JPS63101458A - Water-soluble monoazo compound and method of dyeing and printing fibrous material by using the same - Google Patents

Abstract

NEW MATERIAL:Water-soluble monoazo compds. of formula I [wherein R1, R2 and R3 are each H, a (substd.) lower alkyl; B1 and B2 are each (CH3, OCH3, C2H5, OC2H5, Cl, Br, SO3H or COOH-substd.) phenylene or (SO3H-substd.) naphthylene; Y1 and Y2 are each a group of formula II or III (wherein Z is a group capable of being re moved by an alkali); and m and n are each 0 or 1]. EXAMPLE:Compd. of formula IV. USE:Dyes which dye or print cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc., scarlet. PREPARATION:An aminonapthalenesulfonic acid of formula V (wherein R1 and n are as defined above) is bonded to cyanuric chloride. A diazonium compd. obtd. by diazotizing an anilinesulfonic acid of formula VI (wherein m is as defined above) is added to the condensate and a coupling reaction is carried out under neutral to alkaline conditions to obtain a monoazo compd. of formula VII (wherein m and n are as defined above). The monoazo compd. is condensed with an amine of formula VIII and then an amine of formula IX (wherein R1, R2, B1, R2, Y1 and Y2 are as defined above) to produce the compd. of formula I.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is directed to materials containing hydroxy groups and/or carbon oxide groups, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc., or blends thereof. This invention relates to a water-soluble monoazo compound useful for dyeing and printing pongee and its application.

<Prior art> Reactive dyes can be applied to various dyeing methods and have characteristics such as clear hues and good wet fastness of dyed products, so they are used for dyeing cellulose fibers and polyamide fibers, It has been widely used for textile printing. However, when using reactive dyes for the purpose of obtaining richly dyed products, conventional dyes do not have sufficient dyeing properties, resulting in a decrease in dyeing efficiency, resulting in problems such as dyeing costs and wastewater treatment. It is hoped that the level will improve further.

<Problems to be Solved by the Invention> The present inventors have worked diligently with the aim of finding a dye that is excellent in various dye properties such as fastness, level dyeing property, and water solubility, and has good dyeing properties. As a result of research, it was discovered that a specific metal material had the desired performance.

[Means for Solving the Problem] The present invention provides a free acid having the following general formula (I) R1 [wherein R, R, and R8 are each independently a hydrogen atom or an optionally substituted lower alkyl Indicates the group B, , B
2 is a phenylene group which may be independently substituted with a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a sulfonic acid or a carboxylic acid group, or a naphthylene group which may be substituted with a sulfonic acid group; shows.

Yo and Y are each independently -CH=CH1 or -C
It represents H, CH, and Z, where Z represents a group that is eliminated by the action of an alkali. m and n represent 0 or 1. ] Provided are a water-soluble monoazo compound represented by the following and a method for dyeing or printing a material containing a hydroxyl group or/and a carbonamide group using the water-soluble monoazo compound.

In general formula (1), when R1e Rg and R are lower alkyl groups which may be independently substituted, examples of such groups include those described in JP-A-59-122549.
The groups shown in the above publication are applicable, and methyl and ethyl groups are preferred. Further, it is more preferable that at least one of RItR is a hydrogen atom, and R1 is preferably a hydrogen atom or a methyl group.

The groups shown in are equivalent, among which B, , B! are preferably phenylene groups which may be independently substituted with a methyl group or a methoxy group.

Y1mataha Y! Ka, -CHICM, Z theal case (7)
Z J! , is a group that has the ability to be eliminated by the action of an alkali,
Examples include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, and a halogen atom.

Both Yl and Y2 are preferably β-sulfatoethyl, and some vinyl may be mixed therein.

Particularly preferable monoazo compounds in the general formula (I) are those represented by the following general formulas (11) and (Ill) in the form of free acids.
In the formula, R4 represents a hydrogen atom, a methyl group or an ethyl group.

] [In the formula, R represents a hydrogen atom, methyloxyζ or an ethyl group. ] It is a monoazo compound shown by.

These monoazo compounds are preferably salts of alkali metals or alkaline earth metals, particularly sodium or potassium salts.

The compound of the present invention can be produced, for example, as follows. General formula (IV) H [wherein R3 and n have the above-mentioned meanings. A [nonaphthalene sulfonic acid and cyanuric chloride] are firstly condensed, and this condensate is formed by the general formula (V) [where m has the above-mentioned meaning. ] By adding a diazonium compound obtained by diazotizing the aniline sulfonic acid represented by the above in a conventional manner and coupling in neutral or alkaline conditions, the general formula (Vl) [wherein m and n have the above-mentioned meanings] is obtained. ] was obtained, and the monoazo compound represented by the following general formula (Vl), (■) [wherein, R1, R,, B, , B, , Y, and Y
, has the above meaning. ] The compound represented by the general formula (1) can be obtained by condensing the amines represented by the formula (1) in any order in a secondary or tertiary manner.

The above starting compounds can be acids and/or salts, depending on the reaction conditions.
In particular they are used in the form of alkali metal or alkaline earth metal salts.

The monoazo compound produced according to the present invention can be made into a liquid product by removing inorganic salts and adding stabilizers or dyeability improvers as necessary, or the liquid product or reaction solution can be evaporated. , for example by spray-drying, as well as methods known in general.

It can also be made into a liquid or powdered product through salting out separation by adding an electrolyte.

The monoazo compounds according to the invention can be used as fiber-reactive dyes and can dye textile materials, for example materials containing hydroxy groups or carboxylic acid amide groups.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol. The cellulosic fiber material is preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose a-fibers are, for example, viscose stable and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,6
, polyamide-6, polyamide-11 and polyamide-
It is 4.

For dyeing, methods depending on the reactive group of the fiber-reactive dye can be applied.

For example, in the case of cellulosic fibers, dyeing is carried out using the dye according to the invention and an acid binder such as caustic soda, sodium carbonate, phosphate, silicate or sodium bicarbonate. The dyeing method can be selected depending on the properties and physical shape of the fiber.
For example, an exhaustion method, a textile printing method, a cold pad batch-up method, etc. can be employed.

In the case of exhaustion method, sodium carbonate, trisodium phosphate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as caustic soda. In the case of printing processes, salt or emulsified salts such as sodium alginate or starch ethers and salts such as sodium carbonate, sodium bicarbonate, caustic soda, sodium triphosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds are used. applied to the fiber together with an alkaline or alkali-releasing agent, optionally with the addition of customary printing aids or dispersants, such as urea, dried and subjected to heat treatment, especially in the presence of water vapor. It can be dyed by For cold-batch-up staining,
Caustic soda alone or sodium silicate as an acid binder,
It is padded onto the fibers using sodium carbonate or trisodium phosphate, optionally with the addition of Glauber's salt or salt, and optionally with the addition of a solubilizing agent or penetrating agent such as urea, at room temperature. It can be dyed by winding it up into a roll, leaving it for 8 hours or overnight, washing it with water, and drying it.

The compound of the present invention is characterized in that it exhibits excellent performance on fiber materials, and is particularly suitable for dyeing cellulose-based materials. It is notable for its high exhaustion rate, high fixation rate, and excellent build-up performance. Furthermore, it exhibits level dyeing properties and easy cleaning properties, and has the characteristics that dyeing properties are hardly affected even if there are slight variations in dyeing conditions such as temperature, bath ratio, salt concentration, etc. In addition, light resistance, sweat resistance,
It also has excellent fastness properties such as sweat resistance, acid hydrolysis resistance, washing resistance, and chlorine resistance.

Next, the present invention will be explained by examples.

In the text, parts represent parts by weight.

Example 1 7.4 parts of cyanuric chloride was dispersed in 50 parts of water, and 100 parts of a neutral aqueous solution of 9.8 parts of 6-a[no-1-hydroxynaphthalene-8-sulfonic acid] was added thereto. ~6°
C, stirring was continued at pH 2 to 4 until the raw material 6-amino-1-hydroxynaphthalene-8-sulfonic acid was no longer observed. A solution obtained by diazotizing 9.0 parts of p-anisidine-m-sulfonic acid by a known method was added to the solution of the first condensate obtained in this manner, and the pH was adjusted to 8-8.10-16°.
Coupling is performed at C. After completion of the reaction, N-ethylaniline-8-β-sulfate ethyl sulfo 213.
6 parts of 1-aminobenzene-8-β-sulfatoethyl sulfone were added and the mixture was heated to pH 4-6. Second condensation was carried out at 80-50°C.
The eighth condensation is carried out at . After the reaction was completed, potassium chloride was added for salting out, followed by excessive washing and drying to obtain 80 parts of a monoazo compound having the following structure in the form of a free acid.

Example 2 In the same manner as in Example 1, 6-amino-1-hydroxynaphthalene-8,5-disulfonic acid was used as the azo component to perform the first condensation with cyanuric chloride, and the other same amine components were used. By using this, a monoazo compound having the following structure was obtained in the form of a free acid.

Example 3 The following azo component A and diazo component B1 second condensed adenone component C
A monoazo compound consisting of the 1st and 8th condensed amine components was synthesized in the same manner as in Example 1.

These compounds include the azo component (the azo component that performs the first condensation with cyanuric chloride): Column A, the diazo component: Column B, the second condensed amine component: Column C, the eighth condensed amine component = Column D, and the synthesized Color tone of the monoazo compound on cellulose LA fiber: Characterized by column E.

Example 4 0.8 part of each compound obtained in Examples 1 to 8 was added to 200
of water, add 10 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60°C.

Then, after 20 minutes, 4 parts of carbonated soda are added.

Dye for 1 hour at that temperature. After dyeing, washing and soaping were performed to obtain a scarlet dyed product with excellent fastness.

Example 6 15 parts of each of the compounds obtained in Examples 1 to 8 was added to 60 parts of urea.
1 part in 200 parts of hot water. Add 40 parts of sodium alginate and 960 parts of water to the solution with stirring.
Add 0 parts and 20 parts of sodium bicarbonate. The mixture is then adjusted to 1000 parts with water and lake. This printing paste is used to print cotton fabrics.

After drying, it is steamed at 100-108°C six times, washed with cold water, then hot water, boiled and soaped, washed again and dry-smoked. In this way a dense scarlet print with very good fastnesses was obtained.

Claims (7)

[Claims] (1) In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2 and R_3 are independently hydrogen atoms or optionally substituted lower B indicates an alkyl group
_1 and B_2 may be independently substituted with a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a phenylene group that may be substituted with a sulfonic acid or a carboxylic acid group, or a sulfonic acid group Indicates a naphthylene group. Y_1 and Y_2 independently of each other -CH=C
It represents H_2 or -CH_2CH_2Z, where Z represents a group that is eliminated by the action of an alkali. m and n represent 0 or 1. ] A water-soluble monoazo compound represented by (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 which may be substituted with a methyl group or a methoxy group. (4) The monoazo compound according to any one of claims 1 to 3, wherein Y_1 and Y_2 are both β-sulfatoethyl groups. (5) In the form of free acid, the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R_4 represents a hydrogen atom, a methyl group, or an ethyl group. ] The monoazo compound according to claim 1, which is represented by: (6) In the form of free acid, the following general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [In the formula, R_5 represents a hydrogen atom, a methyl group, or an ethyl group. ] The monoazo compound according to claim 1, which is represented by: (7) In the form of flowing acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2 and R_3 are independently hydrogen atoms or optionally substituted lower alkyl Indicates the group B_1
, B_2 are independently substituted with a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a chlorine atom, a bromine atom, a phenylene group which may be substituted with a sulfonic acid or carboxylic acid group, or a sulfonic acid group. This indicates a good naphthylene group. Y_1 and Y_2 are independently -C
H=CH_2 or -CH_2CH_2Z, where Z represents a group that is eliminated by the action of an alkali. m and n are 0
Or represents 1. ] A method for dyeing or printing a material containing a hydroxyl group and/or a carbonamide group, characterized by using a water-soluble monoazo compound shown in the following.