KR100395790B1 - Method of manufacturing modified polyester fiber - Google Patents

Method of manufacturing modified polyester fiber Download PDF

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KR100395790B1
KR100395790B1 KR1019960066176A KR19960066176A KR100395790B1 KR 100395790 B1 KR100395790 B1 KR 100395790B1 KR 1019960066176 A KR1019960066176 A KR 1019960066176A KR 19960066176 A KR19960066176 A KR 19960066176A KR 100395790 B1 KR100395790 B1 KR 100395790B1
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South Korea
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polyester
polyester fiber
parts
ethylene glycol
sio
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KR1019960066176A
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Korean (ko)
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KR19980047663A (en
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손양국
김정현
박상준
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주식회사 효성생활산업
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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
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • 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
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]

Abstract

PURPOSE: Provided is a modified polyester fiber which involves excellent color depth, and gives high quality image. CONSTITUTION: A method of manufacturing the modified polyester fiber comprising the steps of: making a polyester polymer by the polyester ester-reaction from terephthalate or dimethylterephthalate and ethylene glycol; spinning it; and weight loss-treating it. During the polyester ester reaction, 0.5-5.0wt.% of SiO2 surface-treated by 0.05-10.0wt.% of dimeric fatty acid is put into 100wt.% of polymer expressed by the formula(1). In the formula 1, R indicates alkyl group, and the carbon numbers of R1, R2, R3 and R4 are different from each other with the sum thereof being 31.

Description

개질 폴리에스터 섬유의 제조방법Method of Making Modified Polyester Fiber

본 발명은 개질 폴리에스터 섬유의 제조방법에 관한 것으로 더욱 상세하게로는 테레프탈렌이트산 또는 디메틸레프탈레이트와 에틸렌글리콜을 사용하는 일반적인 폴리에스터 중합 공정 중에 표면 흡착 처리한 SiO2를 투입하여 반응시킴으로써 심색성과 뛰어난 발색성을 부여하는 폴리에스터 섬유의 제조방법에 관한 것이다.The present invention relates to a method for producing a modified polyester fiber, and more particularly, by adding and reacting SiO 2 treated with surface adsorption in a general polyester polymerization process using terephthalic acid or dimethyl lephthalate and ethylene glycol. The present invention relates to a method for producing a polyester fiber that provides excellent color development.

일반적으로 폴리에스터 섬유는 물리·화학적으로 우수한 성질을 갖고 있기 때문에 합성섬유로서 널리 사용되고 있으나 아세테이트, 비스코레이온, 양모, 견, 아크릴 등의 섬유에 비해 심색성이 떨어질 뿐만 아니라 선명성이 미흡한 약점이 있다.In general, polyester fiber is widely used as a synthetic fiber because of its excellent physical and chemical properties, but it has a weaker color depth and less sharpness than fibers such as acetate, biscorayon, wool, silk, and acrylic.

이러한 결점을 해결하기 위하여 염료의 개선이나 폴리에스터 섬유의 화학적 개질들이 시도되고 있으나, 여전히 분산 염료에 있어서는 한계가 있다.In order to solve these drawbacks, improvements in dyes and chemical modifications of polyester fibers have been attempted, but there are still limitations in disperse dyes.

이러한 폴리에스터 섬유의 결점을 보완하기 위한 방법 중의 하나로 폴리에스터 섬유 표면에 저굴절율의 수지를 코팅하는 방법이 제안되어 있다. 그러나 이 방법은 수지를 섬유 표면에 균일하게 부착시키기 어렵고 직물의 촉감이 저해되는 문제점과 저굴적을 수지가 세탁 등에 의해 쉽게 탈락되므로 내구성이 불량한 단점이 있다.As one of the methods for compensating for the drawbacks of the polyester fiber, a method of coating a resin having a low refractive index on the surface of the polyester fiber has been proposed. However, this method has a disadvantage in that it is difficult to uniformly attach the resin to the surface of the fiber and the touch of the fabric is impaired, and the durability is poor because the resin is easily removed by washing or the low refractive index.

폴리에스터 섬유의 상기 결점을 극복하기 위한 또 하나의 방법으로서 섬유 표면을 플라즈마 가공 처리하여 섬유 표면에 미세한 요철을 형성시키는 방법이 있는데, 이 방법은 플라즈마 가공을 위해 별도의 고가 설비를 구비해야 하므로 생산원가가 상승되는 단점이 있다.As another method for overcoming the above drawbacks of polyester fibers, there is a method of forming a fine concavo-convex on the surface of the fiber by plasma processing the fiber surface. This method requires production of a separate expensive facility for plasma processing. There is a downside in cost.

상기한 방법이외에 중합 공정시 첨가제를 투입하고 방사 이후의 공정에서 알칼리 감량처리를 행하여 불용성 미립자를 제거함으로써 섬유 표면에 미세한 요철을 형성시키는 방법이 있다. 예를 들면 일본 특개소 제 56-45922호, 동 제 56-47428호등에는 실리카계 분산입자를 폴리머 중합 공정 중에 투입하여 알칼리 감량처리하여 섬유 표면에 요철을 부여하는 외부입자에 의한 방법이 제시되어 있다. 그러나 이방법에 따르면 만족할 만한 심색성을 유지할 수는 있으나, 입자의 양이 증가됨에 따라 무기미립자의 분산성 및 방사성이 불량해지고 염색 가공시 마찰 등 외력에 의하여 요철부분이 파손되기가 쉽기 때문에 파손된 부분이 색반을 형성하는 단점이 있다.In addition to the above-described method, there is a method of forming fine unevenness on the surface of the fiber by adding an additive during the polymerization step and performing an alkali weight loss treatment in a process after spinning to remove insoluble fine particles. For example, Japanese Patent Application Laid-Open No. 56-45922, Japanese Patent No. 56-47428, etc. disclose a method using external particles in which silica-based dispersed particles are added during a polymer polymerization step to give alkali irregularities to a fiber surface by alkali reduction treatment. have. According to this method, however, satisfactory color depth can be maintained, but as the amount of particles increases, the dispersibility and radioactivity of the inorganic fine particles are poor, and the uneven parts are easily damaged by external forces such as friction during dyeing. There is a disadvantage that the part forms color spots.

한편 내부입자에 의한 방법으로는 중합 공정중에 인화합물과 알칼리 토금속화합물을 투입하여 불용성 알칼리 토금속을 형성시킨 후 방사 이후 알칼리 감량에 의해 용출시킴으로써 섬유 표면에 미세한 요철을 형성시키는 방법이 일본 특개소 제58-13717호, 동 60-59171호 등에 공지되어 있으나 외부입자법에 비해 요철의 깊이가 얕아 만족할 만한 심색성을 얻기 어려운 결점이 있다.On the other hand, as a method using internal particles, insoluble alkaline earth metals are formed by adding phosphorus compounds and alkaline earth metal compounds during the polymerization process and eluting by reducing the weight of alkali after spinning. -13717, 60-59171, etc. are known, but the depth of the unevenness is shallow compared to the external particle method is difficult to obtain a satisfactory deep color.

본 발명은 상기의 문제를 해결하기 위한 것으로서, 심색성이 무수한 새로운 개질 폴리에스터 섬유를 제조하는 방법을 제공함을 그 목적으로 한다.The present invention has been made to solve the above problems, and an object thereof is to provide a method for producing a new modified polyester fiber with a myriad of color depth.

본 발명은 테레프탈레이트산 또는 디메틸테레프탈레이트와 에틸렌글리콜로부터의 폴리에스터 에스테르 반응에 의해 폴리에스터 중합물을 제조한 뒤 이를 방사하고 알칼리 감량 처리하여 폴리에스터 섬유를 제조함에 있어서, 폴리에스터 에스테르 반응중에 이합체지방산으로 표면처리된 SiO2를 투입하여 중합물을 제조함을 특징으로 한다.The present invention is to prepare a polyester polymer by a polyester ester reaction from terephthalate acid or dimethyl terephthalate and ethylene glycol, and then spin and alkali-reduce the polyester fiber to produce a polyester fiber. It is characterized in that the polymerized to prepare a surface-treated into SiO 2 .

이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에서는 먼저 테레프탈레이트산 또는 디메틸테레프탈레이트와 에틸렌글리콜로부터가 폴리에스터 에스테르 반응에 의해 폴리에스터 중합물을 제조할 때, 폴리에스터 에스테르 반응 중에 하기(1)의 일반식으로 나타내어지는 이합체지방산으로 표면처리한 SiO2를 투입하여 중합물을 제조한다.In the present invention, first, when preparing a polyester polymer by terephthalate acid or dimethyl terephthalate and ethylene glycol by a polyester ester reaction, surface treatment with a dimer fatty acid represented by the general formula (1) during the polyester ester reaction SiO 2 was added to prepare a polymer.

(여기서 R은 알칼기를 나타내며, R1, R2, R3, R4의 탄소수는 각각 다르나, 탄소수의 합은 31이다.)(Where R represents an alkali group, and the carbon number of R 1 , R 2 , R 3 , and R 4 is different, but the sum of carbon atoms is 31.)

상기에서 이합체지방산으로 표면처리된 SiO2는 에틸렌글리콜에 상기의 이합체지방산을 투입, 분산시킨 후 SiO2미립자를 혼합시켜서 에텔렌글리콜 슬러리 형태로 제조된 것을 의미한다.SiO 2 surface-treated with dimer fatty acid in the above means that the dimer fatty acid is added to ethylene glycol and dispersed, and then SiO 2 fine particles are mixed to prepare an ethylene glycol slurry.

투입하는 이합체지방산의 양은 폴리머 100 중량부에 대하여 0.05 - 10.0중량부, 더욱 바람직하기로는 1.0 - 8.0중량부인 것이 좋다. 투입량이 0.05 중량부보다 적으면 SiO2표면의 이합체지방산의 흡착량 부족으로 인한 조대입자 형성이 심각하게 야기되며, 10중량부를 초과하여 투입시는 SiO2의 표면에 미흡착한 이합체지방산이 촉매와 착화합물을 형성하는 등 부작용을 일으켜 사물성을 현저히 저하시키는 문제가 발생된다. 또한 상기 (1)식의 이합체지방산으로 표면처리된 SiO2는 폴리에스터 폴리머에 대하여 0.5 - 5 중량%의 양으로 투입하며, 더욱 바람직하게는 1 - 3 중량% 투입한다. 만일 0.5 중량% 보다 적게 투입하면, SiO2입자의 부족으로 알킬리 감량 후 심색효과가 불충분하며, 5 중량% 초과시는 중합시 SiO2입자를 분산시키는데 있어서, 응집 등의 문제를 발생시킨다.The amount of dimer fatty acid to be added is preferably 0.05 to 10.0 parts by weight, more preferably 1.0 to 8.0 parts by weight based on 100 parts by weight of the polymer. Dose is 0.05 if the unit is less than the SiO 2 is caused to the coarse particles to form due to the amount of adsorption of the lack of a dimer fatty acid severity of the surface, the lack of good dimer fatty acid is a catalyst and a complex on the surface of the SiO 2 the time of preparation and is more than 10 parts by weight The problem occurs that causes side effects such as to form a significantly lower objectivity. In addition, SiO 2 surface-treated with the dimer fatty acid of the formula (1) is added in an amount of 0.5 to 5% by weight, more preferably 1 to 3% by weight based on the polyester polymer. If less than 0.5% by weight, the lack of SiO 2 particles, the deep color effect after the alkyli loss is insufficient, and when more than 5% by weight, problems such as aggregation occur in dispersing SiO 2 particles during polymerization.

이와 같이 중합하여 제조한 칩을 기존의 방법으로 방사, 연신하여 알칼리 감량처리하면 심색성이 우수한 섬유를 얻을 수 있다.In this way, if the chip produced by polymerization is spun and stretched by an existing method and subjected to alkali weight loss treatment, fibers having excellent color depth can be obtained.

이하 본 발명을 실시예 및 비교예에 의거하여 설명하면 다음과 같으며, 본 실시예에서 사용되는 부는 중량부를 나타낸다.Hereinafter, the present invention will be described based on Examples and Comparative Examples, and the parts used in the Examples represent parts by weight.

먼저 폴리머의 물성을 평가하는 방법은 다음과 같다.First, the method of evaluating the physical properties of the polymer is as follows.

* 폴리머 내 입자의 분산성 평가* Evaluation of dispersibility of particles in polymers

해당 폴리머를 투과형 전자현미경(Transmission Electron Microscope) 및 이미지 분석기(Image Analyzer)를 이용하여 30,000배 배율로 확대하여 10회 측정하였다.The polymer was measured 10 times at 30,000 times magnification using a transmission electron microscope and an image analyzer.

분산성 평가는 평균 입자 크기, 단위 u㎡ 당 입자 갯수로 평가하였다.Dispersibility was evaluated by average particle size, number of particles per unit of square meter.

* 심색성 평가* Deep color evaluation

칼라측정기(Hunter Lab Scale)를 사용하여 L값을 측정하였다.L value was measured using a color scale (Hunter Lab Scale).

* 극한 점도 측정* Ultimate viscosity measurement

폴리머를 페놀 : 1,1,2,2-테트라콜로로에탄의 3 : 2 혼합 용액에 용해하여 25℃에서 측정하였다.The polymer was dissolved in a 3: 2 mixed solution of phenol: 1,1,2,2-tetracoloethane and measured at 25 ° C.

[실시예 1-3 및 비교예 1 - 2][Example 1-3 and Comparative Examples 1-2]

용매인 메탄올 100부에 상기(1)식의 화합물(상품명 : UNICHEMI사의 PRIPOR 1008번)을 용해한 용액 1부를 에틸렌글리콜 100부에 투입한 후 교반기로 1시간 교반시켜 프리믹싱된 에틸렌글리콜 슬러리를 만들었다. 다음 상기(1)식의 화합물이 프리믹싱된 에틸렌글리콜 슬러리에 1차 입자크기가 35nm인 SiO210부를 투입한 후 5시간 이상 샌드밀링하여 SiO2미립자가 에틸렌글리콜에 균일하게 분산된 슬러리를 제조하였다.1 part of a solution in which the compound of formula (1) (trade name: PRICHEOR 1008 of UNICHEMI Co., Ltd.) dissolved in 100 parts of methanol as a solvent was added to 100 parts of ethylene glycol, followed by stirring for 1 hour to prepare a premixed ethylene glycol slurry. Next, 10 parts of SiO 2 having a primary particle size of 35 nm was added to an ethylene glycol slurry in which the compound of Formula (1) was premixed, followed by sand milling for 5 hours to prepare a slurry in which SiO 2 particles were uniformly dispersed in ethylene glycol. It was.

이와 별도로 테레프탈레이트산 100부, 에틸렌글리콜 180부, 삼산화 안티몬 0.040부를 투입하여 에스테르 교환반응을 하고 이론량의 물을 제거한 후, 상기(1)식의 화합물이 폴리머 100부를 대해 각각 0.01, 1.0, 5.0, 70.0, 20.0부가 되도록 제조한 상기의 SiO2분산 슬러리 3 부를 투입하였다.Separately, 100 parts of terephthalate, 180 parts of ethylene glycol, and 0.040 parts of antimony trioxide were added for transesterification and the theoretical amount of water was removed. The compound of formula (1) was 0.01, 1.0, and 5.0 for 100 parts of polymer, respectively. , 3 parts of the above-described SiO 2 dispersion slurry prepared to be 70.0 and 20.0 parts was added.

이 혼합물에 대하여 상압하 270℃에서 30분간, 30mmHg의 감압하에서 15분간, 고진공하에서 150분간 중축합한 후 생성된 폴리머를 일반적인 방법에 의해 펠렛화 하였다.The resulting polymer was polycondensed at 270 ° C. for 30 minutes at atmospheric pressure, for 15 minutes under reduced pressure of 30 mmHg and for 150 minutes under high vacuum, and then the resulting polymer was pelletized by a general method.

이것을 통상적인 방법으로 건조한 후 방사속도를 2,000m/min으로 방사하여 186d/36f의 미연신사로 제조한 다음 연신비 2.5로 연신하여 75d/36f의 연신사를 얻었다.After drying in a conventional manner, the spinning speed was spun at 2,000 m / min to prepare a non-drawn yarn of 186d / 36f, and then drawn at a draw ratio of 2.5 to obtain a drawn yarn of 75d / 36f.

이 연신사의 제반 물성을 측정하여 다음 표 1에 나타내었다.The physical properties of the drawn yarn were measured and shown in Table 1 below.

본 발명에 의해 제조되는 개질 폴리에스터 섬유는 심색성이 뛰어나 고급스러운 이미지를 갖는다.The modified polyester fiber produced by the present invention is excellent in deep color and has a high-quality image.

Claims (2)

테레프탈레이트산 또는 디메틸테레프탈레이트와 에틸렌글리콜로부터의 폴리에스터 에스테르 반응에 의해 폴리에스터 중합물을 제조한뒤 이를 방사하고 알칼리 감량 처리하여 폴리에스터 섬유를 제조함에 있어서,In preparing a polyester polymer by polyester ester reaction from terephthalate acid or dimethyl terephthalate and ethylene glycol, spinning and alkali-loss treatment to produce polyester fiber, 폴리에스터 에스테르 반응중에 하기(1)의 일반식으로 나타내어지는 폴리머 100 중량부에 대하여 0.05 - 10.0 중량부의 이합체지방산으로 표면처리된 SiO2를 0.5 - 5.0 중량부 투입하여 중합물을 제조하는 것을 특징으로 하는 개질 폴리에스터 섬유의 제조방법.During the polyester ester reaction, 0.5-5.0 parts by weight of SiO 2 surface-treated with 0.05-10.0 parts by weight of dimer fatty acid based on 100 parts by weight of the polymer represented by the general formula (1) was prepared. Method for producing modified polyester fibers. (여기서 R은 알킬기를 나타내며, R1, R2, R3, R4의 탄소수는 각각 다르나, 탄소수의 합은 31이다.)(Where R represents an alkyl group, and R 1 , R 2 , R 3 , and R 4 have different carbon numbers, but the sum of the carbon numbers is 31). 제 1항에 있어서, 이합체지방산으로 표면처리된 SiO2는 에틸렌글리콜에 상기 (1)식으로 표시되는 이합체지방산을 투입, 분산시킨 후 SiO2미립자를 혼합시켜서 에틸렌글리콜 슬러리 형태로 제조된 것임을 특징으로 하는 개질 폴리에스터 섬유의 제조방법.The method of claim 1, wherein SiO 2 surface-treated with dimer fatty acid is prepared in the form of ethylene glycol slurry by mixing and dispersing the dimer fatty acid represented by the formula (1) in ethylene glycol and then mixed with SiO 2 fine particles. Method of producing a modified polyester fiber.
KR1019960066176A 1996-12-16 1996-12-16 Method of manufacturing modified polyester fiber KR100395790B1 (en)

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