WO2018164390A1 - Sbs fiber mat with improved water absorbency and method for manufacturing same - Google Patents

Sbs fiber mat with improved water absorbency and method for manufacturing same Download PDF

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WO2018164390A1
WO2018164390A1 PCT/KR2018/001992 KR2018001992W WO2018164390A1 WO 2018164390 A1 WO2018164390 A1 WO 2018164390A1 KR 2018001992 W KR2018001992 W KR 2018001992W WO 2018164390 A1 WO2018164390 A1 WO 2018164390A1
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sbs
poly
fiber mat
ethylene glycol
mat
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PCT/KR2018/001992
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French (fr)
Korean (ko)
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임정균
양혜진
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순천향대학교 산학협력단
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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
    • D04H1/4326—Condensation or reaction polymers
    • 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
    • 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
    • D04H13/00—Other non-woven fabrics

Definitions

  • the present invention relates to a fiber mat including SBS and a method of manufacturing the same, and more particularly, to a SBS fiber mat having improved water absorption compared to a fiber mat manufactured by SBS alone.
  • SBS generally refers to a block copolymer containing styrene-butadiene-styrene triple block. SBS has various uses, and is widely used for heat modifiers, asphalt modifiers, plastic modifiers, and compounding compounds. It is used.
  • Polystyrene chains in SBS are strong and hard plastics, which enhance the durability of SBS, and polybutadiene is a rubbery material, which acts to make SBS behave like rubber.
  • SBS exhibits the properties of rubber at room temperature and can be melted and molded like plastic when heat is applied.
  • the polymer SBS can be made of fibers (fibers) by a spinning technique such as electrospinning, such SBS fibers are nonwoven in a certain shape, for example, a flat mat shape (non-woven) Can be
  • Electrospinning is the only way to produce continuous, high-volume nanofibers from a variety of polymers and has several advantages: That is, it is possible to produce fibers having various diameters ranging from several nm to several hundred nm, and the equipment is simpler than the conventional nonwoven fabric matrix manufacturing method, and can be applied to a wide range of polymer materials. Electrospinning is the process of producing a non-woven matrix of nanofibers by releasing a millimeter diameter liquid jet through a thin glass tube or nozzle. One side of the electrode is in the polymer solution, and the other is located between the two electrodes with opposite polarities, located in the collector. The polymer solution is radiated once through a thin outlet and the solution evaporates and the fibers are collected in the collector.
  • the potential difference applied depends on the properties of the spinning solution, the molecular weight of the polymer, the viscosity, and the like. If the distance between the outlet and the collector is short, the evaporation of the solvent is not sufficient, so the fibers are entangled with each other as well as with the collector.
  • the principle that nanofibers are made is that as the electric field increases, the liquid at the end of the capillary changes from a hemispherical to a conical form known as the Taylor cone. As the electric field increases further, the repulsive force becomes greater than the surface tension, and the electrostatic liquid is radiated in the form of thin fibers in the Taylor cone at the capillary end.
  • the determinants of the properties of the nanofibers are mainly determined by the properties of the polymer solution and the properties of the electrospinner.
  • Korean Patent Registration No. 10-0943419, Korean Patent Publication No. 10-2011-0105199, and Korean Patent Publication No. 10-2012-0111381 disclose technologies for manufacturing fibers using polymers. It is not disclosed about the technology of manufacturing the SBS, the fiber through the electrospinning and the fiber in a mat shape. In particular, SBS has good elasticity due to the rubber properties, but there is a problem that can not be used in applications that need water absorption because of poor water absorption.
  • the present invention provides a fiber mat comprising SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol).
  • the poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is preferably 2 to 30 parts by weight based on 100 parts by weight of SBS.
  • the present invention provides a method for producing the SBS fiber mat, comprising the steps of mixing and mixing SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) in a solvent to prepare a solution; And it provides a method for producing an SBS fiber mat with improved water absorbency comprising the step of preparing a fiber mat using the solution.
  • the manufacture of the fiber mat of the solution is preferably by electrospinning.
  • the poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) preferably contains 2 to 30 parts by weight based on 100 parts by weight of the SBS.
  • the solvent is preferably at least one selected from dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran (THF), dimethylsiloxane, dimetholformamide and acetonitrile.
  • the solvent is preferably a mixed solvent of THF and DMF.
  • the present invention is made by spinning a solution in which poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is further mixed with SBS to prepare a mat, thereby improving water absorption compared to conventional SBS alone. Fiber mats can be produced.
  • poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is further mixed with SBS to prepare a mat, thereby improving water absorption compared to conventional SBS alone.
  • Fiber mats can be produced.
  • Example 3 In the sample of Example 3 using 1.2 g and 0.072 g of poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol), it can be seen that the water contact angle was very good at 1 degree.
  • Example 8 is a water drop photograph when measuring the contact angle of the fiber mat of Example 1.
  • Example 11 is a graph showing the tensile strength test results for the fiber mat of Example 1.
  • Example 12 is a graph of tensile strength test results for the fiber mat of Example 2.
  • Example 13 is a graph of tensile strength test results for the fiber mat of Example 3.
  • the present invention relates to an SBS fiber mat made of SBS as a main raw material and a method for manufacturing the same.
  • the water absorptivity is not used. Provides a technique for manufacturing the SBS fiber mat.
  • a method for producing an SBS fiber mat comprising: preparing a mixed solution by mixing SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) in a solvent; And it provides a SBS fiber mat manufacturing method comprising the step of preparing the solution into a fiber mat.
  • poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) used for improving water absorption of SBS has a structure as shown in the following Chemical Formula 2.
  • PF-108 is preferably used in an amount of 2 to 30 parts by weight based on 100 parts by weight of SBS.
  • PF-108 is preferably used in an amount of 2 to 30 parts by weight based on 100 parts by weight of SBS.
  • the solvent is preferably at least one selected from dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran (THF), dimethylsiloxane, dimetholformamide (DMF) and acetonitrile.
  • THF tetrahydrofuran
  • DMF dimetholformamide
  • acetonitrile a mixed solvent of THF and DMF was used in the following experiment.
  • the method of preparing the solution into a fiber mat may be various methods, for example, wet spinning, dry spinning, melt spinning, and the like, but electrospinning was used in the experiment of the present invention.
  • SBS vs. SBS fiber mat was prepared by varying the content ratio of PF-108 in three ways.
  • Example 1 was prepared in thickness.
  • 1 is a photograph of a mat of Example 1
  • FIG. 2 is a SEM photograph thereof.
  • Solvent is a total of 8ml mixed solvent of 6ml THF and 2ml DMF
  • Exemplary fiber mat of Example 3 is Wavenumber 1492cm -1, 1451cm -1, 911 has a peak of SBS Styrene or in cm -1, Wavenumber 965cm -1 in or has a peak of SBS Butadiene, Wavenumber 1348cm -1, 1278cm At -1 and 1243 cm -1 , the peak of PF-108 was found. Wavenumber 1100cm -1 showed the peak of COC bond of PF-108.
  • Example 1 0.3ul of distilled water was dropped on the fiber mat of Example 1 and the contact angle was measured using a contact angle meter (DSA10-Mk2 / DO3020 Mk1 / DO3021 Mk2, KRUSS, Germany), and the contact angle was 108 degrees. 8 is a water drop photograph when measuring the contact angle of the fiber mat of Example 1.
  • the contact angle was measured in the same manner for the fiber mat of Example 2, the contact angle was 55 degrees. 9 is a water drop photograph at the time of contact angle measurement for the sample of Example 2.
  • FIG. 9 is a water drop photograph at the time of contact angle measurement for the sample of Example 2.
  • the contact angle was measured in the same manner with the fiber mat of Example 3, and the contact angle was 1 degree.
  • 10 is a water droplet photograph at the time of contact angle measurement for the sample of Example 3.
  • Example 1 After preparing the fiber mat of Example 1 to a length of 3.8cm, 0.869mm size, the elongation rate according to the tensile strength was measured using UTM (DTU-900MHA, Daekyung Tech Co., Korea). When the tensile strength was 107 Pa, the maximum elongation was 7.23 and was broken. 11 is a graph of tensile strength test results.
  • Example 2 After preparing the fiber mat of Example 2 to a length of 3.8cm, 0.860mm size, the elongation rate according to the tensile strength was measured using UTM (DTU-900MHA, Daekyung Tech Co., Korea). When the tensile strength was 273 Pa, the maximum elongation was 10.04 and fractured. 12 is a graph of tensile strength test results.
  • Example 3 After preparing the fiber mat of Example 3 to a length of 3.8cm, 0.855mm size, the elongation rate according to the tensile strength was measured using UTM (DTU-900MHA, Daekyung Tech Co., Korea). When the tensile strength was 308 Pa, the maximum elongation was 10.91 and fractured.
  • Figure 13 is a graph of tensile strength test results.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)

Abstract

A fiber mat formed of SBS has a problem in that the fiber mat cannot be used for a purpose requiring water absorbency due to low water absorbency thereof. However, the present invention is characterized in that a mat is manufactured through spinning after the addition of poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) to SBS, leading to improved water absorbency.

Description

물흡수성이 개선된 SBS 파이버 매트 및 그 제조 방법SBS fiber mat with improved water absorption and manufacturing method thereof
본 발명은 SBS를 포함하는 파이버 매트 및 그 제조 방법에 관한 기술로서, 더욱 구체적으로는 SBS 단독으로 제조되는 파이버 매트에 비해 물흡수성이 개선된 SBS 파이버 매트에 관한 기술이다.The present invention relates to a fiber mat including SBS and a method of manufacturing the same, and more particularly, to a SBS fiber mat having improved water absorption compared to a fiber mat manufactured by SBS alone.
SBS(화학식 1 참조)는 일반적으로 스티렌-부타디엔-스티렌 3중 블록을 포함하고 있는 블록 공중합체를 말하는데, SBS의 용도는 다양하여 열용융 접착제용 이외에도 아스팔트 개질제, 플라스틱 개질제, 컴파운딩용 등으로 널리 사용되고 있다.SBS (see Formula 1) generally refers to a block copolymer containing styrene-butadiene-styrene triple block. SBS has various uses, and is widely used for heat modifiers, asphalt modifiers, plastic modifiers, and compounding compounds. It is used.
<화학식 1><Formula 1>
Figure PCTKR2018001992-appb-I000001
Figure PCTKR2018001992-appb-I000001
SBS 중 폴리스티렌 사슬은 강하고 딱딱한 플라스틱으로 SBS의 내구성을 증진시키는 역할을 하며, 폴리부타디엔은 고무상 물질로 SBS가 고무처럼 거동하도록 하는 역할을 한다. SBS는 상온에서 고무의 성질을 나타내며 열을 가하면 플라스틱과 같이 용융되어 성형이 가능하다. Polystyrene chains in SBS are strong and hard plastics, which enhance the durability of SBS, and polybutadiene is a rubbery material, which acts to make SBS behave like rubber. SBS exhibits the properties of rubber at room temperature and can be melted and molded like plastic when heat is applied.
한편, 고분자인 SBS는 전기방사(electrospinning) 등의 방사 기술에 의해 파이버(fiber, 섬유)로 제조될 수 있으며, 이러한 SBS 파이버는 일정한 형상, 예를 들어, 평평한 매트(mat) 형상으로 부직(nonwoven)될 수 있다. On the other hand, the polymer SBS can be made of fibers (fibers) by a spinning technique such as electrospinning, such SBS fibers are nonwoven in a certain shape, for example, a flat mat shape (non-woven) Can be
전기방사는 다양한 고분자로부터 나노파이버(nano-fiber)를 연속적이고 대량으로 생산할 수 있는 유일한 방법으로서 다음과 같은 여러 가지 장점을 가지고 있다. 즉, 수 nm ~ 수백 nm 크기의 다양한 직경을 가지는 파이버를 생산할 수 있고, 기존의 부직포 형태의 매트릭스 제조법에 비하여 장비가 간단하며, 광범위한 고분자 소재에 적용할 수 있다. 전기방사는 가는 유리관이나 노즐을 통해 밀리미터 직경의 액체 분사물(jet)을 방출시켜 나노섬유로 된 부직포 형태의 매트릭스를 생산하는 공정이다. 전극의 한 극은 고분자 용액 내에, 다른 한극은 수집기(collector)에 위치한 서로 반대 극성을 가지는 두 전극 사이에서 고분자 용액은 가는 방출구를 통하여 한번 방사되면 용액이 증발되고 수집기에 파이버가 모인다. 적용되는 전위차는 방사용액의 특성, 고분자 분자량, 점도 등에 따라 달라진다. 방출구와 수집기 사이의 거리가 짧아지면 용매의 증발이 충분하지 않기 때문에 방사된 섬유는 수집기뿐만 아니라 섬유끼리도 서로 엉키게 된다. 나노 파이버가 만들어지는 원리는 전기장(electric field)이 증가할수록 모세관의 끝의 액체는 반구형(hemispherical)에서 테일러 콘(Tayler cone)이라고 알려진 원뿔 형(conical) 형태로 바뀐다. 전기장이 더 증가하면 반발력이 표면 장력보다 커지게 되고 정전기력을 가진 액체는 모세관 끝의 테일러 콘에서 얇은 파이버 형태로 방사된다. 나노파이버의 특성을 결정하는 요인은 고분자용액의 특성과 전기방사기의 특성에 의해 주로 결정된다.Electrospinning is the only way to produce continuous, high-volume nanofibers from a variety of polymers and has several advantages: That is, it is possible to produce fibers having various diameters ranging from several nm to several hundred nm, and the equipment is simpler than the conventional nonwoven fabric matrix manufacturing method, and can be applied to a wide range of polymer materials. Electrospinning is the process of producing a non-woven matrix of nanofibers by releasing a millimeter diameter liquid jet through a thin glass tube or nozzle. One side of the electrode is in the polymer solution, and the other is located between the two electrodes with opposite polarities, located in the collector. The polymer solution is radiated once through a thin outlet and the solution evaporates and the fibers are collected in the collector. The potential difference applied depends on the properties of the spinning solution, the molecular weight of the polymer, the viscosity, and the like. If the distance between the outlet and the collector is short, the evaporation of the solvent is not sufficient, so the fibers are entangled with each other as well as with the collector. The principle that nanofibers are made is that as the electric field increases, the liquid at the end of the capillary changes from a hemispherical to a conical form known as the Taylor cone. As the electric field increases further, the repulsive force becomes greater than the surface tension, and the electrostatic liquid is radiated in the form of thin fibers in the Taylor cone at the capillary end. The determinants of the properties of the nanofibers are mainly determined by the properties of the polymer solution and the properties of the electrospinner.
고분자를 이용한 전기방사 기술로서, 대한민국 특허등록 제10-0943419호, 대한민국 특허공개 10-2011-0105199호, 대한민국 특허공개 10-2012-0111381호 등에서 고분자를 이용하여 파이버를 제조하는 기술을 공개하고 있으나, SBS를 전기 방사를 통한 파이버 및 상기 파이버를 매트 형상으로 제조하는 기술에 대해서는 공개된 바가 없다. 특히, SBS는 고무 특성으로 인하여 신축성이 좋으나 물흡수성이 나빠 물흡수성이 필요한 용도로는 사용될 수 없는 문제점이 있었다.As an electrospinning technology using polymers, Korean Patent Registration No. 10-0943419, Korean Patent Publication No. 10-2011-0105199, and Korean Patent Publication No. 10-2012-0111381 disclose technologies for manufacturing fibers using polymers. It is not disclosed about the technology of manufacturing the SBS, the fiber through the electrospinning and the fiber in a mat shape. In particular, SBS has good elasticity due to the rubber properties, but there is a problem that can not be used in applications that need water absorption because of poor water absorption.
본 발명의 목적은 SBS를 주원료로 사용하는 SBS 파이버 매트를 제조하는 방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing an SBS fiber mat using SBS as a main raw material.
특히, 본 발명의 목적은 SBS 단독으로 제조되는 파이버 매트에 비해 물흡수성이 증진된 SBS 파이버 매트의 제조 방법을 제공하는 것이다.In particular, it is an object of the present invention to provide a method for producing an SBS fiber mat with improved water absorption compared to a fiber mat made of SBS alone.
특히, 본 발명의 목적은 전기방사를 통해 SBS 파이버 매트의 제조 방법을 제공하는 것이다.In particular, it is an object of the present invention to provide a method for producing SBS fiber mat through electrospinning.
본 발명은 SBS와 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)을 포함하는 파이버 매트를 제공한다.The present invention provides a fiber mat comprising SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol).
특히, SBS 100 중량부에 대하여 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)는 2 내지 30 중량부가 바람직하다.In particular, the poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is preferably 2 to 30 parts by weight based on 100 parts by weight of SBS.
본 발명은 상기 SBS 파이버 매트를 제조하는 방법으로서, 용매에 SBS와 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)을 혼합 및 믹싱하여 용액을 제조하는 단계; 및 상기 용액을 이용하여 파이버 매트로 제조하는 단계를 포함하는 물흡수성이 개선된 SBS 파이버 매트의 제조 방법을 제공한다.The present invention provides a method for producing the SBS fiber mat, comprising the steps of mixing and mixing SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) in a solvent to prepare a solution; And it provides a method for producing an SBS fiber mat with improved water absorbency comprising the step of preparing a fiber mat using the solution.
특히, 상기 용액의 파이버 매트의 제조는 전기방사에 의하는 것이 바람직하다.In particular, the manufacture of the fiber mat of the solution is preferably by electrospinning.
특히, 상기 SBS 100 중량부에 대하여 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)는 2 내지 30 중량부를 포함하는 것이 바람직하다.Particularly, the poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) preferably contains 2 to 30 parts by weight based on 100 parts by weight of the SBS.
특히, 상기 용매는 디클로로메탄, 클로로포름, 톨루엔, 에틸아세테이트, 테트라히드로퓨란(THF), 디메틸실록산, 디메톨포름아미드 및 아세토니트릴 중에서 선택되는 어느 하나 이상인 것이 바람직하다.In particular, the solvent is preferably at least one selected from dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran (THF), dimethylsiloxane, dimetholformamide and acetonitrile.
특히, 상기 용매는 THF와 DMF의 혼합 용매인 것이 바람직하다.In particular, the solvent is preferably a mixed solvent of THF and DMF.
본 발명은 SBS에 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)을 더 혼합한 용액을 방사하여 매트로 제조함으로써, 종래 SBS 단독에 비해 물흡수성이 개선된 SBS 파이버 매트를 제조할 수 있다. 예를 들어, 실험 결과 SBS에 대한 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)의 함량이 증가할수록 물흡수성이 증가함을 알 수 있었으며, 예를 들어, SBS 1.2g, 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜) 0.072g을 이용한 실시예 3의 샘플에서는 수접촉각이 1도로 물흡수성이 매우 우수함을 알 수 있다.The present invention is made by spinning a solution in which poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is further mixed with SBS to prepare a mat, thereby improving water absorption compared to conventional SBS alone. Fiber mats can be produced. For example, as a result of the experiment, it was found that as the content of poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) increased with respect to SBS, water absorption increased. In the sample of Example 3 using 1.2 g and 0.072 g of poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol), it can be seen that the water contact angle was very good at 1 degree.
도 1 및 2는 각각 실시예 1의 매트 샘플의 사진 및 SEM 사진이다.1 and 2 are photographs and SEM photographs of the mat sample of Example 1, respectively.
도 3 및 4는 각각 실시예 2의 매트 샘플의 사진 및 SEM 사진이다.3 and 4 are photographs and SEM photographs of the mat sample of Example 2, respectively.
도 5 및 6은 각각 실시예 3의 매트 샘플의 사진 및 SEM 사진이다.5 and 6 are photographs and SEM photographs of the mat sample of Example 3, respectively.
도 7은 SBS, PF-108, 파이버 매트(실시예 3)에 대한 FT-IR 측정 결과이다.7 shows FT-IR measurement results for SBS, PF-108, and fiber mat (Example 3).
도 8은 실시예 1의 파이버 매트에 대한 접촉각 측정 시의 물방울 사진이다.8 is a water drop photograph when measuring the contact angle of the fiber mat of Example 1.
도 9는 실시예 2의 파이버 매트에 대한 접촉각 측정 시의 물방울 사진이다.9 is a water drop photograph when measuring the contact angle of the fiber mat of Example 2.
도 10은 실시예 3의 파이버 매트에 대한 접촉각 측정 시의 물방울 사진이다.10 is a water drop photograph when measuring the contact angle of the fiber mat of Example 3.
도 11은 실시예 1의 파이버 매트에 대한 인장강도 실험 결과 그래프이다.11 is a graph showing the tensile strength test results for the fiber mat of Example 1.
도 12는 실시예 2의 파이버 매트에 대한 인장강도 실험 결과 그래프이다.12 is a graph of tensile strength test results for the fiber mat of Example 2.
도 13은 실시예 3의 파이버 매트에 대한 인장강도 실험 결과 그래프이다.13 is a graph of tensile strength test results for the fiber mat of Example 3.
본 발명은 SBS를 주원료로 제조된 SBS 파이버 매트 및 그 제조 방법에 관한 기술로서, SBS가 신축성은 좋으나 물흡수성이 낮아 물흡수성이 필요한 용도로 사용되지 못하는 것을 개선하기 위하여 본 발명에서는 물흡수성이 개선된 SBS 파이버 매트를 제조하는 기술을 제공한다.The present invention relates to an SBS fiber mat made of SBS as a main raw material and a method for manufacturing the same. In the present invention, in order to improve that SBS has good elasticity but low water absorptivity, the water absorptivity is not used. Provides a technique for manufacturing the SBS fiber mat.
본 발명에서는 SBS 파이버 매트를 제조하는 방법으로서, 용매에 SBS와 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)을 혼합하여 혼합 용액을 제조하는 단계; 및 상기 용액을 파이버 매트로 제조하는 단계를 포함하는 SBS 파이버 매트 제조 방법을 제공한다.In the present invention, a method for producing an SBS fiber mat, comprising: preparing a mixed solution by mixing SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) in a solvent; And it provides a SBS fiber mat manufacturing method comprising the step of preparing the solution into a fiber mat.
본 발명에서 SBS의 물흡수성 개선을 위하여 사용된 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)은 하기 화학식 2와 같은 구조를 갖는다.In the present invention, poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) used for improving water absorption of SBS has a structure as shown in the following Chemical Formula 2.
<화학식 2><Formula 2>
Figure PCTKR2018001992-appb-I000002
Figure PCTKR2018001992-appb-I000002
폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)의 상용제품으로 바스프사의 Pluronic® F108(이하 PF-108이라 약칭함)이 많이 알려져 있다. 이하 실험에서는 Pluronic® F108를 사용하였다.Poly (ethylene glycol) - b - poly (propylene glycol) - b - poly (hereinafter referred PF-108) (ethylene glycol), a commercial product of BASF Corp. Pluronic ® F108 of this there are many known. In the following experiments it was used a Pluronic ® F108.
본 발명자의 실험 결과 SBS 100 중량부에 대해 PF-108의 함량비가 약 6 중량부 이상이 되는 경우에는 6 중량부일 때와 비슷한 물흡수성(접촉각)을 나타냈다. 가격 경쟁력 및 용매에 대한 용해도 등을 감안하여, SBS 100 중량부에 대해서 PF-108은 2 내지 30 중량부 정도로 사용하는 것이 바람직하나, 상기 범위 이외에서도 SBS 단독의 매트에 비해 물흡수성의 증가는 확인할 수 있었다.As a result of the experiment of the present inventors, when the content ratio of PF-108 is about 6 parts by weight or more based on 100 parts by weight of SBS, water absorption (contact angle) similar to that of 6 parts by weight was shown. In consideration of price competitiveness and solubility in solvents, PF-108 is preferably used in an amount of 2 to 30 parts by weight based on 100 parts by weight of SBS. Could.
상기 용매는 디클로로메탄, 클로로포름, 톨루엔, 에틸아세테이트, 테트라히드로퓨란(THF), 디메틸실록산, 디메톨포름아미드(DMF) 및 아세토니트릴 중에서 선택되는 어느 하나 이상인 것이 바람직하다. 특히, 이하 실험에서는 THF와 DMF의 혼합 용매를 사용하였다.The solvent is preferably at least one selected from dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran (THF), dimethylsiloxane, dimetholformamide (DMF) and acetonitrile. In particular, a mixed solvent of THF and DMF was used in the following experiment.
상기 용액을 파이버 매트로 제조하는 방법은 다양한 방법, 예를 들어, 습식방사, 건식방사, 용융방사 등이 가능하나, 본 발명의 실험에서는 전기방사(electrospinning)를 이용하였다.The method of preparing the solution into a fiber mat may be various methods, for example, wet spinning, dry spinning, melt spinning, and the like, but electrospinning was used in the experiment of the present invention.
이하에서는 실시예 및 실험예를 통하여 본 발명에 대하여 설명하기로 한다.Hereinafter, the present invention will be described through Examples and Experimental Examples.
실시예Example
이하에서는 동일한 혼합 용매에 대해서 SBS vs. PF-108의 함량비를 3가지로 달리하여 SBS 파이버 매트를 제조하였다.Hereinafter, SBS vs. SBS fiber mat was prepared by varying the content ratio of PF-108 in three ways.
<실시예 1><Example 1>
THF 6ml와 DMF 2ml를 혼합하여 총 8ml를 만들고, SBS 1.2g, PF-108 0.024g을 첨가하여 상온에서 4시간 교반하여 용액을 제조하였다. 위에 방법을 통하여 만들어진 용액을 가지고 voltage은 20kvolt, flow rate은 15ul/min, collector와 needle의 거리는 15cm, needle은 27GA를 이용하고 온도 17℃, 습도 23%로 맞추어 6시간 동안 전기방사하여 평균 0.869mm 두께로 파이버 매트(실시예 1)를 제조하였다. 도 1은 실시예 1의 매트의 사진이며, 도 2는 그 SEM 사진이다.6 ml of THF and 2 ml of DMF were mixed to make a total of 8 ml, and 1.2 g of SBS and 0.024 g of PF-108 were added thereto, followed by stirring at room temperature for 4 hours to prepare a solution. With the solution made through the above method, the voltage is 20kvolt, the flow rate is 15ul / min, the distance between the collector and the needle is 15cm, the needle is 27GA, and the temperature is 17 ℃, the humidity is 23%. A fiber mat (Example 1) was prepared in thickness. 1 is a photograph of a mat of Example 1, and FIG. 2 is a SEM photograph thereof.
<실시예 2><Example 2>
THF 6ml와 DMF 2ml를 혼합하여 총 8ml를 만들고 SBS 1.2g, PF-108 0.048g을 첨가하여 상온에서 4시간 교반하여 용액을 제조하였다. 위에 방법을 통하여 만들어진 용액을 가지고 voltage은 20kvolt, flow rate은 15ul/min, collector와 needle의 거리는 15cm, needle은 27GA를 이용하고 온도 17℃, 습도 23%로 맞추어 6시간 동안 전기방사하여 평균 0.860mm 두께로 파이버 매트(실시예 2)를 제조하였다. 도 3은 실시예 2의 매트의 사진이며, 도 4는 그 SEM 사진이다. 6 ml of THF and 2 ml of DMF were mixed to make a total of 8 ml, and 1.2 g of SBS and 0.048 g of PF-108 were added thereto, followed by stirring at room temperature for 4 hours to prepare a solution. With the solution made through the above method, the voltage is 20kvolt, the flow rate is 15ul / min, the distance between the collector and the needle is 15cm, the needle is 27GA and the temperature is 17 ℃, the humidity is 23%. A fiber mat (Example 2) was made by thickness. 3 is a photograph of a mat of Example 2, and FIG. 4 is a SEM photograph thereof.
<실시예 3><Example 3>
THF 6ml와 DMF 2ml를 혼합하여 총 8ml를 만들고 SBS 1.2g, PF-108 0.072g을 첨가하여 상온에서 4시간 교반하여 용액을 제조하였다. 위의 방법을 통하여 만들어진 용액을 가지고 voltage은 20kvolt, flow rate은 15ul/min, collector와 needle의 거리는 15cm, needle은 27GA를 이용하고 온도 17℃, 습도 23%로 맞추어 6시간 동안 전기방사하여 평균 0.855mm 두께로 파이버 매트(실시예 3)를 제조하였다. 도 5는 실시예 3의 매트의 사진이며, 도 6는 그 SEM 사진이다.6 ml of THF and 2 ml of DMF were mixed to make a total of 8 ml, and 1.2 g of SBS and 0.072 g of PF-108 were added thereto, followed by stirring at room temperature for 4 hours to prepare a solution. With the solution made through the above method, the voltage is 20kvolt, the flow rate is 15ul / min, the distance between the collector and the needle is 15cm, the needle is 27GA and the temperature is 17 ℃, the humidity is 23%. A fiber mat (Example 3) was prepared in mm thickness. 5 is a photograph of a mat of Example 3, and FIG. 6 is an SEM photograph thereof.
실시예 1 내지 3의 함량을 정리하면 하기 표 1과 같다.The contents of Examples 1 to 3 are summarized in Table 1 below.
No.No. SBS 함량(g)SBS content (g) PF-108 함량(g)PF-108 content (g)
실시예 1Example 1 1.21.2 0.0240.024
실시예 2Example 2 1.21.2 0.0480.048
실시예 3Example 3 1.21.2 0.0720.072
** 용매는 THF 6ml와 DMF 2ml의 총 8ml 혼합용매** Solvent is a total of 8ml mixed solvent of 6ml THF and 2ml DMF
실험예Experimental Example
상기 실시예에 의해 제조된 3개의 SBS 파이버 매트에 대하여 하기와 같은 실험을 하였다.Three SBS fiber mats prepared by the above examples were tested as follows.
<실험예 1 : FT-IR 분석>Experimental Example 1 FT-IR Analysis
SBS, PF-108 및 실시예 3의 파이버 매트(1.5cm2로 자른 뒤 2번 접음)를 준비하였다. 준비한 3개의 샘플을 가지고 FT-IR 분석을 하였으며, 그 결과는 도 7과 같았다.SBS, PF-108 and the fiber mat of Example 3 (cut to 1.5 cm 2 and folded twice) were prepared. FT-IR analysis was performed using the prepared three samples, and the result was as shown in FIG. 7.
실시예 3의 파이버 매트는 Wavenumber 1492cm-1, 1451cm-1, 911 cm-1에서 SBS의 Styrene의 피크가 나왔으며, Wavenumber 965cm-1에서는 SBS의 Butadiene의 피크가 나왔으며, Wavenumber 1348cm-1, 1278cm-1, 1243cm-1에서는 PF-108의 피크가 나왔다. Wavenumber 1100cm-1에서는 PF-108의 C-O-C결합의 피크가 나왔다.Exemplary fiber mat of Example 3 is Wavenumber 1492cm -1, 1451cm -1, 911 has a peak of SBS Styrene or in cm -1, Wavenumber 965cm -1 in or has a peak of SBS Butadiene, Wavenumber 1348cm -1, 1278cm At -1 and 1243 cm -1 , the peak of PF-108 was found. Wavenumber 1100cm -1 showed the peak of COC bond of PF-108.
<실험예 2 : 접촉각 측정 실험>Experimental Example 2 Contact Angle Measurement Experiment
증류수 0.3ul를 실시예 1의 파이버 매트를 대상으로 위에 떨어뜨리고 Contact angle meter(DSA10-Mk2/DO3020 Mk1/DO3021 Mk2, KRUSS, Germany)을 이용하여 접촉각을 측정하여으며, 접촉각이 108도 나왔다. 도 8은 실시예 1의 파이버 매트에 대한 접촉각 측정 시의 물방울 사진이다.0.3ul of distilled water was dropped on the fiber mat of Example 1 and the contact angle was measured using a contact angle meter (DSA10-Mk2 / DO3020 Mk1 / DO3021 Mk2, KRUSS, Germany), and the contact angle was 108 degrees. 8 is a water drop photograph when measuring the contact angle of the fiber mat of Example 1.
실시예 2의 파이버 매트를 대상으로 동일한 방법으로 접촉각을 측정하였으며, 접촉각이 55도 나왔다. 도 9는 실시예 2의 샘플에 대한 접촉각 측정 시의 물방울 사진이다.The contact angle was measured in the same manner for the fiber mat of Example 2, the contact angle was 55 degrees. 9 is a water drop photograph at the time of contact angle measurement for the sample of Example 2. FIG.
실시예 3의 파이버 매트를 대상으로 동일한 방법으로 접촉각을 측정하였으며, 접촉각이 1도 나왔다. 도 10은 실시예 3의 샘플에 대한 접촉각 측정 시의 물방울 사진이다.The contact angle was measured in the same manner with the fiber mat of Example 3, and the contact angle was 1 degree. 10 is a water droplet photograph at the time of contact angle measurement for the sample of Example 3. FIG.
위의 실험 결과로부터 PF-108의 함량이 증가함에 따라 수접촉각이 작아지며, 이는 SBS 파이버 매트의 물흡수성이 개선되었다는 점을 알 수 있었다. As the content of PF-108 increases, the water contact angle decreases, indicating that the water absorption of SBS fiber mat is improved.
<실험예 3 : 인장강도 실험>Experimental Example 3 Tensile Strength Experiment
실시예 1의 파이버 매트를 길이 3.8cm, 0.869mm 크기로 준비한 후, UTM(DTU-900MHA, 대경테크㈜, 한국)을 이용하여 인장강도에 따른 신장률을 측정하였다. 인장강도가 107Pa일 때 최대 신장률 7.23을 보이고 파단되었다. 도 11은 인장강도 실험 결과 그래프이다.After preparing the fiber mat of Example 1 to a length of 3.8cm, 0.869mm size, the elongation rate according to the tensile strength was measured using UTM (DTU-900MHA, Daekyung Tech Co., Korea). When the tensile strength was 107 Pa, the maximum elongation was 7.23 and was broken. 11 is a graph of tensile strength test results.
실시예 2의 파이버 매트를 길이 3.8cm, 0.860mm 크기로 준비한 후, UTM(DTU-900MHA, 대경테크㈜, 한국)을 이용하여 인장강도에 따른 신장률을 측정하였다. 인장강도가 273Pa일 때 최대 신장률 10.04를 보이고 파단되었다. 도 12는 인장강도 실험 결과 그래프이다.After preparing the fiber mat of Example 2 to a length of 3.8cm, 0.860mm size, the elongation rate according to the tensile strength was measured using UTM (DTU-900MHA, Daekyung Tech Co., Korea). When the tensile strength was 273 Pa, the maximum elongation was 10.04 and fractured. 12 is a graph of tensile strength test results.
실시예 3의 파이버 매트를 길이 3.8cm, 0.855mm 크기로 준비한 후, UTM(DTU-900MHA, 대경테크㈜, 한국)을 이용하여 인장강도에 따른 신장률을 측정하였다. 인장강도가 308Pa일 때 최대 신장률 10.91을 보이고 파단 되었다. 도 13은 인장강도 실험 결과 그래프이다.After preparing the fiber mat of Example 3 to a length of 3.8cm, 0.855mm size, the elongation rate according to the tensile strength was measured using UTM (DTU-900MHA, Daekyung Tech Co., Korea). When the tensile strength was 308 Pa, the maximum elongation was 10.91 and fractured. Figure 13 is a graph of tensile strength test results.

Claims (7)

  1. SBS 및 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)을 포함하여 이루어지는 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트.SBS fiber mat with improved water absorption, comprising SBS and poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol).
  2. 제1항에서, SBS 100 중량부에 대하여 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)은 2 내지 30 중량부인 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트.The SBS fiber mat with improved water absorption of claim 1, wherein the poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is 2 to 30 parts by weight based on 100 parts by weight of SBS. .
  3. 용매에 SBS와 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)을 혼합하여 혼합 용액을 제조하는 단계; 및 상기 용액을 파이버 매트로 제조하는 단계를 포함하는 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트의 제조 방법.Preparing a mixed solution by mixing SBS with poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) in a solvent; And manufacturing the solution into a fiber mat.
  4. 제3항에서, 상기 용액의 파이버 매트로의 제조는 전기 방사인 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트의 제조 방법.The method of claim 3, wherein the preparation of the solution into the fiber mat is electrospinning.
  5. 제3항에서, 상기 SBS 100 중량부에 대하여 폴리(에틸렌 글리콜)-b-폴리(프로필렌 글리콜)-b-폴리(에틸렌 글리콜)은 2 내지 30 중량부인 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트의 제조 방법.[4] The SBS fiber having improved water absorption of claim 3, wherein the poly (ethylene glycol) -b -poly (propylene glycol) -b -poly (ethylene glycol) is 2 to 30 parts by weight based on 100 parts by weight of the SBS. Method of making the mat.
  6. 제3항에서, 상기 용매는 디클로로메탄, 클로로포름, 톨루엔, 에틸아세테이트, 테트라히드로퓨란(THF), 디메틸실록산, 디메톨포름아미드 및 아세토니트릴 중에서 선택되는 어느 하나 이상인 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트의 제조 방법.The method of claim 3, wherein the solvent is any one or more selected from dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran (THF), dimethylsiloxane, dimetholformamide and acetonitrile is improved water absorption Method for producing SBS fiber mat.
  7. 제6항에서, 상기 용매는 THF와 DMF의 혼합 용매인 것을 특징으로 하는 물흡수성이 개선된 SBS 파이버 매트의 제조 방법.The method of claim 6, wherein the solvent is a mixed solvent of THF and DMF.
PCT/KR2018/001992 2017-03-08 2018-02-19 Sbs fiber mat with improved water absorbency and method for manufacturing same WO2018164390A1 (en)

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KR20020063020A (en) * 2001-01-26 2002-08-01 한국과학기술연구원 Method for Preparing Thin Fiber -Structured Polymer Webs
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KR20130017341A (en) * 2011-08-10 2013-02-20 삼성전자주식회사 Strechable conductive nano fiber, strechable conductive electrode using the same and method for producing the same
KR20160066298A (en) * 2014-12-02 2016-06-10 한양대학교 산학협력단 flexible and stretchable piezoelectronic fiber and fabrication method thereof

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KR20120111661A (en) * 2011-04-01 2012-10-10 삼성전자주식회사 Strechable conductive nano fiber, strechable fiber electrode using the same and method for producing the same
KR20130017341A (en) * 2011-08-10 2013-02-20 삼성전자주식회사 Strechable conductive nano fiber, strechable conductive electrode using the same and method for producing the same
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