KR0167001B1 - Process for preparing full-dull polyester resin - Google Patents

Process for preparing full-dull polyester resin Download PDF

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KR0167001B1
KR0167001B1 KR1019940038778A KR19940038778A KR0167001B1 KR 0167001 B1 KR0167001 B1 KR 0167001B1 KR 1019940038778 A KR1019940038778 A KR 1019940038778A KR 19940038778 A KR19940038778 A KR 19940038778A KR 0167001 B1 KR0167001 B1 KR 0167001B1
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titanium dioxide
polyester resin
weight
ethylene glycol
present
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KR1019940038778A
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Korean (ko)
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KR960022661A (en
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김석수
한상흠
이경록
정수윤
정종식
신홍현
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이상운
고려합섬주식회사
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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
    • C08G63/02—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • 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

Abstract

본 발명은 풀덜(full-dull) 폴리에스테르 수지의 제조방법에 관한 것으로, 더욱 상세하게는 고순도 테레프탈산과 에틸렌 글리콜을 반응시키고 여기에 이산화티탄 슬러리를 첨가하여 풀덜 폴리에스테르 수지를 제조하는데 있어서, 에틸렌 글리콜에 분산제로서 다음 구조식(I)로 표시되는 인산 에스테르 화합물을 첨가하여 이산화티탄 미립자의 분산성 및 안정성을 증가시킴으로써 방사 및 연신작업성이 우수한 풀덜 폴리에스테르 수지의 제조방법에 관한 것이다.The present invention relates to a method for producing a full-dull polyester resin, and more particularly, in order to prepare a pulled polyester resin by reacting high purity terephthalic acid with ethylene glycol and adding a titanium dioxide slurry thereto, ethylene glycol The present invention relates to a method for producing a pulled polyester resin excellent in spinning and stretching work by adding a phosphate ester compound represented by the following structural formula (I) as a dispersant to increase the dispersibility and stability of titanium dioxide fine particles.

상기식에서, M은 알카리 금속이며, n은 1 ∼ 8의 정수이다.Wherein M is an alkali metal and n is an integer from 1 to 8.

Description

풀덜 폴리에스테르 수지의 제조방법Method for producing pulled polyester resin

본 발명은 풀덜(full-dull) 폴리에스테르 수지의 제조방법에 관한 것으로, 더욱 상세하게는 고순도 테레프탈산과 에틸렌 글리콜을 반응시키고 여기에 이산화티탄 슬러리를 첨가하여 풀덜 폴리에스테르 수지를 제조하는데 있어서, 에틸렌 글리콜에 분산제로서 다음 구조식(I)로 표시되는 인산 에스테르 화합물을 첨가하여 이산화티탄 미립자의 분산성 및 안정성을 증가시킴으로써 방사 및 연신작업성이 우수한 풀덜 폴리에스테르 수지의 제조방법에 관한 것이다.The present invention relates to a method for producing a full-dull polyester resin, and more particularly, in order to prepare a pulled polyester resin by reacting high purity terephthalic acid with ethylene glycol and adding a titanium dioxide slurry thereto, ethylene glycol The present invention relates to a method for producing a pulled polyester resin excellent in spinning and stretching work by adding a phosphate ester compound represented by the following structural formula (I) as a dispersant to increase the dispersibility and stability of titanium dioxide fine particles.

상기 식에서, M은 알카리 금속이며 n은 1 ∼ 8의 정수이다.Wherein M is an alkali metal and n is an integer from 1 to 8.

현재, 합성섬유는 고유의 특성과 기능성으로 인해 의류소재로 범용화되고 있으며, 고부가가치 제품의 개발을 위해 합성섬유 자체의 단점을 보완하고 새로운 기능을 부여하려는 연구 등이 진행되고 있다.At present, synthetic fibers are being widely used as clothing materials due to their inherent characteristics and functions, and researches are being conducted to supplement the shortcomings of synthetic fibers themselves and to give new functions to develop high value-added products.

이중 폴리에틸렌테레프탈레이트 수지는 심색 및 파스텔 색조의 발현 및 드라이(dry)한 촉감, 우수한 드레이프성 등의 특성을 부여하기 위하여 중합시에 이산화티탄(TiO2)을 2 ∼ 4 중량% 투입하여 풀덜 폴리에스테르 수지를 제조하고 있다.Polyethylene terephthalate resin is made of fully polyester by adding 2 to 4% by weight of titanium dioxide (TiO 2 ) during polymerization to give characteristics such as deep and pastel color tone, dry touch, and excellent drape. Resin is manufactured.

여기서 풀덜 폴리에스테르 수지란 통산 폴리에스테르 수지내에 TiO2를 1 중량% 이상 함유시켜 제조한 수지로서 수지에 소광효과 및 특수기능을 부여할 수 있는 수지를 의미한다.Here, the pulled polyester resin refers to a resin prepared by containing 1 wt% or more of TiO 2 in the total polyester resin, and means a resin that can impart a matting effect and a special function to the resin.

그러나, 이산화티탄 자체의 응집성이 매우 강하여 이산화티탄 슬러리 내에서 뿐만 아니라 폴리에스테르 수지제조 중에서도 응집현상이 일어난다.However, the cohesiveness of titanium dioxide itself is so strong that coagulation occurs not only in the titanium dioxide slurry but also in the production of polyester resin.

이로인해 폴리에스테르 수지 중에 응집된 큰 입자가 존재하면 중합시에 사용되는 각종 필터의 수명을 단축시키며, 방사시에 노즐 팩(Nozzle Pack)의 압력상승을 초래하여 노즐 교환주기를 단축시킨다. 또한, 절사의 요인이 되어 방사작업을 저하시키고, 방사가이드 및 노즐 구금의 마모 등의 악영향을 끼치는 문제가 있다.As a result, the presence of aggregated large particles in the polyester resin shortens the lifespan of various filters used in the polymerization, and induces an increase in the pressure of the nozzle pack during spinning, thereby shortening the nozzle replacement cycle. In addition, there is a problem in that it causes the cutting and lowers the spinning work, adversely affects the wear of the spinning guide and nozzle nozzle.

이들 문제를 해결하기 위한 종래의 방법으로는 첫째, 이산화티탄 표면에 특수한 코팅처리를 한 이산화티탄 제품을 사용하거나, 둘째, 인화합물을 함유하는 이산화티탄을 사용하는 방법, 셋째로는 이산화티탄의 분산성 향상을 위한 분산제를 이산화티탄 슬러리 제조시 이산화티탄과 함께 투입하는 방법 등이 있다.Conventional methods for solving these problems include firstly using a titanium dioxide product having a special coating treatment on the surface of titanium dioxide, or secondly using a titanium dioxide containing phosphorus compound. A method of adding a dispersant for improving acidity together with titanium dioxide in preparing a titanium dioxide slurry.

그러나, 상기 종래 방법들은 이산화티탄 슬러리의 안정성과 폴리에스테르 수지 내에서의 응집방지 및 분산성 향상효과가 충분하지 않았다.However, the conventional methods are not sufficient to improve the stability of the titanium dioxide slurry and the prevention of aggregation and dispersibility in the polyester resin.

이에 본 발명자들은 고순도 테레프탈산과 에틸렌글리콜을 반응시키고 여기에 이산화티탄 미립자를 분산시켜 폴리에스테르 수지를 제조하는데 있어서, 이산화티탄 미립자의 분산성 및 안정성을 대폭 증가시킬 수 있는 분산제로서 인산 에스테르 화합물을 첨가함으로서 이산화티탄 슬러리 뿐만 아니라 폴리머 내에서도 이산화티탄의 분산성 및 안정성을 향상시킨 본 발명을 완성하였다.The present inventors reacted with high-purity terephthalic acid and ethylene glycol to disperse the titanium dioxide fine particles therein to prepare a polyester resin, by adding a phosphate ester compound as a dispersant that can greatly increase the dispersibility and stability of the titanium dioxide fine particles. The present invention has been completed to improve the dispersibility and stability of titanium dioxide not only in the titanium dioxide slurry but also in the polymer.

본 발명은 분산제를 첨가함으로서 이산화티탄의 분산성 및 안정성을 향상시켜 방사 및 연신작업성이 우수한 풀덜 폴리에스테르의 제조방법을 제공하는데 그 목적이 있다.It is an object of the present invention to improve the dispersibility and stability of titanium dioxide by adding a dispersing agent to provide a method for producing pulled polyester having excellent spinning and drawing workability.

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

본 발명은 고순도 테레프탈산과 에틸렌 글리콜을 반응시키고 평균지름이 1 ㎛ 이하인 이산화티탄 미립자를 에틸렌 글리콜에 분산시킨 슬러리를 2 ∼ 4 중량% 첨가하여 풀덜 폴리에스테르 수지를 제조함에 있어서, 상기 이산화티탄 미립자 100 중량부에 대하여 다음 구조식(I)로 표시되는 인산 에스테르 화합물을 0.01 ∼ 3 중량부 첨가하는 것을 그 특징으로 한다.The present invention is to prepare a pulled polyester resin by adding 2 to 4% by weight of a slurry obtained by reacting high purity terephthalic acid with ethylene glycol and dispersing titanium dioxide fine particles having an average diameter of 1 μm or less in ethylene glycol. It is characterized by adding 0.01-3 weight part of the phosphate ester compound represented by following structural formula (I) with respect to a part.

상기식에서, M, n은 상기에서 정의한 바와같다.Wherein M and n are as defined above.

이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 풀덜 폴리에스테르 수지의 제조방법에 있어서, 상기 구조식(I)로 표시되는 분산제의 첨가량이 이산화티탄 100 중량부에 대하여 0.01 중량부 미만이면 이산화티탄의 분산성 개량 효과가 없어지며, 3 중량부를 초과할 경우에는 에틸렌 글리콜에 분산제가 용해되기 어렵고 중합속도가 저하되며 디에틸렌 글리콜의 부생성물의 양이 증가한다.According to the present invention, in the method for producing a pulled polyester resin, when the amount of the dispersant represented by the structural formula (I) is less than 0.01 part by weight based on 100 parts by weight of titanium dioxide, the dispersibility improvement effect of titanium dioxide is lost, and 3 weight When the amount is exceeded, the dispersant is difficult to dissolve in ethylene glycol, the polymerization rate is lowered, and the amount of byproduct of diethylene glycol is increased.

그리고 상기 구조식(I)에서 n값이 1 미만이면 이산화티탄의 분산 효과가 떨어져 응집괴가 발생하고, 8을 초과하면 중합속도를 저해하며, n=3이 가장좋다. 또한, 상기 구조식(I)에서 M은 나트륨, 칼륨, 리튬 또는 세슘 등의 알카리 금속을 나타내며, 칼륨이 특이 좋다.In the structural formula (I), when the n value is less than 1, the dispersion effect of titanium dioxide is lowered, and agglomerates are generated. When the n value is more than 8, the polymerization rate is inhibited, and n = 3 is the best. In addition, M in the formula (I) represents an alkali metal such as sodium, potassium, lithium or cesium, and potassium is particularly preferred.

만일 에틸렌 글리콜에 전해질이며 원자가가 큰 양이온이 존재하면 극미량이라도 이산화티탄 응집이 일어나 분산성에 악영향을 주게 된다.If an ethylene glycol electrolyte and a high valence cation is present, even a small amount of titanium dioxide agglomeration will adversely affect the dispersibility.

따라서, 본 발명에서는 이산화티탄 슬러리 제조시에 에틸렌 글리콜에 존재하는 이물질을 완전히 제거한 후, 양이온을 제거할 수 있는 음이온성이 큰 상기 구조식(I)로 표시되는 분산제인 인산 에스테르 화합물을 이산화티탄 100 중량부에 대하여 0.01 ∼ 3 중량부로 투입하여 잘 용해시킨 후, 1 ㎛ 이하의 이산화티탄 미립자를 투입하여 분산성 및 슬러리 안정성이 향상된 이산화티탄 슬러리를 제조한다.Therefore, in the present invention, after removing the foreign substances present in the ethylene glycol during the production of the titanium dioxide slurry, 100 weight of titanium phosphate ester compound which is a dispersant represented by the above structural formula (I) having a large anionic property capable of removing cations After dissolving well in an amount of 0.01 to 3 parts by weight, the titanium dioxide fine particles of 1 µm or less are added to prepare a titanium dioxide slurry having improved dispersibility and slurry stability.

이때, 이산화티탄 슬러리의 중합 투입시키는 다른 첨가제의 산도(pH)가 이산화티탄 미립자 슬러리의 산도(pH)와 차이가 있으므로 시간 간격을 두고 투입해야하며, 이산화티탄 슬러리의 중합반응조 투입위치는 혼합 효과가 큰 반응조의 벽면쪽으로 한다.At this time, the acidity (pH) of the other additives to be added to the polymerization of the titanium dioxide slurry is different from the acidity (pH) of the titanium dioxide fine particle slurry, so it should be added at intervals, and the polymerization reactor input position of the titanium dioxide slurry has a mixed effect. To the wall of the large reactor.

그리고, 본 발명의 풀덜 폴리에스테르 수지를 제조하는 에스테르화 반응은 먼저, 압력 1 ∼ 2 kg/㎠g 하에서 온도를 230℃로부터 260℃까지 서서히 올리면서 3시간동안 반응시켜 반응 유출수를 제거시킨다. 그 다음 에스테르화율이 80 ∼ 90% 정도 진행되었을 때에 상기에서 제조된 이산화티탄을 폴리에스테르 수지에 대하여 2 ∼ 4 중량% 첨가하고, 에스테르화율이 94 ∼ 97% 진행되었을 때 화합물 전체 양의 50%를 축합 중합조로 이송한다.And, the esterification reaction for producing the pulled polyester resin of the present invention, first reacting for 3 hours while gradually raising the temperature from 230 ° C to 260 ° C under pressure of 1 ~ 2 kg / cm2g to remove the reaction effluent. Then, when the esterification rate was about 80 to 90%, 2 to 4% by weight of the titanium dioxide prepared above was added to the polyester resin, and when the esterification rate was 94 to 97%, 50% of the total amount of the compound was added. Transfer to condensation polymerization tank.

그리고 나서, 초기온도 260 ∼ 270 ℃, 진공도 5 ∼ 10토르(torr)로 축합반응을 시작하여 반응온도 285 ∼ 295 ℃, 진공도 1토르(torr) 이하에서 3 ∼ 4시간 반응시켜 고유점도 0.61 ∼ 0.65의 풀덜 개질 폴리에스테르 수지를 제조한다.Then, the condensation reaction was started at an initial temperature of 260 to 270 ° C. and a vacuum degree of 5 to 10 torr, followed by reaction for 3 to 4 hours at a reaction temperature of 285 to 295 ° C. and a vacuum degree of 1 torr. The intrinsic viscosity was 0.61 to 0.65. A pulley modified polyester resin of was prepared.

이와같이 제조된 개질 폴리에스테르를 예비 결정화한 후 160 ∼ 180 ℃에서 10 ∼ 12시간 진공 건조시켜 수분을 20 ppm 이하로 하여 풍송한 후 질소기류하의 사일로(silo)에 넣은 뒤 280 ∼ 300 ℃ 범위에서 용융 방사하여 권취속도 1000 ∼ 1100 m/분으로 미연신사를 제조한다. 이때 기어펌프에서 걸리는 초기 압력은 100 kg/㎠이고, 압력 상승폭이 급격히 상승한 시기에 노즐 팩을 교체한다. 이때 얻어진 미연신사를 연신하여 본 발명의 풀덜 폴리에스테르 섬유를 제조한다.The modified polyester thus prepared is precrystallized, and then vacuum dried at 160 to 180 ° C. for 10 to 12 hours, and air is blown to 20 ppm or less, and then put in a silo under nitrogen stream, and then melted at a range of 280 to 300 ° C. Spinning is carried out to produce an undrawn yarn at a winding speed of 1000 to 1100 m / min. At this time, the initial pressure applied to the gear pump is 100 kg / ㎠, the nozzle pack is replaced when the pressure rises sharply increased. The unstretched yarn obtained at this time is stretched to prepare pulled polyester fibers of the present invention.

상기와 같은 방법으로 제조된 본 발명의 개조된 풀덜 폴리에스테르 칩은 방사시 노즐 교환주기가 연장되고, 모우발생을 감소시켜 방사성이 향상되고 연신시 작업성이 향상되어 합성섬유의 단점인 반짝거리는 금속광택이 첨가된 내부 미립자의 소광효과에 의해 부드러운 파스텔 색조를 띠게되고, 반발 탄성력이 우수하여 드레이프성을 갖게되어 고품위 외관의 차별화된 원사소재로 유용하게 사용될 수 있다.The modified pulled polyester chip of the present invention manufactured by the above method has an extended nozzle exchange period during spinning, reduces the occurrence of swelling, improves the radioactivity, and improves workability during stretching, and is a shiny metal which is a disadvantage of synthetic fibers. The matting effect of the internal fine particles added to the gloss has a soft pastel color tone, excellent resilience elasticity has a drape property can be usefully used as a differentiated yarn material of high quality appearance.

이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

[실시예 1]Example 1

먼저, 에틸렌 글리콜을 절대등급(absolute rating) 1 ㎛ 필터로 여과하여 이 물질은 완전히 제거한 후, 구조식(I)에서 n=3이고 M이 칼륨인 인산 에스테르 칼륨염 0.025 중량부(이산화티탄 100 중량부에 대하여 0.05 중량부)를 상기의 에틸렌 글리콜 150 중량부에 잘 용해시킨 후 평균입자 크기가 0.35 ㎛인 이산화티탄 미립자 50 중량부를 넣고 24시간 혼합시켜 이산화티탄 슬러리를 제조하였다.First, ethylene glycol was filtered through an absolute rating 1 μm filter to completely remove this material, and then 0.025 part by weight of potassium phosphate ester salt of n = 3 and M in potassium in structural formula (I) (100 parts by weight of titanium dioxide) 0.05 part by weight) was dissolved in 150 parts by weight of ethylene glycol, and then 50 parts by weight of titanium dioxide fine particles having an average particle size of 0.35 μm were added and mixed for 24 hours to prepare a titanium dioxide slurry.

고순도 테레프탈산 747.6 중량부, 에틸렌 글리콜 335.1 중량부를 혼합하여 슬러리(Slurry) 상태로 만들어 에스테르 교환 반응기에 투입하여 질소가스를 순환시키면서 에스테르 교환반응 시작전에 산화안티몬 0.26 중량부 및 기타 첨가제를 에틸렌 글리콜에 용해시켜 용액상태로 투입하였다.747.6 parts by weight of high-purity terephthalic acid and 335.1 parts by weight of ethylene glycol were mixed to make a slurry, and 0.26 parts of antimony oxide and other additives were dissolved in ethylene glycol before the transesterification reaction was started while circulating nitrogen gas. It was added in solution.

이후, 1.2 kg/㎠의 반응 압력하에서 반응온도를 230 ℃에서 260 ℃까지 서서히 올리면서 3시간정도 반응시키면서 유출수를 계외로 제거하였다. 에스테르화율이 83% 진행되었을 때, 이미 제조된 이산화티탄 슬러리를 폴리에스테르 수지에 대하여 2.3 중량부를 첨가하고, 에스테르화율이 96% 진행되었을 때 중합반응조로 이송하여 초기온도 267 ℃, 진공도 5 ∼ 10토르(torr)로 축합중합을 시작하여 반응온도 290℃, 진공도 1토르(torr) 이하에서 3시간 반응시켰다. 고유점도가 0.65에 도달하면 토출, 펠렛(pellet)화하여 칩 상태로 만들고, 140 ℃에서 예비결정화시키고 170℃에서 12시간 진공 건조하여 수분율을 20 ppm으로 낮추어 사일로(silo)로 풍송하여 방사온도 295 ℃로 용융 방사하여 1030 m/분으로 권취한 후, 이 미연신사를 공급원사로 하여 제 1 고뎃 롤러의 온도를 85 ℃, 열고정판 온도 135 ℃에서 연신하였다.Thereafter, the effluent was removed out of the system while reacting for about 3 hours while gradually raising the reaction temperature from 230 ° C. to 260 ° C. under a reaction pressure of 1.2 kg / cm 2. When the esterification rate was 83%, 2.3 parts by weight of the already prepared titanium dioxide slurry was added to the polyester resin, and when the esterification rate was 96%, it was transferred to the polymerization reactor and the initial temperature was 267 ° C. and the vacuum degree was 5 to 10 Torr. Condensation polymerization was started at (torr), and reaction was carried out at a reaction temperature of 290 ° C and a vacuum degree of 1 torr or less for 3 hours. When the intrinsic viscosity reaches 0.65, it is discharged, pelletized into chips, precrystallized at 140 ° C, vacuum-dried at 170 ° C for 12 hours, lowered to 20 ppm of moisture, and then air-flowed into a silo. After melt spinning at < RTI ID = 0.0 > C, < / RTI > and wound at 1030 m / min, the temperature of the first roller was stretched at 85 deg.

[실시예 2]Example 2

상기 구조식(I)에서 n=3이고 M이 칼륨인 인산에스테르 칼륨염을 0.05 중량부 첨가하고 상기 실시예 1과 같은 방법으로 제조하였다.In the formula (I), 0.05 parts by weight of phosphate ester potassium salt in which n = 3 and M is potassium was added, and prepared in the same manner as in Example 1.

[실시예 3]Example 3

상기 구조식(I)에서 n=3이고 M이 칼륨인 인산에스테르 칼륨염을 1.5 중량부 첨가하고 상기 실시예 1과 같은 방법으로 제조하였다.1.5 parts by weight of a phosphate potassium salt of n = 3 and M in potassium in Structural Formula (I) was prepared in the same manner as in Example 1.

[비교예 1]Comparative Example 1

상기 구조식(I)로 표시되는 인산에스테르염을 첨가하지 않고 상기 실시예 1과 같은 방법으로 제조하였다.It was prepared in the same manner as in Example 1 without adding the phosphate ester salt represented by the above formula (I).

[비교예 2]Comparative Example 2

상기 구조식(I)에서 n=9이고 M이 칼륨인 인산에스테르 칼륨염을 0.025 중량부 첨가하고 상기 실시예 1과 같은 방법으로 제조하였다.In the formula (I), 0.025 parts by weight of phosphate ester potassium salt in which n = 9 and M is potassium, was prepared in the same manner as in Example 1.

[실험예]Experimental Example

상기 실시예 1 ∼ 3 및 비교예 1 ∼ 2의 제조과정중 슬러리에서의 이산화티탄 분산성의 측정은 1 ㎛의 필터를 사용하여 여과시험을 하여 갑자기 압력이 상승되는 시간을 측정하였고, 안정성은 각각의 슬러리에 대하여 24시간, 48시간, 일주일동안 방치한 후 여과시험과 침강거리를 측정하였다. 이때, 침강거리가 클수록 안정성은 떨어진다.Measurement of titanium dioxide dispersibility in the slurry during the manufacturing process of Examples 1 to 3 and Comparative Examples 1 to 2 was measured by the filtration test using a filter of 1 ㎛ to measure the time when the pressure suddenly rises, the stability of each After allowing the slurry to stand for 24 hours, 48 hours, and one week, the filtration test and the settling distance were measured. At this time, the greater the settling distance, the lower the stability.

그리고, 폴리머에서의 이산화티탄의 분산성은 폴리머를 시료채취용 칼로 자른후 플라즈마 처리하고 금 미립자로 표면 코팅하여 전자현미경으로 이산화티탄 입자크기와 분포를 하나의 시료당 10회 관찰하여 입자크기가 4 ㎛ 이상인 갯수를 측정하였다.The dispersibility of titanium dioxide in the polymer was measured by cutting the polymer with a sampling knife, and then plasma-treated and surface coated with gold fine particles to observe the titanium dioxide particle size and distribution 10 times per sample by using an electron microscope. The number more than was measured.

제조 후 방사, 연신 작업성을 만권율로 표시하였으며, 절사, 모우발생 등이 있는 것은 비정상분으로 만권에서 제외시켰다. 이와같이 측정한 물성치는 다음 표에 나타낸 바와같다.After manufacturing, the workability of spinning and drawing was expressed in all winding rates, and those with cuts and outbreaks were excluded from the full winding as abnormal. The measured physical properties are as shown in the following table.

상기 표에서 알 수 있듯이 본 발명에 의해 제조된 풀덜 폴리에스테르 수지는 슬러리에서의 이산화티탄의 분산성과 안정성이 비교예에 비하여 우수하고, 폴리머에서의 이산화티탄 분산성도 뛰어나다. 그리고 방사, 연신 작업성도 비교예에 비하여 우수하다.As can be seen from the above table, the pulled polyester resin prepared by the present invention has excellent dispersibility and stability of titanium dioxide in the slurry as compared with the comparative example, and excellent titanium dioxide dispersibility in the polymer. And spinning and drawing workability are also excellent compared with the comparative example.

Claims (1)

고순도 테레프탈산과 에틸렌 글리콜을 반응시키고 평균지름이 1 ㎛이하인 이산화티탄 미립자와 함께 인화합물을 에틸렌 글리콜에 분산시킨 슬러리를 2 ∼ 4 중량% 첨가하여 풀덜 폴리에스테르 수지를 제조함에 있어서, 상기 이산화티탄 미립자 100 중량부에 대하여 다음 구조식(I)로 표시되는 인산 에스테르 화합물을 0.01 ∼ 3 중량부 첨가하되 상기 이산화티탄은 에스테르화율이 80 ∼ 90% 진행되었을 때 첨가하는 것을 특징으로 하는 풀덜 폴리에스테르 수지의 제조방법.In preparing a pulled polyester resin by adding 2 to 4% by weight of a slurry obtained by reacting high-purity terephthalic acid with ethylene glycol and dispersing a phosphorus compound in ethylene glycol with titanium dioxide fine particles having an average diameter of 1 μm or less, the titanium dioxide fine particles 100 0.01 to 3 parts by weight of a phosphate ester compound represented by the following structural formula (I) is added to parts by weight, but the titanium dioxide is added when the esterification rate is 80 to 90%. . 상기식에서, M은 칼륨원자이며, n은 1 ∼ 8의 정수이다.Wherein M is a potassium atom and n is an integer from 1 to 8.
KR1019940038778A 1994-12-29 1994-12-29 Process for preparing full-dull polyester resin KR0167001B1 (en)

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