KR100300916B1 - Manufacturing of polyetherester fibers improved heat resistance - Google Patents
Manufacturing of polyetherester fibers improved heat resistance Download PDFInfo
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- KR100300916B1 KR100300916B1 KR1019990031227A KR19990031227A KR100300916B1 KR 100300916 B1 KR100300916 B1 KR 100300916B1 KR 1019990031227 A KR1019990031227 A KR 1019990031227A KR 19990031227 A KR19990031227 A KR 19990031227A KR 100300916 B1 KR100300916 B1 KR 100300916B1
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- weight
- polyether ester
- heat resistance
- block copolymer
- hard segment
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- 239000000835 fiber Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 229920001400 block copolymer Polymers 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- 210000004177 elastic tissue Anatomy 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 239000011787 zinc oxide Substances 0.000 claims abstract description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000009998 heat setting Methods 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- 239000000306 component Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011084 recovery Methods 0.000 description 7
- 239000008358 core component Substances 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 polyoxybutylene Polymers 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Multicomponent Fibers (AREA)
- Woven Fabrics (AREA)
Abstract
본 발명은 방향족 폴리에스테르를 하드세그먼트로 하고 폴리에테르를 소프트In the present invention, aromatic polyester is used as the hard segment, and polyether is soft.
세그먼트로 하는 내열성이 우수한 폴리에테르에스테르 블록 공중합체의 탄성섬유에Elastic fibers of polyether ester block copolymers having excellent heat resistance as segments
관한 것으로, 시스부분은 융점이 190∼200℃이고, 하드세그먼트의 글리콜 성분이In this regard, the sheath portion has a melting point of 190 to 200 캜, and the glycol component of the hard segment
1,4-사이크로헥산디카르복실산을 사용한 폴리에테르에스테르 블록 공중합체이고 이산화티탄, 산화알루미늄, 산화아연등의 금속산화물이 중합체 중량에 대하여 4∼6중량함유하여 열 세팅시 복사열에 의한 반사율이 높으며 코아부분은 융점이 180∼190℃ 이고 하드세그먼트의 글리콜 성분이 테트라메틸렌글리콜을 사용한 통상의 폴리에테르에스테르 공중합체로 이루어진 내열성이 우수한 폴리에테르에스테르 탄성섬유에 관한 것임.Polyetherester block copolymer using 1,4-cyclohexanedicarboxylic acid, and metal oxides such as titanium dioxide, aluminum oxide, zinc oxide, etc. contain 4 to 6 weight by weight with respect to the polymer weight, and reflectance due to radiant heat during heat setting This high core part relates to a polyether ester elastic fiber having excellent melting resistance of 180 to 190 ° C and a heat-resistant glycol component of a conventional polyether ester copolymer using tetramethylene glycol.
Description
본 발명은 방향족 폴리에스테르를 하드세그먼트로 하고 폴리에테르를 소프트세그먼트로 하는 내열성이 우수한 폴리에테르에스테르 블록공중합체의 탄성섬유에The present invention relates to an elastic fiber of a polyether ester block copolymer having excellent heat resistance using an aromatic polyester as a hard segment and a polyether as a soft segment.
관한 것으로서, 시스부분은 코아부분에비해 융점이 5℃ 이상 높고 금속산화물이 다량 첨가된 폴리에테르에스테르 블록공중합체로 이루어지고 코아부분은 통상의 폴리에테르에스테르 블록공중합체로 이루어져 내열성이 우수한 복합 탄성섬유에 관한 것이다.In this regard, the sheath portion is made of a polyether ester block copolymer having a melting point of 5 ° C. or higher and a large amount of metal oxide added to the core portion, and the core portion is made of a conventional polyether ester block copolymer and has excellent heat resistance. It is about.
일반적으로 열가소성 고무 탄성체인 폴리에테르에스테르 공중합체는 고무와 같은 탄성체의 성질을 가지지만 일반적인 열가소성 고무와 같이 용융성형이 가능하여 화학적으로 경화된 고무의 특성을 보이며 충격저항 및 저온에서의 유연성이 우수하여 다양한 용도로 쓰이는 수지이다. 이러한 폴리에테르에스테르 블록공중합체를 섬유화 하여 탄성섬유로 사용할 경우 내습열성이 우수하여 폴리에스테르섬유와같이 고온 염색이 가능하며 내알카리성이 우수한 특성을 지니고 있다. 그러나 기존의 폴리우레탄계 탄성섬유인 스판덱스에 비해 탄성회복율과 내열성이 낮다는 것이 가장 큰 문제점으로 지적되고 있다.Polyetherester copolymer, which is generally a thermoplastic rubber elastomer, has the same properties as rubber, but can be melt-molded like general thermoplastic rubber to show the characteristics of chemically cured rubber, and has excellent impact resistance and flexibility at low temperatures. This resin is used for various purposes. When the polyether ester block copolymer is fiberized and used as an elastic fiber, it is excellent in moisture and heat resistance, so that high-temperature dyeing is possible like polyester fiber and has excellent alkali resistance. However, it is pointed out that the biggest problem is that the elastic recovery rate and heat resistance are lower than those of the spandex, which is a polyurethane-based elastic fiber.
이는 폴리우레탄계 탄성섬유인 스판덱스에 비해 폴리에테르에스테르 블록공중합체는 하드세그먼트의 결정에 의해 분자쇄를 연결하는 물리적인 가교를 하기 때This is because the polyetherester block copolymer has a physical crosslink that connects the molecular chain by crystal of hard segment, compared to the spandex, which is a polyurethane-based elastic fiber.
문에 탄성회복율에 있어서, 저 신장영역에서는 우수한 회복성을 보이지만 고 신장영역에서는 폴리우레탄에 미치지 못하고, 또한 탄성섬유는 단독으로 사용하지 않고 다른 섬유와 복합하여 사용하는데 사용하는 소재에 따라 다양한 조건의 가공 공정을 거치게 되며 특히 폴리에스테르 섬유와 겸용시 높은 온도의 열고정 공정을 받아야한다. 이때 고온상태에서 폴리에테르에스테르 탄성사는 물리적 가교 역할을 하는 많은 결정 부분들이 용융되어 탄성 특성을 나타낼수 없을 정도로 늘어나거나 용융에 의한 사절이 발생되어 심각한 문제를 야기 시킨다.The elastic recovery rate of the door shows excellent recovery in the low elongation region but less than the polyurethane in the high elongation region, and the elastic fiber is not used alone but in combination with other fibers. Processing process, especially when combined with polyester fiber must be subjected to high temperature heat setting process. At this time, the polyether ester elastic yarn in the high temperature state that many crystal parts that act as a physical crosslinking are melted and stretched to the extent that they cannot exhibit elastic properties, or trimming due to melting occurs, causing serious problems.
따라서 폴리에테르에스테르 블록공중합체의 하드세그먼트의 함량을 높여 탄성섬유를 제조할 경우 결정구조가 커짐으로써 탄성섬유의 내열성을 향상시킬 수는 있지만 소프트 세그먼트의 함량이 줄어들면서 탄성섬유로서 중요한 특성인 신도와 탄성회복율이 급격히 줄어들기 때문에 일정 수준 이상 하드세그먼트의 함량을 높일 수는 없다. 따라서 이러한 문제점을 해결하기 위하여 많은 방법들이 제시되고 있다.Therefore, when manufacturing the elastic fiber by increasing the content of the hard segment of the polyether ester block copolymer, the crystal structure is increased, so that the heat resistance of the elastic fiber can be improved. Since the elastic recovery rate is sharply reduced, it is not possible to increase the content of the hard segment more than a certain level. Therefore, many methods have been proposed to solve this problem.
일본 특개소58-91819호, 특개소58-91820, 특개소59-45349호, 특개소59-45350 및 미국특허 제3,880,976호 등에는 결정핵제를 배합하여 결정화도를 향상시키는 방법과 소프트 세그먼트의 분자량을 증가시키는 방법 및 각종 연신과 열처리를 하는 방법 등이 개시되어 있지만 이와 같은 방법으로는 만족스런 효과를 얻을수 없다. 또한 미국특허 제 4,013,624호에는 3∼6개의 히드록시와 카르복시기를 갖는 다 관능기의 가교제를 공중합 시키는 방법이 개시되어 있지만 이러한 방법은 가교제의 메톡시 부분이 폴리옥시부틸렌글리콜 보다는 테트라메틸렌글리콜과 반응할 가능성이 훨씬 크기 때문에 가교제는 테트라 메틸렌글리콜에 둘러싸여 하드세그먼트로 연결될 가능성이 높다.JP-A-58-91819, JP-A-58-91820, JP-A-59-45349, JP-A-59-45350, and U.S. Patent No. 3,880,976, etc. combine a crystal nucleating agent to improve crystallinity and the molecular weight of soft segments. The increasing method and the method of extending | stretching and heat-processing etc. are disclosed, but such a method cannot obtain a satisfactory effect. U.S. Pat. No. 4,013,624 also discloses a method of copolymerizing a cross-linking agent of a multifunctional group having 3 to 6 hydroxy groups with a carboxyl group, but this method allows the methoxy portion of the crosslinking agent to react with tetramethylene glycol rather than polyoxybutylene glycol. Since the possibilities are much greater, the crosslinking agent is more likely to be surrounded by tetramethylene glycol and linked into hard segments.
이렇게 되면 하드세그먼트의 결정화도가 작아져 가교제 사이의 거리가 충분히 길지 않고 가교제의 분자수준에서 균일한 분산이 없고 가교 밀도가 불균일 해져As a result, the degree of crystallinity of the hard segment becomes small, the distance between the crosslinking agents is not sufficiently long, there is no uniform dispersion at the molecular level of the crosslinking agent, and the crosslinking density becomes uneven.
(부분적인 가교 집중이 일어남) 중합도의 증가에 문제가 있고, 공정에 악영향을 미치게 된다. 또한 탄성섬유 보다 내열성이 우수한 소재를 시스부분에 사용하고 코아부분을 탄성소재로 사용한 시스코아형 복합섬유를 제조하는 방법이 우리나라 공개특허 제91-12439호에 게재되고 있으나 이 또한 시스부분에 사용하는 소재들이 신축성이 낮기 때문에 복합섬유의 신축성이 떨어지는 문제점을 갖고 있다.(Partial crosslinking concentration occurs.) There is a problem in increasing the degree of polymerization and adversely affects the process. In addition, a method of manufacturing a Cisco core composite fiber using a material having better heat resistance than an elastic fiber in the sheath part and a core part as an elastic material is disclosed in Korean Patent Application Publication No. 91-12439. Because of their low elasticity, the elasticity of the composite fiber is poor.
따라서 본 발명에서는 상기한 바와 같은 종래의 방법 보다 훨씬 효과적으로 폴리에테르에스테르계 탄성섬유의 내열성을 향상시키기 위하여 하드세그먼트의 글리콜성분은 1,4-사이크로헥산디메탄올을 사용하고 열 세팅시 복사열에 대한 반사율이 높은 금속산화물을 다량 첨가한 폴리에테르에스테르 블록공중합체를 시스부분에사용하고 코아부분은 통상의 폴리에테르에스테르 블록공중합체를 사용한 탄성 복합섬유를 제조하여 탄성특성을 유지하면서 내열성을 향상시킬 수 있었다.Therefore, in the present invention, the glycol component of the hard segment uses 1,4-cyclohexanedimethanol in order to improve the heat resistance of the polyether ester elastic fiber much more effectively than the conventional method as described above. Polyetherester block copolymer containing a large amount of highly reflective metal oxide is used for the sheath portion, and the core portion can produce elastic composite fibers using conventional polyetherester block copolymer to improve heat resistance while maintaining elastic properties. there was.
이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본발명 폴리에테르에스테르 블록공중합체의 탄성섬유는 내열성을 높이기 위해 시스부분의 폴리에테르에스테르 블록공중합체의 하드세그먼트 성분은 방향족 디카르복실산 및 그의 에스테르 형성성 유도체로 에틸렌글리콜, 테트라메틸렌글리콜,The elastic fiber of the polyetherester block copolymer of the present invention is a hard segment component of the polyetherester block copolymer of the cis portion to increase the heat resistance of the aromatic dicarboxylic acid and its ester-forming derivatives are ethylene glycol, tetramethylene glycol,
헥사메틸렌글리콜, 사이크로헥산디메탄올 및 이의 에스테르 형성상 유도체가 일반적으로 사용되는데 본 발명에서는 방향족 디카르복실산 성분으로 디메틸테레프탈레이트를 사용하고 글리콜 성분으로는 1,4-사이크로헥산 디메탄올을 사용하였다. 소프트세그먼트로는 평균 분자량이 500∼3,000의 폴리옥시테트라메틸렌글리콜을 사용하였다. 하드세그먼트의 조성은 25∼45중량인 것이 바람직하며, 중축합시 금속산화물을 중합체 중량에 대해 4∼6중량되도록 첨가하였으며 이때 사용한 금속산화물로는 이산화티탄, 산화알루미늄, 산화아연 등을 들수 있고, 이때의 고유점도는 1.7∼2.2, 융점은 190∼200℃이다.Hexamethylene glycol, cyclohexanedimethanol and ester-forming derivatives thereof are generally used. In the present invention, dimethyl terephthalate is used as the aromatic dicarboxylic acid component and 1,4-cyclohexane dimethanol is used as the glycol component. Used. As the soft segment, polyoxytetramethylene glycol having an average molecular weight of 500 to 3,000 was used. The hard segment preferably has a composition of 25 to 45 weights, and a metal oxide is added to the polymer weight of 4 to 6 weights during polycondensation. The metal oxides used may include titanium dioxide, aluminum oxide, zinc oxide, and the like. The intrinsic viscosity of is 1.7-2.2, and melting | fusing point is 190-200 degreeC.
또한 코아부분의 통상의 폴리에테르에스테르 블록 공중합체는 디카르복실산성분으로는 디메틸테레프탈레이트를 사용하고 글리콜 성분으로는 테트라메틸렌글리콜을 사용한 하드세그먼트와 평균분자량이 500∼3,000의 폴리옥시테트라메틸렌글리콜을 사용한 소프트 세그먼트로 이루어진다. 하드세그먼트의 조성은 25∼45중량가되도록 하고 융점은 180∼190℃ 수준이다.In addition, the conventional polyether ester block copolymer of the core portion is a hard segment using dimethyl terephthalate as the dicarboxylic acid component and tetramethylene glycol as the glycol component and polyoxytetramethylene glycol having an average molecular weight of 500 to 3,000. Consists of soft segments. The hard segment has a composition of 25 to 45 weights and has a melting point of 180 to 190 ° C.
이렇게 하여 얻어진 두 종의 폴리에테르에스테르 블록 공중합체를 통상의 용융방사로 방사하였으며 방사온도는 240℃이고 방사속도는 500∼750m/min이었다. 이때 시스부분의 구성비는 전체 중량의 20∼40중량가 가장 바람직하다.The two polyether ester block copolymers thus obtained were spun by conventional melt spinning, and the spinning temperature was 240 ° C. and the spinning speed was 500 to 750 m / min. At this time, the composition ratio of the sheath portion is most preferably 20 to 40 weight of the total weight.
본발명 복합 탄성섬유를 제조함에 있어서, 시스부분의 블록공중합체의 탄성특성을 유지하면서 내열성을 향상시킬 수 있도록 하드세그먼트의 글리콜성분을 코아부분과 달리 함으로써 융점이 5℃이상 높은 공중합체를 사용하고, 열세팅시 복사열에 대한 반사율이 높은 금속산화물을 4∼6중량로 섬유 내부에 첨가하여 금속산화물이 섬유외곽을 균일하게 코팅한 효과가 있게 함으로써 가공 공정시 복사열이 섬유내부로 침투하는 것을 차단해 주는 효과를 가질 수 있게 된다. 이때 금속산화물의 함량이 4중량미만이면 복사열의 차단효과가 떨어지고, 6중량를 초과하면 제사작업성이 불량해지는 문제가 있다. 또한 시스부분에 투입되는 금속산화물이 섬유 외부를 코팅하는 효과를 갖기 위해서는 시스부분의 함량이 전체중량의 40중량미만이 되어야한다.In preparing the composite elastic fiber of the present invention, a copolymer having a high melting point of 5 ° C. or more by using a glycol component of the hard segment different from the core part so as to improve the heat resistance while maintaining the elastic properties of the block copolymer of the sheath part. By adding metal oxide with 4 ~ 6 weight of high reflectance to radiant heat during the heat setting inside the fiber, the metal oxide has the effect of uniformly coating the outer edge of the fiber, preventing the penetration of radiant heat into the fiber during processing. Giving effect can be. At this time, when the content of the metal oxide is less than 4 weight, the shielding effect of radiant heat is lowered, and when the content of the metal oxide exceeds 6 weight, there is a problem of poor workability. In addition, the content of the sheath portion should be less than 40 weight of the total weight in order for the metal oxide introduced into the sheath portion to have an effect of coating the outside of the fiber.
시스부분의 중량비가 40중량를 초과하면 시스부분을 형성하는 단면적이 증가함에 따라 금속산화물이 밀집되기 위한 함량비가 증가하게 되어 시스부분의 방사 작업성이 불량해진다. 또한 시스부분의 함량이 전체중량의 20중량미만일 경우는 코아 부분과의 함량비 차이가 많아지기 때문에 균일한 단면형성이 어렵고 시스성분이 코아성분을 충분이 감싸줄수 없게 되는 문제가 있다.When the weight ratio of the sheath portion exceeds 40 weights, the content ratio for densification of the metal oxide increases as the cross-sectional area forming the sheath portion increases, so that the spinning workability of the sheath portion is poor. In addition, if the content of the sheath portion is less than 20% by weight of the total weight because the difference in content ratio with the core portion is difficult to form a uniform cross-section and the sheath component has a problem that can not fully wrap the core component.
따라서 본발명 복합 탄성섬유는 시스부분의 융점이 코아부분에 비해 5℃이상높기 때문에 내열성을 향상시킬 수 있으며 시스성분과 코아성분의 상용성이 우수하고 유동특성이 유사하여 방사작업이 뛰어나고 기존의 내열성 향상을 위한 복합섬유 제조방법과는 달리 탄성특성의 저하가 없는 매우 실용적인 방법인 것입니다.Therefore, the present invention composite elastic fiber can improve the heat resistance because the melting point of the sheath part is higher than 5 ° C higher than the core part, and the compatibility of the sheath component and the core component is excellent and the flow characteristics are similar, so the spinning work is excellent and the existing heat resistance Unlike the composite fiber manufacturing method for improvement, it is a very practical method without deterioration of elastic properties.
실시예 및 비교에의 물성측정은 다음과 같이 하였다.The physical property measurement in an Example and a comparison was performed as follows.
1) 융점(Tm) : Perkin-Elmer사의 DSC-7(시차주사 열분석기)를 사용하였다.1) Melting point (Tm): Perkin-Elmer's DSC-7 (differential scanning thermal analyzer) was used.
2) 강신도 : Inston사의 인장시험기를 사용하여 시료장 10㎝로 하고 200/분의 속 도로 신장시킨 다음 파단시까지의 데니어 강도(g/d) 및 신도를 측정한 다.2) Elongation: Using Inston's tensile tester, make the sample length 10cm, elongate at 200 / min, and measure the denier strength (g / d) and elongation until fracture.
3) 신장회복율 : 시료장 10㎝로 하여 200/분의 속도로 200신도까지 5회 반복하3) Elongation recovery rate: 10cm of sample length is repeated 5 times to 200 elongation at 200 / min.
여 신장시킨 후 하중을 제거하고 시료의 길이(L)를 측정하여 다음 식에 의해 산출한다.After stretching, remove the load, measure the length (L) of the sample and calculate it by the following equation.
순간신장회복율 = 20-(L-10)/20 * 100Instant Elongation Recovery = 20- (L-10) / 20 * 100
4) 내열성 HRZ(Hot rupture time) : 필라멘트를 100신장상태에서 193.5℃ 온도로 가열할 때 사절될까지의 시간을 측정한다.4) Heat resistance Hot rupture time (HRZ): Measures the time until the filament is trimmed when heated to a temperature of 193.5 ° C at 100 elongation.
이하 본 발명을 실시예에 따라 다시 설명한다.Hereinafter, the present invention will be described again according to examples.
실시예 1Example 1
하드세그먼트의 함량이 40중량이고 용융점이 188℃인 코폴리에테르에스테르를 중합하기 위해 디메틸테레프탈레이트 225.9중량부, 테트라메틸렌글리콜 141중량부, 수평균 분자량이 2000인 폴리옥시테트라메틸렌글리콜 360중량부, 티타늄테트라부톡시드 0.3중량부를 질소기류하의 반응기에 넣고 150∼200℃에서 에스테르 교환반응을 진행시킨 후 이론양의 80이상 메탄올을 유출시키고 난 후 안정제로 일가녹스(시바가이기사 제품) 0.5중량부, 티누빈 770(시바가이기사 제품) 2.3중량부를 첨가한 후 200∼240℃로 승온시켜 저진공에서 60분 고진공에서 120분 축중합 반응을 시킨 후 반응을 종료시켰다. 이렇게 하여 얻은 폴리머의 고유점도는 1.95(페놀/테트라클로로에탄 혼합용액을 이용 30℃에서 측정) 용융점도는 3500포아즈(240℃)이었다.225.9 parts by weight of dimethyl terephthalate, 141 parts by weight of tetramethylene glycol, 360 parts by weight of polyoxytetramethylene glycol having a number average molecular weight in order to polymerize a copolyetherester having a content of 40 parts by weight of hard segment and melting point of 188 ° C. 0.3 parts by weight of titanium tetrabutoxide was placed in a reactor under a nitrogen stream, followed by a transesterification reaction at 150-200 ° C., followed by distillation of methanol of 80 or more of the theoretical amount, and 0.5 parts by weight of ilganox (Shibagaiki Co., Ltd.) as a stabilizer. After adding 2.3 parts by weight of Tinuvin 770 (manufactured by Shiva-Geigi Co., Ltd.), the temperature was raised to 200 to 240 ° C., followed by a condensation polymerization reaction for 60 minutes at low vacuum and 120 minutes at high vacuum to terminate the reaction. The inherent viscosity of the polymer thus obtained was 1.95 (measured at 30 ° C using a phenol / tetrachloroethane mixed solution). The melt viscosity was 3500 poise (240 ° C).
또한 용융점도가 197℃인 폴리에테르에스테르를 중합하기 위하여 디메틸테레Dimethyl tere to polymerize polyether ester having a melt viscosity of 197 ° C
프탈레이트 230중량부, 1,4-사이크로 헥사디카르복실산 143중량부, 수 평균 분자량이 2000인 폴리옥시테트라메틸렌글리콜 360중량부를 같은 방법으로 반응시켰고 축중합시 이산화티탄을 테트라 메틸렌글리콜에 20중량슬러리 용액 상태로 금속산화물이 중합물의 5중량되도록 투입하였다.230 parts by weight of phthalate, 143 parts by weight of hexadicarboxylic acid, and 360 parts by weight of polyoxytetramethylene glycol having a number average molecular weight of 2000 were reacted in the same manner. The metal oxide was added in a weight slurry solution so that 5 weight of the polymer was obtained.
이렇게 중합한 폴리머의 고유점도는 1.94이고 용융점도는 3200포아즈였다.Thus polymerized polymer had an inherent viscosity of 1.94 and a melt viscosity of 3200 poise.
전자를 코아성분으로 후자를 시스성분으로 하여 중량비가 3:7인 시스코아형 복합사(방온; 240℃, 방속; 750m/min)인 40데니어의 모노필라멘트사를 제조하였다. 복합사의 물성은 표 1와 같다.Using the former as a core component and the latter as a cis component, a 40 denier monofilament yarn having a weight ratio of 3: 7 (Cisco-type composite yarn (at room temperature; 240 ° C., flux; 750 m / min)) was prepared. Physical properties of the composite yarn are shown in Table 1.
실시예 2Example 2
상기 실시예 1과 같은 방법으로 하고 시스성분을 금속산화물의 함량이 4중량인 폴리에테르에스테르 블록 공중합체를 사용한 것외에는 동일하게 하여 시스코아형 복합사를 얻었다. 복합사의 물성은 표 1와 같다.The same method as in Example 1 was carried out, except that the cis component was used in the same manner except that a polyether ester block copolymer having a metal oxide content of 4 weight was used, to obtain a Cisco core composite yarn. Physical properties of the composite yarn are shown in Table 1.
실시예 3Example 3
상기 실시예 1에서 시스성분과 코아성분의 중량비가 4:6인 것을 제외하고는Except that the weight ratio of the cis component and core component in Example 1 is 4: 6
동일하게 하여 시스코아형 복합사를 얻었다. 복합사의 물성은 표 1와 같다.In the same manner, a Cisco-type composite yarn was obtained. Physical properties of the composite yarn are shown in Table 1.
비교예 1Comparative Example 1
상기예 1에서 시스성분의 폴리에테르에스테르 블록 공중합체의 하드세그먼트성분의 글리콜성분을 1,4-사이크로헥산 디카르복실산 대신에 테트라메틸렌글리콜을 사용한 것을 제외하고는 동일하게 하여 시스코아형 복합사를 얻었다.The glycol component of the hard-segment component of the polyether ester block copolymer of the cis component in Example 1 was the same except that tetramethylene glycol was used instead of 1,4-cyclohexane dicarboxylic acid. Got.
비교예 2Comparative Example 2
상기예 1에서 시스성분과 코아성분의 중량비가 6:4인 것을 제외하고는 동일하게 하여 시스코아형 복합사를 얻었다.A cisco-type composite yarn was obtained in the same manner as in Example 1 except that the weight ratio of the cis component and the core component was 6: 4.
비교예 3Comparative Example 3
상기예 1에서 시스성분과 코아성분의 비가 1:9인 것을 제외하고는 동일하게하여 시스코아형 복합사를 얻었다.A Cisco composite composite yarn was obtained in the same manner as in Example 1 except that the ratio of the cis component and the core component was 1: 9.
비교예 4Comparative Example 4
상기예 1에서 시스성분의 금속산화물의 함량이 3wt인 것을 제외하고는 동일하게하여 시스코아형 복합사를 얻었다.In the same manner as in Example 1, except that the content of the metal oxide of the cis component is 3wt.
비교예 5Comparative Example 5
상기예 1에서 시스성분의 금속산화물의 함량이 7wt인 것을 제외하고는 동일하게하여 시스코아형 복합사를 얻었다.In the same manner as in Example 1, except that the content of the metal oxide of the cis component is 7wt.
표 1Table 1
방사작업성, 단면형성 ○ : 우수 , △ : 보통 , × : 불량Radio workability, cross section ○: Excellent, △: Normal, ×: Poor
본 발명은 열세팅시 복사열에 대한 반사율이 높은 이산화티탄, 산화알루미늄, 산화아연 등의 금속산화물을 다량 함유하는 폴리에테르에스테르 블록 공중합체를 시스성분으로 사용하고, 하드세그먼트의 글리콜 성분을 1,4-사이크로헥산디메탄올을 사용하여 탄성특성을 유지하면서도 내열성이 우수한 폴리에테르에스테르 공중합체의 탄성섬유를 얻을 수 있다.The present invention uses a polyether ester block copolymer containing a large amount of metal oxides such as titanium dioxide, aluminum oxide, zinc oxide, etc. having high reflectance to radiant heat during heat setting as a cis component, and a glycol component of the hard segment 1,4. By using cyclohexane dimethanol, it is possible to obtain elastic fibers of a polyether ester copolymer having excellent heat resistance while maintaining elastic properties.
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