KR20070113365A - Antimicrobial Fiber Manufacturing Method and Antimicrobial Fiber Using Radiation Graft Polymerization - Google Patents

Abstract

The present invention relates to a method for producing an antimicrobial fiber and an antimicrobial fiber using a radiation graft polymerization method, and more specifically, irradiating the fiber with radiation (step 1); Performing the graft polymerization reaction by adding the appropriate metal salt to the reactor after the radiation of the irradiated fiber and the monomer dissolved in a suitable solvent in the step 1 and bubbling; And a step (step 3) of immersing the fiber polymerized by step 2 in a solution in which the antimicrobial metal ions are dissolved, and the antimicrobial fiber produced thereby.

According to the present invention, it is possible to have an antimicrobial property to the surface or the inside of the fiber according to the degree of radiation graft, it can be usefully used in the medical field by producing a fiber that does not decrease the antimicrobial power even if used for a long time.

Description

Manufacturing method of antibacterial textile using radiation graft polymerization and antibacterial textile}

The present invention relates to an antimicrobial fiber production method and antimicrobial fiber using a radiation graft polymerization method.

A bacterium is a type of microorganism that breaks down organic matter, providing valuable nutrients to plants or breaking down organic matter that other organisms cannot digest. The microorganisms can be broadly divided into bacteria and fungi, bacteria are called bacteria, and fungi are called fungi. Bacteria also include non-pathogenic bacteria that we can eat, such as lactic acid bacteria and fermented bacteria. Fungi include penicillin-producing blue molds, edible mushrooms, and yeasts used for alcohol fermentation. Therefore, bacteria that act negatively on our bodies, that is, pathogenic microorganisms can be said to be the target of antibacterial. Representative bacteria include Escherichia coli causing food poisoning, Staphylococcus aureus causing purulent infection, and Pseudomonas aeruginosa causing bronchial inflammation.

The pathogens can be sterilized using ethylene oxide gas or gamma rays in the polymer material, but they are often contaminated by microorganisms such as bacteria when exposed to the air. For example, when the air conditioner filter is contaminated with bacteria or viruses, the bacteria or viruses may be transmitted during operation of the device to cause diseases in the human body. Until now, most of the methods for making fibers have antimicrobial properties include adding an antimicrobial agent or processing an antimicrobial agent. The former has to be combined with a large amount of antimicrobial agent to exhibit antimicrobial activity, but this is also known to have a weak antimicrobial effect. In addition, spraying the antimicrobial agent on the fiber is effective temporarily, but it is difficult to obtain satisfactory results due to the antimicrobial agent is released from the fiber.

Various alternative attempts have been made to solve the problem of the antimicrobial treatment. For example, introduction of an antimicrobial substance by the graft polymerization method is mentioned. The graft polymerization method is a method of side chain addition of another polymer to the main chain polymer, and is a polymerization method that is distinguished from copolymerization in which two or more polymer monomers are constantly repeated to form a main chain. Radiation, ultraviolet rays, and chemical initiators are used for graft polymerization.However, chemical initiators cannot graft polymerize the fiber without any deformation. This can't be done. On the other hand, radiation is the most effective method because it is possible to homogeneously modify the surface of the polymer material. The radiation graft polymerization method is a method of irradiating a base material with radiation to form a radical functional group, and then bonding a polymer branch called a graft chain to the radical. Radiation graft polymerization has been used to produce high-performance materials because it can impart various properties to materials without compromising its physical properties. Modification of the polymer material by irradiation is also applicable to a case where the radiation cannot easily be processed by a chemical method because it has a characteristic that radiation can easily cause a chemical reaction even in a solid or at a low temperature.

On the other hand, in the prior art of the method for imparting antimicrobial properties to polymer materials, Japanese Patent Application Laid-Open No. 94-242301 discloses a method of applying a mixture of phosphoric acid, calcium hydroxide, aluminum hydroxide and nitric acid to a polymer material, and Japanese Patent Application Laid-Open No. 94-242. 91576 discloses a method of imparting antimicrobial activity by treating nylon 66 with silver colloid, and Japanese Patent Application Laid-Open No. 92-149161 discloses a method of imparting antibacterial property to plastics by coating thiosulfate silver salt with silica gel. . U. S. Patent No. 6,767, 508 also discloses a method of treating an alkyl polyglycoside surfactant to impart antimicrobial properties to a nonwoven fabric.

Furthermore, Korean Patent No. 509790 discloses an antibacterial agent for textiles that can give antimicrobial durability to laundry without yellowing the textile product, and an antimicrobial textile product made by treating with the antibacterial agent for textiles. Patent No. 339776 discloses that an antimicrobial agent has a metal having an antimicrobial activity on an N-long chain acyl amino acid attached to a surface of an inorganic particle or a synthetic resin particle by a hydrophilic organic material or directly attached thereto, and the particle is an N-long chain acyl amino acid ion. A process of contacting with a containing aqueous solution, and a step of contacting the particles with a metal containing aqueous solution having an antimicrobial action after the step is disclosed, the Republic of Korea Patent Publication No. 2005-0094449 discloses the processability of fibers or films blended with an antimicrobial composition An antimicrobial composition that can be improved is disclosed.

However, the method of imparting antimicrobial properties in the prior art is a simple treatment method of antimicrobial materials such as coating, blending and immersing the antimicrobial material on the fiber, and it is difficult to have a firm antimicrobial effect on the fiber, and expects a continuous antimicrobial effect. Difficult to do

Therefore, the present inventors adsorb antimicrobial ions to polypropylene, polyethylene, polypropylene-polyethylene copolymer, nylon, polyester, acrylic synthetic fiber, natural fiber and nonwoven fabric to adsorb acrylic acid or methacrylic acid to make the polymer material have antimicrobial properties. During the study, it was possible to have antimicrobial properties on the surface or inside of these fibers depending on the degree of radiation graft, and thus, the present invention was completed by developing a fiber manufacturing method in which the antimicrobial activity does not decrease even when used for a long time.

An object of the present invention is to provide a method for producing antimicrobial fiber using a radiation graft polymerization method.

The present invention also provides an antimicrobial fiber.

Irradiating the fiber to achieve the above object (step 1); Performing the graft polymerization reaction by adding the appropriate metal salt to the reactor irradiated with the fiber irradiated in step 1 and the monomer dissolved in a suitable solvent, followed by bubbling (step 2); And immersing the fiber polymerized by Step 2 in a solution in which the antimicrobial metal ions are dissolved (Step 3).

Hereinafter, the present invention will be described in detail.

Step 1 according to the present invention is a step of irradiating the fiber with radiation.

As the fiber used in step 1, synthetic fibers such as polypropylene, polyethylene, polypropylene-polyethylene copolymer, nylon, polyester synthetic fiber, acrylic synthetic fiber, or cotton, silk, nonwoven fabric, etc. may be used, and mixed thereof. Fibers can be used.

As the radiation used in step 1, gamma rays, electron beams, X-rays, and the like may be used, and gamma rays may be preferably used.

In addition, the gamma ray is preferably irradiated with 1 ~ 500 k㏉, more preferably may be irradiated with 2 ~ 300 k㏉.

Step 2 according to the present invention is a step of performing a graft polymerization reaction by adding the appropriate metal salt after bubbling the irradiated fiber and the monomer dissolved in a suitable solvent in a reactor.

Irradiation methods that can be used for the radiation graft polymerization of step 2 include irradiating fibers with monomers to cause a graft copolymerization reaction and irradiating radiation and then contacting the monomers to cause the graft copolymerization reaction. have.

The former method has the advantage that the operation is simple and the generated radicals can be used immediately so that the radiation dose is at least. However, there is a problem that a large number of homopolymers of monomers are generated, and therefore, a step of removing homopolymers as well as unreacted monomers after the reaction must be accompanied.

On the other hand, the latter method can be used when the homopolymerization of monomers occurs well or when a relatively large amount of irradiation is required to generate the active site of the fiber. This method can be divided into vacuum pre-irradiation and air pre-irradiation depending on the radiation environment. The vacuum pre-irradiation method is to irradiate the fiber under vacuum to generate radicals after generating radicals, and the pre-irradiation method in the air is to irradiate the sample in the presence of air.

However, in the air pre-irradiation method, peroxides may be generated by oxygen. To prevent this, oxygen may be removed by bubbling with nitrogen. However, since some peroxides may be generated in contact with air (oxygen) during the transfer of the sample to the reaction vessel after irradiation, Ag ⁺ , Fe ^{2 +} , Cu ^{2 +} , Zn ^{2 +} , Ni ^{2 +} , Co ² Metal salts including ⁺ and the like were added, preferably FeSO ₄ 7H ₂ O, FeSO ₄ (NH ₄ ) ₂ SO ₄ 6H ₂ O, FeCl ₂ SO ₄ 4H ₂ O, CuSO ₄ 5H ₂ O and the like. The graft reaction may be performed by adding a metal salt of. The added metal salt can inhibit the homopolymer produced by the OH radicals to be produced by peroxide decomposition with the following mechanism. At this time, the concentration of the metal salt is preferably 1 × 10 ^-2 ~ 1 × 10 ^-4 M.

ROOH ⁺ Fe ² + → RO and ⁺ OH ^- + Fe ³ +

As the monomer in step 2 according to the present invention, a monomer having a sulfonic acid group or a carboxyl group or a monomer capable of introducing the functional group after radiation graft polymerization may be used as a functional group capable of introducing an antimicrobial metal ion. Such monomers include acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, chloromethylstyrene, t-butylstyrene, alpha-methylstyrene, 4-methylstyrene, 2-acrylamido-2-methyl propane sulfonic acid, 2 , 3-epoxyponpropyl methacrylate and the like can be used.

In addition, the solvent used to dissolve the monomer is preferably methanol, ethanol, benzene, propanol, butanol, pentanol, dichloroethane, carbon tetrachloride, xylene, water, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide , Hexane, chloroform, methyl ether, ethyl ether, dioxane, cyclohexanone, n-heptane, methyl ethyl ketone, carbon tetrachloride and the like can be used.

At this time, the concentration of the monomer is preferably 1 to 90% by weight, more preferably 3 to 70% by weight based on the solvent used.

Step 3 according to the present invention is a step of immersing the fiber polymerized by step 2 in a solution in which antimicrobial metal ions are dissolved.

The antimicrobial metal ions may be introduced into the ^{Ag +, Fe 2 +, Cu} 2 +, Zn 2 +, Ni 2 +, Co 2 + and the like. In the method of introducing the metal salt into the graft fiber, the metal salt may be dissolved in a solvent, and the antimicrobial fiber into which the metal ion is introduced may be prepared by immersing the fiber in which the monomer is grafted into the solution. Examples of the metal salts are AgNO _2, FeSO ₄ and 7H ₂ O, CuSO ₄ and _{5H 2 O, (CH 3 COO} ) 2 Zn and _{2H 2 O, (CH 3 COO} ) 2 Ni and 4H ₂ O, CoCl ₂ and 6H ₂ O can be used.

The present invention also provides graft polymerized antimicrobial fibers incorporating antimicrobial metal ions. The fiber may preferably be prepared by an antimicrobial fiber production method using the radiation graft polymerization method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are only illustrative of the present invention, and the content of the present invention is not limited by the following Examples and Experimental Examples.

< Example  1> Preparation of antimicrobial fiber incorporating metal ions

Example 1-1 Preparation of Antimicrobial Fibers Incorporating Silver Ions into a Polypropylene Nonwoven Fabric Grafted with Acrylic Acid

The polypropylene nonwoven fabric produced by Hwang Industrial Co., Ltd. was irradiated with gamma rays for 5 k㏉, and then, this was placed in a small graft reactor, and an acrylic acid solution dissolved in methanol was added to the reactor, and then bubbled with nitrogen to remove oxygen from the solution. To suppress homopolymer formation, 2 × 10 ⁻³ M of FeSO ₄ .7H ₂ O metal salt was added to the graft reaction solution.

The reactor was placed in a bath having a temperature of 30 ° C. and reacted for 2 hours. After the reaction, the polypropylene nonwoven fabric was removed from the test tube, and the homopolymer was removed with distilled water at 60 ° C., followed by drying under reduced pressure. The dried nonwoven fabric was made into 2 × 10 ⁻² M AgNO _2. It was immersed in the solution and the nonwoven fabric which silver ion was introduce | transduced was obtained.

Examples 1-2 to 1-7 Preparation of Antimicrobial Fibers Incorporating Metal Ions in Polypropylene Nonwovens Grafted with Acrylic Acid

A metal salt solution 2 × 10 ^-2 M and of FeSO ₄ 7H ₂ O, CuSO ₄ and _{5H 2 O, (CH 3 COO} ) 2 Zn and _{2H 2 O, (CH 3 COO} ) 2 Ni and 4H ₂ O, and CoCl ₂ 6H ₂ O Except for using the solution, a nonwoven fabric into which iron, copper, zinc, nickel and cobalt ions were introduced was obtained in the same manner as in Example 1-1.

< Example  2> Preparation of Antimicrobial Fibers Incorporating Metal Ions

Example 2-1 Preparation of Antimicrobial Fibers Incorporating Silver Ions into a Polypropylene Nonwoven Fabric Grafted with Styrene

In the same manner as in Example 1-1, the gamma ray was irradiated at 50 k㏉, and a styrene solution dissolved in methanol was used instead of the acrylic acid solution dissolved in methanol, and a single body was removed with benzene instead of distilled water, and then the nonwoven fabric was dried under reduced pressure. It was. The dried nonwoven fabric was made into 2 × 10 ⁻² M AgNO _2. It was immersed in the solution and the nonwoven fabric which silver ion was introduce | transduced was obtained.

Examples 2-2 to 2-7: Preparation of Antimicrobial Fibers Incorporating Metal Ions in a Polypropylene Nonwoven Fabric Grafted with Styrene

A metal salt solution 2 × 10 ^-2 M and of FeSO ₄ 7H ₂ O, CuSO ₄ and _{5H 2 O, (CH 3 COO} ) 2 Zn and _{2H 2 O, (CH 3 COO} ) 2 Ni and 4H ₂ O, and CoCl ₂ 6H ₂ O Except for using the solution, a nonwoven fabric into which iron, copper, zinc, nickel and cobalt ions were introduced was obtained in the same manner as in Example 2-1.

< Comparative example  1>

The polypropylene nonwoven fabric produced by the downstream industry was used without any treatment.

< Comparative example  2>

An acrylic acid-grafted nonwoven fabric was obtained in the same manner except for immersing the dried nonwoven fabric in Example 1-1 in a metal salt.

< Comparative example  3>

A styrene-grafted nonwoven fabric was obtained in the same manner except for immersing the dried nonwoven fabric in the metal salt in Example 2-1.

< Reference Example > Graft rate  Measure

Examples 1-1 to 1-6, 2-1 to 2-6, and Comparative Examples 2 to 3 calculate the difference in weight after graft polymerization for the first sample weight after drying under reduced pressure, and the graft ratio according to Equation 1 below. Was obtained.

* W _g is graft polypropylene nonwoven weight

* W _o is the weight of the polypropylene nonwoven fabric before the graft reaction

 The graft ratios of Examples 1-1 to 1-6 and Comparative Example 2 were 97% (6.94 COOH / g mmol), and Examples 2-1 to 2-6 and Comparative Example 3 were 96.7%.

In addition, the amounts of the metal ions introduced in Examples 1-1 to 1-6 and 2-1 to 2-6 are shown in Table 1 below.

< Experimental Example  1> with acrylic acid Grafted  Antimicrobial Evaluation on Polypropylene Nonwovens

Experimental Example 1-1: Evaluation of antimicrobial activity against Escherichia coli

The antimicrobial activity of the nonwoven fabrics prepared in Examples 1-1 to 1-6 and Comparative Examples 1 to 2 for E. coli were evaluated. E. coli was incubated at 36 ° C. for 24 hours in liquid medium (peptone 5.0 g / l, beef extract 3.0 g / l, pH 6.8). After immersing 0.145 g of the nonwoven fabrics of Examples 1-1 to 1-6 and Comparative Examples 1 to 2 in 5 ml of E. coli culture solution, the number of Escherichia coli was confirmed at regular intervals. Check how the number of E. coli are then collected suspension 1 ㎖ of the cells in vitro into a 9 ㎖ sterile diluted 10-fold, diluted 10 ⁸ times this operation is repeated a suitable number of times, and applied to the plate medium at 36 ℃ 1 After one culture, the colony count of Escherichia coli was calculated, and the antimicrobial activity was investigated. The results are shown in Table 2 below.

As shown in Table 2, Examples 1-1, 1-2, and 1-3 were observed to kill E. coli. From this, it can be seen that the polypropylene nonwoven fabric grafted with acrylic acid containing silver, iron or copper prepared by the present invention exhibits excellent antibacterial effect against Escherichia coli.

Experimental Example 1-2: Antimicrobial Evaluation of Staphylococcus

The antimicrobial properties of the nonwoven fabrics prepared in Examples 1-1 to 1-6 and Comparative Examples 1 to 2 against Staphylococcus were examined by the same method as Experimental Example 1-1, and the results are shown in Table 3 below. .

As shown in Table 3, Examples 1-1, 1-2, 1-3, 1-4, and 1-5 killed staphylococcus. Among them, Examples 1-1 to 1-3 showed high antimicrobial activity against Staphylococcus aureus. From this, it can be seen that the polypropylene nonwoven fabric grafted with acrylic acid into which silver, iron or copper ions are prepared according to the present invention exhibits excellent antibacterial effect against Staphylococcus aureus.

Experimental Example 1-3: Antimicrobial Evaluation of Pseudomonas Aeruginosa

The antimicrobial properties of the nonwoven fabric prepared according to Examples 1-1 to 1-6 and Comparative Examples 1 to 2 against Pseudomonas aeruginosa in the same manner as in Experimental Example 1-1 were investigated, and the results are shown in Table 4 below.

As shown in Table 4, Examples 1-1, 1-2, 1-3, 1-4, and 1-5 killed Pseudomonas aeruginosa. In particular, Examples 1-1 to 1-3 showed high antimicrobial activity against Pseudomonas aeruginosa. From this, it can be seen that the polypropylene nonwoven fabric grafted with acrylic acid into which silver, iron or copper ions are prepared according to the present invention exhibits excellent antibacterial effect against Pseudomonas aeruginosa.

< Experimental Example  2> With styrene Grafted  Antimicrobial Evaluation on Polypropylene Nonwovens

Experimental Example 2-1: Evaluation of antimicrobial activity against Escherichia coli

The antimicrobial properties of the nonwoven fabrics prepared in Examples 2-1 to 2-6 and Comparative Examples 1 and 3 for E. coli in the same manner as in Experimental Example 1-1 were investigated, and the results are shown in Table 5 below.

As shown in Table 5, Examples 2-1, 2-2 and 3-3 were observed to kill E. coli. In particular, Examples 2-1 and 2-2 showed high antibacterial activity against Escherichia coli. From this, it can be seen that the polypropylene nonwoven fabric grafted with styrene introduced with silver or iron prepared by the present invention exhibits excellent antibacterial effect against Escherichia coli.

Experimental Example 2-2: Evaluation of antimicrobial activity against staphylococci

The antimicrobial activity of the nonwoven fabrics prepared in Examples 2-1 to 2-6 and Comparative Examples 1 and 3 for Staphylococcus aureus was examined in the same manner as in Experimental Example 1-1, and the results are shown in Table 6 below.

As shown in Table 6, Examples 2-1, 2-2, 2-3, 2-4 and 2-5 killed staphylococcus. In particular, Examples 2-1 and 2-2 showed high antimicrobial activity against Staphylococcus aureus. From this, it can be seen that the polypropylene nonwoven fabric grafted with styrene introduced with silver or iron ions produced by the present invention exhibits excellent antibacterial effect against Staphylococcus aureus.

Experimental Example 2-3: Antimicrobial Evaluation of Pseudomonas Aeruginosa

The antimicrobial properties of the nonwoven fabrics prepared in Examples 2-1 to 2-6 and Comparative Examples 1 and 3 for Pseudomonas aeruginosa in the same manner as in Experimental Example 1-1 were investigated, and the results are shown in Table 7 below.

As shown in Table 7, Examples 2-1, 2-2, 2-3, 2-4 and 2-5 killed Pseudomonas aeruginosa. In particular, Examples 1-1 to 1-3 showed high antimicrobial activity against Pseudomonas aeruginosa. From this, it can be seen that the polypropylene nonwoven fabric grafted with styrene introduced with silver, iron or copper ions prepared by the present invention exhibits excellent antibacterial effect against Pseudomonas aeruginosa.

According to the present invention, it is possible to have an antimicrobial property to the surface or the inside of the fiber according to the degree of radiation graft, it can be usefully used in the medical field by producing a fiber that does not decrease the antimicrobial power even if used for a long time.

Claims (10)

Irradiating the fiber with radiation (step 1); Performing the graft polymerization reaction by adding the appropriate metal salt to the reactor after the radiation of the irradiated fiber and the monomer dissolved in a suitable solvent in the step 1 and bubbling; And  Method of producing an antimicrobial fiber using a radiation graft polymerization method comprising the step (step 3) of immersing the fiber polymerized by the step 2 in a solution in which antimicrobial metal ions are dissolved. According to claim 1, wherein the fiber of step 1 is any one kind of synthetic fibers or cotton, silk, selected from the group consisting of polypropylene, polyethylene, polypropylene-polyethylene copolymer, nylon, polyester synthetic fibers and acrylic synthetic fibers And any one or a mixture of these fibers selected from the group consisting of nonwoven fabrics. The method of claim 1, wherein the radiation of step 1 is any one selected from the group consisting of gamma rays, electron beams and X-rays. The method of claim 3, wherein the radiation is gamma rays, characterized in that the antimicrobial fiber manufacturing method using a radiation graft polymerization method. The method of claim 4, wherein the gamma radiation dose is 1 ~ 500 kPa, Antimicrobial fiber production method using a radiation graft polymerization method. The method of claim 1, wherein the monomer of step 2 is a functional group capable of introducing the metal ion of step 3 is a monomer having a sulfonic acid group or a carboxyl group or a monomer capable of introducing the functional group after radiation graft polymerization Method for producing antimicrobial fiber using radiation graft polymerization method. The method of claim 6, wherein the monomer is acrylic acid, methacrylic acid, vinyl sulfonic acid, vinyl phosphonic acid, chloromethyl styrene, t-butyl styrene, alpha-methyl styrene, 4-methyl styrene, 2-acrylamido-2-methyl A method for producing an antimicrobial fiber using a radiation graft polymerization method, characterized in that it is any one selected from the group consisting of propane sulfonic acid and 2,3-epoxyponpropyl methacrylate. The method of claim 1, wherein the suitable solvent used to dissolve the monomer of step 2 is methanol, ethanol, benzene, propanol, butanol, pentanol, dichloroethane, carbon tetrachloride, xylene, water, dimethylformamide, tetrahydrofuran , Dimethyl sulfoxide, hexane, chloroform, methyl ether, ethyl ether, dioxane, cyclohexanone, n-heptane, methyl ethyl ketone, carbon tetrachloride, any one selected from the group consisting of Antimicrobial fiber production method using the polymerization method. According to claim 8, wherein the concentration of the monomer is antimicrobial fiber production method, characterized in that 1 to 90% by weight based on the solvent used. According to claim 1, wherein the antimicrobial metal ion of step 3 is characterized in that any one or more selected from the group consisting of Ag ⁺ , Fe ^{2 +} , Cu ^{2 +} , Zn ^{2 +} , Ni ²⁺ and Co ^{2 +} . Method for producing antimicrobial fiber using radiation graft polymerization method.