WO2015088060A1 - Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor - Google Patents

Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor Download PDF

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Publication number
WO2015088060A1
WO2015088060A1 PCT/KR2013/011407 KR2013011407W WO2015088060A1 WO 2015088060 A1 WO2015088060 A1 WO 2015088060A1 KR 2013011407 W KR2013011407 W KR 2013011407W WO 2015088060 A1 WO2015088060 A1 WO 2015088060A1
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WO
WIPO (PCT)
Prior art keywords
chain
elastic yarn
polyurethane urea
cyclohexanamine
mdi
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PCT/KR2013/011407
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French (fr)
Korean (ko)
Inventor
이재명
진중성
강연수
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주식회사 효성
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Priority to PCT/KR2013/011407 priority Critical patent/WO2015088060A1/en
Publication of WO2015088060A1 publication Critical patent/WO2015088060A1/en

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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 substituted diisocyanates; Chain extenders; And chain dispersants including cyclohexanamine; 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 includes one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, and the chain terminating agent includes a cyclohexaneamine-based thermosettable polyurethaneurea.
  • the chain dispersant may include 10 to 80 mol% of cyclohexaneamine.
  • the MDI-isomer may be 2,4'-MDI.
  • heat-setability is excellent even at low temperatures, and heat-sensitive fibers are embrittled by heat by performing heat setting at low temperatures on fabrics interwoven with heat-sensitive fibers and the like. It is effective in preventing the curling or streak of the fabric due to the small change in the physical properties of the yarn over time.
  • 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 substituted aliphatic 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'
  • the MDI isomer included in the diisocyanate may be preferably 2,4'-MDI, the content may include 10 to 25 mol% based on the total diisocyanate.
  • the content of 2,4'-MDI is less than 2%, the improvement in setability is insufficient, and if it exceeds 25 mol%, the yarn modulus may sharply decrease.
  • the 2,4'-MDI has a three-dimensional structure, the intermolecular hydrogen bonds or intramolecular hydrogen bonds in the hard segment are weakened, thereby exhibiting the same effect as that of increasing the content of the soft segment. In this way, a lot of soft domains are formed, thereby obtaining an elastic yarn having excellent setability.
  • the capping ratio when the capping ratio is high, it is difficult to control the viscosity of the polymer due to the high content of the hard segment.
  • the 2,4'-MDI acts as the soft segment, it is also possible to increase the capping ratio to about 2.0. It may be possible.
  • 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.
  • the chain extender is for improving the flexibility and heat resistance of the elastic yarn, it can be used alone or mixed with 1,2-diaminopropane.
  • 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 the polyurethane urea.
  • diethylamine is used as a conventional terminator, the strength and modulus of the yarn due to the postpolymerization process over time. Synergy may be manifested while physical properties such as yarn elongation and Max DR 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.
  • cyclohexaneamine is used as a chain terminator, and the cyclohexaneamine suppresses the post-polymerization according to the high calorific value during the spinning process, and minimizes the change in the physical properties due to post-polymerization after yarn calcination. Since the setability is improved, even when thermal setting is performed at a low temperature, thermal taking-off of the counterpart does not occur, thereby improving the appearance of the fabric compared with the conventional one, and it is possible to prevent the curling of paper from occurring in the processed paper after the thermal setting.
  • the chain terminator may preferably include 10 to 80 mol% of cyclohexaneamine based on the total chain terminator.
  • the amount of the chain terminator is less than 10 mol%, the promotion of the postpolymerization cannot be controlled due to the excess diethylamine. If the amount of the chain terminator is greater than 80 mol%, the low modulus is caused by excessive postpolymerization inhibition. And that the increase in polymer viscosity for 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.
  • the measurement is performed at a sample length of 10 cm and a tensile speed of 100 cm / min.
  • the strength and elongation at break are measured, and the load on the yarn at 200% elongation is also measured at 200% modulus.
  • the produced yarn was stretched 100% while being exposed to the air, and then dried and heat treated at 170 ° C. for 1 minute. After cooling to room temperature, the length of the yarn was measured, and the thermal setability of the yarn was calculated according to the following equation.
  • Heat Setability (%) ⁇ (length-initial length after heat treatment) / (height length-initial length) ⁇ ⁇ 100
  • the chain extender used ethylenediamine and 1,2-propane diamine, and the chain stopper used cyclohexanamine.
  • the ratio of the chain extender and the chain dispersant was 9.5: 1
  • the ratio of ethylenediamine and 1,2-propane diamine as the chain extender was 80 mol% and 20 mol%
  • cyclohexanamine as the chain terminator was 80 mol% and 20 mol%
  • the ratio of and diethylamine was 10 mol% and 90 mol%. It was.
  • the amine used was prepared in a total concentration of 7 mol%, and dimethylacetamide was used as a solvent.
  • Example 2 It is the same as Example 1 except using polyurethane urea as 50 mol% and 50 mol% of cyclohexaneamine and diethylamine.
  • the obtained spinning stock solution was dry spun to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Table 1 below.
  • Example 2 It is the same as Example 1 except the polyurethane urea being used as 80 mol% and 20 mol% of cyclohexaneamine and diethylamine.
  • the obtained spinning stock solution was dry spun to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Table 1 below.
  • the obtained spinning stock solution was dry spun to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Table 1 below. Spinning conditions and the like of this polymerized product are the same as in Example 2.
  • Example 1 CR Disintegration Agents [CHA: DEA] Time burglar Shinto 200% M Heat Setability (%)
  • Example 1 1.65 10:90 0 days 1.06 548 6.6 58.4 10 days 1.06 542 6.7 58.2 30 days 1.05 545 6.6 58.2
  • Example 2 1.65 50:50 0 days 1.10 550 6.4 58.8 10 days 1.10 548 6.4 58.4 30 days 1.10 548 6.3 58.4
  • Example 3 1.65 80:20 0 days 1.12 552 6.5 59.2 10 days 1.13 550 6.6 59.4 30 days 1.14 556 6.5 59.0 Comparative Example 1 1.65 0: 100 0 days 1.00 538 6.6 52.7 10 days 1.07 527 6.9 50.1 30 days 1.18 518 7.5 47.7
  • a polyurethane urea elastic yarn having improved heat setability can be obtained.

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

Abstract

The present invention provides a polyurethaneurea elastic yarn having improved thermosetting properties and comprising: poly(tetramethylene ether) glycol; one or more kinds of organic diisocyanates selected from among aromatic, aliphatic, and alicyclic diisocyanates; a chain extender; and a chain terminator including cyclohexanamine.

Description

열세트성이 향상된 폴리우레탄우레아 탄성사 및 그 제조 방법Polyurethane urea elastic yarn with improved heat setability and manufacturing method
본 발명은 열세트성이 우수한 폴리우레탄우레아 탄성사의 제조 방법에 관한 것으로, 더욱 상세하게는 쇄종지제로 부틸아민을 사용하여, 열에 민감한 상대사의 열적 취하가 발생하는 문제를 개선할 수 있고, 물성 경시에 따른 변화를 최소화 할 수 있는 열세트성이 향상된 폴리우레탄우레아 탄성사 및 그 제조 방법에 관한 것이다.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.
일반적으로, 폴리우레탄우레아는 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 예비 중합체(prepolymer)를 얻고, 이 예비 중합체에 적절한 반응을 통해 폴리우레탄우레아 섬유의 방사원액을 만든 후 방사시켜 탄성사를 얻는다.In general, 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.
이러한 폴리우레탄우레아 탄성사는 높은 탄성을 갖는 고유의 특징 때문에 다양한 용도로 활발하게 사용되고 있으며, 그 용도 범위의 확대에 따라 기존의 섬유에 새로운 부가적인 특성이 계속하여 요구되고 있다.These polyurethaneurea elastic yarns are actively used for various uses because of their inherent characteristics of high elasticity, and as the use range thereof is expanded, new additional characteristics of existing fibers are continuously required.
일반적으로 탄성사는 시간 경시에 따른 후중합 과정으로 인해 원사의 강도 및 모듈러스 등의 물성 상승이 발현되는 반면에, 원사의 신도 및 Max DR 등의 물성이 감소되는 현상이 발생할 수 있다.In general, 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.
특히, 생산 시기가 다른 원사를 혼합하여 사용하는 경우, 원단의 세트 정도의 차이 및 원단의 줄(streak)를 유발시키는 문제점이 있었다.In particular, when using a mixture of yarns with different production times, there was a problem of causing a difference in the degree of set of the fabric and streaks of the fabric.
본 발명은 상술한 문제점을 해소하기 위한 것으로, 열세트성이 우수하고 경시에 따른 물성 변화가 적은 폴리우레탄우레아 탄성사를 제조함으로서, 원단의 줄(streak) 발생 억제 및 품위를 향상시키는데 그 주된 목적이 있다.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.
본 발명의 일면은, 폴리(테트라메틸렌 에테르)글리콜; 방향족, 지방족 및 치환족 디이소시아네이트 중에서 선택된 1종 또는 2종 이상의 유기 디이소시아네이트; 쇄연장제; 및 시클로헥산아민을 포함하는 쇄종지제; 를 포함하는 열세트성이 향상된 폴리우레탄우레아 탄성사를 제공한다.One aspect of the present invention, poly (tetramethylene ether) glycol; One or two or more organic diisocyanates selected from aromatic, aliphatic and substituted diisocyanates; Chain extenders; And chain dispersants including cyclohexanamine; It provides a polyurethane urea elastic yarn improved heat setability comprising a.
본 발명의 다른 면은, 폴리올과 디이소시아네이트를 1차 중합하여 예비 중합체를 수득하는 단계; 상기 예비 중합체를 유기 용매에 용해 시키고 쇄연장제 및 쇄종지제를 첨가하여 2차 중합을 수행하여 방사원액을 수득하는 단계; 및 상기 방사원액을 건식 또는 습식방사 시켜 폴리우레탄우레아 탄성사를 수득하는 단계; 를 포함하며, 상기 디이소시아네이트는 방향족, 지방족 및 지환족 디이소시아네이트 중에서 선택된 1종 또는 2종 이상의 유기 디이소시아네이트를 포함하며, 상기 쇄종지제는 시클로헥산아민을 포함하는 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조 방법을 제공한다.Another aspect of the invention, 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 includes one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, and the chain terminating agent includes a cyclohexaneamine-based thermosettable polyurethaneurea. Provided are methods for producing elastic yarns.
본 발명의 일 실시 예에서, 상기 쇄종지제는 시클로헥산아민의 함량이 10 내지 80 몰%을 포함할 수 있다.In one embodiment of the present invention, the chain dispersant may include 10 to 80 mol% of cyclohexaneamine.
본 발명의 일 실시 예에서, 상기 MDI-이성질체는 2,4'-MDI일 수 있다.In one embodiment of the present invention, the MDI-isomer may be 2,4'-MDI.
본 발명의 일 실시 예에 따르면 쇄종지제로 시클로헥산아민을 사용함으로써, 저온에서도 열세트성이 우수하도록 하여 열에 민감한 섬유 등과 교편직한 원단을 낮은 온도에서 열세팅을 실시함으로써 열에 민감한 섬유가 열에 의해 취화되지 않도록 하고, 경시변화에 따른 원사 물성 변화가 적어 교편직물에 변부 말림이나 줄(streak)가 발생하지 않도록 하는 효과가 있다.According to one embodiment of the present invention, by using cyclohexanamine as a chain terminator, heat-setability is excellent even at low temperatures, and heat-sensitive fibers are embrittled by heat by performing heat setting at low temperatures on fabrics interwoven with heat-sensitive fibers and the like. It is effective in preventing the curling or streak of the fabric due to the small change in the physical properties of the yarn over time.
본 발명의 실시를 위한 최적의 형태는 실시예 1 내지 3 이다.The best mode for carrying out the invention is Examples 1-3.
이하, 본 발명의 바람직한 실시 예들을 설명한다. 그러나, 본 발명의 실시 예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. Hereinafter, preferred embodiments of the present invention will be described. 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.
본 발명의 실시 예는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다.The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
덧붙여, 명세서 전체에서 어떤 구성요소를 '포함'한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.In addition, the inclusion of any component throughout the specification means that it may further include other components, except to exclude other components unless specifically stated otherwise.
본 발명의 일 실시 형태에 따른 탄성사는 과량의 디이소시아네이트에 고분자량의 폴리올을 1차 중합시켜 예비 중합체를 얻는다.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.
다음으로, 상기 예비 중합체를 유기 용매에 용해시킨 후, 그 용액에 쇄연장제 및 쇄종지제를 첨가하여 2차 중합을 수행하여 방사원액을 제조한다. 이때, 쇄연장제 및 쇄종지제는 전부 한번에 또는 2개 이상의 단계로 첨가될 수 있다.Next, after dissolving the prepolymer in an organic solvent, a chain extender and a chain terminator are added to the solution to perform secondary polymerization to prepare a spinning stock solution. At this time, the chain extender and chain stopper may be added all at once or in two or more steps.
다음으로, 상기 방사원액을 건식 또는 습식 방사시켜 폴리우레탄우레아 탄성사를 제조한다.Next, a polyurethane urea elastic yarn is manufactured by dry spinning or wet spinning the spinning solution.
본 실시 예에 사용되는 디이소시아네이트는 방향족, 지방족 및 치환족 디이소시아네이트 중에서 선택된 1종 또는 2종 이상의 유기 디이소시아네이트로서, 예컨대 4,4'-디테닐메탄디이소시아네이트, 2,4'-디페닐메탄디이소시아네이트, 1,5'-나프탈렌디이소시아네이트, 1,4'-페닐렌디이소시아네이트, 헥사메틸렌 디이소시아네이트, 1,4'-시클로헥산디이소시아네이트, 4,4'-디시클로헥실 메탄디이소시아네이트, 이소포론디이소시아네이트 등이 있다.The diisocyanate used in this embodiment is one or two or more organic diisocyanates selected from aromatic, aliphatic and substituted aliphatic 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.
이때, 상기 디이소시아네이트에 포함되는 MDI 이성질체는 바람직하게 2,4'-MDI일 수 있으며, 그 함량은 전체 디이소시아네이트에 대하여 10 내지 25 몰%을 포함할 수 있다.At this time, the MDI isomer included in the diisocyanate may be preferably 2,4'-MDI, the content may include 10 to 25 mol% based on the total diisocyanate.
2,4'-MDI의 함량이 2% 미만이면 세트성의 향상 효과가 미흡하고, 25몰%를 초과하면 원사 모듈러스가 급격히 저하되는 문제가 발생할 수 있다. If the content of 2,4'-MDI is less than 2%, the improvement in setability is insufficient, and if it exceeds 25 mol%, the yarn modulus may sharply decrease.
상기 2,4'-MDI는 입체 구조를 가지고 있어 하드 세그먼트(hard segment) 내의 분자간 수소 결합 또는 분자 내 수소 결합이 약화됨으로써, 소프트 세그먼트(soft segment)의 함량이 증가하는 것과 동일한 효과를 나타내므로, 이에 소프트 도메인(soft domain)이 많이 형성되어 세트성이 우수한 탄성사를 수득할 수 있다.Since the 2,4'-MDI has a three-dimensional structure, the intermolecular hydrogen bonds or intramolecular hydrogen bonds in the hard segment are weakened, thereby exhibiting the same effect as that of increasing the content of the soft segment. In this way, a lot of soft domains are formed, thereby obtaining an elastic yarn having excellent setability.
일반적으로 캐핑비가 높게 되면 하드 세그먼트의 고함량으로 인해 중합물의 점도 컨트롤이 어려워지는데, 본 실시 형태에서는 2,4'-MDI가 위와 같이 소프트 세그먼트의 역할을 하기 때문에 캐핑비를 약 2.0까지 상승시키는 것도 가능할 수 있다.In general, when the capping ratio is high, it is difficult to control the viscosity of the polymer due to the high content of the hard segment. In this embodiment, since the 2,4'-MDI acts as the soft segment, it is also possible to increase the capping ratio to about 2.0. It may be possible.
본 발명에서 사용 가능한 폴리올은 폴리테트라메틸렌에테르 글리콜, 폴리프로필렌 글리콜, 폴리카보네이트디올 및 이들의 조합으로 구성된 군에서 선택되는 적어도 1종 이상을 예시할 수 있으나, 본 발명이 이에 한정되는 것은 아니다. 상기 폴리올의 분자량은 500 내지 8000일 수 있으며, 더 바람직하게는 1200 내지 3000일 수 있다.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.
상기 쇄연장제는 탄성사의 유연성 및 내열성을 향상시키기 위한 것으로, 디아민계를 단독으로 사용하거나 1,2-디아미노프로판 등과 혼합하여 사용할 수 있다. The chain extender is for improving the flexibility and heat resistance of the elastic yarn, it can be used alone or mixed with 1,2-diaminopropane.
상기 쇄연장제에 사용되는 디아민류는 에틸렌디아민, 1,2-디아미노프로판, 1,3-디아미노프로판, 1,4-디아미노부탄, 2,3-디아미노부탄, 1,5-디아미노펜탄, 1,6-헥사메틸렌디아민 및 1,4-씨클로헥산디아민 등에서 선택된 1종 또는 2종 이상의 혼합물을 예시할 수 있으며, 본 발명이 이에 한정되는 것은 아니다.Diamines used in the chain extender include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 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.
한편, 폴리우레탄우레아의 분자량을 조절하기 위해 쇄종지제를 사용하게 되는데, 이 쇄종지제로 종래와 같이 디에틸아민 만을 사용하는 경우, 시간 경시에 후중합 과정으로 인해 원사의 강도 및 모듈러스 등의 물성 상승이 발현되는 반면 원사의 신도 및 Max DR 등의 물성은 감소할 수 있다.On the other hand, a chain terminator is used to control the molecular weight of the polyurethane urea. When only diethylamine is used as a conventional terminator, the strength and modulus of the yarn due to the postpolymerization process over time. Synergy may be manifested while physical properties such as yarn elongation and Max DR may decrease.
또한, 생산 시기가 다른 원사를 혼합 사용할 경우 원단의 세트 정도 차이 및 원단의 줄(streak)을 유발시킬 수 있다.In addition, 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.
이에, 본 실시 형태에서는, 쇄종지제로서 시클로헥산아민을 사용하며, 이에 상기 시클로헥산아민 이 방사 과정 중 높은 열량에 따른 후중합의 억제 및 원사 시산 후 후중합에 따른 물성의 변화를 최소화하여 열세트성을 향상시키므로, 낮은 온도에서 열세팅을 실시하여도 상대사의 열적 취하가 일어나지 않아 종래보다 원단의 태를 향상시킬 수 있고, 열세팅 후의 가공지에서는 변무 말림이 발생하는 것을 방지할 수 있다.Thus, in the present embodiment, cyclohexaneamine is used as a chain terminator, and the cyclohexaneamine suppresses the post-polymerization according to the high calorific value during the spinning process, and minimizes the change in the physical properties due to post-polymerization after yarn calcination. Since the setability is improved, even when thermal setting is performed at a low temperature, thermal taking-off of the counterpart does not occur, thereby improving the appearance of the fabric compared with the conventional one, and it is possible to prevent the curling of paper from occurring in the processed paper after the thermal setting.
이때, 상기 쇄종지제는 전체 쇄종지제에 대하여 바람직하게 시클로헥산아민 10 내지 80 몰%을 포함할 수 있다.In this case, the chain terminator may preferably include 10 to 80 mol% of cyclohexaneamine based on the total chain terminator.
쇄종지제의 사용량이 10몰% 미만인 경우 과량의 디에틸아민으로 인해 후중합의 촉진을 제어할 수 없게 되며, 쇄종지제의 사용량이 80몰%를 초과하는 경우 과도한 후중합 억제로 인해 낮은 모듈러스 및 방사를 위한 폴리머 점도 상승이 억제되는 점이 우려될 수 있다.If the amount of the chain terminator is less than 10 mol%, the promotion of the postpolymerization cannot be controlled due to the excess diethylamine. If the amount of the chain terminator is greater than 80 mol%, the low modulus is caused by excessive postpolymerization inhibition. And that the increase in polymer viscosity for spinning is suppressed.
또한, 본 발명에서는 자외선, 대기 스모그, 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 degradation of physical properties due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc., the steric hindrance phenol compound, benzofuran-one compound, semicarbazide, etc. Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably.
나아가, 본 발명의 폴리우레탄우레아 탄성사는 필요시 상기 성분 외에도 이산화티탄, 마그네슘 스테아레이트 등과 같은 첨가제, 산화방지제, 염색성 향상제, 열산화안정제, 항균제, 광안정제 또는 대전방지제 등을 더 포함할 수 있다. 이러한 기타 첨가제의 첨가 방법에는 특별한 제한이 없으며, 적정 혼합과 같은 통상의 방법을 사용할 수 있다.Furthermore, 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. There is no particular limitation on the method of adding these other additives, and conventional methods such as titration mixing can be used.
이하, 실시 예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시 예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
이하에서 실시예 및 비교예를 들어 본 발명에 대해 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
* 원사의 강도 및 신도* Strength and elongation of yarn
자동 강신도 측정장치(MEL기, Textechno社)를 이용하여 시료 길이 10 cm, 인장속도 100 cm/min로 하여 측정한다.Using an automatic elongation measuring device (MEL machine, Textechno Co., Ltd.), the measurement is performed at a sample length of 10 cm and a tensile speed of 100 cm / min.
이때 파단 시의 강도와 신도 값이 측정되며, 원사 200 % 신장시 원사에 걸리는 하중 200 % 모듈러스(modulus)도 측정된다.At this time, the strength and elongation at break are measured, and the load on the yarn at 200% elongation is also measured at 200% modulus.
* 원사의 열세트성* Heat Setability of Yarn
생산된 원사를 대기에 노출된 상태로 100 % 신장한 후, 170 ℃에서 1분간 건열 처리하였다. 이후 실온으로 냉각한 다음, 원사의 길이를 측정하여 아래 식에 따라 원사의 열세트성을 계산하였다.The produced yarn was stretched 100% while being exposed to the air, and then dried and heat treated at 170 ° C. for 1 minute. After cooling to room temperature, the length of the yarn was measured, and the thermal setability of the yarn was calculated according to the following equation.
열세트성(%) = {(열처리후 길이-초기길이)/(신장 길이-초기 길이)}х100Heat Setability (%) = {(length-initial length after heat treatment) / (height length-initial length)} х100
<실시 예 1><Example 1>
캐핑비(CR) 1.65인 디이소시아네이트에 2,4'-MDI 2 몰%와 폴리테트라메틸렌에테르 글리콜을 혼합하여 조제하였다.2 mole% of 2,4'-MDI and polytetramethylene ether glycol were prepared by diisocyanate having a capping ratio (CR) of 1.65.
쇄연장제는 에틸렌디아민과 1,2-프로판 디아민을, 쇄종지제는 시클로헥산아민을 사용하였다. 이때, 쇄연장제와 쇄종지제의 비율은 9.5:1로 하였으며, 쇄연장제로써 에틸렌디아민과 1,2-프로판 디아민의 비율은 80 몰%과 20 몰%로, 쇄종지제로써 시클로헥산아민과 디에틸아민의 비율은 10몰%과 90몰%로 하였다. 하였다. 또한, 사용된 아민은 총 농도 7 몰%로 조제 되었으며, 용제로는 디메틸아세트아마이드를 사용하였다.The chain extender used ethylenediamine and 1,2-propane diamine, and the chain stopper used cyclohexanamine. In this case, the ratio of the chain extender and the chain dispersant was 9.5: 1, and the ratio of ethylenediamine and 1,2-propane diamine as the chain extender was 80 mol% and 20 mol%, and cyclohexanamine as the chain terminator. The ratio of and diethylamine was 10 mol% and 90 mol%. It was. In addition, the amine used was prepared in a total concentration of 7 mol%, and dimethylacetamide was used as a solvent.
이러한 중합물의 고형분 대비 첨가제로서 에틸렌비스(옥시에틸렌)비스-(3-(5-t-부틸-4-히드록시-m-토일)-프로피오네이트) 1.5 중량%, 5,7-디-t-부틸-3-(3,4-디메틸페닐)-3H-벤조퓨란-2-온 0.5 중량%, 1,1,1-1-테트라메틸-4,4-(메틸렌-디-p-페닐렌)디세미카바지드 1 중량%, 폴리(N,N-디에틸-2-아미노에틸 메타크릴레이트) 1 중량%, 이산화티탄 0.1 중량%를 첨가 혼합하여 폴리우레탄우레아 방사원액을 얻었다.Ethylenebis (oxyethylene) bis- (3- (5-t-butyl-4-hydroxy-m-toyl) -propionate) 1.5% by weight, 5,7-di-t as an additive to the solid content of such a polymer -Butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one 0.5 wt%, 1,1,1-1-tetramethyl-4,4- (methylene-di-p-phenylene ) 1% by weight of dimicarbazide, 1% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate), and 0.1% by weight of titanium dioxide were added and mixed to obtain a polyurethaneurea spinning stock solution.
그리고, 위와 같이 수득한 방사원액을 건식 방사하여 40 데니아 3 필라멘트의 폴리우레탄우레아 탄성사를 제조하고, 그 물성을 평가하여 하기 표 1에 나타내었다.In addition, dry spinning the obtained spinning stock solution to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, and evaluated the physical properties are shown in Table 1 below.
<실시 예 2>       <Example 2>
시클로헥산아민과 디에틸아민의 비율 50 몰%와 50몰%로 하여 폴리우레탄우레아를 사용한 것을 제외하고는 실시 예 1과 동일하다.It is the same as Example 1 except using polyurethane urea as 50 mol% and 50 mol% of cyclohexaneamine and diethylamine.
수득한 방사원액은 건식 방사하여 40 데니아 3 필라멘트의 폴리우레탄우레아 탄성사를 제조하고, 그 물성을 평가하여 하기 표 1에 나타내었다.The obtained spinning stock solution was dry spun to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Table 1 below.
<실시 예 3>Example 3
시클로헥산아민과 디에틸아민의 비율 80 몰%와 20몰%로 하여 폴리우레탄우레아를 사용한 것을 제외하고는 실시 예 1과 동일하다.It is the same as Example 1 except the polyurethane urea being used as 80 mol% and 20 mol% of cyclohexaneamine and diethylamine.
수득한 방사원액은 건식 방사하여 40 데니아 3 필라멘트의 폴리우레탄우레아 탄성사를 제조하고, 그 물성을 평가하여 하기 표 1에 나타내었다.The obtained spinning stock solution was dry spun to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Table 1 below.
<비교 예 1><Comparative Example 1>
쇄종지제로 디에틸아민을 사용한 것을 제외하고는 실시 예 2와 동일한 조건으로 제조되었다.It was prepared under the same conditions as in Example 2 except that diethylamine was used as the chain terminator.
수득한 방사원액은 건식 방사하여 40 데니아 3 필라멘트의 폴리우레탄우레아 탄성사를 제조하고, 그 물성을 평가하여 하기 표 1에 나타내었다. 이 중합물의 방사 조건 등은 실시 예 2와 같다.The obtained spinning stock solution was dry spun to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Table 1 below. Spinning conditions and the like of this polymerized product are the same as in Example 2.
표 1
CR 쇄종지제[CHA:DEA] 경시시간 강도 신도 200%M 열세트성(%)
실시예1 1.65 10:90 0일 1.06 548 6.6 58.4
10일 1.06 542 6.7 58.2
30일 1.05 545 6.6 58.2
실시예2 1.65 50:50 0일 1.10 550 6.4 58.8
10일 1.10 548 6.4 58.4
30일 1.10 548 6.3 58.4
실시예3 1.65 80:20 0일 1.12 552 6.5 59.2
10일 1.13 550 6.6 59.4
30일 1.14 556 6.5 59.0
비교예1 1.65 0:100 0일 1.00 538 6.6 52.7
10일 1.07 527 6.9 50.1
30일 1.18 518 7.5 47.7
Table 1
CR Disintegration Agents [CHA: DEA] Time burglar Shinto 200% M Heat Setability (%)
Example 1 1.65 10:90 0 days 1.06 548 6.6 58.4
10 days 1.06 542 6.7 58.2
30 days 1.05 545 6.6 58.2
Example 2 1.65 50:50 0 days 1.10 550 6.4 58.8
10 days 1.10 548 6.4 58.4
30 days 1.10 548 6.3 58.4
Example 3 1.65 80:20 0 days 1.12 552 6.5 59.2
10 days 1.13 550 6.6 59.4
30 days 1.14 556 6.5 59.0
Comparative Example 1 1.65 0: 100 0 days 1.00 538 6.6 52.7
10 days 1.07 527 6.9 50.1
30 days 1.18 518 7.5 47.7
<CHA: 시클로헥산아민, DEA: 디에틸아민><CHA: cyclohexanamine, DEA: diethylamine>
실시 예 1 내지 실시 예 3은, 쇄종지제로 시클로헥산아민과 디에틸 아민을 일정 함량을 사용한 것이며, 비교 예 1은 쇄종지제로 디에틸아민만을 사용한 것이다.In Examples 1 to 3, a certain amount of cyclohexaneamine and diethyl amine was used as the chain terminator, and Comparative Example 1 used only diethylamine as the chain terminator.
상기 표 1을 참조하면, 실시 예 1 내지 실시 예 3의 경우 비교 예 1에 비해 생산 초기 원사의 세트성이 우수하며, 경시시간에 관계없이 균일한 물성을 유지함을 확인할 수 있다.Referring to Table 1, it can be seen that in the case of Examples 1 to 3, compared to Comparative Example 1, the setability of the initial production yarn is excellent, and uniform physical properties are maintained regardless of time.
따라서, 쇄종지제로 시클로헥산아민을 사용하면 종래의 쇄종지제로 디에틸아민을 사용하는 탄성사에 비해 원사의 열세트성이 전반적으로 향상되므로, 저온에서도 열세트성이 우수하도록 하여 열에 민감한 섬유 등과 교편직한 원단을 낮은 온도에서 열세팅을 실시함으로써 열에 민감한 섬유가 열에 의해 취화되지 않도록 하여 원가를 절감하고, 교편직물에 변부 말림이나 줄(streak)가 발생하지 않도록 하는 효과를 기대할 수 있다. Therefore, when cyclohexanamine is used as a chain terminator, the heat setability of yarn is generally improved as compared with elastic yarns using diethylamine as a conventional chain terminator. By heat setting the direct fabric at low temperature, heat-sensitive fibers are not embrittled by heat, thereby reducing the cost and preventing the edges from curling or streaking.
본 발명은 상술한 실시 형태에 의해 한정되는 것이 아니며 첨부된 청구범위에 의해 한정하고자 한다.It is intended that the present invention not be limited by the above embodiments, but rather by the claims appended hereto.
따라서, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 당 기술분야의 통상의 지식을 가진 자에 의해 다양한 형태의 치환, 변형 및 변경이 가능할 것이며, 이 또한 본 발명의 범위에 속한다고 할 것이다.Accordingly, various forms of substitution, modification, and alteration may be made by those skilled in the art without departing from the technical spirit of the present invention described in the claims, which are also within the scope of the present invention. something to do.
본 발명에 따르면, 열 세트성이 향상된 폴리우레탄우레아 탄성사를 얻을 수 있다는 특장점이 있다.According to the present invention, a polyurethane urea elastic yarn having improved heat setability can be obtained.

Claims (6)

  1. 폴리(테트라메틸렌 에테르)글리콜;Poly (tetramethylene ether) glycol;
    방향족, 지방족 및 지환족 디이소시아네이트 중에서 선택된 1종 또는 2종 이상의 유기 디이소시아네이트;One or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates;
    쇄연장제; 및Chain extenders; And
    시클로헥산아민을 포함하는 쇄종지제; 를 포함하는 열세트성이 향상된 폴리우레탄우레아 탄성사.Chain terminators including cyclohexanamine; Polyurethane urea elastic yarn improved heat setability, including.
  2. 제1항에 있어서,The method of claim 1,
    상기 쇄종지제는 전체 쇄종지제에 대하여 시클로헥산아민 10 내지 80 몰%을 포함하는 것을 특징으로 하는 열세트성이 향상된 폴리우레탄우레아 탄성사.The chain dispersant is polyurethane urea elastic yarn with improved heat setability, characterized in that it comprises 10 to 80 mol% of cyclohexanamine with respect to the total chain dispersant.
  3. 제1항에 있어서, 상기 MDI-이성질체는 2,4'-MDI인 것을 특징으로 하는 열세트성이 향상된 폴리우레탄우레아 탄성사.The polyurethane urea elastic yarn of claim 1, wherein the MDI isomer is 2,4′-MDI.
  4. 폴리올과 디이소시아네이트를 1차 중합하여 예비 중합체를 수득하는 단계;First polymerizing the polyol and the diisocyanate to obtain a prepolymer;
    상기 예비 중합체를 유기 용매에 용해 시키고 쇄연장제 및 쇄종지제를 첨가하여 2차 중합을 수행하여 방사원액을 수득하는 단계; 및Dissolving 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
    상기 방사원액을 건식 또는 습식방사 시켜 폴리우레탄우레아 탄성사를 수득하는 단계; 를 포함하며,Dry or wet spinning the spinning stock solution to obtain a polyurethaneurea elastic yarn; Including;
    상기 디이소시아네이트는 방향족, 지방족 및 치환족 디이소시아네이트 중에서 선택된 1종 또는 2종 이상의 유기 디이소시아네이트를 포함하고, 상기 쇄종지제는 시클로헥산아민을 포함하는 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조 방법.The diisocyanate includes one or two or more organic diisocyanates selected from aromatic, aliphatic and substituted diisocyanates, and the chain terminator comprises cyclohexanamine. .
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 쇄종지제는 전체 쇄종지제에 대하여 시클로헥산아민 10 내지 80 몰%을 포함하는 것을 특징으로 하는 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조 방법.The chain dispersant comprises 10 to 80 mol% of cyclohexanamine with respect to the total chain dispersant, characterized in that the thermosetability improved polyurethane urea elastic yarn production method.
  6. 제4항에 있어서, 상기 MDI-이성질체는 2,4'-MDI인 것을 특징으로 하는 열세트성이 향상된 폴리우레탄우레아 탄성사의 제조 방법.The method of claim 4, wherein the MDI isomer is 2,4'-MDI.
PCT/KR2013/011407 2013-12-10 2013-12-10 Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor WO2015088060A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040027882A (en) * 2001-07-24 2004-04-01 라디시스판덱스 코포레이션 Improved spandex compositions
KR20060012279A (en) * 2003-05-05 2006-02-07 인비스타 테크놀러지스 에스.에이.알.엘 High productivity spandex fiber process and product
US20080171831A1 (en) * 2005-03-29 2008-07-17 Adeka Corporation Water Dispersible Polyurethane Composition
KR20110078283A (en) * 2009-12-31 2011-07-07 주식회사 효성 Process for preparing polyurethaneurea elastic fiber with improved heat settable properties
KR20110078784A (en) * 2009-12-31 2011-07-07 주식회사 효성 Manufacturing method of polyurethaneurea elastic fiber by high speed spinning method
KR20120077016A (en) * 2010-12-30 2012-07-10 주식회사 효성 Method of making polyurethaneurea elastic fiber modified by polydimethylsiloxane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040027882A (en) * 2001-07-24 2004-04-01 라디시스판덱스 코포레이션 Improved spandex compositions
KR20060012279A (en) * 2003-05-05 2006-02-07 인비스타 테크놀러지스 에스.에이.알.엘 High productivity spandex fiber process and product
US20080171831A1 (en) * 2005-03-29 2008-07-17 Adeka Corporation Water Dispersible Polyurethane Composition
KR20110078283A (en) * 2009-12-31 2011-07-07 주식회사 효성 Process for preparing polyurethaneurea elastic fiber with improved heat settable properties
KR20110078784A (en) * 2009-12-31 2011-07-07 주식회사 효성 Manufacturing method of polyurethaneurea elastic fiber by high speed spinning method
KR20120077016A (en) * 2010-12-30 2012-07-10 주식회사 효성 Method of making polyurethaneurea elastic fiber modified by polydimethylsiloxane

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