WO2017078479A1 - Fibre élastomère de polyuréthane-urée et son procédé de préparation - Google Patents

Fibre élastomère de polyuréthane-urée et son procédé de préparation Download PDF

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Publication number
WO2017078479A1
WO2017078479A1 PCT/KR2016/012691 KR2016012691W WO2017078479A1 WO 2017078479 A1 WO2017078479 A1 WO 2017078479A1 KR 2016012691 W KR2016012691 W KR 2016012691W WO 2017078479 A1 WO2017078479 A1 WO 2017078479A1
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WO
WIPO (PCT)
Prior art keywords
elastic yarn
polyol
polyurethane urea
yarn
chain extender
Prior art date
Application number
PCT/KR2016/012691
Other languages
English (en)
Korean (ko)
Inventor
기보람
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
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Application filed by 주식회사 효성 filed Critical 주식회사 효성
Publication of WO2017078479A1 publication Critical patent/WO2017078479A1/fr

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Classifications

    • 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
    • D01D1/10—Filtering or de-aerating the spinning solution or melt
    • 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
    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • D—TEXTILES; PAPER
    • 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
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • 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

Definitions

  • the present invention relates to a polyurethane urea elastic yarn and a method for manufacturing the same, and more particularly, polytrimethylene ether glycol as a polyol when preparing a polyurethane prepolymer, and 1,2-polypropylene as a chain extender when preparing a polyurethane urea.
  • Polyurethane urea that is mixed with diamine and has an intrinsic viscosity (IV) of 1.10 or more, low permanent strain, rubber-like properties, and excellent elasticity and resilience.
  • IV intrinsic viscosity
  • An elastic yarn and its manufacturing method are related.
  • polyurethaneurea obtains a prepolymer by reacting a polyol with an excess of diisocyanate compound to form a spinning stock solution of polyurethaneurea fiber through appropriate reaction to the prepolymer, followed by dry or wet spinning to give elastic yarn.
  • These polyurethaneurea elastic yarns are being used for various purposes because of their inherent properties with high elasticity. Recently, as the trend of pursuing the comfort of daily life and increasing the variety of outdoor activities increases, the necessity of various functional fabrics increases and the range of their use is expanded. New additional features continue to be required. In particular, there is an increasing demand for a fabric having excellent recovery ability, soft hand feeling and soft fit, and the development of elastic yarn suitable for this.
  • Polyurethane urea elastic yarn is generally used polytetramethylene ether glycol (PTMG, Polytetramethylene ether glycol) as a polyol, but in this case the rubber material properties (Rubber-like properties) is insufficient to improve the physical properties.
  • PTMG polytetramethylene ether glycol
  • Rubber material properties Rubber-like properties
  • Patent Document 1 KR10-2006-0078015 A (2006.07.05)
  • Patent Document 2 US 6,852,823 A (2005.02.08)
  • an object of the present invention is to provide a polyurethane urea elastic yarn having excellent rubber material properties (Rubber-like properties) and low permanent strain.
  • the present invention has been made to solve the problems of the prior art described above and to achieve the above object, in the production of a conventional polyurethane urea polymer, the first polyol and the second polyol are used alone or in combination,
  • the first polyol component is polytrimethylene ether glycol (PO3G, polytrimethylene ether glycol) is used, as an auxiliary chain extender containing 1,2-propylene diamine of 0.5 to 40.0 mol% or less
  • the final polyurethane urea elastic yarn It provides a polyurethane urea elastic yarn characterized by an intrinsic viscosity (IV) of 1.10 or more, excellent rubber material properties (Rubber-like properties) and low permanent strain.
  • IV intrinsic viscosity
  • the polyol When preparing a prepolymer by reacting a polyol with an excess of diisocyanate compound, the polyol may be used by using a first polyol alone or by mixing a first polyol and a second polyol, wherein the first polyol is polytrimethylene ether. Firstly polymerizing diisocyanate to a polyol component using a mixture of at least one selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like, to obtain a prepolymer;
  • the polyurethaneurea elastic yarn according to the present invention uses 1,2-propylenediamine of 0.5 to 40.0 mol% or less as an auxiliary chain extender to polytrimethylene ether glycol, and has an intrinsic viscosity (IV) of 1.10 or more.
  • IV intrinsic viscosity
  • the polyurethane urea elastic yarn has a low permanent strain and at the same time excellent rubber material properties (Rubber like properties) of 2.0 or more has an excellent recovery of yarn.
  • the fabric produced by applying the polyurethane urea elastic yarn according to the present invention is stretched smoothly and excellent in resilience to maintain good shape even in repeated movements during wearing, so as to be used as a yarn that can be usefully applied in the production of high-quality lightweight foil fabric Suitable for
  • the present invention relates to a polyurethane urea elastic yarn having a low permanent strain and excellent rubber material properties (Rubber-like properties) and a method of manufacturing the same, a polymorph having a permanent strain of 30% or less and a rubber material properties (Rubber-like properties) of 2.0 or more Provide urethane urea elastic yarn. If the permanent strain is higher than this, the shape stability of the fabric is lowered and the appearance is not good at the time of use, which significantly lowers the quality of the fabric. In addition, when rubber material properties (Rubber-like properties) is lower than the above, the recovery of the fabric is lowered and the wearing comfort of the fabric is significantly lowered, so high quality fabrics cannot be expected.
  • the intrinsic viscosity (I.V., intrinsic viscosity) of the polyurethaneurea elastic yarn of the present invention is characterized in that more than 1.10.
  • polytrimethylene ether glycol (PO3G; (Polytrimethylene ether glycol)) is used as a polyol component in the preparation of polyurethane prepolymers for the production of polyurethaneurea elastic yarn, and an auxiliary chain in the production of polyurethaneurea
  • 1,2-propylenediamine (1,2-PDA; 1,2-propylene diamine) may be mixed at 0.5 to 40.0 mol% or less.
  • the elastic yarn according to the embodiment of the present invention polymerizes a polyol in an excess of diisocyanate to obtain a prepolymer, and dissolves it in an organic solvent, and then, by adding a chain extender and a chain terminator to the solution, secondary polymerization is performed.
  • a chain extender and a chain terminator may be added all at once or divided into two or more stages.
  • diisocyanate used in the production of the polyurethaneurea elastic yarn in the present invention are 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1, 4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, or isophorone diisocyanate, etc.
  • At least 1 type or more of Isocyanates can be selected and used.
  • the polyol used in the present invention may be polytrimethylene ether glycol alone or polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, a mixture of alkylene oxide and lactone monomer and poly ( One or more polyols containing polytetramethylene ether glycol are mixed and used in a copolymer of tetramethylene ether) glycol and a copolymer of 3-methyl-tetrahydrofuran and tetrahydrofuran.
  • Polytrimethylene ether glycol has an odd number of -CH 2 groups compared to conventional polyols, and thus inhibits the firm packing between polymer chains due to the folding effect, resulting in crystallization by stretching. It is small and can improve yarn elongation and rubber-like properties.
  • NCO% is preferably in the range of 2.0 to 4.0%. If the isocyanate weight ratio of the prepolymer is less than 2.0% or more than 4.0%, significant physical property degradation occurs.
  • Diamines are used as the chain extender, and examples thereof include ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1, One kind or a mixture of two or more kinds thereof may be exemplified in 5-diaminopentane, 1, 6-hexamethylenediamine, 1,4-cyclohexanediamine and the like.
  • ethylenediamine is used alone as a chain extender, the hard segment in the polymer has a compact structure, whereas when 1,2-propylenediamine is used as an auxiliary chain extender, a hard segment is formed.
  • an amine having a monofunctional group for example, diethylamine, monoethanolamine, dimethylamine and the like can be used.
  • a steric hindrance phenol compound in order to prevent discoloration of the polyurethane urea and deterioration of physical properties due to ultraviolet rays, atmospheric smog, and heat treatment associated with spandex processing, a steric hindrance phenol compound, a benzofuran-one compound, and a semicarbazide Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably.
  • the polyurethaneurea elastic yarn of the present invention may include additives such as titanium dioxide, magnesium stearate, and the like in addition to the above components.
  • the length of the polymer chain is increased to increase the entanglement between the chains, thereby lowering the permanent strain of the yarn and improving power.
  • the NCO% measurement method and the physical properties of the polyurethaneurea elastic yarn of the polymer mentioned in Examples and Comparative Examples to be described later were measured as follows.
  • NCO% was measured according to the following equation (1).
  • NCO% [100 ⁇ 2 ⁇ NCO chemical formula ⁇ (capping ratio-1)] / ⁇ (diisocyanate molecular weight ⁇ capping ratio) + polyol molecular weight ⁇
  • the capping ratio refers to the molar ratio of diisocyanate mole ratio / polyol.
  • the measurement is performed at a sample length of 10 cm and a tensile speed of 100 cm / min. At this time, the strength and elongation at break were measured, and the load on the yarn at 200% elongation was also measured at 200% modulus.
  • MEL machine Textechno Co., Ltd.
  • the sample length is 10cm ⁇ 20 strands and the tensile rate is 100 cm / min. 300% is repeated five times, and the stress at 200% elongation at the first elongation during the fifth elongation and recovery (1 st load @ 200 %) And the difference between the stress at 200% elongation (5 th unload @ 200%) during the 5th recovery divided by the constant 5, the number of repeated elongations.
  • Intrinsic viscosity refers to the viscosity coefficient when there is no interaction between solute incidence, and the following method was used to measure the intrinsic viscosity.
  • Intrinsic viscosity (I.V.) value was calculated according to Flory-Huiggins Equation of Equation 3 with the calculated relative viscosity (R.V.) value.
  • the stress retention rate is 200% (e.g. 10 cm yarn up to 30 cm) when the elastic yarn is stretched five times to 300% (e.g. 10 cm up to 40 cm long).
  • Prepolymer was prepared by first polymerization with diisocyanate.
  • the chain extender the main chain extender was mixed with ethylenediamine and the auxiliary chain extender was mixed with 1,2-propanediamine in a 95: 5 ratio, and the chain terminator was diethylamine.
  • the amine used was prepared in a total of 7 mol%, the solvent was obtained using a polyurethane urea spinning solution using dimethylacetamide.
  • Example 1 was manufactured in the same manner as in Example 1 except that the main chain extender and the auxiliary chain extender in a ratio of 80:20 to prepare a polyurethane urea elastic yarn as shown in Table 1, the physical properties Measured and evaluated in the same manner as shown in Table 1 and Table 2.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 1 except that the viscosity of the polyurethaneurea spinning solution was adjusted to obtain a yarn having an intrinsic viscosity (IV) of 1.1 or more as shown in Table 1 below. And the physical properties are measured and evaluated in the same manner as described above are shown in Table 1 and Table 2.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 2 except that the viscosity of the polyurethaneurea spinning solution was adjusted in order to obtain a yarn having an intrinsic viscosity (IV) of 1.1 or more as shown in Table 1 below. And measured and evaluated the physical properties in the same manner as shown in Table 1 and Table 2 below.
  • IV intrinsic viscosity
  • Example 1 a polyurethane was used to obtain a yarn having 0 mol% of the first polyol, 100 mol% of the second polyol, 100 mol% of the main chain extender as the chain extender, and 1.3 or more intrinsic viscosity (IV). Except that the viscosity of the urea spinning solution was adjusted in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties are measured and evaluated in the same manner as shown in Table 1 and Table 2.
  • Example 1 0 mol% of the first polyol and 100 mol% of the second polyol were used, and the intrinsic viscosity (IV) was 1.3 or more using 80 mol% of the main chain extender as the chain extender and 20 mol% as the auxiliary chain extender. Except for adjusting the viscosity of the polyurethane urea spinning solution to obtain a yarn was carried out in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties were measured and evaluated in the same manner as described in Table 1 and Table 2 shows.
  • Example 1 Except for adjusting the viscosity of the polyurethaneurea spinning solution in Example 1 to obtain a yarn having an intrinsic viscosity (IV) of 0.85 or less by using a ratio of the main chain extender and the auxiliary chain extender as 80:20 mol% as a chain extender. And was carried out in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties are measured and evaluated in the same manner as shown in Table 1 and Table 2 below.
  • IV intrinsic viscosity
  • Example 1 100 mol% of the main chain extender was used as the chain extender, except that the viscosity of the polyurethaneurea spinning solution was adjusted to obtain a yarn having an intrinsic viscosity (IV) of 1.2 or more.
  • Polyurethane urea elastic yarn was prepared, the physical properties are measured and evaluated in the same manner as shown in Table 1 and Table 2.
  • Example 2 In the same manner as in Example 1 except that the viscosity of the polyurethaneurea spinning solution was adjusted to obtain a yarn having an intrinsic viscosity (IV) of 0.85 or less using 100 mol% of the main chain extender as the chain extender. Polyurethane urea elastic yarn was prepared, the physical properties are measured and evaluated in the same manner as shown in Table 1 and Table 2.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une fibre élastique de polyurée-uréthane et son procédé de préparation et, plus particulièrement, une fibre élastomère de polyuréthane-urée et son procédé de préparation, le polytriméthylène éther glycol étant utilisé comme constituant de polyol pendant la prépolymérisation de polyuréthane, et 0,5-40,0 % en mole de polypropylène diamine étant un mélange à l'intérieur de ce dernier et ainsi utilisé comme allongeur de chaîne auxiliaire pendant la préparation de polyuréthane-urée. Dans la présente invention, la viscosité intrinsèque de la fibre est d'au moins 1,10 et, de ce fait, des propriétés de type caoutchouc et une déformation permanente sont améliorées de façon à être excellentes, et l'élasticité et la reprise élastique sont exceptionnelles.
PCT/KR2016/012691 2015-11-04 2016-11-04 Fibre élastomère de polyuréthane-urée et son procédé de préparation WO2017078479A1 (fr)

Applications Claiming Priority (2)

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KR20150154399 2015-11-04
KR10-2015-0154399 2015-11-04

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100415963B1 (ko) * 1999-03-19 2004-01-24 아사히 가세이 가부시키가이샤 폴리우레탄우레아 탄성섬유 및 그 제조방법
KR20080013891A (ko) * 2005-05-09 2008-02-13 인비스타 테크놀러지스 에스.에이.알.엘 높은 에틸렌에테르 함량을 갖는폴리(테트라메틸렌-코-에틸렌에테르) 글리콜로부터의스판덱스
KR20090033402A (ko) * 2006-07-12 2009-04-02 미쓰비시 가가꾸 가부시키가이샤 폴리우레탄의 제조 방법 및 그것으로부터 얻어진 폴리우레탄의 용도
KR20100040730A (ko) * 2007-06-22 2010-04-20 인비스타 테크놀러지스 에스.에이.알.엘. 폴리우레탄 탄성사 및 그의 제조 방법
KR101092038B1 (ko) * 2004-09-02 2011-12-12 인비스타 테크놀러지스 에스.에이.알.엘. 섬유, 직물 및 의류에 대한 마이크로캡슐 처리용 결합제 계

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100415963B1 (ko) * 1999-03-19 2004-01-24 아사히 가세이 가부시키가이샤 폴리우레탄우레아 탄성섬유 및 그 제조방법
KR101092038B1 (ko) * 2004-09-02 2011-12-12 인비스타 테크놀러지스 에스.에이.알.엘. 섬유, 직물 및 의류에 대한 마이크로캡슐 처리용 결합제 계
KR20080013891A (ko) * 2005-05-09 2008-02-13 인비스타 테크놀러지스 에스.에이.알.엘 높은 에틸렌에테르 함량을 갖는폴리(테트라메틸렌-코-에틸렌에테르) 글리콜로부터의스판덱스
KR20090033402A (ko) * 2006-07-12 2009-04-02 미쓰비시 가가꾸 가부시키가이샤 폴리우레탄의 제조 방법 및 그것으로부터 얻어진 폴리우레탄의 용도
KR20100040730A (ko) * 2007-06-22 2010-04-20 인비스타 테크놀러지스 에스.에이.알.엘. 폴리우레탄 탄성사 및 그의 제조 방법

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