WO2011081452A2 - Procédé de fabrication de fibres élastiques à base de polyuréthaneurée dotées d'une propriété améliorée de thermodurcissement - Google Patents

Procédé de fabrication de fibres élastiques à base de polyuréthaneurée dotées d'une propriété améliorée de thermodurcissement Download PDF

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Publication number
WO2011081452A2
WO2011081452A2 PCT/KR2010/009510 KR2010009510W WO2011081452A2 WO 2011081452 A2 WO2011081452 A2 WO 2011081452A2 KR 2010009510 W KR2010009510 W KR 2010009510W WO 2011081452 A2 WO2011081452 A2 WO 2011081452A2
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WO
WIPO (PCT)
Prior art keywords
diisocyanate
polyurethaneurea
elastic yarn
prepolymer
elastic fiber
Prior art date
Application number
PCT/KR2010/009510
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English (en)
Korean (ko)
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WO2011081452A3 (fr
Inventor
진중성
이재명
강연수
Original Assignee
주식회사 효성
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Application filed by 주식회사 효성 filed Critical 주식회사 효성
Publication of WO2011081452A2 publication Critical patent/WO2011081452A2/fr
Publication of WO2011081452A3 publication Critical patent/WO2011081452A3/fr

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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
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80

Definitions

  • the present invention relates to a method for producing a polyurethane urea, and more particularly, the diisocyanate of the polyurethane urea is obtained by mixing isophorone diisocyanate with at least one diisocyanate including 4,4'-diphenylmethane diisocyanate. It relates to a polyurethane urea characterized in that it is produced and an elastic yarn having excellent heat setability produced using the same.
  • Polyurethane urea generally reacts 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 the end of the polyol, and dissolving the prepolymer in a suitable solvent.
  • a polyol which is a high molecular weight diol compound
  • diisocyanate compound to obtain a prepolymer having an isocyanate group at the end of the polyol, and dissolving the prepolymer in a suitable solvent.
  • the diamine-based or diol-based chain extender is added to the solution and the chain terminators such as monoalcohol or monoamine are reacted, a spinning solution of polyurethaneurea fiber is made and then subjected to dry and wet spinning. Elastic fibers are obtained.
  • Polyurethane urea fibers are actively used for various applications because of their inherent characteristics with high elasticity, and as the range of applications thereof expands, new additional characteristics of existing fibers continue to be demanded.
  • polyurethaneurea fibers had a problem that thermal embrittlement of heat-sensitive counterparts (nylon, cotton, silk, wool) occurs in post-processing after knitting due to high heat setting temperature.
  • thermal embrittlement of heat-sensitive counterparts nylon, cotton, silk, wool
  • polyurethaneurea fibers that can be set at low temperatures.
  • Japanese Patent Laid-Open Nos. 63-53287, 63-53288, 43-3939, Japanese Patent Laid-Open No. 7-316922, Korean Patent Laid-Open No. 2001-5854, and Korean Patent Laid-Open 2001 -16788 discloses a method for improving the thermosetability of polyurethane elastic yarns.
  • U.S. Patent No. 6,403,682 disclose methods for improving the heat setability of polyurethane elastic yarns, but still at low temperatures. Because of this lack, it is not applicable to heat sensitive fibers and the like.
  • Japanese Patent Application Laid-open No. Hei 7-82608 and U.S. Patent No. 6,472,494 attempt to improve physical properties by applying 2,4'-diphenylmethane diisocyanate, but are accompanied by heat setability or a decrease in modulus and elastic recovery rate. .
  • the present invention has been invented to solve the above problems, the present invention is to provide a method for producing a polyurethane urea elastic yarn improved heat setability.
  • the diisocyanate used in the production of the polyurethaneurea elastic yarn according to the present invention includes a first diisocyanate and a second diisocyanate, and the first diisocyanate is one or two selected from aromatic, aliphatic and alicyclic diisocyanates. At least one organic diisocyanate, wherein the second diisocyanate is isophorone diisocyanate and the second diisocyanate is present in the range of about 2 to about 25 mole percent of the total diisocyanate.
  • the elastic yarn having excellent heat setability is improved in the state of the fabric by heat setting the heat-sensitive fiber and interwoven fabric at low temperature so that thermal embrittlement does not occur, and edge curling does not occur.
  • the present invention is to produce a polyurethane urea elastic yarn with improved heat setability, by performing heat setting at a low temperature does not cause thermal embrittlement of the other company can improve the appearance of the fabric than the conventional, and the rim curl in the processed paper after heat setting Does not occur.
  • the segmented polyurethaneurea used in the preparation of the elastic yarn of the present invention is prepared by reacting an organic diisocyanate with a polymer diol to prepare a prepolymer, dissolving it in an organic solvent and then reacting with a diamine and a monoamine.
  • the diisocyanate used in the production of the polyurethaneurea elastic yarn used in the present invention includes a first diisocyanate and a second diisocyanate.
  • the first diisocyanate is one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, specifically 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, isophorone diisocyanate Etc.
  • the second diisocyanate is isophorone diisocyanate, and the content of isophorone diisocyanate is suitably 2 to 25 mole% of the total diisocyanate.
  • 4,4'- diphenylmethane diisocyanate is used due to the physical properties of the fiber.
  • the isophorone diisocyanate used in small amounts in the present invention has a three-dimensional structure unlike the existing 4,4'-diphenylmethane diisocyanate, and when added thereto, intramolecular hydrogen bonds or intramolecular bonds in the hard segment due to steric hindrance Hydrogen bonds are formed in a coarse shape, and have substantially the same effect as an increase in the content of the soft segments rather than the hard segments. Therefore, by forming a lot of soft domains (elastic fibers) excellent in the setability can be obtained.
  • the content of isophorone diisocyanate is less than 2%, the settability improvement effect is insufficient, and if the content of isophorone diisocyanate exceeds 25 mol%, the yarn modulus rapidly decreases, so the content of the isophorone diisocyanate in the present invention is within the above range. It is preferable.
  • polymer diol may be exemplified as one kind or a mixture of two or more kinds thereof in polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and the like.
  • Diamines are used as chain extenders, and examples thereof include ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5 One kind or a mixture of two or more kinds thereof, such as -diaminopentane, 1, 6-hexamethylenediamine and 1,4-cyclochlorodiamine, can be exemplified.
  • amines having a monofunctional group for example, diethylamine, monoethanolamine, dimethylamine and the like can be used.
  • the steric hindrance phenol compound in order to prevent discoloration and deterioration of the physical properties of the polyurethane urea due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc.
  • the steric hindrance phenol compound in order to prevent discoloration and deterioration of the physical properties of the polyurethane urea 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 include additives such as titanium dioxide, magnesium stearate, and the like in addition to the above components.
  • 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 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-heated at 100 ° C. for 30 minutes in a relaxed state and dried at room temperature to measure the length (L3) of the yarn.
  • the dry heat setability and heat set efficiency of the yarn was determined according to the following equation. HSE) was calculated.
  • Dry Heat Setability (%) ⁇ (L2-L0) / (L1-L0) ⁇ X 100
  • HSE (%) ⁇ (L3-L0) / (L1-L0) ⁇ X 100
  • 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 70 denier of nylon yarn and 40 denier of elastic yarn prepared above, and the content of elastic yarn was 8% of the total weight of the knitted fabric. to be.
  • the circular knitting fabric made of interlaced nylon / polyurethane urea elastic yarn is treated with pre-setting, dyeing, and final-setting and displayed as an equilateral triangle with a length of 5 cm.
  • Curling% (area of curled triangle / area of original equilateral triangle) X 100
  • Capping ratio (CR) was prepared at a content of 1.65, 5 mol% of isopron 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.
  • the ratio of the chain extender and the chain dispersant was 12.5: 1, and the ratio of ethylenediamine and 1,2-diamino propane was 80 mol% and 20 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 polyurethane spinning yarns of 40 denia 3 filament at a speed of 900m / min by dry spinning, and the physical properties are shown in Table 1 below.
  • Example 2 It is the same as Example 1 except the polyurethaneurea polymer was manufactured by the ratio of 10 mol% of isophorone diisocyanate and 90% of 4,4'- diphenylmethane diisocyanate.
  • the obtained spinning stock solution prepared a polyurethane urea elastic yarn of 40 denier 3 filament at a speed of 900m / min, and evaluated the physical properties are shown in Table 1 below.
  • Example 2 It is the same as Example 1 except the polyurethane urea polymer was manufactured by the content ratio of 25 mol% of isophorone diisocyanate and 75% of 4,4'- diphenylmethane diisocyanate.
  • the obtained spinning stock solution prepared a polyurethane urea elastic yarn of 40 denier 3 filament at a speed of 900m / min, and evaluated the physical properties are shown in Table 1 below.
  • the isophorone diisocyanate content was mixed at 5 mole% or more, and it was confirmed that the heat setability was improved.
  • the heat setability is greatly improved, but the modulus decreases. It can be seen that the larger.

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

Abstract

La présente invention concerne un procédé de fabrication de fibres élastiques à base de polyuréthaneurée dotées d'une propriété améliorée de thermodurcissement à partir de polyols, d'un premier diisocyanate, d'un second diisocyanate et d'un allongeur de chaîne. Le premier diisocynate représente un ou plus de deux types de diisocyanates organiques choisis parmi des diisocyanates aromatiques, aliphatiques, et cycloaliphatiques, et le second diisocynate est du diisocyanate d'isophorone et constitue de 2 à 25 % en moles de la teneur totale en diisocyanates. Les fibres élastiques à base de polyuréthaneurée fabriquées par le procédé ci-dessus ont d'excellentes propriétés de thermodurcissement et le textile tissé avec les fibres élastiques présentent un excellent toucher et ne bouclent pas même avec un thermodurcissement à faible température.
PCT/KR2010/009510 2009-12-31 2010-12-29 Procédé de fabrication de fibres élastiques à base de polyuréthaneurée dotées d'une propriété améliorée de thermodurcissement WO2011081452A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090135050A KR101167377B1 (ko) 2009-12-31 2009-12-31 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조방법
KR10-2009-0135050 2009-12-31

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WO2011081452A2 true WO2011081452A2 (fr) 2011-07-07
WO2011081452A3 WO2011081452A3 (fr) 2011-12-01

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101426208B1 (ko) * 2013-08-20 2014-08-01 주식회사 효성 균일성과 열세트성이 우수한 폴리우레탄우레아 탄성사
WO2015088060A1 (fr) * 2013-12-10 2015-06-18 주식회사 효성 Fil élastique de polyuréthane-urée ayant des propriétés de thermodurcissement améliorées, et son procédé de production
WO2015088059A1 (fr) * 2013-12-10 2015-06-18 주식회사 효성 Fil élastique de polyuréthane-urée à propriétés de thermodurcissement améliorées, et procédé de production dudit fil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010052482A (ko) * 1998-06-02 2001-06-25 빌프리더 하이더 폴리우레탄 우레아, 폴리우레탄 우레아 섬유 및 그의 제조방법
WO2001081443A2 (fr) * 2000-04-26 2001-11-01 E.I. Dupont De Nemours And Company Spandex a haute stabilisation thermique
KR20090046401A (ko) * 2007-11-06 2009-05-11 주식회사 효성 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조방법 및그에 의해 제조되는 폴리우레탄우레아 탄성사
KR20090106288A (ko) * 2008-04-04 2009-10-08 주식회사 효성 우수한 신도 및 합착력을 갖는 폴리우레탄우레아 탄성사 및그의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010052482A (ko) * 1998-06-02 2001-06-25 빌프리더 하이더 폴리우레탄 우레아, 폴리우레탄 우레아 섬유 및 그의 제조방법
WO2001081443A2 (fr) * 2000-04-26 2001-11-01 E.I. Dupont De Nemours And Company Spandex a haute stabilisation thermique
KR20090046401A (ko) * 2007-11-06 2009-05-11 주식회사 효성 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조방법 및그에 의해 제조되는 폴리우레탄우레아 탄성사
KR20090106288A (ko) * 2008-04-04 2009-10-08 주식회사 효성 우수한 신도 및 합착력을 갖는 폴리우레탄우레아 탄성사 및그의 제조방법

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KR101167377B1 (ko) 2012-07-19
KR20110078283A (ko) 2011-07-07
WO2011081452A3 (fr) 2011-12-01

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