WO2015056909A1 - Fil élastique en polyuréthane-urée présentant une élasticité à la traction remarquable et son procédé de préparation - Google Patents

Fil élastique en polyuréthane-urée présentant une élasticité à la traction remarquable et son procédé de préparation Download PDF

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Publication number
WO2015056909A1
WO2015056909A1 PCT/KR2014/009174 KR2014009174W WO2015056909A1 WO 2015056909 A1 WO2015056909 A1 WO 2015056909A1 KR 2014009174 W KR2014009174 W KR 2014009174W WO 2015056909 A1 WO2015056909 A1 WO 2015056909A1
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WO
WIPO (PCT)
Prior art keywords
polyol
elastic yarn
polyurethane urea
urea elastic
prepolymer
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Application number
PCT/KR2014/009174
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English (en)
Korean (ko)
Inventor
이재명
기보람
강연수
Original Assignee
주식회사 효성
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Publication of WO2015056909A1 publication Critical patent/WO2015056909A1/fr

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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
    • 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

Definitions

  • the present invention relates to a method for producing a polyurethane urea elastic yarn excellent in stress retention. More specifically, the polyurethane urea having excellent stress retention rate is characterized in that the elastic yarn is prepared by including polytrimethylene ether glycol as the first polyol in mixing and using the first polyol and the second polyol when preparing the polyurethane prepolymer. It relates to a method for producing elastic yarn.
  • polyurethaneurea obtains a prepolymer by reacting a polyol with an excess of diisocyanate compound, and makes an elastic yarn by spinning after making a spinning stock solution of polyurethaneurea fiber through an appropriate reaction to the prepolymer.
  • the adhesiveness of the prepared spandex is high, which may cause problems such as deterioration of workability during dry spinning and poor degradability.
  • the present invention solves the problems posed by the prior art, and an object thereof is to provide a polyurethane urea improved yarn elongation and stress retention.
  • the present invention has been made to solve the above-described prior art, in producing a conventional polyurethane urea polymer, excellent polyvinyl chloride excellent stress retention, characterized in that the first polyol used alone or in combination with a second polyol Urethane urea elastic yarn and its manufacturing method.
  • the polyol and the excess diisocyanate compound is dissolved by dissolving the prepolymer in a suitable solvent, and then added diamine chain extender to the solution and monoalcohol or
  • the polyol is formed of a first polyol and a second polyol.
  • the first polyol and the second polyol may be selected from one or more of polyether glycol, polyester glycol, polypropylene glycol, and 3-methyltetrahydrofuran.
  • the content of the first polyol is 20 to 100 mol%
  • the content of the second polyol is 0 to 80 mol%
  • the first polyol is characterized by using polytrimethylene ether glycol It is done.
  • Polyurethane urea elastic yarn according to the present invention is characterized in that the stress retention rate is 75% or more at 300% 5 times repeated elongation, heat resistance (power retention before and after heat treatment) is 50% or more.
  • Polyurethane urea elastic yarn according to the present invention by using the polytrimethylene ether glycol as the first polyol when preparing the polyurethane prepolymer, -CH 2 is present in an odd number compared to the existing polyol (polytetramethylene ether glycol) between the polymer chain It prevents the firm packing, and the crystallization by stretching is insignificant, so that the soft characteristics can be expressed.
  • 1 is a graph showing the U% of the yarn.
  • 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 can be selected and used.
  • the polyol used in the present invention is a copolymer of polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, a mixture of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol, 3- And copolymers of methyl-tetrahydrofuran and tetrahydrofuran, and polytrimethylene ether glycol is mixed with one or more polyols including polytetramethylene ether glycol among these polyols, and polytrimethylene ether glycol The content of is 20 to 100 mol% is appropriate.
  • 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, such as 5-diaminopentane, 1, 6-hexamethylenediamine and 1,4-cyclohexanediamine, can be exemplified.
  • 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 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% [100 ⁇ 2 ⁇ NCO chemical formula ⁇ (capping ratio-1)] / ⁇ (diisocyanate molecular weight ⁇ capping ratio) + polyol molecular weight ⁇
  • capping ratio is the diisocyanate molar ratio / polyol molar ratio.
  • the sample is measured at 10cm in length and 100cm / min in tensile speed. At this time, the strength and elongation at break are measured, and the load (200% modulus) on the yarn is also measured at 200% elongation.
  • MEL machine Textechno Co., Ltd.
  • the sample was stretched 300 times five times at a sample length of 10 cm ⁇ 20 and a tensile rate of 100 cm / min, and the power at 200% of five times of recovery and recovery was measured. .
  • a value obtained as a ratio of 5 th unload @ 200% (S2) / 5 th load @ 200% (S1) ⁇ 100%) is used as a measure of how easily the elastic yarn stretches and contracts closely to the skin. The larger this value is, the softer it is stretched with less force, and when it is relaxed, it is always in close contact with the skin to satisfy both the fit and the functionality.
  • the Uster% measuring device (KET-QT) is used to measure the speed of the feeding roller differently depending on the yarn de (20d is 30m / min).
  • the sensor automatically reads the thickness of the yarn dissolved for 20 seconds at a constant speed and calculates the average value to draw a 0% reference line. Based on this value, if the thickness of the yarn read by the sensor per unit time is thicker, the point is recorded in the (+) area compared to the 0% reference line. If the thickness is thin, the point is recorded in the (-) area compared to the 0% reference line. Drawn (see FIG. 1). U% is calculated by calculating the deviation from the 0% reference line. The smaller the value, the better the uniformity of the yarn.
  • the heat treatment of the yarn is 100% elongated while being exposed to the air, followed by dry heat treatment at 190 ° C. for 1 minute, cooling to room temperature, followed by wet heat treatment at 100 ° C. for 30 minutes in a relaxed state, and drying at room temperature.
  • the spinning stock solution obtained as described above was dry spun at 900 m / min to prepare a polyurethane urea elastic yarn of 20 denia 1 filament, and the physical properties thereof were measured and evaluated in the same manner as shown in Table 1 below.
  • Example 1 except that 30 mol% of the first polyol, 70 mol% of the second polyol was carried out in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties were measured in the same manner as described above And evaluated and shown in Table 1 below.
  • Example 1 Except for using 50 mol% of the first polyol, 50 mol% of the second polyol in Example 1 was prepared in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties were measured in the same manner And evaluated and shown in Table 1 below.
  • Example 1 except that 70 mol% of the first polyol, 30 mol% of the second polyol was carried out in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties were measured in the same manner And evaluated and shown in Table 1 below.
  • Example 1 except that 100 mol% of the first polyol, 0 mol% of the second polyol was carried out in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties were measured in the same way And evaluated and shown in Table 1 below.
  • Example 1 except that 0 mol% of the first polyol and 100 mol% of the second polyol were used in the same manner as in Example 1, a polyurethaneurea elastic yarn was manufactured, and the physical properties thereof were measured in the same manner as described above. And evaluated and shown in Table 1 below.
  • polytrimethylene ether glycol when 100% of polytrimethylene ether glycol was used, it showed an excellent effect in terms of stress retention, but it was confirmed that the modulus is lowered.
  • polytrimethylene ether glycol is preferably used in an amount of about 30 to 80 mol% of the total polyol used in prepolymerization.

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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 un fil élastique en polyuréthane-urée présentant une élasticité à la traction remarquable et son procédé de préparation, et plus particulièrement, un fil élastique en polyuréthane-urée préparé par obtention d'un prépolymère en faisant réagir un polyol et un diisocyanate et par première polymérisation d'un polyurethane, filage de la solution par mise en œuvre d'une seconde polymérisation par dissolution du prépolymère dans un solvant et ajout d'un allongeur de chaîne et d'un agent de terminaison de chaîne, le polyol étant un premier polyol et/ou un second polyol, et l'élasticité à la traction du fil élastique en polyurethane-urée étant supérieure ou égale à 70 %. Le fil élastique en polyuréthane-urée de la présente invention préparé par le procédé présente une élasticité à la traction supérieure ou égale à 70 % sans détérioration de la résistance à la chaleur et une uniformité, et un produit tricoté avec le fil élastique présente une sensation douce au toucher et est seyant.
PCT/KR2014/009174 2013-10-15 2014-09-30 Fil élastique en polyuréthane-urée présentant une élasticité à la traction remarquable et son procédé de préparation WO2015056909A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20130122904A KR20150043906A (ko) 2013-10-15 2013-10-15 응력유지율이 우수한 폴리우레탄우레아 탄성사 및 이의 제조방법
KR10-2013-0122904 2013-10-15

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WO2015056909A1 true WO2015056909A1 (fr) 2015-04-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022093790A1 (fr) * 2020-10-27 2022-05-05 Lubrizol Advanced Materials, Inc. Tissu apte à la teinture comprenant des fibres de polyuréthane thermoplastique filées à l'état fondu

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102220251B1 (ko) * 2019-07-25 2021-02-24 효성티앤씨 주식회사 파워와 응력유지율이 향상된 신축사를 포함하는 위방향 신장성 데님 제직물

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050055704A (ko) * 2002-08-09 2005-06-13 이 아이 듀폰 디 네모아 앤드 캄파니 폴리트리메틸렌 에테르 글리콜로부터의 폴리우레탄 및폴리우레탄-우레아 탄성체
KR20060078015A (ko) * 2004-12-30 2006-07-05 주식회사 효성 응력 유지율이 높은 스판덱스 섬유
KR20070071751A (ko) * 2005-12-30 2007-07-04 주식회사 효성 우수한 응력 유지율을 가지는 스판덱스 섬유용 조성물
KR20080080610A (ko) * 2005-12-06 2008-09-04 이 아이 듀폰 디 네모아 앤드 캄파니 폴리트리메틸렌 에테르 연질부를 포함하는 열가소성폴리우레탄

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050055704A (ko) * 2002-08-09 2005-06-13 이 아이 듀폰 디 네모아 앤드 캄파니 폴리트리메틸렌 에테르 글리콜로부터의 폴리우레탄 및폴리우레탄-우레아 탄성체
KR20060078015A (ko) * 2004-12-30 2006-07-05 주식회사 효성 응력 유지율이 높은 스판덱스 섬유
KR20080080610A (ko) * 2005-12-06 2008-09-04 이 아이 듀폰 디 네모아 앤드 캄파니 폴리트리메틸렌 에테르 연질부를 포함하는 열가소성폴리우레탄
KR20070071751A (ko) * 2005-12-30 2007-07-04 주식회사 효성 우수한 응력 유지율을 가지는 스판덱스 섬유용 조성물

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022093790A1 (fr) * 2020-10-27 2022-05-05 Lubrizol Advanced Materials, Inc. Tissu apte à la teinture comprenant des fibres de polyuréthane thermoplastique filées à l'état fondu

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