KR100536340B1 - Polyester resin with excellent hydrophilicity and color development and its manufacturing method - Google Patents
Polyester resin with excellent hydrophilicity and color development and its manufacturing method Download PDFInfo
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- KR100536340B1 KR100536340B1 KR1019980013928A KR19980013928A KR100536340B1 KR 100536340 B1 KR100536340 B1 KR 100536340B1 KR 1019980013928 A KR1019980013928 A KR 1019980013928A KR 19980013928 A KR19980013928 A KR 19980013928A KR 100536340 B1 KR100536340 B1 KR 100536340B1
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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
- C08G63/91—Polymers modified by chemical after-treatment
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- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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Abstract
본 발명은 방향족 디에시드 또는 이들의 에스테르 화합물과 지방족 디올로 이루어진 폴리에스테르의 제조방법에 있어서, 상기 방향족 디에시드 또는 이들의 에스테르 화합물 및 지방족 디올을 1.1:2∼2:2의 몰비로 혼합하고, 여기에 상기 방향족 디에시드 또는 이들의 에스테르 화합물에 대하여 0.1∼1.0몰%의 2,5-디하이드록시테레프탈산을 혼합한 후, 260∼300℃에서 반응시켜 제조된 친수성 및 발색성이 우수한 폴리에스테르 수지 및 이의 제조방법에 관한 것이다. 본 발명에 따른 폴리에스테르 수지는 친수성 및 흡습성이 우수하여 전기충격이나 방전으로 인한 화재사고를 방지할 수 있고, 발색성이 우수하며, 방사·연신공정시 절사 및 단사현상을 일으키지 않으므로 공정이 용이하여 산업적으로 유용하다.The present invention provides a method for producing a polyester comprising an aromatic dieside or an ester compound thereof and an aliphatic diol, wherein the aromatic dieside or an ester compound thereof and an aliphatic diol are mixed in a molar ratio of 1.1: 2 to 2: 2, A polyester resin excellent in hydrophilicity and color development prepared by mixing 0.1 to 1.0 mol% of 2,5-dihydroxyterephthalic acid with respect to the aromatic dieside or an ester compound thereof and reacting at 260 to 300 ° C; It relates to a manufacturing method thereof. The polyester resin according to the present invention has excellent hydrophilicity and hygroscopicity to prevent fire accidents due to electric shock or discharge, and excellent color development, and does not cause cutting and single yarn phenomena during the spinning and stretching process. Useful as
Description
본 발명은 친수성 및 발색성이 우수한 폴리에스테르 수지 및 이의 제조방법에 관한 것으로, 좀 더 상세하게는 지방족 디올(diol)과 방향족 디에시드(diacid) 또는 이들의 에스테르 화합물에 친수성 및 발색성을 높이기 위하여 2,5-하이드록시테레프탈산을 첨가하여 구조적으로 친수성기를 도입시켜 제조되는 친수성 및 발색성이 우수한 폴리에스테르 수지 및 이를 제조하는 방법에 관한 것이다.The present invention relates to a polyester resin having excellent hydrophilicity and color development, and more particularly, to improve hydrophilicity and color development in aliphatic diols and aromatic diacids or ester compounds thereof. The present invention relates to a polyester resin having excellent hydrophilicity and color development by adding 5-hydroxyterephthalic acid to structurally introduce a hydrophilic group, and a method of preparing the same.
일반적으로 폴리에스테르는 화학 구조적으로 카르복실기, 하이드록실기, 아민기 등의 극성기가 없는 소수성기로 된 구조화합물로 물과의 친화력이 없어 정전기로 인한 전기충격(electric shock)이나 방전으로 인한 화재사고까지 불러일으킬 소지가 있어, 폴리에스테르 수지에 친수성 및 흡습성을 도입하려는 노력이 계속되어져 왔으며, 특히 공중합을 이용해 친수성기를 도입하거나 또는 친수성 물질을 블렌딩(bleding)하는 방법이 많이 쓰여 왔다.In general, polyester is a structural compound composed of hydrophobic groups without polar groups such as carboxyl groups, hydroxyl groups, and amine groups in chemical structure, and has no affinity with water, resulting in fire accidents due to electric shock or discharge due to static electricity. There is a possibility of causing, and efforts to introduce hydrophilicity and hygroscopicity into polyester resins have been continued, and in particular, there have been many methods of introducing hydrophilic groups using copolymerization or blending of hydrophilic materials.
대한민국 특허출원 제 93-27817호 (공고번호 96-2881호)는 이 중 후자의 한 예로서, 전 산 성분에 대하여 분자량 600 내지 6000인 폴리테트라메틸렌글리콜 20 내지 60중량%, 무수 트리멜리트산 0.01 내지 5중량% 및 설포네이트 화합물 3 내지 15중량%를 함유하는 주반복단위가 부틸렌테레프탈산인 폴리에테르에스테르 칩(chip)을 일반 폴리에스테르에 대하여 0.5 내지 30중량%로 혼합하여 용융·방사, 제사한 것을 특징으로 하는 친수·제전성 폴리에스테르 섬유가 개시되어 있다. 그러나, 이 방법으로 제조한 폴리에스테르 수지는 방사시 용융혼련에 의하여 일반 폴리에스테르 칩과 폴리에테르에스테르 칩을 균일하게 섞어야 하는데 사출성형기(Extruder)의 혼련 부분의 길이가 충분히 길지 않으므로 불균일하게 섞이게 되어 방사·연신공정시, 절사 및 단사현상 등의 원인이 된다. 이 경우 혼련효과를 좋게 하기 위하여 온도를 상승시키면 열분해 등이 일어날 소지가 있다.Republic of Korea Patent Application No. 93-27817 (Publication No. 96-2881) is one of the latter, 20 to 60% by weight polytetramethylene glycol having a molecular weight of 600 to 6000 with respect to the total acid component, trimellitic anhydride 0.01 Melting, spinning and spinning by mixing 0.5 to 30% by weight of a polyetherester chip having a main repeating unit of butylene terephthalic acid containing from 5 to 5% by weight and 3 to 15% by weight of sulfonate compound Hydrophilic and antistatic polyester fiber characterized by the above-mentioned is disclosed. However, the polyester resin prepared by this method must uniformly mix the general polyester chip and the polyether ester chip by melt kneading during spinning, but because the length of the kneading part of the extruder is not long enough, it is mixed unevenly. During spinning and drawing process, it may cause cutting and single yarn phenomena. In this case, if the temperature is increased in order to improve the kneading effect, there is a possibility of thermal decomposition.
한편, 일본 특개소 제 51-37993호는 전자의 한 예로서 폴리옥시알킬렌 유도체를 중합시 투입하는 방법을 개시하고 있으며, 일본 특개소 제 63-308059호 역시 전자의 한 예로서 폴리옥시알킬렌 유도체와 알킬설폰산 금속염을 중합시 병행하여 투입하는 방법을 개시하고 있으나, 이는 모두 친수·제전성능이 향상되는 반면 방사성이 떨어지고, 폴리머의 내열성에 문제점이 있었다.On the other hand, Japanese Patent Laid-Open No. 51-37993 discloses a method of introducing a polyoxyalkylene derivative during polymerization as an example of the former, and Japanese Patent Laid-Open No. 63-308059 is also a polyoxyalkylene as an example of the former. Although a derivative and an alkylsulfonic acid metal salt are disclosed to be added in parallel during polymerization, all of them have improved hydrophilic and antistatic properties, but have poor radioactivity and have problems in heat resistance of the polymer.
한편, 발색성을 향상시키기 위해서는 중합단계에서 중합촉매에 의해 개선시키는 방법과 후가공 단계에서 발색제 처리를 하여 발색성을 항상시키는 방법이 알려져 있다. 전자의 방법으로는 발색성에 관계있는 중합촉매나 무기계 첨가제(TiO2 등)에 의해 85 이상의 칩을 얻기는 불가능하며 후자의 경우는 내세탁성이 떨어지는 단점이 있다. 그러나, 본 발명에서는 2,5-디하이드록시테레프탈산을 사용함으로써 소량 첨가로 우수한 발색성 및 세탁견뢰도를 얻을 수 있었다.On the other hand, in order to improve the color development, a method of improving by a polymerization catalyst in a polymerization step and a method of always maintaining color development by treating a colorant in a post-processing step are known. In the former method, it is impossible to obtain a chip of 85 or more by a polymerization catalyst or an inorganic additive (TiO 2, etc.) related to color development, and in the latter case, the washing resistance is inferior. However, in the present invention, by using 2,5-dihydroxyterephthalic acid, it was possible to obtain excellent color development and washing fastness with a small amount of addition.
따라서, 본 발명의 목적은 상술한 문제점을 해결할 수 있는 친수성이 우수한 폴리에스테르 수지를 제조하는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide a method for producing a polyester resin excellent in hydrophilicity that can solve the above problems.
본 발명의 다른 목적은 상기 방법으로 제조되는 친수성 및 발색성이 우수한 폴리에스테르 수지를 제공하는데 있다.Another object of the present invention is to provide a polyester resin excellent in hydrophilicity and color development produced by the above method.
상기 목적을 달성하기 위한 본 발명의 방법은 방향족 디에시드 또는 이들의 에스테르 화합물과 지방족 디올로 이루어진 폴리에스테르의 제조방법에 있어서, 방향족 디에시드 또는 이들의 에스테르 화합물 및 지방족 디올을 1.1:2∼2:2의 몰비로 혼합하고, 여기에 하기 화학식 1로 표시되는 2,5-디하이드록시테레프탈산(2,5-dihydroxyterephthallic acid)을 상기 방향족 디에시드 또는 이들의 에스테르 화합물에 대하여 0.1∼1.0몰% 혼합한 후, 260∼300℃에서 반응시키는 것으로 이루어진다.The method of the present invention for achieving the above object is a method for producing a polyester consisting of an aromatic dieside or an ester compound thereof and an aliphatic diol, wherein the aromatic dieside or an ester compound thereof and an aliphatic diol are 1.1: 2 to 2 :: 2, 5-dihydroxy terephthalic acid (2,5-dihydroxyterephthallic acid) represented by the following formula (1) to 0.1 to 1.0 mol% of the aromatic dieside or ester compounds thereof Then, it is made to react at 260-300 degreeC.
상기 다른 목적을 달성하기 위한 본 발명의 친수성 및 발색성이 우수한 폴리에스테르 수지는 상기 방법으로 제조되며, 그 표면저항값이 8∼11을 갖는다.The polyester resin which is excellent in the hydrophilicity and color development property of this invention for achieving the said other objective is manufactured by the said method, and the surface resistance value has 8-11.
이하, 본 발명을 좀 더 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명의 방법은 기존에 알려진 공중합에 의한 방법이지만, 별도의 친수성 화합물을 첨가하는 것이 아니라, 방향족 디에시드 또는 이들의 에스테르 화합물 및 지방족 디올을 1.1:2∼2:2의 몰비로 혼합하고, 여기에 하기 화학식 1로 표시되는 2,5-디하이드록시테레프탈산을 상기 방향족 디에시드 또는 이들의 에스테르 화합물에 대하여 0.1∼1.0몰% 혼합한 후, 260∼300℃에서 반응시켜 친수성 및 발색성이 우수한 폴리에스테르 수지를 제조한다.The method of the present invention is a method by known copolymerization, but instead of adding a separate hydrophilic compound, aromatic diesides or ester compounds thereof and aliphatic diols are mixed in a molar ratio of 1.1: 2 to 2: 2, and 2,5-dihydroxyterephthalic acid represented by the following formula (1) is mixed with 0.1 to 1.0 mol% of the aromatic dieside or ester compounds thereof, and then reacted at 260 to 300 ℃ polyester excellent in hydrophilicity and color development Prepare a resin.
화학식 1Formula 1
상기 화학식 1에서, 2,5-디하이드록시테레프탈산의 카르복실 부분은 지방족 디올과 반응하여 긴 분자쇄를 형성시켜 고분자량의 폴리에스테르를 형성하고, 하이드록시부분은 그대로 잔존하여 상기 폴리에스테르 수지의 친수성화 및 발색성에 기여하며, 소수성 폴리에스테르 수지에 하이드록실기를 도입함에 따라 상기에서 서술한 친수성의 향상 외에 칩 컬러 (color)의 L치가 많이 개선된 즉, 발색성이 우수한 성질도 나타낸다.In Chemical Formula 1, the carboxyl moiety of 2,5-dihydroxyterephthalic acid reacts with aliphatic diol to form a long molecular chain to form a high molecular weight polyester, and the hydroxy moiety remains as it is to of the polyester resin. In addition to the hydrophilicity described above, the L value of the chip color is greatly improved, that is, the color development property is excellent, as it contributes to the hydrophilization and the color development and the introduction of the hydroxyl group to the hydrophobic polyester resin.
한편, 본 발명에 사용되는 지방족 디올은 에틸렌글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥사메틸렌디올 및 디에틸렌글리콜로 이루어진 군으로부터 선택된 하나가 바람직하며, 방향족 디에시드 또는 이들의 에스테르 화합물은 테레프탈산, 이소프탈산, 프탈산, 디메틸테레프탈레이트, 디메틸이소프탈레이트 및 디메틸프탈레이트로 이루어진 군으로부터 선택된 하나가 바람직하다.On the other hand, the aliphatic diol used in the present invention is preferably one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexamethylenediol and diethylene glycol, aromatic dieside Or an ester compound thereof is preferably one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethylisophthalate and dimethylphthalate.
상기 화학식 1로 표시되는 친수성 화합물의 양은 방향족 디에시드 또는 이들의 에스테르 화합물에 대하여 0.1∼1.0몰%가 바람직하다. 상기 화합물의 함량이 0.1몰% 미만이면 하이드록시기의 농도가 낮아 친수성이 떨어지고, 1.0몰%를 초과하면 친수성은 좋아지지만 발색성이 떨어지는 단점이 있다.The amount of the hydrophilic compound represented by the formula (1) is preferably 0.1 to 1.0 mol% based on the aromatic dieside or ester compounds thereof. When the content of the compound is less than 0.1 mol%, the concentration of the hydroxy group is low, the hydrophilicity is lowered. When the content of the compound is more than 1.0 mol%, the hydrophilicity is improved, but the color development is poor.
한편, 바람직한 친수성의 정도는 수지의 용도에 따라 다르지만 일반적으로 의류용으로 적합한 정도의 친수성이라면 수지 내 총 말단 COOH기 함량을 60-120ppm으로 조절함이 바람직하다. 이는 상기 범위 내에서 특히 친수성이 발현되면서도 방사공정시 문제가 되지 않게 하기 위함이다.On the other hand, the degree of preferred hydrophilicity depends on the use of the resin, but in general, if the degree of hydrophilicity suitable for clothing, it is preferable to adjust the total terminal COOH group content in the resin to 60-120ppm. This is to ensure that the hydrophilicity is not a problem during the spinning process, especially within the above range.
방향족 디에시드 또는 이들의 에스테르 화합물과 디올과의 몰비를 조절하여 수지내 총 말단 COOH기 함량을 조절할 수 있는 바, 수지내 총 말단 COOH기 함량을 60-120ppm으로 하기 위해서는 산성분 대 디올 성분의 몰비를 1.1:2∼2:2로 조절함이 바람직하다.The total terminal COOH group content in the resin can be controlled by controlling the molar ratio of the aromatic dieside or its ester compound and diol.The molar ratio of the acid component to the diol component is 60-120 ppm in order to control the total terminal COOH group content in the resin. Is preferably adjusted to 1.1: 2 to 2: 2.
폴리에스테르 수지의 친수성 평가는 제조된 칩을 20㎛정도의 얇은 필름을 만들어 적외선분광기(FT-IR)를 이용하여 남아있는 카르복실산의 3300∼3500cm-1에서의 OH로 인한 흡수 피크(peak)의 면적으로 평가하였다. 여기서, 친수성이 발현되기 위해서는 OH로 인한 흡수 피크의 면적은 50 이상, 흡수거리는 50mm 이상, 표면저항은 8∼11(log(Ω㎝)) 정도의 값이 바람직하며, 이때 상기 표면저항값이 11을 초과하면, 친수성이 떨어지는 문제가 발생한다.Hydrophilicity evaluation of the polyester resin was carried out using a infrared spectroscopy (FT-IR) to make a thin film of about 20㎛ the absorption chip due to the OH of the remaining carboxylic acid at 3300 ~ 3500cm -1 It evaluated by the area of. Herein, in order to express hydrophilicity, an area having an absorption peak due to OH is 50 or more, an absorption distance is 50 mm or more, and a surface resistance of about 8 to 11 (log (Ωcm)) is preferable, wherein the surface resistance value is 11 If exceeded, the problem of inferior hydrophilicity arises.
발색성은 Macbeth의 CE-7700의 Color Eye를 가지고 측정된 컬러(Color) L값으로 평가하였다.The color development was evaluated by Color L value measured with Macbeth's CE-7700 Color Eye.
이하, 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 실시예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.
각종 물성의 측정방법은 다음과 같다.The measurement method of various physical properties is as follows.
<고유점도><Unique viscosity>
건조한 시료를 오르쏘 클로로페놀 (ortho-chlorophenol) 용매에 용해시킨 후 25℃ 오스트발트 점도계에서 측정하였다.The dry sample was dissolved in an ortho-chlorophenol solvent and measured on a 25 ° C. Ostwald viscometer.
<유리전이온도 및 융점>Glass transition temperature and melting point
퍼킨-엘머 시차주사열량 분석기를 이용하여 시료의 유리전이온도, Tg 및 융점, Tm을 10℃/분의 승온속도로 실온에서 300℃까지 측정하였다.The glass transition temperature, Tg and melting point, and Tm of the samples were measured from room temperature to 300 ° C. at a rate of 10 ° C./min using a Perkin-Elmer differential scanning calorimeter.
<강·신도><Gang, Shinto>
인장시험기를 사용하여 실온에서 시료의 강도·신도를 측정하였다.The tensile tester was used to measure the strength and elongation of the sample at room temperature.
<제사성><Sacrality>
폴리에스테르 폴리머를 24시간(50kg) 방사하여 얻은 미연신사를 연신할 때의 절사 및 단사의 횟수에 의하여 평가하였다.It evaluated by the number of cutting | disconnection and single yarn at the time of extending | stretching the undrawn yarn obtained by spinning a polyester polymer for 24 hours (50 kg).
O; 절사, 단사가 거의 없음O; Almost no cutting or single yarn
X; 절사 5회 이상X; 5 times or more
<컬러><Color>
Macbeth의 CE-7700의 Color Eye를 가지고 Color L 및 b값을 측정하였다.Color L and b values were measured using Macbeth's CE-7700 Color Eye.
<흡수거리><Absorption distance>
Birec 법에 의하여 가로 25㎜ ×세로 200㎜의 시료를 수조에 닿게 한 후 실온에서 10분간 방치시킨 후의 올라간 거리를 측정하였다.The raised distance after leaving the sample 25 mm x 200 mm in length by the Birec method in contact with the water tank for 10 minutes at room temperature was measured.
<OH 흡수율><OH absorption rate>
적외선 분광기(FT-IR)를 이용하여 3300-3500㎝-1에서의 남아있는 하이드록시기의 OH로 인한 흡수 피크의 면적을 측정하였다.The area of the absorption peak due to OH of the remaining hydroxyl groups at 3300-3500 cm -1 was measured using an infrared spectrometer (FT-IR).
실시예 1Example 1
테레프탈산과 에틸렌글리콜을 몰비로 1.1:2로 혼합하고, 2,5-디하이드록시테레프탈산을 상기 테레프탈산에 대하여 0.1몰% 혼합한 후, 여기에 제 1촉매로서 칼슘트리아세테이트 (calcium triacetate)를 400ppm, 정색제로 코발트아세테이트(cobalt acetate)를 60ppm, 열안정제로 포스포릭산(phosphoric acid)을 150ppm, 제 2촉매로서 안티몬트리아세테이트(antimon triacetate)를 400ppm 첨가하여 중합온도 280℃, 0.3mmHg의 감압하에서 축중합시켜 고유점도가 0.620(dl/g)이며 분자량 분포가 3.30인 중합물을 얻는다. 이 범위에 있으면 겔화가 일어나지 않고 용융방사 하기에 적당한 융점을 가진다.Terephthalic acid and ethylene glycol were mixed in a molar ratio of 1.1: 2, and 2,5-dihydroxyterephthalic acid was mixed with 0.1 mol% of the terephthalic acid, and then 400 ppm of calcium triacetate was used as the first catalyst. 60 ppm of cobalt acetate as a colorant, 150 ppm of phosphoric acid as a heat stabilizer, and 400 ppm of antimony triacetate as a second catalyst were added, and the polymerization temperature was reduced at 280 ° C under a reduced pressure of 0.3 mmHg. The polymerization yields a polymer having an intrinsic viscosity of 0.620 (dl / g) and a molecular weight distribution of 3.30. If it is in this range, gelation does not occur and it has melting | fusing point suitable for melt spinning.
실시예 2Example 2
실시예 1과 동일조건으로 하되, 테레프탈산과 에틸렌글리콜을 몰비로 1.3:2로 혼합하고, 2,5-디하이드록시테레프탈산을 상기 테레프탈산에 대하여 0.3몰% 혼합하였으며, 얻어진 중합물의 분자량 분포는 3.35였다. 이렇게 하여 얻어진 칩은 겔화가 일어나지 않고 용융방사하기에 적당한 융점을 가진다.Under the same conditions as in Example 1, terephthalic acid and ethylene glycol were mixed in a molar ratio of 1.3: 2, 2,5-dihydroxyterephthalic acid was mixed with 0.3 mol% of the terephthalic acid, and the molecular weight distribution of the obtained polymer was 3.35. . The chip thus obtained has a melting point suitable for melt spinning without gelation.
실시예 3Example 3
테레프탈산과 에틸렌글리콜을 몰비로 1.5:2로 혼합하고, 2,5-디하이드록시테레프탈산의 사용량을 상기 테레프탈산에 대하여 0.5몰%로 한 것 외에는 실시예 1과 같다.Terephthalic acid and ethylene glycol were mixed at a molar ratio of 1.5: 2, and the amount of 2,5-dihydroxyterephthalic acid was adjusted to 0.5 mol% with respect to the terephthalic acid as in Example 1.
실시예 4Example 4
테레프탈산과 에틸렌글리콜을 몰비로 1.7:2로 혼합하고, 2,5-디하이드록시테레프탈산의 사용량을 상기 테레프탈산에 대하여 0.7몰%로 한 것 외에는 실시예 1과 같다.Terephthalic acid and ethylene glycol were mixed in a molar ratio of 1.7: 2, and the amount of 2,5-dihydroxyterephthalic acid was set to 0.7 mol% with respect to the terephthalic acid as in Example 1.
실시예 5Example 5
테레프탈산과 에틸렌글리콜을 몰비로 1.9:2로 혼합하고, 2,5-디하이드록시테레프탈산의 사용량을 상기 테레프탈산에 대하여 0.9몰%로 한 것 외에는 실시예 1과 같다.Terephthalic acid and ethylene glycol were mixed in a molar ratio of 1.9: 2, and the amount of 2,5-dihydroxyterephthalic acid was adjusted to 0.9 mol% based on the terephthalic acid as in Example 1.
실시예 6Example 6
테레프탈산과 에틸렌글리콜을 몰비로 2:2로 혼합하고, 2,5-디하이드록시테레프탈산의 사용량을 상기 테레프탈산에 대하여 1.0몰%로 한 것 외에는 실시예 1과 같다.Terephthalic acid and ethylene glycol were mixed in a 2: 2 molar ratio, and the amount of 2,5-dihydroxy terephthalic acid was adjusted to 1.0 mol% based on the terephthalic acid as in Example 1.
비교예 1Comparative Example 1
실시예 1과 동일조건으로 하되, 테레프탈산과 에틸렌글리콜을 몰비로 1.0:2로 혼합하고, 2,5-디하이드록시테레프탈산은 첨가하지 않았다.Under the same conditions as in Example 1, terephthalic acid and ethylene glycol were mixed in a molar ratio of 1.0: 2, and 2,5-dihydroxyterephthalic acid was not added.
비교예 2Comparative Example 2
실시예 1과 동일조건으로 하되, 테레프탈산과 에틸렌글리콜을 몰비로 1.05:2로 혼합하고, 2,5-디하이드록시테레프탈산을 상기 테레프탈산에 대하여 0.05몰% 혼합하였다.Under the same conditions as in Example 1, terephthalic acid and ethylene glycol were mixed in a molar ratio of 1.05: 2, and 2,5-dihydroxyterephthalic acid was mixed with 0.05 mol% of the terephthalic acid.
비교예 3Comparative Example 3
실시예 1과 동일조건으로 하되, 테레프탈산과 에틸렌글리콜을 몰비로 2.5:2로 혼합하고, 2,5-디하이드록시테레프탈산을 상기 테레프탈산에 대하여 1.5몰% 혼합하였다.Under the same conditions as in Example 1, terephthalic acid and ethylene glycol were mixed at a molar ratio of 2.5: 2, and 2,5-dihydroxyterephthalic acid was mixed with 1.5 mol% of the terephthalic acid.
상기 실시예 및 비교예에 의거하여 상기 화학식 1 및 2로 표시되는 화합물을 첨가하여 제조된 폴리에스테르수지의 특성 결과를 하기 표 1과 표 2에 나타내었다.Based on the Examples and Comparative Examples, the results of the properties of the polyester resin prepared by adding the compounds represented by Formulas 1 and 2 are shown in Table 1 and Table 2.
이상에서 살펴본 바와 같이, 방향족 디에시드 또는 이들의 에스테르 화합물과 지방족 디올로 이루어진 폴리에스테르의 제조방법에 있어서, 상기 화학식 1로 표시되는 2,5-디하이드록시테레프탈산을 첨가시켜 소수성 폴리에스테르 수지에 친수성기가 도입시키는 본 발명의 방법은 폴리에스테르 수지에 우수한 친수성 및 흡습성을 제공하여 전기충격이나 방전으로 인한 화재사고를 방지할 수 있고, 우수한 발색성을 가지며, 방사·연신공정시 절사 및 단사현상을 일으키지 않으므로 공정이 용이하여 산업적으로 유용하게 활용될 수 있다.As described above, in the method for producing a polyester consisting of an aromatic dieside or an ester compound thereof and an aliphatic diol, a hydrophilic group is added to a hydrophobic polyester resin by adding 2,5-dihydroxyterephthalic acid represented by Formula 1 above. The method of the present invention, which provides the polyester resin with excellent hydrophilicity and hygroscopicity, can prevent fire accidents due to electric shock or discharge, has excellent color development, and does not cause cutting and single yarn phenomena during the spinning and stretching process. The process is easy and can be utilized industrially useful.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5556122A (en) * | 1978-10-20 | 1980-04-24 | Teijin Ltd | Preparation of polyester |
| JPS57143323A (en) * | 1981-03-03 | 1982-09-04 | Teijin Ltd | Preparation of polyester |
| JPS5978233A (en) * | 1982-10-28 | 1984-05-07 | Teijin Ltd | Production of polyester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5556122A (en) * | 1978-10-20 | 1980-04-24 | Teijin Ltd | Preparation of polyester |
| JPS57143323A (en) * | 1981-03-03 | 1982-09-04 | Teijin Ltd | Preparation of polyester |
| JPS5978233A (en) * | 1982-10-28 | 1984-05-07 | Teijin Ltd | Production of polyester |
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