KR101180508B1 - Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition - Google Patents
Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition Download PDFInfo
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- D—TEXTILES; PAPER
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- 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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- 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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- 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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- 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
- 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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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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
- 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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- 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
- D10B2401/063—Load-responsive characteristics high strength
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Abstract
본 발명은 강도가 우수한 스판덱스 섬유를 제공하고자 하는 것으로, 상기 스판덱스 섬유용 폴리우레탄 수지 조성물 및 이로부터 제조된 섬유를 제공한다. 상기 폴리우레탄 수지 조성물은 유기디이소시아네이트를 저분자 디올 또는 저분자 디아민과 반응시켜서 제조한 고분자 첨가제를 포함하는 것을 특징으로 한다.The present invention is to provide a spandex fiber excellent in strength, to provide a polyurethane resin composition for the spandex fiber and a fiber prepared therefrom. The polyurethane resin composition is characterized in that it comprises a polymer additive prepared by reacting an organic diisocyanate with a low molecular diol or a low molecular diamine.
Description
본 발명은 강도가 우수한 스판덱스 섬유용 폴리우레탄 수지 조성물 및 이를 포함하는 스판덱스 섬유에 관한 것이다.
The present invention relates to a polyurethane resin composition for spandex fibers having excellent strength and to spandex fibers comprising the same.
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 based fibers having a urethane bond of at least 85% by weight. Generally, spandex fibers extrude a spinning solution, which is a polyurethane resin composition, through a nozzle, and the solvent is dry spinning that introduces a heating gas for evaporation and drying; Wet spinning, which solidifies the polymer while eluting the solvent by passing the spinning water bath, chemical spinning, in which the prepolymer solution with isocyanate in the reaction solution containing an amine chain extender is extruded through a nozzle and subjected to chain extension reaction, or poly The urethane resin composition is prepared through melt spinning which is extruded through a nozzle in a molten state of heat and cooled.
스판덱스 섬유에 있어서 높은 강도를 갖도록 하는 기술은 대단히 중요하다. 스판덱스 섬유의 강도를 향상하기 위해, 종래에는 디이소시아네이트로서 디페닐메탄-4,4'-디이소시아네이트를 사용하되, 여기에 포함되는 디페닐메탄-2,4'-디이소시아네이트를 일반적으로 사용되는 제품 수준보다 높은 함량을 포함하도록 하는 방법을 사용하였다.The technology of having high strength in spandex fibers is of great importance. In order to improve the strength of spandex fibers, conventionally, diphenylmethane-4,4'-diisocyanate is used as the diisocyanate, but the diphenylmethane-2,4'-diisocyanate included therein is generally used. A method was used to contain higher than levels.
예를 들어, 일본 특허 출원번호 1993-226050에서는 스판덱스 섬유를 제조하기 위하여 폴리우레탄우레아 폴리머 합성에 사용하는 디이소시아네이트에 디페닐메탄-2,4'-디이소시아네이트를 1.8 내지 13wt% 포함하도록 하여 스판덱스 섬유를 제조하는 방법을 제시하고 있다.For example, Japanese Patent Application No. 1993-226050 discloses spandex fibers by including diphenylmethane-2,4'-diisocyanate in the diisocyanate used in the synthesis of polyurethaneurea polymer to produce spandex fiber. It provides a method for preparing.
그러나, 이와 같은 종래 방법으로 스판덱스 섬유를 제조할 경우, 스판덱스 섬유의 강도가 충분히 높지 못하여 높은 강도를 필요로 하는 용도에 적용하기에 적합하지 못한 문제점이 있다.However, when the spandex fiber is manufactured by such a conventional method, there is a problem that the strength of the spandex fiber is not high enough to be suitable for use in applications requiring high strength.
따라서, 본 발명은 강도가 우수한 스판덱스 섬유를 형성하기 위한 폴리우레탄 수지 조성물과 상기 폴리우레탄 수지 조성물로부터 제조된 강도가 우수한 스판덱스 섬유를 제공하고자 한다.
Accordingly, the present invention is to provide a polyurethane resin composition for forming a spandex fiber excellent in strength and a high strength spandex fiber prepared from the polyurethane resin composition.
본 발명에 의한 스판덱스 섬유용 폴리우레탄 수지 조성물은 유기 디이소시아네이트와 고분자 디올을 반응시켜 폴리우레탄 전구체를 제조하고 이를 유기용매에 용해한 후 쇄연장제 디아민 및 쇄종지제 모노아민과 반응시킨 후, 고분자 첨가제를 혼합시킴으로써 제조되는 폴리우레탄 수지 조성물로서, 상기 고분자 첨가제의 말단이 메틸기 또는 아민기이고, 고분자 첨가제의 원료로서, 분자쇄 중간이 탄소와 수소 또는 탄소와 산소와 수소로 구성되고 양 말단이 1차 아민인 디아민을 적어도 1종 이상 사용하며, 고분자 첨가제의 수평균 분자량이 2,000 내지 50,000인 것을 특징으로 한다.
The polyurethane resin composition for spandex fiber according to the present invention is prepared by reacting an organic diisocyanate with a polymer diol to prepare a polyurethane precursor, dissolving it in an organic solvent, and then reacting with a chain extender diamine and a chain terminator monoamine. A polyurethane resin composition prepared by mixing a polymer resin, wherein the terminal of the polymer additive is a methyl group or an amine group, and as a raw material of the polymer additive, the middle of the molecular chain is composed of carbon and hydrogen or carbon and oxygen and hydrogen, and both ends are primary At least one diamine, which is an amine, is used, and the number average molecular weight of the polymer additive is 2,000 to 50,000.
본 발명의 다른 바람직한 특징에 의하면, 상기 고분자 첨가제의 수평균 분자량이 5,000 내지 50,000이다.According to another preferred feature of the invention, the number average molecular weight of the polymer additive is 5,000 to 50,000.
본 발명의 다른 바람직한 특징에 의하면, 상기 고분자 첨가제의 고형분이 전체 고형분의 1 내지 25%가 되도록 고분자 첨가제를 한다.According to another preferred feature of the present invention, the polymer additive is added so that the solid content of the polymer additive is 1 to 25% of the total solid content.
본 발명의 다른 바람직한 특징에 의하면, 상기 고분자 첨가제의 원료 중 하나로서 분자량이 200 이상인 디아민을 사용한다.According to another preferred feature of the present invention, diamine having a molecular weight of 200 or more is used as one of the raw materials of the polymer additive.
본 발명에서 상기 폴리우레탄 수지 조성물로부터 제조된 스판덱스 섬유는 내열성의 저하가 없이 강도가 증진되어, 스판덱스 원사를 사용한 편직이나 커버링 등의 후가공 공정성이 향상된다.In the present invention, the spandex fiber prepared from the polyurethane resin composition is enhanced in strength without deteriorating heat resistance, thereby improving post-processing processability such as knitting and covering using a spandex yarn.
따라서 본 발명에 따른 스판덱스 섬유의 신뢰성이 향상되며, 내열성, 고강도 등의 기능이 필요한 용도의 원단에 유용하게 이용될 수 있다.Therefore, the reliability of the spandex fiber according to the present invention is improved, it can be usefully used in the fabric of the application that requires a function such as heat resistance, high strength.
본 발명은 유기디이소시아네이트를 디올 및/또는 디아민, 모노아민과 반응시켜서 제조한 고분자 첨가제를 포함하는 것을 특징으로 한다.The present invention is characterized in that it comprises a polymer additive prepared by reacting an organic diisocyanate with a diol and / or a diamine or a monoamine.
상기 고분자 첨가제는 그 말단이 메틸기 또는 아민기이고, 고분자 첨가제의 원료로서 분자쇄 중간이 탄소와 수소 또는 탄소와 산소와 수소로 구성되고 양 말단이 1차 아민인 디아민을 적어도 1종 이상 사용하며, 고분자 첨가제의 수평균 분자량이 2,000 내지 50,000인 것을 특징으로 한다.The polymer additive has at least one or more diamines whose terminal is a methyl group or an amine group and the raw material of the polymer additive is composed of carbon and hydrogen in the middle of the molecular chain or carbon and oxygen and hydrogen and both ends are primary amines. The number average molecular weight of the polymer additive is characterized in that 2,000 to 50,000.
이 고분자 첨가제의 합성 방법에는 유기디이소시아네이트와 디아민 및/또는 모노아민을 말단기가 아민기 또는 메틸기가 되도록 적절한 당량비로 반응시키는 방법과 유기디이소시아네이트와 저분자 디올을 말단이 이소시아네이트기가 되도록 적절한 당량비로 반응시킨 후에, 이를 디아민 및/또는 모노아민과 반응시켜 최종적으로 말단기가 아민기 또는 메틸기가 되도록 하는 방법이 있다. 상기 반응은 균일한 반응을 위하여 용매상에서 이루어질 수 있다.The method for synthesizing the polymer additive includes reacting an organic diisocyanate with a diamine and / or a monoamine in an appropriate equivalent ratio such that the terminal group is an amine group or a methyl group, and reacting the organic diisocyanate and a low molecular diol in an equivalent equivalent ratio such that the terminal is an isocyanate group. Thereafter, there is a method of reacting it with diamines and / or monoamines so that the terminal group is finally an amine group or a methyl group. The reaction can be carried out in a solvent for uniform reaction.
상기 고분자 첨가제에 있어서, 유기 디이소시아네이트로는 디페닐메탄-4,4'-디이소시아네이트, 헥사메틸렌디이소시아네이트, 톨루엔디이소시아네이트, 부틸렌디이소시아네이트, 이소포론디이소시아네이트 및 수소화된 P,P-메틸렌디이소시아네이트 등이 사용될 수 있다.In the polymer additive, organic diisocyanates include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, isophorone diisocyanate and hydrogenated P, P-methylene diisocyanate And the like can be used.
상기 저분자 디올의 예로는 에틸렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, N-메틸디에탄올아민, N-부틸디에탄올아민, t-부틸디에탄올아민 등이 있다.Examples of the low molecular diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, N-methyldiethanolamine, N-butyldiethanolamine, t-butyl diethanolamine, and the like.
상기 디아민의 예로는 에틸렌디아민, 1,2-디아미노프로판, 1,3-디아미노프로판, 헥사메틸렌디아민, 히드라진, 비스-(3-아미노프로필)-메틸아민 등이 있으며, 분자량이 200이상인 디아민도 사용될 수 있다. 분자량이 200이하인 디아민을 사용할 경우에는 용해도 및 중합 제어에 문제가 있다.
Examples of the diamines include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, hexamethylenediamine, hydrazine, bis- (3-aminopropyl) -methylamine, and diamines having a molecular weight of 200 or more. May also be used. When using diamine whose molecular weight is 200 or less, there exists a problem in solubility and superposition | polymerization control.
또한 상기 모노아민은 쇄종지제로서 사용되며, 이의 예로는 디에틸아민, 모노에탄올아민, 디메틸아민, N-부틸아민, 디부틸아민 등이 있다.In addition, the monoamine is used as a chain terminator, and examples thereof include diethylamine, monoethanolamine, dimethylamine, N-butylamine, dibutylamine, and the like.
이러한 방법으로 제조된 최종 수평균분자량은 2000 내지 50000이다. 이보다 더 낮을 경우, 스판덱스 섬유를 포함하는 원단의 염색 등 후가공 공정에서 유출되어 원하는 효과를 얻을 수 없으며, 이보다 더 높을 경우에는 첨가제가 불균일해지고 저장 및 방사 공정에서 공정성 저하를 일으킨다.The final number average molecular weight prepared in this way is 2000 to 50000. If it is lower than this, the desired effect may not be obtained by spilling in a post-processing process such as dyeing of a fabric including spandex fibers, and if it is higher than this, additives may be uneven and processability may be reduced in storage and spinning processes.
본 발명의 스판덱스 섬유에 사용되는 세그먼트 폴리우레탄 수지 조성물은 당 분야에 공지된 바와 같이 유기 디이소시아네이트 및 고분자 디올을 반응시켜 폴리우레탄 전구체를 제조한 후, 이를 유기 용매에 용해시킨 후 저분자 디아민 및 저분자 모노아민과 반응시킨 후, 상기된 고분자 첨가제를 혼합시킴으로써 제조된다.The segmented polyurethane resin composition used in the spandex fiber of the present invention is prepared by reacting an organic diisocyanate and a polymer diol to prepare a polyurethane precursor, as it is known in the art, and then dissolving it in an organic solvent, followed by low molecular diamine and low molecular mono. After reacting with an amine, it is prepared by mixing the polymer additives described above.
여기서, 고분자 첨가제의 고형분이 전체 고형분의 1 내지 25 중량%가 되도록 고분자 첨가제를 포함한다. 고형분이 1중량% 미만이면 물성 개선이 되지 않는 문제가 있고, 고형분이 25 중량% 초과하면 미그레이션되어 공정 문제 발생의 문제가 있다.
Here, the polymer additive is included so that the solid content of the polymer additive is 1 to 25% by weight of the total solid content. If the solid content is less than 1% by weight, there is a problem that the physical properties are not improved, and if the solid content is more than 25% by weight, there is a problem of migrating process.
상기 폴리우레탄 수지 조성물에 있어서, 유기 디이소시아네이트로는 디페닐메탄-4,4'-디이소시아네이트, 헥사메틸렌디이소시아네이트, 톨루엔디이소시아네이트, 부틸렌디이소시아네이트, 이소포론디이소시아네이트 및 수소화된 디페닐메탄-4,4'-디이소시아네이트 등이 사용될 수 있다.In the polyurethane resin composition, as the organic diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, isophorone diisocyanate and hydrogenated diphenylmethane-4 , 4'-diisocyanate and the like can be used.
상기 고분자 디올로는 분자량이 1500 내지 3100인 폴리테트라메틸렌에테르글리콜이 바람직하다. 분자량이 1500 미만이면 원사의 신도가 낮아서 스판덱스 원사로서의 기능이 저하되는 문제가 있고, 3100을 초과하면 결정화도가 너무 높아서 탄성이 정상적으로 발현되지 않는다.As the polymer diol, polytetramethylene ether glycol having a molecular weight of 1500 to 3100 is preferable. If the molecular weight is less than 1500, there is a problem that the elongation of the yarn is low and the function as the spandex yarn is lowered. If the molecular weight is more than 3100, the crystallinity is too high and elasticity is not normally expressed.
상기 디아민류는 쇄연장제로서 사용되며, 이의 예로는 에틸렌디아민, 1,2-디아미노프로판, 1,3-디아미노프로판, 헥사메틸렌디아민, 히드라진, 비스-(3-아미노프로필)-메틸아민 등이 있다.The diamines are used as chain extenders, and examples thereof include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, hexamethylenediamine, hydrazine, bis- (3-aminopropyl) -methylamine Etc.
또한 상기 모노아민은 쇄종지제로서 사용되며, 이의 예로는 디에틸아민, 모노에탄올아민, 디메틸아민, N-부틸아민, 디부틸아민 등이 있다.In addition, the monoamine is used as a chain terminator, and examples thereof include diethylamine, monoethanolamine, dimethylamine, N-butylamine, dibutylamine, and the like.
아울러, 본 발명은 상기 폴리우레탄 수지 조성물로부터 제조된 스판덱스 섬유를 제공한다. In addition, the present invention provides a spandex fiber prepared 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 present invention can be well understood by the following examples, the following examples are for illustrative purposes of the present invention and are not intended to limit the protection scope of the present invention.
고분자 첨가제 용액의 제조Preparation of Polymer Additives Solution
1,4-부탄디올 90g과 수소화된 디페닐메탄-4,4'-디이소시아네이트 340g을 반응기에 투입하였다. 질소가스기류 중에서 90℃, 90분간 교반하면서 반응시켜, 양말단에 이소시아네이트를 지닌 폴리우레탄 전구체를 제조하였다. 상기 폴리우레탄 전구체에 디메틸아세트아마이드 700g을 가하고 용해시켜 폴리우레탄 전구체 용액을 얻었다. 그리고 에틸렌디아민 17g과 N-부틸아민 4g을 디메틸아세트아마이드 100g에 용해하고, 10℃에서 상기 전구체 용액에 서서히 첨가하면서 반응시켜 고분자 첨가제 용액을 제조하였다.90 g of 1,4-butanediol and 340 g of hydrogenated diphenylmethane-4,4'-diisocyanate were charged to the reactor. The reaction was stirred at 90 ° C. for 90 minutes in a nitrogen gas stream to prepare a polyurethane precursor having an isocyanate at the sock end. 700 g of dimethylacetamide was added to the polyurethane precursor and dissolved to obtain a polyurethane precursor solution. Then, 17 g of ethylenediamine and 4 g of N-butylamine were dissolved in 100 g of dimethylacetamide, and reacted while gradually adding the precursor solution at 10 ° C. to prepare a polymer additive solution.
폴리우레탄 수지 조성물의 제조Preparation of Polyurethane Resin Composition
디페닐메탄-4,4'디이소시아네이트 190g과 폴리테트라메틸렌에테르글리콜 (분자량 1800) 790g을 반응기에 투입하였다. 질소가스기류 중에서 90℃, 90분간 교반하면서 반응시켜, 양말단에 이소시아네이트를 지닌 폴리우레탄 전구체를 제조하였다. 상기 폴리우레탄 전구체에 디메틸아세트아마이드 1460g을 가하고 용해시켜 폴리우레탄 전구체 용액을 얻었다. 그리고 에틸렌디아민 20g과 디에틸아민 3g을 디메틸아세트아마이드 400g에 용해하고 10℃에서 상기 전구체 용액에 첨가하여, 말단이 메틸기 또는 아민기인 고분자 용액을 얻었으며, 여기에 상기 고분자 첨가제 용액을 고분자 첨가제의 고형분 비율이 5%가 되도록 균일하게 혼합하여 스판덱스 섬유의 제조에 사용될 폴리우레탄 수지 조성물을 제조하였다.190 g of diphenylmethane-4,4 'diisocyanate and 790 g of polytetramethylene ether glycol (molecular weight 1800) were charged to a reactor. The reaction was stirred at 90 ° C. for 90 minutes in a nitrogen gas stream to prepare a polyurethane precursor having an isocyanate at the sock end. 1460 g of dimethylacetamide was added to the polyurethane precursor and dissolved to obtain a polyurethane precursor solution. 20 g of ethylenediamine and 3 g of diethylamine were dissolved in 400 g of dimethylacetamide and added to the precursor solution at 10 ° C. to obtain a polymer solution having a methyl group or an amine terminal, and the polymer additive solution was added to the solid content of the polymer additive. The polyurethane resin composition to be used in the preparation of the spandex fiber was prepared by uniformly mixing the ratio to 5%.
스판덱스 섬유의 제조Preparation of Spandex Fiber
상기 폴리우레탄 수지 조성물을 탈포시킨 후, 방사 원액으로 사용하여 건식방사 공정에 의해 4필라멘트 40 데니어의 탄성사, 즉 스판덱스 섬유를 제조하였다. 방사온도는 250℃로 조정하였다.After defoaming the polyurethane resin composition, an elastic yarn of 4 filaments 40 denier, that is, spandex fibers was prepared by a dry spinning process using a spinning stock solution. Spinning temperature was adjusted to 250 ° C.
실시예 1에서 고분자 첨가제의 폴리우레탄 전구체를 제조함에 있어서 1,4-부탄디올과 수소화된 디페닐메탄-4,4'-디이소시아네이트의 몰비가 1 : 1.5가 되도록 투입하고, 나머지는 실시예 1과 동일한 방법으로 탄성사를 제조하였다.In preparing the polyurethane precursor of the polymer additive in Example 1, the molar ratio of 1,4-butanediol and hydrogenated diphenylmethane-4,4'-diisocyanate is 1: 1.5, and the rest is An elastic yarn was produced in the same manner.
제조되는 고분자 첨가제의 고형분 농도가 35%가 되도록 먼저 반응기에 용매 디메틸아세트아미드와 분자량이 2000인 폴리옥시-1,2-프로필렌디아민을 투입하여 균일하게 혼합하여 10℃로 냉각시키고, 10℃ 상태에서 교반하면서 폴리옥시-1,2-프로필렌디아민과 수소화된 디페닐메탄-4,4'-디이소시아네이트의 몰비가 1.3 : 1이 되도록 디페닐메탄-4,4'-디이소시아네이트를 서서히 투입하며 반응시켜, 양말단에 아민기를 지닌 고분자 첨가제 용액을 제조하고, 나머지는 실시예 1과 동일한 방법으로 탄성사를 제조하였다.
First, solvent dimethylacetamide and a polyoxy-1,2-propylenediamine having a molecular weight of 2000 were added to the reactor so that the solid content concentration of the prepared polymer additive was 35%, uniformly mixed, and cooled to 10 ° C. While stirring, diphenylmethane-4,4'-diisocyanate is gradually added to react so that the molar ratio of polyoxy-1,2-propylenediamine and hydrogenated diphenylmethane-4,4'-diisocyanate is 1.3: 1. , A polymer additive solution having an amine group in the sock end was prepared, and the rest of the elastic yarn was prepared in the same manner as in Example 1.
[비교예 1] Comparative Example 1
실시예 1과 동일한 방법으로 스판덱스 섬유를 제조하되, 고분자 첨가제를 포함시키지 않고 폴리우레탄 수지 조성물만으로 스판덱스 섬유를 제조하였다.
Spandex fibers were prepared in the same manner as in Example 1, but the spandex fibers were prepared using only a polyurethane resin composition without including a polymer additive.
[비교예 2]Comparative Example 2
실시예 1과 동일한 방법으로 스판덱스 섬유를 제조하되, 고분자 첨가제의 고형분 비율이 0.5%가 되도록 하여 스판덱스 섬유를 제조하였다.
Spandex fibers were prepared in the same manner as in Example 1, but the spandex fibers were prepared such that the solid content ratio of the polymer additive was 0.5%.
[비교예 3][Comparative Example 3]
실시예 1과 동일한 방법으로 스판덱스 섬유를 제조하되, 고분자 첨가제의 고형분 비율이 30%가 되도록 하여 스판덱스 섬유를 제조하였다.
Spandex fibers were prepared in the same manner as in Example 1, but the spandex fibers were prepared such that the solid content ratio of the polymer additive was 30%.
[평가예] [Evaluation example]
상기 실시예 1 내지 3 및 비교예 1 내지 3의 탄성사들의 강도와 신도를 측정하였다. The strength and elongation of the elastic yarns of Examples 1 to 3 and Comparative Examples 1 to 3 were measured.
좀 더 상세하게는, 인스트론사의 INSTRON 5565를 사용하여, 게이지 길이 2인치로 설정하고 탄성사 장섬유 샘플을 500mm/분의 일정 연신 속도로 연신하여, 탄성사가 절단되는 시점의 파단 강도와 파단 신도를 측정하였다.More specifically, using Instron's INSTRON 5565, the gauge length was set to 2 inches and the elastic filament long fiber sample was stretched at a constant drawing speed of 500 mm / min to break the breaking strength and elongation at break. Measured.
또 내열성의 경우는, 원사를 300%로 신장시킨 상태에서 190℃ 온도의 오븐에서 1분간 열처리를 한 후, 상기의 방법으로 파단 강도를 측정하여, 열처리 전후의 강도 비율을 계산함으로써 원사 내열성을 측정하였다.In the case of heat resistance, after heat treatment in an oven at 190 ° C. for 1 minute while the yarn is stretched to 300%, the breaking strength is measured by the above method, and the yarn heat resistance is measured by calculating the strength ratio before and after the heat treatment. It was.
상기와 같이 측정한 강도와 신도, 내열성을 표 1에 나타내었다. 그 결과, 본 발명에 따른 실시예 1 내지 3의 탄성사들은 비교예 1 내지 2보다 약 20% 가량 강도가 증가되었으며, 된 것을 확인할 수 있다. 비교예 3은 일반적인 용도의 스판덱스로 사용되기에는 신도가 너무 저하되었다.The strength, elongation, and heat resistance measured as described above are shown in Table 1. As a result, it can be seen that the elastic yarns of Examples 1 to 3 according to the present invention had about 20% more strength than Comparative Examples 1 to 2. In Comparative Example 3, the elongation was too low to be used as a general purpose spandex.
비록 본 발명이 상기 언급된 바람직한 실시예와 관련하여 설명되었지만, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 따라서 첨부된 특허청구범위는 본 발명의 요지에 속하는 이러한 수정이나 변형을 포함한다.
Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims include such modifications and variations as fall within the spirit of the invention.
Claims (6)
상기 고분자 첨가제의 수평균 분자량이 5,000 내지 50,000인 것을 특징으로 하는 스판덱스 섬유용 폴리우레탄 수지 조성물.The method of claim 1,
Polyurethane resin composition for spandex fibers characterized in that the number average molecular weight of the polymer additive is 5,000 to 50,000.
상기 고분자 첨가제의 수평균 분자량이 10,000 내지 50,000인 것을 특징으로 하는 스판덱스 섬유용 폴리우레탄 수지 조성물.The method of claim 1,
Polyurethane resin composition for spandex fibers characterized in that the number average molecular weight of the polymer additive is 10,000 to 50,000.
상기 고분자 첨가제의 고형분이 전체 고형분의 1 내지 25%가 되도록 고분자 첨가제를 포함하는 것을 특징으로 하는 스판덱스 섬유용 폴리우레탄 수지 조성물.The method of claim 1,
Polyurethane resin composition for spandex fibers, characterized in that it comprises a polymer additive so that the solid content of the polymer additive is 1 to 25% of the total solid content.
상기 고분자 첨가제의 원료 중 하나로서 분자량이 200 이상인 디아민을 사용하는 것을 특징으로 하는 스판덱스 섬유용 폴리우레탄 수지 조성물.The method of claim 1,
Polyurethane resin composition for spandex fibers characterized in that a diamine having a molecular weight of 200 or more as one of the raw materials of the polymer additive.
Spandex fiber manufactured using the polyurethane resin composition for spandex fibers of any one of Claims 1-5.
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