KR100821899B1 - A diazo type dyes and a method of manufacturing the same and fiber dyed thereby - Google Patents

Abstract

The present invention relates to azo dyes having a structure represented by the following Chemical Formula 1, in which a dye intermediate having an azo group is bound to a diazotization-coupling reaction with a metal pyrithione antibacterial agent having excellent antimicrobial properties, a method for preparing the same, and a fiber dyed therewith. .

(Formula 1)

(In Formula 1, M is Cu or Zn, and A is a chromophore having an azo group.)

The azo dye of the present invention can impart sufficient antimicrobial properties to the textile product only by the dyeing process, and thus does not require an additional step for providing antimicrobial properties, and the color of the textile product is not discolored due to decomposition of the dye, and the antimicrobial properties are maintained for a long time.

Antibacterial, Dye, Metal Pyrithione, Azo, Dye Intermediates, Diazo-Coupling

Description

Azo dyes, methods of making and fibers dyed therein {A diazo type dyes and a method of manufacturing the same and fiber dyed hence}

The present invention is a strong antimicrobial reactor, azo dyes prepared by combining a metal pyrithione (Metal Pyrichion) -based antimicrobial agent to the intermediate of the dye having a diazo group, and a preparation method thereof, and dyed with the azo dyes and various colors and antimicrobial It is about a fiber having at the same time.

In general, textile products used in clothing and bedding, etc. must go through a dyeing process for coloring the textile material in the desired color according to the consumer's various tastes.

However, various fiber products manufactured as described above are inhabited by microorganisms due to poor storage, or by contact with the human body as a nutrient source of the secretions of the human body, the microorganisms inhabit and multiply, threatening the health of the human body, or causing odors in the products, Discoloration and withdrawal may occur, which may be a major factor in degrading product quality, such as durability and color fastness.

For this reason, textile products may be a carrier or a habitat for pathogen invasion. If they are given antimicrobial properties, they can prevent the growth and proliferation of microorganisms, preventing infectious diseases, preventing odors, and preventing fiber contamination and embrittlement. Functional fiber products will be obtained.

Usually, antibacterial and deodorant processing methods are largely divided into post-treatment processing methods and yarn improvement methods. In the post-treatment processing method, the dye component is extracted from natural substances such as tricotweed, which has antimicrobial properties, to give antimicrobial properties (Korean Patent Publication No. 2000-007593), and antimicrobial components such as organometallic compounds and organic substances are crosslinked with fibers. Heat-fixing method on the fiber surface with reactive resin, and adsorption-fixing method of antimicrobial material on the fiber surface. In the yarn improvement method, a method of mixing and spinning an inorganic antimicrobial agent between polymers in a manufacturing step of synthetic fiber and containing the inside of the fiber, a method of dispersing the copper compound in the fiber during coagulation and regeneration of the regenerated fiber, and There is a method of synthesizing a polymer by making an organic copolymer component having antibacterial properties.

On the other hand, antibacterial and deodorant processing is not for the purpose of sterilization or treatment, but is a process for suppressing the growth and growth of bacteria and fungi on the fiber. shall. In this sense, organometallic compounds such as organometallic mercury compounds, organotin compounds, organocopper compounds, and organozinc compounds used in the post-treatment process have very good bactericidal properties. Is used in Japan, the United States, etc., most of which are not used in textile processing for garments, but are used in some areas such as carpets, wallpaper, etc. that do not come into contact with the human body. Moreover, these organometallic compounds have problems in adhesion to fibers and durability of laundry, and thus have a limit in enduring antimicrobial properties.

In addition, general organic antimicrobial materials are easier to process than inorganic ones, and have been widely used until now because they do not affect mechanical properties, transparency, color, etc., but as mentioned above, the antimicrobial effect is not sustained and in particular, heat resistance. Use is limited in that it is inferior. In addition, some organic antimicrobial substances cause problems such as skin irritation and tearing. In addition, dyes extracted from natural materials have the advantage of imparting antimicrobial properties from the dyeing stage, but due to seasonal limitations, the extraction of dyes is limited and the disadvantages of using the mordant salt method using another heavy metal to improve the fastness, which is a disadvantage of natural dyes. have.

Inorganic antimicrobial material is a substitute for inorganic ions such as zeolite, silica, alumina, etc. and metal ions with excellent antimicrobial properties such as silver, copper and zinc, and has a three-dimensional skeletal structure with fine pores. great. On the other hand, metals such as silver and copper and zinc are one of the few metals with strong antibacterial activity and high safety, and have been found to be harmless to the human body. Inorganic type has high heat resistance compared to conventional organic type antimicrobial material and has high stability such as not causing volatilization and decomposition. Therefore, it can be applied to a wide range of applications.The antimicrobial effect of inorganic type antimicrobial material is expressed by active oxygen ions. It has an outstanding advantage that you cannot see. However, metal ions such as silver, copper and zinc may deteriorate the resin or cause yellowing, which may significantly lower commodity value. In addition, the inorganic antimicrobial material is generally more than a few microns in average particle size and wide range of particle size distribution may be the cause of trimming when mixed with fine fibers.

Meanwhile, Korean Patent Laid-Open Publication No. 2002-0057322 proposes a method of synthesizing a red reactive antimicrobial dye and an antibacterial deodorization process using the antimicrobial dye, but the reactive antimicrobial dye may be applied only to cotton due to the nature of the dye structure. There was a problem that could not be applied to living fibers such as furniture and carpets.

The present invention has been proposed to solve the problems of conventional antimicrobial materials, and an object of the present invention is to provide azo dyes including a strong antimicrobial group and a method for producing the same.

Specifically, the present invention provides a method for preparing an azo dye by introducing a metal pyrithione-based antimicrobial agent having excellent antimicrobial activity into a disperse dye matrix used for fibers.

In addition, it gives the antibacterial processing to the textile products from the dyeing process, and does not require any additional process for the purpose of antibacterial, and the dye is decomposed, so that the color of the knitted fabric is not discolored, and the antibacterial property is long lasting. Another object is to provide antimicrobial fibers.

Hereinafter, the present invention will be described in detail.

In the azo dye of the present invention, a dye intermediate (chromophore) having an azo group is bonded to the metal pyrithione type antimicrobial agent of the following general formula (3) by a diazotization-coupling reaction to have a structure of the following Chemical Formula 1.

(Formula 1)

(In Formula 1, M is Cu or Zn, and A is a chromophore having an azo group.)

(Formula 3)

(In Formula 3, M is Cu or Zn.)

The present invention is a dye intermediate (chromophore) having an azo group in a metal pyrithione (Metal Pyrichion) -based antibacterial agent of the general formula (3) which has excellent antimicrobial properties and can be applied as a dye having a low molecular weight, and is combined with a diazotization-coupling reaction. It is characterized by.

The chromophore having an azo group in the formula (1) has the structure of the following general formula (6) or (7).

(Formula 6)

(Formula 7)

The azo dye of the general formula (1) is a diazotization reaction of (i) P-nitro aniline of the general formula (1) or 2-amino-4-nitrophenol of the general formula (2) with hydrochloric acid and sodium nitrite, (ii) It is prepared by the azo-coupling reaction with the metal pyrithione-based antimicrobial agent of Formula 3 above.

(Formula 1)

(Formula 2)

Specific examples of the metal pyrithione-based antimicrobial agent of Formula 3 include zinc pyrithione (Zimc Pyrichion) of formula 4 and copper pyrithione (Copper Pyrichion) of formula 5.

(Formula 4)

(Formula 5)

More specifically, after the diazotization reaction of P-nitroaniline (P-nitroaniline) of Formula 1 with hydrochloric acid and sodium nitrite, it is azo-coupling with copper pyrithione (Copper Pyrichion) of Formula 5 When reacted, an azo dye of the following Chemical Formula 2 is prepared.

(Formula 2)

In addition, after the diazotization reaction of 2-amino-4-nitrophenol (2-amino-4-nitrophenol) of the general formula (2) with hydrochloric acid and sodium nitrite, it is copper pyrithione and the azo-couple of the general formula (5) Ring reaction yields an azo dye of formula (3).

(Formula 3)

In addition, after the diazotization reaction of the P-nitro aniline of the general formula (1) with hydrochloric acid and sodium nitrite, and then azo-coupling the zinc pyrithione of the general formula (4) to prepare an azo dye of formula (4) do.

(Formula 4)

In addition, after the diazotization reaction of 2-amino-4-nitrophenol of the general formula (2) with hydrochloric acid and sodium nitrite, the azo-coupling reaction with zinc pyrithione of the general formula (4) Dyes are prepared.

(Formula 5)

Hereinafter, the present invention will be described in detail through examples.

Example  One

0.01 moles of p-nitroaniline (p-nitroaniline) of Formula 1 are dispersed in distilled water of 5 ° C. or less, and then a small amount of hydrochloric acid is added to dissolve and stirred. Next, 0.01 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction according to the following reaction formula.

In a separate container, 0.01 mol of copper pyrithione (Copper Pyrichion) of Formula 5 is dissolved in distilled water with a small amount of hydrochloric acid, and the temperature is kept below 5 ° C. The diazotization liquid prepared above is gradually added to this solution, and a coupling reaction is advanced. After the reaction was completed, the pH was adjusted to 7, filtered with a filter paper, and dried to prepare an azo-based yellow dye of Chemical Formula 2.

Example  2

0.01 mol of 2-amino-4-nitrophenol (2) is dispersed in distilled water of 5 ° C. or less, and then a small amount of hydrochloric acid is added to dissolve and stirred. Next, 0.01 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction according to the following reaction formula.

In a separate vessel, 0.01 mol of copper pyrithione (Copper Pyrichion) of Formula 5 is dissolved in distilled water together with a small amount of hydrochloric acid, and the temperature is maintained at 5 ° C or lower. The diazotization liquid prepared above is gradually added to this solution, and a coupling reaction is advanced. After the reaction was completed, the pH was adjusted to 7, filtered with a filter paper, and dried to prepare an azo-based yellow dye of Chemical Formula 3.

Example  3

0.01 mole of P-nitroaniline (p-nitroaniline) of Formula 1 is dispersed in distilled water of 5 ° C. or less, and then a small amount of hydrochloric acid is added to dissolve while stirring. Next, 0.01 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction according to the following reaction formula.

In a separate container, 0.01 mol of zinc pyrithione (Zinc Pyrichion) of Formula 4 is dissolved in distilled water together with a small amount of HCl, and the temperature is kept below 5 ° C. The diazotization liquid prepared above is gradually added to this solution, and a coupling reaction is advanced. After the reaction was completed, the pH was adjusted to 7, filtered with a filter paper, and dried to prepare an azo-based yellow dye of Chemical Formula 4.

Example  4

0.01 mol of 2-amino-4-nitrophenol (2) is dispersed in distilled water of 5 ° C. or less, and then a small amount of hydrochloric acid is added to dissolve and stirred. Next, 0.01 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction according to the following reaction formula.

In a separate vessel, 0.01 mol of zinc pyrithione (Zinc Pyrichion) of Formula 4 is dissolved in distilled water together with a small amount of hydrochloric acid, and the temperature is kept below 5 ° C. The diazotization liquid prepared above is gradually added to this solution, and a coupling reaction is advanced. After the reaction was completed, the pH was adjusted to 7, filtered with a filter paper and dried to prepare an azo-based yellow dye of Chemical Formula 5.

Antimicrobial Test

After adding glacial acetic acid and a dispersant to a 1.0% aqueous solution of the azo dyes obtained in Examples 1 to 4 to make a salt solution, immersed polyester fabric therein, proceeding dyeing at 130 ℃ 60 minutes, dyed through soaping and drying A fabric was obtained. The results of the antimicrobial test on the dyed fabric are shown in [Table 1].

division Bacteriostatic reduction (%) Strain I Strain II Azo dyes of formula 2 prepared in Example 1  99.5  98.7 Azo dyes of formula 3 prepared in Example 2  99.6  99.8 Azo dyes of formula 4 prepared in Example 3  99.9  98.1 Azo dyes of formula 5 prepared in Example 4  99.9  99.9

Antimicrobial Test Conditions

● Test Method: KSK 0693-200

Test species: 1) Strain I: Staphylococcus aureus ATCC 6538

                2) Strain Ⅱ: klebsiella pneumoniae ATCC 4352

● Concentration of inoculated bacteria: 1) Strain I-1.3 × 10 ⁵ / ml

2) Strain Ⅱ-1.5 × 10 ⁵ pcs / ml

The azo dye of the present invention can impart sufficient antimicrobial properties to the textile product only by the dyeing process, and thus does not require an additional step for providing antimicrobial properties, and the color of the textile product is not discolored due to decomposition of the dye, and the antimicrobial properties are maintained for a long time.

Claims (5)

Azo dyes having the structure of Formula 1 Formula 1

[In Formula 1, M is Cu or Zn, and A is a chromophore having an azo group.] The azo dye according to claim 1, wherein the chromophore having an azo group has a structure represented by the following general formula (6) or (7). (Formula 6)

(Formula 7)

P-nitroanirin of formula 1 or 2-amino-4-nitrophenol of formula 2 is subjected to diazotization reaction with hydrochloric acid and sodium nitrite, and the metal pyrithione type antimicrobial agent of formula 3 and azo-couple Method for producing azo dye having a structure of formula 1 characterized in that ring reaction (Formula 1)

(Formula 2)

(Formula 3)

[In Formula 3, M is Cu or Zn.] (Formula 1)

[In Formula 1, M is Cu or Zn, and A is a chromophore having an azo group.] The method of claim 3, wherein the chromophore having an azo group has a structure represented by the following general formula (6) or (7). (Formula 6)

(Formula 7)

Textile Dyed with the Azo Dye of Paragraph 1