KR960011604B1 - Highly-soluble polyester resin compositions and fiber - Google Patents
Highly-soluble polyester resin compositions and fiber Download PDFInfo
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- KR960011604B1 KR960011604B1 KR1019940009832A KR19940009832A KR960011604B1 KR 960011604 B1 KR960011604 B1 KR 960011604B1 KR 1019940009832 A KR1019940009832 A KR 1019940009832A KR 19940009832 A KR19940009832 A KR 19940009832A KR 960011604 B1 KR960011604 B1 KR 960011604B1
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- isophthalate
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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- 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
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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
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- Chemical Or Physical Treatment Of Fibers (AREA)
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Abstract
Description
본 발명은 이용성 폴리에스테르 수지 조성물 및 섬유에 관한 것으로서, 더욱 상세하게는 기계적 내후성과 가수분해성이 양호하며, 섬유화하였을때 섬유의 물리적 성질이 우수하고 특히 수지 및 섬유 제조공 정성이 우수한 이용성 폴리에스테르 수지 및 섬유에 관한 것이다.The present invention relates to a water-soluble polyester resin composition and a fiber, and more particularly, to a water-soluble polyester resin having good mechanical weather resistance and hydrolyzability, and having excellent physical properties of the fiber when fiberized, and particularly excellent resin and fiber manufacturing process. It is about a fiber.
이용성/수용성 섬유는 종래부터 자수바닥 소재로 사용되거나 일반 직물 또는 편물에서 새로운 외관이나 촉감을 발현하기 위한 소재로 사용되어 왔으며 최근에는 면직물을 제조함에 있어 꼬임수를 줄임으로서 부드러운 촉감을 향상시키는 소재로 그 용도가 넓어지고 있다.Usability / water-soluble fiber has been used as a material for embroidery flooring or as a material for expressing a new appearance or feel in general fabrics or knitted fabrics. Recently, it is a material that improves soft touch by reducing the number of twists in manufacturing cotton fabrics. Its use is expanding.
종래에는, 상기의 용도로 주로 수용성 폴리비닐알콜 섬유(이하, PVA 섬유)를 사용하는 경우가 거의 대부분을 차지하였으며, 상기의 PVA 섬유는 개질된 폴리비닐알콜의 중합도가 1700~3500 정도인 수지를 용제에 녹여 건식방사 후 건열처리, 아세탈화하여 제조된 것으로서, 이 섬유는 고온다습한 조건에서 수분을 흡습하여 강도 및 신도 등 기본적인 기계적 물성이 약해지며 또한 수분에 의해 쉽게 팽윤되므로 직물의 형태 안정성이 불량해지는 등 상기 PVA 섬유로 제품을 제조하는데에는 적절한 온도 및 습도의 유지가 필히 요구되는 문제점이 있으며 또한 PVA 섬유는 끓는 물 중에서도 완전 용해되는 등 용해성이 우수한 반면에, 용해시 PVA 섬유의 고분자 결합이 절단되지 않고 완전한 고분자 상태로 물에 용해되어 있기 때문에 폐수 처리시 환경오염의 측정기준이 되는 생물학적 산소요구량(BOD) 및 화학적 산소요구량(COD)의 값이 상당히 높아 폐수처리에 소요되는 비용이 상대적으로 높다. 이러한 PVA 섬유의 단점을 해결하기 위하여 이용성/수용성 합성수지에 대한 연구가 진행되었는데, 특히 폴리에스테르 수지를 이용한 연구가 활발하여 일본 특공소 63-159525 및 일본 특공소 63-165516에서는 테레프탈산과 에틸렌글리콜을 주성분으로 하여 5-나트륨설포이소프탈산, 이소프탈산, 분자량 400~6000의 폴리옥시알킬글리콜 및 선상 에스테르 형성성 디카르본산 등을 공중합시켜 수지를 합성하고 이를 섬유화하는 방법이 제안되어 있다.Conventionally, the use of water-soluble polyvinyl alcohol fibers (hereinafter referred to as PVA fibers) is mainly used for the above-mentioned applications, and the PVA fibers have a resin having a degree of polymerization of modified polyvinyl alcohol of about 1700 to 3500. It is manufactured by dissolving it in a solvent and drying it after dry spinning and acetalizing it. This fiber absorbs moisture under high temperature and high humidity conditions, weakens basic mechanical properties such as strength and elongation, and swells easily by moisture. There is a problem in that it is necessary to maintain the appropriate temperature and humidity in manufacturing the product with the PVA fiber, such as poor, and also the PVA fiber is excellent solubility, such as completely dissolved in boiling water, while the polymer bond of the PVA fiber Measurement standard of environmental pollution during wastewater treatment because it is not cut and dissolved in water in a completely polymer state The biological oxygen demand (BOD) and the chemical oxygen demand (COD) are very high, resulting in relatively high costs for wastewater treatment. In order to solve the shortcomings of PVA fiber, research on usability / water-soluble synthetic resins has been conducted. In particular, researches using polyester resins have been actively conducted. A method of synthesizing a resin by copolymerizing 5-sodium sulfoisophthalic acid, isophthalic acid, polyoxyalkylglycol having a molecular weight of 400 to 6000, linear ester-forming dicarboxylic acid, or the like, and fiberization thereof has been proposed.
그러나 상기 방법에 의해 제조된 수지는 30~40몰%의 공중합 물질이 첨가되어 있어서 수지의 제조 공정성은 물론 섬유화하기 위한 용융방사 및 연신하는 제사 공정성이 극히 불량하며 또한 제조된 섬유도 강도가 0.6~1.0g/데니어 수준으로 이를 이용하여 제직, 제편 등의 가공공정 등을 거치게 되면 사절이 심하게 발생되어 생산효율이 저하함은 물론 제품의 품질도 불량하여지는 단점이 있다.However, the resin produced by the above method is 30 ~ 40 mol% of the copolymer is added, the resin manufacturing process, as well as melt spinning and elongation processability of the fiber spinning is extremely poor, and the produced fiber is also 0.6 ~ strength 1.0g / denier level is used to go through the process of weaving, weaving, etc., severely generated thread trimming, resulting in poor production efficiency and poor product quality.
따라서 본 발명은 이러한 문제점을 해결한 것으로 가성소오다 1% 이하의 약알칼리 농도의 조건에서 용이하게 용해, 가수분해되며 강도, 내열성 등의 물리적 성질이 우수하고 열가소성으로서 상용의 설비로 용융방사가 가능한 섬유 고분자를 사용하여 이용성 폴리에스테르 섬유를 제조하는데 그 목적이 있다.Therefore, the present invention solves this problem, and is easily dissolved and hydrolyzed under the condition of weak alkali concentration of caustic soda less than 1%, and has excellent physical properties such as strength and heat resistance, and can be melt spun as a commercial facility as thermoplastic. The purpose is to prepare usable polyester fibers using fiber polymers.
이하, 본 발명을 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 테레프탈산 또는 디메틸테레프탈레이트의 에스테르 형성성 디에시드에 대하여 2~7몰%의 5-나트륨설포 이소프탈레이트 또는 5-나트륨설포 디메틸이소프탈레이트와 수평균 분자량이 2500~20000인 폴리알킬렌옥사이드 성분 5~15중량% 그리고 아래식(1)로 표현되는 화합물 0.5~5중량%를 함유하는 것을 특징으로 하는 폴리에스테르 수지 조성물에 관한 것이다.The present invention relates to a polyalkylene oxide component having 2 to 7 mol% of 5-sodium sulfo isophthalate or 5-sodium sulfo dimethyl isophthalate and a number average molecular weight of 2500 to 20000 with respect to ester-forming dieside of terephthalic acid or dimethyl terephthalate. It is related with the polyester resin composition characterized by containing 5 to 15 weight% and 0.5 to 5 weight% of a compound represented by following formula (1).
단, n : 5~20 사이의 정수Where n is an integer between 5 and 20
X : -OSO3-, -SO3-, -COOH-, 또는 페닐X: -OSO 3- , -SO 3- , -COOH-, or phenyl
M : 알칼리 또는 알칼리 토금속에 속하는 무기금속M: inorganic metals belonging to alkali or alkaline earth metals
또한 본 발명은 상기 수지 조성물을 용융, 방사, 연신하여 제조된 폴리에스테르 섬유를 포함한다.The present invention also includes polyester fibers produced by melting, spinning, and stretching the resin composition.
이하, 본 발명을 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 약 알칼리 수용액에서 용이하게 분해 및 용해되는 폴리에스테르 섬유에 관한 것으로서, 수지 및 섬유제조 공정성이 우수하고 물리적인 특성이 우수한 섬유를 제조할 수 있는 이용성 폴리에스테르 수지조성물 및 섬유에 관한 것이다.The present invention relates to a polyester fiber which is easily decomposed and dissolved in a weak alkaline aqueous solution, and relates to a usable polyester resin composition and fiber which can produce a fiber having excellent resin and fiber manufacturing processability and excellent physical properties.
본 발명에서 사용된 5-나트륨설포 이소프탈레이트 또는 5-나트륨설포 디메틸이소프탈레이트, 폴리에틸렌테레프탈레이트의 치밀한 결정구조를 비결정구조로 변화시켜 용해성을 상승시키는 역할을 하며, 폴리알킬렌옥사이드 성분은 이 화합물 자체의 친수성과 높은 유동성으로 용해/분해성을 촉진하여 알칼리에 의한 가수분해 특성을 향상시킨다.5-sodium sulfo isophthalate or 5-sodium sulfo dimethyl isophthalate, polyethylene terephthalate used in the present invention to change the crystal structure of the amorphous structure to increase the solubility, the polyalkylene oxide component is the compound itself Its hydrophilicity and high fluidity promotes solubility / degradability to improve hydrolysis characteristics by alkali.
또한 화합물(1)은 구조 중에 친수성 부분과 소수성 부분을 동시에 포함하고 있어 소수성인 폴리에스테르와 친수성인 폴리알킬렌옥사이드 부분의 가교역할을 하여 알칼리 의한 가수분해 중의 용해/분해를 촉진하는 역할을 한다.In addition, the compound (1) contains a hydrophilic portion and a hydrophobic portion at the same time in the structure to serve as a crosslinking role of the hydrophobic polyester and the hydrophilic polyalkylene oxide portion to play a role of promoting dissolution / decomposition during hydrolysis by alkali.
그리고 수지 조성물 중에서 에스테르 형성성 디에시드에 대해 5-나트륨설포 이소프탈레이트 또는 5-나트륨설포 디메틸이소프탈레이트의 함량은 2~7몰%가 적당한 바, 2몰% 미만에서는 용해/분해성이 부족하여 이를 해결하려면 가성소오다의 투입량이 많아지게 되어 후공정에서 같이 사용되는 다른 섬유를 취화 또는 분해시키는 문제가 있으며, 7몰%를 초과할 때는 섬유형성성 수지의 제조 및 섬유화 제조공정성이 매우 불량하게 되는 단점이 있다.In addition, the content of 5-sodium sulfo isophthalate or 5-sodium sulfo dimethylisophthalate in the resin-forming dieside in the resin composition is 2 ~ 7 mol% is suitable, and less than 2 mol% solve the lack of solubility / degradability To this end, the amount of caustic soda is increased so that there is a problem of embrittlement or decomposition of other fibers used together in the post-process, and when it exceeds 7 mol%, the manufacturing process of fiber-forming resin and fiberization manufacturing process becomes very poor. There is this.
그리고 수평균 분자량 2,500~20,000인 수용성 폴리알킬렌옥사이드 성분의 함량은 5~15중량%가 적당한바, 5중량% 미만에서는 용해가공 공정시간이 길어져 경제성이 저하하며, 15중량%를 초과할때는 섬유 제조공정성이 불량하여지며 제조된 섬유의 강도가 낮아진다.And the content of the water-soluble polyalkylene oxide component having a number average molecular weight of 2,500 ~ 20,000 is 5 ~ 15% by weight is appropriate, less than 5% by weight of the process of dissolution processing is long, economic efficiency is lowered, when the fiber exceeds 15% by weight The processability is poor and the strength of the fiber produced is low.
본 발명에 의해 제조된 섬유를 완전히 분해/용해하는 가공조건은 가성소오다 0.3~1중량% 또는/및 음이온 계면활성제 또는 음이온과 비이온 계면활성제 혼합물을 임계미셀농도(CMC)량으로 조성된 수용액에서 70~98℃로 20분 이내이다. 여기에서 이용성 섬유를 분해/용해함에 있어 계면활성제를 첨가하는 것은 분해물들 중 일부 물에 용해되지 않는 것을 유화-분산시켜 기계장치 내에 침적되는 것을 방지하고 아울러 가수분해를 촉진하기 위한 것으로서 이를 첨가하지 않아도 이용성 섬유의 용해/분해성이 저하되지는 않는다.Processing conditions for completely decomposing / dissolving the fibers produced by the present invention are caustic soda 0.3-1% by weight or / and an aqueous solution in which an anionic surfactant or an anionic and nonionic surfactant mixture is prepared in a critical micelle concentration (CMC) amount. It is within 20 minutes from 70 to 98 ℃. The addition of a surfactant here in the decomposition / dissolution of the usable fiber is intended to emulsify-disperse some of the decomposition products insoluble in water to prevent deposition in the machinery and to promote hydrolysis. The solubility / degradability of the usable fiber is not lowered.
또한, 본 발명에 의해 제조된 이용성 폴리에스테르 섬유는 인장강도가 3.0g/데니어 이상으로 우수하고 고온, 다습한 환경에서도 물성의 변화가 없으며 또한 제조된 섬유를 분해/용해하는 공장기구도 1.0중량% 이하의 가성소오다 수용액에서 처리함으로서 섬유를 가수분해하여 저분자 상태로 분해/용해하거나 저중합체(Oligomer)를 유화 분산하는 방법이므로 비교적 간편한 잇점이 있다.In addition, the usable polyester fiber produced according to the present invention has excellent tensile strength of 3.0 g / denier or more, and does not change physical properties even in a high temperature and high humidity environment, and also 1.0% by weight of a factory mechanism for decomposing / dissolving the manufactured fiber. By treating in a caustic aqueous soda solution as follows, the fiber is hydrolyzed to decompose / dissolve in a low molecular state or to emulsify and disperse oligomers.
이와 같이 수지 조성물이 저분자 상태로 분해/용해되기 때문에 용해되어 고분자 상태로 있는 폴리비닐알콜에 비하여 폐수처리시 상대적으로 낮은 산소 요구량을 보이므로 환경 오염방지의 효과도 뛰어나다.As such, since the resin composition is decomposed / dissolved in a low molecular state, it exhibits a relatively low oxygen demand during wastewater treatment as compared to polyvinyl alcohol which is dissolved and has a high polymer state, and thus is excellent in preventing environmental pollution.
그리고, 본 발명에 의하여 제조된 수지는 용해형 극세사의 제조시 용해부분의 수지로 사용할 수 있고 단독으로 섬유화하여 자수바닥, 분리직편물 및 기타 제품구성 일부를 제거하여 차별화 또는 신규의 부가가치 제품을 제조할때 소재로 이용할 수 있다.In addition, the resin produced according to the present invention can be used as a resin of the dissolved part in the manufacture of a dissolution type microfiber, and by fabricating alone to remove the embroidery bottom, separate knitted fabric and other parts of the product to produce a differentiated or new value-added product When used as a material.
본 발명에서 섬유의 특성을 확인하는 방법은 다음과 같다.In the present invention, the method of confirming the properties of the fibers is as follows.
* 강 도 : 만능 인장시험기(UTM)에서 일정 속도로 섬유를 신장시키면서 섬유가 절단되는 시점의 강력을 섬유의 데니어로 나눈 수치.* Strength: The value obtained by dividing the strength of the fiber at the time of cutting the fiber by denier while stretching the fiber at a constant speed in the universal tensile tester (UTM).
* 잔류율 : 제조된 섬유를 양말짜기 제편기에서 편직한 후 건조하여 10g 수준을 정확히 칭량하여 0.5중량%의 85℃ 가성소오다 수용액에서 20분간 처리한 후 200메쉬의 거름망으로 거른 후 거름망에 모여진 비 분해/용해물의 건조중량으로부터 계산하였다.* Residual rate: Knitted fibers were knitted in a hosiery knitting machine, dried, weighed exactly 10g, treated in 0.5% by weight aqueous solution of 85 ℃ caustic soda for 20 minutes, filtered through a 200 mesh sieve, and then collected in a sieve. Calculated from the dry weight of non-degradation / lysate.
이하, 실시예를 통하여 본 발명을 더욱 상세하게 설명하겠는 바, 실시예에 의하여 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
[실시예 1-5]Example 1-5
디메틸테레프탈레이트 1000부, 에틸렌글리콜 640부, 5-나트륨설포 디메틸이소프탈레이트를 소정량 및 교환반응 촉매로서 초산나트륨 2수염을 1.3부 첨가하여 3시간에 걸쳐 온도를 150℃에서 220℃까지 서서히 가열하여 승온하면서 반응에 의해 발생되는 메탄올을 계외로 유출하면서 에스테르 교환반응을 행하였다. 이론적인 메탄올 유출량의 95% 이상이 유출되면 에스테르 교환반응을 종료시키고 소정의 폴리에틸렌글리콜과 화합물(1)을 소정량 투입하고 안정제로서 트리메틸인산 0.46부, 중축합 반응촉매로서 삼산화안티몬 0.38부를 첨가한 후 20분간 교반하면서 내부온도를 240℃로 승온하였다. 얻어진 생성물을 미리 240℃로 가열된 중축합 반응조로 옮기고 상압의 질소 분위기 하에서 15분간 교반하여 내용물을 안정화시킨 후 60분간에 걸쳐 내부온도를 240℃에서 280℃로 승온하면서 반응계를 0.1mmHg까지 감압하고 이후에는 280℃, 0.1mmHg의 상태에서 원하는 수준의 용융점도에 도달할 때까지 반응을 지속하여 소정 물성의 수지를 얻어 칩화하였다. 얻어진 수지를 통상방법에 따라 건조하고 용융 압출형 방사기에서 방사온도 270℃, 방사속도 1200m/분으로 용융방사하여 미연신사를 제조하고 이를 공급로울러, 열처리 플레이트 및 연신로울러로 구성된 연신기에서 최종적인 연신사의 파단 신도가 30~40%인 40D/12F의 섬유를 제조하여 각각의 측정 결과를 표 1에 나타내었다.1,000 parts of dimethyl terephthalate, 640 parts of ethylene glycol, 5-sodium sulfo dimethyl isophthalate and 1.3 parts of sodium acetate dihydrate were added as an exchange reaction catalyst, and the temperature was gradually heated from 150 ° C to 220 ° C over 3 hours. The transesterification reaction was carried out while the methanol generated by the reaction was discharged out of the system while raising the temperature. When 95% or more of the theoretical methanol flowed out, the transesterification reaction was terminated, a predetermined amount of polyethylene glycol and compound (1) were added, 0.46 parts of trimethyl phosphate as a stabilizer and 0.38 parts of antimony trioxide as a polycondensation reaction catalyst were added. The internal temperature was raised to 240 ° C. while stirring for 20 minutes. The resulting product was transferred to a polycondensation reactor previously heated to 240 ° C., stirred for 15 minutes in a nitrogen atmosphere at atmospheric pressure to stabilize the contents, and the reaction system was decompressed to 0.1 mmHg while raising the internal temperature from 240 ° C. to 280 ° C. over 60 minutes. Thereafter, the reaction was continued until the desired level of melt viscosity was reached at 280 ° C. and 0.1 mmHg, thereby obtaining and chipping a resin having a predetermined physical property. The resin thus obtained was dried according to a conventional method and melt spun at a melt extrusion type spinning machine at a spinning temperature of 270 ° C. and a spinning speed of 1200 m / min to prepare a non-stretched yarn, which was finally stretched in a stretching machine composed of a feed roller, a heat treatment plate and a stretching roller. 40D / 12F fiber having an elongation at break of 30 to 40% was prepared and shown in Table 1 for each measurement result.
[비교예 1]Comparative Example 1
폴리에틸렌글리콜을 첨가하지 않은 것 이외에는 실시예와 동일한 방법으로 수지를 제조하여 섬유를 제조하였으며 측정 결과를 표 1에 나타내었다.Except not adding polyethylene glycol to prepare a fiber by preparing a resin in the same manner as in Example and the measurement results are shown in Table 1.
[비교예 2]Comparative Example 2
폴리에틸렌테레프탈레이트 40D/12F 섬유를 사용하여 용해 특성을 조사하였다.The dissolution properties were investigated using polyethylene terephthalate 40D / 12F fibers.
※ DMS : 5-나트륨설포 디메틸이소프탈레이트※ DMS: 5-sodium sulfo dimethylisophthalate
※ PEG : 폴리에틸렌글리콜※ PEG: polyethylene glycol
※ SDBS : 소디움 도데실 벤젠 설포네이트※ SDBS: Sodium Dodecyl Benzene Sulfonate
Claims (4)
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| KR1019940009832A KR960011604B1 (en) | 1994-05-04 | 1994-05-04 | Highly-soluble polyester resin compositions and fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101414211B1 (en) * | 2013-11-28 | 2014-07-10 | 도레이케미칼 주식회사 | Fabric comprising a hollow fiber with C-shaped cross-section and method for manufacturing thereof |
| KR101487941B1 (en) * | 2013-11-20 | 2015-02-06 | 도레이케미칼 주식회사 | Alkali extractable co-polyester for the manufacture of complex fiber, method for manufacturing thereof and complex fiber comprising the same |
| US10947644B2 (en) | 2013-08-02 | 2021-03-16 | Toray Advanced Materials Korea Inc. | C-shaped composite fiber, C-shaped hollow fiber thereof, fabric including same, and method for manufacturing same |
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| KR102230781B1 (en) * | 2019-08-29 | 2021-03-23 | 주식회사 휴비스 | Eco-friendly Water Soluble Polyester-based Sea Island Yarn |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10947644B2 (en) | 2013-08-02 | 2021-03-16 | Toray Advanced Materials Korea Inc. | C-shaped composite fiber, C-shaped hollow fiber thereof, fabric including same, and method for manufacturing same |
| KR101487941B1 (en) * | 2013-11-20 | 2015-02-06 | 도레이케미칼 주식회사 | Alkali extractable co-polyester for the manufacture of complex fiber, method for manufacturing thereof and complex fiber comprising the same |
| WO2015076540A1 (en) * | 2013-11-20 | 2015-05-28 | 도레이케미칼 주식회사 | Copolyester readily soluble in alkali, for preparing conjugate fiber, preparation method therefor, and conjugate fiber containing same |
| KR101414211B1 (en) * | 2013-11-28 | 2014-07-10 | 도레이케미칼 주식회사 | Fabric comprising a hollow fiber with C-shaped cross-section and method for manufacturing thereof |
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