KR101409444B1 - Manufacturing method of polyurethane non-woven fabric using electrospinning - Google Patents
Manufacturing method of polyurethane non-woven fabric using electrospinning Download PDFInfo
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- KR101409444B1 KR101409444B1 KR1020130077844A KR20130077844A KR101409444B1 KR 101409444 B1 KR101409444 B1 KR 101409444B1 KR 1020130077844 A KR1020130077844 A KR 1020130077844A KR 20130077844 A KR20130077844 A KR 20130077844A KR 101409444 B1 KR101409444 B1 KR 101409444B1
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- urethane prepolymer
- polyester urethane
- thermosetting polyester
- polyurethane
- electrospinning
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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
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/06—Feeding liquid to the spinning head
- D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
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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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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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
- D04H1/4326—Condensation or reaction polymers
- D04H1/4358—Polyurethanes
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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
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
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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
- D10B2401/04—Heat-responsive characteristics
-
- 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
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
본 발명은 전기방사를 이용하여 극세섬유로 이루어진 폴리우레탄 부직포를 제조하는 방법에 관한 것이다.
The present invention relates to a method for producing a polyurethane nonwoven fabric made of ultrafine fibers using electrospinning.
폴리우레탄 섬유는 신축성 및 탄력성이 우수하고, 인장응력, 회복성 등의 기계적 성질, 열적 성질이 비교적 우수하므로, 의류 분야는 물론, 의료용, 전자 소재용 등 각종 소재로 그 응용범위가 확대되고 있다.Polyurethane fibers are excellent in stretchability and elasticity, and have relatively good mechanical properties such as tensile stress and recoverability and thermal properties. Therefore, the polyurethane fibers are being applied to various materials such as medical applications and electronic materials as well as clothing.
특히, 스포츠나 여가 활동에 대한 관심의 증가, 다양한 스포츠용 의복의 필요성에 대한 요청, 의복 착용시의 쾌적성과 안정성을 강조하는 소비자들의 욕구는 폴리우레탄 섬유를 이용한 의복에 대한 관심을 증가시켜 왔다. 예를 들어 아웃도어 스포츠용 기능성 의복은 단순한 옷이 아니라, 자연 현상으로부터 신체를 안전하고 쾌적하게 보호해 주는 장비로서의 역할이 강조되고 있으며, 그 소재로서 널리 사용되는 폴리우레탄 투습방수 직물은 부분적인 기능의 향성 및 기본 기능성의 유지와 더불어 쾌적성, 보온성, 신축성 등의 복합적 기능이 요구되고 있다.Especially, the interest of consumers who emphasize the interest in sports and leisure activities, the demand for various sports clothes, comfort and stability in wearing clothes has increased the interest in clothes using polyurethane fiber. For example, functional apparel for outdoor sports is emphasized not only as clothes, but also as a device for safely and comfortably protecting the body from natural phenomena. The polyurethane breathable waterproof fabric widely used as the material is a partial function A combination of functions such as comfort, warmth, stretchability, and the like are required in addition to the maintenance of the orientation and basic functionality.
전기방사에 의한 폴리우레탄 부직포는 섬유 직경 및 적층수를 조절함으로서 기공의 크기를 조절할 수 있으므로, 그 자체 또는 섬유 원단에 전기방사되어 전술한 기능성 의복은 물론 다양한 산업분야에 이미 이용되고 있다.The polyurethane nonwoven fabric by electrospinning can control the size of the pores by controlling the fiber diameter and the number of laminated layers. Therefore, the polyurethane nonwoven fabric is already used in various industrial fields as well as the above-mentioned functional apparel.
전기방사에 의해 제조된 폴리우레탄 부직포는 열가소성 폴리우레탄을 용융시킨 용융액 또는 열가소성 폴리우레탄을 용매에 용해시킨 용액을 방사액으로 하여 제조한다. 제조된 부직포는 부직포를 구성하는 폴리우레탄 극세섬유 사이의 엉킴과 적층에 의한 단순한 물리적 상호작용에 의해 그 형태를 유지한다. 따라서, 세탁이나 외부 마찰 등의 외력에 의해 필링이 일어나거나 분리되기가 쉬어 내구성에 대한 개선이 필요하다. 더불어, 열가소성인 폴리우레탄을 사용함으로 인하여 내열성에도 한계가 있다.
The polyurethane nonwoven fabric produced by electrospinning is prepared by dissolving a thermoplastic polyurethane melt or a thermoplastic polyurethane in a solvent as a spinning solution. The produced nonwoven fabric maintains its shape by the entanglement between the polyurethane microfine fibers constituting the nonwoven fabric and the simple physical interaction by the lamination. Therefore, peeling may occur due to external force such as washing or external friction, and separation may be facilitated, and improvement in durability is required. In addition, heat resistance is limited due to the use of thermoplastic polyurethane.
따라서, 본 발명이 이루고자 하는 과제는 상기한 문제점을 해결하여, 외력에 대한 내구성 및 내열성이 개선된 폴리우레탄 부직포를 전기방사하여 제조하는 방법을 제공하는데 있다.
SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method of manufacturing a polyurethane nonwoven fabric with improved durability against external forces and heat resistance.
상기 과제를 달성하기 위하여, 본 발명에 따른 폴리우레탄 부직포의 제조방법은,In order to achieve the above object, the present invention provides a method for producing a polyurethane non-
(S1) 열가소성 폴리우레탄, 열경화성 폴리에스테르 우레탄 프레폴리머 및 상기 열경화성 폴리에스테르 우레탄 프레폴리머의 가교제를 용매에 용해시켜 방사용액을 준비하는 단계;(S1) preparing a spinning solution by dissolving a thermoplastic polyurethane, a thermosetting polyester urethane prepolymer and a crosslinking agent of the thermosetting polyester urethane prepolymer in a solvent;
(S2) 상기 방사용액을 전기방사 구금을 이용하여 전기방사하여 웹을 형성하는 단계; 및(S2) electrospinning the spinning solution with an electrospinning tool to form a web; And
(S3) 상기 웹을 열처리하여 상기 열경화성 폴리에스테르 우레탄 프레폴리머를 경화시키는 단계를 포함한다.(S3) heat-treating the web to cure the thermosetting polyester urethane prepolymer.
본 발명에 따른 폴리우레탄 부직포의 제조방법에 있어서, In the method for producing a polyurethane nonwoven fabric according to the present invention,
상기 열경화성 폴리에스테르 우레탄 프레폴리머의 함량은 열가소성 폴리우레탄 100 중량부를 기준으로 5 내지 85 중량부인 것이 바람직하고, 20 내지 60 중량부인 것이 더욱 바람직하다.The content of the thermosetting polyester urethane prepolymer is preferably 5 to 85 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane.
본 발명에 따른 폴리우레탄 부직포의 제조방법에 있어서,In the method for producing a polyurethane nonwoven fabric according to the present invention,
상기 방사용액은 가교 촉진제를 더 함유할 수 있다. 또한, 상기 방사용액은 섬유 원단의 표면에 전기방사하여 섬유 원단의 표면에 결합된 형태로 폴리우레탄 부직포를 제조할 수 있다.
The spinning solution may further contain a crosslinking accelerator. In addition, the spinning solution may be produced by electrospinning the surface of the fiber fabric to bind the surface of the fiber fabric to the polyurethane nonwoven fabric.
본 발명의 제조방법에 따라 방사된 웹은 열가소성 폴리우레탄과 열경화성 폴리에스테르 우레탄 프레폴리머가 혼합된 극세섬유로 형성된다. 열처리에 따라 극세섬유에 함유된 열경화성 폴리에스테르 우레탄 프레폴리머가 경화되면, 극세섬유의 내부, 극세섬유들 사이에서 가교반응이 진행되어 3차원 망상 구조가 형성된다. 이에 따라, 내열성, 세탁 내구성, 내마찰성 등이 개선된 폴리우레탄 부직포가 얻어진다. 즉, 열가소성 폴리우레탄 성분의 혼합량에 따라 원하는 정도의 탄성이 부여되며, 열경화성 폴리에스테르 우레탄 프레폴리머의 경화에 따른 가교반응으로 인하여 내구성과 내열성이 보강된 폴리우레탄 부직포를 얻을 수 있다.
According to the manufacturing method of the present invention, the spun web is formed of microfine fibers mixed with a thermoplastic polyurethane and a thermosetting polyester urethane prepolymer. When the thermosetting polyester urethane prepolymer contained in the microfine fibers is cured by the heat treatment, the cross-linking reaction proceeds between the microfine fibers and the microfine fibers to form a three-dimensional network structure. Thereby, a polyurethane nonwoven fabric improved in heat resistance, durability and friction resistance can be obtained. That is, a desired degree of elasticity is imparted according to the mixing amount of the thermoplastic polyurethane component, and a polyurethane nonwoven fabric reinforced by durability and heat resistance due to the crosslinking reaction caused by the curing of the thermosetting polyesterurethane prepolymer can be obtained.
이하, 본 발명에 대하여 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.
Hereinafter, the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.
이하, 본 발명에 따른 폴리우레탄 부직포의 제조방법에 대하여 상세히 설명한다.Hereinafter, a method for producing a polyurethane nonwoven fabric according to the present invention will be described in detail.
먼저, 열가소성 폴리우레탄, 열경화성 폴리에스테르 우레탄 프레폴리머 및 상기 열경화성 폴리에스테르 우레탄 프레폴리머의 가교제를 용매에 용해시켜 방사용액을 준비한다(S1 단계).First, a spinning solution is prepared by dissolving a thermoplastic polyurethane, a thermosetting polyester urethane prepolymer and a crosslinking agent of the thermosetting polyester urethane prepolymer in a solvent (Step S1).
열가소성 폴리우레탄의 제조방법은 잘 알려져 있다. 즉, 폴리에스테르폴리올 또는 폴리에테르폴리올과 같은 하이드록시 말단기를 함유하는 선형 폴리올과, 양 말단에 이소시아네이트기를 함유하는 디이소시아네이트 화합물을 반응시켜 제조되며, 필요에 따라 사슬연장제, 모노아민 화합물 등의 말단정지제, 기타 첨가제를 첨가하여 제조된다.Methods of making thermoplastic polyurethanes are well known. That is, it is prepared by reacting a linear polyol containing a hydroxy end group such as a polyester polyol or a polyether polyol with a diisocyanate compound containing an isocyanate group at both terminals, and optionally, a chain extender, a monoamine compound Terminal stopping agents, and other additives.
폴리올로는 선형상의 호모 또는 공중합체로 이루어지는 각종 디올, 예를 들어 폴리에스테르디올, 폴리에테르디올, 폴리에스테르아미드디올, 폴리아크릴디올, 폴리티오에스테르디올, 폴리티오에테르디올, 폴리카보네이트디올, 또는 이들의 혼합물 또는 공중합체가 사용될 수 있다. 보다 구체적인 예로는 폴리옥시에틸렌글리콜, 폴리옥시프로필렌글리콜, 폴리테트라메틸렌에테르글리콜, 테트라메틸렌기와 3-메틸테트라케틸렌기로 이루어진 공중합 폴리에테르글리콜 등의 폴리알킬렌에테르글리콜을 예시할 수 있다.Examples of the polyol include various diols comprising a linear homo or copolymer such as a polyester diol, a polyether diol, a polyester amide diol, a polyacryl diol, a polythioester diol, a polythioether diol, a polycarbonate diol, ≪ / RTI > may be used. More specific examples include polyalkylene ether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, copolymer polyether glycol composed of tetramethylene group and 3-methyl tetra ketylene group.
하드 세그먼트 역할을 하는 디이소시아네이트 화합물로는 방향족, 지방족 또는 지환족 디이소시아네이트가 사용되는데, 예를 들러 4,4'디페닐케탄디이소시아네이트, 1,3- 및 1,4-시클로헥실렌디이소시아네이트, 1,6-헥사메틸렌디이소시아네이트, 트리메틸렌디이소시아네이트, 테트라메틸렌디이소시아네이트, 이소포론디이소시아네이트 등을 들 수 있으나 이에 한정되는 것은 아니다.As the diisocyanate compound serving as a hard segment, an aromatic, aliphatic or alicyclic diisocyanate is used, for example, 4,4'-diphenyl ketadiisocyanate, 1,3- and 1,4-cyclohexylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, and the like, but are not limited thereto.
사슬연장제로는 디아민 하합물 또는 디올 화함물을 들 수 있으며, 예를 들어 메틸렌디아민, 에탄올디아민, 1,2-프로필렌디아민 등의 디아민 화합물과, 에틸렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 네오펜틸 글리콜 등의 디올 화합물이 있으나, 이에 한정되는 것은 아니다.Examples of the chain extender include a diamine compound or a diol compound. Examples of the chain extender include diamine compounds such as methylene diamine, ethanol diamine, and 1,2-propylene diamine, and ethylene glycol, 1,3-propanediol, 1,4 -Butanediol, neopentyl glycol, and the like, but are not limited thereto.
말단정지제로는 모노에탄올아민, 디에탄올아민, 디이소프로필아민과 같은 모노아민계 화합물을 들 수 있다.Examples of the terminal terminating agent include monoamine compounds such as monoethanolamine, diethanolamine and diisopropylamine.
한편, 열경화성 폴리에스테르 우레탄 프레폴리머로는 공지의 이액형 열경화성 폴리에스테르 우레탄 프레폴리머를 사용할 수 있는데, 예를 들어 하기 반응식 1에 따라 형성된 프레폴리머를 사용할 수 있으나 이에 한정되지 않는다. 이러한 열경화성 폴리에스테르 우레탄 프레폴리머는 접착제 용도로 사용되는 공지의 열경화성 폴리에스테르 우레탄 프레폴리머로서, 바람직한 수평균 분자량은 800 내지 30,000이다.On the other hand, as the thermosetting polyester urethane prepolymer, a known two-component thermosetting polyester urethane prepolymer can be used. For example, a prepolymer formed according to the following reaction formula 1 may be used, but not limited thereto. Such a thermosetting polyester urethane prepolymer is a known thermosetting polyester urethane prepolymer used for an adhesive, and the number average molecular weight is preferably 800 to 30,000.
[반응식 1][Reaction Scheme 1]
상기 반응식 1에서, R은 알킬이거나, 톨루엔 디이소시아네이트, 4,4-디페닐 메탄 디이소시아네이트와 같은 아로마틱, 이소포론 디이소시아네이트와 같은 알리파틱 등이다. In the above Reaction Scheme 1, R is alkyl or aromatic such as toluene diisocyanate, 4,4-diphenylmethane diisocyanate, aliphatics such as isophorone diisocyanate, and the like.
상기 열경화성 폴리에스테르 우레탄 프레폴리머를 가교시키기 위한 가교제로는 공지의 성분들이 사용될 수 있는데, 예를 들어 하기 반응식 2의 다관능성 이소시아네이트를 들 수 있으나, 이에 한정되는 것은 아니다.As the crosslinking agent for crosslinking the thermosetting polyester urethane prepolymer, known components may be used. For example, the polyfunctional isocyanate of the following Reaction Formula 2 may be used, but the present invention is not limited thereto.
[반응식 2][Reaction Scheme 2]
상기 반응식 1에서, TDI는 톨루엔디이소시아네티트임.In the above Reaction Scheme 1, TDI is toluene diisocyanate.
용매로는 톨루엔, m메틸레틸케톤 등이 사용될 수 있으며, 이에 한정되는 것은 아니다.As the solvent, toluene, m-methyl ethyl ketone and the like can be used, but it is not limited thereto.
상기 열경화성 폴리에스테르 우레탄 프레폴리머의 함량은 열가소성 폴리우레탄 100 중량부를 기준으로 5 내지 85 중량부인 것이 바람직하고, 20 내지 60 중량부인 것이 더욱 바람직하다. 이러한 범위에서, 열가소성 폴리우레탄 성분에 따른 탄성이 적절히 부여될 수 있고, 열경화성 폴리에스테르 우레탄 프레폴리머의 경화에 따른 가교반응으로 인하여 내구성과 내열성이 보강된 폴리우레탄 부직포를 얻을 수 있다. The content of the thermosetting polyester urethane prepolymer is preferably 5 to 85 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane. Within this range, the elasticity of the thermoplastic polyurethane component can be appropriately imparted, and a polyurethane nonwoven fabric reinforced by durability and heat resistance due to the crosslinking reaction caused by the curing of the thermosetting polyesterurethane prepolymer can be obtained.
또한, 가교제의 함량은 열가소성 폴리우레탄 100 중량부를 기준으로 2 내지 50 중량부인 것이 바람직하다.
The content of the crosslinking agent is preferably 2 to 50 parts by weight based on 100 parts by weight of the thermoplastic polyurethane.
전술한 조성의 방사용액은 필요에 따라 3급 아민과 같은 공지의 가교 촉진제를 더 함유할 수 있으며, 안료, 슬립제 등의 첨가제를 더 포함할 수 있다.The spinning solution having the above-mentioned composition may further contain a known crosslinking accelerator such as a tertiary amine, if necessary, and may further contain additives such as pigment and slip agent.
전술한 조성의 방사용액의 구체적인 예로는, 열가소성 폴리우레탄 100중량부, 열경화성 폴리에스테르 우레탄 프레폴리머 35 중량부, 가교제 2 중량부를 400 중량부의 용매에 용해시킨 것을 사용할 수 있다.Specific examples of the spinning solution having the above-mentioned composition include 100 parts by weight of a thermoplastic polyurethane, 35 parts by weight of a thermosetting polyester urethane prepolymer, and 2 parts by weight of a crosslinking agent in 400 parts by weight of a solvent.
이어서, 전술한 방법으로 준비한 방사용액을 전기방사 구금을 이용하여 전기방사하여 웹을 형성한다(S2 단계).Subsequently, the spinning solution prepared by the above-described method is electrospun using an electrospinning tool to form a web (step S2).
폴리우레탄 방사용액을 전기방사하여 웹을 형성하는 방법과 조건은 당업계에 잘 알려져 있다. 예를 들어 대한민국 공개특허 2012-0049763호, 대한민국 등록특허 0792894 등에는 폴리우레탄 방사용액을 이용하여 전기방사하는 방법과 그 원리 및 조건 등이 상세히 기재되어 있다. 전기방사에 의해 폴리우레탄 방사용액은 극세섬유로 이뤄어진 웹으로 형성된다. Methods and conditions for electrospunning a polyurethane spinning solution to form a web are well known in the art. For example, Korean Patent Publication No. 2012-0049763 and Korean Patent No. 0792894 disclose a method of electrospinning using a polyurethane emulsion and its principle and conditions in detail. By electrospinning, the polyurethane spinning solution is formed into a web made of ultra-fine fibers.
이 때, 방사용액은 콜렉터의 기재 표면에 전기방사하여 독립적인 웹을 형성할 수 있으나, 섬유 원단의 표면에 전기방사하여 섬유 원단의 표면에 결합된 형태로 제조할 수도 있다. 섬유 원단의 표면에 직접 방사용액을 전기방사하면, 원단과 적층하는 별도의 공정 없이도 섬유 원단에 폴리우레탄 부직포를 결합시킬 수 있다. At this time, the spinning solution may be electrospun to the surface of the substrate of the collector to form an independent web, but it may also be produced by being electrospun on the surface of the fiber fabric to be bonded to the surface of the fiber fabric. When the spinning solution is directly spun onto the surface of the fiber fabric, the polyurethane nonwoven fabric can be bonded to the fiber fabric without a separate process of laminating with the fabric.
본 발명의 (S2) 단계에 따라 전기방사된 웹은 열가소성 폴리우레탄과 열경화성 폴리에스테르 우레탄 프레폴리머가 혼합된 극세섬유로 형성되어 있다.According to the step (S2) of the present invention, the electrospun web is formed of microfine fibers in which a thermoplastic polyurethane and a thermosetting polyester urethane prepolymer are mixed.
그런 다음, 상기 웹을 열처리하여 상기 열경화성 폴리에스테르 우레탄 프레폴리머를 경화시킨다(S3 단계).Then, the web is heat-treated to cure the thermosetting polyester urethane prepolymer (step S3).
열처리 온도는 열경화성 폴리에스테르 우레탄 프레폴리머와 가교제의 가교반응을 진행할 수 있는 범위로 설정하는데, 이러한 열처리 온도 역시 당업계에 잘 알려져 있다. The heat treatment temperature is set within a range in which a cross-linking reaction between the thermosetting polyester urethane prepolymer and the crosslinking agent can proceed, and such a heat treatment temperature is also well known in the art.
열처리에 따라 극세섬유에 함유된 열경화성 폴리에스테르 우레탄 프레폴리머와 가교제가 반응하여 가교반응(경화반응)이 진행된다. 열경화성 폴리에스테르 우레탄 프레폴리머와 가교제가 극세섬유의 내외부에 혼재되어 있으므로, 가교반응은 극세섬유의 내부와 극세섬유들 사이에서 모두 진행된다. 즉, 가교반응의 진행에 따라 극세섬유 내부는 물론 극세섬유들 사이에서도 3차원 망상 구조가 형성된다. 이에 따라, 극세섬유 자체의 내열성, 내구성이 증대되며, 접촉하는 극세섬유들 사이에서도 가교반응이 진행되므로, 극세섬유들 사이에는 견고한 화학결합이 형성된다. 즉, 내열성, 세탁 내구성, 내마찰성 등이 개선된 폴리우레탄 부직포가 얻어진다.
As a result of the heat treatment, the thermosetting polyester urethane prepolymer contained in the microfine fibers reacts with the crosslinking agent to proceed the crosslinking reaction (curing reaction). Since the thermosetting polyester urethane prepolymer and the crosslinking agent are mixed in the inner and outer portions of the microfine fibers, the crosslinking reaction proceeds both inside the microfine fibers and between the microfine fibers. That is, as the crosslinking reaction progresses, a three-dimensional network structure is formed not only within the microfine fibers but also between the microfine fibers. As a result, the heat resistance and durability of the superfine fiber itself are increased, and the crosslinking reaction proceeds even between the superfine fibers to be contacted, so that a strong chemical bond is formed between the superfine fibers. That is, a polyurethane nonwoven fabric improved in heat resistance, durability and friction resistance can be obtained.
이와 같이, 본 발명의 제조방법에 따르면, 극세섬유 사이의 엉킴과 적층에 의한 단순한 물리적 상호작용에 의해 그 형태를 유지하는 종래의 폴리우레탄 부직포와는 달리, 극세섬유들이 서로 견고히 화학결합되어 있으며, 극세섬유 자체의 내열성과 내구성도 개선된다.As described above, according to the production method of the present invention, unlike the conventional polyurethane nonwoven fabric in which the microfine fibers are retained in their form by the entanglement between the microfine fibers and the simple physical interaction by lamination, the microfine fibers are chemically bonded to each other, The heat resistance and durability of the superfine fiber itself are also improved.
따라서, 본 발명의 제조방법에 따른 폴리우레탄 부직포는 세탁이나 외부 마찰 등의 외력에 의해 필링이 일어나거나 분리되는 형상이 개선되며, 내열성도 향상된다. Therefore, the polyurethane nonwoven fabric according to the production method of the present invention is improved in the shape in which peeling occurs or is separated by an external force such as washing or external friction, and the heat resistance is also improved.
Claims (4)
(S2) 상기 방사용액을 전기방사 구금을 이용하여 전기방사하여 웹을 형성하는 단계; 및
(S3) 상기 웹을 열처리하여 상기 열경화성 폴리에스테르 우레탄 프레폴리머를 경화시키는 단계를 포함하는 폴리우레탄 부직포의 제조방법.(S1) preparing a spinning solution by dissolving a thermoplastic polyurethane, a thermosetting polyester urethane prepolymer and a crosslinking agent of the thermosetting polyester urethane prepolymer in a solvent;
(S2) electrospinning the spinning solution with an electrospinning tool to form a web; And
(S3) heat-treating the web to cure the thermosetting polyester urethane prepolymer.
상기 열경화성 폴리에스테르 우레탄 프레폴리머의 함량은 열가소성 폴리우레탄 100 중량부를 기준으로 5 내지 85 중량부인 것을 특징으로 하는 폴리우레탄 부직포의 제조방법.The method according to claim 1,
Wherein the content of the thermosetting polyester urethane prepolymer is 5 to 85 parts by weight based on 100 parts by weight of the thermoplastic polyurethane.
상기 방사용액은 가교 촉진제를 더 함유하는 것을 특징으로 하는 폴리우레탄 부직포의 제조방법.3. The method according to claim 1 or 2,
Wherein the spinning solution further contains a crosslinking accelerator.
상기 방사용액을 섬유 원단의 표면에 전기방사하는 것을 특징으로 하는 폴리우레탄 부직포의 제조방법.3. The method according to claim 1 or 2,
Characterized in that the spinning liquid is electrospun onto the surface of the fiber fabric.
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