KR101083773B1 - A flame retardant polyester with excellent color tone, and a process of preparing the same - Google Patents
A flame retardant polyester with excellent color tone, and a process of preparing the same Download PDFInfo
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- KR101083773B1 KR101083773B1 KR1020040028862A KR20040028862A KR101083773B1 KR 101083773 B1 KR101083773 B1 KR 101083773B1 KR 1020040028862 A KR1020040028862 A KR 1020040028862A KR 20040028862 A KR20040028862 A KR 20040028862A KR 101083773 B1 KR101083773 B1 KR 101083773B1
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- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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Abstract
본 발명은 색상이 우수한 난연성 폴리에스테르 및 그의 제조방법에 관한 것으로서, 폴리에스테르의 중축합 반응시에 인계난연제와 보색제로 코발트 아세테이트를 함께 첨가하여 한계 산소지수(LOI)가 28∼35 이고, 색차계 기준 b 값이 1.0∼3.0 인 난연성 폴리에스테르를 제조한다. 본 발명의 난연성 폴리에스테르는 섬유, 필름 및 성형품 등에 사용 된다.
The present invention relates to a flame-retardant polyester excellent in color and a method for manufacturing the same, wherein the polyoxygen-condensation reaction of the polyester has a limiting oxygen index (LOI) of 28 to 35 by adding cobalt acetate as a phosphorus flame retardant and a complementing agent, and a color difference meter. Flame retardant polyesters having a standard b value of 1.0 to 3.0 are prepared. Flame retardant polyesters of the present invention are used in fibers, films and molded articles.
난연성, 폴리에스테르, 인계난연제, 보색제, 코발트 아세테이트, 색상Flame Retardant, Polyester, Phosphorus Flame Retardant, Compensator, Cobalt Acetate, Color
Description
본 발명은 색상이 우수한 난연성 폴리에스테르 및 그의 제조방법에 관한 것이다. 보다 구체적으로는, 폴리에스테르의 중축합시에 인계난연제와 보색제로 코발트 아세테이트를 함께 첨가하여 색상이 우수하고 난연성이 향상된 폴리에스테르를 제조하는 방법에 관한 것이다.The present invention relates to a flame retardant polyester excellent in color and a method for producing the same. More specifically, the present invention relates to a method for producing a polyester having excellent color and improved flame retardancy by adding cobalt acetate as a phosphorus flame retardant and a complementary agent during polycondensation of polyester.
일반적으로 폴리에스테르는 열적 성질, 기계적 성질, 화학약품에 대한 저항성 및 성형성 등이 우수하여 섬유, 필름 또는 플라스틱 제품으로 많이 이용되고 있다. 그러나 이 같은 폴리에스테르는 난연성에 있어서 착화 후에는 급속히 연소하기 쉬운 단점을 갖고 있다. 이 때문에 인테리어 분야의 섬유, 필름, 성형품 및 엔지니어링 플라스틱 등에 있어서는 난연성, 특히 자기소화성을 갖는 폴리에스테르의 개발이 시장으로부터 요구되고 있다.In general, polyester is excellent in thermal properties, mechanical properties, chemical resistance and moldability, and is widely used as a fiber, film or plastic product. However, such a polyester has a disadvantage in flame retardancy that is easy to burn rapidly after ignition. For this reason, the development of the flame-retardant, especially self-extinguishing polyester in fiber, film, molded article, engineering plastics, etc. in the interior field is calculated | required from the market.
폴리에틸렌테레프탈레이트 섬유에 난연성을 부여하기 위한 종래 방법으로는 방사후에 섬유표면에 난연제를 코팅하는 방법과, 중합 후 방사 이전 단계에서 비반 응성 난연제를 첨가하여 혼합방사하는 방법 등이 이용되어 왔다. 그러나, 섬유표면에 난연제를 표면처리하는 방법은 반복 사용할 때 내구성 저하 등의 문제가 있었다.As a conventional method for imparting flame retardancy to polyethylene terephthalate fibers, a method of coating a flame retardant on the surface of the fiber after spinning and a method of mixing and spinning a non-reactive flame retardant by adding a non-reactive flame retardant in the pre-spinning step after polymerization have been used. However, the method of surface-treating the flame retardant on the fiber surface has problems such as deterioration in durability when repeatedly used.
한편, 최근에는 폴리에스테르 폴리머 제조시 난연제를 중합공정 중에 투입하여 공중합 내지 블랜드시켜 원사 자체에 고유한 난연성을 부여하는 방법이 연구되어 오고 있다. 구체적으로, 폴리에스테르 중합시에 원료와 함께 반응형 난연제를 투입하여 난연성을 부여하거나, 성형시에 폴리에스테르 수지와 첨가형 난연제를 혼합하여 난연성을 부여 하였다. On the other hand, in recent years, a method of incorporating a flame retardant during the polymerization process in the production of a polyester polymer to copolymerize or blend to impart inherent flame resistance to the yarn itself has been studied. Specifically, the flame retardant was imparted by adding a reactive flame retardant together with the raw material during polyester polymerization, or the flame retardance was imparted by mixing a polyester resin and an additive flame retardant during molding.
그 대표적인 난연제로는 크게 할로겐 함유 화합물과 금속 산화물의 혼합물, 질소 함유 화합물 및 인 함유 화합물로 나누어 진다. 그러나 상기 방법은 이들 난연제 중에서 어느 것을 사용하여도 제품 물성에 좋지 않은 영향을 주는 단점이 있었기 때문에 그때그때의 반응 조건에 따라 난연제를 선택하여 사용 하였다. 또한, 상기 방법은 후처리 방법에 비해 내구성과 난연 성능이 우수하다고 보고되어 있지만, 반응형 난연제의 종류에 따라 많은 문제점이 대두되어 왔다.Representative flame retardants are largely divided into a mixture of halogen-containing compounds and metal oxides, nitrogen-containing compounds and phosphorus-containing compounds. However, since the above method had a disadvantage of adversely affecting product properties even when using any of these flame retardants, the flame retardant was selected according to the reaction conditions at that time. In addition, the method is reported to be superior in durability and flame retardant performance compared to the post-treatment method, but many problems have been raised depending on the type of reactive flame retardant.
예를들어, 할로겐계 난연제를 사용하면 난연성이 발현된다 하더라도 공중합체가 착색이 되고, 내광성이 떨어지는 단점이 있다. 또한 인계 난연제를 사용할 때에도 난연제 자체의 열적 안정성이 낮기 때문에 공중합체가 변색되는 단점이 있다. For example, when the halogen flame retardant is used, even if the flame retardancy is expressed, the copolymer becomes colored and has the disadvantage of poor light resistance. In addition, even when the phosphorus-based flame retardant is used, there is a disadvantage in that the copolymer discolors because the thermal stability of the flame retardant itself is low.
이러한 점을 극복하기 위하여 일본특허공개공보 소 57-212251호와 일본 특허공개공보 소 59-191716호 등에서는 폴리에스테르 공중합시 중축합 반응이 어느정도 진행된 뒤에 난연제와 중축합 촉매를 넣는 방법을 제시하고 있으나, 위와 같은 문 제점을 완전히 해결하지는 못하였다.In order to overcome this problem, Japanese Patent Laid-Open Publication No. 57-212251 and Japanese Patent Laid-Open Publication No. 59-191716 disclose a method of adding a flame retardant and a polycondensation catalyst after a certain degree of polycondensation reaction has occurred in polyester copolymerization. However, this problem has not been completely solved.
본 발명의 목적은 이와 같은 종래방법의 문제점들을 해소할 수 있도록 난연성과 동시에 색상도 우수한 폴리에스테르를 제조하기 위한 것이다.
An object of the present invention is to produce a polyester flame retardant and excellent color at the same time to solve the problems of the conventional method.
본 발명은 폴리에스테르의 중축합시에 인계 난연제를 첨가하여 난연성 폴리에스테르를 제조할때 인계 난연제의 낮은 열적안정성으로 인해 최종제품이 변색되어 색상이 나빠지는 현상을 효과적으로 방지하는 방법을 제공하고자 한다. 또한, 본 발명은 난연성과 동시에 색상도 우수한 난연성 폴리에스테르를 제공하고자 한다.
The present invention is to provide a method for effectively preventing the discoloration of the final product due to the low thermal stability of the phosphorus-based flame retardant when producing a flame-retardant polyester by adding a phosphorus-based flame retardant during the polycondensation of the polyester. In addition, the present invention is to provide a flame retardant polyester excellent in flame retardancy and color at the same time.
이와 같은 과제를 달성하기 위하여 본 발명에서는 폴리에스테르의 중축합 반응시에 인계난연제와 보색제로 코발트 아세테이트를 함께 첨가하여 한계 산소지수(LOI)가 28∼35 이고, 색차계 기준 b 값이 1.0∼3.0 인 난연성 폴리에스테르를 제조한다. In order to achieve the above object, the present invention adds cobalt acetate as a phosphorus-based flame retardant and a complementary agent during the polycondensation reaction of polyester, and has a limit of oxygen index (LOI) of 28 to 35, and a color difference reference b value of 1.0 to 3.0. Phosphorus flame retardant polyester is prepared.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명은 통상의 방법과 같이 중축합 촉매 하에서 폴리에스테르를 중축합 할 때 난연성 부여를 위해 하기 일반식(Ⅰ)의 인계난연제를 첨가함과 동시에 색상개선을 위해 하기 일반식(Ⅱ)의 코발트 아세테이트도 함께 첨가하여 난연성 폴리에 스테르를 제조함을 특징으로 한다.The present invention adds a phosphorous flame retardant of formula (I) below to impart flame retardancy when polycondensing a polyester under a polycondensation catalyst as in a conventional method, and simultaneously improves color and cobalt acetate of formula (II) It is also characterized by the addition of a flame retardant polyester to the addition.
상기 식(Ⅰ)에서, R1 과 R2 는 같거나 서로 다른기로서 수소, 하이드록시에틸 또는 하이드록시프로필기 이다.In the formula (I), R 1 and R 2 are the same or different groups and are hydrogen, hydroxyethyl or hydroxypropyl groups.
상기 일반식(Ⅰ)의 인계 난연제는 3-히드록시페닐프로판카르본산, (2'-히드록시에틸)-3-히드록시페닐포스피닐프로판에스테르 또는 이들의 유도체 등이며, 중합된 난연성 폴리에스테르내 인원자 함량이 1,000∼10,000ppm이 될 수 있도록 인계난연제의 첨가량을 조절하는 것이 바람직 하다.The phosphorus flame retardant of formula (I) is 3-hydroxyphenylpropanecarboxylic acid, (2'-hydroxyethyl) -3-hydroxyphenylphosphinylpropane ester or derivatives thereof, and the like in a polymerized flame retardant polyester. It is desirable to adjust the amount of phosphorus-based flame retardant so that the phosphorus content is 1,000 to 10,000 ppm.
폴리에스테르 내 인함량이 1,000ppm 미만일 때에는 폴리에스테르의 난연성능이 떨어질 수 있고, 10,000ppm을 초과할 경우에는 폴리에스테르의 열적, 기계적 물성 등의 저하를 가져올 수 있다. When the phosphorus content in the polyester is less than 1,000 ppm, the flame retardant performance of the polyester may be lowered. When the phosphorus content in the polyester is more than 10,000 ppm, the thermal and mechanical properties of the polyester may be reduced.
또한, 보색제인 코발트 아세테이트는 폴리에스테르에 대해 30∼300ppm 정도를 첨가하는 것이 바람직 하다. 30ppm 미만일 때에는 색상 개선 효과가 미미하게 될 수 있으며, 300ppm을 초과할 때에는 디에틸렌글리콜 생성 및 카르복실 말단기의 증가와 같은 부반응이 증가하고 색상 또한 저하될 수 있다.In addition, it is preferable that cobalt acetate which is a complement agent adds about 30-300 ppm with respect to polyester. When the content is less than 30 ppm, the color improvement effect may be insignificant, and when it is more than 300 ppm, side reactions such as diethylene glycol production and an increase in carboxyl end groups may be increased, and color may also be reduced.
중축합 촉매로는 통상의 폴리에스테르 중축합 공정에서와 같이 삼산화안티몬 이나 티탄 등을 사용한다.As the polycondensation catalyst, antimony trioxide, titanium or the like is used as in a conventional polyester polycondensation step.
이상에서 설명한 본 발명의 제조방법으로 제조된 난연성 폴리에스테르는 한계 산소지수(LOI)가 28∼35 이고, 색차계 기준 b 값이 1.0∼3.0 으로 우수한 난연성과 색상을 나타 낸다.The flame-retardant polyester produced by the production method of the present invention described above exhibits excellent flame retardancy and color with a limit oxygen index (LOI) of 28 to 35 and a color difference reference b value of 1.0 to 3.0.
이와 같은 결과는 보색제로 폴리에스테르 중축합시 첨가되는 상기 일반식(Ⅱ)의 코발트 아세테이트가 상기 일반식(Ⅰ)의 인계난연제의 열적안정성을 보완해 주기 때문인 것으로 추측 된다.These results are presumed to be because the cobalt acetate of formula (II) added during polyester polycondensation as a complementary agent complements the thermal stability of the phosphorus-based flame retardant of formula (I).
본 발명에 있어서 색상계 기준 b값, L값 및 L값/b값 은 니폰 덴쇼쿠(Nippon denshoku) 모델 No. SE-2000을 이용하여 측정 하였고, 한계산소지수(LOI)는 ASTM D-2863-70에 의한 산소계수 가연성 게이지로 측정 하였다.In the present invention, the color system reference b value, L value, and L value / b value are Nippon denshoku model No. It was measured using SE-2000, and the limit oxygen index (LOI) was measured by the oxygen coefficient flammability gauge according to ASTM D-2863-70.
이하, 실시예 및 비교실시예를 통하여 본 발명을 더욱 구체적으로 살펴 본다. 하기 실시예들은 본 발명을 구체적으로 설명하는 것으로서 본 발명의 범주를 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The following examples illustrate the invention in detail and do not limit the scope of the invention.
실시예 1Example 1
테레프탈산 100 중량부에 대하여 에틸렌글리콜 50 중량부를 에스테르화 반응기에 투입한 후, 1.0kg/㎠의 압력으로 가압하여 물을 반응기 외로 유출시키면서 에스테르 반응을 진행시켜 비스-(β-옥시에틸)테레프탈레이트를 제조한다. 계속해서 여기에 인계난연제인 3-히드록시페닐포스피닐프로판카르본산 6 중량부와 코발트 아세테이트 0.0034 중량부를 첨가하고 삼산화안티몬(중축합 촉매) 존재 하에서 고온 및 고진공의 통상적인 폴리에스테르 반응조건으로 중축합 반응을 진행한 후, 팰 릿(Pellet) 형상으로 고분자(폴리에스테르)를 제조 하였다. 제조한 폴리에스테르의 난연성을 평가한 결과와 색차계를 이용하여 측정한 L값 및 b값은 표 2와 같다.50 parts by weight of ethylene glycol was added to the esterification reactor with respect to 100 parts by weight of terephthalic acid, and then pressurized at a pressure of 1.0 kg / cm 2 to proceed with the ester reaction while leaving water out of the reactor to obtain bis- (β-oxyethyl) terephthalate. Manufacture. Subsequently, 6 parts by weight of 3-hydroxyphenylphosphinylpropanecarboxylic acid and 0.0034 parts by weight of cobalt acetate as a phosphorus-based flame retardant were added thereto, and polycondensation was carried out under conventional polyester reaction conditions of high temperature and high vacuum in the presence of antimony trioxide (polycondensation catalyst). After proceeding with the reaction, a polymer (polyester) was prepared in a pellet form. The results of evaluating the flame retardance of the produced polyester and the L value and b value measured using a color difference meter are shown in Table 2.
실시예 2 ~ 실시예 4 및 비교실시예 1 ~ 비교실시예 2Example 2-Example 4 and Comparative Example 1-Comparative Example 2
인계난연제의 첨가량과 코발트 아세테이트의 첨가량을 표 1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 고분자(폴리에스테르)를 제조 하였다. 제조한 폴리에스테르의 난연성을 평가한 결과와 색차계를 이용하여 측정한 L값 및 b값은 표 2와 같다.A polymer (polyester) was prepared under the same process and conditions as in Example 1, except that the amount of phosphorus-based flame retardant and the amount of cobalt acetate were changed as shown in Table 1. The results of evaluating the flame retardance of the produced polyester and the L value and b value measured using a color difference meter are shown in Table 2.
<표 1> 제조조건<Table 1> Manufacturing Conditions
<표 2>폴리에스테르 물성 평가 결과Table 2: Polyester Property Evaluation Results
(LOI)Marginal oxygen index
(LOI)
본 발명은 난연성이 우수함과 동시에 색상도 양호하여 섬유, 필름 또는 플라스틱 제품 등의 제조에 유용하다.The present invention is excellent in flame retardancy and good color, which is useful for the production of fibers, films or plastic products.
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| KR1020040028862A KR101083773B1 (en) | 2004-04-27 | 2004-04-27 | A flame retardant polyester with excellent color tone, and a process of preparing the same |
| PCT/KR2005/001181 WO2005103112A1 (en) | 2004-04-27 | 2005-04-25 | A flame retardant polyester with excellent color tone, and a process of preparing the same |
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| CN101200820B (en) * | 2006-12-13 | 2010-05-19 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
| CN106279765B (en) * | 2015-06-11 | 2019-06-25 | 东丽纤维研究所（中国）有限公司 | A kind of fire retardant and preparation method thereof uses the copolyesters of the fire retardant and the preparation method of copolyesters and purposes |
| KR102545781B1 (en) | 2016-03-31 | 2023-06-19 | 도레이첨단소재 주식회사 | Manufacturing method of sea-island complex fiber, manufacturing method of nonflammable resin including the same and sea-island complex fiber thereby |
| KR102545783B1 (en) | 2016-03-31 | 2023-06-19 | 도레이첨단소재 주식회사 | Manufacturing method of sea-island complex fiber, manufacturing method of nonflammable resin including the same and sea-island complex fiber thereby |
| KR102163330B1 (en) | 2019-04-08 | 2020-10-08 | 도레이첨단소재 주식회사 | Polysester resin for flame retardant fiber, Flame retardant fiber with excellent dyeing properties using the same and Manufacturing methof thereof |
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| JPH0616796A (en) * | 1992-07-03 | 1994-01-25 | Teijin Ltd | Production of flame-retardant polyester |
| KR20000065704A (en) * | 1999-04-08 | 2000-11-15 | 조민호 | Flame retardent polyester resin composition having high quality properties |
| KR20010101553A (en) * | 1999-01-19 | 2001-11-14 | 겐지 시미즈 | Flame-retardant polyester fiber, woven or knitted flame-retardant polyester fiber fabric, nonwoven flame-retardant polyester fiber fabric, and woven or knitted suede fabric |
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| JPH0616796A (en) * | 1992-07-03 | 1994-01-25 | Teijin Ltd | Production of flame-retardant polyester |
| KR20010101553A (en) * | 1999-01-19 | 2001-11-14 | 겐지 시미즈 | Flame-retardant polyester fiber, woven or knitted flame-retardant polyester fiber fabric, nonwoven flame-retardant polyester fiber fabric, and woven or knitted suede fabric |
| KR20000065704A (en) * | 1999-04-08 | 2000-11-15 | 조민호 | Flame retardent polyester resin composition having high quality properties |
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