JPS6390571A - Water-soluble monoazo coloring matter and dyeing method using said coloring matter - Google Patents

Abstract

NEW MATERIAL:A compound in the form of a free acid expressed by formula I [R<1> is H or methyl; R<2> and R<4> are H or (substituted) lower alkyl; R<3> and R<5> are H, lower alkyl, lower alkoxy or halogen, provided that R<3> and R<4> are not H when R<2> is H or methyl; Y is -CH=CH2 or -CH2CH2OSO3H]. EXAMPLE:A compound expressed by formula II. USE:A dye, capable of dyeing cellulose and nitrogen-containing fibers to a bluish red color and suitable for dyeing by a dip dyeing or cold pad batch method. PREPARATION:For example, 1-hydroxy-3,6-disulfo-8-aminonaphthalene is successively condensed with cyanuric chloride and an aniline compound expressed by formula III in an aqueous medium to give a compound expressed by formula IV, which is then condensed with a compound expressed by formula V to synthesize a coupling component expressed by formula VI. On the other hand, a compound expressed by formula VII is diazotized and coupled with the compound expressed by formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a red water-soluble monoazo dye having a novel structure and a dyeing method using the same.

(Prior Art) Methods for dyeing cellulose or nitrogen-containing fibers using water-soluble reactive dyes have been practiced for a long time, and various reactive dyes have been proposed. For example, dyes with vinyl sulfone type reactive groups are known as typical dyes, but although this type of dye generally has a good reactive dyeing rate, it has poor chlorine fastness (chlorine fastness in tap water). Furthermore, in order to obtain a richly dyed object when dyeing with the dip dyeing method, it was necessary to use a large amount of electrolytes such as salt, 50 to 100 g per liter of dyeing bath. . The use of such a large amount of electrolyte also affects the treatment of dyeing wastewater, resulting in an increase in dyeing costs.

For example, the dye shown by the following structural formula listed in Example 4 of Japanese Patent Publication No. 39-18184 has a vinyl sulfone group bonded to the dye matrix via a triazine ring, so its chlorine fastness is considerably improved. However, the amount of electrolyte used during dyeing is required to be 50 g #1 or more.

On the other hand, the dye shown by the following structural formula listed in Example 1 of Japanese Patent Publication No. 46-824 can be dyed well even with a small amount of electrolyte of 20 to 30 g/l during dip dyeing, but it has poor durability. Chlorine fastness is extremely poor.

In view of the above circumstances, the present applicant has investigated reactive dyes that require only a small amount of electrolyte during dyeing and have excellent chlorine fastness, and have developed a dye represented by the structural formula below. I discovered this and filed an application first. (Unexamined Japanese Patent Publication No. 60-260654) (Problems to be Solved by the Invention) Although the dye having the above structure is comprehensively excellent, it is an object of the present invention to further provide peripheral compounds of this dye. be.

[Structure of the invention]

(Means for Solving the Problems) That is, the present invention provides the following general formula [wherein,
R1 represents a hydrogen atom or a methyl group, R2 and R
4 represents a hydrogen atom or a lower alkyl group which may have a substituent; R3 and R' represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, provided that R2 is a hydrogen atom or a methyl group; With respect to water-soluble monoazo dyes represented by (10) I=CH□ group or 1002C11,050,H group], where both R3 and R4 are not hydrogen atoms, Furthermore, it relates to a dyeing method characterized in that the water-soluble monoazo dye described above is used as one reactive dye when dyeing fibers containing cellulose or nitrogen-containing fibers by dip dyeing or cold pad patch method in the presence of an electrolyte.

Hereinafter, one aspect of the present invention will be explained in detail.

In the water-soluble monoazo dye represented by the general formula (1), the lower alkyl group which may have a substituent represented by R2 and R4 is usually a C1 to C4 linear or branched alkyl group. Substituted alkyl groups or e.g.
Examples include alkyl groups substituted with hydroxyl groups, cyano groups, halogen atoms, and alkoxy groups, such as 2-hydroxyethyl groups, 2-cyanoethyl groups, cyanomethyl groups, 2-chloroethyl groups, and 3-ethoxypropyl groups.

Further, the halogen atom represented by R3 and Rs usually includes a chlorine atom, a bromine atom, a fluorine atom,
On the other hand, examples of lower alkyl groups and lower alkoxy groups include methyl group, ethyl group, propyl group, methoxy group,
Examples include linear or branched alkyl groups having 1 to 4 carbon atoms, such as ethoxy groups, and alkoxy groups.

In addition, in the present invention, in the above general formula, when R2 is a hydrogen atom or a methyl group, both R3 and R4 are not hydrogen atoms.

The dye of the present invention exists in the form of a free acid or a salt thereof, and the salts are usually alkali metal salts and alkaline earth metal salts, with lithium salts, sodium salts, and potassium salts being particularly preferred.

The azo dye of the present invention represented by the general formula [I] can be produced by the following method. For example, 1-hydroxy-3,6-disulfo-8-aminonaphthalene is combined with cyanuric chloride and general formula (II) (wherein R2 and R
2 is the same as defined above) are sequentially condensed in an aqueous medium to form a compound represented by the following general formula (m) (wherein R2 and R3 are the same as defined above), and further to this compound. A compound represented by the following general formula (IV) (wherein R4, ns and Y are the same as defined above) is condensed in an aqueous medium, and the compound represented by the following general formula (V) (wherein R3-R5 and Y are the same as defined above) is condensed in an aqueous medium. Synthesize the coupling component shown in (same as the definition). On the other hand, the following general formula (
VI) (wherein R1 is the same as defined above) is diazotized by a conventional method, and this is coupled with the compound represented by (V) to form the front nail general formula (1).
) monoazo dyes can be produced. Although the usual salting-out method is used to obtain the desired product from the reaction solution, the reaction solution can also be spray-dried as it is.

The monoazo dye of the present invention can be widely used as a dye paper for dyeing fibers and cloth, a dye for coloring synthetic resins, a dye for inkjet printers, etc., but especially as a dye. It is suitable as a reactive dye for dyeing.

When using the monoazo dye of the present invention as a dye, target fibers include, for example, cotton, viscose rayon,
Examples include cellulose fibers such as cuproammonium rayon and hemp, and nitrogen-containing fibers such as polyamide, wool, and silk.6 Note that these wt fibers may also be mixed fibers such as polyester and triacetate.

In order to dye cellulose or nitrogen-containing fibers using the monoazo dye of the present invention, dyeing is usually carried out according to a conventional method in the presence of an acid binder consisting of an inorganic alkali such as bicarbonate of soda or sodium carbonate, or an organic base such as triethylamine. be able to. In the present invention, particularly when dyeing is performed by the dip dyeing method or the cold batch method, the excellent effect of reducing the amount of electrolytes such as mirabilite or common salt used can be exhibited, which is preferable. In this case, the amount of electrolyte used is usually 5 to 30 g per 1 liter of dyeing bath.In this way, in the present invention, a sufficiently rich dyed product can be obtained with about 115 to 10 L/10 of the normally used electrolytic IR amount. be able to. Further, the dyeing temperature is usually preferably about 40 to 80°C.

Furthermore, the monoazo dye of the present invention can be applied to other dyeing methods to which vinyl sulfone type reactive dyes can be applied, such as textile printing and pad steam methods.

(Examples) Hereinafter, the method of the present invention will be specifically explained by examples, but the present invention is not limited to the following examples.

Example 1 A dye bath prepared by dissolving 0.2 g of an azo dye represented by the following structural formula in the form of free a-acid in 200 mQ of water and adding and dissolving 2 g of Glauber's salt (the proportion of Glauber's salt used was 10 gin) was added to an unmercerized dye bath. 10g cotton stockinette
Then, 3.0g of soda carbonate was added and dyed at 50℃ for 1 hour.
Washing with water, soaping, washing with water, and drying were performed to obtain a bluish-red dyed product.

The degree of dyeing of this dye is very high despite the small amount of Glauber's salt used, and the dyed product obtained is extremely dense.
0 ppm) is very good at grade 5, and the light fastness (JIS
L-0842) was also extremely good at grade 5.

The monoazo dye used in this example was produced by the following method.

31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfone fi and 18.5 g of cyanuric chloride.
After condensation at 0°C or lower, 12.3 g of N-methyl-m-toluidine was condensed at 20°C to produce a compound of the following formula. On the other hand, 4-methyl-aniline-2-sulfone W1
18.7g was diazotized by a conventional method, and coupled with the above condensate to produce a compound of the following formula, and 3
-(β-hydroxyethyl)sulfonylaniline sulfate 28.1 was added and condensed at 90°C, followed by salting out with potassium chloride to produce the above azo dye.

Example 2 40 g of an azo dye represented by the following structural formula (% formula %) in the form after 'fi separation was dissolved in 9800 mM heat,
Cool to 25°C and add 20+n of 32.5% caustic soda.
U and 25 g of Glauber's salt were added, and water was further added to bring the total amount to 12 at 25°C. This bath (glauber's salt usage rate 25g, l
), squeeze it with a 70% pick-up, roll it up, seal it with polyethylene film, and store it at 25°C.
After being left in a room for 20 hours, the dyed product was washed first with cold water and then with hot water, then finished by soaping, washing with water, and drying.

The degree of dyeing with this dye was very high, and the cotton satin was uniformly dyed in a deep bluish red color. In addition, the chlorine fastness of the dyed fabric was very excellent at grade 5.

Note that the monoazo dye used in this example was manufactured according to Example 1.

Example 3 A cotton cloth was dyed using a monoazo dye represented by the following general formula (free acid) in a manner similar to Example 1, and the results are shown in Table 1.

(The following is a blank space) [Effects of the Invention] The monoazo dye of the present invention is a novel water-soluble monoazo dye having a vinyl sulfone type reactive group, and is useful as a red color dye.

In particular, when this dye is used as a reactive dye when dyeing cellulose or nitrogen-containing fibers by dip dyeing method or cold pad batch method, various fastnesses such as chlorine fastness are good, and It exhibits excellent reactive dyeing properties even with small amounts of electrolytes such as glauber's salt and common salt, and can produce richly dyed products. Therefore, the content of electrolyte and unreacted dye in dyeing wastewater is reduced, which is desirable from the viewpoint of wastewater treatment.

Claims (4)

[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 represents a hydrogen atom or a methyl group, and R
^2 and R^4 represent a hydrogen atom or a lower alkyl group that may have a substituent, and R^3 and R^5 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom (however, When R^2 is a hydrogen atom or a methyl group, both R^3 and R^4 are not hydrogen atoms), Y is -CH=CH_2 group or -C
H_2CH_2OSO_3H group] is a water-soluble monoazo dye. (2) When dyeing fibers containing cellulose or nitrogen-containing fibers by the dip dyeing method or the cold pad batch method in the presence of an electrolyte, the following general formula [I] ▲ is used as a reactive dye in the form of a free acid. There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, R^1 represents a hydrogen atom or a methyl group, and R
^2 and R^4 represent a hydrogen atom or a lower alkyl group that may have a substituent, and R^3 and R^5 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom (however, When R^2 is a hydrogen atom or a methyl group, both R^3 and R^4 are not hydrogen atoms), Y is -CH=CH_2 group or -C
A dyeing method characterized by using a water-soluble monoazo dye represented by H_2CH_2OSO_3H group. (3) The dyeing method according to claim 2, wherein the amount of electrolyte used is 5 to 30 g per liter of dyeing bath. (4) The dyeing method according to claim 2, wherein the dyeing temperature is 20 to 80°C.