is rolled up, closed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, washed by a conventional method, and dried to finish. The dyeings obtained are all uniform and dark yellow. In addition, the light fastness, sweat resistance, sweat and sunlight resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance of this dyed product are all good. It also shows good properties with respect to thermochromic properties and phototropic properties.

Example 13 20 parts of the reactive dye mixtures of Examples 1 to 4 were each dissolved in hot water and then cooled to 25 ° C. To this dye solution, 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate, and 20 parts of sodium bicarbonate were added, and further, water was added at 25 ° C. to make the total amount 1000 parts, and this liquid was used as a padding solution. Pad the cotton fabric. The padded cotton fabric is dried at 120 ° C. for 2 minutes,
The dye is then fixed by steaming at 100 ° C. for 5 minutes. The dyeings obtained are all uniform and dark yellow, and the dyeings are light-, sweat-, sweat-and-sun-resistant, chlorine-, hydrolysis-, alkali-, wash- and peroxidation-resistant. All the fastnesses of the washing property are good, and the thermochromic property and the phototropic property show good properties.

Claims (9)

[Claims] (1) The form of the free acid is represented by the following general formula (I): (I) wherein R1 and R2 independently represent a hydrogen atom or an optionally substituted lower alkyl group;
Represents an optionally substituted lower alkyl group;
Represents a phenylene group which may be substituted, and A represents
Represents a phenylene group which may be substituted, or an alkylene group having 2 to 6 carbon atoms which may be substituted and whose carbon chain may be interrupted by a hetero atom, and n represents 2 or 3 , M represents 1 or 2, Z1 and Z
2 are independently of each other -CH = CH2 or -CH2C
Represents H2-Z, wherein Z represents a group capable of leaving by the action of an alkali. ] A reactive dye mixture comprising two or more of the monoazo compounds represented by the following formula: 2. The mixture according to claim 1, wherein R3 is a methyl group. 3. The mixture according to claim 1, wherein A is a phenylene group which may be substituted. 4. The method according to claim 1, wherein A is an alkylene group having 2 to 6 carbon atoms which may be substituted and whose carbon chain may be interrupted by a hetero atom. blend. 5. The mixture according to claim 1, wherein A is ethylene or trimethylene. 6. The mixture according to claim 1, wherein m is 1 and the group represented by OR3 is located at the meta position of the carbon atom to which the azo group is bonded. 7. The compound represented by the general formula (I) is converted to a compound represented by the general formula (II): (II) (wherein, R1, R2, R3, A, Y, Z1 and Z2 are
This has the meaning described in claim 1. The mixture according to any one of claims 1 to 6, which is a compound represented by the formula: 8. The mixture according to claim 1, wherein the compound represented by the general formula (II) is contained in an amount of 50 to 100% based on the total weight of the monoazo compound. 9. A method of dyeing or printing a fiber material, comprising using the mixture according to claim 1.