KR101134507B1 - Process Of Producing Polyester Fiber Containing Antimicrobial Through Melt?Blending Method - Google Patents

Abstract

In the present invention, the polyester resin in a chip state is evenly mixed with an antimicrobial agent at a ratio of 90:10 to 99: 1 by weight, and then melt blended at 120 to 265 ° C. using a melting apparatus to produce pellets, and then spun with a melt spinning machine. The present invention relates to a method for producing an antimicrobial-containing polyester fiber using a melt blending method, characterized in that phase separation during filament manufacturing through blending and melt spinning with a polyester-based resin using an antimicrobial agent having excellent heat resistance. It is possible to provide a polyester filament that does not occur, the mechanical properties such as the elongation of the filament to be produced can be excellently expressed, and the antibacterial effect can be effectively maintained for a long time.

Polyester resin, antibacterial agent, blending, melt spinning

Description

Process of Producing Polyester Fiber Containing Antimicrobial Through Melt? Blending Method}

The present invention relates to a method for producing polyester fibers containing antimicrobial agents, and more particularly, to a method of melt spinning polyester fibers containing antimicrobial agents using a melt blending method.

The fibrous material has a problem in that it is easy to attach various bacteria due to its large surface area. Attachment of such bacteria forms a biofilm on the fiber surface and leads to infection, which may cause problems such as inflammation and additional surgery. In particular, about 250,000 cases of artificial blood vessels are performed annually in the United States. Despite the strict sterile environment of the operating room and the use of antibiotics during surgery, about 2-6% of all cases have been infected. About half of them are dying. Therefore, it is necessary to develop a medical fiber having antimicrobial properties loaded with an antimicrobial agent in order to suppress infection by harmful bacteria when the medical fiber is applied to the human body.

In addition, it is necessary to secure a fabric material manufacturing technology that differentiates the structure and performance of each use for the manufacture of medical devices such as various implants for use in the human body, and implants for artificial blood vessels. In addition, non-toxic polyester material as a material used in the human body is urgently needed. Such non-toxic medical textile materials can expand the development potential of the textile industry.

 Antibacterial agents such as quinolone, which are widely used in medical fibers having antimicrobial properties loaded with such antimicrobial agents, have excellent antimicrobial effects against Gram-positive bacteria and negative bacteria, and their structure is similar to that of disperse dyes. It was possible to impart antimicrobial activity to textile products. In the case of imparting antimicrobial properties to textile products by the post-treatment process such as color rendering method, there was a problem that antimicrobial properties may be reduced by frequent washing of textile products.

 On the other hand, Korean Patent Publication No. 10-2007-0032951 provides a pharmaceutical active polymer compound that provides antimicrobial activity in vivo, the pharmaceutical active polymer is provided using a step polymerization method. In the prior art, there is provided a pharmaceutically active polymer compound in a copolymerization method, which has a problem of deterioration of polymer properties along with high cost.

Therefore, in the present invention, in applying an antimicrobial material having excellent antimicrobial effect against Gram-positive bacteria and negative bacteria to a polyester-based fiber material, it is possible to minimize the deterioration of the efficacy even by washing without degrading the properties of the fiber material. It is technical to manufacture antimicrobial fiber by using melt blending method so that antimicrobial substance is eluted quickly when applied to human body embedding fiber such as implant or medical fiber such as wound protection agent, so that antimicrobial effect does not appear only at the beginning and lasts for a long time. It is a task.

According to the present invention, a polyester resin in a chip state is evenly mixed with an antimicrobial agent at a ratio of 90:10 to 99: 1 by weight, and then melt blended at 120 to 265 ° C. using a melting apparatus to produce pellets, followed by a melt spinning machine. Provided is a method for producing an antimicrobial-containing polyester fiber using a melt blending method, characterized in that it is spun to.

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

The method for producing the antimicrobial-containing polyester fiber of the present invention is a method to have a significantly improved antimicrobial sustaining effect as compared to the method of immersing the polyester fiber in the conventional antimicrobial solution. It is a method of melt spinning by melt blending a resin and an antibacterial agent.

First, the antimicrobial agent used in the method for producing the antimicrobial-containing polyester fiber of the present invention is any one of a tetracycline-based, quinolone-based, biguanide-based and triclosan-based antimicrobial agents. It is preferable to use, and in particular, the quinolone-based antimicrobial agent in the present invention is particularly preferably used cyprofloxacin of the formula (1).

[Formula 1]

The cyprofloxacin can be confirmed that the melting occurs at about 145 ℃ as in the DSC analysis of Figure 1, because the thermal decomposition occurs at 300 ℃ or more in the TGA analysis of Figure 2 has excellent thermal stability of the antimicrobial structure It is suitable for melt spinning by blending with polyester resin in pellet state because it does not cause deformation or deterioration of antibacterial effect.

The polyester resin may be any one of polyethylene terephthalate, poly ( p- dioxanone), polyglycolide (poly (glycolide)), and poly (L-lactide). It is preferable to use.

The melting temperature of the polyester resin is poly ( p- dioxanone) 110 ° C. (PDO), polylactide (poly (L-lactide) 175 ° C. (PLA) as shown in FIG. 4. Poly (glycolide) is 225 ° C (PGA) and polyethylene terephthalate is around 275 ° C (PET).

In the present invention, the polyester resin in a chip state is evenly mixed with a powdery quinolone antibacterial agent in a ratio of 90:10 to 99: 1 by weight, and then melt blended at 120 to 265 ° C. using a melting apparatus to produce pellets. After filament is produced by spinning with a melt spinning machine.

When the cyprofloxacin is contained in 1 ~ 10% of the total weight of the filament, the melt temperature of the polyester resin is lowered and melt-blended at 120 ~ 265 ℃, which is the crosslinking of the polyester material This is because the action is reduced. In addition, the melting temperature of cyprofloxacin and polyester resin blends did not appear separately between the cyprofloxacin and polyester materials, but between the melting temperatures of cyprofloxacin and polymer materials. It is excellent in compatibility (phase) does not occur during filament manufacturing, mechanical properties such as the elongation of the filament to be produced can be excellently expressed.

As in the present invention, the antimicrobial agent-containing polyester fiber obtained by blending a polyester resin and an antimicrobial agent by melt spinning has a feature that the antimicrobial agent elutes very slowly from the fiber and thus the antimicrobial effect can be maintained for a very long time.

According to the present invention, a phase separation does not occur when filament is manufactured through blending and melt spinning with a polyester resin using an antibacterial agent having excellent heat resistance, and mechanical properties such as elongation of the filament to be manufactured can be excellently expressed, and antibacterial effect It was possible to provide a polyester filament which can be kept effective for a long time.

The following examples are given as non-limiting examples of the method for producing the antimicrobial agent-containing polyester fibers of the present invention.

EXAMPLES 1-4

1. Samples and Reagents

Commercially available quinolone antibacterial agent, Cyprofloxacin of Chemical Formula 1 was used as it is without purification, and as polyester-based materials, PET (polyethylene terephthalate: Example 1), PDO (poly ( p −) dioxanone): Example 2), PGA (poly (glycolide): Example 3), PLA (poly (L-lactide): Example 4) were used, respectively.

[Formula 1]

2. Antibacterial Melt Blending

PET, PDO, PLA, and PGA resins in a chip state were evenly mixed with Ciprofloxacin in a ratio of 9: 1 by weight, respectively, and then each resin shown in FIG. Melt blended at a temperature of about 10 ° C. higher than the melting temperature to prepare pellets having a diameter of 10 mm and a thickness of 1 mm.

3. Preparation of Antimicrobial-Containing PET Fibers

The pellets were supplied with a melt spinning machine to prepare an unstretched PET fiber containing antibacterial agent.

[Comparative Examples 1-3]

After preparing an antimicrobial solution in which Cyprofloxacin was dissolved at a concentration of 5 mg / ml in 0.2% HCl aqueous solution, 80 minutes of pick-up after immersing the PET fabric in the antimicrobial solution for about 10 minutes. Padded) and washed with water at 210 ° C. for 2 minutes (Comparative Example 1), 5 (Comparative Example 2), and 10 minutes (Comparative Example 3).

The antimicrobial release behavior was analyzed using a calibration curve prepared in advance by eluting the antimicrobial processed PET fabric for 2 hours at 140 ° C.

The physical properties of the fabric woven from the fiber of the above example and the fabric of the comparative example were measured as follows.

1. Thermal Analysis

Thermal properties of the antimicrobial and polyester materials were evaluated by differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA).

2. Antimicrobial Susceptibility Evaluation

For each sample to an antimicrobial for aureu s Staphylococcus (S. aureus), and Escherichia coli (E. coli) using the disk diffusion method of measuring the disk NCCLS eokjedae length were evaluated for antimicrobial susceptibility.

3. Results and Discussion

1) Thermal Properties of Cyprofloxacin

Cyprofloxacin can be seen that melting occurs at 145 ° C. as in the DSC analysis of FIG. 1. In addition, in the TGA analysis of FIG.

2) Antimicrobial Processing of PET Fiber

Cyprofloxacin has a chemical structure similar to that of a disperse dye, as shown in FIG. 3. Disperse dyes are hydrophobic structures with some polar groups and are mainly used for dyeing hydrophobic fibers such as PET. Therefore, cyprofloxacin is expected to make some bonds with PET fibers by the interaction of hydrogen bonds and polar groups with PET fibers like disperse dyes. Cyprofloxacin aqueous solution exhibits a maximum absorption wavelength at 241 nm and a linear relationship with absorbance at low concentrations to enable quantitative analysis of elution. 3 shows the calibration curve for cyprofloxacin.

In order to confirm the inclusion of cyprofloxacin in the PET fiber, the PET fiber treated under various heat treatment conditions was eluted with cyprofloxacin at 140 ° C. to evaluate the cyprofloxacin content in the PET fiber (Table 1). ) It was confirmed that cyprofloxacin elutes under high temperature conditions. It is thought that the elution of cyprofloxacin is possible because the molecular mobility of the amorphous portion of PET is increased at a temperature above the glass transition temperature (Tg). It can be confirmed that the amount eluted is smaller the higher the elution temperature and the longer the treatment time.

Extraction condition Comparative Example 1 Comparative Example 2 Comparative Example 3 140 ℃, 2 hrs 95.9% 87.2% 68.5%

3) Thermal Properties of Cyprofloxacin / Polyester Composites

Melting temperature of the polyester-based material of the present invention is shown in the vicinity of ~ 110 ℃ (PDO), ~ 175 ℃ (PLA), ~ 225 ℃ (PGA), ~ 275 ℃ (PET) as shown in FIG. Therefore, cyprofloxacin and melt blending were performed at a temperature of about 10 ~ 20 ℃ higher than the melting temperature of each material. PET and PGA with high melting temperatures caused browning due to high temperatures. 5 shows the DSC analysis results of the composite prepared by melt-melt blending with cyprofloxacin and each polyester-based material. It can be seen that the melting temperature of each polyester material is greatly reduced as it contains about 10% of cyprofloxacin. This can be interpreted as the result of cyprofloxacin acting as a plasticizer to reduce the interaction of polyester material. In addition, the melting temperature of the blend did not appear separately between the cyprofloxacin and the polyester material, but between the melting temperature of the cyprofloxacin and the polymer material, so that the compatibility of the antimicrobial agent and the polyester-based polymer material was excellent. Judging.

4) Antimicrobial Activity of Cyprofloxacin / Polyester Composites

The evaluation results of the antimicrobial susceptibility evaluation of S. aureus and E. coli bacteria of the polyester fabric pellet of the present invention prepared by the PET fabric and the melt blending method of padding cyprofloxacin is shown in Figs. 7 and Table 2. In the evaluation of antimicrobial susceptibility, the presence of growth inhibition zone of 22 mm for S. aureus and 18 mm for E. coli is considered to be susceptible to the bacteria. The samples prepared by the padded fabric and the melt blending method exhibited superior antibacterial activity against S. aureus and E. coli , respectively, with inhibition zones of 24 mm and 36 mm or more.

 division S. aureus
Inhibition
Zone (mm) Susceptibility E. coli
Inhibition
Zone (mm) Susceptibility Example 1
(PET) 32 positive 36 positive Example 2
(PGA) 28 positive 36 positive Example 3
(PDO) 36 positive 42 positive Example 4
(PLA) 32 positive 40 positive Comparative Example 1 34 positive 40 positive Comparative Example 2 30 positive 40 positive Comparative Example 3 24 positive 36 positive

5) Characteristics of Cyprofloxacin / PET Fiber

Figure 8 shows a picture of the PET fibers in the unstretched state prepared by the melt spinning method, Figure 9 shows an electron micrograph. When cyprofloxacin was added, some yellowing occurred. As a result of electron microscopic analysis, both antimicrobial phase separation and defects were not found on the surface. Antimicrobial activity also shows excellent results (S 10 and 11) for S. aureus and E. coli , confirming that the use of cyprofloxacin as an antimicrobial agent for the production of antimicrobial PET fibers.

division S. aureus
Inhibition
Zone (mm) Susceptibility E. coli
Inhibition
Zone (mm) Susceptibility Example 1 34 positive 32 positive

1 is a DSC curve of cyprofloxacin, the antimicrobial agent used in the present invention,

Figure 2 is a TGA curve of the antibacterial cyprofloxacin used in the present invention,

3 is a calibration curve for cyprofloxacin,

Figure 4 is a DSC curve of the polyester resin used in the present invention,

5 is a blended DSC curve of the polyester of the present invention and an antimicrobial agent,

6 is S. aureus of polyester pellets Antimicrobial susceptibility evaluation results for bacteria (① PET fabric (210 ℃, 10 min.), ② PET fabric (210 ℃, 5 min.), ③PET fabric (210 ℃, 2 min.), ④ PGA, ⑤ PDO, ⑥ PLA, ⑦ PET),

Figure 7 shows the results of evaluation of antimicrobial susceptibility to E. coli bacteria of polyester pellets (① PET fabric (210 ℃, 10 min.), ② PET fabric (210 ℃, 5 min.), ③ PET fabric (210 ℃, 2 min.), ④ PGA, ⑤ PDO, ⑥ PLA, ⑦ PET.),

8 is a photograph of the antimicrobial agent-containing polyester fiber of the present invention,

9 is an SEM image of the antimicrobial agent-containing polyester fiber of the present invention (a: × 100; b: × 500; c: × 1000),

10 is a photograph showing the inhibition zone for S. aureus bacteria of the antimicrobial agent-containing polyester fiber of the present invention,

Figure 11 is a photograph showing the inhibition zone for E. coli bacteria of the antimicrobial agent-containing polyester fiber of the present invention.

Claims (5)

Chip-like polyester resin is mixed evenly with the quinolone antibacterial agent of the formula (1) in a ratio of weight ratio of 90:10 ~ 99: 1, melt blended at 120 ~ 265 ℃ using a melting apparatus to produce a pellet form and then melt A method for producing an antimicrobial-containing polyester fiber using a melt blending method, characterized in that the spinning with a spinning machine. [Formula 1]

delete delete The method of claim 1, wherein the polyester resin is polyethylene terephthalate, poly ( p- dioxanone), polyglycolide (poly (glycolide)), poly (L-lactide) Method for producing an antimicrobial-containing polyester fiber using a melt blending method, characterized in that any one of). An antimicrobial-containing polyester fiber prepared by melt spinning by the method of claim 1 or 4.

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