KR101439736B1 - Process Spandex composition having improved productivity - Google Patents
Process Spandex composition having improved productivity Download PDFInfo
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- KR101439736B1 KR101439736B1 KR1020130007970A KR20130007970A KR101439736B1 KR 101439736 B1 KR101439736 B1 KR 101439736B1 KR 1020130007970 A KR1020130007970 A KR 1020130007970A KR 20130007970 A KR20130007970 A KR 20130007970A KR 101439736 B1 KR101439736 B1 KR 101439736B1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
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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
- D02G3/22—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
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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
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
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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
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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
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
Abstract
본 발명은 유기 디이소시아네이트와 고분자 디올을 반응시켜 폴리우레탄 전구체를 제조하고 이를 유기용매에 용해한 후 쇄연장제 디아민 및 쇄종지제 모노아민과 반응시켜 수지 조성물을 조제함에 있어 고분자 디올에 분자량이 90 내지 600인 저분자 디올을 혼합하여 수지 조성물을 조제하는 것을 특징으로 하는 생산성 향상이 가능한 스판덱스 섬유의 제조방법을 제공하기 위한 것이다The present invention relates to a process for preparing a resin composition by reacting an organic diisocyanate with a polymer diol to prepare a polyurethane precursor, dissolving the organic precursor in an organic solvent, and reacting the mixture with a chain extender diamine and a chain cadmium monoamine, And a low molecular weight diol having a weight-average molecular weight of 500 to 600, to prepare a resin composition, and to provide a method for producing spandex fiber capable of improving productivity
Description
본 발명은 생산성 향상이 가능한 스판덱스 섬유의 제조방법에 관한 것이다. 더욱 상세하게, 본 발명은 폴리우레탄 수지 조성물로부터 제조된 스판덱스 섬유의 내열성 및 기타 물성의 저하 및 변화없이 방사 점도 시간 만을 단축시켜서 생산성을 향상시킬 수 있는 스판덱스 섬유의 제조방법에 관한 것이다.The present invention relates to a process for producing spandex fibers capable of improving productivity. More particularly, the present invention relates to a process for producing spandex fibers which can improve productivity by shortening the spinning viscosity time without deteriorating or changing the heat resistance and other physical properties of the spandex fibers produced from the polyurethane resin composition.
스판덱스 섬유는 85중량% 이상의 우레탄(urethane) 결합을 갖는 고신축성 폴리우레탄계 섬유로서 널리 알려져 있다. 일반적으로 스판덱스 섬유는 폴리우레탄 수지 조성물인 방사용액을 노즐을 통해 압출하고, 용매는 증발 및 건조하기 위해 가열기체를 도입하는 건식방사; 방사 수욕을 통과시켜 용매를 용출시키면서 동시에 폴리머를 응고시키는 습식방사, 아민 쇄연장제를 함유하는 반응액 중에 이소시아네이트를 지닌 전구체(prepolymer) 용액을 노즐을 통해 압출시켜 쇄연장 반응시키는 화학방사, 또는 폴리우레탄 수지 조성물을 가열용융상태에서 노즐을 통해 압출하고 냉각시키는 용융방사를 통해 제조된다.Spandex fibers are widely known as highly stretchable polyurethane fibers having urethane bonds of 85 wt% or more. Generally, spandex fibers are extruded through a nozzle with a spinning solution, which is a polyurethane resin composition, the solvent is dry spinning, in which a heating gas is introduced to evaporate and dry; A chemical spinning process in which a prepolymer solution containing isocyanate is extruded through a nozzle to effect a chain extension reaction in a reaction solution containing wet spinning or amine chain extender which coagulates the polymer while allowing the solvent to pass through a spinning water bath, The urethane resin composition is produced by melt spinning in which the composition is extruded through a nozzle in a heated molten state and cooled.
이와 같은 종래 방법으로 스판덱스 섬유를 제조할 경우, 방사를 하기 위하여 스판덱스 중합물의 점도를 방사에 적합하도록 충분히 올려야하고, 방사점도까지 점도를 상승시키기 위하여 일정시간이 필요로 하게된다.When the spandex fiber is prepared by the conventional method, the viscosity of the spandex polymer is increased enough to be suitable for spinning and a certain time is required to increase the viscosity to the spinning viscosity.
이에 본 발명은 내열성 및 기타 물성의 저하 및 변화없이 방사 점도 도달 시간만을 단축함으로써 생산성을 비약적으로 증대시킬 수 있는 생산성 향상이 가능한 스판덱스 섬유의 제조방법을 제공하는데 그 목적이 있다.Accordingly, it is an object of the present invention to provide a method for producing spandex fiber capable of dramatically increasing productivity by shortening the time to reach the spinning viscosity without deteriorating heat resistance and other physical properties.
본 발명의 스판덱스 섬유용 폴리우레탄 수지 조성물의 제조는 유기 디이소시아네이트와 고분자 디올을 반응시켜 폴리우레탄 전구체를 제조하고 이를 유기용매에 용해한 후 쇄연장제 디아민 및 쇄종지제 모노아민과 반응시켜 수지 조성물을 조제함에 있어 고분자 디올에 분자량이 90 내지 600인 저분자 디올을 혼합하여 수지 조성물을 조제하는 것을 특징으로 한다. The polyurethane resin composition for spandex fiber of the present invention is produced by reacting an organic diisocyanate with a polymeric diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and reacting the resultant mixture with a chain extender diamine and a chain cadmium monoamine, And a low molecular weight diol having a molecular weight of 90 to 600 is mixed with the polymer diol in the preparation thereof to prepare a resin composition.
본 발명에 따른 폴리우레탄 수지 조성물로부터 제조된 스판덱스 섬유는 내열성 및 기타 물성의 저하 및 변화없이 방사 점도 도달 시간만을 단축함으로써 생산성을 비약적으로 증대시킬 수 있다.The spandex fiber prepared from the polyurethane resin composition according to the present invention can dramatically increase the productivity by shortening the spinning viscosity reaching time without deteriorating or changing the heat resistance and other physical properties.
이와 같은 본 발명을 다음에서 상세하게 설명하기로 한다. Hereinafter, the present invention will be described in detail.
본 발명은 고분자 디올에 저분자량의 디올이 혼합된 스판덱스 섬유용 폴리우레탄 수지 조성물을 제공한다.The present invention provides a polyurethane resin composition for spandex fibers in which a low molecular weight diol is mixed with a polymer diol.
본 발명의 스판덱스 섬유에 사용되는 세그먼트 폴리우레탄 수지 조성물은 당 분야에서 공지된 바와 같이 유기 디이소시아네이트 및 고분자 디올을 반응시켜 폴리우레탄 전구체를 제조한 후, 이를 유기 용매에 용해시킨 후 디아민 및/또는 모노아민과 반응시킴으로써 제조를 한다. The segment polyurethane resin composition used in the spandex fiber of the present invention may be prepared by reacting an organic diisocyanate and a polymeric diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and then adding a diamine and / Amine in the presence of a base.
본 발명의 바람직한 구현예에 의하면, 상기 고분자 디올에 분자량이 90 내지 600인 저분자 디올을 혼합한다. 여기서 사용할 수 있는 저분자 디올로는 예를 들면, 분자량(Mw)이 600 이하인 디올류, 에틸렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥산디올 등이 있으며, 그 배합량은 약 0.5중량% 내지 1중량%가 바람직하다.According to a preferred embodiment of the present invention, the low molecular weight diol having a molecular weight of 90 to 600 is mixed with the high molecular weight diol. Examples of the low molecular weight diol to be used herein include diols having a molecular weight (Mw) of 600 or less, ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, Is preferably from about 0.5% to 1% by weight.
상기에서 디이소시아네이트는 4,4'-디페닐메탄디이소시아네이트, 1,5'-나프탈렌디이소시아네이트, 1,4'-페닐렌디이소시아네이트, 헥사메틸렌 디이소시아네이트, 1,4'-시클로헥산디이소시아네이트, 4,4'-디시클로헥실 메탄디이소시아네이트, 및 이소포론디이소시아네이트 등을 예로 들 수 있다The diisocyanate is exemplified by 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4 , 4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate, and the like
상기 고분자 디올로는 분자량이 1750 내지 3100인 폴리테트라메틸렌에테르글리콜이 바람직하다. 만일 분자량이 1750 미만이면 섬유의 신도가 낮아서 스판덱스 섬유로의 기능이 저하되는 문제가 있고, 3100을 초과하면 결정화도가 너무 높아서 탄성이 정상적으로 발현되지 않게 된다. As the polymer diol, polytetramethylene ether glycol having a molecular weight of 1750 to 3100 is preferable. If the molecular weight is less than 1,750, the elongation of the fiber is low and the function as the spandex fiber is deteriorated. If the molecular weight is more than 3,100, the degree of crystallinity is too high and the elasticity is not normally expressed.
상기 폴리올은 폴리테트라메틸렌에테르 글리콜, 폴리프로필렌 글리콜, 폴리카보네이트디올, 알킬렌옥사이드와 락톤모노머의 혼합물과 폴리(테트라메틸렌에테르)글리콜의 공중합체, 및 3-메틸-테트라히드로푸과 테트라히드로푸란의 공중합체로 이루어진 군에서 선택된 1종 이상일 수 있다.The polyol is selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, a copolymer of a mixture of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol, and a copolymer of 3-methyl- Or a combination thereof.
상기 쇄연장제는 에틸렌디아민, 1, 2-디아미노프로판, 1, 3-디아미노프로판, 1,4-디아미노부탄, 2,3-디아미노부탄, 1,5-디아미노펜탄, 및 1, 6-헥사메틸렌디아민, 1,4-씨클로헥산디아민, 및 에틸렌 트리아민으로 이루어진 군에서 선택된 1종 이상일 수 있다.The chain extender may be selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, , 6-hexamethylenediamine, 1,4-cyclohexanediamine, and ethylene triamine.
상기 쇄종지제는 1 관능기를 갖는 아민, 예를 들어 디에틸아민, 모노에탄올아민, 또는 디메틸아민일 수 있다.The chain terminator may be an amine having one functional group, for example, diethylamine, monoethanolamine, or dimethylamine.
아울러, 본 발명은 상기 폴리우레탄 수지 조성물로부터 제조된 스판덱스 섬유를 제공한다.In addition, the present invention provides a spandex fiber produced from the polyurethane resin composition.
본 발명은 하기의 실시예에 의하여 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것으로 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The following examples are provided for the purpose of illustrating the invention and are not intended to limit the scope of protection of the invention.
실시예Example 1 One
[폴리우레탄 수지조성물의 제조][Preparation of polyurethane resin composition]
수평균 분자량이 1800인 폴리테트라메틸렌글리콜(PTMG)과 4,4'-디페닐메탄디이소시아네이트를 몰비로 1:1.7에 1,4-부탄디올 (분자량 90) 0.5중량%을 함께 반응기에 투입하고, 질소가스기류 중에서 90℃, 90분간 교반하면서 반응시켜, 양말단에 이소시아네이트를 캡핑 반응(Capping Reaction)을 실시하였다. 이렇게 만들어진 폴리우레탄 전구체를 디메틸아세트아미드(DMAc)에 38중량%로 녹여 프리폴리머 용액을 만들었다.(PTMG) having a number average molecular weight of 1800 and 4,4'-diphenylmethane diisocyanate in a molar ratio of 1: 1.7 and 0.5% by weight of 1,4-butanediol (molecular weight 90) And the mixture was allowed to react in a nitrogen gas stream at 90 캜 for 90 minutes while stirring to perform an isocyanate capping reaction at both ends. The prepared polyurethane precursor was dissolved in dimethylacetamide (DMAc) at 38 wt% to prepare a prepolymer solution.
쇄연장제로 에틸렌디아민을 단독 사용하거나 1,2-프로필렌디아민과 혼합 사용하여 쇄종지제 디에틸아민과 15:1의 당량비로 혼합하고 디메틸아세트아미드에 녹여 7% 아민 용액을 만들었다.Ethylenediamine was used as a chain extender, or 1,2-propylenediamine was mixed with an ethylenediamine chain in an equivalent ratio of 15: 1, and the mixture was dissolved in dimethylacetamide to prepare a 7% amine solution.
상기 프리폴리머 용액과 아민 용액을 NCO기와 아민기의 당량비가 아민기가 더 많고 고유점도가 1.1이 되도록 고속으로 교반하며 쇄연장 반응을 시켜 고형분 35%의 폴리우레탄우레아 방사원액을 제조하였으며, 이 방사원액을 점도가 4000 Poise가 될 때까지 40°C에서 4rpm으로 교반시켜 방사 용액을 만들었다.The prepolymer solution and the amine solution were subjected to a chain extension reaction at a high speed with stirring so that the equivalence ratio of the NCO group and the amine group was larger than that of the amine group and the intrinsic viscosity was 1.1 to prepare a polyurethane-urea spinning solution having a solid content of 35% The spinning solution was made by stirring at 4 ° C at 40 ° C until the viscosity reached 4000 Poise.
[스판덱스 섬유의 제조][Production of spandex fiber]
폴리우레탄 수지조성물을 탈포시킨 후 방사 원액으로 사용하였으며, 건식방사 공정에서 방사온도를 250℃로 조정하여 4 필라멘트 40 데니어의 탄성사, 즉 스판덱스 섬유를 제조하였다.The polyurethane resin composition was defoamed and used as a spinning solution. The spinning temperature was adjusted to 250 ° C in a dry spinning process to prepare a 4-filament 40 denier elastic yarn, that is, a spandex fiber.
실시예Example 2 2
실시예 1에서 저분자 디올로서 1,4-부탄디올(분자량 100)을 0.7중량%를 고분자디올과 함께 반응기에 투입하는 것을 제외하고는 실시예 1과 동일하게 실시한다.The procedure of Example 1 was repeated, except that 0.7 weight% of 1,4-butanediol (molecular weight: 100) as a low molecular weight diol was added to the reactor together with the polymeric diol.
실시예Example 3 3
실시예 1에서 저분자 디올로서 1,4-부탄디올(분자량 200)을 1중량%를 고분자디올과 함께 반응기에 투입하는 것을 제외하고는 실시예 1과 동일하게 실시한다.The procedure of Example 1 was repeated, except that 1 weight% of 1,4-butanediol (molecular weight 200) as a low molecular weight diol was added to the reactor together with the polymer diol.
비교예Comparative Example 1 One
실시예 1에서 저분자 디올을 사용하지 않고 고분자디올만을 반응기에 투입하는 종래의 방법으로 실시하는 것을 제외하고는 실시예 1과 동일하게 실시한다.Example 1 was carried out in the same manner as in Example 1, except that only the polymer diol was fed into the reactor without using the low molecular diol.
상기 실시예 1 내지 3과 비교예 1에 대한 방사점도 도달시간을 측정한 결과를 다음 표 1에 나타내었다. 다음 표 1에서 방사점도 도달시간은 고형분 35%의 폴리우레탄우레아 방사원액을 점도가 4000 Poise가 될 때까지 40°C에서 4rpm으로 교반시키며, 방사 원액이 4000P 이상이 되는 시간을 비교한 것이다.The results of measuring the radial viscosity reaching times for Examples 1 to 3 and Comparative Example 1 are shown in Table 1 below. In Table 1, the radial viscosity reaching time is the time when the polyurethane-urea spinning solution having a solid content of 35% is stirred at 4 rpm at 40 ° C until the viscosity reaches 4000 Poise, and the time when the spinning solution becomes 4000 P or more is compared.
이상, 본 발명의 바람직한 예에 대해 어느 정도 특정적으로 설명했지만, 이것들에 대해 여러 가지의 변경을 할 수 있는 것은 당연하다. 따라서, 본 발명의 범위 및 정신으로부터 이탈하는 일 없이, 본 명세서 중에서 특정적으로 기재된 모양과는 다른 모양으로 본 발명을 실시할 수 있다는 것은 당연한 것으로 이해될 수 있다.
Although the preferred embodiments of the present invention have been described in detail to some extent, it is natural that various modifications can be made to them. It is therefore to be understood that the invention may be practiced otherwise than as specifically described herein without departing from the scope and spirit of the invention.
Claims (3)
상기 저분자 디올은 그 분자량이 90 내지 600이고, 0.5중량% 내지 1중량%를 배합하여서 되는 것을 특징으로 하는 생산성 향상이 가능한 스판덱스 섬유의 제조방법.A polyurethane precursor is prepared by reacting an organic diisocyanate with a polymeric diol, dissolving the organic precursor in an organic solvent, and reacting the mixture with a chain extender diamine and a chain cadmium monoamine to prepare a resin composition. The resin composition is prepared by mixing a low- In the spandex fiber,
Wherein the low molecular weight diol has a molecular weight ranging from 90 to 600 and comprises 0.5% by weight to 1% by weight of the low molecular weight diol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100207282B1 (en) * | 1997-08-01 | 1999-07-15 | 한형수 | Process for preparing polyurethane polymer having excellent viscosity of stability |
| JP2002088571A (en) | 2000-09-11 | 2002-03-27 | Du Pont Toray Co Ltd | Method for manufacturing polyurethane fiber |
| KR100528640B1 (en) | 1996-10-11 | 2005-11-16 | 아르코 케미컬 테크날러쥐. 엘.피. | Improved spandex elastomer |
| KR101180508B1 (en) | 2010-12-31 | 2012-09-06 | 주식회사 효성 | Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100528640B1 (en) | 1996-10-11 | 2005-11-16 | 아르코 케미컬 테크날러쥐. 엘.피. | Improved spandex elastomer |
| KR100207282B1 (en) * | 1997-08-01 | 1999-07-15 | 한형수 | Process for preparing polyurethane polymer having excellent viscosity of stability |
| JP2002088571A (en) | 2000-09-11 | 2002-03-27 | Du Pont Toray Co Ltd | Method for manufacturing polyurethane fiber |
| KR101180508B1 (en) | 2010-12-31 | 2012-09-06 | 주식회사 효성 | Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition |
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