KR100839512B1 - Antibacterial acidic dyes having the sulphonamides as diazo component and antibacterial fiber thereby - Google Patents

Abstract

The present invention relates to an acidic antimicrobial dye in which a dye intermediate is bonded to a sulfonamide-based antimicrobial agent in a diazotization-coupling reaction as a powerful antimicrobial reactor.

Acidic antimicrobial dye compound of the present invention has a red and yellow color to express a variety of colors when mixed, and dyeing the fiber using this shows a strong antimicrobial properties to inhibit the growth or growth of microorganisms to prevent infectious diseases, prevention of odor, fiber Functional antibacterial fiber products can be produced that can prevent contamination and embrittlement.

Acid antibacterial dyes, sulfonamides, antibacterial fibers, antibacterial agents, antimicrobial.

Description

Antibacterial acidic dyes having the sulphonamides as diazo component and antibacterial fiber

The present invention relates to an acidic antimicrobial dye prepared by combining a sulfa agent, that is, a sulfonamide-based antimicrobial agent, with an intermediate of a dye and a strong antimicrobial reactor, and the antimicrobial fiber dyed with the acidic antimicrobial dye having various colors 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 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.

In addition, as an antibacterial deodorization process using an organic dye, there is a method of imparting antimicrobial properties to cotton using a reactive dye synthesized using an antimicrobial agent as specified in Korean Patent No. 2002-0057322 'red antimicrobial dye'.

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. Now, it is used in Japan, the United States, etc., and most of them are not used in textile processing for garments, but are used in some fields such as carpets, wallpaper, and other industries that do not come into contact with human bodies. 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 excellent 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.

As an antibacterial deodorization processing method using organic dyes, the Republic of Korea Patent No. 2002-0057322 'red antimicrobial dye' is limited to the nature of the dye structure can be applied, and in fact, in many areas for the antibacterial is required (furniture, Carpets, interior fibers, etc.) is not applicable, there is a limit in the color choice to synthesize only the red dye.

In addition, by applying the silver-containing antimicrobial agent, the initial antimicrobial can be given, but may cause a problem that the antimicrobial gradually decreases due to the detachment of silver ions due to washing during use.

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. Specifically, the present invention provides an acidic antimicrobial dye prepared by introducing a sulfonamide-based antimicrobial agent having excellent antimicrobial activity into an acid dye base material used for fibers.

In addition, the antimicrobial processing applied to this textile product is given from the dyeing process, and no additional process for the purpose of antimicrobial is required, and the uniform antimicrobial property is maintained even after several washings. Another object is to provide an antimicrobial fiber having excellent durability which is long lasting.

The present invention relates to an acidic antimicrobial dye prepared by binding a sulfonamide-based antimicrobial agent as a diazo compound to an intermediate of the dye as a strong antimicrobial reactor.

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

Specifically, the present invention relates to an acidic antimicrobial dye in which a dye intermediate is bonded to a sulfa agent, ie, a sulfonamide antimicrobial agent, in a diazotization-coupling reaction and a functional antimicrobial fiber using the same.

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 are used to inhibit the metabolic functions such as nucleic acid synthesis of enzymes in microorganisms and to provide antimicrobial activity.

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 agent that suppresses development. Prontosil® rubrum, developed by German scientist Gerhard Domagk in 1932, was metabolized into in-vivo sulfanylamide, and a large number of derivatives have been synthesized since it was first identified as a potent antimicrobial effect. Sulfonamides have a common sulfanylamide molecular structure, and there are various types of sulfonamide-based antibacterial agents such as sulfapyridine, sulfadiazine, sulfamerazine, and sulfamethoxine. , Sulfapyrazine, phthalylsulfathiazole, sulfathiazole, mafenide, sulfadimidine, sulfamethazine, sulfamethoxazole, sulfamethoxazole Sulfanilamide, sulfamethoxypyridazine, sulfaguanidine, sulfadimethoxine, sulfisoxazole, sulfadoxine, sulfamethizole, sulfamethizole Sulfasalazine, sulfinpyrazone, and the like. All the sulfonamide antibacterial agents mentioned above can be used as dye intermediates in the present invention.

As a preferred embodiment, in the present invention, among the sulfonamide-based antimicrobial agents of the general formula (1) amino acid (4-amino-N-2) Pyrimidinylbenzenesulfonamide) to synthesize dyes.

(Formula 1) Sulfaazine

Sulfadiazine is a lymphogranuloma caused by meningitis, chancroid, acute urinary tract infection, and chloroquine-resistant plasmodia caused by Haemophilus influenzae. It is an effective sulfa agent for the treatment and prevention of infectious diseases such as venereum) and early signs of falciparum malaria.

In a preferred embodiment of the present invention, (a) a diazotization reaction of sulfadiazine of the following general formula (1), preferably of sulfonamide-based antimicrobial agent, with hydrochloric acid and sodium nitrite first, (b) the following general formula (2) 3-methyl-l-1- (p-sulfophenyl) -s-pyrazolone) or Formula 3 (γ-sodiumsulfonyl--7-amino-α-naphthol, hereinafter referred to as 'γ-acid') The second azo-coupling reaction provides an acidic antimicrobial dye of formula (1).

(Formula 1) Sulfaazine

(Formula 2) 3-methyl-1-l (p-sulfophenyl) -s-pyrazolone

Γ-acid

(Wherein A is 3-methyl-l-1- (p-sulfophenyl) -s-pyrazolone or γ-acid)

In a preferred embodiment of the present invention, the 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 2-methyl of the general formula 2 Combining -l-1- (p-sulfophenyl) -s-pyrazolone with an azo-coupling reaction provides an acidic antimicrobial dye of formula (2).

(Formula 1) Sulfaazine

(Formula 2) 3-methyl-1-l (p-sulfophenyl) -s-pyrazolone

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

In another preferred embodiment of the present invention, the 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 γ- Coupling the acid with an azo-coupling reaction provides an acidic antimicrobial dye of formula (3).

(Formula 1) Sulfaazine

Γ-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 Yellow Acidic Antibacterial Dye of Formula 2

(Formula 2)

Dissolve 0.02 mol of sulfadiazine (formula 1) in distilled water of 5 ° C or less, and add 6 ml of hydrochloric acid (HCl) to stir and 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 below.

In a separate reaction vessel, 0.02 mole of 3-methyl-1-1- (p-sulfophenyl) -s-pyrazolone (Formula 2) was dissolved in distilled water together with 0.01 mole of sodium carbonate (Na ₂ CO ₃ ). Keep below 5 ° C.

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 acidic antimicrobial 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 1.0% aqueous solution of the acidic antimicrobial dye compound of Formula 2 thus obtained, followed by dyeing at 130 ° C. for 60 minutes to prepare dyed antimicrobial fibers by soaping and drying.

Example 2: Preparation of Red Acidic Antibacterial 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 sulfadiazine (formula 1) in distilled water of 5 ° C or less, and add 6 ml of hydrochloric acid (HCl) to stir and 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 3 below.

Γ-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, filtered through a filter paper through salting, and dried to obtain a red acidic antimicrobial dye according to the present invention.

The salt solution was prepared by adding glacial acetic acid and a dispersant to 1.0% aqueous solution of the acidic antimicrobial dye compound of Formula 3 thus obtained, followed by dyeing at 130 ° C. for 60 minutes to prepare dyed antimicrobial fibers by 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 dyes using the antimicrobial test method of the fabric, 0 wash, 10 wash, 20 wash, respectively 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.

Test Sample Bacteriostatic reduction rate (%) Strain 1 Strain 2 0 wash Yellow Antibacterial Dye 1% o.w.f. 99.9 99.9 Red Antibacterial Dye 1% o.w.f. 99.9 99.9 10 washes Yellow Antibacterial Dye 1% o.w.f. 99.9 99.9 Red Antibacterial Dye 1% o.w.f. 99.9 99.9 20 washes Yellow Antibacterial Dye 1% o.w.f. 99.9 99.9 Red Antibacterial Dye 1% o.w.f. 99.9 99.9

Antimicrobial Test

The antimicrobial test conditions for the acidic antimicrobial fibers 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 .

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 (5)

An acidic antimicrobial dye having a structure represented by the following Formula 1 in which a dye intermediate is bonded to a sulfonamide-based antimicrobial agent by a diazotization-coupling reaction. (Formula 1)

(Wherein A is 3-methyl-l-1- (p-sulfophenyl) -s-pyrazolone or γ-acid) delete The method of claim 1, wherein the sulfonamide-based antimicrobial agent is sulfapyridine, sulfadiazine, sulfamerazine, sulfamethoxine, sulfapyrazine, phthalyl sulfatiazole ( phthalylsulfathiazole, sulfathiazole, mafenide, sulfadimidine, sulfamethazine, sulfamethoxazole, sulfanilamide, sulfamethoxypipyridazine sulfamethoxypyridazine, sulfaguanidine, sulfadimethoxine, sulfisoxazole, sulfadoxine, sulfamethizole, sulfasalazine or sulfinpyrazone Acidic antibacterial dye, characterized in that selected from. The acidic antimicrobial dye according to claim 1, wherein the dye intermediate is 3-methyl-1-1- (p-sulfophenyl) -s-pyrazolone or γ-acid. The antimicrobial fiber dyed with the acidic antimicrobial dye of claim 1.