KR100218710B1 - The manufacture method of the polyurethane elastic yarn - Google Patents

The manufacture method of the polyurethane elastic yarn Download PDF

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KR100218710B1
KR100218710B1 KR1019950051262A KR19950051262A KR100218710B1 KR 100218710 B1 KR100218710 B1 KR 100218710B1 KR 1019950051262 A KR1019950051262 A KR 1019950051262A KR 19950051262 A KR19950051262 A KR 19950051262A KR 100218710 B1 KR100218710 B1 KR 100218710B1
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South Korea
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elastic yarn
spinning
temperature
thermoplastic polyurethane
polyurethane elastic
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KR1019950051262A
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Korean (ko)
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KR970062100A (en
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장재홍
조대현
김근열
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구광시
주식회사코오롱
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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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • 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
    • 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
    • D01D5/08—Melt spinning methods
    • D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
    • 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
    • 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

Abstract

본 발명은 하드세그멘트성분을 디아이소시아네이트와 디올로하고 소프트세그멘트 성분을 폴리올로 하는 열가소성 폴리우레탄을 용융방사하여 탄성사를 제조하는 방법에 관한 것으로서, 열가소성 폴리우레탄의 방사필라멘트를 구금히부에 열방생장치를 부착하여 구금하부에서 냉각부까지에 열을 부여하는 것을 특징으로 하며, 이러한 본 발명에 의하면 용융방사에서 세데니어사의 제조시에도 과냉각에 의해 물성이 저하되지 않는 폴리우레탄 탄성사를 경제성있게 제조할 수 있게 된다.The present invention relates to a method for producing an elastic yarn by melt spinning a thermoplastic polyurethane comprising diisocyanate and diol as a hard segment component and a polyol as a soft segment component. It is characterized in that the heat is applied from the lower part to the cooling part by attaching, and according to the present invention, it is possible to economically produce a polyurethane elastic yarn that does not deteriorate in physical properties due to supercooling even in the manufacture of sedenite in melt spinning do.

Description

폴리우레탄 탄성사 제조방법Polyurethane Elastic Yarn Manufacturing Method

제1도는 본 발명의 실시예에서 사용한 열방생 장치의 구조를 개략적으로 나타낸 도면임.1 is a view schematically showing the structure of a heat radiation device used in the embodiment of the present invention.

본 발명은 하드세그멘트성분을 디아이소시아네이트와 디올로하고 소프트세그멘트 성분을 폴리올로 하는 열가소성 폴리우레탄을 용융방사하여 탄성사를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing an elastic yarn by melt spinning a thermoplastic polyurethane having a hard segment component as a diisocyanate and a diol and a soft segment component as a polyol.

일반적으로 탄성사로는 폴리우레탄을 주성분으로 하는 스판덱스섬유와 폴리에테르에스테르를 주성분으로 하는 섬유 등이 있는데, 폴리에테르에스테르 탄성사는 염색성 및 내염소성은 우수하나 탄성회복율이 떨어져서 용도가 제한되고 있다, 폴리우레탄 탄성사의 경우에는 건식 또는 습식으로 대별되는 용액방사공법과 용융방사공법등에 의해 제조된다.In general, elastic yarns include spandex fibers mainly composed of polyurethane and fibers mainly composed of polyether esters. Polyetherester elastic yarns have excellent dyeing and chlorine resistance, but their application is limited due to their low elastic recovery. In the case of elastic yarn, it is manufactured by a solution spinning method and a melt spinning method, which are roughly classified into dry or wet methods.

용액방사식의 경우에는 화학적 가교를 형성하여 상대적으로 우수한 열안정성과 우수한 신축 및 탄성회복성질을 가지므로 널리 이용되고 있으나, 설비비가 많이 들고 용매회수설비 등을 필요로 하는 등의 문제가 있다. 또한 세데니어사의 제조에 있어서 건식방사의 경우 세데니어를 제조하는 것을 가능하나 권취속도가 한정되어 생산성 향상이 어렵고 세데니어로 갈수록 용액의 용해도 분포의 불균일로 제품의 불균일에 따른 질이 떨어질 뿐 아니라 원사의 단면도 불규칙하여 제직등 후가공에서의 효율증대가 불가능하였다. 습식 방사의 경우도 권취속도가 건식의 1/3 수준으로 생산성에 문제가 있고 태데니어사의 방사에서 냉각의 효율면에서 이점이 있어 태데니어의 품질은 우수하나 세데니어사의 제조는 불가능하다.Solution spinning is widely used because it forms chemical crosslinks and has relatively excellent thermal stability and excellent stretch and elastic recovery properties. However, there are problems such as high equipment costs and the need for solvent recovery facilities. In the case of dry denier, it is possible to manufacture sedenier in the case of dry spinning, but it is difficult to improve productivity due to the limited winding speed, and the quality of the yarn is not only deteriorated due to the non-uniformity of the solubility distribution of the solution toward cedenier. Due to the irregular cross-sectional view, it was impossible to increase the efficiency in post processing such as weaving. In the case of wet spinning, the winding speed is 1/3 of dryness, which is a problem in productivity and the cooling efficiency in spinning of denden yarn is excellent.

반면에 용융방사법은 신축 및 탄성회복성질이 떨어지나 설비비와 용매회수과정의 생략에 의한 환경친화성이 있고, 세데니어의 방사에서 사의 균제도가 우수하여 스타킹용사등으로 용도가 급격히 신장되고 있어 일본을 중심으로 상업화하기 시작하여 날로 증가 추세에 있고 이의 상업화를 검토하거나 사업에 참여하는 기업이 증가일로에 있다. 그러나 용융방사법에 사용되는 열가소성 폴리우레탄 폴리머는 중합기술의 미비로 방사시 폴리머의 용융을 위해 열을 가하면 열분해 되는 현상으로 사의 내열성이 불량하여 염색, 열세트등의 후가공시 열안정성이 문제가 되었으나 현재에는 중합기술의 발전으로 내열성의 향상 및 내관성, 내염소성 등이 향상된 폴리머의 제조가 가능하여졌으며,용매의 불필요성에 의해 세데니어 제조시 균제도가 우수하고 방사속도의 고속화 및 자동화도 가능하여 제조비용이 저렴하여 더욱 사용범위가 확대되고 있다.On the other hand, melt spinning method has low elasticity and elastic recovery properties, but it is environmentally friendly due to elimination of equipment cost and solvent recovery process, and excellent use of yarn uniformity in sedenier spinning. Increasingly, companies are starting to commercialize and are increasing in number. However, the thermoplastic polyurethane polymer used in the melt spinning method is thermally decomposed when heat is applied to melt the polymer during spinning due to inadequate polymerization technology.The heat resistance of the yarn is poor, resulting in problems of thermal stability during dyeing and heat processing. Due to the development of polymerization technology, it is possible to manufacture polymers with improved heat resistance, improved pipe resistance, chlorine resistance, etc.Because of no need of solvents, excellent uniformity in sedenier manufacturing, speed of spinning and automation are possible. Because of this low cost, the range of use is further expanded.

일반적인 엘라스토머의 경우 화학적인 가교결합을 통한 3차원구조를 가지고 있어 가교후 망사구조를 형성하여 탄성회복거동을 하는데, 열가소성 엘라스토머는 수소결합 등의 분자간 인력을 통한 물리적 가교를 형성하므로 충분한 열을 가하여 유동상태에서 전단력을 가할 때 3차원 구조를 형성하는 분자간 인력이 파괴되어 압출 또는 사출공정이 가능하게 된다. 상기 열가소성 폴리우레탄의 경우-(A-B)n-으로 표기되는 블록공중합체로 결정화가 가능한 높은 융점의 블록(하드세그멘트)과 상대적으로 매우 낮은 유리전이온도를 갖는 비정형블록(소프트세그먼트)으로 구성된다. 이러한 탄성사의 신축기구는 가교점의 역할을 하는 하드 도메인(Hhard domain)에 의해 소프트세그멘트가 연결되어 발현되므로 하드 도메인과 소프트 도메인(soft domain)의 미세 상분리가 잘되어야 신도 및 탄성회복률 등의 물성이 향상된다. 미세 상분리현상은 하드 및 소프트세그멘트의 성분, 하드세그멘트비 및 온도에 영향을 받는 데, 세데니어사의 제조시에는 섬유의 과냉각 현상에 의해 상분리 정도가 낮게 되어 초기 모듈러스의 상승, 신도의 저하 및 탄성회복률의 저하가 일어나게 된다.In general, the elastomer has a three-dimensional structure through chemical crosslinking to form a network structure after crosslinking to perform elastic recovery behavior.A thermoplastic elastomer forms physical crosslinking through intermolecular attraction such as hydrogen bonding, so that sufficient flow is applied. When the shear force is applied in the state, the intermolecular attraction that forms the three-dimensional structure is destroyed to enable the extrusion or injection process. In the case of the thermoplastic polyurethane, it is composed of a block having a high melting point (hard segment) capable of crystallizing with a block copolymer represented by-(AB) n -and an amorphous block (soft segment) having a relatively very low glass transition temperature. The elastic mechanism of the elastic yarn is expressed by soft segments connected by hard domains serving as crosslinking points, so the fine phase separation between the hard domains and the soft domains requires good physical properties such as elongation and elastic recovery rate. Is improved. The fine phase separation is affected by hard and soft segment composition, hard segment ratio and temperature.In the manufacture of sedenier, the degree of phase separation becomes low due to the supercooling of the fiber, which leads to an increase in initial modulus, decrease in elongation and elastic recovery rate. Will cause a decrease.

따라서 본 발명은 세데니어사의 제조시에도 과냉각에 의해 물성이 저하되지 않는 폴리우레탄 탄성사를 제조하는 것을 목적으로 한다.Therefore, an object of the present invention is to produce a polyurethane elastic yarn that does not lower the physical properties due to subcooling even during the manufacture of sedenier.

상기한 목적을 달성하기 위하여 본 발명자들은 용융방사에 의한 폴리우레탄 탄성사 제조시 물성을 향상시키기 위해 구금하부에 열방생장치를 부착하여 구금하부에서 냉각부까지의 열을 부여하게 되면 미세상분리도가 증가하여 과냉각에 의해 물성이 저하되지 않는다는 사실을 발견하였고, 그 결과 본 발명을 완성하게 된 것이다.In order to achieve the above object, the present inventors attach a heat radiation device to the lower part of the cell in order to improve physical properties when manufacturing the polyurethane elastic yarn by melt spinning, and when the heat is imparted from the lower part to the cooling part, the degree of fine phase separation is increased. It was found that the physical properties are not lowered by the supercooling, and as a result the present invention has been completed.

그러므로 본 발명에 의하면, 섬유용 열가소성 폴리우레탄 칩을 사용하여 용융방사를 한 후 구금하부에 온도 160~240의 열발생장치를 이용, 열처리하는 공정을 포함하는 것을 특징으로 하는 폴리우레탄 탄성사의 제조방법이 제공된다.Therefore, according to the present invention, after the melt spinning using a thermoplastic polyurethane chip for the fiber, the temperature 160 ~ 240 under the detention Provided is a method for producing a polyurethane elastic yarn comprising a step of heat treatment using a heat generator of the.

본 발명의 방사과정을 바람직한 예를 들어 간략히 설명하면, 방사용 열가소성 폴리우레탄 칩을 압출기에서 용융하여 폴리머 관을 통과한 폴리머는 사의 데니어 조절이 가능한 계량 설비인 방사용 펌프를 통하여 방사팩 및 방사구금을 거쳐 용융상태로 압출방사되고, 방사구금 하단에 설치한 열발생 방치에 의해 160~240의 온도로 열처리된다. 그 다음에는 통상의 가공과정을 거쳐 최종제품으로 제조된다. 즉, 상기한 열처리 후에는 예를 들어 온도 15~35, 상대습도 30이하의 냉각풍에 의해 냉각 고화되고, 방사오일로 피복되며, 제1 및 제2고뎃트 롤러를 통하여 사의 장력이 조절되고 권취장치에 의해 권취된다.Briefly describing the spinning process of the present invention with a preferred example, the polymer passed through the polymer pipe by melting the thermoplastic polyurethane chip for spinning in the extruder is a spin pack and spinneret through a spinning pump which is a denier adjustable metering equipment Extruded spinning in the molten state through the heat generation, 160 ~ 240 by heat generation left installed on the bottom of the spinneret Heat treatment to a temperature of. After that, it is manufactured into a final product through normal processing. That is, after the heat treatment described above, for example, the temperature 15 to 35 , Relative humidity 30 It cools and solidifies by the following cooling wind, it is coat | covered with spinning oil, the tension of a yarn is adjusted through the 1st and 2nd goth roller and it is wound up by the winding-up apparatus.

열발생장치에 의한 열보정이 없을 때에는 구금하부의 온도는 130~140로 세데니어사의 제조시 과냉각의 원인이 된다. 그러나, 본 발명에 따라 열발생장치에 의해 열보정을 행하게 되면, 구금 하부 온도는 섬도 등의 방사조건에 따라 20~100가 높아지게 되며, 이에 따라 열가소성 폴리우레탄 탄성사는 고화점이 연장되고, 높은 온도에 의하여 미세상분리가 촉진되고, 냉각부에서의 냉각 또한 지연시킴으로 결과적으로 미세상분리도를 높게 한다. 따라서 본 방법을 적용할 경우에 30데니어 이하로 제조된 열가소성 폴리우레탄 탄성사의 과냉각현상에 의한 신도저하 및 초기 모듈러스(M150) 값의 증가를 막아 세데니어의 우수한 폴리우레탄 탄성사를 제조할 수 있게 된다.If there is no heat compensation by the heat generating device, the temperature in the lower part of the cap is 130 ~ 140 This is the cause of supercooling in the manufacture of cedenier. However, when the heat correction is performed by the heat generating device according to the present invention, the lower temperature of the detention is 20 ~ 100 depending on the spinning conditions such as fineness As a result, the thermoplastic polyurethane elastic yarn has a high solidification point, and the microphase separation is promoted by the high temperature, and the cooling in the cooling unit is also delayed, thereby increasing the degree of microphase separation. Therefore, when the present method is applied, the elongation decrease and initial modulus due to the supercooling phenomenon of the thermoplastic polyurethane elastic yarn manufactured to 30 denier or less (M150) By preventing the increase of) value, it is possible to manufacture the excellent polyurethane elastic yarn of cedenier.

이하, 본 발명을 비한정적인 실시예의 방법으로 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail by way of non-limiting examples.

[실시예 1]Example 1

섬유형성성 열가소성 폴리우레탄 폴리머를 진공건조기를 사용하여 온도 85에서 5시간 동안 건조하여 충분히 수분을 제거한 다음에 방사온도 230, 열발생장치 온도 180, 냉각풍 온도 20, 냉각풍속도 0.3m/min, 방사속도 500m/min으로 방사, 열처리하여 40데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.Fibrous Thermoplastic Polyurethane Polymer Using a Vacuum Dryer at a Temperature of 85 Dry for 5 hours to remove enough moisture, and then spin temperature 230 , Heat generator temperature 180 Cooling wind temperature 20 , 40 m denier thermoplastic polyurethane elastic yarn was produced by spinning and heat treatment at a cooling wind speed of 0.3m / min, spinning speed of 500m / min.

사용된 열발생장치를 첨부도면에 도시되는 바와 같이 주물로된 이중벽(11)내에 가열코일(12)이 장착된 내부중공형의 원통형 열발생장치(10)였으며, 방사구금에서 방출된 필라멘트가 이 장치(10)의 중공부를 통과하면서 열처리된다.The heat generating device used was an internal hollow cylindrical heat generating device 10 having a heating coil 12 mounted in a double wall 11 made of a casting, as shown in the accompanying drawings. Heat treatment is performed while passing through the hollow portion of the device 10.

[실시예 2]Example 2

열발생장치(10)의 온도를 195로 한 것을 제외하고는 실시예 1과 동일한 절차를 반복하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.The temperature of the heat generator 10 is 195 The same procedure as in Example 1 was repeated except that the thermoplastic polyurethane elastic yarn of 40 denier was prepared.

[실시예 3]Example 3

열발생장치(10)의 온도를 210로 한 것을 제외하고는 실시예 1과 동일한 절차를 반복하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.The temperature of the heat generator 10 is 210 The same procedure as in Example 1 was repeated except that the thermoplastic polyurethane elastic yarn of 40 denier was prepared.

[실시예 4]Example 4

열발생장치(10)의 온도를 225로 한 것을 제외하고는 실시예 1과 동일한 절차를 반복하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.The temperature of the heat generating device 10 is 225 The same procedure as in Example 1 was repeated except that the thermoplastic polyurethane elastic yarn of 40 denier was prepared.

[실시예 5]Example 5

냉각풍 온도를 15로 한 것을 제외하고는 실시예 2와 동일한 절차를 반복하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.Cooling wind temperature 15 The same procedure as in Example 2 was repeated except that the thermoplastic polyurethane elastic yarn of 40 denier was prepared.

[실시예 6]Example 6

열발생장치(10)의 온도를 225로 한 것을 제외하고는 실시예 1과 동일한 절차를 반복하여 20 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.The temperature of the heat generating device 10 is 225 The same procedure as in Example 1 was repeated except that the thermoplastic polyurethane elastic yarn of 20 denier was prepared.

[비교예 1]Comparative Example 1

섬유형성성 열가소성 폴리우레탄 폴리머를 진공건조기를 사용하여 온도 85에서 5시간 동안 건조하여 충분히 수분을 제거한 다음에 방사온도 230, 냉각풍 온도 20, 냉각풍 속도 0.3m/min, 방사속도 500m/min으로 방사, 열처리하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.Fibrous Thermoplastic Polyurethane Polymer Using a Vacuum Dryer at a Temperature of 85 Dry for 5 hours to remove enough moisture, and then spin temperature 230 Cooling wind temperature 20 , 40 m denier thermoplastic polyurethane elastic yarn was produced by spinning and heat treatment at a cooling wind speed of 0.3m / min, spinning speed of 500m / min.

[비교예 2]Comparative Example 2

비교예 1과 같은 조건으로 하되 방사온도를 225로 하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.Under the same conditions as in Comparative Example 1, the spinning temperature is 225 40 denier thermoplastic polyurethane elastic yarn was manufactured as the above.

[비교예 3]Comparative Example 3

비교예 1과 같은 조건으로 하되 냉각풍 온도를 15로 하여 40 데니어의 열가소성 폴리우레탄 탄성사를 제조하였다.Under the same conditions as in Comparative Example 1, but the cooling wind temperature is 15 40 denier thermoplastic polyurethane elastic yarn was manufactured as the above.

[비교예 4][Comparative Example 4]

비교예 1과 같은 조건으로 하여 20 데니어의 열가소성 폴리우레탄 탄성사를] 제조하였다.20 denier thermoplastic polyurethane elastomer was manufactured under the same conditions as in Comparative Example 1.

[비교예 5][Comparative Example 5]

비교예 1과 같은 조건으로 하되 열발생장치(10)의 온도를 250로 하여 행하였다. 이 예는 과열처리에 의해 물성이 불균일해지는 문제가 있었다.Under the same conditions as in Comparative Example 1, the temperature of the heat generating device 10 is 250 It was done by. This example had a problem that the physical properties became uneven by overheating.

상기한 실시예 및 비교예의 폴리우레탄 탄서사에 대하여 다음과 같은 방법으로 물성을 측정하였다. 측정결과는 하기 표 1에 제시된다.The physical properties of the polyurethane tancers of the above-described examples and comparative examples were measured by the following method. The measurement results are shown in Table 1 below.

Claims (1)

섬유용 열가소성 폴리우레탄 칩을 사용하여 용융방사를 한 후 구금 하부에 온도 160~240의 열발생장치를 이용, 열처리하는 공정을 포함하는 것을 특징으로 하는 폴리우레탄 탄성사의 제조방법.After melt spinning using thermoplastic polyurethane chips for textiles, the temperature is 160-240 Method for producing a polyurethane elastic yarn comprising the step of heat treatment using the heat generating device of the.
KR1019950051262A 1995-12-18 1995-12-18 The manufacture method of the polyurethane elastic yarn KR100218710B1 (en)

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