KR20070023909A - Dyes and a method of manufacturing the same and fiber dyed thereby - Google Patents

Abstract

Provided is a dye for fibrous products, which imparts antibacterial and anti-mould effects to fibrous products, causes no discoloration of the fibrous products, and maintains antibacterial and anti-mould effects for a long period of time. The dye has a structure represented by the following formula(1) or (2). In formulae(1) and (2), A represents an azo group-containing chromophore. The dye is obtained by the method comprising the steps of: carrying out diazotization of p-nitroaniline or 2-amino-4-nitrophenol with hydrochloric acid and sodium nitrite; and carrying out azo-coupling between the diazotizated product and 2-pyridinethiol-1-oxide sodium salt.

Description

Dyes and a method of manufacturing the same and fiber dyed {Dyes and a method of manufacturing the same and fiber dyed hence}

The present invention relates to a dye prepared by combining a chromophore having a diazo group with a sodium pyrithione-based antibacterial anti-inflammatory agent having excellent antibacterial and antifungal properties, and a method of manufacturing the same, and a dye dyed with the dye to have a superior antimicrobial and antifungal property. It is about.

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 vehicle or habitat for invading pathogens. If antimicrobial and anti-inflammatory properties are given to textile products, they can prevent the growth and proliferation of microorganisms, preventing infectious diseases, preventing odors, and preventing fiber contamination and embrittlement. It will be possible to obtain functional fiber products.

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 limitations in having permanent antimicrobial properties due to problems with adhesion to fibers and durability of washing.

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, zinc and the like may degrade the resin or cause yellowing, thereby significantly lowering the 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 cause the 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 the conventional antimicrobial material, and an object of the present invention is to provide a dye including a strong antimicrobial anti-vibration group and a method for producing the same.

Specifically, the present invention is a method for preparing a dye by introducing 2-pyridinethiol-1-oxide sodium salt having excellent antimicrobial and antifungal properties to the disperse dye matrix used in the fiber To provide.

In addition, the present invention does not require an additional process for the purpose of antibacterial and antibacterial by giving antimicrobial and anti-binding properties to the textile product at the time of dyeing, the dye is decomposed and the color of the knitted fabric is not discolored, It is another object to provide a sustained antibacterial-antitussive fiber.

Hereinafter, the present invention will be described in detail.

In the dye of the present invention, a chromophore having an azo group in 2-pyridinethiol-1-oxide sodium salt of the following general formula (3) is bonded by a diazotization-coupling reaction to have a structure represented by the following Chemical Formula 1 or Chemical Formula 2.

(Formula 1)

(In Formula 1, A is a chromophore having an azo group.)

(Formula 2)

(In Formula 2, A is a chromophore having an azo group.)

(Formula 3)

In the present invention, a chromophore having an azo group in 2-pyridinethiol-1-oxide sodium salt of Formula 3, which has excellent antimicrobial and antifungal properties and has a low molecular weight, can be applied as a dye. It features.

The chromophore having an azo group in the formula (1) has the structure of the following general formula (4) or (5).

(Formula 4)

(Formula 5)

The dye of Formula 1 or Formula 2 is (i) a diazotization reaction of P-nitroaniline of Formula 1 or 2-amino-4-nitrophenol of Formula 2 with hydrochloric acid and sodium nitrite, (ii) It is prepared by the azo-coupling reaction with 2-pyridinethiol-1-oxide sodium salt of the general formula (3).

(Formula 1)

(Formula 2)

More specifically, after the diazotization reaction of P-nitroaniline (P-nitroaniline) of Formula 1 with hydrochloric acid and sodium nitrite, it is 2-pyridinethiol-1-oxide sodium salt and azo- of Formula 3 The coupling reaction produces a dye of formula 3 or 4 below.

(Formula 3)

(Formula 4)

In addition, after the diazotization reaction of 2-amino-4-nitrophenol (2-amino-4-nitrophenol) of Formula 2 with hydrochloric acid and sodium nitrite, it is 2-pyridinethiol-1-oxide of Formula 3 The azo-coupling reaction with sodium salt produces a dye of formula (5) or (6).

(Formula 5)

(Formula 6)

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 mole of 2-pyridinethiol-1-oxide sodium salt of Formula 3 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 through a filter paper, and dried to prepare a dye of Chemical Formula 3.

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 2-pyridinethiol-1-oxide sodium salt of Formula 3 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 a dye of Chemical Formula 5.

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 vessel, 0.01 mol of 2-pyridinethiol-1-oxide sodium salt of Formula 3 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 a dye of 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 2-pyridinethiol-1-oxide sodium salt of Formula 3 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 through a filter paper and dried to prepare a dye of Chemical Formula 6.

Antimicrobial Test

After adding glacial acetic acid and a dispersant to a 1.0% aqueous solution of the dyes obtained in Examples 1 to 4 to make a salt solution, immersed polyester fabric therein, followed by dyeing at 130 ° C. for 60 minutes, followed by soaping and drying to dye the fabric. Got it. The results of the antimicrobial test on the dyed fabric are shown in [Table 1].

division Bacteriostatic reduction (%) Strain I Strain II Dye of formula 3 prepared in Example 1 99.5 98.7 Dye of formula 5 prepared in Example 2 99.6 99.8 Dye of formula 4 prepared in Example 3 99.9 98.1 Dye of formula 6 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 dye of the present invention can impart sufficient antimicrobial and antifungal properties only to the textile product by a dyeing process, and thus does not require an additional process for providing antimicrobial and antifungal properties, and the color of the fiber product is not discolored due to decomposition of the dye. Aggression is maintained for a long time.

Claims (5)

A dye having the structure of Formula 1 or Formula 2 (Formula 1)

(In Formula 1, A is a chromophore having an azo group.) (Formula 2)

(In Formula 2, A is a chromophore having an azo group.) The dye according to claim 1, wherein the chromophore having an azo group has a structure represented by the following general formula (4) or (5). (Formula 4)

(Formula 5)

After the diazotization reaction of P-nitroaniline of formula 1 or 2-amino-4-nitrophenol of formula 2 with hydrochloric acid and sodium nitrite, it was 2-pyridinethiol-1-oxide sodium of formula 3 Method for preparing a dye having a structure of formula (1) or (2) characterized in that the azo-coupling reaction with salt (2-Pyridinethiol-1-oxide sodium salt) (Formula 1)

(Formula 2)

(Formula 3)

(Formula 1)

(A in Formula 1 is a chromophore having an azo group.) (Formula 2)

(In Formula 2, 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 (4) or (5). (Formula 4)

(Formula 5)

Textile Dyed with the Dye of Claim 1