JP2943219B2 - Bisazo compound and method for dyeing or printing fiber material using the same - Google Patents

Description

The present invention relates to a material containing a hydroxyl group and / or an amide group, in particular, cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber or leather, and a blend thereof. The present invention relates to an improved compound which is suitable for dyeing and printing fibers and which enables light-fast and wet-fast dark blue dyeing, and its application.

<Prior Art> A bisazo compound having a triazinyl group and a plurality of vinylsulfone-based reactive groups in the same molecule is known in JP-A-63-118376.
For example, the build-up property is insufficient, and a further improvement in level is desired.

<Problems to be Solved by the Invention> Conventionally, various reactive dyes have been widely used in the field of dyeing and printing of fiber materials. However, the state of the art is not satisfactory in view of the high requirements for suitability for a particular dyeing process and the increasing requirements for the fastness of dyeings.

The above-mentioned known reactive dyes are insufficient in solubility, dyeing performance (eg, build-up property) and fastness,
There is a strong desire to provide further improved dyes.

The importance of excellent build-up properties is a very important factor in today's increasingly demanding economy of dyeing direction.

Means for Solving the Problems The present inventors have intensively studied for the purpose of improving the above-mentioned disadvantages of the known dyes and finding new compounds that can widely satisfy the requirements required for the dyes, and as a result, completed the present invention.

<Means for Solving the Problems> The present invention is represented by the following general formula (I) in the form of a free acid. Wherein 式 represents chlorine or fluorine, Z ₁ and Z ₂ independently represent -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z ′,
Z 'represents a group which is eliminated by the action of an alkali. A represents a phenylene or naphthylene group which may be substituted. B is the following formula (In the formula, * is a bond connected to the azo group, R ₃ is hydrogen,
Represents a methyl group or a sulfo group. ). D represents a naphthylene group which may be substituted by a sulfo. R ₁ and R ₂ independently represent hydrogen or an optionally substituted alkyl group. _{１ 1} and Χ ₂
Represents an NH ₂ group and the other represents an OH group. And a method for dyeing or printing a fiber material characterized by using the bisazo compound.

Among dyeing performance of the general formula (I) bisazo compounds represented by, preferably chi ₂ is NH ₂ group chi ₁ is in OH groups, expressed in the form of free acid, the following general formula (II) Wherein Z ₁ , Z ₂ , A, B, D, Χ, R ₁ and R ₂ have the above-mentioned meanings. And a bisazo compound represented by the following formula:

In the general formula (I), the phenylene and naphthylene represented by A are preferably substituted by one or two substituents selected from the group consisting of methyl, ethyl, ethoxy, ethoxy, chloro, bromo and sulfo. Examples of phenylene or naphthylene which may be substituted with sulfo, for example, (Wherein the bond indicated by ** is Means a bond leading to a group. ) And the like, and preferably, And the like.

As the group represented by B, (In the formula, the bond indicated by * has the above-mentioned meaning.) And the like. And the like.

D is naphthylene optionally substituted with sulfo, for example, (In the formula, the bond indicated by *** is the other -N = N-
Means a bond leading to a group. ) And so on.

Among them, those having a sulfo group at the ortho position of the azo group are preferable, for example, Etc. can be given.

Examples of the group capable of leaving under the action of an alkali represented by Z ′ include sulfate, thiosulfate, phosphate, acetate, and halogen.
Of these, sulfates are preferred.

As the optionally substituted alkyl represented by R ₁ and R ₂ , C _{1 to} C ₄ alkyl is preferable, and as the optionally substituted group, hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, Alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfunamoyl are preferred.

Preferred R ₁ and R ₂ include, for example, hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxy Propyl, 2-hydroxybutyl, 3-hydroxybutyl,
-Hydroxybutyl, 2,3-dihydroxypropyl, 3,4
-Dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxyethyl, 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-methoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl,
4-ethoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 8-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-
Sulfamoylpropyl and 4-sulfamoylbutyl can be mentioned. Above all, hydrogen, methyl or ethyl is preferable, and particularly preferably, R ₁ is hydrogen, methyl or ethyl, and R ₂ is hydrogen.

The compound of the present invention exists in the form of a free acid or a salt thereof, and particularly, an alkali metal salt and an alkaline earth metal salt, particularly, a soda salt, a potassium salt, and a lithium salt are preferable.

The compound of the present invention can be produced, for example, as follows. The following general formula (III) Wherein B, D, R ₂ , X ₁ , X ₂ and Z ₁ have the above-mentioned meaning. And a compound represented by the following general formula (IV) Wherein R ₁ , A and Z ₂ have the above-mentioned meaning. The compound of the general formula (I) can be obtained by condensing any of the amines represented by the following formulas with 2,4,6-trihalogeno-s-triazine in any order.

The order of the condensation reaction with 2,4,6-trihalogeno-s-triazine is not particularly limited, and the reaction conditions are not particularly limited.
PH 2 to 9 at 40 ° C to 40 ° C, and secondarily at temperature 0 to 70 ° C.
The compound represented by the general formula (I) or a salt thereof can be obtained by condensation while adjusting to H2 to H9.

As the raw material 2,4,6-trihalogeno-s-triazine, cyanuric chloride or cyanuric fluoride is used.

As [Compound Z ₁ is a hydrogen atom in the general formula (III)] dye matrix in the present invention, for example, 1-hydroxy-2- (1'-sulfonaphth-2'
Ilazo) -7- (5 "-amino-2" -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphth-2'-
Isoazo) -7- (5 "-amino-2" -sulfophenylazo) -8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- ( 1 "-sulfonaphth-2" -ylazo) -8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphth-2'-
Isoazo) -7- (5 "-amino-2", 4 "-disulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphth-2'-
Ilazo) -7- (5 "-amino-2", 4 "-disulfophenylazo) -8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2- (5'-amino-2 ', 4'-disulfophenylazo) -7- (1 "-sulfonaphtho-
2 "-ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2 ', 4'-disulfophenylazo) -7- (1" -sulfonaphtho-
2 "-ylazo) -8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2- (1 ', 7'-disulfonaphtho-
2'-isoazo) -7- (5 "-amino-2" -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfo Phenylazo) -7- (1 ", 7" -disulfophenylnaphth-2 "-ylal) -8-aminonaphthalene-3,6
-Disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (6 "-sulfonaphth-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (8 "-sulfonaphth-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy- 2- (5'-amino-2'-sulfophenylazo) -7- (6 "-sulfonaphtho-2" -isoazo) -8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2- (1 '-Sulfonaphtho-2'-
Ilazo) -7- (4 "-amino-2" -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphth-2'-
Ilazo) -7- (4 "-amino-2", 5 "-disulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphth-2'-
Isoazo) -7- (4 "-amino-2", 5 "-disulfophenylazo) -8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2- (1'-sulfo-5'- Aminomethylnaphth-2'-ylazo) -7- (1 "-sulfonaphth-2" -ylazo) -8-aminonaphthalene-3,
6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphth-2'-
Ilazo) -7- (1 "-sulfo-5" -aminomethylnaphth-2 "-ylazo) -8-aminonaphthalene-3,
6-disulfonic acid, 1-hydroxy-2- (5'-aminomethyl-4'-
Methyl-2'-sulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho-2 ' −
Isoazo) -7- (5 "-aminomethyl-4" -methyl-2 "-sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho-2 '-
Ilazo) -7- (1 ", 7" -disulfo-5 "-aminomethylnaphth-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho) -2'-
Ilazo) -7- (5 "-amino-4" -methyl-2 "
-Sulfophenylazo) -8-aminonaphthalene-3,6
-Disulfonic acid, and the like.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing a material containing a hydroxy group or a carbonamide group. The material is preferably used in the form of a fibrous material or a blend thereof.

The hydroxy-containing material is a natural or synthetic hydroxy-containing material, such as a cellulosic fibrous material or a regenerated product thereof and polyvinyl alcohol. Cellulose fiber materials are cotton and other vegetable fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

Carbonamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
4.

The compound of the present invention can be applied to the above-mentioned materials, particularly to the above-mentioned fibrous materials, in a fiber or printing manner by a method depending on physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, sodium carbonate, tertiary sodium phosphate, in the presence of an acid binder such as caustic soda, optionally a neutral salt, for example, sodium sulfate or sodium chloride,
If desired, dissolution aids, penetrants or leveling agents may be used in combination at relatively low temperatures. Neutral salts which promote the exhaustion of the dye can be added only after the original dyeing temperature has been reached or before, optionally in portions.

When dyeing cellulose fibers according to the padding method,
After padding and drying at elevated temperature at room temperature, it can be fixed by steaming or dry heat.

When printing on cellulose fibers, in one phase,
For example, by printing with a printing paste containing baking soda or other acid condensing agent, and then by steaming at 100 to 160 ° C., or in two phases, for example, by printing with a neutral or weakly acidic printing paste, this is a hot electrolyte. Pass through an alkaline bath containing, or overpadding with an alkaline electrolyte containing padding solution,
It can be carried out by steaming or dry heat treatment.

In printing pastes, sizing or emulsifying agents such as, for example, sodium alginate or starch ethers, if desired,
For example, it is used in combination with a usual printing aid and / or dispersant such as urea.

Acid binders suitable for immobilizing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heating. In particular, mention may be made of hydroxides of alkali metals and alkali metal salts of inorganic or organic acids of weak to moderate strength, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first exhausting the acid or weakly acidic dye bath under control of the pH value and then changing it to a neutral and possibly alkaline pH value for fixing. I can do it. Dyeing can be carried out usually at a temperature of 60 to 120 ° C., but in order to achieve levelness, a conventional leveling agent, for example, a condensation product of cyanuric chloride with 3 times mol of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. Particularly suitable for dyeing cellulosic fiber materials, good light fastness and sweat and sun fastness, excellent wet fastness, such as washing, washing, peroxide washing, chlorine, sweat and acid hydrolysis resistance And it has alkali resistance, and also good friction resistance and iron resistance.

In addition, it has excellent build-up properties, leveling properties and wash-off properties, and also has good solubility and exhaustion / fixing properties,
It is characterized by the fact that it is hardly affected by fluctuations in the dyeing temperature and the dyeing bath ratio and a dyed product of stable quality can be obtained.

It is also characterized by little discoloration of the obtained dyed product during fixation or resin processing, and little change due to contact with a basic substance during storage.

Hereinafter, the present invention will be described in detail with reference to examples. In the example,
Parts and% represent parts by weight and% by weight, respectively.

Example 1 2,4-Diaminobenzenesulfonic acid 4.70
And 4.61 parts of cyanuric chloride, followed by 6.95 parts of 1-aminobenzene-3-betasulfatoethylsulfone.
After diazotization, coupling with 7.73 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid under strong acidity, and further 2-naphthylamino-6-
Beta sulfate ethyl sulfone-1-sulfonic acid
Coupling with 10.25 parts of the diazo compound. By salting out the reaction solution with sodium chloride, the following formula is obtained in the form of a free acid. The bisazo compound shown by was obtained.

Example 2 2-Naphthylamine-6- used in Example 1
Beta sulfate ethyl sulfone-1-sulfonic acid, 2,4-diaminobenzenesulfonic acid, 1-amino-
8-hydroxynaphthalene-3,6-disulfonic acid, 1-
Synthesized in the same manner as in Example 1 using the compounds in the following table, column 2, column 3, column 4 and column 5 in place of aminobenzene-3-betasulfateethylsulfone,
Each corresponding bisazo compound was obtained and dyed to obtain a dyed product having a color tone shown in the sixth column of the following table.

Example 3 In the same manner as in Example 1, except that the coupling order of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and two kinds of diazo compounds was reversed, the following formula was obtained in the form of a free acid. The bisazo compound shown by was obtained.

Example 4 In the table of Example 2, the corresponding bisazo compound was synthesized in the same manner as in Example 3 using the compound represented by No. in the first column.

Example 5 In Examples 1 to 4, cyanuric fluoride was used instead of cyanuric chloride, and a corresponding bisazo compound was synthesized in the same manner.

Example 6 Each of the bisazo compounds 0.1 and 0.3 described in Examples 1 to 5
And 0.6 parts were dissolved in 200 parts of water, 10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 60 ° C., and 4 parts of sodium carbonate was added, followed by dyeing for 1 hour. Washing, soaping, washing and drying were performed to obtain a navy dyed product having excellent fastness properties and good build-up properties.

Example 7 Each of the bisazo compounds described in Examples 1 to 5 was used to prepare a color paste having the following composition.

Bisazo compound 5 parts Urine 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, and after intermediate drying, 100 After steaming at ℃ for 5 minutes, washing with water, soaping, washing with water and drying, a navy print having excellent fastnesses was obtained.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takeshi Sumi 3-1-98 Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (56) References JP-A-57-198757 (JP, A (58) Fields surveyed (Int. Cl. ⁶ , DB name) C09B 62/513 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] (1) When represented in the form of a free acid, the following general formula (I) [Wherein, Χ represents chlorine or fluorine, Z ₁ and Z ₂ independently represent —SO ₂ CH ＝ CH ₂ , or —SO ₂ CH ₂ CH ₂ Z ′, and Z ′ represents an alkali Represents a leaving group. A is
Represents a phenylene or naphthylene group which may be substituted; B is the following formula (In the formula, * is a bond connected to the azo group, R ₃ is hydrogen,
Represents a methyl group or a sulfo group. ). D represents a naphthylene group which may be substituted by a sulfo. R ₁ and R ₂ independently represent hydrogen or an optionally substituted alkyl group. _{１ 1} and Χ ₂
Represents an NH ₂ group and the other represents an OH group. A bisazo compound represented by the formula: 2. A compound represented by the following general formula (II): [Wherein, Z ₁ , Z ₂ , A, B, D, Χ, R ₁ and R ₂ have the meaning described in claim 1. The compound according to claim 1, which is represented by the formula: 3. The compound according to claim 1, wherein D is a naphthylene group having a sulfo group at the ortho position of the azo group. 4. The compound according to claim 1, wherein R ₁ and R ₂ are each independently hydrogen, methyl or ethyl. Wherein Z ₁ and Z _2, -SO ₂ CH = CH ₂ independently of one another
Or a compound according to any one of claims 1 to 4 is _{-SO 2 CH 2 CH 2 OSO 3} H. 6. A method for dyeing or printing a fiber material, comprising using the bisazo compound according to claim 1.