KR101187276B1 - Antibacterial Finish Of Polypropylene fabrics Using Cardanol Antibacterial-agents - Google Patents
Antibacterial Finish Of Polypropylene fabrics Using Cardanol Antibacterial-agents Download PDFInfo
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
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- D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
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- D06M15/70—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
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Abstract
본 발명은 폴리프로필렌섬유의 항균가공방법에 관한 것으로서 보다 상세하게는 천연물로서 인체에 유해하지 않고 성능이 우수한 카다놀을 이용한 항균가공방법에 관한 것이다. 본 발명에 의해 소수성의 카다놀을 수중에 안정하게 유화하는 기술을 확보하고 또한 폴리프로필렌섬유에 처리된 후 카다놀 성분이 세탁에 의해 섬유로부터 떨어져 나가지 않고 섬유상에 잔류하여 지속적으로 항균기능성을 나타낼 수 있도록 세탁견뢰도를 향상시킬 수 있었다.The present invention relates to an antimicrobial processing method of polypropylene fiber, and more particularly, to an antimicrobial processing method using cardanol having excellent performance as a natural product and not harmful to a human body. According to the present invention, a technique of stably emulsifying hydrophobic cardanol in water is secured, and after being treated to polypropylene fiber, the cardanol component can remain on the fiber without being separated from the fiber by washing, thereby exhibiting antibacterial function continuously. So that the laundry fastness could be improved.
Description
본 발명은 폴리프로필렌섬유의 항균가공방법에 관한 것으로서 보다 상세하게는 천연물로서 인체에 유해하지 않고 성능이 우수한 카다놀을 이용한 항균가공방법에 관한 것이다. The present invention relates to an antimicrobial processing method of polypropylene fiber, and more particularly, to an antimicrobial processing method using cardanol having excellent performance as a natural product and not harmful to a human body.
기능성 섬유소재의 개발은 합성 섬유에 흡수, 흡습성을 부여하고 보다 천연섬유에 가깝게 만들려는 노력으로부터 시작되었는데, 현재에는 천연섬유 이상의 흡수, 흡습 성능을 가진 합성섬유가 계속 개발되고 있다. 특히, 생활안전과 기능성 및 건강과 관련된 기능성 섬유는 점차적으로 그 수요가 늘어나고 있으며, 수요대체를 위한 새로운 기능성 섬유의 개발도 지속적으로 이루어지고 있으며, 최근 색채, 외관 등인 감성과 더불어 기능성에 대한 관심을 보이는 소비자의 추세를 반영하기 위한 고부가가치형 복합 기능성 섬유 제품이 요구되고 있다.The development of functional fiber materials began with efforts to give absorbent and hygroscopic properties to synthetic fibers and to bring them closer to natural fibers. Currently, synthetic fibers having more absorbent and hygroscopic properties than natural fibers are being developed. In particular, functional fiber related to life safety, functionality and health is gradually increasing in demand, and development of new functional fiber for replacement of demand is being made continuously. There is a need for high value added multifunctional fiber products to reflect the trend of visible consumers.
이러한 요구에 부응하여 현재 각광받고 있는 폴리프로필렌 필라멘트는 강도가 우수하며, 혼방성이 좋은 소수성 필라멘트로서, 다른 합성필라멘트와는 달리, 동일한 중량의 원단일지라도 비중이 낮으므로 벌키(bulky)성이 우수하고, 흡수율이 매우 낮아 피부를 항상 건조한 상태를 유지하여 운동 중이나 후에도 항상 쾌적함을 유지할 수 있으며, 또한 천연/합성 필라멘트를 통틀어 가장 낮은 열전도율로 인하여 열손실이 적고, 이로 인해 체온을 일정하게 유지시켜 주게 되고, 수분이 필라멘트 내부로 침투하지 않게 되므로 그냥 흔들어 떨어뜨려 제거할 수 있게 되며, 세탁이 용이하며 건조 속도가 빨라 의류용이나 홈인테리어용으로 각광받고 있다.Polypropylene filament, which is currently in the spotlight in response to such demands, is excellent in strength and blended hydrophobic filament. Unlike other synthetic filaments, the specific weight is low even in the fabric of the same weight, so the bulky property is excellent. It has a very low absorption rate, so it keeps your skin dry all the time and keeps your comfort even after exercise.Also, the heat loss is low due to the lowest thermal conductivity throughout the natural / synthetic filament, which keeps the body temperature constant. As moisture does not penetrate into the filament, it can be removed simply by shaking it off. It is easy to wash and has a fast drying speed.
또한, 세균, 곰팡이, 박테리아 등이 서식할 수 있는 환경을 제공하지 않으며, 비활성의 폴리머이므로 냄새, 핏자국, 얼룩, 화학약품 등에 반응하지 않으며, 정전기에 대해서도 매우 안정적이다.In addition, it does not provide an environment in which bacteria, fungi, bacteria, etc. can inhabit, and because it is an inert polymer, it does not react to odors, blood stains, stains, chemicals, etc., and is very stable against static electricity.
이러한 폴리프로필렌계 섬유의 기능성 가공의 연구개발은 지속적으로 이루어지고 있는데, 특히, 인체유해 미생물로부터 인체를 보호하기 위한 목적을 실현하기 위해서 항균성을 지속적으로 부여하는 기술이 요구되고 있다.The research and development of the functional processing of such polypropylene fiber has been made continuously, in particular, in order to realize the purpose for protecting the human body from harmful microorganisms, there is a demand for a technology that continuously gives antimicrobial properties.
항균제는 합성항균제와 천연항균제로 나뉘고, 합성항균제로는 4급 암모늄염계, 유기금속계, 페놀계 등이 주류를 이루지만 이러한 합성항균제는 세포독성이 커서 항균성능은 우수하지만 사용량에 있어서 제한적이다. 천연항균제로는 다양한 것들이 있을 수 있지만 가격이 비싸고 항균성능이 떨어지며, 견뢰도가 낮아 성능대비 경제성이 우수하지 않다. 따라서 최근 웰빙트랜드에 부응하여 폴리프로필렌섬유의 항균가공에 있어서 천연물로서 인체에 유해하지 않고 성능이 우수한 항균가공의 필요성이 특히 요구되고 있다.Antibacterial agents are divided into synthetic antibacterial agents and natural antimicrobial agents. Synthetic antimicrobial agents are mainly composed of quaternary ammonium salts, organometallic compounds, and phenolic compounds. However, these antimicrobial agents have high cytotoxicity and are limited in usage. Natural antimicrobial agents can be a variety of things, but the price is expensive, the antibacterial performance is low, and the fastness is not excellent economic performance compared to performance. Therefore, in order to meet the well-being trend recently, the necessity of antimicrobial processing excellent in performance as a natural product in the antimicrobial processing of polypropylene fiber is excellent.
천연항균제로서는 카다놀이 최근 각광을 받고 있는데, 옻나무과에 속하는 캐슈너트의 추출물성분 중의 하나인 카다놀은 천연의 방수, 방부, 방충작용을 가지는 기능성 물질로서 페놀의 메타위치에 탄소수가 15개인 곁가지를 가지고 있으며, 곁가지의 각지 다른 위치에 mono-, dien-, trien-의 탄소이중결합을 가지는 소수성의 복잡한 구조의 화합물종이다. As a natural antibacterial agent, cardanol has recently been in the spotlight. Cardanol, one of the extracts of the cashew nut belonging to the lacquer family, is a functional substance having a natural waterproofing, antiseptic, and insect repellent effect. It is a compound of hydrophobic complex structure with carbon double bonds of mono-, dien- and trien- at different positions of side branches.
이러한 카다놀이 우수한 항균성을 가지고 있음은 주지의 사실이지만 이러한 카다놀은 물에 용해하지 않는 소수성의 물질이므로 물을 사용하는 섬유공정에 적용하는 것이 불가능하고 섬유에 처리된다 하더라도 카다놀 성분이 세탁에 의해 섬유로부터 떨어져 나가는 세탁견뢰도불량의 문제점이 있었다. It is well known that such cardanol has excellent antimicrobial properties, but since such cardanol is a hydrophobic material that does not dissolve in water, it is impossible to apply it to a fiber process using water, and even if the cardanol component is treated by fiber, There was a problem of poor laundry fastness falling off the fiber.
그러므로 본 발명에서는 이러한 소수성의 카다놀을 폴리프로필렌섬유에 응용하는 기술을 제공함으로써 천연물로서 인체에 유해하지 않고 성능이 우수한 항균기능성 섬유제품을 제조하는 것을 기술적과제로 한다.Therefore, in the present invention, by providing a technology for applying such hydrophobic cardanol to polypropylene fiber, it is a technical task to produce an antimicrobial functional fiber product having excellent performance without being harmful to the human body as a natural product.
이를 해결하기 위해 본 발명에서는 소수성의 카다놀을 수중에 안정하게 유화하는 기술을 확보하고 또한 더불어 섬유에 처리된 후 카다놀 성분이 떨어져 나가지 않고 섬유상에 잔류하여 지속적으로 항균기능성을 나타낼 수 있도록 하는 것을 핵심기술로 한다.In order to solve this problem, the present invention secures a technique of stably emulsifying hydrophobic cardanol in water, and furthermore, after treatment with the fiber, the cardanol component does not fall off and remains on the fiber to continuously exhibit antibacterial function. It is a core technology.
그러므로 본 발명에 의하면, 카다놀 5~20중량%와 폴리에틸렌옥사이드계 계면활성제 5~20중량% 및 잔부로서 물로 이루어진 유화상태의 항균가공액을 준비한 후, 상기 항균가공액을 사용하여 폴리프로필렌섬유를 처리한 후 상온의 물을 사용하여 세정하는 것을 특징으로 하는 카다놀계의 천연항균제를 이용한 폴리프로필렌섬유의 항균가공방법이 제공된다.
Therefore, according to the present invention, after preparing 5 to 20% by weight of cardanol, 5 to 20% by weight of polyethylene oxide surfactant, and the remainder of the antimicrobial processing solution of water, the polypropylene fiber is prepared using the antimicrobial processing solution. Provided is an antimicrobial processing method of polypropylene fiber using cardanol-based natural antimicrobial agent, which is washed with water at room temperature after treatment.
이하 본 발명을 보다 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명은 천연항균제인 카다놀을 이용하여 폴리프로필렌섬유의 항균가공을 하는 방법에 관한 것으로서 소수성의 카다놀을 수중에 안정하게 유화하여 섬유에 대한 처리능을 향상함과 동시에 섬유에 처리된 후 카다놀 성분이 떨어져 나가지 않고 섬유상에 잔류할 수 있도록 하는 항균가공방법에 관한 것이다.The present invention relates to a method for antimicrobial processing of polypropylene fiber using cardanol, a natural antimicrobial agent, which stabilizes emulsified hydrophobic cardanol in water and improves the processing ability of the fiber and is treated on the fiber It relates to an antimicrobial processing method that allows the danol component to remain on the fiber without falling off.
본 발명의 항균가공방법에서 항균제로 사용되는 카다놀은 옻나무과에 속하는 캐슈너트의 추출물성분 중의 하나로서 천연의 방수, 방부, 방충작용을 가지는 기능성 물질로서 페놀의 메타위치에 탄소수가 15개인 곁가지를 가지고 있으며, 곁가지의 각지 다른 위치에 mono-, dien-, trien-의 탄소이중결합을 가지는 공지된 소수성의 복잡한 구조의 화합물종이다. 카다놀은 화학구조내에 긴 탄소수를 가지는 곁가지, 즉 알킬기를 가지고 있으며 이로 인해 아주 높은 소수성이 나타나는데, 이러한 소수성으로 인해 폴리프로필렌 섬유를 포함하는 다양한 소수성의 합성섬유에 대해 친화력을 나타낼 수 있으며, 또한 구조내에 있는 페놀기의 수산기(-OH)는 각종 천연섬유와 수소결합 등을 통해 친화력을 가지게 할 수 있다. Cardanol used as an antimicrobial agent in the antimicrobial processing method of the present invention is a functional substance having a natural waterproof, antiseptic, and insect repellent effect as one of the extract components of the cashew nut belonging to the lacqueraceae, and has a side branch having 15 carbon atoms in the meta position of phenol. It is a known hydrophobic complex compound species having carbon double bonds of mono-, dien- and trien- at different positions of the side branches. Cardanol has a long carbon number in the chemical structure, i.e. an alkyl group, which results in very high hydrophobicity, which can show affinity for various hydrophobic synthetic fibers, including polypropylene fibers. The hydroxyl group (-OH) of the phenol group in it can have affinity through various natural fibers and hydrogen bonds.
상기 카다놀은 물에 용해하지 않는 소수성의 물질이므로 물을 사용하는 섬유공정에 적용하는 것이 불가능하고 섬유에 처리된다 하더라도 카다놀 성분이 세탁에 의해 섬유로부터 떨어져 나가는 문제점이 있으므로 본 발명에서는 소수성의 카다놀을 물에서 안정하게 유화시키기 위하여 최적의 유화제를 선정하였다. Since the cardanol is a hydrophobic material that does not dissolve in water, it is impossible to apply it to a fiber process using water, and even if the fiber is treated, the cardanol component is separated from the fiber by washing. The optimal emulsifier was selected to stably emulsify danol in water.
유화제의 선정에 있어서 중요한 사항은 유화의 안정성만이 아니라 섬유에 처리한 후 유화제는 세탁 등에 의해 제거되더라도 카다놀 성분은 섬유상에 지속적으로 잔류시키는 것이다. 이를 위해서 본 발명에서는 카다놀 5~20중량%와 폴리에틸렌옥사이드계 계면활성제 5~20중량% 및 잔부로서 물로 이루어진 유화상태의 항균가공액을 준비한다. 상기 폴리에틸렌옥사이드계 계면활성제가 5중량%미만이면 블렌딩 현상이 발생하여 수용성화되지 못해 섬유용 조제로써 사용할수 없는 문제점이 있고, 20중량%를 초과하는 경우에는 친수성부여에 저해가 될 수 있다.An important point in the selection of emulsifiers is that not only the stability of the emulsifier but also the emulsifier after the treatment on the fiber is continuously retained on the fiber even if the emulsifier is removed by washing or the like. To this end, in the present invention, 5 to 20% by weight of cardanol, 5 to 20% by weight of polyethylene oxide-based surfactant, and the remainder are prepared in an emulsified antimicrobial solution composed of water. If the polyethylene oxide-based surfactant is less than 5% by weight, there is a problem in that the blending phenomenon is not so water-soluble and can not be used as a preparation for the fiber, if it exceeds 20% by weight may be impaired hydrophilicity.
섬유에 처리된 카다놀은 자체의 친화력으로 섬유에 잔류할 수 있으나, 사용된 계면활성제는 수용성이므로 세정시 물에 용해되어 제거됨으로써 결국 섬유상에는 카다놀만이 잔류하게 된다. 그러나 본 발명에서는 카다놀과 폴리에틸렌옥사이드계 계면활성제의 양호한 유화상태를 통해 카다놀의 긴 알킬 곁가지가 섬유의 구조내부로 침투하여 섬유속에 깊숙이 들어감으로써 세정시 제거되지 않도록 할 수 있는데, 이러한 효과는 소수성 섬유인 폴리프로필렌섬유에서 더욱 크게 나타난다. 경우에 따라서는 프로판올(propanol) 또는 부탄올(butanol)을 카다놀 100중량부 대비 5~10중량부 추가하여 유화를 보다 원활히 할 수 있다.The cardanol treated on the fiber may remain on the fiber with its own affinity, but since the surfactant used is water-soluble, it is dissolved in water and removed during washing, so that only cardanol remains on the fiber. However, in the present invention, through the good emulsification state of the cardanol and polyethylene oxide surfactant, the long alkyl side branch of the cardanol can penetrate into the structure of the fiber and go deep into the fiber to prevent it from being removed during cleaning. It is larger in polypropylene fibers, which are fibers. In some cases, propanol or butanol may be added to 5 to 10 parts by weight based on 100 parts by weight of cardanol to more easily emulsify.
본 발명에서 상기 항균가공액을 사용하여 섬유를 처리하는 공정은 침염법과 패딩법을 사용할 수 있는데, 먼저 침염법의 경우에는 섬유중량대비 5~20배의 항균가공액을 사용하여 섬유를 침지시키고 40~130℃에서 30~60분간 처리하며, 패딩법의 경우에는 섬유중량대비 5~100배의 항균가공액을 사용하여 섬유를 패딩하고 105~180℃에서 5~20분간 처리한다. 상기 처리가 완료된 폴리프로필렌섬유는 상온의 물을 사용하여 세정하여 계면활성제성분을 제거하게 된다.In the present invention, the process of treating the fiber using the antimicrobial processing liquid may be used by the dyeing method and the padding method. Treated for 30 ~ 60 minutes at ~ 130 ℃, in the case of the padding method, the fiber is padded using an antibacterial processing solution of 5 to 100 times the weight of the fiber and treated for 5 to 20 minutes at 105 ~ 180 ℃. The treated polypropylene fiber is washed with water at room temperature to remove the surfactant component.
본 발명에서 사용되는 항균제인 카다놀은 소수성이므로 근본적으로 물을 이용한 세정공정에 대해서는 내구성이 어느 정도 확보되지만 지속적인 내구성은 약하다. 이러한 장시간에 대한 내구성의 향상을 위해 추가적인 바인더와 가교제를 사용하여 섬유에 대한 친화력의 향상과 함께 내구성의 향상을 이룰 수 있다. Cardanol, which is an antimicrobial agent used in the present invention, is hydrophobic, and thus, it is fundamentally secured to some extent with respect to a washing process using water, but its durability is weak. In order to improve durability for such a long time, an additional binder and a crosslinking agent may be used to improve the durability and the affinity for the fiber.
본 발명에서는 상기 항균가공액에 항균가공액 100 중량부 대비 아크릴계바인더 1~10중량부 및 가교제 0.5~2중량부를 추가하여 혼합한 항균가공액을 제조하여 폴리프로필렌섬유에 처리한 후 일정조건에서 열처리함으로써 소수성의 카다놀이 바인더와 가교제에 의해 섬유에 완전고착되도록 하여 카다놀의 내구성은 크게 향상되어 견뢰도가 향상된다. In the present invention, by adding 1 ~ 10 parts by weight of acrylic binder and 0.5 ~ 2 parts by weight of crosslinking agent to 100 parts by weight of the antimicrobial processing solution to prepare a mixed antimicrobial processing solution and heat treatment at a certain condition after treatment to polypropylene fiber As a result, the hydrophobic cardanol binder and the crosslinking agent are completely adhered to the fiber, and the durability of the cardanol is greatly improved and the fastness is improved.
본 발명에서 폴리프로필렌섬유는 경우에 따라서는 타섬유와 혼방을 한 것을 사용할 수도 있겠는데, 면, 레이온과 같은 음이온성을 가지는 섬유와 양모, 실크, 아크릴과 같은 양이온성을 가지는 섬유에 따라 상기 항균가공액의 처방을 조절할 수 있다. 음이온성을 가지는 섬유, 즉, 면 또는 레이온과의 혼방에서는 이온계 계면활성제를 항균가공액에 추가하는 것이 바람직하며, 양이온성을 가지는 섬유, 즉 양모, 실크, 아크릴 중 어느 하나와의 혼방에서는 음이온계 계면활성제를 추가하는 것이 바람직하다. 추가되는 양은 카다놀 100중량부 대비 0.1~0.3중량부가 바람직하다. In the present invention, the polypropylene fiber may be mixed with other fibers in some cases, but the antibacterial fiber according to the fiber having anionic properties such as cotton and rayon and cationic fibers such as wool, silk, and acrylic Prescription of the processing liquid can be adjusted. In blends with anionic fibers, ie cotton or rayon, it is preferable to add an ionic surfactant to the antimicrobial processing liquid, and in blends with any one of cationic fibers, ie wool, silk or acrylic, anion It is preferable to add a surfactant. The amount added is preferably 0.1 to 0.3 parts by weight relative to 100 parts by weight of cardanol.
따라서 본 발명에 의하여 소수성의 카다놀을 수중에 안정하게 유화하는 기술을 확보하고 또한 폴리프로필렌섬유에 처리된 후 카다놀 성분이 세탁에 의해 섬유로부터 떨어져 나가지 않고 섬유상에 잔류하여 지속적으로 항균기능성을 나타낼 수 있도록 세탁견뢰도를 향상시킬 수 있었다.Therefore, according to the present invention, the technology of stably emulsifying hydrophobic cardanol in water is secured, and after treatment with polypropylene fiber, the cardanol component remains on the fiber without being separated from the fiber by washing, and thus exhibits antibacterial function continuously. Wash fastness could be improved.
이하 다음의 실시 예에서는 본 발명의 카다놀계의 천연항균제를 이용한 폴리프로필렌섬유의 항균가공방법에 대한 비한정적인 예시를 하고 있다.The following examples are given as non-limiting examples of the antimicrobial processing method of polypropylene fiber using the cardanol-based natural antibacterial agent of the present invention.
[실시예 1] Example 1
카다놀 100g과 폴리에틸렌옥사이드계 계면활성제 50g을 상온에서 교반혼합하고, 여기에 물 850g을 추가하여 교반하여 유화상태의 항균가공액을 준비한 후, 섬유중량대비 10배의 상기 항균가공액에 폴리프로필렌직물을 침지시키고 80℃의 온도에서 50분간 처리한 후 상온의 물을 사용하여 충분히 세정함으로써 카다놀만 섬유상에 남기고 계면활성제 성분은 모두 제거하여 항균가공을 완료하였다.
100 g of cardanol and 50 g of polyethylene oxide-based surfactant are stirred and mixed at room temperature, and 850 g of water is added thereto, followed by stirring to prepare an emulsified antimicrobial solution, and a polypropylene fabric is added to the antimicrobial solution 10 times the fiber weight. After immersing and treating for 50 minutes at a temperature of 80 ℃ and thoroughly washed with water at room temperature to leave on the cardanolman fiber only to remove all surfactant components to complete the antibacterial processing.
[실시예 2] [Example 2]
카다놀 100g과 폴리에틸렌옥사이드계 계면활성제 50g을 상온에서 교반혼합하고, 여기에 물 850g을 추가하여 교반하여 유화상태의 항균가공액을 준비한 후, 섬유중량대비 100배의 상기 항균가공액을 사용하여 폴리프로필렌직물을 패딩하고 160℃의 온도에서 10분간 처리한 후 상온의 물을 사용하여 수세조를 통해 충분히 세정함으로써 카다놀만 섬유상에 남기고 계면활성제 성분은 모두 제거하여 항균가공을 완료하였다.
100 g of cardanol and 50 g of polyethylene oxide-based surfactant are stirred and mixed at room temperature, and 850 g of water is added thereto, followed by stirring to prepare an antimicrobial solution in an emulsified state. The propylene fabric was padded and treated at a temperature of 160 ° C. for 10 minutes and then thoroughly washed with a water bath using water at room temperature, leaving only cardanol fibers on the fibers and removing all surfactant components to complete antimicrobial processing.
[실시예 3][Example 3]
상기 실시예 1에서 사용한 항균가공액에 항균가공액 100 중량부 대비 아크릴계바인더 5 중량부 및 가교제 2중량부를 추가한 항균가공액을 사용하여 패딩법으로 섬유에 처리하고 160℃ 온도에서 10분간 처리하였다.
The antimicrobial solution used in Example 1 was treated with fibers by padding method using an antimicrobial solution added with 5 parts by weight of an acrylic binder and 2 parts by weight of a crosslinking agent with respect to 100 parts by weight of the antibacterial solution, and then treated at 160 ° C. for 10 minutes. .
상기 실시예 1 내지 3에 의해 항균가공된 직물의 항균성 및 세탁내구성을 평가하여 아래 표 1에 나타내었다.The antimicrobial and wash durability of the antimicrobial fabrics processed by Examples 1 to 3 were shown in Table 1 below.
Claims (5)
The method of claim 1, wherein the antimicrobial solution further comprises a quaternary ammonium salt-based cationic surfactant or anionic surfactant.
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