WO2015088059A1 - Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil - Google Patents

Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil Download PDF

Info

Publication number
WO2015088059A1
WO2015088059A1 PCT/KR2013/011406 KR2013011406W WO2015088059A1 WO 2015088059 A1 WO2015088059 A1 WO 2015088059A1 KR 2013011406 W KR2013011406 W KR 2013011406W WO 2015088059 A1 WO2015088059 A1 WO 2015088059A1
Authority
WO
WIPO (PCT)
Prior art keywords
chain
elastic yarn
butylamine
polyurethane urea
yarn
Prior art date
Application number
PCT/KR2013/011406
Other languages
English (en)
Korean (ko)
Inventor
이재명
진중성
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
Priority to PCT/KR2013/011406 priority Critical patent/WO2015088059A1/fr
Publication of WO2015088059A1 publication Critical patent/WO2015088059A1/fr

Links

Classifications

    • 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
    • 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
    • D01F6/72—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyureas

Definitions

  • the present invention relates to a method for producing a polyurethane urea elastic yarn having excellent heat setability, and more particularly, by using butylamine as a chain terminator, it is possible to improve the problem of the thermal withdrawal of the thermally sensitive partner yarns,
  • the present invention relates to a polyurethaneurea elastic yarn having improved heat setability capable of minimizing changes due to the present invention and a method of manufacturing the same.
  • 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 elastic yarn may exhibit physical properties such as strength and modulus of yarn due to post-polymerization process over time, while reducing elongation of yarn and physical properties such as Max DR.
  • the present invention is to solve the above-mentioned problems, the main purpose is to improve the streak generation and quality of the fabric by producing a polyurethane urea elastic yarn having excellent heat setability and little change in physical properties over time have.
  • poly (tetramethylene ether) glycol One or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates; Chain extenders; And chain dispersants including n-butylamine; It provides a polyurethane urea elastic yarn improved heat setability comprising a.
  • the first step of polymerizing the polyol and diisocyanate to obtain a prepolymer Dissolving the prepolymer in an organic solvent and adding a chain extender and a chain terminator to perform secondary polymerization to obtain a spinning stock solution; And drying or wet spinning the spinning stock solution to obtain a polyurethaneurea elastic yarn;
  • the diisocyanate comprises one or two or more organic diisocyanates selected from aromatic, aliphatic and cycloaliphatic diisocyanates, and the chain terminator is n-butylamine-enhanced thermosettable polyurethane
  • the chain terminator is n-butylamine-enhanced thermosettable polyurethane
  • the chain dispersant may contain 10 to 80 mol% of n-butylamine.
  • heat-setability is excellent even at low temperature
  • heat-sensitive fibers are heat-set by performing heat setting at low temperature on the heat-sensitive fibers and interwoven fabrics. It does not embrittle, and the change of yarn properties with the change over time has the effect of preventing edge curling or streaks in the fabric.
  • the best mode of the present invention was the elastic yarns of Examples 1-3.
  • the elastic yarn according to one embodiment of the present invention is first polymerized with a high molecular weight polyol to an excess of diisocyanate to obtain a prepolymer.
  • a chain extender and a chain terminator are added to the solution to perform secondary polymerization to prepare a spinning stock solution.
  • the chain extender and chain stopper may be added all at once or in two or more steps.
  • a polyurethane urea elastic yarn is manufactured by dry spinning or wet spinning the spinning solution.
  • the diisocyanate used in this embodiment is one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, such as 4,4'-ditenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexamethylene diisocyanate, 1,4'-cyclohexanediisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone Diisocyanate and the like.
  • aromatic diisocyanates such as 4,4'-ditenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexamethylene diisocyanate, 1,4'-cycl
  • 2,4'-MDI has a three-dimensional structure is weakened between the intramolecular hydrogen bonds or intramolecular hydrogen bonds in the hard segment, thereby exhibiting the same effect as increasing the content of the soft segment To this end, a large number of soft domains are formed, thereby obtaining an elastic yarn having excellent setability.
  • the polyol usable in the present invention may illustrate at least one or more selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and combinations thereof, but the present invention is not limited thereto.
  • the molecular weight of the polyol may be 500 to 8000, more preferably 1200 to 3000.
  • Diamines used in the chain extender include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-di
  • 1,2-diaminopropane 1,3-diaminopropane
  • 1,4-diaminobutane 1,4-diaminobutane
  • 2,3-diaminobutane 1,5-di
  • One or two or more mixtures selected from aminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine and the like can be exemplified, but the present invention is not limited thereto.
  • a chain terminator is used to control the molecular weight of polyurethaneurea.
  • the postpolymerization time and post-calcination time are increased according to the high calorific value during the spinning process. Due to the post-polymerization process over time, the physical properties such as the strength and modulus of the yarn may be expressed, while the elongation, the Max DR, and the properties of the yarn may decrease.
  • the use of different yarns in the production time may cause a difference in the degree of set of fabric and streaks of the fabric.
  • n-butylamine is used as a chain terminator, and since the n-butylamine minimizes the change of physical properties due to postpolymerization to improve thermosetability, heat setting is performed at low temperature. Even if the other party's thermal withdrawal does not occur, the appearance of the fabric can be improved as compared with the conventional one, and the curled paper can be prevented from occurring in the processed paper after heat setting.
  • the chain terminator may preferably comprise 10 to 80 mol% of n-butylamine relative to the total chain terminator.
  • the amount of the chain terminator is less than 10 mol%, it is not possible to control the promotion of the postpolymerization due to the excess diethylamine, and if the amount of the chain terminator is more than 80 mol%, It may be concerned that the rise in polymer viscosity for modulus and spinning is suppressed.
  • the steric hindrance phenol compound in order to prevent discoloration of the polyurethane urea and degradation of physical properties due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc.
  • the steric hindrance phenol compound in order to prevent discoloration of the polyurethane urea and degradation of physical properties due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc.
  • the steric hindrance phenol compound in order to prevent discoloration of the polyurethane urea and degradation of physical properties due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc.
  • 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 further include additives such as titanium dioxide and magnesium stearate, antioxidants, dyeing enhancers, thermal oxidation stabilizers, antibacterial agents, light stabilizers or antistatic agents, if necessary.
  • additives such as titanium dioxide and magnesium stearate, antioxidants, dyeing enhancers, thermal oxidation stabilizers, antibacterial agents, light stabilizers or antistatic agents.
  • Capping ratio (CR) was prepared at a content of 1.65, 5 mol% of 2,4'-diphenylmethane diisocyanate and 95 mol% of 4,4'-diphenylmethane diisocyanate.
  • the chain extender used ethylenediamine and 1,2-diamino propane mentioned above, and the chain stopper used diethylamine and n-butylamine.
  • the ratio of chain extender and chain dispersant was 12.5: 1, the ratio of ethylenediamine and 1,2-diamino propane was 80 mol% and 20 mol%, and the ratio of n-butylamine and diethylamine was 10. It was set as mol% and 90 mol%.
  • the amine used was prepared in a total concentration of 7 mol%, and dimethylacetamide was used as a solvent.
  • the spinning stock solution obtained as described above was prepared by 20 spines of polyurethane urea elastic yarn at a speed of 900 m / min by dry spinning, and the physical properties are shown in Table 1 and Table 2 below.
  • a polyurethaneurea elastic yarn was prepared in the same manner as in Example 1, except that the polyurethaneurea polymer was prepared in a ratio of 50 mol% of n-butylamine and diethylamine and 50 mol% of diethylamine.
  • the physical properties were evaluated and shown together in Tables 1 and 2 below.
  • a polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that the polyurethane urea polymer was prepared in a ratio of 80 mol% of n-butylamine and diethylamine and 20 mol% of diethylamine.
  • the physical properties were evaluated and shown together in Tables 1 and 2 below.
  • Example 2 Without the addition of n-butylamine, it was prepared under the same conditions as in Example 1 except that 20 denia polyurethane urea elastic yarn was prepared at a speed of 900 m / min.
  • Example 1 100 mol% of n-butylamine was added, and it manufactured by the same conditions as Example 1 except having manufactured 20 denia polyurethane urea elastic yarn at a speed
  • the initial yarn (L0) was 100% elongated (L1) while exposed to the atmosphere, and then subjected to dry heat treatment at 170 ° C. for 1 minute, cooled to room temperature, and then the length (L2) of the yarn was measured.
  • Dry heat-treated yarn was moist heat treated at 100 ° C. for 30 minutes in a relaxed state and dried at room temperature to measure the length (L3) of the yarn, and the dry heat setability and heat set efficiency (HSE) of the yarn was calculated according to the following equation. It was.
  • Dry Heat Setability (%) ⁇ (L2-L0) / (L1-L0) ⁇ X 100
  • HSE (%) ⁇ (L3-L0) / (L1-L0) ⁇ X 100
  • the polymer of viscosity 2000 Poise prepared according to the type and content of chain extenders and different chain dispersants, was stirred at 8 rpm for 72 hours using a double helical stirrer after adding 700 g to a laboratory reactor. . At this time, 40 degrees of water was passed through the laboratory reactor, and the viscosity was measured every 24 hours to measure the viscosity lapse rate, and the viscosity lapse rate was calculated by the difference between the viscosity (V1) and the initial viscosity (V0, 2000 Poise) after 72 hours. .
  • Viscosity Tracing Rate (Poise / hr) (V1-V0) / 72hr
  • the elastic knitted fabric and nylon yarn were manufactured using a circular knitting machine having a diameter of 32 inches, a 28 gauge, and a 96 feeder. This circular knitted fabric was knitted using 100 denier of PET yarn and 20 denier of elastic yarn prepared above, and the content of the elastic yarn was 8% of the total weight of the knitted fabric. to be.
  • Example 1 0 days 1.18 503 4.0 56 10 days 1.20 506 4.0 56 30 days 1.19 505 4.0 56
  • Example 2 0 days 1.20 512 4.0 60 10 days 1.20 511 4.1 59 30 days 1.21 514 4.0 60
  • Example 3 0 days 1.18 515 3.9 67 10 days 1.17 515 4.0 66 30 days 1.19 518 3.9 66
  • Comparative Example 1 0 days 1.20 495 4.0 50 10 days 1.25 480 4.2 48 30 days 1.28 472 4.3 46 Comparative Example 2 0 days 1.23 545 3.3 72 10 days 1.22 543 3.4 70 30 days 1.22 548 3.3 71
  • a polyurethane urea elastic yarn having improved heat setability can be obtained.

Landscapes

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

Abstract

La présente invention concerne un fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées et comprenant du poly(tétraméthylène-éther)glycol, un ou plusieurs types de diisocyanates organiques choisis parmi des diisocyanates aromatiques, aliphatiques et alicycliques, un allongeur de chaîne, et un terminateur de chaîne comprenant de la n-butylamine.
PCT/KR2013/011406 2013-12-10 2013-12-10 Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil WO2015088059A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2013/011406 WO2015088059A1 (fr) 2013-12-10 2013-12-10 Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2013/011406 WO2015088059A1 (fr) 2013-12-10 2013-12-10 Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil

Publications (1)

Publication Number Publication Date
WO2015088059A1 true WO2015088059A1 (fr) 2015-06-18

Family

ID=53371351

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/011406 WO2015088059A1 (fr) 2013-12-10 2013-12-10 Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil

Country Status (1)

Country Link
WO (1) WO2015088059A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040027882A (ko) * 2001-07-24 2004-04-01 라디시스판덱스 코포레이션 개선된 스판덱스 조성물
US20040068080A1 (en) * 2002-10-04 2004-04-08 Hong Liu Spandex of a particular composition and process for making same
KR20060012279A (ko) * 2003-05-05 2006-02-07 인비스타 테크놀러지스 에스.에이.알.엘 고생산성 스판덱스 섬유 공정 및 제품
KR20110078283A (ko) * 2009-12-31 2011-07-07 주식회사 효성 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조방법
KR20110078784A (ko) * 2009-12-31 2011-07-07 주식회사 효성 고속방사용 폴리우레탄우레아 탄성사의 제조방법
KR20120077016A (ko) * 2010-12-30 2012-07-10 주식회사 효성 폴리디메틸실록산으로 개질된 폴리우레탄우레아 탄성사의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040027882A (ko) * 2001-07-24 2004-04-01 라디시스판덱스 코포레이션 개선된 스판덱스 조성물
US20040068080A1 (en) * 2002-10-04 2004-04-08 Hong Liu Spandex of a particular composition and process for making same
KR20060012279A (ko) * 2003-05-05 2006-02-07 인비스타 테크놀러지스 에스.에이.알.엘 고생산성 스판덱스 섬유 공정 및 제품
KR20110078283A (ko) * 2009-12-31 2011-07-07 주식회사 효성 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조방법
KR20110078784A (ko) * 2009-12-31 2011-07-07 주식회사 효성 고속방사용 폴리우레탄우레아 탄성사의 제조방법
KR20120077016A (ko) * 2010-12-30 2012-07-10 주식회사 효성 폴리디메틸실록산으로 개질된 폴리우레탄우레아 탄성사의 제조방법

Similar Documents

Publication Publication Date Title
WO2016104956A1 (fr) Élasthanne présentant une propriété de teinture améliorée
WO2011081441A2 (fr) Procédé de préparation de fils élastiques ayant d'excellentes puissance et élongation
WO2011081447A2 (fr) Procédé de fabrication de fibres élastiques à base de polyuréthaneurée obtenues par filage à vitesse élevée
WO2011081452A2 (fr) Procédé de fabrication de fibres élastiques à base de polyuréthaneurée dotées d'une propriété améliorée de thermodurcissement
WO2015026051A1 (fr) Fil élastique en polyuréthane-urée ayant d'excellentes propriétés d'uniformité et de fixage thermique
WO2011081450A2 (fr) Procédé de fabrication d'une fibre élastique de polyuréthane-urée haute performance
WO2016085189A1 (fr) Fibre élastomère de polyuréthane-urée usinable à basse température
KR101396107B1 (ko) 열세트성이 향상된 폴리우레탄우레아 탄성사 및 그 제조 방법
WO2015088059A1 (fr) Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil
WO2015056909A1 (fr) Fil élastique en polyuréthane-urée présentant une élasticité à la traction remarquable et son procédé de préparation
WO2017022946A1 (fr) Fibre élastique de polyuréthane-urée dotée d'une uniformité et d'une force excellentes et son procédé de fabrication
WO2012091480A2 (fr) Procédé de fabrication d'un fil élastique de polyuréthane-urée ayant une résistance et une force de rappel excellentes
WO2015088060A1 (fr) Fil élastique de polyuréthane-urée ayant des propriétés de thermodurcissement améliorées, et son procédé de production
JPH10310934A (ja) 弾性糸およびその製法ならびにポリウレタンウレア溶液
KR101395973B1 (ko) 열세트성이 향상된 폴리우레탄우레아 탄성사 및 그 제조 방법
WO2018080063A1 (fr) Fil élastique en polyuréthane-urée ayant un allongement élevé, et procédé de fabrication de celui-ci
KR20100070884A (ko) 초저온에서의 열세트성이 우수한 폴리우레탄우레아 탄성사의 제조방법
WO2013103159A1 (fr) Procédé de fabrication d'un fil élastique comportant une puissance élevée et fil élastique à haute puissance fabriqué l'utilisant
KR20140094357A (ko) 우수한 파워 및 탄성회복율을 갖는 폴리우레탄우레아 탄성사 및 이의 제조방법
WO2015088061A1 (fr) Procédé pour produire un fil élastique de polyuréthane-urée pour une filature à grande vitesse
WO2017022947A1 (fr) Fil élastique de polyuréthane-urée ayant une excellente propriété de déroulement et son procédé de fabrication
KR101453649B1 (ko) 폴리우레탄 우레아 탄성 섬유 및 그 제조 방법
WO2019132182A1 (fr) Fil élastique de polyuréthane-urée présentant une aptitude à la teinture améliorée et son procédé de fabrication
WO2012091491A2 (fr) Procédé de fabrication d'un fil élastique de polyuréthane-urée ayant une excellente résistance et un excellent allongement
KR102685474B1 (ko) 열세트성이 향상된 폴리우레탄우레아 탄성사 및 그의 제조방법

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: 13899155

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: 13899155

Country of ref document: EP

Kind code of ref document: A1