KR20070023910A - Reactive antibiotics and antibacterial fiber treated thereby - Google Patents

Abstract

A reactive antibiotic and an antibacterial fiber treated by the same are provided to have a combination structure of the fluorine quinoline group antibiotics and a reactive group capable of performing a covalent bond by the natural fiber. A reactive group is mixed with the fluorine quinoline group antibiotics. The fluorine quinoline group antibiotics is selected from the group consisting of norfloxacin, ciprofloxacin, enoxacin, lomefloxacin, sparfloxacin and grepafloxacin. The reactive group is selected from the group consisting of cyanuric chloride group, vinyl sulfone group and alpha-bromoacrylamide group. The antibacterial fiber is processed by the reactive antibiotic.

Description

Reactive antibiotics and antibacterial fiber treated thereby

The present invention relates to a reactive antimicrobial agent having a structure in which a reactive group capable of covalent bonding with natural fibers to a fluoroquinolone antibiotic having strong antimicrobial properties and an antibacterial fiber treated therewith.

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 product, 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 can 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 inorganic antibiotics between polymers in the manufacturing stage of synthetic fibers and incorporating them into the fibers, and solidifying and dispersing the copper compound in the fibers during the regeneration process, 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 the purpose of sterilization or treatment, but is a process to suppress the growth and growth of bacteria or fungi on the fiber, and it must be absolutely safe to the human body while maintaining the antibacterial effect at a certain level rather than high antibacterial activity. do. 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 laundry durability.

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.

The present invention has been proposed in order to solve the problems of the conventional antimicrobial material used as the dye as described above, the object of the present invention is a reactive antimicrobial agent having a strong antimicrobial group without safety problems such as deterioration, yellowing phenomenon, etc. To provide.

Specifically, the present invention has excellent antibacterial activity of norfloxacin, ciprofloxacin, ciprofloxacin, enoxacin, lomefloxacin, sparfloxacin, and grepaflo The present invention provides a reactive antimicrobial agent in which a reactive group capable of covalently bonding with natural fibers is introduced into a fluoroquinolone antibiotic such as Grepafloxacin.

Another object of the present invention is to provide an antimicrobial fiber which is treated with the reactive antimicrobial agent as described above for a long time.

In order to achieve the above object, the present invention provides a reactive antibacterial agent having a structure in which a reactive group capable of covalent bonding with natural fibers is bonded to a fluoroquinolone antibiotic having excellent antimicrobial properties.

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

Commonly used antibiotics are penicillin. Sulfonamides, fluoroquinolones, tetracyclines, aminoglucosides and the like. Among them, they are widely used and can be used as intermediates of dyes such as tetracycline, sulfonamide, and quinolone. In the present invention, a fluoroquinolone antibiotic which inhibits the metabolic function of enzymes in microorganisms and gives antimicrobial activity was used.

Fluoroquinolone antibiotics are a new broad spectrum antibiotic with good oral absorption with good tissue penetration and relatively long duration of action, which have a mechanism of action that binds DNA and interferes with its replication. It contains a 4-quinolone ring structure and fluoro at its 6-position, and some have 1-piperazinyl groups at the 7-position, so-called fluoro 4-quinolones. Fluoroquinoline antibiotics include Escherichia coli, Klebsiella, Enterobacter, Serratia, Proteus mirabilis, Proteus indole-positive bacteria, Citrobacterium, Salmonella, Shigella, Haemophilus, Staphylococcus, Gom, Effective against Streptococcus, Pneumococcus, Pseudomonas, Acinetobacter, Clostridium (Wellch), Mycoplasma, Chlamydia trichomatis, etc., much more than quinolone agents or nalidixic acid It is a presynthetic chemotherapeutic agent that exerts a broad and powerful antimicrobial action.

Fluoroquinolone antibiotics, which are steadily researched and widely used, are very effective in the treatment of bacterial diseases and are produced by total synthesis, unlike penicillin or cephalosporin antibiotics, which are highly antimicrobial and semisynthetic. It has the important feature that oral administration is possible. In addition, the antimicrobial action is different from the other agents currently in use, the mechanism of action, and the antibacterial action by the plasmid is not achieved, so resistant bacteria are not common. Fluoroquinolone antibiotics inactivate DNA gyase, an enzyme necessary for DNA replication of bacteria that cleaves cyclic DNA to complete supercoiling such as joint, torsion and relaxation, and ATP hydrolysis. Let's do it. Therefore, inactivation of these enzymes causes abnormalities in the chromosome, which eventually leads to disinfection and propagation of the bacteria, thus showing a bactericidal effect.

The effect of introducing a fluorine atom at the C-6 position of a fluoroquinolone antibiotic was to enhance the action of the DNA gyase on antimicrobial activity by 2 to 17 times depending on the type of substituent at the C-7 position. , Increases the cell penetration of the antimicrobial agent by 2 to 70 times. Moreover, maximum effect is shown when piperazinyl group is added to C-7 position.

The fluoroquinolone antibiotics used in the present invention are presently various and can be selected from the group consisting of norflosacine, ciproflosacine, enoxacsin, lomeflosacine, spartaflosacine and grepaflosacine, Among these, it is most preferable to use romefloxacin which is easy to synthesize.

Fluoroquinoline-based antibiotics having strong antimicrobial properties used in the present invention may be of the following types.

Norfloxacin

Ciprofloxacin

Enoxacin

Lomefloxacin

Sparfloxacin

Grepafloxacin

All antibiotics mentioned above in the present invention can be used as intermediates of the present invention. As a specific example, when combined with various reactive groups capable of covalent bonding with natural fiber by using lomefloxacin as an intermediate among these fluoroquinolone antibiotics, a reactive antimicrobial agent of Chemical Formula 1 is provided.

(Wherein A is a reactive group capable of covalent bonding with natural fibers, R ₁ is hydrogen or methyl, R ₂ is ethyl or cyclopropane, and R ₃ is hydrogen or fluorine).

In Chemical Formula 1, a reactive group capable of covalent bonding with natural fibers is selected from the group consisting of cyanuric chloride group, vinyl sulfone group, and α-bromoacrylamide group. 1 type etc.

In a preferred embodiment of the present invention, condensation reaction of lomeflosacine of the following general formula (1) with a cyanuric chloride dispersion of the following general formula (2) produces a reactive antimicrobial agent of formula (2).

(Formula 1) Lomefloxacin

(General Formula 2) Cyanuric Chloride

As another preferred embodiment of the present invention, the condensation reaction of lomefloxacin of the general formula (1) with the dispersion of α, β-dibromopropionyl chloride (α, β-dibromopropionyl chloride) of the general formula 3 Reactive antibacterial agents are provided.

(Formula 1) Lomefloxacin

(Formula 3) α, β-dibromopropionyl chloride (α, β-dibromopropionyl chloride)

In another preferred embodiment of the present invention, after the first condensation reaction of lomefloxacin of the general formula (1) with cyanuric chloride of the general formula (2), the reaction solution is P-aminobenzene vinyl sulfone of the general formula (4) or Second condensation reaction with m-aminobenzene vinyl sulfone of general formula (5) provides a reactive antimicrobial agent of formula (4).

(Formula 4) P-aminobenzene vinyl sulfone

Wherein x is H or Na

(Formula 5) m-aminobenzene vinyl sulfone

Wherein x is H or Na

Wherein x is H or Na

Hereinafter, the present invention will be described in more detail with reference to Examples.

However, the following examples are merely specific embodiments of the present invention and do not limit the scope of the present invention.

Example  1: Preparation of Reactive Antibacterial Agent of Formula 2

0.01 mole of cyanuric chloride of the general formula (2) is added to a small amount of acid and uniformly dispersed while maintaining in 0 to 5 ° C. while stirring in 100 ml of distilled water. And 45.7 parts by weight of lomefloxacin of the general formula 1 was added to distilled water, and a small amount of acid was added thereto, followed by dissolution while keeping the temperature below 5 ° C. The condensation reaction was allowed to proceed for 2 hours while slowly adding the dissolved lomeflosacine solution to cyanuric chloride. After the reaction was completed, the mixture was cooled, neutralized, removed with water, and dried in vacuo to obtain a reactive antibacterial agent represented by the following Chemical Formula 2.

Example  2: Preparation of Reactive Antibacterial Agent of Formula 3

After adding 0.01 mole of lomefloxacin of the general formula 1 to distilled water, a small amount of acid was added thereto, and then dissolved at a temperature of 5 ° C. or lower. Into a separately prepared burette is added 0.01mole of α, β-dibromopropionyl chloride of the general formula (3), and then slowly added to the lomefloxacin solution, the condensation reaction proceeds for 2 hours. After completion of the first reaction, the temperature of the reaction solution was maintained at 20 ° C., while adding a KOH 10% solution in the reaction, while maintaining the pH at 12, the debromination reaction was performed. After completion of the debromination reaction, the reaction solution is neutralized, water is removed, and dried in vacuo to obtain a reactive antimicrobial agent of Chemical Formula 3 below.

Example  3: Preparation of Reactive Antibacterial Agent of Formula 4

0.01 mole of cyanuric chloride of the general formula (2) is added to a small amount of acid and uniformly dispersed while maintaining at 0-5 ° C. while stirring in 100 ml of distilled water. And 45.7 parts by weight of lomefloxacin of the general formula 1 was added to distilled water, and a small amount of acid was added thereto, followed by dissolution while keeping the temperature below 5 ° C. The first condensation reaction solution was prepared by conducting the condensation reaction for 2 hours while slowly adding the dissolved lomefloxacin solution to the cyanuric chloride solution.

After completion of the first condensation reaction, 0.01-mole of P-aminobenzene vinyl sulfone (P-aminobenzene vinyl sulfone) of Formula 4 was dissolved in a separately prepared beaker and then slowly added to the first condensation reaction solution to proceed with the second condensation reaction. At this time, the temperature of the reactor is maintained at about 40 ℃. After completion of the reaction, the reaction solution was neutralized, water was removed, and dried in vacuo to obtain a reactive antimicrobial agent of the formula (4).

Thus prepared 0.1% owf aqueous solution of the reactive antimicrobial agent of Formula 2 was added to glacial acetic acid to make an antimicrobial treatment solution, and then added cotton fiber to the treated 30 minutes at 40 ℃, followed by soaping and drying to prepare an antimicrobial fiber. .

Another 0.1% owf aqueous solution of the reactive antimicrobial agent of Chemical Formula 3 was added thereto, glacial acetic acid was added thereto to prepare an antimicrobial treatment solution, and then, cotton fibers were added thereto, followed by treatment at 98 ° C. for 30 minutes, followed by soaping and drying to prepare antimicrobial fibers. .

Another 0.1% owf aqueous solution of the reactive antimicrobial agent of Formula 4 was made, and sodium carbonate was added thereto to prepare an antimicrobial treatment solution, and then, cotton fibers were added thereto, followed by 30 minutes of treatment at 60 ° C., followed by soaping and drying to prepare antimicrobial fibers. .

The results of testing the antimicrobial properties of the antimicrobial fiber treated as described above are as follows.

Antimicrobial Test

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

1.Test Method: KSK 0693-2001

2. Test strains: 1) Strain 1: Staphylococcus aureus ATCC 6538

              2) Strain 2: Klebsiella pneumoniae ATCC 4352

3. Inoculation concentration: 1) Strain I-1.3 × 10 ⁵ / ml

2) Strain Ⅱ-1.5 × 10 ⁵ pcs / ml

Antimicrobial Test Result of Dyed Antibacterial Fiber division Bacteriostatic reduction (%) Strain I Strain II Example 1 (Formula 2) 99.9 99.9 Example 2 (Formula 3) 99.9 99.9 Example 3 (Formula 4) 99.9 99.9

The present invention forms a covalent bond with natural fibers to impart antimicrobial properties and antifungal properties without affecting the color of the fiber can be produced functional antibacterial fibers.

Claims (5)

Reactive antimicrobial agent characterized in that the reactive group is bonded to a fluoroquinolone antibiotic. The reactive antimicrobial agent according to claim 1, wherein the reactive antimicrobial agent has a structure represented by the following Chemical Formula 1. (Formula 1)

(Wherein A is a reactive group capable of covalent bonding with natural fibers, R ₁ is hydrogen or methyl, R ₂ is ethyl or cyclopropane, and R ₃ is hydrogen or fluorine). The method of claim 1, wherein the fluoroquinolone antibiotics are norfloxacin, Ciprofloxacin, Enoxacin, Lomefloxacin, Sparfloxacin and Reactive antimicrobial agent, characterized in that one species selected from the group consisting of grepafloxacin. [Claim 3] The reactive group of claim 1 or 2, wherein the reactive group capable of covalent bonding with natural fibers is cyanuric chloride group, vinyl sulfone group, and α-bromoacrylamide group. Reactive antimicrobial agent, characterized in that one selected from the group consisting of. The antimicrobial fiber processed by the reactive antimicrobial agent of claim 1.