WO2018080063A1 - Polyurethaneurea elastic yarn having high elongation, and manufacturing method therefor - Google Patents

Polyurethaneurea elastic yarn having high elongation, and manufacturing method therefor Download PDF

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Publication number
WO2018080063A1
WO2018080063A1 PCT/KR2017/011324 KR2017011324W WO2018080063A1 WO 2018080063 A1 WO2018080063 A1 WO 2018080063A1 KR 2017011324 W KR2017011324 W KR 2017011324W WO 2018080063 A1 WO2018080063 A1 WO 2018080063A1
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Prior art keywords
elastic yarn
mol
polyurethaneurea
elongation
polyurethane urea
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PCT/KR2017/011324
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French (fr)
Korean (ko)
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이재명
기보람
강연수
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(주)효성
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Publication of WO2018080063A1 publication Critical patent/WO2018080063A1/en

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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
    • D01D1/06—Feeding liquid to the spinning head
    • 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
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
    • 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
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D02G3/22—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
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/061—Load-responsive characteristics elastic

Definitions

  • the present invention relates to a polyurethane urea elastic yarn and a manufacturing method thereof, and more particularly to a polyurethane urea elastic yarn having a high elongation without deterioration of thermal stability and a method for manufacturing the same.
  • Polyurethaneurea is generally a primary polymerization reactant that reacts a polyol with an excess of diisocyanate compound to obtain a prepolymer having isocyanate groups at both ends of the polyol, and the prepolymer is dissolved in a suitable solvent and then dissolved in the solution. After adding a diamine-based or diol-based chain extender and reacting a chain terminator such as monoalcohol or monoamine, etc. to form a spinning solution of polyurethaneurea fibers, polyurethaneurea elastic yarn is formed by dry and wet spinning. Get
  • polyurethaneurea elastic yarns are used in various applications because of their inherent properties with excellent elasticity and elastic recovery ability, and as the range of applications thereof is expanded, new additional properties are continuously required for existing fibers.
  • polyurethaneurea elastic yarn is used as a fabric by mixing with heat-sensitive counterparts (nylon, silk, cotton, etc.). If the yarn's elongation is low, there is a high possibility of trimming during knitting and knitting DR (Draw ratio, tensile) B) cannot be increased, resulting in a decrease in productivity. In order to solve this problem, the demand for polyurethane urea elastic yarn having a high elongation has increased, and in the meantime, efforts have been made to improve the elongation of polyurethane urea elastic yarn in the elastic yarn manufacturers.
  • the most commonly used method for improving the elongation of polyurethaneurea elastic yarn by elastic yarn manufacturers is to increase the ratio of soft segments by applying a low capping ratio during polymerization of polyol and diisocyanate, High molecular weight polyols were used to increase the chain length of the soft segments.
  • the above technique may be difficult to manage due to a significant decrease in the viscosity aging rate of the polymer, the thermal stability of the polyurethane urea elastic yarn is lowered, such as thermal embrittlement and yellowing of the fabric by a high heat treatment process for setting during fabric finishing There may be drawbacks.
  • the polyurethane urea elastic yarn formed by reacting a polyol which is a high molecular weight diol compound and an excess of a diisocyanate compound butanol is 200 to 3000 ppm or less
  • Preparing a polyurethane precursor by polymerizing the polyol and diisocyanate added thereto, and then dissolving it in a solvent to prepare a prepolymer solution. 70 to 100 mol% of ethylenediamine as a chain extender in the prepolymer, 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender, and diethylamine as a chain terminator.
  • the NCO% of the prepolymer is 2.30 to 3.00%.
  • the chain terminator necessarily includes diethylamine, and uses a mixture of one or more selected from the group consisting of monoethanolamine, dimethylamine, butylamine, and cyclohexylamine. It is characterized by.
  • Polyurethane urea elastic yarn of the present invention is characterized in that the elongation is more than 500%, the maximum draw ratio (Maximum Draw Ratio) is 4.8 or more, the thermal stability is 40% or more.
  • the polymerization degree (IV) immediately after the production of the polyurethaneurea elastic yarn (within one week) is maintained at 1.0 to 1.5 or less.
  • the present invention by producing a polyurethane urea elastic yarn with excellent elongation without deterioration of thermal stability, it is possible to ensure excellent knitting workability and productivity and to prevent thermal embrittlement in the fabric heat setting process.
  • the present invention is to prepare a polyurethane precursor by polymerizing a polyol and diisocyanate to which butanol is added in an amount of 200 to 3000 ppm or less to prepare a polyurethane precursor, and then dissolving it in a solvent to prepare a prepolymer solution; 70 to 100 mol% of ethylenediamine as a chain extender in the prepolymer, 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender, and diethylamine as a chain terminator.
  • auxiliary chain terminator is added and reacted to prepare a polyurethaneurea spinning stock solution; And spinning and winding the polyurethane urea spinning stock solution, the elongation being 500% or more, the maximum draw ratio of 4.8 or more, and the polyurethane urea characterized in that the thermal stability is 40% or more. It provides a method for producing an elastic yarn.
  • the chain extender and the chain terminator may be added all at once or divided into two or more stages.
  • Non-limiting examples of the diisocyanate used in the preparation of the polyurethaneurea elastic yarn in the present invention are 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexa Methylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, and the like.
  • these diisocyanates 4,4'-diphenylmethane diisocyanate, etc. It may be used, it is preferable to use one or a mixture of two or more in the above enumerated group.
  • the polyols used in the present invention are polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymers of alkylene oxide and lactone monomers and poly (tetramethylene ether) glycol, 3-methyl
  • polytetramethylene ether glycol polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymers of alkylene oxide and lactone monomers and poly (tetramethylene ether) glycol, 3-methyl
  • the copolymer of tetrahydrofuran and tetrahydrofuran and the like it can be exemplified as one or a mixture of two or more thereof, but is not necessarily limited thereto.
  • the NCO% of the prepolymer is preferably in the range of 2.30 to 3.00% to properly maintain the physical properties of the polyurethane urea elastic yarn to maintain the content of the hard segment. If the NCO% of the prepolymer is less than 2.30% or more than 3.00%, a serious decrease in physical properties of the elastic yarn is caused.
  • the polyol used in the present invention is characterized in that 200 to 3000 ppm of butanol is added to the polyol.
  • the butanol in the polyol is added, it is combined with diisocyanate to form a short length polymer chain.
  • the chain of length acts as a plasticizer between existing long polymer chains, thereby improving the elongation of polyurethaneurea elastic yarn.
  • the elongation improving effect is insignificant, and when it exceeds 3000 ppm, the physical properties of the polyurethane urea elastic yarn decrease.
  • diamines are used as the chain extender, and in the present invention, 70 to 100 mol% of ethylenediamine and 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender. It is preferable to mix and use.
  • chain terminator of polyurethaneurea necessarily contains an amine having one functional group, for example, diethylamine, and mixes one or two or more selected from monoethanolamine, dimethylamine, butylamine, cyclohexylamine, and the like. Can be used.
  • auxiliary chain terminators listed above are not easily eliminated. Therefore, when the chain terminator and the auxiliary chain terminator are used in combination, unlike the conventional chain terminator, diethylamine, it is not easily eliminated, and the yarn IV can be lowered through post-polymerization inhibition during spinning. Therefore, the elongation of the elastic yarn can be improved.
  • the content of at least one auxiliary chain terminator selected from the above materials is preferably 0 to 50 mol% or less, and when it exceeds 50 mol%, it is difficult to form a viscosity suitable for spinning due to excessive suppression of postpolymerization and insufficient spinning processability. Can be.
  • Diethylenetriamine or triethylenetetramine may be used as the viscosity stabilizer in the second polymerization, but is not limited thereto.
  • the IV (Intrinsic viscosity) of the elastic yarn is maintained at 1.0 to 1.5 or less, the length of the polymer chain is reduced compared to the elastic yarn of more than 1.5, so that the probability of entanglement between the polymer chains is reduced. Since this becomes low, the elongation of the elastic yarn can be improved.
  • 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.
  • Polyurethane urea elastic yarn prepared by the manufacturing method as described above is characterized in that the elongation is more than 500%, the maximum draw ratio (Maximum Draw Ratio) is 4.8 or more, the thermal stability is 40% or more.
  • the polyurethaneurea elastic yarn prepared by the method according to a preferred embodiment of the present invention is characterized in that the IV immediately after production (within a week) maintains 1.0 to 1.5 or less.
  • 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.
  • Viscosity elapsed per hour [Poise / hr] (viscosity after 72hr stirring-initial viscosity) / 72
  • the measurement is performed at load cell 32 cN, sample length 10 cm, and tensile speed 100 cm / min. At this time, the strength and elongation at break are measured, and the load 200% modulus applied at 200% elongation of elastic yarn is also measured.
  • MEL machine manufactured by Textechno
  • the elastic yarn is different depending on the type of yarn, but it is stretched to some extent to be wound on the branch pipe.
  • the winding shrinkage rate refers to the degree of change in the length of the elastic yarn that is contracted after dissolution in the state wound around the branch pipe.
  • the elastic yarn is mounted on the contact roller, a weight corresponding to the denier is placed at the zero point of the starting point, and the elastic yarn is automatically dismissed one round to measure the length of shrinkage after 10 seconds.
  • Winding Shrinkage% (Length of Equipment Rotation (Circumference of 1 Roller, 533mm)-Length of Shrink Yarn) / Length of Rotation of Equipment (Roll of Cylinder, 533mm) * 100
  • the DM measuring device consists of four rollers coated with chromium on aluminum and a central plastic (polyacetal) sensor.
  • the first roller is a feed roller that supplies the yarn, and the yarn is wound on the winder roller after the third roller after measuring the tension applied to the yarn in the sensor through the path as shown in FIG.
  • the speed ratio of the first roller and the third roller is set to 1: 3 (draft ratio 3.0) to solve for about 5 minutes, and the yarn tension value measured by the sensor is defined as the DM (dynamic modulus) value.
  • the speed of the roller is set to 50 rpm in the first, the second in the power off, the third 200 rpm, the fourth is set to 180 rpm.
  • Yarn is wound once on the first roller, the second roller just passes, eight times on the third roller, but not through the ceramic guides.
  • Max. DR 3rd roller rpm value / 1st roller rpm value without trimming
  • the yarn was stretched 100% in air (17.0 ⁇ 34.0cm) and fixed with aluminum tape in a square frame, and then dried and treated at 190 ° C for 1 minute using a mini tenter (manufactured by Daelim Starlet Co., Ltd., DL-2015). Using a water bath (manufactured by HAHN SHIN SCIENIIFIC Co., Ltd., Water bath), perform non-water treatment at 100 ° C for 30 minutes. At this time, the frame where the yarn is fixed should be sufficiently submerged in 100 water.
  • the elastic yarn is immersed in petroleum ether for 10 minutes to remove the emulsion, and dried in an oven at 90 ° C. for 20 minutes to evaporate the remaining petroleum ether. 0.4 kg of LiCL was added to 1 kg of DMAc, and completely dissolved at room temperature to prepare 0.01 M LiCL DMAc.
  • the elastic yarn from which the emulsion is removed is placed in a concentration of about 0.5% in 0.01M LiCL DMAc, stirred for about 4 hours, and dissolved in a viscous tube. After 25 ° C thermostat viscous tube is stabilized for about 20 minutes, measure the time to pass between the intervals of the predetermined interval and compare the blank value to calculate R.V. (relative viscosity) and calculate I.V. This reflects the content of minerals contained in the yarn.
  • I.V. SQRT (R.V.-2 * LN (1 + R.V. / 2)) / 0.5 * (1-% inorganic content)
  • T1 time it took for sample to pass between intervals of viscous tubes
  • T0 blank time it took for material to pass between intervals of viscous tubes
  • blank 0.01M LiCL DMAc
  • Polytetramethylene glycol containing 1200 ppm of 4,4'-diphenylmethane diisocyanate and butanol was prepared so that the NCO% was 2.75% with a capping ratio (CR) of 1.73.
  • 100 mol% of ethylenediamine was used as the chain extender, 70 mol% of diethylamine and 30 mol% of cyclohexylamine were used as the chain terminator, and the ratio of the chain extender and the chain terminator was 10: 1.
  • the amine used was prepared in a total concentration of 7 mol%, and 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 900 m / min to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof are shown in Table 1 below.
  • Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that 90 mol% of ethylenediamine and 10 mol% of 1,2-propanediamine were mixed as a chain extender, and the physical properties thereof were evaluated in Table 1 below. Indicated.
  • Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that 80 mol% of ethylenediamine and 20 mol% of 1,2-propanediamine were mixed as a chain extender, and the physical properties thereof were evaluated in Table 1 below. Indicated.
  • Example 1 Same as Example 1 except that 80 mol% of ethylenediamine and 20 mol% of 1,2-propanediamine were mixed as a chain extender, and 50 mol% of diethylamine and 50 mol% of cyclohexylamine were used as a chain terminator. It was carried out to prepare a polyurethane urea elastic yarn, it is shown in Table 1 to evaluate the physical properties.
  • Polyurethane urea elastic yarn was prepared in the same manner as in Example 1, except that 70 mol% of ethylenediamine and 30 mol% of 1,2-propanediamine were mixed as a chain extender, and the physical properties thereof are shown in Table 1 below. It was.
  • the preparation of the prepolymer was carried out in the same manner as in Example 1 except that polytetramethylene glycol containing 2400 ppm of butanol was used, and 90 mol% of ethylenediamine and 10 mol% of 1,2-propanediamine were mixed as a chain extender.
  • Polyurethane urea elastic yarn was prepared, and the physical properties thereof are shown in Table 1.
  • the polyurethaneurea elastic yarn was prepared in the same manner as in Example 1, and the physical properties thereof are shown in Table 1 below.
  • Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that polytetramethylene glycol without butanol was used and 100 mol% of diethylamine was used as the chain terminator when preparing the prepolymer. It is shown in Table 1 to evaluate.
  • Polytetramethylene glycol without 4,4'-diphenylmethane diisocyanate and butanol was prepared with a capping ratio (CR) of 1.83 so that the NCO% was 3.10%, and 100 mol% of diethylamine was used as the chain terminator. Except that was prepared in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties are shown in Table 1 to evaluate the properties.
  • NCO% buOH [ppm] EDA / 1,2-PDA DEA / CHA Viscosity elongation rate Strength [g / d] Elongation [%] PR [%] DM [g] Max.DR 5 th unload @ 200% [g / d] Thermal Stability [%] Yarn I.V.
  • Example 1 2.75 1200 100/0 70/30 82 1.37 538 7.8 7.5 5.21 0.029 51.5 1.34
  • Example 2 2.75 1200 90/10 70/30 74 1.42 545 7.4 7.0 5.35 0.028 50.9 1.30
  • Example 3 2.75 1200 80/20 70/30 63 1.38 552 6.8 6.4 5.41 0.027 49.5 1.28
  • Example 4 2.75 1200 80/20 50/50 46 1.25 564 6.4 6.0 5.52 0.025 40.0 1.14
  • Example 5 2.75 1200 70/30 70/30 52 1.36 556 6.7 6.2 5.43 0.024 45.1 1.27
  • Example 6 2.75 2400 90/10 70/30 48 1.12 579 6.3 5.9 5.58 0.024 41.3 1.22 Comparative Example 1 2.75 1200 100/0 100/0 95 1.18 500 14.3 9.7 4.55 0.030 51.4 1.56 Comparative Example 2 2.75 0 100/0 100/0 103 1.15 470 15.3 10.2 4.40 0.031 52.4 1.64 Compar
  • ⁇ 1,2-PDA 1,2-diaminopropane (auxiliary chain extender)
  • ⁇ CHA cyclohexylamine (auxiliary chain terminator)

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a polyurethaneurea elastic yarn having excellent thermal stability and a high elongation, and a manufacturing method therefor, and provides a method for manufacturing a polyurethaneurea elastic yarn, comprising the steps of: preparing a polyurethane precursor by polymerizing diisocyanate and a polyol containing 200-3,000 ppm or less of butanol, and then preparing a prepolymer solution by dissolving the same in a solvent; preparing a polyurethaneurea spinning dope solution by adding, to the prepolymer, 70-100 mol% of ethylenediamine as a chain extender, 0-30 mol% of 1,2-diaminopropane as an auxiliary chain extender, 50-100 mol% of diethylamine as a chain terminator, and 0-50 mol% of an auxiliary chain terminator, and reacting the same; and spinning and winding the polyurethaneurea spinning dope solution, wherein the elongation is at least 500%, the maximum draw ratio is at least 4.8 or more, and the thermal stability is at least 40%. A polyurethaneurea elastic yarn manufactured by the method has excellent elongation and Max. DR, and exhibits an effect of enabling productivity to improve during flat knitting if the elastic yarn is used, and enabling thermal degradation to be prevented in a heat setting process during processing of a fabric.

Description

높은 신도를 갖는 폴리우레탄우레아 탄성사 및 이의 제조방법 Polyurethane urea elastic yarn having high elongation and its manufacturing method
본 발명은 폴리우레탄우레아 탄성사 및 이의 제조방법에 관한 것으로, 보다 상세하게는 열 안정성의 저하 없이 높은 신도를 갖는 폴리우레탄우레아 탄성사 및 이의 제조방법에 관한 것이다.The present invention relates to a polyurethane urea elastic yarn and a manufacturing method thereof, and more particularly to a polyurethane urea elastic yarn having a high elongation without deterioration of thermal stability and a method for manufacturing the same.
폴리우레탄우레아는 일반적으로 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 폴리올의 양 말단에 이소시아네이트기를 가지는 예비중합체(prepolymer)를 얻는 1차 중합 반응물과, 상기 예비중합체를 적절한 용매에 용해시킨 후 그 용액에 디아민계 또는 디올계 사슬 연장제를 첨가하고 모노알코올 또는 모노아민 등과 같은 사슬 종결제 등을 반응시키는 단계를 거쳐 폴리우레탄우레아 섬유의 방사액을 만든 후, 건식 및 습식 방사에 의해 폴리우레탄우레아 탄성사를 얻는다. Polyurethaneurea is generally a primary polymerization reactant that reacts a polyol with an excess of diisocyanate compound to obtain a prepolymer having isocyanate groups at both ends of the polyol, and the prepolymer is dissolved in a suitable solvent and then dissolved in the solution. After adding a diamine-based or diol-based chain extender and reacting a chain terminator such as monoalcohol or monoamine, etc. to form a spinning solution of polyurethaneurea fibers, polyurethaneurea elastic yarn is formed by dry and wet spinning. Get
이러한 폴리우레탄우레아 탄성사는 우수한 탄성 및 탄성회복력을 갖는 고유의 특성 때문에 다양한 용도로 사용되고 있으며, 그 용도 범위가 확대됨에 따라 기존의 섬유에 새로운 부가적인 특성이 계속하여 요구되고 있다.These polyurethaneurea elastic yarns are used in various applications because of their inherent properties with excellent elasticity and elastic recovery ability, and as the range of applications thereof is expanded, new additional properties are continuously required for existing fibers.
일반적으로 폴리우레탄우레아 탄성사는 열에 민감한 상대사(나일론, 실크, 면 등)와의 혼용 편직하여 원단으로 사용되는데, 원사의 신도가 낮으면 편직 작업 중 사절이 발생할 확률이 크고 편직 DR(Draw ratio, 인장비)을 증가시킬 수 없어, 생산성의 저하가 발생한다. 이러한 문제를 해결하기 위해 높은 신도를 갖는 폴리우레탄우레아 탄성사에 대한 수요가 증가하여, 그간 탄성사 제조 업체에서는 폴리우레탄우레아계 탄성사의 신도를 향상시키기 위한 노력이 지속적으로 이루어져 왔다.In general, polyurethaneurea elastic yarn is used as a fabric by mixing with heat-sensitive counterparts (nylon, silk, cotton, etc.). If the yarn's elongation is low, there is a high possibility of trimming during knitting and knitting DR (Draw ratio, tensile) B) cannot be increased, resulting in a decrease in productivity. In order to solve this problem, the demand for polyurethane urea elastic yarn having a high elongation has increased, and in the meantime, efforts have been made to improve the elongation of polyurethane urea elastic yarn in the elastic yarn manufacturers.
그간 탄성사 제조 업체에서 폴리우레탄우레아 탄성사의 신도 향상을 위해 종래에 가장 보편적으로 사용해 온 방법은, 폴리올과 디이소시아네이트의 중합 시 낮은 캐핑비(Capping ratio)를 적용하여 소프트 세그먼트의 비율을 증가시키는 것과, 고분자량의 폴리올(Polyol)을 사용하여 소프트 세그먼트(Soft segment)의 사슬 길이를 증가시키는 것이었다. 그러나 상기의 기술은 중합물의 점도 경시율이 크게 감소하여 관리가 어려울 수 있고, 폴리우레탄우레아 탄성사의 열 안정성이 저하되어 원단 후가공 중 세팅을 위한 높은 열처리 공정 의해 열적 취화가 일어나고 원단이 황변되는 등의 단점이 있을 수 있다.In the meantime, the most commonly used method for improving the elongation of polyurethaneurea elastic yarn by elastic yarn manufacturers is to increase the ratio of soft segments by applying a low capping ratio during polymerization of polyol and diisocyanate, High molecular weight polyols were used to increase the chain length of the soft segments. However, the above technique may be difficult to manage due to a significant decrease in the viscosity aging rate of the polymer, the thermal stability of the polyurethane urea elastic yarn is lowered, such as thermal embrittlement and yellowing of the fabric by a high heat treatment process for setting during fabric finishing There may be drawbacks.
즉, 아직까지는 우수한 신도와 열 안정성을 동시에 갖는 폴리우레탄우레아 탄성사를 제조하는 기술은 완벽히 정립되지 않은 상태이다.That is, the technology for producing a polyurethane urea elastic yarn having both excellent elongation and thermal stability at the same time is not completely established.
상기한 목적을 달성하기 위하여, 본 발명의 적절한 실시 형태에 따르면, 고분자량의 디올 화합물인 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 이루어진 폴리우레탄우레아 탄성사에 있어서, 부탄올(butanol)이 200 내지 3000ppm 이하로 첨가된 폴리올 및 디이소시아네이트를 중합하여 폴리우레탄 전구체를 제조한 후 용매에 용해하여 예비중합체 용액을 제조하는 단계; 상기 예비중합체에 사슬 연장제로 에틸렌디아민 (Ethylenediamine)을 70 내지 100mol%, 보조 사슬 연장제로 1,2-디아미노프로판(1,2-diaminopropane)을 0 내지 30mol%,, 사슬 종결제로 디에틸아민(diethylamine)을 50 내지 100mol%, 보조 사슬 종결제를 0 내지 50mol% 첨가하고 반응시켜 폴리우레탄우레아 방사원액을 제조하는 단계; 및 상기 폴리우레탄우레아 방사원액을 방사 및 권취하는 단계를 포함하고, 신도가 500% 이상이고, 최대연신비율(Maximum Draw Ratio, Max. DR)이 4.8 이상이며, 열 안정성이 40% 이상인 것을 특징으로 하는 폴리우레탄우레아 탄성사의 제조방법을 제공한다. In order to achieve the above object, according to a preferred embodiment of the present invention, in the polyurethane urea elastic yarn formed by reacting a polyol which is a high molecular weight diol compound and an excess of a diisocyanate compound, butanol is 200 to 3000 ppm or less Preparing a polyurethane precursor by polymerizing the polyol and diisocyanate added thereto, and then dissolving it in a solvent to prepare a prepolymer solution. 70 to 100 mol% of ethylenediamine as a chain extender in the prepolymer, 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender, and diethylamine as a chain terminator. adding 50 to 100 mol% diethylamine) and 0 to 50 mol% auxiliary chain terminator and reacting to prepare a polyurethaneurea spinning stock solution; And spinning and winding the polyurethane urea spinning stock solution, the elongation being 500% or more, the maximum draw ratio (Maximum Draw Ratio, Max. DR) of 4.8 or more, and thermal stability of 40% or more. It provides a method for producing a polyurethane urea elastic yarn.
본 발명의 바람직한 일례에 따르면, 상기 예비중합체의 NCO%는 2.30 내지 3.00% 이다.According to a preferred embodiment of the present invention, the NCO% of the prepolymer is 2.30 to 3.00%.
본 발명의 다른 적절한 실시 형태에 따르면, 사슬 종결제는 디에틸아민을 반드시 포함하며, 모노에탄올아민, 디메틸아민, 부틸아민, 사이클로헥실아민으로 이루어진 군에서 선택된 1종 또는 그 이상을 혼합하여 사용하는 것을 특징으로 한다. According to another suitable embodiment of the present invention, the chain terminator necessarily includes diethylamine, and uses a mixture of one or more selected from the group consisting of monoethanolamine, dimethylamine, butylamine, and cyclohexylamine. It is characterized by.
본 발명의 폴리우레탄우레아 탄성사는 신도가 500% 이상이고, 최대연신비율(Maximum Draw Ratio)이 4.8 이상이며, 열 안정성이 40% 이상인 것을 특징으로 한다. Polyurethane urea elastic yarn of the present invention is characterized in that the elongation is more than 500%, the maximum draw ratio (Maximum Draw Ratio) is 4.8 or more, the thermal stability is 40% or more.
본 발명의 또다른 바람직한 일례에 따르면, 폴리우레탄우레아 탄성사의 생산 직후(1주일 이내) 중합도(IV)는 1.0 내지 1.5 이하를 유지하는 것이 특징이다.According to another preferred embodiment of the present invention, the polymerization degree (IV) immediately after the production of the polyurethaneurea elastic yarn (within one week) is maintained at 1.0 to 1.5 or less.
본 발명은 열 안정성의 저하 없이 신도가 우수한 폴리우레탄우레아 탄성사를 제조함으로써, 우수한 편직 작업성과 생산성을 확보할 수 있고 원단 열세팅 공정에서의 열적 취화를 방지하는 효과를 나타낸다.The present invention by producing a polyurethane urea elastic yarn with excellent elongation without deterioration of thermal stability, it is possible to ensure excellent knitting workability and productivity and to prevent thermal embrittlement in the fabric heat setting process.
이하, 본 발명의 폴리우레탄우레아 탄성사에 대해 보다 상세하게 설명한다. 그러나, 본 발명의 실시 예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. 덧붙여, 명세서 전체에서 어떤 구성 요소를 '포함'한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있다는 것을 의미한다.Hereinafter, the polyurethane urea elastic yarn of this invention is demonstrated in detail. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, "including" a certain component throughout the specification means that it may further include other components, except to exclude other components unless specifically stated otherwise.
본 발명은, 부탄올(butanol)이 200 내지 3000ppm 이하로 첨가된 폴리올 및 디이소시아네이트를 중합하여 폴리우레탄 전구체를 제조한 후 용매에 용해하여 예비중합체 용액을 제조하는 단계; 상기 예비중합체에 사슬 연장제로 에틸렌디아민 (Ethylenediamine)을 70 내지 100mol%, 보조 사슬 연장제로 1,2-디아미노프로판(1,2-diaminopropane)을 0 내지 30mol%, 사슬 종결제로 디에틸아민(diethylamine)을 50 내지 100mol%, 보조 사슬 종결제를 0 내지 50mol% 첨가하고 반응시켜 폴리우레탄우레아 방사원액을 제조하는 단계; 및 상기 폴리우레탄우레아 방사원액을 방사 및 권취하는 단계를 포함하고, 신도가 500% 이상이고, 최대연신비율(Maximum Draw Ratio)이 4.8 이상이며, 열 안정성이 40% 이상인 것을 특징으로 하는 폴리우레탄우레아 탄성사의 제조방법을 제공한다. The present invention is to prepare a polyurethane precursor by polymerizing a polyol and diisocyanate to which butanol is added in an amount of 200 to 3000 ppm or less to prepare a polyurethane precursor, and then dissolving it in a solvent to prepare a prepolymer solution; 70 to 100 mol% of ethylenediamine as a chain extender in the prepolymer, 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender, and diethylamine as a chain terminator. ) To 50 to 100 mol%, 0 to 50 mol% auxiliary chain terminator is added and reacted to prepare a polyurethaneurea spinning stock solution; And spinning and winding the polyurethane urea spinning stock solution, the elongation being 500% or more, the maximum draw ratio of 4.8 or more, and the polyurethane urea characterized in that the thermal stability is 40% or more. It provides a method for producing an elastic yarn.
이때, 사슬 연장제 및 사슬 종결제는 전부 한 번에 첨가되거나 또는 2개 이상의 단계로 구분하여 첨가될 수 있다.At this time, the chain extender and the chain terminator may be added all at once or divided into two or more stages.
본 발명에서 폴리우레탄우레아 탄성사의 제조에 사용되는 디이소시아네이트의 비제한적인 예로는 4,4'-디페닐메탄디이소시아네이트, 1,5'-나프탈렌디이소시아네이트, 1,4'-페닐렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 1,4'-시클로헥산디이소시아네이트, 4,4'-디시클로헥실메탄디이소시아네이트, 이소포론디이소시아네이트 등이 있으나, 이들 디이소시아네이트 중, 4,4'-디페닐메탄디이소시아네이트 등이 사용될 수 있으며, 상기 열거 군에서 1종 또는 2종 이상의 혼합물을 사용하는 것이 바람직하다. Non-limiting examples of the diisocyanate used in the preparation of the polyurethaneurea elastic yarn in the present invention are 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexa Methylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, and the like. Among these diisocyanates, 4,4'-diphenylmethane diisocyanate, etc. It may be used, it is preferable to use one or a mixture of two or more in the above enumerated group.
본 발명에서 사용되는 폴리올은 폴리테트라메틸렌에테르 글리콜, 폴리트리메틸렌에테르 글리콜, 폴리프로필렌 글리콜, 폴리카보네이트디올, 알킬렌옥사이드와 락톤모노머의 혼합물과 폴리(테트라메틸렌에테르)글리콜의 공중합체, 3-메틸-테트라히드로푸란과 테트라히드로푸란의 공중합체 등에서 1종 또는 이들의 2종 이상의 혼합물로 예시할 수 있으나, 반드시 이들로 제한되는 것은 아니다.The polyols used in the present invention are polytetramethylene ether glycol, polytrimethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymers of alkylene oxide and lactone monomers and poly (tetramethylene ether) glycol, 3-methyl In the copolymer of tetrahydrofuran and tetrahydrofuran and the like, it can be exemplified as one or a mixture of two or more thereof, but is not necessarily limited thereto.
이때, 상기 예비중합체의 NCO%는 폴리우레탄우레아 탄성사로서의 적정한 물성 발현을 위하여 2.30 내지 3.00%의 범위를 갖게 하여 하드 세그먼트의 함량을 적정하게 유지하는 것이 바람직하다. 만약 예비 중합체의 NCO%가 2.30% 미만이거나 3.00%를 초과하면 탄성사의 심각한 물성 저하가 초래된다.At this time, the NCO% of the prepolymer is preferably in the range of 2.30 to 3.00% to properly maintain the physical properties of the polyurethane urea elastic yarn to maintain the content of the hard segment. If the NCO% of the prepolymer is less than 2.30% or more than 3.00%, a serious decrease in physical properties of the elastic yarn is caused.
본 발명에서 사용하는 폴리올은 폴리올 내에 부탄올 200 내지 3000ppm이 첨가된 것이 특징인데, 폴리올 내 부탄올(butanol)을 첨가하면, 디이소시아네이트와 결합하여 짧은 길이의 고분자 사슬(polymer chain)을 형성하고, 이 짧은 길이의 사슬이 기존의 긴 고분자 사슬 사이에서 가소제(plasticizer)의 역할을 해 폴리우레탄우레아 탄성사의 신도가 향상되는 효과가 있다. The polyol used in the present invention is characterized in that 200 to 3000 ppm of butanol is added to the polyol. When the butanol in the polyol is added, it is combined with diisocyanate to form a short length polymer chain. The chain of length acts as a plasticizer between existing long polymer chains, thereby improving the elongation of polyurethaneurea elastic yarn.
폴리올 내에 첨가되는 부탄올이 200ppm 미만이면, 신도 향상 효과가 미미하고, 3000ppm을 초과할 경우 폴리우레탄우레아 탄성사의 물성이 저하된다. When the butanol added in the polyol is less than 200 ppm, the elongation improving effect is insignificant, and when it exceeds 3000 ppm, the physical properties of the polyurethane urea elastic yarn decrease.
한편, 상기 사슬 연장제로는 디아민류가 사용되며, 본 발명에서는 에틸렌디아민 (Ethylenediamine)을 70 내지 100mol%, 보조 사슬 연장제로 1,2-디아미노프로판(1,2-diaminopropane)을 0 내지 30mol% 혼합하여 사용하는 것이 바람직하다. Meanwhile, diamines are used as the chain extender, and in the present invention, 70 to 100 mol% of ethylenediamine and 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender. It is preferable to mix and use.
폴리우레탄우레아 탄성사에 물리적인 힘을 가해 신장시키면 하드 세그먼트(hard segment)의 변형이 발생하는데, 에틸렌디아민은 강한 수소 결합을 형성하여 신장에 저항을 하는 반면 1,2-디아미노프로판은 상대적으로 신장에 대한 저항이 약화되므로, 보조 쇄연장제로 1,2-디아미노프로판을 혼합하여 사용할 경우 탄성사의 신도가 향상될 수 있다. 따라서 사슬 연장제 및 보조 사슬 연장제의 함량이 상기 범위를 벗어나게 되면, 탄성사의 신도 향상 효과가 최대한 발현되기 어렵다.Physical stretching of polyurethaneurea elastic yarn causes deformation of hard segments. Ethylenediamine forms strong hydrogen bonds to resist stretching, while 1,2-diaminopropane is relatively elongated. Since resistance to weakens, the elongation of elastic yarn may be improved when 1,2-diaminopropane is used as an auxiliary chain extender. Therefore, when the content of the chain extender and the auxiliary chain extender is out of the above range, the elongation improving effect of the elastic yarn is hardly expressed.
또한, 폴리우레탄우레아의 사슬 종결제로는 1관능기를 갖는 아민, 예를 들어 디에틸아민을 반드시 포함하고, 모노에탄올아민, 디메틸아민, 부틸아민, 사이클로헥실아민 등에서 선택된 1종 또는 2종 이상을 혼합하여 사용할 수 있다.In addition, the chain terminator of polyurethaneurea necessarily contains an amine having one functional group, for example, diethylamine, and mixes one or two or more selected from monoethanolamine, dimethylamine, butylamine, cyclohexylamine, and the like. Can be used.
상기 열거된 보조 사슬종결제는 쉽게 탈락되지 않는다. 따라서 사슬 종결제와 보조 사슬 종결제를 혼합하여 사용하면, 기존의 사슬 종결제인 디에틸아민을 단독으로 사용했을 때와 달리 쉽게 탈락되지 않아서 방사 중 후중합 억제를 통해 원사 IV를 하향시킬 수 있고, 이로 인해 탄성사의 신도 향상이 가능한 것이다.The auxiliary chain terminators listed above are not easily eliminated. Therefore, when the chain terminator and the auxiliary chain terminator are used in combination, unlike the conventional chain terminator, diethylamine, it is not easily eliminated, and the yarn IV can be lowered through post-polymerization inhibition during spinning. Therefore, the elongation of the elastic yarn can be improved.
상기의 물질 중 선택된 1종의 보조 사슬 종결제의 함량은 0 내지 50mol% 이하가 바람직하며, 50mol%를 초과하는 경우 후중합의 과도한 억제로 인해 방사에 적합한 점도 형성이 어렵고, 방사 공정성이 미흡해질 수 있다.The content of at least one auxiliary chain terminator selected from the above materials is preferably 0 to 50 mol% or less, and when it exceeds 50 mol%, it is difficult to form a viscosity suitable for spinning due to excessive suppression of postpolymerization and insufficient spinning processability. Can be.
2차 중합 시 점도 안정제로 디에틸렌트리아민(Diethylenetriamine) 또는 트리에틸렌테트라아민(triethylenetetramine)이 사용될 수 있으나, 이에 한정되는 것은 아니다.Diethylenetriamine or triethylenetetramine may be used as the viscosity stabilizer in the second polymerization, but is not limited thereto.
생산 직후(1주일 이내) 탄성사의 IV(Intrinsic viscosity, 중합도)를 1.0 내지 1.5 이하로 유지할 경우, 1.5 초과인 탄성사 대비 고분자 사슬(polymer chain)의 길이가 감소하여 고분자 사슬 간 꼬임(entanglement)의 확률이 낮아지기 때문에 탄성사의 신도를 향상시킬 수 있다. Immediately after production (within one week), if the IV (Intrinsic viscosity) of the elastic yarn is maintained at 1.0 to 1.5 or less, the length of the polymer chain is reduced compared to the elastic yarn of more than 1.5, so that the probability of entanglement between the polymer chains is reduced. Since this becomes low, the elongation of the elastic yarn can be improved.
또한, 본 발명에서는 자외선, 대기 스모그 및 스판덱스 가공에 수반되는 열처리 과정 등에 의한 폴리우레탄우레아의 변색과 물성 저하를 방지하기 위해, 방사원액에 입체장애 페놀계 화합물, 벤조퓨란-온계 화합물, 세미카바자이드계 화합물, 벤조 트리아졸계 화합물, 중합체성 3급 아민 안정제 등을 적절히 조합하여 첨가할 수 있다.In addition, in the present invention, 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.
나아가, 본 발명의 폴리우레탄우레아 탄성사는 상기 성분 외에도 이산화티탄, 마그네슘 스테아레이트 등과 같은 첨가제를 포함할 수 있다. Furthermore, 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.
전술한 바와 같은 제조방법으로 제조된 폴리우레탄우레아 탄성사는 신도가 500% 이상이고, 최대연신비율(Maximum Draw Ratio)이 4.8 이상이며, 열 안정성이 40% 이상인 것을 특징으로 한다. Polyurethane urea elastic yarn prepared by the manufacturing method as described above is characterized in that the elongation is more than 500%, the maximum draw ratio (Maximum Draw Ratio) is 4.8 or more, the thermal stability is 40% or more.
또한, 본 발명의 바람직한 실시예에 따른 방법에 의해 제조된 폴리우레탄우레아 탄성사는 생산 직후(1주일 이내) IV가 1.0 내지 1.5이하를 유지하는 것을 특징으로 한다. In addition, the polyurethaneurea elastic yarn prepared by the method according to a preferred embodiment of the present invention is characterized in that the IV immediately after production (within a week) maintains 1.0 to 1.5 or less.
이하, 구체적인 실시예 및 비교예를 통하여 본 발명의 우수성을 상세하게 설명하고자 하나, 이러한 실시예들은 단지 본 발명을 예증하기 위한 것으로서 본 발명의 범위를 제한하는 것으로 해석되어서는 안 된다. Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but these examples are merely to illustrate the present invention and should not be construed as limiting the scope of the present invention.
후술하는 실시예 및 비교예에서 언급한 폴리머의 NCO% 측정법 및 폴리우레탄우레아 탄성사의 물성 은 아래와 같이 측정하였다.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% 측정법* NCO% measurement
NCO%=[100*2*NCO화학식량*(캡핑비-1)]/{(디이소시아네이트분자량*캡핑비)+폴리올 분자량}NCO% = [100 * 2 * NCO chemical formula * (capping ratio-1)] / {(diisocyanate molecular weight * capping ratio) + polyol molecular weight}
상기 식에서 캡핑비는 디이소시아네이트 몰비/폴리올 몰비이다.Where the capping ratio is the diisocyanate molar ratio / polyol molar ratio.
*점도 경시율 측정법* Viscosity lapse measurement method
1L 반응기에 2차 중합물 800g을 계량하고, 중합물의 온도를 40℃로 유지하면서(40℃ 온수를 반응기 jacket에 통수) 8rpm의 속도로 교반하면서 24hr 간격으로 점도를 측정한 후 시간당 점도 경시율을 계산한다. 800 g of the secondary polymer was weighed in a 1 L reactor, and the viscosity was measured at 24 hr intervals while stirring at a rate of 8 rpm while maintaining the temperature of the polymer at 40 ° C. (40 ° C. hot water was passed through the reactor jacket). do.
시간당 점도경시율[Poise/hr] = (72hr 교반 후 점도 - 초기 점도)/72Viscosity elapsed per hour [Poise / hr] = (viscosity after 72hr stirring-initial viscosity) / 72
*원사의 강도 및 신도* Strength and elongation of yarn
자동 강신도 측정장치(MEL기, Textechno社 제조)를 이용하여 load cell 32cN, 시료길이 10cm, 인장속도 100 cm/min로 하여 측정한다. 이때 파단 시의 강도와 신도 값이 측정되며, 탄성사 200 % 신장 시에 걸리는 하중 200% 모듈러스(modulus)도 측정된다. Using an automatic elongation measuring device (MEL machine, manufactured by Textechno), the measurement is performed at load cell 32 cN, sample length 10 cm, and tensile speed 100 cm / min. At this time, the strength and elongation at break are measured, and the load 200% modulus applied at 200% elongation of elastic yarn is also measured.
*PR(권취 수축율%)* PR (% Winding Shrinkage)
탄성사는 사종에 따라 차이는 있으나, 어느 정도 스트레치(stretch)하여 지관에 감기도록 되어 있는데, 권취 수축율은 지관에 감겨있는 상태에서 해사 후 탄성사가 수축되어 길이가 변화하는 정도를 말한다. 탄성사를 contact roller 위에 거치시키고, 시작점의 0점 위치에 데니어(denier)에 맞는 분동을 건 뒤, 자동으로 탄성사를 1바퀴 해사시켜 10초 경과 후 수축이 발생한 길이를 측정하여 권취 수축율을 계산한다.The elastic yarn is different depending on the type of yarn, but it is stretched to some extent to be wound on the branch pipe. The winding shrinkage rate refers to the degree of change in the length of the elastic yarn that is contracted after dissolution in the state wound around the branch pipe. The elastic yarn is mounted on the contact roller, a weight corresponding to the denier is placed at the zero point of the starting point, and the elastic yarn is automatically dismissed one round to measure the length of shrinkage after 10 seconds.
권취 수축율% = (장비 회전 길이(Roller 1회전 시 원주 길이, 533mm) - 수축된 원사의 길이) / 장비 회전 길이(Roller 1회전 시 원주 길이, 533mm) * 100Winding Shrinkage% = (Length of Equipment Rotation (Circumference of 1 Roller, 533mm)-Length of Shrink Yarn) / Length of Rotation of Equipment (Roll of Cylinder, 533mm) * 100
*DM(dynamic modulus)* DM (dynamic modulus)
수동 DM 측정 장치(㈜룩테크社 제조)로 측정한다. DM 측정 장치는 알루미늄 소재에 표면이 크롬으로 코팅된 4개의 roller와 가운데 플라스틱(폴리아세탈, polyacetal) sensor로 이루어진다. 첫 번째 roller는 원사를 공급해주는 feed roller이고 원사는 도 1과 같은 경로를 거쳐 sensor에서 원사에 걸리는 tension을 측정한 뒤 세 번째 roller를 지나 winder roller에 감김. 첫 번째 roller와 세 번째 roller의 속도 비율을 1:3으로 세팅(draft ratio 3.0)하여 약 5분간 해사하며 sensor에서 측정되는 원사 tension값을 DM(dynamic modulus)값으로 정한다.It is measured by a manual DM measuring device (manufactured by Luck Tech Co., Ltd.) The DM measuring device consists of four rollers coated with chromium on aluminum and a central plastic (polyacetal) sensor. The first roller is a feed roller that supplies the yarn, and the yarn is wound on the winder roller after the third roller after measuring the tension applied to the yarn in the sensor through the path as shown in FIG. The speed ratio of the first roller and the third roller is set to 1: 3 (draft ratio 3.0) to solve for about 5 minutes, and the yarn tension value measured by the sensor is defined as the DM (dynamic modulus) value.
[도 1]1
Figure PCTKR2017011324-appb-I000001
Figure PCTKR2017011324-appb-I000001
*Max. DR(Maximum Draw Ratio)* Max. Maximum Draw Ratio (DR)
수동 DM 측정 장치(㈜룩테크社 제조)를 사용하되, 탄성사의 사도와 롤러의 속도를 다르게 하여 측정한다. 도 2와 같이, 롤러의 속도를 첫 번째는 50rpm, 두 번째는 전원을 끄고, 세 번째는 200rpm, 네 번째는 180rpm으로 세팅한다. 원사는 첫 번째 롤러에서 1번 감고, 두 번째 롤러는 그냥 지나가고, 세 번째 롤러에서 8번 감되, 세라믹 가이드는 거치지 않도록 한다. 세팅 후 시작하여 1분간 사절 여부를 확인하고, 사절이 일어나지 않으면, 세 번째와 네 번째 roller의 회전수를 각각 올려가며 반복한다. 만약 세 번째 롤러의 속도를 216rpm으로 세팅 후 30초 경과 후에 사절이 발생하면 215rpm, 30초 경과 전에 사절이 발생하면 214rpm으로 최대 속도값을 취하여 Max. DR을 계산하며, Max. DR값이 클수록 고신도 임을 의미한다.Use a manual DM measuring device (manufactured by Luck Tech Co., Ltd.), but measure the elastic yarn's yarn and the roller's speed differently. 2, the speed of the roller is set to 50 rpm in the first, the second in the power off, the third 200 rpm, the fourth is set to 180 rpm. Yarn is wound once on the first roller, the second roller just passes, eight times on the third roller, but not through the ceramic guides. Start after setting and check for 1 minute of trimming. If no trimming occurs, repeat the third and fourth rollers by increasing the number of revolutions. If trimming occurs 30 seconds after the third roller speed is set to 216 rpm, if thread trimming occurs after 215 rpm, 30 seconds later, the maximum speed value will be set to 214 rpm. Calculate the DR, Max. The larger the DR value, the higher the reliability.
Max. DR = 사절이 발생하지 않은 상태의 세 번째 롤러 rpm값 / 첫번째 롤러 rpm값Max. DR = 3rd roller rpm value / 1st roller rpm value without trimming
[도 2]2
Figure PCTKR2017011324-appb-I000002
Figure PCTKR2017011324-appb-I000002
*원사 power (5th unload@200%)Yarn power (5th unload @ 200%)
자동 강신도 측정장치(MEL기, Textechno社 제조)를 이용하여 load cell 32cN, 시료 길이 10cmX20가닥, 인장속도 100cm/min으로 300% 5회 반복 신장하여 5회차 회복 중 200% 구간에서의 파워를 측정한 뒤 가닥 수와 de로 나눠준다.Using an automatic elongation measuring device (MEL machine, manufactured by Textechno Co.), load cell 32cN, sample length 10cmX20 strand, 300% stretched five times at a tensile speed of 100cm / min, and measured the power in the 200% section during the fifth recovery. Divide by the number of back strands and de.
*열처리 후 파워 (5th unload @200%)Power after heat treatment (5th unload @ 200%)
원사를 대기 상태에서 100% 신장(17.0→34.0cm)시켜 사각 틀에 알루미늄 테이프로 고정한 뒤, 미니 텐터(㈜대림스타렛社 제조, DL-2015)를 사용하여 190 온도에 1분간 건열 처리를 하고, 워터 배스(㈜HAHN SHIN SCIENIIFIC Co.社 제조, Water bath)를 사용하여 100℃로 30분간 비수 처리 한다. 이 때 원사를 고정한 틀은 100 물 속에 충분히 잠기도록 한다. 자동 강신도 측정장치(MEL기, Textechno社 제조)를 이용하여 load cell 32cN로 300% 5회 반복 신장하여 5회차 회복 중 200% 구간에서의 파워를 측정한 뒤 원사 가닥 수와 de로 나눠준다.The yarn was stretched 100% in air (17.0 → 34.0cm) and fixed with aluminum tape in a square frame, and then dried and treated at 190 ° C for 1 minute using a mini tenter (manufactured by Daelim Starlet Co., Ltd., DL-2015). Using a water bath (manufactured by HAHN SHIN SCIENIIFIC Co., Ltd., Water bath), perform non-water treatment at 100 ° C for 30 minutes. At this time, the frame where the yarn is fixed should be sufficiently submerged in 100 water. Using an automatic elongation measuring device (MEL machine, manufactured by Textechno Co.), stretch 300% 5 times with a load cell 32cN, measure the power at 200% of the 5th recovery, and divide it by the number of yarn strands and de.
*열 안정성(열처리 전/후 파워유지율) [%]* Thermal stability (Power retention before and after heat treatment) [%]
열처리 후 원사 파워(5th unload @200%) / 미처리 원사 파워(5th unload @200%) X 100Yarn power after heat treatment (5 th unload @ 200%) / Untreated yarn power (5 th unload @ 200%) X 100
*원사 I.V.(Intrinsic Viscosity, 고유 점도)* Yarn I.V. (Intrinsic Viscosity, Intrinsic Viscosity)
탄성사를 petroleum ether에 10분간 담궈 유제를 제거하고, 90℃ 오븐에서 20분간 건조하여 잔여 petroleum ether를 증발시킨다. DMAc 1kg에 LiCL 0.4524g을 넣고 상온에서 완전 용해시켜 0.01M LiCL DMAc를 조제한다. 유제를 제거한 탄성사를 0.01M LiCL DMAc에 약 0.5% 농도로 넣고, 약 4hr 교반하여 충분히 용해시킨 후 점도관에 투입한다. 25℃ 항온조 점도관을 넣고 약 20분간 안정화 시킨 후 정해진 간격의 눈금 사이를 통과하는 시간을 측정하여 blank값과 비교하여 R.V.(relative viscosity)를 계산한 후 I.V.를 계산한다. 이 때 원사 내 포함되어 있는 무기물의 함량을 반영한다.The elastic yarn is immersed in petroleum ether for 10 minutes to remove the emulsion, and dried in an oven at 90 ° C. for 20 minutes to evaporate the remaining petroleum ether. 0.4 kg of LiCL was added to 1 kg of DMAc, and completely dissolved at room temperature to prepare 0.01 M LiCL DMAc. The elastic yarn from which the emulsion is removed is placed in a concentration of about 0.5% in 0.01M LiCL DMAc, stirred for about 4 hours, and dissolved in a viscous tube. After 25 ° C thermostat viscous tube is stabilized for about 20 minutes, measure the time to pass between the intervals of the predetermined interval and compare the blank value to calculate R.V. (relative viscosity) and calculate I.V. This reflects the content of minerals contained in the yarn.
R.V. = (T1 - T0) / T0 * 2R.V. = (T1-T0) / T0 * 2
I.V. = SQRT (R.V. - 2*LN(1 + R.V. / 2)) / 0.5 * (1-무기물 함량%)I.V. = SQRT (R.V.-2 * LN (1 + R.V. / 2)) / 0.5 * (1-% inorganic content)
(T1 = 시료가 점도관의 일정 간격 사이를 통과하는데 걸린 시간, T0 = blank 물질이 점도관의 일정 간격 사이를 통과하는데 걸린 시간, blank = 0.01M LiCL DMAc)(T1 = time it took for sample to pass between intervals of viscous tubes, T0 = blank time it took for material to pass between intervals of viscous tubes, blank = 0.01M LiCL DMAc)
실시예 1Example 1
4,4'-디페닐메탄디이소시아네이트와 부탄올이 1200ppm 포함된 폴리테트라메틸렌 글리콜을 캡핑비(CR) 1.73으로 NCO%가 2.75%가 되도록 제조하였다. 사슬 연장제로는 에틸렌디아민을 100mol% 사용하였고, 사슬 종결제로는 디에틸아민을 70mol%, 사이클로헥실아민을 30mol% 혼합하여 사용하였으며, 사슬 연장제와 사슬 종결제의 비율은 10:1로 하였고, 사용된 아민은 총 농도 7몰%로 제조하였으며, 용매로는 디메틸아세트아마이드를 사용하여 최종 중합물의 고형분 함량이 35중량%인 폴리우레탄우레아 방사 용액을 얻었다.Polytetramethylene glycol containing 1200 ppm of 4,4'-diphenylmethane diisocyanate and butanol was prepared so that the NCO% was 2.75% with a capping ratio (CR) of 1.73. 100 mol% of ethylenediamine was used as the chain extender, 70 mol% of diethylamine and 30 mol% of cyclohexylamine were used as the chain terminator, and the ratio of the chain extender and the chain terminator was 10: 1. The amine used was prepared in a total concentration of 7 mol%, and 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 900m/min 속도로 건식 방사하여 40데니아 3 필라멘트의 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.The spinning stock solution obtained as described above was dry spun at 900 m / min to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof are shown in Table 1 below.
실시예 2Example 2
사슬 연장제로 에틸렌디아민을 90mol%, 1,2-프로판디아민을 10mol% 혼합하여 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that 90 mol% of ethylenediamine and 10 mol% of 1,2-propanediamine were mixed as a chain extender, and the physical properties thereof were evaluated in Table 1 below. Indicated.
실시예 3Example 3
사슬 연장제로 에틸렌디아민을 80mol%, 1,2-프로판디아민을 20mol% 혼합하여 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that 80 mol% of ethylenediamine and 20 mol% of 1,2-propanediamine were mixed as a chain extender, and the physical properties thereof were evaluated in Table 1 below. Indicated.
실시예 4Example 4
사슬 연장제로 에틸렌디아민 80mol%와 1,2-프로판디아민 20mol%를 혼합하여 사용하고, 사슬 종결제로 디에틸아민 50mol%와 사이클로헥실아민 50mol%를 혼합하여 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Same as Example 1 except that 80 mol% of ethylenediamine and 20 mol% of 1,2-propanediamine were mixed as a chain extender, and 50 mol% of diethylamine and 50 mol% of cyclohexylamine were used as a chain terminator. It was carried out to prepare a polyurethane urea elastic yarn, it is shown in Table 1 to evaluate the physical properties.
실시예 5Example 5
사슬 연장제로 에틸렌디아민 70mol%와 1,2-프로판디아민 30mol%를 혼합하여 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Polyurethane urea elastic yarn was prepared in the same manner as in Example 1, except that 70 mol% of ethylenediamine and 30 mol% of 1,2-propanediamine were mixed as a chain extender, and the physical properties thereof are shown in Table 1 below. It was.
실시예 6Example 6
예비 중합체 조제 시 부탄올이 2400ppm 포함된 폴리테트라메틸렌 글리콜을 사용하고, 사슬 연장제로 에틸렌디아민 90mol%와 1,2-프로판디아민 10mol%를 혼합하여 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.The preparation of the prepolymer was carried out in the same manner as in Example 1 except that polytetramethylene glycol containing 2400 ppm of butanol was used, and 90 mol% of ethylenediamine and 10 mol% of 1,2-propanediamine were mixed as a chain extender. Polyurethane urea elastic yarn was prepared, and the physical properties thereof are shown in Table 1.
비교예 1Comparative Example 1
사슬 종결제로 디에틸아민을 100mol% 사용하는 것을 제외하고는 실시예 1 과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Except that 100 mol% of diethylamine was used as the chain terminator, the polyurethaneurea elastic yarn was prepared in the same manner as in Example 1, and the physical properties thereof are shown in Table 1 below.
비교예 2Comparative Example 2
예비 중합체 조제 시 부탄올이 포함되지 않은 폴리테트라메틸렌 글리콜을 사용하고, 사슬 종결제로 디에틸아민을 100mol% 사용하는 것을 제외하고는 실시예 1 과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that polytetramethylene glycol without butanol was used and 100 mol% of diethylamine was used as the chain terminator when preparing the prepolymer. It is shown in Table 1 to evaluate.
비교예 3Comparative Example 3
4,4'-디페닐메탄디이소시아네이트와 부탄올이 포함되지 않은 폴리테트라메틸렌 글리콜을 캡핑비(CR) 1.83으로 NCO%가 3.10%가 되도록 제조하고, 사슬 종결제로 디에틸아민을 100mol% 사용하는 것을 제외하고는 실시예 1 과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.Polytetramethylene glycol without 4,4'-diphenylmethane diisocyanate and butanol was prepared with a capping ratio (CR) of 1.83 so that the NCO% was 3.10%, and 100 mol% of diethylamine was used as the chain terminator. Except that was prepared in the same manner as in Example 1 to prepare a polyurethane urea elastic yarn, the physical properties are shown in Table 1 to evaluate the properties.
비교예 4Comparative Example 4
예비 중합체 조제 시 부탄올이 3600ppm 포함된 폴리테트라메틸렌 글리콜을 사용하고, 사슬 연장제로 에틸렌디아민 90mol%와 1,2-프로판디아민 10mol%를 혼합하여 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.When preparing the prepolymer, the process was carried out in the same manner as in Example 1 except that polytetramethylene glycol containing 3600 ppm of butanol was used, and 90 mol% of ethylenediamine and 10 mol% of 1,2-propanediamine were mixed as a chain extender. Polyurethane urea elastic yarn was prepared, and the physical properties thereof are shown in Table 1.
NCO%NCO% buOH[ppm]buOH [ppm] EDA/1,2-PDAEDA / 1,2-PDA DEA/CHADEA / CHA 점도경시율Viscosity elongation rate 강도[g/d]Strength [g / d] 신도[%]Elongation [%] PR[%]PR [%] DM[g]DM [g] Max.DRMax.DR 5th unload@ 200%[g/d]5 th unload @ 200% [g / d] 열안정성[%]Thermal Stability [%] 원사I.V.Yarn I.V.
실시예1Example 1 2.752.75 12001200 100/0100/0 70/3070/30 8282 1.371.37 538538 7.87.8 7.57.5 5.215.21 0.0290.029 51.551.5 1.341.34
실시예2Example 2 2.752.75 12001200 90/1090/10 70/3070/30 7474 1.421.42 545545 7.47.4 7.07.0 5.355.35 0.0280.028 50.950.9 1.301.30
실시예3Example 3 2.752.75 12001200 80/2080/20 70/3070/30 6363 1.381.38 552552 6.86.8 6.46.4 5.415.41 0.0270.027 49.549.5 1.281.28
실시예4Example 4 2.752.75 12001200 80/2080/20 50/5050/50 4646 1.251.25 564564 6.46.4 6.06.0 5.525.52 0.0250.025 40.040.0 1.141.14
실시예5Example 5 2.752.75 12001200 70/3070/30 70/3070/30 5252 1.361.36 556556 6.76.7 6.26.2 5.435.43 0.0240.024 45.145.1 1.271.27
실시예6Example 6 2.752.75 24002400 90/1090/10 70/3070/30 4848 1.121.12 579579 6.36.3 5.95.9 5.585.58 0.0240.024 41.341.3 1.221.22
비교예1Comparative Example 1 2.752.75 12001200 100/0100/0 100/0100/0 9595 1.181.18 500500 14.314.3 9.79.7 4.554.55 0.0300.030 51.451.4 1.561.56
비교예2Comparative Example 2 2.752.75 00 100/0100/0 100/0100/0 103103 1.151.15 470470 15.315.3 10.210.2 4.404.40 0.0310.031 52.452.4 1.641.64
비교예3Comparative Example 3 3.103.10 00 100/0100/0 100/0100/0 121121 1.011.01 450450 18.218.2 14.314.3 4.034.03 0.0330.033 54.754.7 1.781.78
비교예4Comparative Example 4 2.752.75 36003600 90/1090/10 70/3070/30 3434 1.041.04 610610 5.85.8 5.35.3 5.705.70 0.0210.021 36.836.8 1.151.15
※ buOH = butanol※ buOH = butanol
※ 1,2-PDA = 1,2-diaminopropane (보조 사슬 연장제)※ 1,2-PDA = 1,2-diaminopropane (auxiliary chain extender)
※ CHA = cyclohexylamine (보조 사슬 종지제)※ CHA = cyclohexylamine (auxiliary chain terminator)
※ 40de/3fila., 방사 속도 900m/min 기준※ 40de / 3fila., Based on 900m / min spinning speed
상기 [표 1]과 같이, 부탄올이 3000ppm 미만으로 포함된 폴리올을 사용하고, 보조 사슬 연장제를 30mol% 이하, 보조 사슬 종결제를 50mol% 이하로 사용할 경우, 원사의 열 안정성이 40% 이상으로 우수하면서도 높은 신도와 Max. DR이 얻어짐을 확인할 수 있다.As shown in [Table 1], when using a polyol containing butanol less than 3000ppm, when the auxiliary chain extender 30mol% or less, the auxiliary chain terminator 50mol% or less, the thermal stability of the yarn to 40% or more Excellent, high elongation and Max. It can be confirmed that DR is obtained.
이상, 본 발명의 바람직한 예에 대해 어느 정도 특정적으로 설명했지만, 이것들에 대해 여러 가지의 변경을 할 수 있는 것은 당연하다. 따라서, 본 발명의 범위 및 정신으로부터 이탈하는 일 없이, 본 명세서 중에서 특정적으로 기재된 모양과는 다른 모양으로 본 발명을 실시할 수 있다는 것은 당연한 것으로 이해될 수 있다.As mentioned above, although the preferable example of this invention was demonstrated to some extent, it is natural that various changes can be made about these. Therefore, it can be understood that the present invention can be carried out in a shape different from that specifically described in the present specification, without departing from the scope and spirit of the present invention.

Claims (5)

  1. 부탄올(butanol)이 200 내지 3000ppm 이하로 첨가된 폴리올 및 디이소시아네이트를 중합하여 폴리우레탄 전구체를 제조한 후 용매에 용해하여 예비중합체 용액을 제조하는 단계; Preparing a prepolymer solution by polymerizing a polyol and diisocyanate to which butanol is added in an amount of 200 to 3000 ppm or less to prepare a polyurethane precursor, and then dissolving it in a solvent;
    상기 예비중합체에 사슬 연장제로 에틸렌디아민 (Ethylenediamine)을 70 내지 100mol%, 보조 사슬 연장제로 1,2-디아미노프로판(1,2-diaminopropane)을 0 내지 30mol%,, 사슬 종결제로 디에틸아민(diethylamine)을 50 내지 100mol%, 보조 사슬 종결제를 0 내지 50mol% 첨가하고 반응시켜 폴리우레탄우레아 방사원액을 제조하는 단계; 및70 to 100 mol% of ethylenediamine as a chain extender in the prepolymer, 0 to 30 mol% of 1,2-diaminopropane as an auxiliary chain extender, and diethylamine as a chain terminator. adding 50 to 100 mol% diethylamine) and 0 to 50 mol% auxiliary chain terminator and reacting to prepare a polyurethaneurea spinning stock solution; And
    상기 폴리우레탄우레아 방사원액을 방사 및 권취하는 단계를 포함하고, Spinning and winding up the polyurethaneurea spinning stock solution;
    신도가 500% 이상이고, 최대연신비율(Maximum Draw Ratio)이 4.8 이상이며, 열 안정성이 40% 이상인 것을 특징으로 하는 폴리우레탄우레아 탄성사의 제조 방법.Elongation is 500% or more, the maximum draw ratio (Maximum Draw Ratio) is 4.8 or more, the thermal stability is a manufacturing method of the polyurethane urea elastic yarn, characterized in that 40% or more.
  2. 제1항에 있어서, The method of claim 1,
    상기 예비중합체 NCO%는 2.30 내지 3.00%인 것을 특징으로 하는 폴리우레탄우레아 탄성사의 제조 방법.The prepolymer NCO% is a method of producing a polyurethane urea elastic yarn, characterized in that 2.30 to 3.00%.
  3. 제1항에 있어서, The method of claim 1,
    사슬 종결제는 디에틸아민을 반드시 포함하고, 모노에탄올아민, 디메틸아민, 부틸아민, 사이클로헥실아민으로 이루어진 군에서 선택된 1종 또는 그 이상을 혼합하여 사용하는 것을 특징으로 하는 폴리우레탄우레아 탄성사의 제조 방법.The chain terminator necessarily includes diethylamine, and the polyurethaneurea elastic yarn is manufactured by mixing one or more selected from the group consisting of monoethanolamine, dimethylamine, butylamine, and cyclohexylamine. Way.
  4. 제1항 내지 제3항 중 어느 한 항의 방법으로 제조되고, 신도가 500% 이상이고, 최대연신비율(Maximum Draw Ratio)이 4.8 이상이며, 열 안정성이 40% 이상인 것을 특징으로 하는 폴리우레탄우레아 탄성사.A polyurethaneurea elastic yarn manufactured by the method of any one of claims 1 to 3, having an elongation of 500% or more, a maximum draw ratio of 4.8 or more, and a thermal stability of 40% or more. .
  5. 제4항에 있어서, The method of claim 4, wherein
    폴리우레탄우레아 탄성사의 생산 직후(1주일 이내) 중합도(IV)는 1.0 이상 1.5 이하를 유지하는 것을 특징으로 하는 폴리우레탄우레아 탄성사.Polyurethane urea elastic yarn, characterized in that the polymerization degree (IV) is maintained at 1.0 or more and 1.5 or less immediately after production of the polyurethane urea elastic yarn (within one week).
PCT/KR2017/011324 2016-10-24 2017-10-13 Polyurethaneurea elastic yarn having high elongation, and manufacturing method therefor WO2018080063A1 (en)

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