KR100839514B1 - Antibacterial dyes and a method of preparing the same and antibacterial fiber thereby - Google Patents

Abstract

The present invention relates to an anthraquinone-based antimicrobial dye having a chromophore having an anthraquinone group in a previous step of a fluoroquinolone antibiotic as a powerful antimicrobial reactor, and a method for producing the same.

The antimicrobial dye compound of the present invention is capable of producing various types of dyes by applying various types of chromophores, and is used as a high-quality dye because of its high fastness and clear color tone. Functional antimicrobial fiber products can be prepared that can inhibit the growth and proliferation of microorganisms, prevent infectious diseases, prevent odors, and prevent fiber contamination and embrittlement.

Antibacterial dyes, anthraquinones, romefloxacin, fluoroquinolines, antibacterial fibers.

Description

Antibacterial dyes and a method of preparing the same and antibacterial fiber

The present invention relates to an anthraquinone-based antimicrobial dye having a chromophore having an anthraquinone group attached to a previous step of a fluoroquinolone antibiotic as a powerful antimicrobial reactor, a method for producing the same, and an antimicrobial fiber dyed with the antimicrobial dye.

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 inorganic antibiotics between polymers in the manufacturing stage of synthetic fibers and incorporating them into the fibers, coagulating in the manufacturing stage of regenerated fibers, and finely dispersing the copper compound inside the fibers during the regeneration process, and There is a method of synthesizing a polymer by making an organic copolymer component having antibacterial properties.

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 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 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 and zinc may deteriorate the resin or cause yellowing, which may significantly lower 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, Carpet, interior fibers, etc.) there is a limit that can not be applied.

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 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 to have an antimicrobial dye containing a strong antimicrobial group without the problems of safety, deterioration, yellowing, etc. To provide.

In addition, it provides antibacterial processing to the textile products from the dyeing process, and does not require any additional process for the purpose of antimicrobial, and provides antibacterial fiber that lasts for a long time as long as the dye is decomposed and the color of the knitted fabric is not faded. For other purposes.

In order to achieve the above object, the present invention provides an anthraquinone-based antimicrobial dye having a structure in which a variety of compounds having an anthraquinone group as a chromophore is combined with a previous step of a fluoroquinolone-based antibiotic as a powerful antimicrobial reactor, and a method for preparing the same.

The present invention also provides a functional antimicrobial fiber having both color and antimicrobial properties by dyeing the fiber with the antimicrobial dye.

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 them, they are widely used and can be used as intermediates of dyes such as tetracycline, sulfonamide, and quinolone.

Of these, fluoroquinolone antibiotics are a new broad-spectrum antibiotic with good oral absorption with good tissue penetration and relatively long action time, which have a mechanism of action that binds to DNA and interferes with its replication. It contains a 4-quinolone ring structure and fluorine 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.

Specifically, the present invention is an antimicrobial substance having a mechanism of imparting antimicrobial activity by inhibiting the metabolic function of enzymes in microorganisms among these substances, norfloxacin, ciproflo, which has excellent antimicrobial activity on the dye matrix used for the fiber. Ciprofloxacin, Enoxacin, Lomefloxacin, Perfloxacin, Levofloxacin, Ofloxacin, Sparfloxacin or Grepafloxacin Provided are antibacterial dyes incorporating Fluoro-Quinolone-based antibiotics such as Grepafloxacin.

Norfloxacin

Ciprofloxacin

Enoxacin

Perfloxacin

Ofloxacin

Lomefloxacin

Levofloxacin                     

Sparfloxacin

Grepafloxacin

The antibiotics mentioned above have a structure that can be converted into dyes due to their chemical structure. However, since the dyes for polyester have a low molecular weight structure in order to facilitate the penetration into the fiber under high temperature and high pressure conditions, it is possible to manufacture the dye using the antimicrobial agent having a high molecular weight, but in actual polyester fabric In case of dyeing, it does not penetrate into the fiber and remains on the surface, so it is removed in the washing or room temperature condition and has a problem of increasing the amount of use in order to have an appropriate level of antibacterial activity.

Therefore, in the present invention, the preceding step of the above-mentioned fluoroquinolone antibiotics having antimicrobial activity and small molecular weight can be used as a starting material.

Accordingly, the present invention provides an anthraquinone-based antimicrobial dye in which a chromophore having an anthraquinone group is bonded to a previous step of a fluoroquinolone antibiotic, and an antibacterial fiber dyed using the same.

The prestage material of the fluoroquinolone antibiotic used as the starting material in the present invention is preferably a prestage material of Norfloxacin, a prestage material of Ciprofloxacin, a prestage material of Enoxacin, Lomefloxacin Pre-Stage Material, Perfloxacin Pre-Stage Material, Levofloxacin Pre-Stage Material, Ofloxacin Pre-Stage Material, Sparfloxacin Pre-Stage Material Or a previous step of grepafloxacin.

More preferably, antimicrobial dyes may be synthesized using Lome-1, which is a preliminary substance of Lomefloxacin, which has antibacterial activity and has a low molecular weight.                     

(Formula 1) Lome-1

When Lome-1 (Lome-1) is used as a starting material and various chromophores having an anthraquinone group are combined thereto, an anthraquinone-based antimicrobial dye of Formula 1 is provided.

(Wherein A represents a chromophore having an anthraquinone group, R ₁ is an ethyl group or a cyclopropyl group, and R ₂ is hydrogen or fluorine).

The chromophore having the anthraquinone group is preferably 2-aminoanthraquinone (formula 2), 6-chloro-4,8-diamino-1,5-dihydroxy anthraquinone (formula 3), or 6- Chloro-4,8-diamino-1,5-dihydroxy anthraquinone (formula 4).                     

General formula 2) 2-aminoanthraquinone

6-chloro-4,8-diamino-1,5-dihydroxy anthraquinone

6-chloro-4,8-diamino-1,5-dihydroxy anthraquinone

Furthermore, the chromophore used in the present invention is not limited to the above general formulas 2 to 4, and chromophores having all kinds of anthraquinone groups can be used.

Hereinafter, the manufacturing method of the anthraquinone antimicrobial dye by this invention is demonstrated concretely.                     

After uniformly dispersing the chromophore having Lome-1 (Lome-1, Formula 1) and an anthraquinone group, reacting the dispersion at 90 to 100 ° C. in the presence of pyridine, cooling to room temperature, adding water and stirring After filtration, an anthraquinone-based antimicrobial dye having the structure of Formula 1 may be synthesized.

Specifically, as a preferred embodiment of the present invention, after homogeneously dispersing 2-aminoanthraquinone (2-aminoanthraquinone, Formula 2) as a chromophore having Lome-1 (Lome-1, Formula 1) and an anthraquinone group, After reacting the dispersion in the presence of pyridine at 90 ~ 100 ℃, cooled to room temperature, stirred by adding water and then filtered to synthesize an anthraquinone-based antimicrobial dye having a structure of formula (2).

(Formula 1) Lome-1

General formula 2) 2-aminoanthraquinone

In other words, as a preferred embodiment of the present invention, when the fluoroquinol antibiotic of the preceding step, Lome-1 and chromophore having an anthraquinone group, is reacted under the above conditions, As an anthraquinone-based antimicrobial dye of Formula 2 may be synthesized.

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 Red Antimicrobial Dye of Formula 2

Next, 57.2 parts of Lome-1 (formula 1) and 47.1 parts of 2-aminoanthraquinone were added to 100 ml of DMSO and then uniformly dispersed with stirring. 16.7 parts of pyridine was added to the homogeneously dispersed solution, followed by reaction for 1 hour while maintaining the temperature at 90 to 100 ° C.                     

After the reaction was cooled to room temperature, 150ml of water was added thereto, stirred for about 10 minutes, and filtered to obtain an anthraquinone-based red antibacterial dye having the structure of Chemical Formula 2.

Antimicrobial Evaluation

After adding glacial acetic acid and a dispersant to a 1.0% aqueous solution of the red antimicrobial dye compound obtained as described above, a salt solution was prepared, and then dyed at 130 ° C. for 60 minutes to prepare dyed antimicrobial fibers by soaping and drying.

KS K 0693-2001, the results of the antimicrobial test on the antimicrobial fiber dyed as described above using the antimicrobial test method of the fabric under the following antimicrobial test conditions are shown in Table 1.

Antimicrobial Test Result of Dyed Antibacterial Fiber division Bacteriostatic reduction (%) Strain I Strain II Blank - - Red antibacterial dye 99.9 98.4

Antimicrobial Test

The antimicrobial test conditions for the 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

Antimicrobial dye compound containing a fluoroquinolone-based antimicrobial agent in the molecule according to the present invention is capable of producing various types of dyes by applying a variety of chromophores, high color fastness and clear color to be used as a high-quality dye, using By dyeing the fibers, it shows strong antimicrobial properties, and can inhibit the growth and proliferation of microorganisms, thereby producing functional antimicrobial fiber products that can prevent infectious diseases, prevent odors, and prevent fiber contamination and embrittlement.

In addition, according to the present invention, the antimicrobial processing to be applied to textile products is given from the dyeing process, and an additional process for the purpose of antibacterial is not necessary, and the antimicrobial activity lasts for a long time unless the dye is decomposed to discolor the color of the knitted fabric. It is possible to manufacture antimicrobial fiber products with excellent durability .

Claims (7)

delete delete delete An anthraquinone-based antimicrobial dye having a structure of Formula 1 below. (Formula 1)

(Wherein A represents a chromophore having an anthraquinone group, R ₁ is an ethyl group or a cyclopropyl group, and R ₂ is hydrogen or fluorine). The anthraquinone-based antimicrobial dye according to claim 4, wherein the chromophore is 2-aminoanthraquinone. After homogeneously dispersing Lome-1 and 2-aminoanthraquinone, the dispersion was reacted at 90 to 100 ° C. in the presence of pyridine, and then cooled to room temperature and stirred by adding water. Method for producing an anthraquinone-based antimicrobial dye having a structure of formula (1), characterized in that the filtration after filtering. Antimicrobial fiber dyed with the antimicrobial dye of claim 4.