JPH0826239B2 - Water-soluble monoazo compound and method for dyeing or printing fiber material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-soluble monoazo compound and a method for dyeing or printing a fiber material using the same.

BACKGROUND ART Reactive dyes can be applied with various dyeing methods,
It has been widely used as a dye for dyeing and printing cellulosic fibers and polyamide fibers because of its excellent features such as vivid hue and good wet fastness of dyed products.
However, when a reactive dye is used for the purpose of obtaining a dense dyed product, the conventional material does not have sufficient build-up properties, so that a phenomenon of a decrease in dyeing efficiency is often recognized, and dyeing cost, wastewater treatment, etc. From there is hoped for further improvement.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The inventors of the present invention have earnestly studied for the purpose of finding a dye having excellent build-up properties, which is excellent in various dye properties such as various fastnesses, leveling properties, and water solubility. As a result of the experiment, it was found that the specific compound had the desired performance.

The present invention provides the following general formula (I) in the form of a free acid. [In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an optionally substituted lower alkyl group, and B ₁ and B ₂ independently of each other represent a methyl group, a methoxy group, an ethyl group or ethoxy. A phenylene group which may be substituted with a group, a chlorine atom, a bromine atom, a sulfonic acid group or a carboxylic acid group, or a naphthylene group which may be substituted with a sulfonic acid group.
Y ₁ and Y ₂ each independently represent —CH═CH ₂ or —CH ₂ CH ₂ Z, where Z is a group capable of leaving by the action of an alkali. R ₄
Is a hydrogen atom, a methyl group or a sulfonic acid group, R ₅ is a methyl group, a carboxylic acid group or a C _1-4 alkoxycarbonyl group, and R ₆ is a hydroxyl group or an amino group. A represents an optionally substituted phenyl group or naphthyl group. ] The water-soluble monoazo compound shown by these and the method of dyeing or printing a fiber material using the same are provided.

As the optionally substituted lower alkyl group represented by R ₁ , R ₂ and R ₃ in the general formula (I), an alkyl group having 1 to 4 carbon atoms is preferable, A hydroxy group is a hydroxy group,
Cyano group, alkoxy group, halogen group, carboxy group,
A carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group and a sulfamoyl group are preferred.

Preferred R ₁ , R ₂ and R ₃ include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, 2- Hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, Cyanomethyl group, 2-cyanoethyl group, 3-
Cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3
-Methoxypropyl group, 3-ethoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2
-Bromoethyl group, 3-chloropropyl group, 3-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 3
-Carboxypropyl group, 4-carboxybutyl group, 1,
2-dicarboxyethyl group, carbamoylmethyl group, 2
-Carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group,
3-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group,
4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-
Methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 3-methylcarbonyloxypropyl group, 3-ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2 -Sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 3
Examples thereof include -sulfamoylpropyl group and 4-sulfamoylbutyl group.

Among them, particularly preferable R ₁ , R ₂ and R ₃ include a hydrogen atom, a methyl group or an ethyl group.

Further, at least one of R ₁ and R ₂ is more preferably a hydrogen atom, and R ₃ is more preferably a hydrogen atom or a methyl group.

In the general formula (I), they may be independently substituted by a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a sulfonic acid group or a carboxylic acid group represented by B ₁ and B _2. Examples of the phenylene group include (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. ) And so on.

Further, examples of the naphthylene group represented by B ₁ and B ₂ which may be independently substituted with a sulfonic acid group include, for example, (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. ) And the like.

Among them, it is preferable that B ₁ and B ₂ are each independently a phenylene group which may be substituted with a methyl group or a methoxy group.

When Y ₁ or Y ₂ is —CH ₂ CH ₂ Z, Z is a group capable of leaving by the action of an alkali, for example, a sulfate ester group,
Examples thereof include a thiosulfate group, a phosphate group and a halogen atom. Preferable Y ₁ and Y ₂ are both cases of β-sulfatoethyl, in which vinyl may be partially mixed.

In formula (I), the optionally substituted phenyl group represented by A is preferably methyl group, ethyl group, methoxy group, ethoxy group, halogen, acetylamino group, propionylamino group, nitro group, sulfone. The phenyl group which is substituted with 1, 2 or 3 substituents selected from the group of acid group and carboxy group, and the optionally substituted naphthyl group represented by A is
A naphthyl group substituted with 1, 2 or 3 sulfonic acid groups.

Particularly preferred compounds in the above general formula (I) are represented by the following general formula (II) in the form of a free acid. [In the formula, R ₇ and R ₈ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ₉ and R ₁₀ independently represent a hydrogen atom, a methyl group, a methoxy group or a sulfonic acid group. m
Represents 0, 1 or 2. R ₅ and R ₆ have the meanings given above. ] It is a monoazo compound shown by these.

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

The compound of the present invention can be produced, for example, as follows.

Aromatic amine represented by the following general formula (III) A-NH ₂ (III) (wherein A has the above-mentioned meaning) is diazotized to give the following general formula (IV): (In the formula, R ₃ , R ₄ , R ₅ , and R ₆ have the above-mentioned meanings.) By coupling with a pyrazolone derivative represented by the formula from weakly acidic to weakly alkaline, the following general formula (V) (In the formula, A, R ₃ , R ₄ , R ₅ and R ₆ have the above-mentioned meanings) to obtain a monoazo compound.

Then, a compound represented by the general formula (V) and the following general formula (VI) (In the formula, R ₁ , B ₁ and Y ₁ have the above-mentioned meanings.) The compound represented by the formula ( ₁ ) is adjusted in any order in an aqueous medium to pH 2 to pH 9 at a temperature of -10 ° C to 40 ° C. However, while secondarily adjusting the pH to 2 to 9 at a temperature of 20 ° C to 70 ° C, it is condensed with cyanuric chloride or cyanuric fluoride, and further the following general formula (VII) (In the formula, R ₂ , B ₂ and Y ₂ have the above-mentioned meanings.) At a temperature of 40 ° C. to 90 ° C. and a pH of 2 to p.
The compound of the general formula (I) or a salt thereof can be obtained by condensation while adjusting to H9.

Alternatively, the compound represented by the general formula (IV) and cyanuric chloride are added in an aqueous medium at a temperature of -10 ° C to 40 ° C at pH 2 to pH 9
After condensing while adjusting to, a weakly acidic to weakly alkaline coupling with the diazonium salt of the aromatic amine represented by the general formula (III), then the compound represented by the general formula (VI) and the general formula (VII ) In any order, primarily at a temperature of 20 ° C to 70 ° C and a pH of 2 to p
Secondly, while adjusting to H9, pH at a temperature of 40 ° C to 90 ° C
The compound of the general formula (I) or a salt thereof can also be obtained by condensation while adjusting the pH to 2 to pH 9.

Examples of the aromatic amine represented by the general formula (III) include 2-aminobenzenecell sulfonic acid 2-amino-5-methylbenzenesulfonic acid 2-amino-5-ethylbenzenesulfonic acid 2-amino-5-methoxybenzenesulfone. Acid 2-Amino-5-ethoxybenzenesulfonic acid 2-Amino-5-chlorobenzenesulfonic acid 2-Amino-5-bromobenzenesulfonic acid 2-Amino-5-acetylaminobenzenesulfonic acid 2-Amino-5-propionylamino Benzenesulfonic acid 2-Amino-5-nitrobenzenesulfonic acid 2-Amino-4-chloro-5-methylbenzenesulfonic acid 2-Amino-5-chloro-4-methylbenzenesulfonic acid 2-Amino-4-methoxybenzenesulfonic acid 2-amino-4-ethoxybenzenesulfonic acid 3 Amino-4-methylbenzenesulfonic acid 3-Amino-4-ethylbenzenesulfonic acid 3-Amino-4-methoxybenzenesulfonic acid 3-Amino-4-ethoxybenzenesulfonic acid 3-Amino-4-chlorobenzenesulfonic acid 3-Amino- 4-Bromobenzenesulfonic acid 4-amino-8-methylbenzenesulfonic acid 4-amino-3-ethylbenzenesulfonic acid 4-amino-3-methoxybenzenesulfonic acid 4-amino-3-ethoxybenzenesulfonic acid 4-amino-3 -Chlorobenzenesulfonic acid 4-Amino-3-nitrobenzenesulfonic acid 2-Aminobenzene-1,4-disulfonic acid 2-Aminobenzene-1,5-disulfonic acid 2-Aminobenzoic acid 2-Amino-4-methoxybenzoic acid 2 -Amino-5-methoxybenzoic acid 2-amino-4- Acetylaminobenzoic acid 2-amino-5-acetylaminobenzoic acid 2-amino-4-sulfobenzoic acid 2-amino-5-sulfobenzoic acid 4-amino-2,5-dimethylbenzenesulfonic acid 4-amino-2, 5-Diethylbenzenesulfonic acid 4-amino-2,5-dimethoxybenzenesulfonic acid 4-amino-2,5-diethoxybenzenesulfonic acid 4-amino-2,5-dichlorobenzenesulfonic acid 4-amino-2,5- Dibromobenzenesulfonic acid 4-amino-2-methyl-5-methoxybenzenesulfonic acid 4-amino-2-methyl-5-ethoxybenzenesulfonic acid 2-amino-5-methylbenzene 1,4-disulfonic acid 2-amino- 5-ethylbenzene-1,4-disulfonic acid 2-amino-5-methoxybenzene-1,4-disulfonic acid 2-amino-5-ethoxyben 1,4-disulfonic acid 2-amino-5-acetylaminobenzene-1,4-disulfonic acid 2-amino-5-propionylaminobenzene 1,4-disulfonic acid 2-aminonaphthalene-1-sulfonic acid 2- Aminonaphthalene-1,5-disulfonic acid 2-Aminonaphthalene-1,7-disulfonic acid 2-Aminonaphthalene-1,5,7-trisulfonic acid 2-Aminonaphthalene-3,6-disulfonic acid 2-Aminonaphthalene- 3,8-disulfonic acid 2-aminonaphthalene-3,6,8-trisulfonic acid 2-aminonaphthalene-4,8-disulfonic acid 2-aminonaphthalene-6,8-disulfonic acid 2-aminonaphthalene-4,6 , 8-trisulfonic acid and the like can be mentioned.

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

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or regenerated products thereof and polyvinyl alcohol. Cellulose fiber materials are cotton, and other vegetable fibers such as linen,
Hemp, jute and mirror fibers are preferred. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

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

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material by a method depending on physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, sodium carbonate, sodium phosphate tribasic, in the presence of an acid binder such as caustic soda, optionally a neutral salt, such as sodium sulfate or salt,
If desired, a solubilizing agent, a penetrating agent, or a leveling agent is used in combination, and the reaction is carried out at a relatively low temperature. 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 at room temperature or elevated temperature and drying, it can be fixed by steaming or dry heat.

When printing on cellulose fibers, in one phase, for example with a printing paste containing baking soda or other acid binder, then by steaming at 100-160 ℃, or in two phases, for example medium It can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment.

In the printing paste, a sizing or emulsifying agent such as sodium alginate or starch ether is optionally used,
For example, it is used in combination with a usual printing aid and / or a dispersant such as urea.

Suitable acid binders for fixing the compounds according to 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 on heating. In particular, alkali metal hydroxides and alkali metal salts of weak or medium-strength inorganic or organic acids are mentioned, of which soda salts and potassium salts are particularly preferable. Examples of such an acid binder include caustic soda, caustic potash, baking soda, sodium carbonate, sodium formate, potassium carbonate, sodium dibasic or tribasic phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic and natural polyamide and polyurethane fibers should be carried out by first exhausting from an acidic or weakly acidic dyeing bath under the control of a pH value, and then changing it to a neutral, and possibly alkaline, pH value for fixing. Can be done by Dyeing is usually carried out at a temperature of 60 to 120 ° C., but in order to achieve level dyeing, a common leveling agent such as a condensation product of cyanuric chloride and 3 times moles 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. Especially suitable for dyeing cellulosic fiber materials, good light resistance and sweat sunshine resistance, excellent wet resistance, such as washing resistance, peroxide washing resistance, sweat resistance, participation water decomposition resistance and alkali resistance. , With even better rub resistance and iron resistance. In addition, it has excellent build-up properties, level dyeing and waste-off properties, good solubility and high exhaustion / fixing properties, and dyes of stable quality that are not easily affected by changes in dyeing temperature and dyebath ratio. It is characterized in that it can be obtained.

The present invention is described in detail below with reference to examples. In the examples, parts and% represent parts by weight and% by weight, respectively.

Example 1 To a liquid prepared by dispersing 9.2 parts of cyanuric chloride in 100 parts of water at 0 to 10 ° C, 7.6 parts of 1- (4'-aminophenyl) -8-methylpyrazolone-5 was added and condensed, and then 2- A coupling was carried out by adding 15 parts of a diazonium salt of aminonaphthalene-1,5-disulfonic acid.

Further, 16.5 parts of 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone and 14.1 parts of 1-aminobenzene-8-β-sulfatoethylsulfone were successively condensed by a conventional method and then salted out. , In the form of free acid A monoazo compound represented by

Example 2 15 parts of 2-aminonaphthalene-1,5-disulfonic acid were diazotized by a conventional method and coupled with 11.6 parts of 1- (2'-sulfo-4'-aminophenyl) -31-methylpyrazolone-5. It was Next, 9.2 parts of cyanuric chloride and 14.1 of 1-aminobenzene-4-β-sulfatoethyl sulfone
Parts were sequentially condensed by a conventional method. Further, 14.1 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone is condensed at 70 to 80 ° C. under weak acidity and salted out to give the following formula in the form of free acid. A monoazo compound represented by

Examples 3 to 36 Instead of 2-aminonaphthalene-1,5-disulfonic acid of Example 1, the compound (III) shown in the second column of the following table was replaced with 1- (4 '
-Aminophenyl) -3-methylpyrazolone-5 in place of compound (IV) in column 3 and 1-N-ethylaminobenzene-4-β-sulfatoethylsulfone in place of compound in column 4 (VI) with 1-aminobenzene-3
Compound (VII) in the fifth column was used in place of -β-sulfatoethylsulfone, and synthesis was carried out in the same manner as in Example 1 to obtain 3-36 monoazo compounds. It showed a color on the cellulose fibers.

Example 37 Monoazo Compounds 0.1, 0.3 and 0.6 as Described in Example 1
Each part is dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton are added, the temperature is raised to 60 ° C., 4 parts of sodium carbonate is added, and dyeing is carried out for 1 hour. After washing with water, soaping, washing with water and drying, a bright yellow dyeing product having various fastnesses, especially fastness to sunlight and sweat, and having very good build-up properties and good discharge properties was obtained.

This compound also has excellent solubility and has good levelness and dyeing reproducibility.

Example 38 0.3 parts of each of the monoazo compounds described in Examples 2-36
Dissolve in 00 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton
Raise the temperature to 50 ° C. Then, after 30 minutes, 4 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a yellow dyed product having various fastnesses, especially fastness to sunlight and sweat.

Example 39 Color paste composition Monoazo compound described in Example 1 5 parts Urea 5 parts Sodium alkylate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition is mercerized synthetic cotton After printing on broad, after intermediate drying, steaming at 100 ℃ for 5 minutes, wash with hot water, soaping, hot water, and dry to finish.

In this way, a clear yellow print having excellent various fastnesses was obtained.

Claims (6)

[Claims] 1. The following general formula (I) in the form of a free acid. [In the formula, R ₁ , R ₂ and R ₃ independently represent a hydrogen atom or an optionally substituted lower alkyl group, and B ₁ and B ₂ independently of each other represent a methyl group, a methoxy group, an ethyl group or ethoxy. A phenylene group optionally substituted with a group, a chlorine atom, a bromine atom, a sulfonic acid group or a carboxylic acid group, or a naphthylene group optionally substituted with a sulfonic acid group. Y ₁ and Y ₂ each independently represent —CH═CH ₂ or —CH ₂ CH ₂ Z, where Z is a group capable of leaving by the action of an alkali.
R ₄ represents a hydrogen atom, a methyl group or a sulfonic acid group, R ₅ represents a methyl group, a carboxylic acid group or a C _1-4 alkoxycarbonyl group, and R ₆ represents a hydroxyl group or an amino group. A represents an optionally substituted phenyl group or naphthyl group. ] The water-soluble monoazo compound shown by these. 2. The monoazo compound according to claim ₁ , wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a methyl group or an ethyl group. 3. The monoazo compound according to claim 1 or 2, wherein B ₁ and B ₂ are each independently a phenylene group optionally substituted with a methyl group or a methoxy group. 4. The monoazo compound according to claim 1, 2, or 3, wherein Y ₁ and Y ₂ are simultaneously β-sulfatoethyl group. 5. The following general formula (II) in the form of a free acid. [In the formula, R ₇ and R ₈ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ₉ and R ₁₀ independently represent a hydrogen atom, a methyl group, a methoxy group or a sulfonic acid group. m
Represents 0, 1 or 2. R ₅ and R ₆ have the meanings given in claim 1. ] The monoazo compound of Claim 1 shown by these. 6. The following general formula (I) in the form of a free acid. [In the formula, R ₁ , R ₂ and R ₃ independently represent a hydrogen atom or an optionally substituted lower alkyl group, and B ₁ and B ₂ independently of each other represent a methyl group, a methoxy group, an ethyl group or ethoxy. A phenylene group optionally substituted with a group, a chlorine atom, a bromine atom, a sulfonic acid group or a carboxylic acid group, or a naphthylene group optionally substituted with a sulfonic acid group. Y ₁ and Y ₂ each independently represent —CH═CH ₂ or —CH ₂ CH ₂ Z, where Z is a group capable of leaving by the action of an alkali.
R ₄ represents a hydrogen atom, a methyl group or a sulfonic acid group, R ₅ represents a methyl group, a carboxylic acid group or a C _1-4 alkoxycarbonyl group, and R ₆ represents a hydroxyl group or an amino group. A represents an optionally substituted phenyl group or naphthyl group. ] The dyeing or printing method of the textile material characterized by using the water-soluble monoazo compound shown by these.