KR100821900B1 - Antibacterial acid dyes and method of preparing the same and antibacterial fiber thereby - Google Patents

Abstract

The present invention relates to an antimicrobial acid dye having a structure represented by the following formula (1) in which two identical sulfonamide antibacterial agents having strong antimicrobial properties to an acid dye are combined in a diazotization-coupling reaction, and a method for preparing the same.

Wherein R ₁ is H or OH, R ₂ is H, NH ₂ or sulfonamide-based antimicrobial agent (A), R ₃ is H, SO ₃ H or sulfonamide-based antimicrobial agent (A), and R ₄ is H or SO ₃ H, and A is a sulfonamide antimicrobial agent.)

The antimicrobial acid dye compound of the present invention has strong antimicrobial properties and dark colors, and dyeing fibers using the same can prevent infectious diseases, prevent odors, prevent contamination and embrittlement of fibers, and have a functional antibacterial fiber product having a dark color. Can be prepared.

Antibacterial acid dye, sulfonamide, antibacterial fiber, sulfadiazine, antibacterial.

Description

Antibacterial acid dyes and preparation method thereof and antibacterial fiber using the same {Antibacterial acid dyes and method of preparing the same and antibacterial fiber

The present invention is an antimicrobial acid dye having two strong sulfonamide antimicrobial agents having strong antimicrobial properties to an acid dye, a method of preparing the same, and a method of preparing the same and dyeing the antimicrobial acid dyes described above to simultaneously have various colors and antimicrobial properties. It relates to antibacterial fibers.

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 a synthetic fiber and interposing the inside of the fiber, and a method of dispersing the copper compound inside the fiber during the coagulation and regeneration process of a regenerated fiber, and antimicrobial activity There is a method of synthesizing a polymer by making an organic copolymer component having a.

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 substituted with inorganic ion such as zeolite, silica, alumina and other metal ions with excellent antimicrobial properties such as copper and zinc, and has a three-dimensional skeletal structure with fine pores. . On the other hand, metals such as copper and zinc are one of the few metals with strong antibacterial activity and high safety, and have been proved to be harmless to 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 excellent advantage that you cannot see. However, metal ions such as copper and zinc may deteriorate 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 be the cause of trimming when mixed with fine fibers.

The present invention has been proposed to solve the problems of the conventional antimicrobial material used as the dye as described above, an object of the present invention is to provide an acid dye containing a strong antimicrobial group and a method for producing the same.

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.

The present invention relates to an antimicrobial acid dye having a structure represented by the following formula (1) and two antimicrobial fibers dyed by combining the same sulfonamide antimicrobial agent having antimicrobial activity to an acid dye in a diazotization-coupling reaction.

(Formula 1)

Wherein R ₁ is H or OH, R ₂ is H, NH ₂ or sulfonamide-based antimicrobial agent (A), R ₃ is H, SO ₃ H or sulfonamide-based antimicrobial agent (A), and R ₄ is H or SO ₃ H, and A is a sulfonamide antimicrobial agent.)

In addition, the present invention (i) diazotization reaction of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite, and then (ii) 6-amino-4hydroxynaphthalene-2-sulfonic acid, 7-amino-4 After azo-coupling reaction with one selected from the group consisting of hydroxynaphthalene-2-sulfonic acid and 4-amino-5-hydroxy naphthalene-1-sulfonic acid, (i) sulfadiazine or sulfameti The present invention relates to a method for preparing an antimicrobial acid dye having the structure of Chemical Formula 1, wherein the azine is subjected to azo-coupling reaction with a reactant subjected to diazotization with hydrochloric acid and sodium nitrite.

Hereinafter, the configuration of the present invention will be described in more detail.

Commonly used antimicrobial agents are penicillin. Sulfonamides, fluoroquinolones, tetracyclines, aminoglucosides and the like. Among these, it is widely used and can be used as an intermediate of dyes such as tetracycline, sulfonamide, and quinolone.

In the present invention, sulfonamide-based antimicrobial agents, particularly silver-containing sulfonamide-based antimicrobials, which inhibit metabolic functions such as nucleic acid synthesis of enzymes in microorganisms and impart antimicrobial properties, were used.

Sulfonamide drugs, or sulfonamides, are a type of antimicrobial agent with SO ₂ NH ₂ groups, which collectively refer to derivatives of sulfanilamide that antagonize the folate synthesis of microorganisms. streptococci, pneumococci, etc.), Gram-negative cocci (meningococci, gonococci, etc.), Gram-positive bacteria (Escherichia coli, shigellae, etc.), and various other bacteria It is an antibacterial substance that suppresses development. Prontosil rubrum, developed by German scientist Gerhard Domagk in 1932, was metabolized into in-vivo sulfanylamides, and a large number of derivatives have been synthesized since it was first shown to express potent antimicrobial effects. Sulfonamides have a sulfanylamide molecular structure in common and come in a variety of varieties. There are various types of sulfonamide-based antimicrobial agents such as sulfapyridine, sulfadiazine, silversulfadiazine, sulfamerazine, sulfamethoxine, and sulfapyrazine. ), Phthalylsulfathiazole, sulfathiazole, mafenide, sulfadimidine, sulfamethazine, sulfamethoxazole, sulfanilamide , Sulfamethoxypyridazine, sulfaguanidine, sulfadimethoxine, sulfisoxazole, sulfadoxine, sulfamethizole, sulfasalzine And sulfinpyrazone.

In the present invention, among the sulfonamide-based antimicrobial agents most commonly used as an antimicrobial agent and excellent antimicrobial effect among them, sulfadiazine (monosilver-4-amino-N-pyrimidylbenzenesulfonamide) ) [Hereinafter referred to as "sulfadiazine"] or sulfamethiazine (4-amino-N-5-diazole benzenesulfonamide) of the following general formula 2 (hereinafter referred to as "sulfathiazine") It is desirable to synthesize dyes.

(Formula 1) Sulfaazine

(Formula 2) Sulfamethazine

Sulfadiazine and sulfamethazine are effective against yeast as well as antimicrobial ability against many Gram-positive and Gram-negative microorganisms, and are topical and external anti-infective agents for the prevention and treatment of second and third degree burn sepsis. Zero is used.

In addition, as said acid dye, 6-amino-4 hydroxy naphthalene- 2-sulfonic acid of following General formula (3), 7-amino-4 hydroxy naphthalene-2- sulfonic acid of following General formula (4), or following General formula (5). 4-amino-5-hydroxy naphthalene-1-sulfonic acid and the like are used.

6-amino-4hydroxynaphthalene-2-sulfonic acid

7-Amino-4hydroxynaphthalene-2-sulfonic acid

4-amino-5-hydroxy naphthalene-1-sulfonic acid

It describes a method for producing an antimicrobial acid dye of formula 1 according to the present invention. Specifically, in the present invention, (i) diazotization reaction of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite, and (ii) it is 6-amino-4hydroxynaphthalene-2-sulfonic acid, 7-amino Azo-coupling reactions with one selected from the group consisting of -4 hydroxynaphthalene-2-sulfonic acid and 4-amino-5-hydroxy naphthalene-1-sulfonic acid (iii) followed by sulfadiazine or An azo-coupling reaction is performed by reacting sulfathiazine with diazotization with hydrochloric acid and sodium nitrite to synthesize an antimicrobial acid dye having the structure of Chemical Formula 1.

In a preferred embodiment of the present invention, the sulfadiazine of the general formula 1 of the sulfonamide-based antimicrobial agent is subjected to a diazotization reaction with hydrochloric acid and sodium nitrite, and then the 6-amino-4 hydroxy naphthalene-2 of the general formula 3 After combining sulfonic acid and azo-coupling reaction, the sulfadiazine of the following general formula 1 is diazotized with hydrochloric acid and sodium nitrite and then reacted with azo-coupling reaction secondly. An antibacterial acid dye is provided.

(General Formula 1) Silver Sulfa Diazine

6-amino-4hydroxynaphthalene-2-sulfonic acid

(상기식에서, SO₃Na는 SO₃H로 대체될 수 있다.)

(In the above formula, SO ₃ Na may be replaced with SO ₃ H.)

In another preferred embodiment of the present invention, the sulfamethazine of the general formula (2) of the sulfonamide-based antimicrobial agent is subjected to a diazotization reaction with hydrochloric acid and sodium nitrite, which is then 6-amino-4-hydroxy of the general formula (3) After combining naphthalene-2-sulfonic acid with an azo-coupling reaction, the sulfamethazine of the following formula (2) is diazotized with hydrochloric acid and sodium nitrite in azo-coupling reaction. An antimicrobial acid dye of formula (3) is provided.

(Formula 2) Sulfamethazine

6-amino-4hydroxynaphthalene-2-sulfonic acid

(In the above formula, SO ₃ Na may be replaced with SO ₃ H.)

Features and other advantages of the present invention as described above will become more apparent from the description of the non-limiting examples described below. However, the following examples are merely illustrative as specific embodiments of the present invention and should not be understood as limiting the scope of the present invention.

Example 1: Preparation of Blue Acidic Antibacterial Dye of Formula 2

After dispersing 0.01 mol of sulfadiazine of Formula 1 in distilled water at 3 ° C., 6 ml of hydrochloric acid (HCl) is added thereto, followed by stirring to dissolve. Next, 0.01 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction as in Scheme 1 below. .

Next, in a separate reaction vessel, 0.01 mol of 6-amino-4hydroxynaphthalene-2-sulfonic acid of Formula 3 was dissolved in distilled water together with 0.01 mol of sodium carbonate (Na ₂ CO ₃ ), and then the temperature was changed to 3 ° C. Keep it.

The diazotization solution prepared above is slowly added to this solution, and the azo-coupling reaction proceeds as shown in Scheme 2 to obtain a red reaction solution.

Next, in a separate container, 0.01 mol of sulfadiazine of Formula 1 was dispersed in distilled water at 3 ° C., and 6 ml of hydrochloric acid (HCl) was added thereto, followed by stirring to dissolve. Next, 0.02 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction as in Scheme 1. At this time, the obtained diazotized solution was added to the red reaction solution of Scheme 2, and the azo-coupling reaction was carried out as in Scheme 3 while maintaining the pH at 7 while maintaining the temperature at 4 ° C.

Next, after the reaction is completed, the pH is adjusted to 7 and filtered through a filter paper through salting process, followed by drying, to obtain a yellow acidic antimicrobial dye according to the present invention as shown in Chemical Formula 2.

Example 2: Preparation of Blue Acidic Antibacterial Dye of Formula 3

After dispersing 0.01 moles of sulfamethiazine of Formula 2 in distilled water at 3 ° C., 6 ml of hydrochloric acid (HCl) is added thereto, followed by stirring to dissolve. Then, slowly add 0.01 mol of sodium nitrite (NaNO ₂ ) to this solution, and proceed with the diazotization reaction as in the following Scheme 1.

(Scheme 1)

Next, in a separate reaction vessel, 0.01 mol of 6-amino-4hydroxynaphthalene-2-sulfonic acid of Formula 3 is dissolved in distilled water together with 0.01 mol of sodium carbonate (Na ₂ CO ₃ ), and then 3 ° C. or less. To keep.

The diazotization solution prepared above is slowly added to this solution, and the azo-coupling reaction proceeds as shown in Scheme 2 to obtain a red reaction solution.

(Scheme 2)

Next, in a separate container, 0.01 mol of sulfamethazine of Formula 2 is dispersed in distilled water at 3 ° C., and 6 ml of hydrochloric acid (HCl) is added thereto, followed by stirring to dissolve. Next, 0.02 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction as in Scheme 1. At this time, the obtained diazotized solution was added to the red reaction solution of Scheme 2 and the azo-coupling reaction was carried out as in Scheme 3 while maintaining the pH at 7 while maintaining the temperature at 3 ° C.

(Scheme 3)

Next, after the reaction is completed, the pH is adjusted to 7, filtered through a filter paper through a dyeing process and dried, a blue acidic antimicrobial dye according to the present invention as shown in Formula 3 is obtained.

The salt solution was prepared by adding glacial acetic acid and a dispersant to the 1.0% aqueous solution of the acidic antimicrobial dye compounds of Formula 2 and Formula 3 thus obtained, followed by dyeing at 98 ° C. for 60 minutes to prepare dyed antibacterial fibers through soaping and drying.

<Antimicrobial Evaluation>

KS K 0693-2001, a nylon plain weave fabric dyed at a concentration of 1% owf using the synthesized yellow and red dye using the antimicrobial test method of the fabric 0 times washing, 10 times washing, 20 times washing After each trial, antimicrobial evaluation was performed.

The antimicrobial test results of the antimicrobial fibers dyed as described above are as shown in Table 1 below. Table 1 demonstrates the antimicrobial and laundry durability of the antimicrobial dyes according to the invention.

Antimicrobial Evaluation Results division Bacteriostatic reduction (%) Strain 1 Strain 2 0 wash Example 1 0 wash 99.9 99.9 10 washes 99.9 99.9 10 washes 20 washes 99.9 99.9 Example 2 0 wash 99.9 99.9 20 washes 10 washes 99.9 99.9 20 washes 99.9 99.9

Antimicrobial Test

The antimicrobial test conditions for the silver-containing antimicrobial fiber of the present invention are as follows:

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

             2) Strain 2: Klebsiella pneumoniae ATCC 4352

2. Concentration of inoculum: 1) Strain 1: 1.3 X 10 ⁵ / ml

2) Strain 2: 1.5 X 10 ⁵ pcs / ml

3. Increase rate: 1) Strain 1: 40-fold multiplication

                   2) Strain 2: 46-fold multiplication

4. Control: Nylon (KS K 0905 -1996)

5. Nonionic Surfactant: Tween80 (0.05%)

As described above, the acidic antimicrobial dye compound according to the present invention has red and yellow color, and when mixed, expresses various colors, and when dyeing fibers using the same, it exhibits strong antimicrobial properties to inhibit the growth or proliferation of microorganisms, thereby preventing infectious diseases, Functional antibacterial fiber products which can prevent odors and prevent contamination and embrittlement of fibers can be prepared.

According to the present invention, the antimicrobial processing to be applied to textile products is given from the dyeing process, and no additional process for the purpose of antimicrobial is required, and uniform washing is maintained even after several washings. It is possible to produce a highly durable antibacterial fiber product that does not discolor and lasts for a long time .

Claims (5)

An antimicrobial acidic dye having the structure of Formula 1 by combining two identical sulfonamide antibacterial agents with an acidic dye in a diazotization-coupling reaction. (Formula 1)

Wherein R ₁ is H or OH, R ₂ is H, NH ₂ Or a sulfonamide antimicrobial agent (A), R ₃ is H, SO ₃ H or a sulfonamide antimicrobial agent (A), R ₄ is H or SO ₃ H, and A is a sulfonamide antimicrobial agent.) The antimicrobial acid dye according to claim 1, wherein the sulfone-based antibacterial agent is sulfadiazine of the following general formula (1) or sulfamethazine of the following general formula (2) (Formula 1) Sulfaazine

(Formula 2) Sulfamethazine

The acid dye according to claim 1, wherein the acid dye is 6-amino-4hydroxy naphthalene-2-sulfonic acid of the general formula 3, 7-amino-4hydroxy naphthalene-2-sulfonic acid of the general formula 4 and general formula 5 Antimicrobial acid dye which is one selected from the group consisting of 4-amino-5-hydroxy naphthalene-1-sulfonic acid 6-amino-4hydroxynaphthalene-2-sulfonic acid

7-Amino-4hydroxynaphthalene-2-sulfonic acid

4-amino-5-hydroxy naphthalene-1-sulfonic acid

(Iii) diazotization of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite, followed by (ii) 6-amino-4hydroxy naphthalene-2-sulfonic acid, 7-amino-4hydroxy naphthalene- After an azo-coupling reaction with one selected from the group consisting of 2-sulfonic acid and 4-amino-5-hydroxy naphthalene-1-sulfonic acid, (i) sulfadiazine or sulfamethiazine was again hydrochloric acid and A method for producing an antimicrobial acid dye having a structure represented by the following Chemical Formula 1, wherein the reactant reacted with sodium nitrite with an azo-coupling reaction. (Formula 1)

Wherein R ₁ is H or OH, R ₂ is H, NH ₂ Or a sulfonamide antimicrobial agent (A), R ₃ is H, SO ₃ H or a sulfonamide antimicrobial agent (A), R ₄ is H or SO ₃ H, and A is a sulfonamide antimicrobial agent.) The antimicrobial fiber dyed with the antimicrobial acid dye of claim 1.