KR0152280B1 - Process for preparing antistatic polyester fiber - Google Patents

Process for preparing antistatic polyester fiber

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Publication number
KR0152280B1
KR0152280B1 KR1019920026181A KR920026181A KR0152280B1 KR 0152280 B1 KR0152280 B1 KR 0152280B1 KR 1019920026181 A KR1019920026181 A KR 1019920026181A KR 920026181 A KR920026181 A KR 920026181A KR 0152280 B1 KR0152280 B1 KR 0152280B1
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South Korea
Prior art keywords
polyester
general formula
compound
antistatic
polyester fiber
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KR1019920026181A
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Korean (ko)
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KR940014520A (en
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한석호
김문찬
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배도
동양폴리에스터주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

본 발명은 공중합 방식에 의한 제전성 폴리에스터 섬유의 제조방법이 제공되는 것으로, 폴리옥시알킬렌글리콜화합물 및 비반응성 알킬술폰산리튬염과 함께 일반식(1)의 피페라진계 화합물을 첨가하여 공중합하는 것이며 제전성능이 우수하면서도 고유의 폴리에스터 섬유 물성이 유지되는 효과를 갖는다.The present invention provides a method for producing an antistatic polyester fiber by a copolymerization method, which is copolymerized by adding a piperazine compound of the general formula (1) together with a polyoxyalkylene glycol compound and a non-reactive lithium sulfonate salt. It has an effect of maintaining excellent polyester fiber properties while having excellent antistatic performance.

Description

제전성 폴리에스터 섬유의 제조방법Manufacturing method of antistatic polyester fiber

본 발명은 제전성이 우수하면서도 일반 폴리에스터 섬유의 장점을 잃지 않는 폴리에스터 제전사의 개량된 제조방법에 관한 것이다.The present invention relates to an improved manufacturing method of polyester electrostatic yarn, which is excellent in antistatic properties and does not lose the advantages of ordinary polyester fiber.

폴리에스터 섬유는 내열성, 내약품성, 강신도, 결정성, 굴곡강도 등의 물성이 우수하여 의류용으로 크게 각광을 받고 있지만 저온이며 저습도인 지역이나, 겨울철에는 안감이나, 란제리, 화운데이션, 기타 무진복이나 운동복 등 특수 기능복으로 사용하기에는 마찰에 의한 정전기의 발생으로 먼지들이 흡착, 오염이 쉽게 되고 착용자에게 쇼크나 불쾌감을 주게 되는 문제점이 있다. 이러한 정전기적인 장애를 해결하기 위하여 많은 방법들이 제안되었다. 폴리옥시알킬렌글리콜에 메타크릴레이트나 비스페놀을 사용하고 플라즈마방법으로 후가공처리하여 대전방지기능을 부여하는 방법이 있으나. 이 방법은 세탁후 제전성이 급격히 떨어지는 단점이 있었다. 이러한 내세탁성 문제를 해결하고 영구적인 제전성을 부여하기 위하여 일본공개특허공보 소52-47071호 및 동52-47072호에서 소개된 폴리알킬렌글리콜과 알킬술폰산나트륨을 사용하여 폴리머를 개질하는 방법이 최근 많이 사용되고 있다. 알킬술폰산나트륨은 폴리머에 이온성기를 도입시켜 전하의 이동을 활발하게 하고 또한 폴리알킬렌글리콜의 공중합물과의 상승작용으로 우수한 제전성능을 발현시킬수 있는 장점을 가지고 있다. 그러나, 알킬술폰산나트륨은 폴리머내부에서의 분산성이 나쁘고 방사시 팩압을 증가시키는 요인이 된다.Polyester fiber is attracting much attention for clothing because of its excellent properties such as heat resistance, chemical resistance, elongation, crystallinity, and flexural strength. In order to use it as a special functional clothing such as sportswear, there is a problem that the dust is easily adsorbed and contaminated by the generation of static electricity by friction, and shock or discomfort to the wearer. Many methods have been proposed to solve this electrostatic disturbance. There is a method of imparting antistatic function by using methacrylate or bisphenol in polyoxyalkylene glycol and post-processing by plasma method. This method has a disadvantage in that the antistatic property is sharply reduced after washing. In order to solve this problem of washing resistance and to impart permanent antistatic properties, a method of modifying a polymer using polyalkylene glycol and sodium alkyl sulfonate introduced in Japanese Patent Laid-Open Nos. 52-47071 and 52-47072 is disclosed. This has been used a lot lately. Sodium alkyl sulfonate has an advantage of expressing excellent antistatic performance by introducing an ionic group into the polymer to promote charge transfer and synergy with a copolymer of polyalkylene glycol. However, sodium alkyl sulfonate is poor in dispersibility inside the polymer and causes a pack pressure increase during spinning.

또한 방사노즐 내부에 나트륨 금속염이 잔존하는 경우가 생겨 방사불량이 생기고 팩교환주기가 짧아져 방사작업성이 떨어지고 폴리머내부에서의 분산성이 나빠. 염색불량의 원인이 되기도 한다.In addition, sodium metal salts may remain inside the spinning nozzles, resulting in poor spinning and shorter pack replacement cycles, resulting in poor spinning workability and poor dispersibility within the polymer. It can also cause dyeing problems.

본 발명은 이러한 문제점을 해결한 것으로 이를 보다 상세히 설명하면 다음과 같다.The present invention solves this problem and will be described in more detail as follows.

본 발명은 폴리옥시알킬렌글리콜화합물 및 비반응성 알킬술폰산리튬염과 함께 하기 일반식(1)의 피페라진계 화합물을 첨가하여 공중합하는 것을 특징으로 제전성 폴리에스터 섬유의 제조방법에 관한 것이다.The present invention relates to a method for producing an antistatic polyester fiber, wherein the polyoxyalkylene glycol compound and the non-reactive alkylsulfonic acid salt are added together and copolymerized with a piperazine compound of the following general formula (1).

(상기에서, R1:NH2, 알킬기 또는 수소,(In the above, R 1 : NH 2 , an alkyl group or hydrogen,

M:Li, Na, KM: Li, Na, K

n1, n2:1-100의 정수)n 1 , n 2 : integer of 1-100)

본 발명에서 상기 일반식(1)의 피페라진 화합물은 전체 폴리에스터 대비 0.001-1중량%가 바람직하며, 0.001중량% 이하일 경우에는 제전성이 부족하고 1중량% 이상일 경우는 점도상승으로 방사불량의 원인이 된다.In the present invention, the piperazine compound of the general formula (1) is preferably 0.001-1% by weight relative to the total polyester, and if it is 0.001% by weight or less, the antistatic property is insufficient, and in the case of 1% by weight or more, the radiation is poor in radiation. Cause.

본 발명에서 사용하는 폴리옥시알킬렌글리콜은 수평균 분사량이 2000-3000인 하기 일반식(2)의 화합물이 가장 바람직하며, 전체 폴리에스터 대비 0.01-3.5중량%로 투입하여 폴리에스터 주쇄말단에 공중합시킨다. 이때 투입량이 0.01중량 이하일 경우 제전성이 극히 불량해지고 3.5중량% 이상일 경우는 사의 기본물성이 저하된다.The polyoxyalkylene glycol used in the present invention is most preferably a compound of formula (2) having a number-average injection amount of 2000-3000, and copolymerized at the polyester main chain end by adding 0.01-3.5% by weight relative to the total polyester. Let's do it. In this case, when the amount is 0.01 weight or less, the antistatic property is extremely poor, and when 3.5 weight% or more, the basic physical properties of the yarn are reduced.

(상기에서, R2:C1-C13인 알킬기 또는 H(In the above, R 2 : C 1 -C 13 Alkyl group or H

R3:C2-C16인 알킬렌기R 3 : C 2 -C 16 alkylene group

n3:20-150의 정수)n 3 : an integer from 20-150)

본 발명에서 사용하는 비반응성 알킬술폰산리튬염은 하기 일반식(3)의 비반응성 폴리알킬술폰산리튬이 특히 바람직하며 전체 폴리에스터 대비 0,01-2중량%도 투입하는 것이 좋다. 이의 투입함량이 상기 범위 이상일 경우디에틸렌글리콜(DEG)의 함량이 많아져서 동일 용융점도에서 중합물을 배출할 경우 고유점도가 높아져 사물성에서 신도가 너무 낮아지는 단점이 있고 범위보다 적을 경우에는 점도가 낮아져서 곤란하게 된다.The non-reactive lithium sulfonate salt used in the present invention is particularly preferably non-reactive polyalkyl sulfonate lithium of the general formula (3), and 0,01-2% by weight relative to the total polyester is also preferably added. If the input content is more than the above range, the content of diethylene glycol (DEG) increases, so that when the polymer is discharged at the same melt viscosity, the intrinsic viscosity becomes high and elongation is too low in the object, and the viscosity is less than the range. It becomes low and becomes difficult.

(상기식에서 , R4:C3-C25인 알킬기 또는 C7-C30인 아릴기)(In the formula, R 4 : C 3 -C 25 Alkyl group or C 7 -C 30 An aryl group)

본 발명에서는 또한 일반적으로 알려진 바와 같이 축중합시 촉매로서 Sb2O3를 200-400ppm 첨가하고 하기와 같은 인화합물을 10-200ppm 첨가한 후 2시간 동안 반응 진행시킴으로써 열안정성을 높일수 있다.In the present invention, as is generally known, thermal stability may be improved by adding 200-400 ppm of Sb 2 O 3 as a catalyst during condensation polymerization and reacting for 2 hours after adding 10-200 ppm of the following phosphorus compounds.

본 발명에서 공중합 방법은 폴리에킬렌테레프탈레이트 올리고머 중합조에 테레프탈산과 에틸렌글리콜의 혼합슬러리를 투입하고 올리고머를 제조한후 여기에 상술한 일반식(1),(2) 및 (3) 화합물을 촉매 등의 첨가제와 함께 소정량으로 투입한 후 통상의 반응조건으로 중합을 행하면 족하기 때문에 상세한 설명은 생략한다.In the present invention, the copolymerization method is prepared by injecting a mixed slurry of terephthalic acid and ethylene glycol into a polyalkylene terephthalate oligomer polymerization tank and preparing an oligomer, and then using the above general formulas (1), (2) and (3) as catalysts Since the polymerization is carried out under the usual reaction conditions after addition in a predetermined amount with the additive of, the detailed description is omitted.

이같은 본 발명에 따른 폴리에스터 제전사는 폴리에스터 섬유 고유의 물성을 저해하지 않으면서도 제전성능이 우수하여 의류용 및 기능복에 널리 사용이 가능하다.Such polyester antistatic yarn according to the present invention is excellent in antistatic performance without compromising the inherent properties of the polyester fiber can be widely used in clothing and functional clothing.

[실시예]EXAMPLE

(1) 디메틸렌글리콜(DEG)량 : 히드라진 수화물로 폴리에스터를 열분해하고 이것을 가스크로마토그래피로 측정한다.(1) Dimethylene glycol (DEG) amount: Pyrolyse the polyester with hydrazine hydrate and measure this by gas chromatography.

(2) 비저항 : 항온항습실에서 일본 TOA사의 전기저항측정기를 사용하여 측정한다.(2) Resistivity: Measured by using an electric resistance measuring instrument of TOA of Japan in a constant temperature and humidity room.

(3) 마찰대전압, 반감기 : 가네보식 마찰대전압 측정기를 사용하여 측정한다.(3) Friction band voltage, half-life: Measured using a Kanebo friction belt voltage meter.

*비저항, 마찰대전압, 반감기는 온도 20±2℃, 습도 40±2 RH%에서 측정하였다.* Specific resistance, friction band voltage and half-life were measured at 20 ± 2 ℃ and 40 ± 2 RH% humidity.

폴리에틸렌테레프탈레이트 올리고머 10kg이 함유된 중합조를 250℃로 유지하면서 테레프탈산 8645g과 에틸렌글리콜 3875g이 잘 혼합된 슬러리를 6시간에 걸쳐서 투입하여 20kg의 올리고머를 제조한 후 다른 중합조로 10kg을 옮긴다. 이 올리고머에 삼산화안티몬 5g과 일반식(2)의 화합물 C12H25O(C2H4O)40H 100g과 일반식(3)의 화합물 C12H25SO3Li 10g 및 일반식(1)의 NH2(CH2)10 (CH2)10SO3Na 5g을 투입하고, 280℃에서 반응시켜 본 발명의 폴리에스터를 제조하였다. 얻어진 중합체를 통상의 방법으로 건조한 후, 방사하여 얻어진 미연신사를 80℃로 유지된 가열로울러 및 120℃로 유지된 열반에 의해 1070m/min의 연신속도로 연신하여 75d/36f의 연신사르라 제조하고 물성을 평가하였다.While maintaining a polymerization tank containing 10 kg of polyethylene terephthalate oligomer at 250 ° C., a slurry in which 8645 g of terephthalic acid and 3875 g of ethylene glycol were well mixed was added over 6 hours to prepare a 20 kg oligomer, and then 10 kg was transferred to another polymerization tank. To this oligomer, 5 g of antimony trioxide, compound C 12 H 25 O (C 2 H 4 O) 40 H of General Formula (2), compound C 12 H 25 SO 3 Li of General Formula (3), and General Formula (1) ) NH 2 (CH 2 ) 10 5 g of (CH 2 ) 10 SO 3 Na was added and reacted at 280 ° C. to prepare a polyester of the present invention. After drying the obtained polymer by a conventional method, the undrawn yarn obtained by spinning was drawn at a drawing speed of 1070 m / min by a heating roller maintained at 80 ° C. and a hotbed kept at 120 ° C. to prepare a drawn yarn of 75 d / 36f. Physical properties were evaluated.

[실시예 2-4 및 비교예 1-2]Example 2-4 and Comparative Example 1-2

공중화합성분의 조성을 표1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하고 물성을 평가하였다.Except for changing the composition of the copolymer compound as shown in Table 1 was carried out in the same manner as in Example 1 to evaluate the physical properties.

Claims (3)

폴리에틸렌테레프탈레이트 올리고머가 함유된 중합조에 테레프탈산과 에틸렌글리콜의 혼합 슬러리가 투입하여 올리고머를 제조한 후 폴리옥시알킬렌글리콜화합물 및 비반응성 알킬술폰산리튬염과 함께 일반식(1)의 피페라진계 화합물을 폴리에스터 대비 0.001 내지 1중량% 첨가하여 폴리에스터를 공중합하고, 공중합한 폴리에스터를 건조한 후 용융방사하여 연신하는 단계를 포함하는 제전성 폴리에스터 섬유의 제조방법.A mixed slurry of terephthalic acid and ethylene glycol was added to a polymerization tank containing a polyethylene terephthalate oligomer to prepare an oligomer, and then a piperazine compound of the general formula (1) together with a polyoxyalkylene glycol compound and a non-reactive alkylsulfonate lithium salt was prepared. Method for producing an antistatic polyester fiber comprising the step of copolymerizing the polyester by adding 0.001 to 1% by weight relative to the polyester, and drying the copolymerized polyester after melt spinning. (상기에서, R1:NH2, 알킬기 또는 수소, M:Li, Na, K n1, n2:1-100의 정수)(In the above, R 1 : NH 2 , an alkyl group or hydrogen, an integer of M: Li, Na, K n 1 , n 2 : 1-100) 제1항에 있어서, 상기 폴리옥시알킬렌글리콜 화합물은 수평균분자량이 2,000 내지 3,000인 하기 일반식(2)의 화합물이고, 폴리에스터 전량대비 0.01 내지 3.5중량%로 첨가하는 것을 특징으로 하는 제전성 폴리에스터 섬유의 제조방법.The method of claim 1, wherein the polyoxyalkylene glycol compound is a compound of the general formula (2) having a number average molecular weight of 2,000 to 3,000, antistatic properties, characterized in that added to 0.01 to 3.5% by weight relative to the total amount of polyester Method for producing polyester fiber. (상기에서, R2:C1∼C13인 알킬기 또는 H R3:C2∼C16인 알킬렌기 n3:20∼150의 정수)(In the above, an alkyl group of R 2 : C 1 -C 13 or an alkylene group of HR 3 : C 2 -C 16 n 3 : 20 to 150) 제1항에 있어서, 상기 비반응성 알킬술폰산리튬염은 하기 일반식(3)의 비반응성 폴리알킬술폰산리튬이고, 첨가량이 폴리에스터 전량대비 0,01∼2중량%임을 특징으로 하는 제전성 폴리에스터 섬유의 제조방법.The non-reactive lithium sulfonate salt of the non-reactive polyalkyl sulfonate of the general formula (3) is an antistatic polyester, characterized in that the addition amount is 0,01 to 2% by weight relative to the total amount of polyester Method of making fibers. (여기에서 , R4:C3-C25인 알킬기 또는 C7-C30인 아릴기)(Here, an alkyl group having R 4 : C 3 -C 25 or an aryl group having C 7 -C 30 )
KR1019920026181A 1992-12-29 1992-12-29 Process for preparing antistatic polyester fiber KR0152280B1 (en)

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