KR100821898B1 - Silver-containing antibacterial acid dyes and preparation method thereof and antibacterial fiber using the same - Google Patents

Abstract

The present invention relates to a silver-containing antimicrobial acid dye having a structure represented by the following formula (1) by binding a dye intermediate to a silver-containing sulfonamide-based antimicrobial agent as a strong antimicrobial reactor, and a method for preparing the same.

(Formula 1)

Wherein R ₁ is H or NH ₂ , R ₂ is H, Cl, SO ₃ Na or SO ₃ H, R ₃ is H, NHCOCH ₂ COCH ₃ , NHCONH ₂ or NH ₂ , and R ₄ is H , SO ₃ Na or SO ₃ H)

The silver-containing antimicrobial acid dye compound of the present invention has a yellow color, and when mixed, expresses various colors, and when dyeing the fiber by using the same, it shows strong antimicrobial properties and inhibits the growth or proliferation of microorganisms to prevent infectious diseases, prevent odor, and Functional antibacterial fiber products can be produced that can prevent contamination and embrittlement.

Silver-containing, antibacterial acid dyes, sulfonamides, antibacterial fibers, silver sulfadiazine, antibacterial.

Description

Silver-containing antimicrobial acid dyes and preparation method thereof and antibacterial fiber using the same {Antibacterail acid dyes containing silver and a method of preparing the same and antibacterial fiber

The present invention is a strong antimicrobial reactor, a sulfonamides-based antimicrobial agent, in particular a silver-containing antimicrobial acid dye prepared by binding a silver-containing sulfa agent to the intermediate of the dye, and a method for producing the same, and dyed with the silver-containing antimicrobial acid dyes in various colors An antimicrobial fiber having both antimicrobial and antimicrobial properties.

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 give antimicrobial properties to textile products, they can prevent the growth and proliferation of microorganisms, preventing infectious diseases, preventing odors, and preventing fiber contamination and embrittlement. You will be able to get a textile product.

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 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, 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 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 particular, the present invention using the silver sulfadiazine containing silver ions (Ag ⁺ ) in consideration of the antimicrobial action of silver ions (Ag ⁺ ) and the antibacterial action of the sulfa agent itself act more powerfully. It was completed.

Specifically, the present invention is a sulfonamide-based antimicrobial agent having excellent antibacterial activity on the acid dye matrix used in the fiber The present invention provides a method for preparing an antibacterial acid dye by introducing silversulfadiazine.

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 a silver-containing antimicrobial acid dye represented by the following formula (1) containing a silver (Ag) -containing sulfa agent, that is, a silver-containing sulfonamide as a diazo compound, and a method for producing the same.

The present invention also relates to a functional antimicrobial fiber having various colors and antimicrobial properties by dyeing with the silver-containing antimicrobial acid dye.

Wherein R ₁ is H or NH ₂ , R ₂ is H, Cl, SO ₃ Na or SO ₃ H, R ₃ is H, NHCOCH ₂ COCH ₃ , NHCONH ₂ or NH ₂ , and R ₄ is H , SO ₃ Na or SO ₃ H)

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, a sulfonamide-based antimicrobial agent is used to impart antimicrobial activity by inhibiting metabolic functions such as nucleic acid synthesis of enzymes in microorganisms.

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 common molecular structure of sulfanylamides, and there are various types of sulfonamide-based antimicrobials, such as sulfapyridine, sulfadiazine, silversulfadiazine, and sulfamerazine ( sulfamerazine, sulfamethoxine, sulfapyrazine, phthalylsulfathiazole, sulfathiazole, mafenide, sulfadimidine, sulfamethazine Sulfamethoxazole, Sulfanilamide, Sulfamethoxypyridazine, Sulfaguanidine, Sulfaguanidine, Sulfamethoxine, Sulfaxazole, Sulfadoxine , Sulfamethizole, sulfasalazine, sulfinpyrazone, and the like.

In the present invention, the silver sulfadiazine (monosilver-4-amino-N-pyrimidyl) of the general formula 1, which is the most easily used as an intermediate of the dye, and the sulfonamide-based antimicrobial agent, which is most commonly used as an intermediate of dyes. Benzenesulfonamide) to synthesize the dye.

(General Formula 1) Silver Sulfa Diazine

Silver sulfadiazine is a derivative of sulfadiazine and is effective against yeast as well as antimicrobial ability against many gram-positive and gram-negative microorganisms, and is effective for the prevention and treatment of second and third degree burn sepsis. Used as a topical and external anti-infective.

It describes a method for producing a silver-containing antimicrobial acid dye of the formula (1) according to the present invention. Specifically, in the present invention, after (a) diazotizing the silver sulfadiazine of the following general formula (1) first with hydrochloric acid and sodium nitrite, (b) 3-aminophenylurea of the following general formula (2), general formula (3) 2-aminobenzene-1,4-disulfonic acid of formula 4, 3-oxo-N-phenylbutyamide of formula 4 or N- (2-chloro- of formula 5 The antibacterial acid dye of Formula 1 may be synthesized by performing an azo-coupling reaction with phenyl) -3-oxo-butyamide (N- (2-Chloro-phenyl) -3-oxo-butyramide) in a second step. .

(General Formula 1) Silver Sulfa Diazine

(General Formula 2) 3-Aminophenylurea

2-aminobenzene-1,4-disulfonic acid

3-oxo-N-phenylbutyamide (3-oxo-N-phenyl-butyramide)

(Formula 5) N- (2-Chloro-phenyl) -3-oxo-butyramid (N- (2-Chloro-phenyl) -3-oxo-butyramide)

(Formula 1)

Wherein R ₁ is H or NH ₂ , R ₂ is H, Cl, SO ₃ Na or SO ₃ H, R ₃ is H, NHCOCH ₂ COCH ₃ , NHCONH ₂ or NH ₂ , and R ₄ is H , SO ₃ Na or SO ₃ H)

In a preferred embodiment of the present invention, the silver sulfadiazine of the general formula (1) of the sulfonamide-based antimicrobial agent as a dye intermediate first subjected to the diazotization reaction with hydrochloric acid and sodium nitrite, and then The combination of 3-aminophenylurea of Formula 2 with an azo-coupling reaction provides a silver-containing antimicrobial acid dye of Formula 2 below.

(General Formula 1) Silver Sulfa Diazine

(General Formula 2) 3-Aminophenylurea

In another preferred embodiment of the present invention, the silver sulfadiazine of the general formula 1 of the sulfonamide-based antimicrobial agent as a dye intermediate in the first diazotization reaction with hydrochloric acid and sodium nitrite, and then The combination of 2-aminobenzene-1,4-disulfonic acid of Formula 3 with an azo-coupling reaction provides a silver-containing antimicrobial acid dye of Formula 3 below.

(General Formula 1) Silver Sulfa Diazine

2-aminobenzene-1,4-disulfonic acid

Where 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 Silver-Containing Acidic Antibacterial Dye of Formula 2

(Formula 2)

Dissolve 0.02 mol of silver sulfadiazine in distilled water of 5 ° C or less, and then add 6 ml of hydrochloric acid (HCl) to dissolve it with stirring. 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 below.

In a separate reaction vessel, 0.02 mol of 3-aminophenylurea (formula 2) is dissolved in distilled water with 0.01 mol of hydrochloric acid (HCl), and the temperature is maintained at 5 ° C or lower.

The diazotization solution prepared above is slowly added to this solution, and then the azo-coupling reaction is performed as in Scheme 2 below.

After the reaction was completed, the pH was adjusted to 7, filtered through a filter paper through salting, and dried to obtain a yellow silver-containing antimicrobial acid dye according to the present invention as shown in Chemical Formula 2.

The salt solution was prepared by adding glacial acetic acid and a dispersant to a 1.0% aqueous solution of the silver-containing antimicrobial acid dye compound of Formula 2 thus obtained, and then dyed at 130 ° C. for 60 minutes to prepare dyed antimicrobial fibers by soaping and drying.

Example 2: Preparation of Silver-Containing Antimicrobial Acid Dye of Formula 3

(Formula 3)

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

Dissolve 0.02 mol of silver sulfadiazine in distilled water of 5 ° C or less, and then add 6 ml of hydrochloric acid (HCl) to dissolve it with stirring. Next, 0.02 mol of sodium nitrite (NaNO ₂ ) was slowly added to the solution to proceed with the diazotization reaction as in Scheme 3 below.

2-aminobenzene-1,4-disulfonic acid (formula 3) in a separate reaction vessel After dissolving 0.02 mole in 0.01 mole of sodium carbonate (Na ₂ CO ₃ ) in distilled water and maintaining the temperature below 5 ℃.

The diazotization solution prepared above is slowly added to this solution, and then the azo-coupling reaction is performed as in Scheme 4 below.

After the reaction was completed, the pH was adjusted to 7 and filtered through a filter paper through salting, followed by drying, according to the present invention as shown in Formula 2 above. A yellow silver-containing antibacterial acid dye is obtained.

The salt solution was prepared by adding glacial acetic acid and a dispersant to a 1.0% aqueous solution of the silver-containing antimicrobial acid dye compound of Formula 2 thus obtained, and then dyed at 130 ° C. for 60 minutes to prepare dyed antimicrobial fibers by soaping and drying.

<Antimicrobial Evaluation>

KS K 0693-2001, Silver-containing antimicrobial acid dye according to the present invention by performing an antimicrobial test on a nylon plain weave fabric dyed at a concentration of 1% owf using the yellow dye synthesized using the antimicrobial test method of the fabric To demonstrate the antimicrobial properties of the following Table 1 was obtained.

Test Sample Bacteriostatic reduction rate (%) Strain 1 Strain 2 Formula 2 antimicrobial dye 1% o.w.f. 99.9 99.9 Formula 3 antimicrobial dye 1% o.w.f. 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. Growth rate: 1) Strain 1: 34-fold growth

                   2) Strain 2: 32-fold multiplication

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

5. Nonionic Surfactant: Tween80 (0.05%)

As described above, the silver-containing antimicrobial acid dye compound according to the present invention has a yellow color, and when mixed, expresses various colors, and when dyeing fibers using the same, it exhibits strong antimicrobial properties and inhibits the growth or proliferation of microorganisms to prevent 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 the textile product is given from the dyeing process, and an additional process for the purpose of antimicrobial is not necessary, and the dye is decomposed so that the color of the woven or knitted fabric is not discolored, and the antimicrobial property lasts for a long time. Durable antibacterial fiber products can be produced .

Although the present invention has been described in detail only with respect to the embodiments described above, it can be changed or modified within the spirit and scope of the present invention will be apparent to those skilled in the art to which the present invention pertains. It should be limited by the claims.

Claims (3)

The antimicrobial acid dye having the structure of Formula 1. (Formula 1)

Wherein R ₁ is H or NH ₂ , R ₂ is H, Cl, SO ₃ Na or SO ₃ H, R ₃ is H, NHCOCH ₂ COCH ₃ , NHCONH ₂ or NH ₂ , and R ₄ is H , SO ₃ Na or SO ₃ H) (a) diazotization of silver sulfadiazine with hydrochloric acid and sodium nitrite, (b) 3-aminophenylurea, 2-aminobenzene-1, 4-disulfonic acid, 3-oxo-N-phenylbuty Silver, characterized by synthesizing the antimicrobial acid dye of Formula 1 by proceeding an azo-coupling reaction with one compound selected from amide and N- (2-chloro-phenyl) -3-oxo-butyramid Method for producing a containing antimicrobial acid dye. (Formula 1)

Wherein R ₁ is H or NH ₂ , R ₂ is H, Cl, SO ₃ Na or SO ₃ H, R ₃ is H, NHCOCH ₂ COCH ₃ , NHCONH ₂ or NH ₂ , and R ₄ is H , SO ₃ Na or SO ₃ H) The antimicrobial fiber dyed with the silver containing antimicrobial acid dye of Claim 1.