[go: up one dir, main page]

WO2018135818A1 - Polyurethane urea elastic yarn with excellent elongation and manufacturing method therefor - Google Patents

Polyurethane urea elastic yarn with excellent elongation and manufacturing method therefor Download PDF

Info

Publication number
WO2018135818A1
WO2018135818A1 PCT/KR2018/000661 KR2018000661W WO2018135818A1 WO 2018135818 A1 WO2018135818 A1 WO 2018135818A1 KR 2018000661 W KR2018000661 W KR 2018000661W WO 2018135818 A1 WO2018135818 A1 WO 2018135818A1
Authority
WO
WIPO (PCT)
Prior art keywords
elastic yarn
elongation
polyurethane urea
urea elastic
yarn
Prior art date
Application number
PCT/KR2018/000661
Other languages
French (fr)
Korean (ko)
Inventor
이재명
강연수
Original Assignee
주식회사 효성
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 효성 filed Critical 주식회사 효성
Publication of WO2018135818A1 publication Critical patent/WO2018135818A1/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • D01D1/02—Preparation of spinning solutions
    • 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

Definitions

  • the present invention relates to a polyurethane urea elastic yarn excellent in elongation and a method for producing the same. More specifically, the use of multifunctional materials can improve elongation after covering by maintaining the permanent strain at 25% or less without lowering the spinning processability and heat resistance (% pre- and post-thermal power retention) of the elastic yarn. Polyurethane urea elastic yarn and a method for producing the same.
  • Polyurethane urea elastic fiber is manufactured by dry or wet spinning polyurethane urea-based polymer, and has excellent elasticity and elastic recovery power, so it is used for swimwear, inner wear, out wear, stocking, diaper, etc. Depending on the application, it is used by mixing with nylon, polyester and the like (covering yarn).
  • Polyurethaneurea polymers generally react with a polyol, which is a high molecular weight diol compound, and an excess of diisocyanate compound to obtain a prepolymer having an isocyanate group at both ends of the polyol and the prepolymer in an appropriate solvent.
  • a diamine-based or diol-based chain extender and a chain terminator such as monoalcohol or monoamine are added and reacted to form a spinning solution of polyurethaneurea fiber after drying.
  • polyurethaneurea elastic fibers by wet spinning.
  • Polyurethane urea elastic yarns are covered by other companies, for example, nylon, polyester, cotton, etc. as described above, and are used for knitting for socks, stockings, etc. In order to ensure excellent knitting workability, after covering Elastic yarn with excellent elongation is needed.
  • the elongation of the polyurethane urea elastic yarn has been improved.
  • the elongation of the polyurethane urea is not sufficiently expressed after the covering, and the soft segment content of the polymer is excessively increased to improve the elongation.
  • heat resistance power retention (%) before and after heat treatment
  • an object of the present invention is to provide a polyurethane urea elastic yarn and a manufacturing method thereof that can improve elongation so as to secure excellent knitting workability even after covering the polyurethane urea elastic yarn. .
  • the polyurethane prepolymer comprises a 0.1 to 5 mol% cross-linking agent of 2-ethyl-2- (hydroxymethyl) -1,3-propanediol It features.
  • the polyurethaneurea elastic yarn is characterized in that the elongation of the yarn is 600% or more, the permanent strain is 25% or less.
  • the polyurethane urea elastic yarn is characterized in that the spinning processability is 95% or more.
  • polyurethane urea elastic yarn is characterized in that 120 denier.
  • Polyurethane urea elastic yarn of the present invention while maintaining good spinning processability, the elongation is more than 600%, the permanent strain is excellent in 25% or less has the effect of improving the elongation of the covering yarn after the covering operation.
  • a polyurethane prepolymer by mixing a polyol and diisocyanate, to prepare a polyurethane urea elastic yarn using 0.1 to 5 mol% of a crosslinking agent as a multifunctional material It is a way.
  • it is a polyurethane urea elastic yarn of 120 denier, elongation of 600% or more and permanent strain of 25% or less.
  • a polyurethane urea based on polyols, diisocyanates and chain extenders wherein the diisocyanates are at least one organic diisocyanate selected from aromatic, aliphatic and alicyclic diisocyanates
  • polyurethane urea elastic yarn which is 600% or more in elongation and maintains 25% or less in permanent strain.
  • the diisocyanate is 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexamethylene di At least one selected from the group consisting of isocyanate, 1,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate and mixtures thereof, preferably 4, 4'-diphenylmethane diisocyanate.
  • the polyol may be one or two or more selected from the group consisting of polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, and combinations thereof.
  • the polyol and diisocyanate are reacted, and 0.1 to 5 mol% of a crosslinking agent such as 2-ethyl-2- (hydroxymethyl) -1,3-propanediol as a polyfunctional material.
  • a crosslinking agent such as 2-ethyl-2- (hydroxymethyl) -1,3-propanediol
  • the diisocyanate is at least one organic diisocyanate selected from aromatic, aliphatic and alicyclic diisocyanates
  • the multifunctional material when added to the prepolymer preparation step, there is an effect that can increase the resilience to the contrast physical deformation by acting as a crosslinking agent for the molecular chains.
  • the kind of the solvent usable in the above production method is not particularly limited.
  • DMAc, DMF, DMSO, N-methylpyrrolidinone (NMP) or a mixed solvent thereof may be used.
  • diamines may be used as the chain extender, and examples thereof include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 2,3-diamino. Butane, 1,5-diaminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and combinations thereof, and one or more selected from the group consisting of, but are not necessarily limited thereto. .
  • the chain terminator amines having a monofunctional group, for example, diethylamine, monoethanolamine, dimethylamine, cyclohexylamine and the like can be used.
  • the chain extender and chain terminator may be added all at once or in two or more steps. Chain extenders and chain terminators are preferably dissolved in a suitable solvent.
  • the produced polyurethane urea spinning stock solution is dry-spun to obtain a polyurethane urea elastic yarn having a characteristic of 120 deg. Class and having an elongation of at least 600% and a permanent strain of 25% or less.
  • Polyurethane urea elastic yarn of the present invention has the advantage of improving the elongation after covering (covering) without reducing the spinning processability (95% or more) and heat resistance of the elastic yarn by using a multifunctional material.
  • 4,4'-diphenylmethane diisocyanate, polytetramethylene ether glycol, and polytrimethylene ether glycol are used at a capping ratio (CR) of 1.55, and 2-ethyl-2- (hydroxylmethyl) -1,3 as a crosslinking agent.
  • a prepolymer was prepared using 0.1 mol% propanediol. 100 mol% of ethylenediamine was used as the chain extender, 100 mol% of diethylamine was used as the chain terminator, and the ratio of the chain extender and the chain terminator was 15: 1, and the total amine used was 7 mol%.
  • a dimethylacetamide was used as a solvent to obtain a polyurethaneurea spinning solution having a solid content of 35% by weight of the final polymer.
  • the spinning stock solution obtained as described above was dry-spun at a speed of 700 m / min to prepare a polyurethane urea elastic yarn of 120 denier 8 filaments, and the physical properties thereof are shown in Table 1 below.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that 1.5 mol% of the crosslinking agent was added.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that 5.0 mol% of the crosslinking agent was added.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that no crosslinking agent was added.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that 10.0 mol% of the crosslinking agent was added.
  • Strength and elongation of yarn Measured with an automatic elongation measuring device (MEL machine, Textechno) at a sample length of 10cm and a tensile speed of 100cm / min. At this time, the strength and elongation at break are measured, and the 200% modulus of load on the yarn is also measured at 200% elongation.
  • MEL machine Automatic elongation measuring device
  • Yarn Permanent Strain (%): Using an automatic elongation measuring device (MEL machine, Textechno Co., Ltd.), 10 cm ⁇ 20 strands were stretched 300 times five times at a tensile rate of 100 cm / min, and then recovered for 30 seconds. Permanent strain is calculated from the difference between the length (L1) and the initial sample length.
  • elongation [%] and permanent strain [%] while maintaining excellent spinning processability (95% or more) and heat resistance levels All of them appeared to be excellent, and thereby it was found that the elongation (%) of the covering company was improved.
  • the crosslinking agent is not added, the elongation is improved, but the elongation of the covering yarn is decreased due to insufficient permanent strain, and when added in excess, the permanent strain [%] and the heat resistance [%] are good, but the elongation is excessive. It was found that the elongation (%) of the covering company could not be satisfactorily obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a polyurethane urea elastic yarn and a manufacturing method therefor, wherein the polyurethane urea elastic yarn maintains an elastic yarn elongation of 600% or more and a permanent strain of 25% or less while maintaining spinning processability and heat resistance characteristics due to the use of a polyfunctional material, and thus can achieve elongation improvement after a covering work.

Description

신율이 우수한 폴리우레탄우레아 탄성사 및 그의 제조방법Polyurethane urea elastic yarn with excellent elongation and its manufacturing method
본 발명은 신율이 우수한 폴리우레탄우레아 탄성사 및 그의 제조방법에 관한 것이다. 더욱 상세하게, 다관능성 물질의 사용으로 탄성사의 방사 공정성과 내열성(열처리 전/후 파워 유지율%)을 저하시키지 않으면서 영구 변형률을 25% 이하로 유지하여 커버링(covering) 작업 후 신율을 향상시킬 수 있는 폴리우레탄우레아 탄성사 및 그의 제조방법에 관한 것이다.The present invention relates to a polyurethane urea elastic yarn excellent in elongation and a method for producing the same. More specifically, the use of multifunctional materials can improve elongation after covering by maintaining the permanent strain at 25% or less without lowering the spinning processability and heat resistance (% pre- and post-thermal power retention) of the elastic yarn. Polyurethane urea elastic yarn and a method for producing the same.
폴리우레탄우레아 탄성섬유는 폴리우레탄우레아계 중합체를 건식 또는 습식 방사하여 제조되며, 탄성과 탄성회복력이 우수하여 수영복, 이너웨어(inner wear), 아웃웨어(out wear), 스타킹(stocking), 기저귀 등에 사용되며, 용도에 따라서 나일론, 폴리에스테르 등과 혼용(커버링 사: covered yarn)하여 사용된다.Polyurethane urea elastic fiber is manufactured by dry or wet spinning polyurethane urea-based polymer, and has excellent elasticity and elastic recovery power, so it is used for swimwear, inner wear, out wear, stocking, diaper, etc. Depending on the application, it is used by mixing with nylon, polyester and the like (covering yarn).
폴리우레탄우레아 고분자는 일반적으로 고분자량의 디올 화합물인 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 폴리올의 양 말단에 이소시아네이트기를 가지는 예비중합체(prepolymer)를 얻는 1차 중합 반응과 상기 예비중합체를 적절한 용매에 용해시킨 후 그 용액에 디아민계 또는 디올계 사슬 연장제, 및 모노알코올 또는 모노아민 등과 같은 사슬 종결제 등을 첨가하여 반응시키는 2차 중합단계를 거쳐, 폴리우레탄우레아 섬유의 방사액을 만든 후 건식 및 습식 방사에 의해 폴리우레탄우레아 탄성 섬유로 제조된다.Polyurethaneurea polymers generally react with a polyol, which is a high molecular weight diol compound, and an excess of diisocyanate compound to obtain a prepolymer having an isocyanate group at both ends of the polyol and the prepolymer in an appropriate solvent. After dissolution, a diamine-based or diol-based chain extender and a chain terminator such as monoalcohol or monoamine are added and reacted to form a spinning solution of polyurethaneurea fiber after drying. And polyurethaneurea elastic fibers by wet spinning.
폴리우레탄우레아 탄성사는 앞에서 설명한 바와 같이 상대사, 예를 들면 나일론, 폴리에스터, 면 등으로 커버링(covering)하여 양말, 스타킹 등의 용도로 편직하여 사용되는데, 우수한 편직 작업성을 확보하기 위해서는 커버링 후 신율이 우수한 탄성사가 필요하다.Polyurethane urea elastic yarns are covered by other companies, for example, nylon, polyester, cotton, etc. as described above, and are used for knitting for socks, stockings, etc. In order to ensure excellent knitting workability, after covering Elastic yarn with excellent elongation is needed.
커버링 사의 신율 향상을 위해 종래에는 폴리우레탄우레아 탄성사의 신도를 향상시켜 왔으나, 신도가 높아도 커버링 후 신율이 충분히 발현되지 않는 경우가 많았고, 신도 향상을 위해 중합물 내 소프트 세그먼트(soft segment) 함량을 과도히 증가시킬 경우 건식 방사 중 공정성이 저하되고 탄성사의 물성, 예를 들면 내열성(열처리 전후의 파워 유지율(%))이 감소하는 단점이 있었다.In order to improve the elongation of the covering yarn, the elongation of the polyurethane urea elastic yarn has been improved. However, even when the elongation is high, the elongation of the polyurethane urea is not sufficiently expressed after the covering, and the soft segment content of the polymer is excessively increased to improve the elongation. When increasing, there is a disadvantage in that the processability during dry spinning is lowered and the properties of the elastic yarn, for example, heat resistance (power retention (%) before and after heat treatment) decrease.
이에 본 발명은 이와 같은 문제점을 해결하기 위한 것으로, 폴리우레탄우레아 탄성사의 커버링 후에도 우수한 편직 작업성을 확보할 수 있도록 신율을 향상시킬 수 있는 폴리우레탄우레아 탄성사 및 그의 제조방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a polyurethane urea elastic yarn and a manufacturing method thereof that can improve elongation so as to secure excellent knitting workability even after covering the polyurethane urea elastic yarn. .
전술한 기술적 과제를 해결하기 위하여, 본 발명의 한 실시 예에 의한 신율이 우수한 폴리우레탄우레아 탄성사의 제조방법은, In order to solve the above technical problem, a method of producing a polyurethane urea elastic yarn excellent in elongation according to an embodiment of the present invention,
폴리올과 디이소시아네이트를 반응시켜 폴리우레탄 예비중합체를 수득하는 단계; 상기 예비중합체를 유기용매에 용해시켜 사슬연장제 및 사슬종결제를 첨가하여 2차 중합을 수행하여 방사원액을 수득하는 단계; 및 상기 방사원액을 건식 방사시켜 폴리우레탄우레아 탄성사를 제조하는 방법에 있어서, 상기 폴리올과 디이소시아네이트를 반응시켜 폴리우레탄우레아 예비 중합체를 수득하는 단계에서, 다관능성 물질로서 가교 결합제로 2-에틸-2-(히드록실메틸)-1,3-프로판디올을 0.1 내지 5몰%를 첨가하는 것을 특징으로 한다. Reacting the polyol and diisocyanate to obtain a polyurethane prepolymer; Dissolving the prepolymer in an organic solvent to perform a second polymerization by adding a chain extender and a chain terminator to obtain a spinning stock solution; And dry spinning the spinning stock solution to produce a polyurethaneurea elastic yarn, wherein in the step of reacting the polyol and diisocyanate to obtain a polyurethaneurea prepolymer, 2-ethyl-2 as a crosslinking agent as a polyfunctional material. 0.1-5 mol% of-(hydroxymethyl) -1,3-propanediol is added.
본 발명의 다른 실시 예에 의한 폴리우레탄우레아 탄성사는, 폴리리우레탄 예비 중합체가 2-에틸-2-(히드록실메틸)-1,3-프로판디올의 가교 결합제를 0.1 내지 5몰% 포함하는 것을 특징으로 한다. Polyurethane urea elastic yarn according to another embodiment of the present invention, the polyurethane prepolymer comprises a 0.1 to 5 mol% cross-linking agent of 2-ethyl-2- (hydroxymethyl) -1,3-propanediol It features.
또한, 폴리우레탄우레아 탄성사는 원사의 신도가 600% 이상이고, 영구 변형률이 25% 이하인 것을 특징으로 한다. In addition, the polyurethaneurea elastic yarn is characterized in that the elongation of the yarn is 600% or more, the permanent strain is 25% or less.
또한, 폴리우레탄우레아 탄성사는 방사 공정성이 95% 이상인 것을 특징으로 한다. In addition, the polyurethane urea elastic yarn is characterized in that the spinning processability is 95% or more.
또한, 폴리우레탄우레아 탄성사는 120 데니아 인 것을 특징으로 한다.In addition, the polyurethane urea elastic yarn is characterized in that 120 denier.
본 발명의 폴리우레탄우레아 탄성사는 양호한 방사 공정성을 유지하면서도 신도가 600% 이상이고, 영구 변형률이 25% 이하로 우수하여 커버링 작업 후 커버링 사의 신율을 향상시킬 수 있는 효과가 있다. Polyurethane urea elastic yarn of the present invention, while maintaining good spinning processability, the elongation is more than 600%, the permanent strain is excellent in 25% or less has the effect of improving the elongation of the covering yarn after the covering operation.
또한, 다관능성 물질이 예비 중합체 제조 단계에 첨가되면, 분자 사슬들에 대해 가교제 역할을 함으로써 대비 물리적 변형에 대한 회복력을 증대시킬 수 있는 효과가 있다.In addition, when the multifunctional material is added to the prepolymer preparation step, there is an effect that can increase the resilience to the contrast physical deformation by acting as a crosslinking agent for the molecular chains.
본 발명의 하나의 실시 예에 의하면, 폴리올과 디이소시아네이트를 혼합하여 폴리우레탄 예비 중합체를 제조하는 단계에서, 다관능성 물질로서 가교 결합제를 0.1 내지 5몰%를 사용하여서 되는 폴리우레탄우레아 탄성사를 제조하는 방법인 것이다. According to one embodiment of the present invention, in the step of preparing a polyurethane prepolymer by mixing a polyol and diisocyanate, to prepare a polyurethane urea elastic yarn using 0.1 to 5 mol% of a crosslinking agent as a multifunctional material It is a way.
본 발명의 다른 실시 예에 의하면, 120데니아이며 신도가 600% 이상, 영구 변형률이 25% 이하인 폴리우레탄우레아 탄성사인 것이다. According to another embodiment of the present invention, it is a polyurethane urea elastic yarn of 120 denier, elongation of 600% or more and permanent strain of 25% or less.
본 발명의 하나의 실시 예에 의하면, 폴리올, 디이소시아네이트 및 사슬 연장제를 기재로 하는 폴리우레탄우레아를 포함하며, 상기 디이소시아네이트는 방향족, 지방족 및 지환족 디이소시아네이트 중에서 선택된 1종 이상의 유기 디이소시아네이트이고, 신도 600% 이상이고, 영구 변형률이 25% 이하를 유지할 수 있는 폴리우레탄우레아 탄성사이다.According to one embodiment of the invention, a polyurethane urea based on polyols, diisocyanates and chain extenders, wherein the diisocyanates are at least one organic diisocyanate selected from aromatic, aliphatic and alicyclic diisocyanates Polyurethane urea elastic yarn, which is 600% or more in elongation and maintains 25% or less in permanent strain.
본 발명에서 상기 디이소시아네이트는 4,4'-디페닐메탄디이소시아네이트, 2,4'-디페닐메탄디이소시아네이트, 1,5'-나프탈렌디이소시아네이트, 1,4'-페닐렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 1,4'-시클로헥산디이소시아네이트, 4,4'-디시클로헥실메탄디이소시아네이트, 이소포론디이소시아네이트 및 이들의 혼합물로 구성되는 군에서 선택되는 1종 이상일 수 있고, 바람직하게는 4,4'-디페닐메탄디이소시아네이트일 수 있다.In the present invention, the diisocyanate is 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexamethylene di At least one selected from the group consisting of isocyanate, 1,4'-cyclohexanediisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate and mixtures thereof, preferably 4, 4'-diphenylmethane diisocyanate.
상기 폴리올은 폴리테트라메틸렌에테르 글리콜, 폴리트리메틸렌에테르글리콜, 폴리프로필렌글리콜, 폴리카보네이트디올 및 이들의 조합으로 구성된 군에서 선택되는 1종 또는 2종 이상일 수 있다.The polyol may be one or two or more selected from the group consisting of polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, and combinations thereof.
본 발명의 다른 실시 예에 의하면, 폴리올과 디이소시아네이트를 반응시키고 다관능성 물질로서 가교 결합제, 예를 들면 2-에틸-2-(히드록실메틸)-1,3-프로판디올을 0.1 내지 5몰%를 첨가하여 폴리우레탄 예비중합체를 수득하는 단계로서, 상기 디이소시아네이트는 방향족, 지방족 및 지환족 디이소시아네이트 중에서 선택된 1종 이상의 유기 디이소시아네이트이고; 상기 예비중합체를 유기용매에 용해시켜 사슬연장제 및 사슬종결제를 첨가하여 2차 중합을 수행하여 방사원액을 수득하는 단계; 및 상기 방사원액을 건식 방사시켜 120de급 원사의 신도가 600% 이상 및 영구 변형률 25% 이하로 유지되는 특성을 갖는 폴리우레탄우레아 탄성사를 수득하는 단계를 포함하는 폴리우레탄우레아 탄성사의 제조방법인 것이다. According to another embodiment of the present invention, the polyol and diisocyanate are reacted, and 0.1 to 5 mol% of a crosslinking agent such as 2-ethyl-2- (hydroxymethyl) -1,3-propanediol as a polyfunctional material. Adding a to obtain a polyurethane prepolymer, wherein the diisocyanate is at least one organic diisocyanate selected from aromatic, aliphatic and alicyclic diisocyanates; Dissolving the prepolymer in an organic solvent to perform a second polymerization by adding a chain extender and a chain terminator to obtain a spinning stock solution; And dry spinning the spinning solution to obtain a polyurethane urea elastic yarn comprising the step of obtaining a polyurethane urea elastic yarn having a characteristic that the elongation of 120de grade yarn is maintained at 600% or more and less than 25% permanent strain.
본 발명에서, 다관능성 물질이 예비 중합체 제조 단계에 첨가되면, 분자 사슬들에 대해 가교제 역할을 함으로써 대비 물리적 변형에 대한 회복력을 증대시킬 수 있는 효과가 있다.In the present invention, when the multifunctional material is added to the prepolymer preparation step, there is an effect that can increase the resilience to the contrast physical deformation by acting as a crosslinking agent for the molecular chains.
상기 제조방법에서 사용 가능한 용매의 종류는 특별히 제한되지 않는데, 예를 들면 DMAc, DMF, DMSO, N-메틸피롤리디논(NMP) 또는 이들의 혼합용매를 사용할 수 있다.The kind of the solvent usable in the above production method is not particularly limited. For example, DMAc, DMF, DMSO, N-methylpyrrolidinone (NMP) or a mixed solvent thereof may be used.
본 발명에서 사슬연장제로는 디아민류가 사용될 수 있는데, 그 예로는 에틸렌디아민, 1,2-디아미노프로판, 1,3-디아미노프로판, 1,4-디아미노부탄, 2,3-디아미노부탄, 1,5-디아미노펜탄, 1,6-헥사메틸렌디아민, 1,4-씨클로헥산디아민 및 이들의 조합으로 구성된 군에서 선택되는 1종 이상을 들 수 있으나, 반드시 이들로 제한되는 것은 아니다. 사슬 종결제로는 1 관능기를 갖는 아민, 예를 들어 디에틸아민, 모노에탄올아민, 디메틸아민, 시클로헥실아민 등이 사용될 수 있다. 본 발명의 폴리우레탄우레아를 제조하는데 있어서, 사슬연장제 및 사슬종결제는 전부 한번에 또는 2개 이상의 단계로 첨가될 수 있다. 사슬연장제 및 사슬종결제는 적합한 용매 중에 용해시키는 것이 바람직하다.In the present invention, diamines may be used as the chain extender, and examples thereof include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 2,3-diamino. Butane, 1,5-diaminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and combinations thereof, and one or more selected from the group consisting of, but are not necessarily limited thereto. . As the chain terminator, amines having a monofunctional group, for example, diethylamine, monoethanolamine, dimethylamine, cyclohexylamine and the like can be used. In preparing the polyurethaneurea of the present invention, the chain extender and chain terminator may be added all at once or in two or more steps. Chain extenders and chain terminators are preferably dissolved in a suitable solvent.
이어서 생성된 폴리우레탄우레아 방사원액을 건식 방사시켜 120de급이며 원사의 신도가 600% 이상 및 영구 변형률이 25% 이하를 유지할 수 있는 특성을 갖는 폴리우레탄우레아 탄성사를 수득할 수 있다.Subsequently, the produced polyurethane urea spinning stock solution is dry-spun to obtain a polyurethane urea elastic yarn having a characteristic of 120 deg. Class and having an elongation of at least 600% and a permanent strain of 25% or less.
본 발명의 폴리우레탄우레아 탄성사는 다관능성 물질의 사용으로 탄성사의 방사 공정성(95% 이상)과 내열성을 저하시키지 않으면서 커버링(covering) 작업 후 신율을 향상시킬 수 있는 장점이 있다. Polyurethane urea elastic yarn of the present invention has the advantage of improving the elongation after covering (covering) without reducing the spinning processability (95% or more) and heat resistance of the elastic yarn by using a multifunctional material.
이하 본 발명을 실시 예에 의거하여 상세히 설명하면 다음과 같으며, 이하의 실시 예는 단지 설명의 목적을 위한 것으로 본 발명의 보호범위를 제한하고자 하는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following examples, and the following examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.
실시예 1Example 1
4,4'-디페닐메탄디이소시아네이트와 폴리테트라메틸렌에테르 글리콜과 폴리트리메틸렌에테르글리콜을 캡핑비(CR) 1.55로 하고, 가교 결합제로서 2-에틸-2-(히드록실메틸)-1,3-프로판디올을 0.1몰% 사용하여 예비중합체를 제조하였다. 사슬 연장제로는 에틸렌디아민을 100mol% 사용하였고, 사슬 종결제로는 디에틸아민을 100mol% 사용하였으며, 사슬 연장제와 사슬 종결제의 비율은 15:1로 하였고, 사용된 아민은 총 농도 7몰%로 제조하였으며, 용매로는 디메틸아세트아마이드를 사용하여 최종 중합물의 고형분 함량이 35중량%인 폴리우레탄우레아 방사 용액을 얻었다.4,4'-diphenylmethane diisocyanate, polytetramethylene ether glycol, and polytrimethylene ether glycol are used at a capping ratio (CR) of 1.55, and 2-ethyl-2- (hydroxylmethyl) -1,3 as a crosslinking agent. A prepolymer was prepared using 0.1 mol% propanediol. 100 mol% of ethylenediamine was used as the chain extender, 100 mol% of diethylamine was used as the chain terminator, and the ratio of the chain extender and the chain terminator was 15: 1, and the total amine used was 7 mol%. A dimethylacetamide was used as a solvent to obtain a polyurethaneurea spinning solution having a solid content of 35% by weight of the final polymer.
상기와 같이 수득한 방사 원액을 700m/min 속도로 건식 방사하여 120데니아 8 필라멘트의 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.The spinning stock solution obtained as described above was dry-spun at a speed of 700 m / min to prepare a polyurethane urea elastic yarn of 120 denier 8 filaments, and the physical properties thereof are shown in Table 1 below.
실시예 2Example 2
가교 결합제를 1.5 몰%를 첨가하는 것 외에는 실시 예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였다. A polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that 1.5 mol% of the crosslinking agent was added.
실시예Example 3 3
가교 결합제를 5.0 몰%를 첨가하는 것 외에는 실시 예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였다.. A polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that 5.0 mol% of the crosslinking agent was added.
비교예 1Comparative Example 1
가교 결합제를 첨가하지 않는 것 외에는 실시 예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였다. A polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that no crosslinking agent was added.
비교예 2Comparative Example 2
가교 결합제를 10.0 mol%를 첨가하는 것 외에는 실시 예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였다. A polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that 10.0 mol% of the crosslinking agent was added.
상기 실시예 및 비교예에서 제조된 폴리우레탄우레아 탄성사의 방사공정성[%], 강도[g/d], 신도[%], 영구 변형율[%], 내열성[%] 및 커버링 사의 신율[%]을 다음과 같은 방법으로 측정하고 그 결과를 표 1에 나타내었다.Spinning processability [%], strength [g / d], elongation [%], permanent strain [%], heat resistance [%] and elongation [%] of the covering yarns of the polyurethaneurea elastic yarns prepared in Examples and Comparative Examples Measured as follows and the results are shown in Table 1.
[측정 방법][How to measure]
1. 방사 공정성: 실제 생산량/이론 생산량[%]1. Radiation Fairness: Actual Output / Theoretical Yield [%]
2. 원사의 강도 및 신도: 자동 강신도 측정장치(MEL기, Textechno사)를 이용하여 시료길이 10cm, 인장속도 100cm/min로 하여 측정함. 이때 파단 시의 강도와 신도 값이 측정되며, 원사 200% 신장 시 원사에 걸리는 하중 200% 모듈러스(modulus)도 측정됨.2. Strength and elongation of yarn: Measured with an automatic elongation measuring device (MEL machine, Textechno) at a sample length of 10cm and a tensile speed of 100cm / min. At this time, the strength and elongation at break are measured, and the 200% modulus of load on the yarn is also measured at 200% elongation.
3. 원사 영구 변형률(%): 자동 강신도 측정장치(MEL기, Textechno사)를 이용하여 시료 길이 10cm×20가닥, 인장속도 100cm/min으로 300% 5회 반복 신장시킨 후 30초간 회복 후 변형된 길이(L1)와 초기 시료 길이의 차이로 영구 변형률을 계산함.3. Yarn Permanent Strain (%): Using an automatic elongation measuring device (MEL machine, Textechno Co., Ltd.), 10 cm × 20 strands were stretched 300 times five times at a tensile rate of 100 cm / min, and then recovered for 30 seconds. Permanent strain is calculated from the difference between the length (L1) and the initial sample length.
영구 변형률(%) = (변경 길이 L1 - 초기 길이)/초기 길이 * 100Permanent Strain (%) = (Change Length L1-Initial Length) / Initial Length * 100
4. 열처리 후 파워 (5th unload at 200%): 원사를 대기 상태에서 100% 신장하여, 190℃ 건열 1분, 100℃ 비수 30분 처리한 뒤 자동 강신도 측정장치(MEL기, Textechno사)를 이용하여 300% 5회 반복 신장하여 5회차 회복 중 200% 구간에서의 파워를 측정한 뒤 가닥수 및 de로 나눠줌.4. Power after heat treatment (5 th unload at 200%): The yarn is stretched 100% in the air, treated with 190 ℃ dry heat for 1 minute and 100 ℃ non-water for 30 minutes, and then subjected to automatic elongation measuring device (MEL, Textechno). Using 300% stretch 5 times, measure the power at 200% of the 5th recovery and divide by the number of strands and de.
5. 내열성(열처리 전/후 파워유지율(%)): 열처리 후 원사 파워/미처리 원사 파워 × 1005. Heat resistance (Power retention before and after heat treatment (%)): Yarn power after heat treatment / untreated yarn power × 100
6. 커버링 사 신율(%): no-tension 상태에서 시료를 10cm 길이로 샘플링 한 후, 초하중 100g을 매단 상태에서 최대로 늘어나는 길이를 측정하여 비율을 계산함.6. Covering elongation rate (%): After sampling the sample in 10-cm length in no-tension state, calculate the ratio by measuring the maximum length of the super load 100g in the suspended state.
가교결합제[mol%]Crosslinker [mol%] 방사 공정성[%]Radiation Fairness [%] 강도[g/d]Strength [g / d] 신도[%]Elongation [%] 영구변형률[%]Permanent strain [%] 내열성[%]Heat resistance [%] covering사 신율[%]covering company elongation [%]
실시예1Example 1 0.50.5 9595 1.101.10 640640 24.324.3 48.548.5 301301
실시예2Example 2 1.51.5 9696 1.171.17 628628 21.021.0 50.150.1 310310
실시예3Example 3 5.05.0 9898 1.121.12 610610 19.819.8 52.352.3 323323
비교예1Comparative Example 1 0.00.0 8989 1.031.03 685685 26.226.2 45.845.8 288288
비교예2Comparative Example 2 10.010.0 100100 1.561.56 558558 18.718.7 53.953.9 315315
* 탄성사: 120 de/1fila, 사속 700m/min 기준* Elastic yarn: 120 de / 1fila, standard speed 700m / min
* 커버링 사: 상대사 나일론 70d, DR 5.0 작업 기준* Covering company: based on counterpart nylon 70d, DR 5.0
본 발명에 의하면, 실시 예 1 내지 3의 경우와 같이 가교 결합제를 0.5 내지 5.0 mol%를 첨가할 경우 우수한 방사 공정성(95% 이상)과 내열성 수준을 유지하면서 신도[%]와 영구 변형률[%]이 모두 우수하게 나타났고, 그로 인하여 커버링 사의 신율[%]이 향상되는 것을 알 수 있었다. 반면에 가교 결합제를 첨가하지 않을 경우에는 신도가 향상되나 영구 변형률이 미흡하여 커버링사의 신율이 감소하고, 과량으로 첨가할 경우에는 영구 변형률[%]과 내열성[%]은 양호하나, 신도가 과도히 감소하여 커버링 사의 신율[%]도 만족할만한 결과를 얻을 수 없다는 것을 알 수 있었다. According to the present invention, when adding 0.5 to 5.0 mol% of the crosslinking agent as in Examples 1 to 3, elongation [%] and permanent strain [%] while maintaining excellent spinning processability (95% or more) and heat resistance levels All of them appeared to be excellent, and thereby it was found that the elongation (%) of the covering company was improved. On the other hand, when the crosslinking agent is not added, the elongation is improved, but the elongation of the covering yarn is decreased due to insufficient permanent strain, and when added in excess, the permanent strain [%] and the heat resistance [%] are good, but the elongation is excessive. It was found that the elongation (%) of the covering company could not be satisfactorily obtained.
이상에서 실시 예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 청구범위에 기재된 본 발명의 기술적 사상으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although described above with reference to the embodiments, those skilled in the art can understand that the present invention can be variously modified and changed without departing from the spirit of the invention described in the claims below. will be.

Claims (5)

  1. 폴리올과 디이소시아네이트를 반응시켜 폴리우레탄 예비중합체를 수득하는 단계; 상기 예비중합체를 유기용매에 용해시켜 사슬연장제 및 사슬종결제를 첨가하여 2차 중합을 수행하여 방사원액을 수득하는 단계; 및 상기 방사원액을 건식 방사시켜 폴리우레탄우레아 탄성사를 제조하는 방법에 있어서, Reacting the polyol and diisocyanate to obtain a polyurethane prepolymer; Dissolving the prepolymer in an organic solvent to perform a second polymerization by adding a chain extender and a chain terminator to obtain a spinning stock solution; In the method for producing a polyurethane urea elastic yarn by dry spinning the spinning stock solution,
    상기 폴리올과 디이소시아네이트를 반응시켜 폴리우레탄 예비 중합체를 수득하는 단계에서, 2-에틸-2-(히드록실메틸)-1,3-프로판디올의 가교 결합제를 0.1 내지 5 몰%를 첨가하는 것을 특징으로 하는 신율이 우수한 폴리우레탄우레아 탄성사의 제조방법. In the step of reacting the polyol and diisocyanate to obtain a polyurethane prepolymer, 0.1 to 5 mol% of a crosslinking agent of 2-ethyl-2- (hydroxymethyl) -1,3-propanediol is added. Method for producing a polyurethane urea elastic yarn excellent in elongation.
  2. 폴리우레탄 예비 중합체가 2-에틸-2-(히드록실메틸)-1,3-프로판디올의 가교 결합제를 0.1 내지 5 몰% 포함하는 것을 특징으로 하는 신율이 우수한 폴리우레탄우레아 탄성사.A polyurethane urea elastic yarn having excellent elongation, wherein the polyurethane prepolymer contains 0.1 to 5 mol% of a crosslinking agent of 2-ethyl-2- (hydroxylmethyl) -1,3-propanediol.
  3. 제 2 항에 있어서, 폴리우레탄우레아 탄성사는 원사의 신도가 600% 이상이고, 영구 변형률이 25% 이하인 것을 특징으로 하는 신율이 우수한 폴리우레탄우레아 탄성사.The polyurethaneurea elastic yarn having excellent elongation according to claim 2, wherein the polyurethaneurea elastic yarn has an elongation of at least 600% and a permanent strain of 25% or less.
  4. 제 2 항에 있어서, 폴리우레탄우레아 탄성사는 방사 공정성이 95% 이상인 것을 특징으로 하는 신율이 우수한 폴리우레탄우레아 탄성사.The polyurethaneurea elastic yarn having excellent elongation according to claim 2, wherein the polyurethaneurea elastic yarn has a spinning processability of 95% or more.
  5. 제 2 항에 있어서, 폴리우레탄우레아 탄성사는 120 데니아 인 것을 특징으로 하는 신율이 우수한 폴리우레탄우레아 탄성사.The polyurethane urea elastic yarn having excellent elongation according to claim 2, wherein the polyurethane urea elastic yarn is 120 denier.
PCT/KR2018/000661 2017-01-18 2018-01-15 Polyurethane urea elastic yarn with excellent elongation and manufacturing method therefor WO2018135818A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20170008918 2017-01-18
KR10-2017-0008918 2017-01-18

Publications (1)

Publication Number Publication Date
WO2018135818A1 true WO2018135818A1 (en) 2018-07-26

Family

ID=62908942

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/000661 WO2018135818A1 (en) 2017-01-18 2018-01-15 Polyurethane urea elastic yarn with excellent elongation and manufacturing method therefor

Country Status (1)

Country Link
WO (1) WO2018135818A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100100816A (en) * 2007-10-22 2010-09-15 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Soft, elastic, plasticizer-free thermoplastic polyurethane and process to synthesize the same
KR20120123687A (en) * 2010-01-22 2012-11-09 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Crosslinkable thermoplastic polyurethane
KR20140094357A (en) * 2013-01-22 2014-07-30 주식회사 효성 Polyurethanurea elastic yarn having improved power and elastic recovery and method for preparing the same
JP2014141548A (en) * 2013-01-22 2014-08-07 Mitsubishi Chemicals Corp Method for producing polyurethane
JP2015189886A (en) * 2014-03-28 2015-11-02 三菱化学株式会社 Polyurethane and method for producing polyurethane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100100816A (en) * 2007-10-22 2010-09-15 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Soft, elastic, plasticizer-free thermoplastic polyurethane and process to synthesize the same
KR20120123687A (en) * 2010-01-22 2012-11-09 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Crosslinkable thermoplastic polyurethane
KR20140094357A (en) * 2013-01-22 2014-07-30 주식회사 효성 Polyurethanurea elastic yarn having improved power and elastic recovery and method for preparing the same
JP2014141548A (en) * 2013-01-22 2014-08-07 Mitsubishi Chemicals Corp Method for producing polyurethane
JP2015189886A (en) * 2014-03-28 2015-11-02 三菱化学株式会社 Polyurethane and method for producing polyurethane

Similar Documents

Publication Publication Date Title
WO2016085189A1 (en) Polyurethane-urea elastomeric fiber with low-temperature workability
KR101148583B1 (en) A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and elongation
KR101426208B1 (en) Polyurethaneurea elastic fiber with high uniformity and excellent heat settable property
KR101157335B1 (en) A Process for Preparing Polyurethaneurea Elastic Fiber having high Power
WO2011081447A2 (en) Method for manufacturing high-speed spinning polyurethaneurea elastic fiber
KR101167377B1 (en) Process for Preparing polyurethaneurea elastic fiber with improved heat settable properties
KR101578156B1 (en) Polyurethanurea elastic fiber having an excellent indexes of evenness and power and method of manufacturing the same
WO2015056909A1 (en) Polyurethane urea elastic yarn having remarkable tensile resilience and preparation method therefor
WO2018135818A1 (en) Polyurethane urea elastic yarn with excellent elongation and manufacturing method therefor
KR101312843B1 (en) A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and good recovery
JP4487112B2 (en) Polyurethane elastic fiber and method for producing the same
KR101396107B1 (en) Polyurethaneurea elastic fiber with improved heat setting property and manufacturing method thereof
JP4362803B2 (en) Polyurethane elastic fiber and method for producing the same
KR20140094357A (en) Polyurethanurea elastic yarn having improved power and elastic recovery and method for preparing the same
KR20100070884A (en) A process for preparing polyurethaneurea elastic fiber with excellent heat settable property at low temperature
KR102846041B1 (en) Method for preparing polyurethanurea elastic yarn with improved heat resistance and elasticity recovery
KR101453649B1 (en) Polyurethaneurea elastic fiber and manufacturing method of the same
KR101255453B1 (en) A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and elongation
WO2018080063A1 (en) Polyurethaneurea elastic yarn having high elongation, and manufacturing method therefor
KR100680108B1 (en) Low fixation spandex at low temperature
WO2013103159A1 (en) Method for manufacturing elastic yarn having high power and high power elastic yarn manufactured using same
KR101253420B1 (en) Polyurethaneurea Elastic Fiber having high Power and Process for Preparing it
KR101183433B1 (en) A Process for Preparing Polyurethaneurea Elastic Fiber with Improved Strength and elongation
JP2002363823A (en) Hygroscopic polyurethane elastic fiber and method for producing the same
WO2015088060A1 (en) Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18742036

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18742036

Country of ref document: EP

Kind code of ref document: A1