KR20230051373A - Composition for multifunctional nanofiber formation, preparation method thereof, multifunctional nanofiber, porous filtration filter by the multifunctional nanofiber, and filtration device - Google Patents
Composition for multifunctional nanofiber formation, preparation method thereof, multifunctional nanofiber, porous filtration filter by the multifunctional nanofiber, and filtration device Download PDFInfo
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- KR20230051373A KR20230051373A KR1020210134203A KR20210134203A KR20230051373A KR 20230051373 A KR20230051373 A KR 20230051373A KR 1020210134203 A KR1020210134203 A KR 1020210134203A KR 20210134203 A KR20210134203 A KR 20210134203A KR 20230051373 A KR20230051373 A KR 20230051373A
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- nanofibers
- multifunctional
- composition
- forming
- metal oxide
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F13/00—Details common to, or for air-conditioning, air-humidification, ventilation or use of air currents for screening
- F24F13/28—Arrangement or mounting of filters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0631—Electro-spun
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/13—Physical properties anti-allergenic or anti-bacterial
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/04—Filters
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Abstract
Description
본 발명은 다기능성 나노섬유 형성용 조성물, 이의 제조방법, 다기능성 나노섬유, 다기능성 나노섬유가 적용된 다공성 여과필터 및 여과장치에 관한 것으로, 보다 구체적으로 뛰어난 여과성능, 유해가스 분해 성능 및 항균 효과를 갖고, 재생 성능도 우수한 다기능성 나노섬유 형성용 조성물, 이의 제조방법, 다기능성 나노섬유, 다기능성 나노섬유가 적용된 다공성 여과필터 및 여과장치에 관한 것이다.The present invention relates to a composition for forming multifunctional nanofibers, a method for producing the same, multifunctional nanofibers, and a porous filtration filter and filtration device to which the multifunctional nanofibers are applied, and more specifically, excellent filtration performance, harmful gas decomposition performance, and antibacterial effect. It relates to a composition for forming multifunctional nanofibers having excellent regeneration performance, a method for producing the same, a multifunctional nanofiber, and a porous filtration filter and a filtration device to which the multifunctional nanofiber is applied.
세계보건기구(World Health Organization; 이하, 'WHO'라 칭함)의 2016년 보고에 따르면, 전세계적으로 대기오염으로 연간 700만 명의 사망자가 발생하며 이러한 높은 사망률은 주로 미립자의 흡인으로 기인한다고 발표하였다. 공기역학적 직경이 2.5 ㎛미만의 미세입자인 PM2.5는 고체와 액체상태의 유기물 혹은 무기물의 복잡한 혼합물로서 곰팡이, 박테리아, 바이러스와 같은 생물학적 유기체 및 휘발성 유기화합물(VOCs)과 같은 가스 상의 오염물질을 운반할 수 있다. According to a 2016 report by the World Health Organization (hereinafter referred to as 'WHO'), 7 million deaths occur annually due to air pollution worldwide, and this high mortality rate is mainly due to inhalation of particulate matter. . PM 2.5 , fine particles with an aerodynamic diameter of less than 2.5 μm, is a complex mixture of solid and liquid organic or inorganic matter that carries biological organisms such as fungi, bacteria and viruses, and gaseous pollutants such as volatile organic compounds (VOCs). can do.
WHO에서 권고하는 PM2.5의 연간 한계는 10 ㎍/m3이지만, 한국을 비롯한 많은 국가가 이를 충족시키지 못하고 있다. 특히, 공기역학적 직경이 1 ㎛ 미만의 PM1.0은 흡인 시 폐와 폐포에 깊숙이 침투하여 만성 혹은 급성의 심장병, 폐암, 천식을 포함한 호흡기 문제 등 다양한 건강 문제를 야기한다. The annual limit of PM 2.5 recommended by WHO is 10 μg/m 3 , but many countries, including Korea, do not meet it. In particular, PM 1.0 with an aerodynamic diameter of less than 1 μm penetrates deep into the lungs and alveoli when inhaled, causing various health problems such as chronic or acute heart disease, lung cancer, and respiratory problems including asthma.
또한, 호흡기계 전염성 높은 바이러스인 COVID-19의 주요 감염 경로는 부유 비말의 흡인이다. 이에 따라 효율적인 마스크 소재 개발의 필요성이 대두되고 있다.In addition, the main route of transmission of COVID-19, a highly contagious respiratory virus, is aspiration of suspended droplets. Accordingly, the need for efficient mask material development is emerging.
종래에는 나노섬유에 금속산화물 나노입자를 도입할 때 전구체로부터 시작하여 나노섬유 내에 광촉매를 담지하는 방법을 주로 사용하였다. 그러나 이러한 방법은 나노섬유 내 금속산화물 나노입자의 분산을 용이하게 할 수는 있지만, 시간이 오래 걸리고, 일정한 크기의 금속산화물 나노입자가 형성되지 못하는 문제점이 있었다. 또한, 이러한 방법은 제조된 나노섬유의 형태적 안정화를 위하여 일반적으로 열처리 과정을 거침으로써 공정이 복잡해질 수 있다. Conventionally, when introducing metal oxide nanoparticles into nanofibers, a method of supporting a photocatalyst in nanofibers starting from a precursor has been mainly used. However, although this method can facilitate the dispersion of metal oxide nanoparticles in nanofibers, it takes a long time and has problems in that metal oxide nanoparticles of a certain size cannot be formed. In addition, in this method, the process may be complicated by generally undergoing a heat treatment process for morphological stabilization of the manufactured nanofibers.
예를 들어, 대한민국 공개특허공보 10-2013-0070333A는 이산화티타늄 전구체와 산화아연 전구체가 혼합된 고분자 혼합 용액을 전기방사하여 나노섬유를 만든 후, 가수분해 반응 및 열처리 과정을 통해 최종적으로 산화아연 나노입자와 이산화티타늄 나노입자를 포함하는 기능성 나노섬유를 구체적으로 제시하고 있다. 하지만 상기 대한민국 공개특허공보는, 가수분해시간이 오래 걸리고, 열처리과정을 400 내지 550 ℃에서 수행하여야 하는 문제점이 있었다. 또한, 상기 대한민국 공개특허공보는 실란계 화합물에 의해 개질된 개질 금속산화물 나노입자를 구체적으로 개시하지 못하고 있고, 상기 개질 금속산화물 나노입자를 통해 금속산화물 나노입자를 방사된 나노섬유 상에 균일하게 분산시켜 우수한 여과성능, 유해가스 분해효과 및 항균성능을 발휘할 수 있는 과제해결원리를 일절 제시하지 못하고 있다.For example, Korean Patent Laid-Open Publication No. 10-2013-0070333A discloses that nanofibers are made by electrospinning a polymer mixture solution in which a titanium dioxide precursor and a zinc oxide precursor are mixed, and then finally zinc oxide nanofibers are subjected to a hydrolysis reaction and heat treatment process. Particles and functional nanofibers containing titanium dioxide nanoparticles are specifically presented. However, the Korean Patent Laid-open Publication has a problem in that the hydrolysis time is long and the heat treatment process must be performed at 400 to 550 °C. In addition, the Republic of Korea Patent Publication does not specifically disclose modified metal oxide nanoparticles modified by a silane-based compound, and the metal oxide nanoparticles are uniformly dispersed on the spun nanofibers through the modified metal oxide nanoparticles. However, it has not been able to present any problem-solving principles that can demonstrate excellent filtration performance, harmful gas decomposition effect, and antibacterial performance.
본 발명의 목적은, 상기 문제점을 해결하기 위한 것으로 다기능성 나노섬유 내에 개질 금속산화물 나노입자를 균일하게 분산시킬 수 있는 다기능성 나노섬유 형성용 조성물을 제공하는 것이다.An object of the present invention, to solve the above problems, is to provide a composition for forming multifunctional nanofibers capable of uniformly dispersing modified metal oxide nanoparticles in multifunctional nanofibers.
본 발명의 다른 목적은, 상기 다기능성 나노섬유 형성용 조성물을 구현할 수 있는 다기능성 나노섬유 형성용 조성물의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing a composition for forming multifunctional nanofibers capable of implementing the composition for forming multifunctional nanofibers.
본 발명의 또 다른 목적은, 여과효율이 뛰어나고, 높은 유속에서도 안정적 여과가 가능함과 동시에, 높은 항균 성능 및 유해가스분해 성능을 갖는 다기능성 나노섬유를 제공하는 것이다.Another object of the present invention is to provide multifunctional nanofibers having excellent filtration efficiency, stable filtration even at high flow rates, and high antibacterial performance and harmful gas decomposition performance.
본 발명의 또 다른 목적은, 상기 다기능성 나노섬유를 포함하는 다공성 여과필터를 제공하는 것이다.Another object of the present invention is to provide a porous filter comprising the multifunctional nanofibers.
본 발명의 또 다른 목적은, 상기 다공성 여과필터를 포함하는 여과장치를 제공하는 것이다.Another object of the present invention is to provide a filtering device including the porous filter.
본 발명의 목적들은 이상에서 언급한 목적으로 제한되지 않으며, 언급되지 않은 본 발명의 다른 목적 및 장점들은 하기의 설명에 의해서 이해될 수 있고, 본 발명의 실시예에 의해 보다 분명하게 이해될 것이다. 또한, 본 발명의 목적 및 장점들은 청구범위에 나타낸 수단 및 그 조합에 의해 실현될 수 있음을 쉽게 알 수 있을 것이다.The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned above can be understood by the following description and will be more clearly understood by the examples of the present invention. It will also be readily apparent that the objects and advantages of the present invention may be realized by means of the instrumentalities and combinations indicated in the claims.
상기 목적을 달성하기 위한 본 발명의 일 실시예는 고분자 화합물 및 금속산화물 나노입자에서 유래된 개질 금속산화물 나노입자를 포함하고, 상기 개질 금속산화물 나노입자는, 실란계 화합물에 의해 개질된 것인 다기능성 나노섬유 형성용 조성물을 제공한다.An embodiment of the present invention for achieving the above object includes modified metal oxide nanoparticles derived from a polymer compound and metal oxide nanoparticles, and the modified metal oxide nanoparticles are modified by a silane-based compound A composition for forming functional nanofibers is provided.
상기 목적을 달성하기 위한 본 발명의 다른 실시예는 (S1) 고분자 화합물과 제2 용매를 혼합하여 고분자 혼합 용액을 제조하는 단계, (S2) 가수분해된 실란계 화합물과 금속산화물 나노입자를 혼합하여 개질 금속산화물 나노입자를 제조하는 단계 및 (S3) 상기 개질 금속산화물 나노입자와 상기 고분자 혼합 용액을 혼합하여 다기능성 나노섬유 형성용 조성물을 제조하는 단계를 포함하는 다기능성 나노섬유 형성용 조성물의 제조방법을 제공한다.Another embodiment of the present invention for achieving the above object is (S1) preparing a polymer mixture solution by mixing a polymer compound and a second solvent, (S2) mixing a hydrolyzed silane-based compound and metal oxide nanoparticles Preparing a composition for forming a multifunctional nanofiber comprising preparing a modified metal oxide nanoparticle and (S3) mixing the modified metal oxide nanoparticle and the polymer mixture to prepare a composition for forming a multifunctional nanofiber provides a way
상기 목적을 달성하기 위한 본 발명의 또 다른 실시예는 다기능성 나노섬유 형성용 조성물로 제조된 다기능성 나노섬유를 제공한다.Another embodiment of the present invention for achieving the above object provides a multifunctional nanofiber made of a composition for forming a multifunctional nanofiber.
상기 목적을 달성하기 위한 본 발명의 또 다른 실시예는 상기 다기능성 나노섬유를 포함하는 다공성 여과필터를 제공한다.Another embodiment of the present invention for achieving the above object provides a porous filter comprising the multi-functional nanofibers.
상기 목적을 달성하기 위한 본 발명의 또 다른 실시예는 상기 다공성 여과필터를 포함하는 여과장치를 제공한다.Another embodiment of the present invention for achieving the above object provides a filtering device including the porous filter.
본 발명에 따르면, 주사전자현미경(Scanning Electron Microscope; 이하 SEM이라 한다)을 이용한 다기능 나노섬유사의 표면 관찰과 비표면적 분석(BET, specific surface area)을 통해 다기능 나노섬유사의 직경 감소와 표면 거칠기 증가를 확인할 수 있다. 이를 통해, 여과의 대상이 되는 초미세분진과 다기능성 나노섬유사의 마찰력 증가로 여과효율을 향상시키고, 높은 유속에서도 안정적 여과가 가능하며, 밀도 높은 구조와 미세기공의 형성을 증가시켜 높은 여과성능을 기대할 수 있다. 또한, 본 발명에 따르면 개질 금속산화물 나노입자를 다기능성 나노섬유에 담지함으로써, 유해가스분해능과 항균기능을 동시에 보유하며, 호흡기에 직접 노출되는 마스크 소재로 활용될 수 있는 다기능성 나노섬유를 제공할 수 있다.According to the present invention, the reduction in the diameter of the multifunctional nanofiber yarn and the increase in surface roughness are observed through surface observation and specific surface area analysis (BET) of the multifunctional nanofiber yarn using a scanning electron microscope (hereinafter referred to as SEM). You can check. Through this, the filtration efficiency is improved by increasing the frictional force of ultra-fine dust and multifunctional nanofiber yarns, which are subject to filtration, and stable filtration is possible even at high flow rates, and high filtration performance is achieved by increasing the formation of dense structures and micropores. can be expected In addition, according to the present invention, by supporting modified metal oxide nanoparticles in multifunctional nanofibers, it is possible to provide multifunctional nanofibers that simultaneously possess harmful gas decomposition and antibacterial functions and can be used as mask materials directly exposed to the respiratory tract. can
상술한 효과와 더불어 본 발명의 구체적인 효과는 이하 발명을 실시하기 위한 구체적인 내용을 설명하면서 함께 기술한다.In addition to the above effects, specific effects of the present invention will be described together while explaining specific details for carrying out the present invention.
도 1a는, 본 발명의 일 실시예에 따른 다기능성 나노섬유 형성용 조성물에서, 금속산화물 나노입자가 개질되는 과정을 나타낸 모식도이다.
도 1b는 본 발명의 일 실시예에 따른 다기능성 나노섬유의 제조방법을 간략히 나타낸 흐름도이다.
도 2는 본 발명의 일 실시예에 따른 다기능성 나노섬유 형성용 조성물을 전기방사하는데 사용되는 전기방사장치를 나타낸 것이다.
도 3은, 비교예 1에 따른 나노섬유(a)와 비교예 2에 따른 나노섬유(b) 각각을 SEM으로 관찰한 결과를 나타낸 것이다.
도 4는 제조예 1-1에 따른 나노섬유 형성용 조성물로 제조된 나노섬유를 SEM으로 관찰한 것이고, 상기 나노섬유 형성용 조성물의 점도와 상기 나노섬유의 직경의 상관관계를 나타낸 것이다.
도 5는 상기 제조예 1-1에 따른 나노섬유의 에너지 분산형 X-선 분석기(Energy Dispersive X-ray Spectroscopy; EDX) 스펙트럼을 분석한 결과(a); 상기 제조예 1-1에 따른 나노섬유의 X선 회절분석(X-ray diffraction; XRD) 결과(b); 및 비표면적 분석장비(BET surface area and porosimetry analyzer)를 이용하여 상기 제조예 1-1에 따른 나노섬유의 비표면적과 기공율(c); 을 나타낸 것이다.
도 6은 제조예 1-1에 따른 나노섬유로 제조된 여과장치의, 미세먼지의 크기에 따른 여과효율(a) 및 ZnO의 함량에 따른 여과효율 및 압력강하(b)를 나타낸 것이다.
도 7은 제조예 1-1에 따른 나노섬유가 첨가된 메틸렌 블루 혼합 용액의 흡광도(a) 및 제조예 1-1에 따른 나노섬유가 첨가된 메틸렌 블루 혼합 용액에서 메틸렌 블루의 분해 효율(b)을 나타낸 것이다.
도 8은 제조예 1-1에 따른 나노섬유의 항균 성능을 평가한 것이다.
도 9는 제조예 1-2에 따른 다기능성 나노섬유의 항균 성능을 평가한 것이다.
도 10은, 비교예 4에 따른 나노섬유에서의 ZnO 나노입자(a) 및 실시예 1-1 내지 1-3에 따른 나노섬유에서의 개질 ZnO 나노입자 (b~d) 각각의 SEM 사진을 나타낸 것이다.
도 11은 비교예 4에 따른 나노섬유(a~b) 및 실시예 1-1 내지 1-3에 따른 나노섬유(c~e) 각각을 SEM으로 관찰한 것이다.
도 12는 비교예 5에 따른 나노섬유(a~b) 및 실시예 2-1 내지 2-3에 따른 나노섬유(c~f) 각각을 SEM으로 관찰한 것이다.
도 13은 제조예 1-2에 따른 나노섬유로 제조된 여과장치의 여과효율(a) 및 품질계수(b)를 나타낸 것이다.
도 14는 비교예 5에 따른 나노섬유의 재생 성능 효과를 입증하기 위한 실험이다.
도 15는 비교예 4 대비, 시간의 경과에 따른 실시예 1-1 내지 1-3에 따른 나노섬유의 메티렌 블루 분해 효율을 나타낸 것이다.
도 16은 비교예 5 대비, 시간의 경과에 따른 실시예 2-1 내지 2-3에 따른 나노섬유의 메틸렌 블루 분해 효율을 나타낸 것이다.1A is a schematic diagram showing a process in which metal oxide nanoparticles are modified in a composition for forming multifunctional nanofibers according to an embodiment of the present invention.
Figure 1b is a flow chart briefly showing a method for manufacturing multifunctional nanofibers according to an embodiment of the present invention.
2 shows an electrospinning apparatus used for electrospinning a composition for forming multifunctional nanofibers according to an embodiment of the present invention.
Figure 3 shows the results of observing each of the nanofibers (a) according to Comparative Example 1 and the nanofibers (b) according to Comparative Example 2 by SEM.
4 is a SEM observation of nanofibers prepared from the composition for forming nanofibers according to Preparation Example 1-1, and shows a correlation between the viscosity of the composition for forming nanofibers and the diameter of the nanofibers.
Figure 5 is the result of analyzing the energy dispersive X-ray spectroscopy (EDX) spectrum of the nanofiber according to Preparation Example 1-1 (a); X-ray diffraction (XRD) of the nanofiber according to Preparation Example 1-1 (X-ray diffraction; XRD) result (b); and specific surface area and porosity (c) of the nanofiber according to Preparation Example 1-1 using a BET surface area and porosimetry analyzer; is shown.
6 shows the filtration efficiency (a) according to the size of fine dust and the filtration efficiency and pressure drop (b) according to the ZnO content of the filtration device made of nanofibers according to Preparation Example 1-1.
Figure 7 is the absorbance of the methylene blue mixed solution to which nanofibers were added according to Preparation Example 1-1 (a) and the decomposition efficiency of methylene blue in the methylene blue mixed solution to which nanofibers were added according to Preparation Example 1-1 (b) is shown.
8 is an evaluation of the antibacterial performance of nanofibers according to Preparation Example 1-1.
9 is an evaluation of the antibacterial performance of multifunctional nanofibers according to Preparation Example 1-2.
10 shows SEM images of ZnO nanoparticles (a) in nanofibers according to Comparative Example 4 and modified ZnO nanoparticles (b to d) in nanofibers according to Examples 1-1 to 1-3, respectively. will be.
11 is a SEM observation of nanofibers (a to b) according to Comparative Example 4 and nanofibers (c to e) according to Examples 1-1 to 1-3, respectively.
12 is a SEM observation of nanofibers (a to b) according to Comparative Example 5 and nanofibers (c to f) according to Examples 2-1 to 2-3, respectively.
Figure 13 shows the filtration efficiency (a) and quality factor (b) of the filtration device made of nanofibers according to Preparation Example 1-2.
14 is an experiment to demonstrate the regeneration performance effect of nanofibers according to Comparative Example 5.
15 shows the methylene blue decomposition efficiency of the nanofibers according to Examples 1-1 to 1-3 over time, compared to Comparative Example 4.
Figure 16 shows the methylene blue decomposition efficiency of the nanofibers according to Examples 2-1 to 2-3 over time, compared to Comparative Example 5.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 각 구성을 보다 상세히 설명하나, 이는 하나의 예시에 불과할 뿐, 본 발명의 권리범위가 다음 내용에 의해 제한되지 아니한다.Hereinafter, each configuration of the present invention will be described in more detail so that those skilled in the art can easily practice it, but this is only one example, and the scope of the present invention is Not limited.
본 명세서에서 '고분자 화합물/금속산화물 나노입자 나노섬유'는, 고분자 화합물로 제조된 나노섬유가, 금속산화물 나노입자를 함유하는 나노 굵기의 섬유로 정의된다. 예를 들어, 'PAN/ZnO 나노섬유'는 PAN으로 제조된 나노섬유가 ZnO 나노입자를 함유하는 나노섬유로 정의된다. In the present specification, 'polymer compound/metal oxide nanoparticle nanofiber' is defined as a nano-thickness fiber in which a nanofiber made of a polymer compound contains metal oxide nanoparticles. For example, 'PAN/ZnO nanofibers' are defined as nanofibers made of PAN containing ZnO nanoparticles.
본 발명의 일 실시예는, 고분자 화합물 및 금속산화물 나노입자에서 유래된 개질 금속산화물 나노입자를 포함하고, 상기 개질 금속산화물 나노입자는, 실란계 화합물에 의해 개질된 것인 다기능성 나노섬유 형성용 조성물이다.An embodiment of the present invention includes modified metal oxide nanoparticles derived from a polymer compound and metal oxide nanoparticles, and the modified metal oxide nanoparticles are modified by a silane-based compound for forming multifunctional nanofibers. is a composition
이하에서는, 본 발명의 구성을 보다 상세히 설명한다.Hereinafter, the configuration of the present invention will be described in more detail.
1. 다기능성 나노섬유 형성용 조성물1. Composition for Forming Multifunctional Nanofibers
본 발명에 따른 다기능성 나노섬유 형성용 조성물은 고분자 화합물을 포함한다. The composition for forming multifunctional nanofibers according to the present invention includes a polymer compound.
본 발명에 따른 고분자 화합물은 폴리아크릴로니트릴(polyacrylonitrile; PAN), 폴리비닐리덴플로라이드(polyvinylidene fluoride, PVDF), 폴리메틸메타크릴레이트(poly(methyl methacrylate), PMMA) 폴리비닐클로라이드(polyvinyl chloride, PVC), 폴리테트라플루오로에틸렌 (polytetrafluoroethylene, PTFE), 폴리우레탄(polyurethane, PU), 폴리카프로락톤(polycaprolactone, PCL), 폴리아크릴아마이드(polyacrylamide), 폴리아마이드(polyamide), 폴리(N-이소프로필아크릴아마이드)(poly(N-isopropylacrylamide), PNIPAAm), 폴리아크릴산(polyacrylic acid, PAA), 폴리아크릴레이트(polyacrylate), 폴리카르복실레이트(polycarboxylate), 폴리에틸렌이민(polyethylenimine), 폴리메타크릴산(poly(methacrylic acid)), 폴리에틸렌옥사이드(polyethylene oxide, PEO), 폴리비닐피롤리돈(polyvinylpyrrolidone, PVP) 및 폴리비닐알코올(polyvinyl alcohol)로 이루어진 군에서 선택된 어느 하나일 수 있고, 바람직하게는 폴리아크릴로니트릴(Polyacrylonitrile; PAN), 폴리비닐리덴플로라이드(polyvinylidene fluoride, PVDF) 및 폴리아마이드(polyamide)로 이루어진 군에서 선택된 어느 하나일 수 있다.The polymer compound according to the present invention is polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), poly(methyl methacrylate) (PMMA), polyvinyl chloride, PVC), polytetrafluoroethylene (PTFE), polyurethane (PU), polycaprolactone (PCL), polyacrylamide, polyamide, poly(N-isopropyl) acrylamide) (poly(N-isopropylacrylamide), PNIPAAm), polyacrylic acid (PAA), polyacrylate, polycarboxylate, polyethylenimine, polymethacrylic acid (poly (methacrylic acid)), polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), and polyvinyl alcohol. It may be any one selected from the group consisting of nitrile (Polyacrylonitrile; PAN), polyvinylidene fluoride (PVDF), and polyamide.
본 발명에 따른 고분자 화합물의 중량평균분자량은 10,000 내지 700,000 g/mol일 수 있고, 바람직하게는 90,000 내지 150,000 g/mol일 수 있다. 상기 고분자 화합물의 중량평균분자량은 전구체 용액의 점도와 전도도에 영향을 끼칠 수 있는 바, 궁극적으로는 직조되는 섬유의 두께에 영향을 줄 수 있다. 따라서 상기 고분자 화합물의 중량평균분자량이 상기 수치 범위 미만일 경우 직조가 되지 않거나 섬유의 강도가 낮아지는 문제가 생겨 다공성 필터가 제대로 형성되지 못할 수 있으며; 상기 수치 범위를 초과할 경우 섬유의 굵기가 너무 증가하여 여과필터를 구성하였을 때, 미세먼지 포집효율을 낮추는 문제가 생길 수 있다.The weight average molecular weight of the polymer compound according to the present invention may be 10,000 to 700,000 g/mol, preferably 90,000 to 150,000 g/mol. The weight average molecular weight of the polymer compound may affect the viscosity and conductivity of the precursor solution, and ultimately, the thickness of the woven fiber. Therefore, when the weight average molecular weight of the polymer compound is less than the above range, the porous filter may not be properly formed due to problems such as not being woven or the strength of the fiber being lowered; If the above numerical range is exceeded, the thickness of the fiber increases too much, and when the filtration filter is configured, a problem of lowering the fine dust collection efficiency may occur.
본 발명에 따른 고분자 화합물의 함량은 상기 다기능성 나노섬유 형성용 조성물의 전체 중량을 기준으로 5 내지 15 중량%, 바람직하게는 7 내지 12 중량%, 더욱 바람직하게는 8 내지 10 중량%일 수 있다. 상기 고분자 화합물의 함량이 상기 수치 범위 미만일 경우, 점도가 낮아 나노섬유의 형성이 어려울 수 있고, 전기방사 시 고분자가 비드 형태로 분사되는 문제가 생길 수 있다. 상기 고분자 화합물의 함량이 상기 수치 범위를 초과할 경우, 용액의 점도가 지나치게 높아져 전기방사가 어려워질 수 있다. The content of the polymer compound according to the present invention may be 5 to 15% by weight, preferably 7 to 12% by weight, more preferably 8 to 10% by weight based on the total weight of the composition for forming multifunctional nanofibers. . When the content of the polymer compound is less than the above numerical range, it may be difficult to form nanofibers due to low viscosity, and a problem may occur in that the polymer is sprayed in a bead form during electrospinning. When the content of the polymer compound exceeds the above numerical range, the viscosity of the solution becomes excessively high, making electrospinning difficult.
본 발명에 따른 개질 금속산화물 나노입자는 금속산화물 나노입자에서 유래된 것일 수 있다. 상기 개질 금속산화물 나노입자는 실란계 화합물에 의해 개질된 것일 수 있다. The modified metal oxide nanoparticles according to the present invention may be derived from metal oxide nanoparticles. The modified metal oxide nanoparticles may be modified by a silane-based compound.
종래의 통상적인 금속산화물 나노입자는 실란계 화합물로 개질되지 않는 나노입자로, 상기 고분자 화합물로 제조된 나노섬유에서 응집체를 형성하여 상기 나노섬유 내에 균일하게 분산되지 못하는 문제점이 있었다. 이로 인해 난분해성 독성 유기염료에 대해 분해 효율이 낮거나 초미세분진 등에 대한 여과효율이 상대적으로 낮은 문제점이 발생하였다. 본 발명에 따르면, 개질 금속산화물 나노입자를 상기 고분자 화합물로 제조된 나노섬유에 도입함으로써, 응집체가 형성되는 것을 방지하여 난분해성 독성 유기염료에 대한 분해 효율 및 초미세분진 등에 대한 여과효율을 향상시킬 수 있다.Conventional metal oxide nanoparticles are nanoparticles that are not modified with a silane-based compound, and have a problem in that they are not uniformly dispersed in the nanofibers by forming aggregates in nanofibers made of the polymer compound. As a result, problems such as low decomposition efficiency for non-degradable toxic organic dyes or relatively low filtration efficiency for ultrafine dust occurred. According to the present invention, by introducing the modified metal oxide nanoparticles into the nanofibers made of the polymer compound, the formation of aggregates is prevented to improve the decomposition efficiency of non-degradable toxic organic dyes and the filtration efficiency of ultrafine dust. can
상기 금속산화물 나노입자는 ZnO, SnO2, ZrO2, TiO2, WO3 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나일 수 있고, 바람직하게는 ZnO 또는 TiO2일 수 있다. 상기 금속산화물 나노입자는 가시광선 하에서 유해물질과 항균 작용을 수행할 수 있다. 특히, ZnO의 경우 다른 나노입자와 달리, 인체 유해성이 낮아 인체의 피부에 직접 맞닿는 마스크에 쉽게 적용될 수 있는 이점을 가지고 있다. The metal oxide nanoparticles may be any one selected from the group consisting of ZnO, SnO 2 , ZrO 2 , TiO 2 , WO 3 and combinations thereof, preferably ZnO or TiO 2 . The metal oxide nanoparticles can perform harmful substances and antibacterial action under visible light. In particular, in the case of ZnO, unlike other nanoparticles, it has a low harmfulness to the human body and has the advantage of being easily applied to a mask that comes into direct contact with the human skin.
본 발명에 따른 실란계 화합물은 상기 금속산화물 나노입자를 개질함으로써 개질 금속산화물 나노입자를 구현할 수 있고, 상기 개질 금속산화물 나노입자를 상기 고분자 화합물로 제조된 나노섬유 내에 골고루 분산시킬 수 있다.The silane-based compound according to the present invention can implement modified metal oxide nanoparticles by modifying the metal oxide nanoparticles, and the modified metal oxide nanoparticles can be evenly dispersed in nanofibers made of the polymer compound.
상기 실란계 화합물은 예를 들어, 비닐트리스(2-메톡시에톡시)실란, 비닐트리에톡시실란, 비닐트리메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 2-(3,4-에폭시사이클로헥실)-에틸트리메톡시실란, 3-글리시딜옥시프로필트리메톡시실란, 3-글리시딜옥시프로필메틸디에톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란, 3-아미노프로필메틸디에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-클로로프로필트리메톡시실란, 3-클로로프로필트리에톡시실란, 3-머캅토프로필트리메톡시실란 및 3-머캅토프로필트리에톡시실란으로 이루어진 군에서 선택된 어느 하나일 수 있다. 다만 본 발명의 기술사상이 이에 제한되는 것은 아니고, 금속산화물 나노입자를 개질할 수 있는 실란계 화합물이면 모두 적용될 수 있다. The silane-based compound is, for example, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, N-2 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyl Methyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane And it may be any one selected from the group consisting of 3-mercaptopropyltriethoxysilane. However, the technical idea of the present invention is not limited thereto, and any silane-based compound capable of modifying metal oxide nanoparticles can be applied.
상기 개질 금속산화물 나노입자의 함량은 상기 다기능성 나노섬유 형성용 조성물의 전체 중량을 기준으로 0 초과 15 중량% 이하, 바람직하게는 0.1 내지 13 중량%, 더욱 바람직하게는 5 내지 12 중량%일 수 있다. 상기 개질 금속산화물 나노입자의 함량이 상기 수치 범위 미만일 경우, 유해 물질 분해 능력 및 항균 효과가 충분하지 못할 수 있고, 상기 수치 범위를 초과할 경우 개질 금속산화물 나노입자가 나노섬유에서 응집체를 형성하는 문제점이 생길 수 있다.The content of the modified metal oxide nanoparticles may be greater than 0 and 15% by weight or less, preferably 0.1 to 13% by weight, more preferably 5 to 12% by weight based on the total weight of the composition for forming the multifunctional nanofibers. there is. When the content of the modified metal oxide nanoparticles is less than the above range, harmful substance decomposition ability and antibacterial effect may not be sufficient, and when the content of the modified metal oxide nanoparticles exceeds the above range, the modified metal oxide nanoparticles form aggregates in nanofibers. this can happen
광촉매 기능을 갖는 상기 개질 금속산화물 나노입자를 구현하기 위해, 상기 금속산화물 나노입자와 상기 실란계 화합물의 중량비(금속산화물 나노입자: 실란계 화합물)는 1:0.25 내지 1:10일 수 있고, 바람직하게는 1: 0.5 내지 1: 2 일 수 있고, 더욱 바람직하게는 1: 0.5 내지 1: 1 일 수 있다. 상기 금속산화물 나노입자와 상기 실란계 화합물의 중량비가 상기 수치 범위를 벗어날 경우, 난분해성 독성 유기염료에 대한 분해 효율이 충분히 개선되지 못할 수 있다.In order to implement the modified metal oxide nanoparticles having a photocatalytic function, the weight ratio of the metal oxide nanoparticles and the silane-based compound (metal oxide nanoparticles: silane-based compound) may be 1:0.25 to 1:10, preferably. Preferably it may be 1: 0.5 to 1: 2, and more preferably 1: 0.5 to 1: 1. When the weight ratio of the metal oxide nanoparticles to the silane-based compound is out of the range, the decomposition efficiency of the non-decomposable toxic organic dye may not be sufficiently improved.
본 발명에 따른 다기능성 나노섬유 형성용 조성물은 제1 용매를 더 포함할 수 있다. 상기 제1 용매는 상기 고분자 화합물을 용해시키는 용매로, 고분자의 종류에 따라 적절히 선택될 수 있다. The composition for forming multifunctional nanofibers according to the present invention may further include a first solvent. The first solvent is a solvent for dissolving the polymer compound, and may be appropriately selected according to the type of polymer.
상기 제1 용매는 예를 들어, N, N-디메틸폼아미드(N, N-dimethylformamide; DMF) 디메틸설폭사이드(dimethyl sulfoxide; DMSO) 디메틸아세트아미드(N,N-dimethylacetamide; DMAc), N-메틸-2-피롤리돈(N-methyl-2-pyrrolidone; NMP), 탄소수 1 내지 6의 저급 알코올류 화합물, 테트라하이드로퓨란(tetrahydrofuran; THF), 아세톤(Acetone) 및 메틸에틸케톤(MEK)으로 이루어지는 군에서 선택되는 1종 이상의 극성 혹은 중성 유기용매일 수 있다. 다만 본 발명의 기술사상이 이에 제한되는 것은 아니다.The first solvent is, for example, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (N, N-dimethylacetamide; DMAc), N-methyl -2-pyrrolidone (N-methyl-2-pyrrolidone; NMP), a lower alcohol compound having 1 to 6 carbon atoms, tetrahydrofuran (THF), acetone (Acetone) and methyl ethyl ketone (MEK) It may be one or more polar or neutral organic solvents selected from the group. However, the technical idea of the present invention is not limited thereto.
2. 다기능성 나노섬유 형성용 조성물의 제조방법2. Manufacturing method of composition for forming multi-functional nanofibers
본 발명의 다른 실시예는, (S1) 고분자 화합물과 제2 용매를 혼합하여 고분자 혼합 용액을 제조하는 단계, (S2) 가수분해된 실란계 화합물과 금속산화물 나노입자를 혼합하여 개질 금속산화물 나노입자를 제조하는 단계 및 (S3) 상기 개질 금속산화물 나노입자와 상기 고분자 혼합 용액을 혼합하여 다기능성 나노섬유 형성용 조성물을 제조하는 단계를 포함하는 다기능성 나노섬유 형성용 조성물의 제조방법이다. 전술한 부분과 반복된 설명은 간략히 설명하거나 생략한다.In another embodiment of the present invention, (S1) preparing a polymer mixture solution by mixing a polymer compound and a second solvent, (S2) mixing a hydrolyzed silane-based compound and metal oxide nanoparticles to modify metal oxide nanoparticles It is a method for producing a composition for forming a multifunctional nanofiber comprising the step of preparing a step of preparing and (S3) mixing the modified metal oxide nanoparticle and the polymer mixture solution to prepare a composition for forming a multifunctional nanofiber. The foregoing parts and repeated descriptions are briefly described or omitted.
상기 (S1) 단계에서 상기 제2 용매는 상기 제1 용매와 동일할 수 있다. In the step (S1), the second solvent may be the same as the first solvent.
상기 (S2) 단계에서 상기 가수분해된 실란계 화합물은 가수분해 용매와 실란계 혼합물을 혼합하여 제조된 것일 수 있다. 구체적으로, 상기 실란계 화합물과 상기 가수분해 용매의 중량비는 약 1: 50 내지 1: 200일 수 있다.The silane-based compound hydrolyzed in step (S2) may be prepared by mixing a hydrolysis solvent and a silane-based mixture. Specifically, the weight ratio between the silane-based compound and the hydrolysis solvent may be about 1:50 to 1:200.
본 발명에 따른 가수분해 용매로, 상기 실란계 화합물을 가수분해할 수 있는 용매면 제한되지 않고 모두 이용될 수 있다. 상기 가수분해 용매는 예를 들어, 탄소 수 1 내지 2의 간단한 알코올류 화합물, 물 및 이들의 혼합물로 이루어진 군에서 선택된 어느 하나일 수 있고, 바람직하게는 에탄올일 수 있다.As the hydrolysis solvent according to the present invention, any solvent capable of hydrolyzing the silane-based compound may be used without limitation. The hydrolysis solvent may be, for example, any one selected from the group consisting of simple alcohol compounds having 1 to 2 carbon atoms, water, and mixtures thereof, and preferably ethanol.
이하, 도 1a를 참고하여 개질 금속산화물 나노입자가 제조되는 과정을 설명한다.Hereinafter, a process of manufacturing modified metal oxide nanoparticles will be described with reference to FIG. 1A.
도 1a는, 본 발명의 일 실시예에 따른 다기능성 나노섬유 형성용 조성물에서, 금속산화물 나노입자가 개질되는 과정을 나타낸 모식도이다.1A is a schematic diagram showing a process in which metal oxide nanoparticles are modified in a composition for forming multifunctional nanofibers according to an embodiment of the present invention.
도 1a를 참고하면, 실란계 화합물은 가수분해 용매에 의해 완전히 가수분해되어 Si-OH 작용기를 함유하는 가수분해된 실란계 화합물이 제조될 수 있다. 상기 가수분해된 실란계 화합물은 금속산화물 나노입자를 개질하여, 상기 금속산화물 나노입자를 상기 Si-OH 작용기의 산소 원자에 결합시켜 개질 금속산화물 나노입자가 구현될 수 있다. 그 후, 상기 개질 금속산화물 나노입자는 상기 고분자 화합물과 유기 잔기(organic end)를 통해 연결될 수 있다.Referring to FIG. 1A , the silane-based compound may be completely hydrolyzed by a hydrolysis solvent to produce a hydrolyzed silane-based compound containing a Si—OH functional group. The hydrolyzed silane-based compound may modify metal oxide nanoparticles, and bond the metal oxide nanoparticles to oxygen atoms of the Si—OH functional group to realize modified metal oxide nanoparticles. Then, the modified metal oxide nanoparticle may be connected to the polymer compound through an organic end.
상기 다기능성 나노섬유 형성용 조성물의 전체 중량을 기준으로, 상기 고분자 혼합 용액의 함량은, 85 중량% 이상 100 중량% 미만, 바람직하게는 88 내지 98.8중량%, 더욱 바람직하게는 88 내지 91 중량%일 수 있고, 상기 개질 금속산화물 나노입자의 함량은 0 중량% 초과 15 중량% 이하일 수 있고, 바람직하게는 1.2 내지 12 중량%, 더욱 바람직하게는 9 내지 12 중량%일 수 있다.Based on the total weight of the multifunctional nanofiber-forming composition, the content of the polymer mixture solution is 85% by weight or more and less than 100% by weight, preferably 88 to 98.8% by weight, more preferably 88 to 91% by weight. , and the content of the modified metal oxide nanoparticles may be greater than 0% by weight and less than or equal to 15% by weight, preferably 1.2 to 12% by weight, more preferably 9 to 12% by weight.
3. 다기능성 나노섬유3. Multifunctional nanofibers
본 발명의 또 다른 실시예는 상기 다기능성 나노섬유 형성용 조성물로 제조된 다기능성 나노섬유이다. Another embodiment of the present invention is a multifunctional nanofiber prepared from the composition for forming the multifunctional nanofiber.
상기 다기능성 나노섬유는, 20 내지 25℃, 상대습도 40 내지 50%, 전압 15 내지 20kV, 방사거리 10 내지 20cm, 및 니들직경 21 내지 23gauge에서 상기 다기능성 나노섬유 형성용 조성물을 전기방사하여 제조된 것일 수 있다.The multifunctional nanofibers are prepared by electrospinning the composition for forming multifunctional nanofibers at 20 to 25 ° C, relative humidity of 40 to 50%, voltage of 15 to 20 kV, spinning distance of 10 to 20 cm, and needle diameter of 21 to 23 gauge. may have been
상기 다기능성 나노섬유의 직경은 261 내지 422nm일 수 있다. 본 명세서에서 다기능성 나노섬유의 '직경'은 다기능성 나노섬유를 이루는 섬유사의 평균직경을 의미하는 것으로 정의된다. The multifunctional nanofibers may have a diameter of 261 to 422 nm. In the present specification, the 'diameter' of the multifunctional nanofiber is defined to mean the average diameter of the fibers constituting the multifunctional nanofiber.
또한, 상기 다기능성 나노섬유의 비표면적(BET, specific surface area)은 10 내지 36 m2/g일 수 있다.In addition, the specific surface area (BET, specific surface area) of the multifunctional nanofibers may be 10 to 36 m 2 /g.
상기 다기능성 나노섬유 형성용 조성물의 점도는 344 내지 737 cP일 수 있다.The composition for forming the multifunctional nanofibers may have a viscosity of 344 to 737 cP.
이하, 도 1b를 참고하여 본 발명의 또 다른 실시예에 따른 다기능성 나노섬유의 제조방법을 설명한다.Hereinafter, a method for manufacturing multifunctional nanofibers according to another embodiment of the present invention will be described with reference to FIG. 1B.
도 1b는 본 발명의 일 실시예에 따른 다기능성 나노섬유의 제조방법을 간략히 나타낸 흐름도이다.Figure 1b is a flow chart briefly showing a method for manufacturing multifunctional nanofibers according to an embodiment of the present invention.
도 1b를 참고하면, PAN과 개질 ZnO 나노입자를 혼합하여 다기능성 나노섬유 형성용 조성물을 제조할 수 있다. 상기 다기능성 나노섬유 형성용 조성물은 전기방사 용액일 수 있다. Referring to FIG. 1B , a composition for forming multifunctional nanofibers may be prepared by mixing PAN and modified ZnO nanoparticles. The composition for forming the multifunctional nanofibers may be an electrospinning solution.
도 2는 본 발명의 일 실시예에 따른 다기능성 나노섬유 형성용 조성물을 전기방사하는데 사용되는 전기방사장치를 나타낸 것이다.2 shows an electrospinning apparatus used for electrospinning a composition for forming multifunctional nanofibers according to an embodiment of the present invention.
도 2를 참고하면, 상기 전기방사장치를 이용하여 상기 전기방사 용액에 고전압을 가하여 다기능성 나노섬유를 제조할 수 있다. 상기 전기방사장치는 고전압 발생장치, 토출부 및 나노섬유를 수집하는 집진판(collector)을 포함할 수 있다. Referring to FIG. 2 , multifunctional nanofibers may be prepared by applying a high voltage to the electrospinning solution using the electrospinning device. The electrospinning device may include a high voltage generator, a discharge unit, and a collector for collecting nanofibers.
상기 고전압 발생장치는 상기 전기방사 용액에 고전압을 인가하는 장치일 수 있고, 상기 토출부는 실린지 펌프(syringe pump), 튜브 및 니들(needle)을 포함할 수 있다. 상기 실린지 펌프를 통해 상기 전기방사 용액이 일정한 속도로 유입되도록 유입량을 조절할 수 있고, 상기 전기방사 용액을 상기 니들을 통해 토출시킬 수 있다. 상기 튜브의 끝 부분에서 상기 전기방사 용액은 그 자체의 장력에 의해 달라붙을 수 있다. The high voltage generator may be a device for applying a high voltage to the electrospinning solution, and the discharge unit may include a syringe pump, a tube, and a needle. An inflow amount may be adjusted so that the electrospinning solution flows in at a constant rate through the syringe pump, and the electrospinning solution may be discharged through the needle. At the end of the tube, the electrospinning solution may stick by its own tension.
이하, 전기방사장치에 관한 상세한 설명은 통상의 기술자에게 자명하므로 생략한다.Hereinafter, a detailed description of the electrospinning apparatus will be omitted because it is obvious to those skilled in the art.
4. 다공성 여과필터 및 이를 포함하는 여과장치4. Porous filter and filtration device including the same
본 발명의 또 다른 실시예는 상기 다기능성 나노섬유를 포함하는 다공성 여과필터이다. Another embodiment of the present invention is a porous filter comprising the multifunctional nanofibers.
상기 다공성 여과필터는 초미세먼지에 대한 높은 포집 효율 및 낮은 압력강하와 가시광선 하에서 효과적인 광촉매 활성, 박테리아에 대한 항균성, 세척을 통한 기능의 재생이 가능하다는 점에서 상업 및 산업현장에서의 요구를 만족시킬 수 있다.The porous filter satisfies the needs of commercial and industrial fields in that it has high collection efficiency for ultrafine dust, low pressure drop, effective photocatalytic activity under visible light, antimicrobial activity against bacteria, and function reproduction through washing. can make it
본 발명의 또 다른 실시예는 상기 다공성 여과필터를 포함하는 여과장치이다. 상기 여과장치는 마스크, 공기청정기, 환기설비 및 에어컨으로 이루어진 군에서 선택된 어느 하나일 수 있고, 건물 공조용 환기장치나 자동차 분야에도 다양하게 적용될 수 있다.Another embodiment of the present invention is a filtering device including the porous filter. The filtering device may be any one selected from the group consisting of a mask, an air purifier, a ventilation system, and an air conditioner, and may be variously applied to a ventilation device for building air conditioning or an automobile field.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명하나, 이는 하나의 예시에 불과할 뿐, 본 발명의 권리범위가 다음 내용에 의해 제한되지 아니한다. Hereinafter, an embodiment of the present invention will be described in detail so that those skilled in the art can easily practice it, but this is only one example, and the scope of the present invention is Not limited.
[제조준비예 1: 시료 및 시약][Manufacturing Preparation Example 1: Samples and Reagents]
전기방사 용액 준비단계에서 고분자를 용해시키기 위해 N, N-디메틸폼아미드(N, N-dimethylformamide; 이하 DMF라 한다)를 사용하였으며, 고분자로는 중량평균분자량이 150,000 g/mol인 폴리아크릴로나이트릴(Polyacrlonitrile; 이하 PAN이라 한다)을 사용하였다. 고분자 혼합 용액에 첨가물로는 금속산화물 나노입자인 ZnO 나노입자(ZnO, Particle size = 20 nm, 99% purity)를 사용하였고, ZnO 나노입자를 개질하기 위해 3-메타크릴옥시프로필트리메톡시실란(3-methacryloxypropyltrimethoxysilane; MPTMS, 97% purity, Alfa Aesar, China)을 사용하였다.In order to dissolve the polymer in the electrospinning solution preparation step, N, N-dimethylformamide (hereinafter referred to as DMF) was used, and polyacrylonite having a weight average molecular weight of 150,000 g/mol was used as the polymer. A reel (Polyacrlonitrile; hereinafter referred to as PAN) was used. ZnO nanoparticles (ZnO, Particle size = 20 nm, 99% purity), which are metal oxide nanoparticles, were used as additives to the polymer mixture solution, and 3-methacryloxypropyltrimethoxysilane ( 3-methacryloxypropyltrimethoxysilane; MPTMS, 97% purity, Alfa Aesar, China) was used.
[제조예 1-1: 나노섬유 형성용 조성물의 제조][Preparation Example 1-1: Preparation of composition for forming nanofibers]
DMF(9.54mL)에 PAN을 첨가한 후, 이들을 4시간 동안 교반하여 하기 표 1과 같은 PAN 혼합 용액을 제조하였다. 상기 PAN 혼합 용액에, ZnO 나노입자를 첨가한 후, 이들을 20시간 동안 교반하였다. 상기 PAN 혼합 용액의 균일한 분산을 위해, 4시간 동안 초음파 수조에서 추가적으로 교반하여 하기 표 1에 비교예에 따른 나노섬유 형성용 조성물을 제조하였다.After adding PAN to DMF (9.54mL), they were stirred for 4 hours to prepare a PAN mixed solution as shown in Table 1 below. After adding ZnO nanoparticles to the PAN mixed solution, they were stirred for 20 hours. For uniform dispersion of the PAN mixed solution, it was additionally stirred in an ultrasonic water bath for 4 hours to prepare a composition for forming nanofibers according to Comparative Examples in Table 1 below.
[제조예 1-2: 다기능성 나노섬유 형성용 조성물의 제조][Preparation Example 1-2: Preparation of composition for forming multifunctional nanofibers]
MPTMS에 의한 ZnO 나노입자의 개질을 위해, 먼저 MPTMS와 ZnO 나노입자의 중량비(MPTMS:ZnO)가 0.5, 1 및 2이 되도록, MPTMS(0.5g, 1g, 2g)를 각각 에탄올(100 mL)에 한 방울씩 첨가한 후, 이들을 1 시간 동안 교반하여 MPTMS의 완전한 가수분해를 보장하였다. 상기 가수분해된 혼합 용액에 ZnO 나노입자 1 g을 첨가한 후, 추가로 5 시간 동안 교반하였다. 이후, 상기 ZnO 나노입자의 분산을 위해 상기 교반된 혼합용액을 90분 동안 초음파 교반을 하여 예비 개질 ZnO 나노입자를 제조하였다. 과도하게 공급된 MPTMS을 제거하기 위해 상기 예비 개질 ZnO 나노입자를 에탄올로 3회 세척한 후, 90℃에서 8 시간 동안 오븐 건조 및 제분하여 최종적으로 개질 ZnO 나노입자를 제조하였다. 하기 표 2와 같이, 상기 개질 ZnO 나노입자를 상기 PAN 혼합 용액에 첨가하여 하기 실시예에 따른 다기능성 나노섬유 형성용 조성물을 제조하였다.For the modification of ZnO nanoparticles by MPTMS, first, MPTMS (0.5 g, 1 g, 2 g) was dissolved in ethanol (100 mL) so that the weight ratios (MPTMS:ZnO) of MPTMS and ZnO nanoparticles were 0.5, 1, and 2, respectively. After adding dropwise, they were stirred for 1 hour to ensure complete hydrolysis of MPTMS. After adding 1 g of ZnO nanoparticles to the hydrolyzed mixed solution, the mixture was further stirred for 5 hours. Then, in order to disperse the ZnO nanoparticles, the stirred mixed solution was subjected to ultrasonic agitation for 90 minutes to prepare pre-modified ZnO nanoparticles. After washing the pre-modified ZnO nanoparticles with ethanol three times to remove excessively supplied MPTMS, the modified ZnO nanoparticles were finally prepared by oven drying and milling at 90° C. for 8 hours. As shown in Table 2 below, the modified ZnO nanoparticles were added to the PAN mixed solution to prepare a composition for forming multifunctional nanofibers according to the following examples.
[제조예 2: 나노섬유의 제조][Preparation Example 2: Preparation of nanofibers]
상기 제조예 1-1 및 1-2에 따른 나노섬유 형성용 조성물을 각각 니들 23 gauge, 전압 20 kV, 방사거리 15 cm, 용액 공급속도 1 mL/hr, 온도 25℃ 및 습도 50%에서 전기방사하여, 나노섬유를 제조하였다. The compositions for forming nanofibers according to Preparation Examples 1-1 and 1-2 were electrospun at a needle of 23 gauge, a voltage of 20 kV, a spinning distance of 15 cm, a solution supply rate of 1 mL/hr, a temperature of 25° C. and a humidity of 50%, respectively. Thus, nanofibers were prepared.
이하, 제조예 1-1에 따른 나노섬유 형성용 조성물을 전기방사하여 제조된 나노섬유를 '제조예 1-1에 따른 나노섬유'라 칭하고, 상기 제조예 1-2에 따른 나노섬유 형성용 조성물을 전기방사하여 제조된 나노섬유를 '제조예 1-2에 따른 나노섬유'라 칭한다.Hereinafter, nanofibers prepared by electrospinning the composition for forming nanofibers according to Preparation Example 1-1 are referred to as 'nanofibers according to Preparation Example 1-1', and the composition for forming nanofibers according to Preparation Example 1-2 The nanofibers prepared by electrospinning are referred to as 'nanofibers according to Preparation Example 1-2'.
[실험예 1: 비교예 1 및 비교예 2에 따른 나노섬유의 SEM 사진][Experimental Example 1: SEM pictures of nanofibers according to Comparative Examples 1 and 2]
도 3은, 비교예 1에 따른 나노섬유(a)와 비교예 2에 따른 나노섬유(b) 각각을 SEM으로 관찰한 결과를 나타낸 것이다.Figure 3 shows the results of observing each of the nanofibers (a) according to Comparative Example 1 and the nanofibers (b) according to Comparative Example 2 by SEM.
도 3을 참고하면, 비교예 2에 따른 나노섬유의 표면 거칠기가 ZnO 나노입자가 PAN에 도입됨으로써, 비교예 1에 따른 나노섬유의 표면거칠기 대비, 현저히 증가하였음을 확인할 수 있다. 이를 통해, 상기 나노섬유의 표면거칠기의 증가로 인해, 모든 입경의 미세입자에 대한 여과성능이 향상될 것임을 유추할 수 있다.Referring to FIG. 3 , it can be confirmed that the surface roughness of the nanofibers according to Comparative Example 2 was significantly increased compared to the surface roughness of the nanofibers according to Comparative Example 1 by introducing ZnO nanoparticles into PAN. Through this, it can be inferred that the filtration performance for fine particles of all particle sizes will be improved due to the increase in surface roughness of the nanofibers.
[실험예 2: 제조예 1-1에 따른 나노섬유의 SEM 사진 및 상기 나노섬유의 직경과 상기 나노섬유 형성물의 점도와의 상관관계][Experimental Example 2: Correlation between SEM pictures of nanofibers and the diameter of the nanofibers and the viscosity of the nanofiber formation according to Preparation Example 1-1]
도 4는 제조예 1-1에 따른 나노섬유 형성용 조성물로 제조된 나노섬유를 SEM(a~e)으로 관찰한 것이고, 상기 나노섬유 형성용 조성물의 점도와 상기 나노섬유사의 직경의 상관관계(f)를 나타낸 것이다.Figure 4 is an SEM (a ~ e) observation of nanofibers prepared from the composition for forming nanofibers according to Preparation Example 1-1, and the correlation between the viscosity of the composition for forming nanofibers and the diameter of the nanofibers ( f) is shown.
도 4를 참고하면, 상기 제조예 1-1에 따른 나노섬유 형성용 조성물의 점도는 ZnO의 함량이 증가할수록 감소함을 확인할 수 있다. 또한, 상기 제조예 1-1에 따른 나노섬유의 직경은 ZnO의 함량이 증가할수록 감소함을 확인할 수 있다. 다만, 예외적으로 비교예 1 및 2를 참고하면, ZnO의 함량이 상기 나노섬유 형성용 조성물의 전체 중량을 기준으로 0 중량%에서 3 중량%로 증가할 때, 상기 나노섬유의 직경이 소폭 증가하였다.Referring to FIG. 4, it can be seen that the viscosity of the composition for forming nanofibers according to Preparation Example 1-1 decreases as the ZnO content increases. In addition, it can be seen that the diameter of the nanofiber according to Preparation Example 1-1 decreases as the ZnO content increases. However, referring to Comparative Examples 1 and 2 as an exception, when the content of ZnO increased from 0% by weight to 3% by weight based on the total weight of the composition for forming nanofibers, the diameter of the nanofibers increased slightly. .
[실험예 3: 제조예 1-1에 따른 나노섬유의 EDX, XRD 및 BET 비표면적 및 기공율 분석][Experimental Example 3: EDX, XRD and BET specific surface area and porosity analysis of nanofibers according to Preparation Example 1-1]
도 5는 상기 제조예 1-1에 따른 나노섬유의 에너지 분산형 X-선 분석기(Energy Dispersive X-ray Spectroscopy; EDX) 스펙트럼을 분석한 결과(a); 상기 제조예 1-1에 따른 나노섬유의 X선 회절분석(X-ray diffraction; XRD) 결과(b); 및 비표면적 분석장비(BET surface area and porosimetry analyzer)를 이용하여 상기 제조예 1-1에 따른 나노섬유의 비표면적과 기공율(c); 을 나타낸 것이다.Figure 5 is the result of analyzing the energy dispersive X-ray spectroscopy (EDX) spectrum of the nanofiber according to Preparation Example 1-1 (a); X-ray diffraction (XRD) of the nanofiber according to Preparation Example 1-1 (X-ray diffraction; XRD) result (b); and specific surface area and porosity (c) of the nanofiber according to Preparation Example 1-1 using a BET surface area and porosimetry analyzer; is shown.
도 5(a)를 참고하면, 상기 제조예 1-1에 따른 나노섬유의 화학적 구성에 ZnO가 도입되었음을 확인할 수 있다.Referring to FIG. 5 (a), it can be confirmed that ZnO was introduced into the chemical composition of the nanofibers according to Preparation Example 1-1.
도 5(b)를 참고하면, 비교예 1에 따른 나노섬유(PZ0)와 달리, 비교예 2 내지 5에 따른 나노섬유(PZ3, PZ6, PZ9, PZ12)의 결정구조에 ZnO가 도입되었음을 확인할 수 있다.Referring to FIG. 5 (b), unlike the nanofibers (PZ0) according to Comparative Example 1, it can be confirmed that ZnO was introduced into the crystal structure of the nanofibers (PZ3, PZ6, PZ9, and PZ12) according to Comparative Examples 2 to 5. there is.
도 5(c)를 참고하면, 상기 제조예 1-1에 따른 나노섬유의 질소 기체에 대한흡착량 및 탈착량을 비교한 결과, ZnO의 함량이 증가할수록 상기 제조예 1-1에 따른 나노섬유의 비표면적(BET, specific surface area)과 미세기공이 증가함을 확인할 수 있다.Referring to Figure 5 (c), as a result of comparing the amount of adsorption and desorption of the nanofibers according to Preparation Example 1-1 to nitrogen gas, as the content of ZnO increases, the nanofibers according to Preparation Example 1-1 It can be confirmed that the specific surface area (BET) and micropores of
[실험예 4: 제조예 1-1에 따른 나노섬유의 여과 성능 시험][Experimental Example 4: Filtration performance test of nanofibers according to Preparation Example 1-1]
상기 제조예 1-1에 따른 나노섬유의 여과성능을 평가하기 위하여 염화 포타슘(Potassium chloride; 이하, 'KCl'이라 칭함)을 미립화 장치(Atomizer)를 이용하여 미립화(Size range 0.265 ~ 1 μm, Mean size 0.375 μm)하고 미립화된 KCl 입자의 여과 전, 후 입자 농도를 두 대의 입자 분광계(Grimm 11-A, Grimm 1.109, Grimm Co., Germany)를 이용하여 측정하였고 차압 마노미터(Manometer)(Ulfa Technolngy Co.Ltd., South Korea)를 이용하여 상기 나노섬유를 이용한 KCl 미립자 여과 시 압력강하를 측정하였다. 측정된 입자의 농도를 통해 여과 전, 후의 여과효율을 산정하고 산정된 여과효율과 측정된 압력강하를 이용하여 다기능성 나노섬유의 품질계수를 산정하여 평가하였다. 여과성능 시험 과정은 다음과 같은 단계로 이루어진다.In order to evaluate the filtration performance of the nanofibers according to Preparation Example 1-1, potassium chloride (hereinafter referred to as 'KCl') was atomized using an atomizer (Size range 0.265 ~ 1 μm, Mean size 0.375 μm) and the particle concentration before and after filtration of the micronized KCl particles were measured using two particle spectrometers (Grimm 11-A, Grimm 1.109, Grimm Co., Germany), and differential pressure manometer (Ulfa Technolngy Co., Ltd.) Ltd., South Korea) was used to measure the pressure drop during filtration of KCl particulates using the nanofibers. The filtration efficiency before and after filtration was calculated through the concentration of the measured particles, and the quality factor of the multifunctional nanofiber was calculated and evaluated using the calculated filtration efficiency and the measured pressure drop. The filtration performance test process consists of the following steps.
(1) KCl을 증류수에 용해하여 농도가 0.5 mol/L인 용액을 제조한다.(1) Dissolve KCl in distilled water to prepare a solution with a concentration of 0.5 mol/L.
(2) 미립화 장치(Atomizer)를 이용하여 상기 용액으로부터 에어로졸(Aerosol)을 형성한다.(2) An aerosol is formed from the solution using an atomizer.
(3) 형성된 에어로졸을 실리카겔(Silica gel)이 채워진 건조기를 통과시켜 수분을 제거한다. (3) The formed aerosol is passed through a dryer filled with silica gel to remove moisture.
(4) 건조된 에어로졸을 상기 제조예 1-1에 따른 나노섬유가 장착된 여과장치에 통과시킨다.(4) The dried aerosol is passed through a filtration device equipped with nanofibers according to Preparation Example 1-1.
(5) 여과 전, 후의 입자농도를 측정하여 여과효율을 계산한다. (5) Calculate the filtration efficiency by measuring the particle concentration before and after filtration.
(6) 여과 전, 후의 압력강하를 측정하여 품질계수를 계산한다.(6) Calculate the quality factor by measuring the pressure drop before and after filtration.
품질계수(QF)는 하기 수학식 1에 의해 계산된다.The quality factor (Q F ) is calculated by
[수학식 1] [Equation 1]
상기 수학식 1에서, QF는 품질계수, η은 여과효율, △P는 압력강하를 의미한다. In
도 6은 제조예 1-1에 따른 나노섬유로 제조된 여과장치의, 미세먼지의 크기에 따른 여과효율(a) 및 ZnO의 함량에 따른 여과효율 및 압력강하(b)를 나타낸 것이다.6 shows the filtration efficiency (a) according to the size of fine dust and the filtration efficiency and pressure drop (b) according to the ZnO content of the filtration device made of nanofibers according to Preparation Example 1-1.
도 6(a)을 참고하면, 나노섬유 내 ZnO 나노입자의 함량을 증가시킴으로써, 모든 입경의 미세입자에 대한 여과 성능을 향상시킬 수 있다. 이는 ZnO 함량의 증가로 인한 상기 나노섬유의 표면 거칠기의 증가와 비표면적 증가로 설명할 수 있다. 특히, 300 nm의 미세입자를 대상으로 상기 비교예 1에 따른 나노섬유로 제조된 여과장치(PZ0)는 69.41%만큼 여과하였으나, ZnO의 함량을 3 중량% 높인 상기 비교예 2에 따른 나노섬유로 제조된 여과장치(PZ3)는 85.59%의 여과효율을 나타냈다. 더 나아가, 상기 비교예 5에 따른 나노섬유로 제조된 여과장치(PZ12)의 여과효율은 98.8%로, 다른 나노섬유로 제조된 여과장치의 여과효율 대비, 크게 향상되었음을 확인할 수 있다.Referring to FIG. 6(a), by increasing the content of ZnO nanoparticles in nanofibers, the filtration performance of fine particles of all particle sizes can be improved. This can be explained by the increase in surface roughness and specific surface area of the nanofibers due to the increase in ZnO content. In particular, the filtration device (PZ0) made of nanofibers according to Comparative Example 1 for 300 nm fine particles filtered 69.41%, but the nanofibers according to Comparative Example 2 with the ZnO content increased by 3% by weight The manufactured filtration device (PZ3) showed a filtration efficiency of 85.59%. Furthermore, it can be seen that the filtration efficiency of the filtering device (PZ12) made of nanofibers according to Comparative Example 5 is 98.8%, which is greatly improved compared to the filtration efficiency of filtering devices made of other nanofibers.
도 6(b)를 참고하면, ZnO의 함량이 증가할수록 상기 제조예 1-1에 따른 나노섬유로 제조된 여과장치의 여과효율이 증가함을 확인할 수 있고, 상기 제조예 1-1에 따른 나노섬유로 제조된 여과장치의 압력강하는 여과효율과 유사한 증가 추세를 보였다. 특히, 비교예 1에 따른 나노섬유로 제조된 여과장치(PZ0)의 압력강하는 약 20Pa의 압력강하를 보인 반면, ZnO의 함량을 높임으로써, 비교예 5에 따른 나노섬유로 제조된 여과장치(PZ12)의 압력강하는 약 48 Pa의 압력강하를 보였다. 이로 인해, 비교예 5에 따른 나노섬유로 제조된 여과장치(PZ12)는 0.092 Pa-1의 높은 품질계수를 가지게 되었다. 한편, 비교예 5에 따른 나노섬유로 제조된 여과장치(PZ12)는 15cm/s의 면 속도(face velocity)에서, 143 Pa의 압력강하 및 0.0299 Pa-1의 품질계수를 보였고, 이는 모든 여과속도에서 300 nm 크기의 KCl 입자에 대한 여과효율이 98% 이상으로, 전반적으로 우수한 여과성능을 나타냄을 알 수 있다.Referring to FIG. 6(b), it can be seen that the filtration efficiency of the filtration device made of nanofibers according to Preparation Example 1-1 increases as the content of ZnO increases, and the nanofibers according to Preparation Example 1-1 increase. The pressure drop of the filter device made of fiber showed an increasing trend similar to the filtration efficiency. In particular, the pressure drop of the filtering device (PZ0) made of nanofibers according to Comparative Example 1 showed a pressure drop of about 20 Pa, while the filtering device made of nanofibers according to Comparative Example 5 by increasing the content of ZnO ( The pressure drop of PZ12) was about 48 Pa. Due to this, the filtering device (PZ12) made of nanofibers according to Comparative Example 5 had a high quality factor of 0.092 Pa -1 . On the other hand, the filtration device (PZ12) made of nanofibers according to Comparative Example 5 exhibited a pressure drop of 143 Pa and a quality factor of 0.0299 Pa -1 at a face velocity of 15 cm/s, which was shown at all filtration rates. It can be seen that the filtration efficiency for KCl particles with a size of 300 nm is more than 98%, indicating excellent filtration performance overall.
하기 표 3은 상기 비교예 1 내지 5에 따른 나노섬유로 제조된 여과장치에 대하여, 여과속도를 5.3cm/s, 10cm/s 및 15cm/s 각각 다르게 하여 여과시험을 수행하였을 때, 미세입자의 입경 별 여과효율을 나타낸 것이다.Table 3 below shows the filtration rate of 5.3 cm/s, 10 cm/s, and 15 cm/s for the filtration devices made of nanofibers according to Comparative Examples 1 to 5, respectively, when the filtration test was performed. It shows the filtration efficiency by particle size.
비교예 1
Comparative Example 1
비교예 2
Comparative Example 2
비교예 3
Comparative Example 3
비교예 4
Comparative Example 4
비교예 5
Comparative Example 5
[실험예 5: 제조예 1-1에 따른 나노섬유의 광촉매 활성 실험][Experimental Example 5: Photocatalytic activity test of nanofibers according to Preparation Example 1-1]
상기 제조예 1-1에 따른 나노섬유에 함유된 ZnO의 광촉매 활성을 평가하기 위하여, 난분해성 독성 유기염료인 메틸렌 블루(Methylene Blue; 이하, 'MB'라 한다) 용액을 이용하였다. 구체적으로, 광촉매 활성 평가 방법은 다음과 같은 단계로 이루어졌다.In order to evaluate the photocatalytic activity of ZnO contained in the nanofibers according to Preparation Example 1-1, a solution of methylene blue (hereinafter referred to as 'MB'), a non-decomposable toxic organic dye, was used. Specifically, the photocatalytic activity evaluation method consisted of the following steps.
(1) 증류수 60 mL에 1% 메틸렌 블루 용액을 혼합하여 농도가 10 ppm인 메틸렌 블루 혼합 용액을 제조하였다.(1) A 1% methylene blue solution was mixed with 60 mL of distilled water to prepare a methylene blue mixed solution having a concentration of 10 ppm.
(2) 상기 메틸렌 블루 혼합 용액을 10 mL 분취하여 시료 1로 설정하였다. (2) 10 mL of the methylene blue mixed solution was aliquoted and set as
(3) 상기 제조예 1-1에 따른 나노섬유에 흡착되어 낮아진 메틸렌 블루의 초기농도를 산정하기 위해, 상기 제조예 1-1에 따른 나노섬유 25 mg을 상기 메틸렌 블루 혼합 용액에 첨가하고 30분 동안 빛이 없는 상태에서 교반한 후, 3 mL를 분취하여 시료 2로 설정하였다.(3) In order to calculate the initial concentration of methylene blue lowered by adsorption to the nanofibers according to Preparation Example 1-1, 25 mg of nanofibers according to Preparation Example 1-1 were added to the methylene blue mixed solution and kept for 30 minutes After stirring in the absence of light for a while, 3 mL was aliquoted and set as
(4) 가시광선 전구를 통해 빛을 1시간 동안 조사하고 매 10분 마다 시료를 분취한다. (4) Light is irradiated for 1 hour through a visible light bulb, and samples are collected every 10 minutes.
(5) 채취한 시료를 664 nm에서 흡광광도계를 통해 흡광도를 측정하고 하기 수학식 2를 통해 메틸렌 블루의 분해역학을 평가하였다. (5) The absorbance of the collected sample was measured using an absorbance photometer at 664 nm, and the decomposition kinetics of methylene blue was evaluated through
[수학식 2] [Equation 2]
-ln(C/Co) = Kt-ln(C/Co) = Kt
여기서, K는 1차 반응속도 상수(min-1), t는 반응시간(min), -ln(C/Co)를 시간에 대한 함수로 작성하였으며, K는 선형의 기울기로 서로 다른 광촉매 함량에서 반응이 얼마나 빠르게 진행되는지를 평가하고 메틸렌 블루가 분해되는 능력을 비교하는 데 이용할 수 있다.Here, K is the first-order reaction rate constant (min -1 ), t is the reaction time (min), -ln (C / Co) is written as a function of time, and K is a linear slope at different photocatalyst contents It can be used to evaluate how fast the reaction proceeds and to compare the ability of methylene blue to decompose.
도 7은 제조예 1-1에 따른 나노섬유가 첨가된 메틸렌 블루 혼합 용액의 흡광도(a) 및 제조예 1-1에 따른 나노섬유가 첨가된 메틸렌 블루 혼합 용액에서 메틸렌 블루가 분해되는 분해 효율(b)을 나타낸 것이다.Figure 7 shows the absorbance (a) of the methylene blue mixed solution to which nanofibers were added according to Preparation Example 1-1 and the decomposition efficiency of methylene blue decomposition in the methylene blue mixed solution to which nanofibers were added according to Preparation Example 1-1 ( b) is shown.
도 7(a)를 참고하면, 초기 30 분 동안 비교예 1에 따른 나노섬유가 첨가된 메틸렌 블루 혼합 용액은, 섬유 구조에 MB 염료가 흡수되어 낮은 감소량의 흡광도를 보였다. Referring to FIG. 7 (a), the methylene blue mixed solution to which the nanofibers according to Comparative Example 1 were added for the initial 30 minutes showed a low absorbance due to the absorption of the MB dye in the fiber structure.
반면에, 비교예 2 내지 5에 따른 나노섬유가 첨가된 메틸렌 블루 혼합 용액은 각각의 ZnO 나노입자가 고형으로 존재하기 때문에, 비교예 1 대비, 높은 감소량의 흡광도를 보였다. 한편, 순수한 ZnO 나노입자는 메틸렌 블루 혼합 용액에 직접 노출되어 빠르게 분해되었다. On the other hand, the methylene blue mixed solution to which the nanofibers were added according to Comparative Examples 2 to 5 showed a high decrease in absorbance compared to Comparative Example 1 because each ZnO nanoparticle existed in a solid state. On the other hand, pure ZnO nanoparticles were rapidly decomposed by direct exposure to the methylene blue mixture solution.
도 7(b)를 참고하면, 비교예 1에 따른 나노섬유는 가시광선 조사 하에서 1시간 동안 29.97%의 분해 효율을 보였고, 이는 섬유 표면과 기공에서의 흡수에 기인한 것으로 이해할 수 있다. Referring to Figure 7 (b), the nanofibers according to Comparative Example 1 showed a decomposition efficiency of 29.97% for 1 hour under visible light irradiation, which can be understood as due to absorption at the fiber surface and pores.
한편, ZnO 나노입자의 메틸렌 블루를 분해하는 분해 효율은 동일한 조건에서 65.33%에 도달했다. 또한, PAN으로 제조된 나노섬유에 담지된 ZnO 나노입자의 함량을 증가시킴으로써 분해 효율의 명백한 개선을 관찰할 수 있었다. Meanwhile, the decomposition efficiency of ZnO nanoparticles to decompose methylene blue reached 65.33% under the same conditions. In addition, an obvious improvement in degradation efficiency could be observed by increasing the content of ZnO nanoparticles supported on nanofibers made of PAN.
비교예 2에 따른 나노섬유(PZ3)의 분해 효율은 57.6%로, PAN 나노섬유의 분해 효율 대비, 2배 이상에 해당하였다. 특히, ZnO의 함량이 증가함에 따라 메틸렌 블루의 분해 효율이 증가하는 추세를 보여준다. 비교예 5에 따른 나노섬유(PZ12)는 가시광선 하에서 70.12%로 높은 분해 효율에 도달했으며, 비교예 4에 따른 나노섬유(PZ9)와 비교예 5에 따른 나노섬유(PZ12)의 분해 효율은 순수한 ZnO 나노입자보다 높은 분해 효율을 보여주는데, 이는 PAN으로 제조된 나노섬유의 흡수력으로 설명될 수 있다.The decomposition efficiency of the nanofibers (PZ3) according to Comparative Example 2 was 57.6%, corresponding to more than twice the decomposition efficiency of the PAN nanofibers. In particular, as the content of ZnO increases, the decomposition efficiency of methylene blue shows an increasing trend. The nanofiber (PZ12) according to Comparative Example 5 reached a high decomposition efficiency of 70.12% under visible light, and the decomposition efficiency of the nanofiber (PZ9) according to Comparative Example 4 and the nanofiber (PZ12) according to Comparative Example 5 was pure. It shows a higher degradation efficiency than ZnO nanoparticles, which can be explained by the absorption capacity of nanofibers made of PAN.
[실험예 6-1: 제조예 1-1에 따른 나노섬유의 항균 성능 평가][Experimental Example 6-1: Evaluation of antibacterial performance of nanofibers according to Preparation Example 1-1]
도 8은 제조예 1-1에 따른 나노섬유의 항균 성능을 평가한 것이다.8 is an evaluation of the antibacterial performance of nanofibers according to Preparation Example 1-1.
상기 제조예 1-1에 따른 나노섬유의 항균 성능을 평가하기 위하여 대장균(Gram-negative E. coli bacteria; ATCC®25922)을 이용한 표준 한천판 확산법(The standard agar disk diffusion method, Heattey, 1944)을 이용하였다. In order to evaluate the antimicrobial performance of the nanofibers according to Preparation Example 1-1, the standard agar disk diffusion method (Heattey, 1944) using E. coli (Gram-negative E. coli bacteria; ATCC ® 25922) was used. used
항균 성능 평가방법은 하기와 같다. The antibacterial performance evaluation method is as follows.
(1) 상기 대장균(Gram-negative E. coli bacteria)을 멸균 배양 배지에 균일하게 분포시켜 37℃에서 24시간 배양시킨다. (1) The Gram-negative E. coli bacteria are uniformly distributed in a sterile culture medium and incubated at 37° C. for 24 hours.
(2) 상기 제조예 1-1에 따른 나노섬유(직경 8 mm)를 멸균하여 대장균이 배양된 배양 접시에 위치시킨다. (2) The nanofibers (8 mm in diameter) according to Preparation Example 1-1 are sterilized and placed on a culture dish in which E. coli is cultured.
(3) 상기 배양 접시를 37℃에서 24시간 추가로 배양하여 관찰되는 억제구역의 지름을 측정한다.(3) The culture dish is additionally incubated at 37° C. for 24 hours to measure the diameter of the inhibition zone observed.
도 8(a)를 참고하면, 비교예 1에 따른 나노섬유(PZ0)의 경우 억제구역(inhibition zone)을 관찰할 수 없었으나, 도 8(b)~8(e)를 참고하면, 나머지 비교예 2 내지 5에 따른 나노섬유의 경우 억제구역을 관찰할 수 있었다. 억제구역에 관한 원리는 ZnO 미세입자에 대전된 음전하와 양전하에 의한 정전기적 상호작용으로 박테리아의 단백질 세포를 파괴할 수 있는 산화 스트레스를 초래하는 단계 및 ZnO 미세입자에 의해 과산화수소(H2O2)와 초과산화물이온(Superoxide ion)과 같은 활성산소종(Reactive oxygen species; 이하, 'ROS'라 한다)이 간접 생성되어, 이들이 ROS에 의한 박테리아의 세포 단백질 구조를 붕괴하고 RNA 및 DNA에 손상을 초래하는 단계로 이루어진다.Referring to FIG. 8 (a), in the case of the nanofiber (PZ0) according to Comparative Example 1, no inhibition zone was observed, but referring to FIGS. 8 (b) to 8 (e), the rest of the comparison In the case of the nanofibers according to Examples 2 to 5, inhibition zones could be observed. The principle of the inhibition zone is the step of causing oxidative stress that can destroy bacterial protein cells by electrostatic interaction by negative and positive charges charged on ZnO microparticles and hydrogen peroxide (H 2 O 2 ) by ZnO microparticles. Reactive oxygen species (hereinafter referred to as 'ROS') such as and superoxide ion are indirectly generated, which disrupts the cell protein structure of bacteria by ROS and causes damage to RNA and DNA. is made up of steps
또한, 도 8(f)를 참고하면, ZnO의 함량이 증가할수록 억제구역의 지름이 증가함을 확인할 수 있다.In addition, referring to FIG. 8(f), it can be confirmed that the diameter of the inhibition zone increases as the content of ZnO increases.
[실험예 6-2: 제조예 1-2에 따른 나노섬유의 항균 성능 평가][Experimental Example 6-2: Evaluation of antibacterial performance of nanofibers according to Preparation Example 1-2]
도 9는 제조예 1-2에 따른 다기능성 나노섬유의 항균 성능을 평가한 것이다. 항균 성능 평가방법으로 전술한 실험예 6-1과 동일한 방법을 사용하였다.9 is an evaluation of the antibacterial performance of multifunctional nanofibers according to Preparation Example 1-2. The same method as in Experimental Example 6-1 described above was used as an antibacterial performance evaluation method.
도 9를 참고하면, 비교예 4, 5, 실시예 1-1 내지 실시예 1-3 및 실시예 2-1 내지 2-3에 따른 나노섬유 각각의 항균 성능을 억제구역의 지름으로 정리하여 하기 표 4에 표시하였다.Referring to Figure 9, the antibacterial performance of each of the nanofibers according to Comparative Examples 4 and 5, Examples 1-1 to 1-3, and Examples 2-1 to 2-3 is summarized as the diameter of the inhibition zone as follows Table 4 shows.
상기 표 4에서 비교예 4 및 실시예 1-1 내지 1-3을 참고하면, 실란의 함량이 증가함에 따라 억제구역의 지름이 증가함을 확인할 수 있었고, 특히 실시예 1-3의 항균 성능은 비교예 4 대비, 항균성이 향상되었음을 확인할 수 있었다.Referring to Comparative Example 4 and Examples 1-1 to 1-3 in Table 4, it was confirmed that the diameter of the inhibition zone increased as the content of silane increased, and in particular, the antibacterial performance of Examples 1-3 Compared to Comparative Example 4, it was confirmed that the antibacterial property was improved.
상기 표 4에서 비교예 5 및 실시예 2-1 내지 2-3을 참고하면, 실란의 함량이 증가할수록 ZnO 나노입자가 균일하게 분산되지 못해 항균성이 저하됨을 확인할 수 있었고, 특히 실시예 2-1의 항균 성능이 비교예 5 대비 현저하게 향상되었음을 확인할 수 있었다.Referring to Comparative Example 5 and Examples 2-1 to 2-3 in Table 4, it was confirmed that as the content of silane increased, the ZnO nanoparticles were not uniformly dispersed, resulting in a decrease in antibacterial properties. In particular, Example 2-1 It was confirmed that the antibacterial performance of was significantly improved compared to Comparative Example 5.
[실험예 7: 나노섬유에 담지된 ZnO 나노입자의 SEM 사진][Experimental Example 7: SEM picture of ZnO nanoparticles supported on nanofibers]
도 10은, 비교예 4에 따른 나노섬유에서의 ZnO 나노입자(a) 및 실시예 1-1 내지 1-3에 따른 나노섬유에서의 개질 ZnO 나노입자 (b~d) 각각의 SEM 사진을 나타낸 것이다.10 shows SEM images of ZnO nanoparticles (a) in nanofibers according to Comparative Example 4 and modified ZnO nanoparticles (b to d) in nanofibers according to Examples 1-1 to 1-3, respectively. will be.
도 10을 참고하면, 통상적인 ZnO 나노입자가 응집되는 것과 달리, MPTMS에 의해 개질된 ZnO 나노입자(이하, '개질 ZnO 나노입자'라 한다)는 개질되지 않은 ZnO 나노입자 대비, 응집체를 형성하지 않고 나노섬유 내에 골고루 분산되는 것을 확인할 수 있다.Referring to FIG. 10, unlike typical ZnO nanoparticles that aggregate, ZnO nanoparticles modified by MPTMS (hereinafter referred to as 'modified ZnO nanoparticles') do not form aggregates compared to unmodified ZnO nanoparticles. It can be seen that it is evenly dispersed within the nanofibers.
[실험예 8-1: 개질 ZnO 나노입자의 분산성 효과 입증 실험][Experimental Example 8-1: Demonstration of Dispersion Effect of Modified ZnO Nanoparticles]
도 11은 비교예 4에 따른 나노섬유(a~b) 및 실시예 1-1 내지 1-3에 따른 나노섬유(c~e) 각각을 SEM으로 관찰한 것이다.11 is a SEM observation of nanofibers (a to b) according to Comparative Example 4 and nanofibers (c to e) according to Examples 1-1 to 1-3, respectively.
도 11(a~b)를 참고하면, 실란계 화합물로 개질되지 않은 통상적인 ZnO 나노입자가 PAN으로 제조된 나노섬유에 응집체를 형성한 상태로 담지되어 있거나, 고르게 분포되지 못함을 확인할 수 있다.Referring to FIG. 11 (a to b), it can be seen that conventional ZnO nanoparticles not modified with a silane-based compound are supported on nanofibers made of PAN in the form of aggregates or are not evenly distributed.
도 11(c~e)를 참고하면, 실시예 1-1 내지 1-3에 따른 나노섬유 내에 개질 ZnO 나노입자가 골고루 분산되어 응집체를 형성하지 않음을 확인할 수 있다. 이를 통해, 실란계 화합물은 PAN으로 제조된 나노섬유에 개질 ZnO 나노입자가 골고루 분산되게 할 수 있다.Referring to FIG. 11(c to e), it can be confirmed that the modified ZnO nanoparticles are evenly dispersed in the nanofibers according to Examples 1-1 to 1-3 and do not form aggregates. Through this, the silane-based compound can evenly disperse the modified ZnO nanoparticles in the nanofibers made of PAN.
[실험예 8-2: 개질 ZnO 나노입자의 분산성 효과 입증 실험][Experimental Example 8-2: Demonstration of Dispersion Effect of Modified ZnO Nanoparticles]
도 12는 비교예 5에 따른 나노섬유(a~b) 및 실시예 2-1 내지 2-3에 따른 나노섬유(c~f) 각각을 SEM으로 관찰한 것이다.12 is a SEM observation of nanofibers (a to b) according to Comparative Example 5 and nanofibers (c to f) according to Examples 2-1 to 2-3, respectively.
도 12(a~b)를 참고하면, 도 11의 결과와 마찬가지로 실란계 화합물로 개질되지 않은 통상적인 ZnO 나노입자가 PAN으로 제조된 나노섬유에 응집체를 형성한 상태로 담지되어 있거나, 고르게 분포되지 못함을 확인할 수 있다.Referring to FIG. 12 (a to b), similar to the results of FIG. 11, conventional ZnO nanoparticles not modified with a silane-based compound are supported on nanofibers made of PAN in the form of aggregates, or are not evenly distributed. can confirm that it is not.
도 12(c~f)를 참고하면, 실시예 2-1 내지 2-3에 따른 나노섬유 내에 개질 ZnO 나노입자가 골고루 분산되어 응집체를 형성하지 않음을 확인할 수 있다. 이를 통해, 실란계 화합물은 PAN으로 제조된 나노섬유에 개질 ZnO 나노입자가 골고루 분산되게 할 수 있다.Referring to FIG. 12(c to f), it can be confirmed that the modified ZnO nanoparticles are evenly dispersed in the nanofibers according to Examples 2-1 to 2-3 and do not form aggregates. Through this, the silane-based compound can evenly disperse the modified ZnO nanoparticles in the nanofibers made of PAN.
[실험예 9: 제조예 1-2에 따른 나노섬유로 제조된 여과장치의 여과효율 및 품질계수 평가][Experimental Example 9: Evaluation of filtration efficiency and quality factor of the filtration device made of nanofibers according to Preparation Example 1-2]
도 13은 제조예 1-2에 따른 나노섬유로 제조된 여과장치의 여과효율(a) 및 품질계수(b)를 나타낸 것이다. 상기 제조예 1-2에 따른 나노섬유로 제조된 여과장치는 상기 실험예 4에서 전술한 방법으로 제조되었다.Figure 13 shows the filtration efficiency (a) and quality factor (b) of the filtration device made of nanofibers according to Preparation Example 1-2. A filtration device made of nanofibers according to Preparation Example 1-2 was manufactured by the method described in Experimental Example 4.
도 13(a)를 참고하면 실시예 1-1과 실시예 1-2 따른 나노섬유로 제조된 여과장치는 각각 비교예 4와 대비하여 동등 또는 그 이상의 여과효율을 보임을 확인할 수 있고, 실시예 2-1 내지 실시예 2-2에 따른 나노섬유로 제조된 여과장치는 비교예 5와 대비하여 동등 또는 그 이상의 여과효율을 보임을 확인할 수 있다.Referring to FIG. 13 (a), it can be seen that the filtration devices made of nanofibers according to Examples 1-1 and 1-2 show equal or higher filtration efficiencies compared to Comparative Example 4, respectively. It can be seen that the filtering devices made of the nanofibers according to Examples 2-1 to 2-2 showed equal or higher filtration efficiencies compared to Comparative Example 5.
도 13(b)를 참고하면 실시예 1-1 내지 1-3에 따른 여과장치의 품질계수는 Silane/ZnO(w/w)가 증가할수록 높아짐을 확인할 수 있는 반면, 실시예 2-1 내지 2-2에 따른 여과장치의 품질계수는 Silane/ZnO(w/w)가 증가할수록 낮아짐을 확인할 수 있다.Referring to FIG. 13 (b), it can be confirmed that the quality factor of the filtration device according to Examples 1-1 to 1-3 increases as Silane / ZnO (w / w) increases, whereas Examples 2-1 to 2 It can be seen that the quality factor of the filter according to -2 decreases as Silane/ZnO (w/w) increases.
[실험예 10: 비교예 5에 따른 나노섬유의 재생 성능 효과 입증실험][Experimental Example 10: Demonstration of regeneration performance effect of nanofibers according to Comparative Example 5]
도 14는 비교예 5에 따른 나노섬유의 재생 성능 효과를 입증하기 위한 실험이다. 구체적으로, 상기 실험예 9와 동일한 방법으로 상기 비교예 5에 따른 나노섬유로 제조된 여과장치의 여과성능 테스트를 수행한 후, 증류수를 이용하여 여과성능을 수행한 상기 여과장치를 세척하였다. 그 후, 여과성능 테스트 후의 상기 비교예 5에 따른 나노섬유와 증류수를 이용하여 세척한 상기 비교예 5에 따른 나노섬유를 SEM으로 관찰하여 비교하였다. 14 is an experiment to demonstrate the regeneration performance effect of nanofibers according to Comparative Example 5. Specifically, after performing the filtration performance test of the filtration device made of the nanofibers according to Comparative Example 5 in the same manner as in Experimental Example 9, the filtration device, which performed the filtration performance, was washed with distilled water. Then, the nanofibers according to Comparative Example 5 after the filtration performance test and the nanofibers according to Comparative Example 5 washed with distilled water were observed and compared by SEM.
도 14(a, c)를 참고하면 비교예 5에 따른 나노섬유는 여과성능 실험 후, KCl 미립자에 대해 상기 비교예 5에 따른 나노섬유가 필터 기능을 수행하였음을 확인할 수 있다. 또한, 도 14(e)를 참고하면 비교예 5에 따른 나노섬유의 EDX를 분석한 결과, KCl 미립자가 검출됨을 확인할 수 있다.Referring to Figure 14 (a, c), it can be confirmed that the nanofibers according to Comparative Example 5 performed a filter function for the KCl particulates after the filtration performance test. In addition, referring to FIG. 14 (e), as a result of analyzing the EDX of the nanofibers according to Comparative Example 5, it can be confirmed that KCl fine particles are detected.
도 14(b, d)를 참고하면, 상기 여과성능을 수행한 비교예 5에 따른 나노섬유를 증류수를 이용하여 세척한 결과, 응집체를 형성했던 KCl 미립자가 증류수에 용해되어 제거됨을 확인할 수 있다. 또한, 도 14(f)를 참고하면, 증류수로 세척된 이후에는 상기 여과성능을 수행한 비교예 5에 따른 나노섬유에 KCl 미립자가 검출되지 않음을 확인할 수 있고, 이를 통해 상기 여과성능을 수행한 비교예 5에 따른 나노섬유를 세척하여 다시 재사용이 가능하다는 점을 유추할 수 있다.Referring to Figure 14 (b, d), as a result of washing the nanofibers according to Comparative Example 5, which performed the filtration performance, using distilled water, it was confirmed that the KCl particles that formed aggregates were dissolved in distilled water and removed. In addition, referring to FIG. 14 (f), after washing with distilled water, it can be confirmed that no KCl particles are detected in the nanofibers according to Comparative Example 5 in which the filtration performance was performed, and through this, the filtration performance was performed. It can be inferred that the nanofibers according to Comparative Example 5 can be washed and reused again.
[실험예 11-1: 실시예 1-1 내지 1-3에 따른 나노섬유의 메틸렌 블루 분해 효율 평가][Experimental Example 11-1: Evaluation of Methylene Blue Decomposition Efficiency of Nanofibers According to Examples 1-1 to 1-3]
도 15는 비교예 4 대비, 시간의 경과에 따른 실시예 1-1 내지 1-3에 따른 나노섬유의 메티렌 블루 분해 효율을 나타낸 것이다. 측정방법은 상기 실험예 5와 동일한 방법으로 수행되었다.15 shows the methylene blue decomposition efficiency of the nanofibers according to Examples 1-1 to 1-3 over time, compared to Comparative Example 4. The measurement method was performed in the same manner as in Experimental Example 5.
도 15를 참고하면, 실시예 1-1 내지 1-3에 따른 나노섬유의 메틸렌 블루에 대한 분해 효율은 ZnO의 함량을 기준으로 실란계 화합물의 함량이 증가할수록, 증가하였음을 확인할 수 있다. 즉, 실시예 1-1 내지 1-3에 따른 나노섬유에 개질 ZnO 나노입자가 도입됨으로써, 비교예 4 대비 메틸렌 블루에 대한 분해 효율이 현저하게 향상되었음을 확인할 수 있다.Referring to FIG. 15, it can be seen that the decomposition efficiency of the nanofibers according to Examples 1-1 to 1-3 to methylene blue increased as the content of the silane-based compound increased based on the content of ZnO. That is, by introducing the modified ZnO nanoparticles into the nanofibers according to Examples 1-1 to 1-3, it can be confirmed that the decomposition efficiency of methylene blue compared to Comparative Example 4 is significantly improved.
[실험예 11-2: 실시예 2-1 내지 2-3에 따른 나노섬유의 메틸렌 블루 분해 효율 평가][Experimental Example 11-2: Evaluation of Methylene Blue Decomposition Efficiency of Nanofibers According to Examples 2-1 to 2-3]
도 16은 비교예 5 대비, 시간의 경과에 따른 실시예 2-1 내지 2-3에 따른 나노섬유의 메틸렌 블루 분해 효율을 나타낸 것이다. 측정방법은 상기 실험예 5와 동일한 방법으로 수행되었다.16 shows the methylene blue decomposition efficiency of the nanofibers according to Examples 2-1 to 2-3 over time, compared to Comparative Example 5. The measurement method was performed in the same manner as in Experimental Example 5.
도 16을 참고하면, 실시예 2-1에 따른 나노섬유의 메틸렌 블루에 대한 분해 효율이 다른 실시예들보다 더 높음을 확인할 수 있다. Referring to FIG. 16, it can be seen that the decomposition efficiency of the nanofibers according to Example 2-1 to methylene blue is higher than that of other Examples.
또한, 실시예 2-1 내지 2-3에 따른 나노섬유에 개질 ZnO 나노입자가 도입됨으로써, 비교예 5 대비 메틸렌 블루에 대한 분해 효율이 현저하게 향상되었음을 확인할 수 있다.In addition, it can be confirmed that the decomposition efficiency of methylene blue compared to Comparative Example 5 is significantly improved by introducing the modified ZnO nanoparticles into the nanofibers according to Examples 2-1 to 2-3.
이상에서 본 발명의 바람직한 실시예들에 대하여 상세하게 설명하였지만 본 발명의 권리 범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리 범위에 속하는 것이다.Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It falls within the scope of the right of invention.
Claims (20)
금속산화물 나노입자에서 유래된 개질 금속산화물 나노입자; 를 포함하고,
상기 개질 금속산화물 나노입자는,
실란계 화합물에 의해 개질된 것인
다기능성 나노섬유 형성용 조성물.high molecular compounds; and
Modified metal oxide nanoparticles derived from metal oxide nanoparticles; including,
The modified metal oxide nanoparticles,
which is modified by a silane-based compound
A composition for forming multifunctional nanofibers.
상기 고분자 화합물은,
폴리아크릴로니트릴(polyacrylonitrile; PAN), 폴리비닐리덴플루오라이드(polyvinylidene fluoride, PVDF), 폴리메틸메타크릴레이트(poly(methyl methacrylate), PMMA) 폴리비닐클로라이드(polyvinyl chloride, PVC), 폴리테트라플루오로에틸렌 (polytetrafluoroethylene, PTFE), 폴리우레탄(polyurethane, PU), 폴리카프로락톤(polycaprolactone, PCL), 폴리아크릴아마이드(polyacrylamide), 폴리아마이드(polyamide), 폴리(N-이소프로필아크릴아마이드)(poly(N-isopropylacrylamide), PNIPAAm), 폴리아크릴산(polyacrylic acid, PAA), 폴리아크릴레이트(polyacrylate), 폴리카르복실레이트(polycarboxylate), 폴리에틸렌이민(polyethylenimine), 폴리메타크릴산(poly(methacrylic acid)), 폴리에틸렌옥사이드(polyethylene oxide, PEO), 폴리비닐피롤리돈(polyvinylpyrrolidone, PVP) 및 폴리비닐알코올(polyvinyl alcohol)로 이루어진 군에서 선택된 어느 하나인
다기능성 나노섬유 형성용 조성물.According to claim 1,
The polymer compound,
Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), poly(methyl methacrylate) (PMMA), polyvinyl chloride (PVC), polytetrafluoro Ethylene (polytetrafluoroethylene, PTFE), polyurethane (PU), polycaprolactone (PCL), polyacrylamide, polyamide, poly(N-isopropylacrylamide) (poly(N -isopropylacrylamide), PNIPAAm), polyacrylic acid (PAA), polyacrylate, polycarboxylate, polyethylenimine, poly(methacrylic acid), polyethylene Any one selected from the group consisting of polyethylene oxide (PEO), polyvinylpyrrolidone (PVP) and polyvinyl alcohol
A composition for forming multifunctional nanofibers.
상기 고분자 화합물의 함량은,
상기 다기능성 나노섬유 형성용 조성물의 전체 중량을 기준으로 5 내지 15 중량%인,
다기능성 나노섬유 형성용 조성물.According to claim 1,
The content of the polymer compound is,
5 to 15% by weight based on the total weight of the multifunctional nanofiber-forming composition,
A composition for forming multifunctional nanofibers.
상기 금속산화물 나노입자는,
ZnO, SnO2, ZrO2, TiO2, WO3 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나인
다기능성 나노섬유 형성용 조성물.According to claim 1,
The metal oxide nanoparticles,
Any one selected from the group consisting of ZnO, SnO 2 , ZrO 2 , TiO 2 , WO 3 and combinations thereof
A composition for forming multifunctional nanofibers.
상기 실란계 화합물은,
비닐트리스(2-메톡시에톡시)실란, 비닐트리에톡시실란, 비닐트리메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 2-(3,4-에폭시사이클로헥실)-에틸트리메톡시실란, 3-글리시딜옥시프로필트리메톡시실란, 3-글리시딜옥시프로필메틸디에톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란, 3-아미노프로필메틸디에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-클로로프로필트리메톡시실란, 3-클로로프로필트리에톡시실란, 3-머캅토프로필트리메톡시실란 및 3-머캅토프로필트리에톡시실란으로 이루어진 군에서 선택된 어느 하나인,
다기능성 나노섬유 형성용 조성물.According to claim 1,
The silane-based compound,
Vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 2-(3 ,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-amino Propylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxy Any one selected from the group consisting of silane,
A composition for forming multifunctional nanofibers.
상기 개질 금속산화물 나노입자의 함량은,
상기 다기능성 나노섬유 형성용 조성물의 전체 중량을 기준으로 0 초과 15 중량% 이하인,
다기능성 나노섬유 형성용 조성물.According to claim 1,
The content of the modified metal oxide nanoparticles,
More than 0 and 15% by weight or less based on the total weight of the multifunctional nanofiber-forming composition,
A composition for forming multifunctional nanofibers.
상기 금속산화물 나노입자와 상기 실란계 화합물의 중량비는 1: 0.25 내지 1:10인,
다기능성 나노섬유 형성용 조성물. According to claim 1,
The weight ratio of the metal oxide nanoparticle and the silane-based compound is 1: 0.25 to 1:10,
A composition for forming multifunctional nanofibers.
제1 용매; 를 더 포함하는
다기능성 나노섬유 형성용 조성물.According to claim 1,
a first solvent; further comprising
A composition for forming multifunctional nanofibers.
(S2) 가수분해된 실란계 화합물과 금속산화물 나노입자를 혼합하여 개질 금속산화물 나노입자를 제조하는 단계; 및
(S3) 상기 개질 금속산화물 나노입자와 상기 고분자 혼합 용액을 혼합하여 다기능성 나노섬유 형성용 조성물을 제조하는 단계; 를 포함하는
다기능성 나노섬유 형성용 조성물의 제조방법.(S1) preparing a polymer mixture solution by mixing a polymer compound and a second solvent;
(S2) preparing modified metal oxide nanoparticles by mixing the hydrolyzed silane-based compound and the metal oxide nanoparticles; and
(S3) preparing a composition for forming multifunctional nanofibers by mixing the modified metal oxide nanoparticles and the polymer mixture solution; containing
A method for preparing a composition for forming multifunctional nanofibers.
상기 가수분해된 실란계 화합물은,
가수분해 용매와 실란계 화합물을 혼합하여 제조된 것인,
다기능성 나노섬유 형성용 조성물의 제조방법.According to claim 9,
The hydrolyzed silane-based compound,
It is prepared by mixing a hydrolysis solvent and a silane-based compound,
A method for preparing a composition for forming multifunctional nanofibers.
상기 실란계 화합물과 상기 가수분해 용매의 중량비는 1: 50 내지 1: 200인,
다기능성 나노섬유 형성용 조성물의 제조방법.According to claim 10,
The weight ratio of the silane-based compound and the hydrolysis solvent is 1: 50 to 1: 200,
A method for preparing a composition for forming multifunctional nanofibers.
상기 다기능성 나노섬유 형성용 조성물의 전체 중량을 기준으로
상기 고분자 혼합 용액의 함량은,
85 중량% 이상 100 중량% 미만이고,
상기 개질 금속산화물 나노입자의 함량은,
0 중량% 초과 15 중량% 이하인,
다기능성 나노섬유 형성용 조성물의 제조방법.According to claim 9,
Based on the total weight of the multifunctional nanofiber-forming composition
The content of the polymer mixture solution,
85% by weight or more and less than 100% by weight,
The content of the modified metal oxide nanoparticles,
More than 0% by weight and up to 15% by weight,
A method for preparing a composition for forming multifunctional nanofibers.
상기 다기능성 나노섬유는,
20 내지 25℃, 상대습도 40 내지 50%, 전압 15 내지 20kV, 방사거리 10 내지 20cm, 및 니들직경 21 내지 23gauge에서 상기 다기능성 나노섬유 형성용 조성물을 전기방사하여 제조된 것인,
다기능성 나노섬유.According to claim 13,
The multifunctional nanofibers,
20 to 25 ℃, relative humidity 40 to 50%, voltage 15 to 20kV, spinning distance 10 to 20cm, and needle diameter 21 to 23gauge of the composition for forming the multifunctional nanofibers prepared by electrospinning,
Multifunctional nanofibers.
상기 다기능성 나노섬유의 직경은 261 내지 422nm인
다기능성 나노섬유.According to claim 13,
The diameter of the multifunctional nanofiber is 261 to 422 nm
Multifunctional nanofibers.
상기 다기능성 나노섬유의 비표면적(BET, specific surface area)은 10 내지 36 m2/g인
다기능성 나노섬유.According to claim 13,
The specific surface area (BET, specific surface area) of the multifunctional nanofiber is 10 to 36 m 2 /g
Multifunctional nanofibers.
상기 다기능성 나노섬유 형성용 조성물의 점도는 344 내지 737 cP인
다기능성 나노섬유.According to claim 13,
The viscosity of the multifunctional nanofiber-forming composition is 344 to 737 cP.
Multifunctional nanofibers.
상기 여과장치는,
마스크, 공기청정기, 환기설비 및 에어컨으로 이루어진 군에서 선택된 어느 하나인,
여과장치.
According to claim 19,
The filter device is
Any one selected from the group consisting of masks, air purifiers, ventilation equipment and air conditioners,
filter device.
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| KR20130070333A (en) | 2011-12-19 | 2013-06-27 | 서울대학교산학협력단 | Fabrication of zno nanoparticles embedded tio2 nanofibers by electrospinning and antibactericidal application under uv, visible light and without light irradiation |
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