KR100703607B1 - Methof of manufacturing poly-vinyl-alcohol nano fiber non-woven - Google Patents
Methof of manufacturing poly-vinyl-alcohol nano fiber non-woven Download PDFInfo
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- KR100703607B1 KR100703607B1 KR1020050118817A KR20050118817A KR100703607B1 KR 100703607 B1 KR100703607 B1 KR 100703607B1 KR 1020050118817 A KR1020050118817 A KR 1020050118817A KR 20050118817 A KR20050118817 A KR 20050118817A KR 100703607 B1 KR100703607 B1 KR 100703607B1
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- polyvinyl alcohol
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4309—Polyvinyl alcohol
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/06—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
Abstract
본 발명은 폴리비닐알코올 나노 섬유 부직포의 제조방법에 관한 것으로, 폴리비닐알코올 수지를 증류수에 용해하여 소정의 고형성분을 가지는 방사용액을 형성하는 용해 단계; 상기 용해 단계에서 형성된 방사용액을 전기방사장치의 전압이 걸려있는 노즐을 통해 방사하여 컬렉터(collector)상에 집적하여 폴리비닐알코올 나노 웹(web)을 생성하는 전기방사 단계; 및The present invention relates to a method for producing a polyvinyl alcohol nanofiber nonwoven fabric, comprising: dissolving a polyvinyl alcohol resin in distilled water to form a spinning solution having a predetermined solid component; An electrospinning step of generating a polyvinyl alcohol nano web by spinning the spinning solution formed in the dissolving step through a nozzle on which a voltage of an electrospinning device is applied to accumulate on a collector; And
상기 전기방사 단계에서 생성된 폴리비닐알코올 나노 웹을 유리전이온도 이상의 온도로부터 결정화온도 이하의 온도로 열처리하는 열처리 단계;를 포함하는 것을 특징으로 한다.And heat-treating the polyvinyl alcohol nanoweb generated in the electrospinning step from a temperature above a glass transition temperature to a temperature below a crystallization temperature.
본 발명에 의한 폴리비닐알코올 나노 섬유 부직포의 제조방법은 열처리를 통한 결정성의 향상과 부분가교를 통한 내수성의 향상으로 용도의 전개를 쉽게 할 수 있으며, 용매로 증류수만을 이용하고, 어떤 화학적 처리를 하지 않음으로서 폴리비닐알코올이 가지는 생체적합성의 고유한 성질을 변화시키지 않으면서도 전기방사시 제조되는 나노웹의 특성을 발현시킴으로써 의료용 응용분야로의 폭넓은 확대를 가질 수 있는 장점이 있다.The method for producing a polyvinyl alcohol nanofiber nonwoven fabric according to the present invention can be easily developed by improving the crystallinity through heat treatment and the water resistance through partial crosslinking, using only distilled water as a solvent, and not performing any chemical treatment. By not expressing the properties of the nanoweb prepared during electrospinning without changing the inherent properties of the biocompatibility of polyvinyl alcohol has the advantage that it can have a broad expansion into medical applications.
전기방사, 폴리비닐알코올, PVA, 생체친화성고분자 Electrospinning, polyvinyl alcohol, PVA, biocompatible polymer
Description
도 1은 본 발명에 의한 폴리비닐알코올 나노 섬유 부직포의 제조방법을 나타낸 도면.1 is a view showing a method for producing a polyvinyl alcohol nanofiber nonwoven fabric according to the present invention.
도 2는 본 발명의 제1 실시예로, 150℃에서 열처리 후의 폴리비닐알코올 나노 섬유 부직포의 SEM 사진.Figure 2 is a first embodiment of the present invention, a SEM photograph of a polyvinyl alcohol nanofiber nonwoven fabric after heat treatment at 150 ℃.
도 3은 본 발명의 제2 실시예로, 170℃에서 열처리 후의 폴리비닐알코올 나노 섬유 부직포의 SEM 사진.Figure 3 is a second embodiment of the present invention, a SEM photograph of a polyvinyl alcohol nanofiber nonwoven fabric after heat treatment at 170 ℃.
도 4는 본 발명의 제3 실시예로, 190℃에서 열처리 후의 폴리비닐알코올 나노 섬유 부직포의 SEM 사진.Figure 4 is a third embodiment of the present invention, a SEM photograph of a polyvinyl alcohol nanofiber nonwoven fabric after heat treatment at 190 ℃.
도 5는 열처리를 하지 않은 폴리비닐알코올 나노 섬유 부직포의 SEM 사진.5 is a SEM photograph of a polyvinyl alcohol nanofiber nonwoven fabric not subjected to heat treatment.
도 6은 210℃에서 열처리 후의 폴리비닐알코올 나노 섬유 부직포의 SEM 사진.6 is a SEM photograph of a polyvinyl alcohol nanofiber nonwoven fabric after heat treatment at 210 ° C.
<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>
S10 : 용해 단계 S20 : 전기방사 단계S10: dissolution step S20: electrospinning step
S30 : 열처리 단계S30: heat treatment step
본 발명은 폴리비닐알코올 나노 섬유 부직포의 제조 방법에 관한 것으로, 더욱 상세하게는 우수한 내수성을 가지는 섬유직경이 1~500nm 수준인 초극세 섬유로 구성된 폴리비닐알코올 나노 섬유 부직포를 전기방사법으로 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a polyvinyl alcohol nanofiber nonwoven fabric, and more particularly, to a method for producing a polyvinyl alcohol nanofiber nonwoven fabric composed of ultra-fine fibers having a fiber diameter of 1 to 500 nm having excellent water resistance. It is about.
일반적으로 알코올기(-OH)를 포함하는, -(CH2CHOH)n-의 분자식을 가지는 폴리비닐알코올 수지는 환경친화적인 생체친화성고분자로 알려져 있지만, 수지 자체가 갖고 있는 친수성 때문에 전기방사로 인한 나노 스케일의 크기변화에 따른 내수성의 취약함으로 인해 많은 용도로의 사용이 제한되어 왔다.Generally, polyvinyl alcohol resin having a molecular formula of-(CH2CHOH) n -containing an alcohol group (-OH) is known as an environmentally friendly biocompatible polymer, but due to the hydrophilicity of the resin itself, Due to the weakness of water resistance due to the change in scale size, its use for many purposes has been limited.
미국공개특허공보 제20030215624호에는 종래의 폴리비닐알코올 웹 제조방법이 개시되어 있다.US Patent Publication No. 20030215624 discloses a conventional polyvinyl alcohol web manufacturing method.
종래의 폴리비닐알코올 웹 제조방법은 폴리비닐알코올 수용액에 비이온성 계면활성제를 첨가하고, 전기방사 하여 웹을 제조하고, 메탄올에 침지시켜 폴리비닐알코올 웹을 제조한다.In the conventional polyvinyl alcohol web manufacturing method, a nonionic surfactant is added to an aqueous polyvinyl alcohol solution, electrospun to prepare a web, and immersed in methanol to prepare a polyvinyl alcohol web.
그러나 종래의 제조 방법으로 제조된 폴리비닐알코올 웹의 경우 비록 내수성을 향상시킬 수 있지만, 유기용제의 사용으로 인한 의료용 용도로의 사용에 많은 제약이 있었다.However, in the case of the polyvinyl alcohol web manufactured by the conventional manufacturing method, although the water resistance can be improved, there are many limitations in the use for medical use due to the use of the organic solvent.
본 발명은 상기와 같은 문제점을 해결하기 위하여 제안된 것으로서, 증류수에 폴리비닐알코올 수지를 용해시키고 전기방사하여 제조된 나노 웹을 진공 열처리하여 결정성의 향상 및 부분 가교 반응을 일으켜 내수성을 향상시킴으로써 상처보호용 와운드 드레스(Wound dress)나 인공피부 등과 같은 의료용으로 유용한 나노 섬유 부직포를 간단한 제조공정으로 제조할 수 있는 폴리비닐알코올 나노 섬유 부직포의 제조방법을 제공하는데 그 목적이 있다.The present invention has been proposed to solve the above problems, by dissolving polyvinyl alcohol resin in distilled water and vacuum heat treatment of the nano-web prepared by electrospinning to improve the crystallinity and partial crosslinking reaction to improve water resistance for wound protection It is an object of the present invention to provide a method for producing a polyvinyl alcohol nanofiber nonwoven fabric which can manufacture a nanofiber nonwoven fabric useful for medical purposes such as a wound dress or artificial skin in a simple manufacturing process.
상기 기술적 과제를 이루기 위한 본 발명에 따른 폴리비닐알코올 나노 섬유 부직포의 제조방법은 폴리비닐알코올 수지를 증류수에 용해하여 소정의 고형성분을 가지는 방사용액을 형성하는 용해 단계; 상기 용해 단계에서 형성된 방사용액을 전기방사장치의 전압이 걸려있는 노즐을 통해 방사하여 컬렉터(collector)상에 집적하여 폴리비닐알코올 나노 웹(web)을 생성하는 전기방사 단계; 및 상기 전기방사 단계에서 생성된 폴리비닐알코올 나노 웹을 유리전이온도 이상의 온도로부터 결정화 온도 이하의 온도로 열처리하는 열처리 단계;를 포함하는 것을 특징으로 한다.Method for producing a polyvinyl alcohol nanofiber nonwoven fabric according to the present invention for achieving the above technical problem is a dissolving step of dissolving a polyvinyl alcohol resin in distilled water to form a spinning solution having a predetermined solid component; An electrospinning step of generating a polyvinyl alcohol nano web by spinning the spinning solution formed in the dissolving step through a nozzle on which a voltage of an electrospinning device is applied to accumulate on a collector; And heat-treating the polyvinyl alcohol nano web generated in the electrospinning step from a temperature above a glass transition temperature to a temperature below a crystallization temperature.
이하에서는 본 발명의 구체적인 실시예를 도면을 참조하여 상세히 설명하도록 한다.Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명에 의한 폴리비닐알코올 나노 섬유 부직포의 제조방법을 나타낸 것으로 폴리비닐알코올을 증류수에 용해하는 용해 단계(S10), 용해된 폴리비닐알코올을 전기방사하는 전기방사 단계(S20) 및 전기방사된 폴리비닐알코올을 열처리하는 열처리 단계(S30)로 구성된다.1 shows a method for producing a polyvinyl alcohol nanofiber nonwoven fabric according to the present invention, a dissolution step (S10) of dissolving polyvinyl alcohol in distilled water, an electrospinning step (S20) of electrospinning the dissolved polyvinyl alcohol, and an electric It consists of a heat treatment step (S30) for heat treating the spun polyvinyl alcohol.
용해 단계(S10)에서는 중합도 200 ~ 7,000, 검화도 85mol% 이상 폴리비닐알코올을 용매에 용해하여 고형성분이 9g/dl인 방사용액을 형성한다.In the dissolution step (S10), polyvinyl alcohol having a degree of polymerization of 200 to 7,000 and saponification degree of 85 mol% or more is dissolved in a solvent to form a spinning solution having a solid component of 9 g / dl.
용매는 증류수를 사용하는데 증류수를 사용하는 이유는 후술할 전기방사 단계(S20)후 폴리비닐알코올 나노 웹의 수분 및 통기성이 좋고, 세균으로부터 상처를 보호하고 체액이 스며들지 않기 때문에 상처치유 후 제거가 용이하기 때문이다.The solvent uses distilled water, but the reason for using distilled water is that the water and breathability of the polyvinyl alcohol nano web after the electrospinning step (S20) to be described later is good because it protects the wound from bacteria and does not penetrate the body fluid so that the removal after the wound is healed. Because it is easy.
전기방사 단계(S20)에서는 용해 단계(S10)에서 형성된 방사용액을 전기방사장치의 전압이 걸려있는 노즐을 통해 방사하여 컬렉터상에 집적한다.In the electrospinning step (S20), the spinning solution formed in the dissolving step (S10) is spun through a nozzle on which the voltage of the electrospinning device is applied and integrated on the collector.
전기방사시 인가전압을 15 kV 이상으로 하게되면 충분한 전기방사의 효과를 얻을 수 있다.When the applied voltage is 15 kV or more during electrospinning, sufficient electrospinning effect can be obtained.
열처리 단계(S30)에서는 폴리비닐알코올 나노웹을 열처리하여 결정성을 향상시킨다.In the heat treatment step (S30) to improve the crystallinity by heat-treating the polyvinyl alcohol nanoweb.
이 경우 열처리시 어떠한 가교제도 사용하지 않고 부분 가교화 반응을 진행시킴으로서 상기 나노웹의 내수성을 향상시킨다.In this case, a partial crosslinking reaction is performed without using any crosslinking agent during heat treatment, thereby improving water resistance of the nanoweb.
열처리는 유리전이 온도 이상, 결정화 온도 이하에서 행하는 것이 바람직한데, 결정화 온도 이상에서 열처리를 하게 되면 폴리비닐알코올 나노 웹이 열분해되고, 너무 낮은 온도에서 열처리를 하게 되면 열처리의 효과가 없다. 따라서, 열처리 단계는 폴리비닐알코올의 유리전이 온도(Tg)인 80℃ 이상에서 결정화 온도(Tcc)인 190℃ 이하에서 이루어진다.The heat treatment is preferably carried out above the glass transition temperature and below the crystallization temperature. When the heat treatment is performed above the crystallization temperature, the polyvinyl alcohol nanoweb is thermally decomposed, and when the heat treatment is performed at a too low temperature, there is no effect of the heat treatment. Therefore, the heat treatment step is performed at 80 ° C. or more, which is the glass transition temperature (Tg) of polyvinyl alcohol, at 190 ° C. or less, which is the crystallization temperature (Tcc).
도 2 내지 도 4는 본 발명의 실시예들로서, 각각 150℃, 170℃, 190℃에서 열처리 후의 폴리비닐알코올 나노 섬유 부직포의 SEM 사진을 나타낸 것이다.2 to 4 illustrate embodiments of the present invention, which illustrate SEM images of polyvinyl alcohol nanofiber nonwoven fabrics after heat treatment at 150 ° C., 170 ° C., and 190 ° C., respectively.
도 5는 열처리를 실시하지 않은 경우의 나노 웹의 전자현미경 사진을 나타낸 것이다.5 shows an electron micrograph of the nanoweb when the heat treatment is not performed.
도 6은 폴리비닐알코올 나노 웹의 결정화 온도 이상의 온도인 210℃에서 열처리한 경우의 나노 웹의 전자현미경 사진을 나타낸 것이다. Figure 6 shows an electron micrograph of the nano-web when the heat treatment at 210 ℃, the temperature above the crystallization temperature of the polyvinyl alcohol nano-web.
도 2 내지 도 6에 의한 각각의 물성은 열처리후의 폴리비닐알코올의 중량 감소율을 계산함으로서 알 수 있는데, 제조된 나노웹을 각각 가로 5cm, 세로 5cm 크기로 자른 후 일반적으로 폴리비닐알코올이 완전하게 용해되는 조건인 95℃의 증류수에 10분간 침지한 후 24시간동안 상온에서 건조시킨다. 그런 후 침지전과 침지후의 나노웹의 무게를 정량함으로써 나노웹의 무게 감소율을 계산한다.Each of the physical properties according to FIGS. 2 to 6 can be seen by calculating the weight reduction rate of polyvinyl alcohol after heat treatment. After cutting the prepared nanoweb into 5 cm and 5 cm, respectively, polyvinyl alcohol is generally completely dissolved. After dipping in distilled water at 95 ° C. for 10 minutes, it is dried at room temperature for 24 hours. Then, the weight reduction rate of the nanoweb is calculated by quantifying the weight of the nanoweb before and after immersion.
표 1은 각각의 온도에서 열처리 후의 폴리비닐알코올 나노 웹의 중량 감소율을 나타낸 것이다.Table 1 shows the weight reduction rate of the polyvinyl alcohol nano web after heat treatment at each temperature.
표 1에 의하면 150℃에서 열처리를 하였을때 다소 큰 중량감소율을 보이고, 170℃와 190℃에서 열처리를 하였을 때는 다소 작은 중량 감소율을 보임을 알 수 있다. 또한 폴리비닐알코올 나노 웹의 결정화온도보다 높은 온도인 210℃에서 열처리를 하였을 때는 열분해가 됨을 알 수 있다.According to Table 1, when the heat treatment at 150 ℃ shows a rather large weight loss rate, when the heat treatment at 170 ℃ and 190 ℃ it can be seen that a slightly smaller weight reduction rate. In addition, it can be seen that the thermal decomposition is performed when the heat treatment at a temperature higher than the crystallization temperature of the polyvinyl alcohol nano web 210 ℃.
상기의 결과로 사용자는 원하는 결정의 상태에 있는 폴리비닐알코올 나노 섬유 부직포를 선택할 수 있다.As a result of this, the user can select the polyvinyl alcohol nanofiber nonwoven fabric in the state of the desired crystal.
이상에서 본 발명에 대한 기술사상을 첨부 도면과 함께 서술하였지만 이는 본 발명의 바람직한 실시예를 예시적으로 설명한 것이지 본 발명을 한정하는 것은 아니다. 또한 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 누구나 본 발명의 기술적 사상의 범주를 이탈하지 않는 범위 내에서 다양한 변형 및 모방이 가능함은 명백한 사실이다.The technical spirit of the present invention has been described above with reference to the accompanying drawings. However, the present invention has been described by way of example only, and is not intended to limit the present invention. In addition, it is apparent that any person having ordinary knowledge in the technical field to which the present invention belongs may make various modifications and imitations without departing from the scope of the technical idea of the present invention.
본 발명에 의한 폴리비닐알코올 나노 섬유 부직포의 제조방법은 열처리를 통한 결정성의 향상과 부분가교를 통한 내수성의 향상으로 용도의 전개를 쉽게 할 수 있는 장점이 있다.The method for producing a polyvinyl alcohol nanofiber nonwoven fabric according to the present invention has an advantage in that the development of the application can be easily performed by improving crystallinity through heat treatment and water resistance through partial crosslinking.
또한 본 발명의 경우 용매로 증류수만을 이용하고, 어떤 화학적 처리를 하지 않음으로 인하여 폴리비닐알코올이 가지는 생체적합성의 고유한 성질을 변화시키지 않으면서도 전기방사시 제조되는 나노웹의 특성을 발현시킴으로써 의료용 응용분야로의 폭넓은 확대를 가질 수 있는 장점이 있다.In addition, in the case of the present invention, by using only distilled water as a solvent, without any chemical treatment, by expressing the characteristics of the nanoweb prepared during electrospinning without changing the inherent properties of the biocompatibility of polyvinyl alcohol, medical applications It has the advantage of having a broad expansion into the field.
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| KR20160033384A (en) * | 2014-09-18 | 2016-03-28 | 재단법인대구경북과학기술원 | Preparation method of dry-type skin care pack composed of nano fiber web and non-woven fabric, dry-type skin care pack prepared by the same, and skin care method using the dry-type skin care pack |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101033278B1 (en) | 2009-06-25 | 2011-05-09 | 이화여자대학교 산학협력단 | Improved preparation method of PVA nanofiber membrane using electrospinning |
| KR20160033384A (en) * | 2014-09-18 | 2016-03-28 | 재단법인대구경북과학기술원 | Preparation method of dry-type skin care pack composed of nano fiber web and non-woven fabric, dry-type skin care pack prepared by the same, and skin care method using the dry-type skin care pack |
| KR101643814B1 (en) | 2014-09-18 | 2016-07-28 | 재단법인대구경북과학기술원 | Preparation method of dry-type skin care pack composed of nano fiber web and non-woven fabric, dry-type skin care pack prepared by the same, and skin care method using the dry-type skin care pack |
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