WO2014035162A1 - Non-halogen flame retardant polycyclohexylenedimethylene terephthalate resin composition - Google Patents
Non-halogen flame retardant polycyclohexylenedimethylene terephthalate resin composition Download PDFInfo
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- WO2014035162A1 WO2014035162A1 PCT/KR2013/007779 KR2013007779W WO2014035162A1 WO 2014035162 A1 WO2014035162 A1 WO 2014035162A1 KR 2013007779 W KR2013007779 W KR 2013007779W WO 2014035162 A1 WO2014035162 A1 WO 2014035162A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- 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
-
- 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
- C08K7/14—Glass
Definitions
- Non-halogen flame retardant polycyclonuclear silane dimethylene terephthalate resin composition Non-halogen flame retardant polycyclonuclear silane dimethylene terephthalate resin composition
- the present invention relates to a non-halogen flame-retardant polycyclonuclear silane dimethylene terephthalate resin composition, and more particularly to a non-halogen flame-retardant polycyclonuclear silane dimethylene terephthalate resin composition excellent in flame retardancy and excellent in heat resistance and discoloration resistance. It is about.
- Typical polymers include OPA-based PA46 (Stanyl®, DSM), PPA (Polypht ha 1 amide or PACT black NylonOT; typical products include Zytel HTN, Amodel and Grivory) and PA9T (Black NylonOT; Genestar®), ii) a wholly aromatic holester-based liquid crystalline polymer (Liquid crystalline polymer; LCP; representative products Xydar and Sumikasuper), and iii) aliphatic ring compound monomers Polyester-based PCT (Poly (Cyclohexylene dimethyl ene terephthalate); DuPont's Thermx) is a representative product.
- PCT has a slower crystallization rate than PBT, but is much faster than PET and can be injection molded, but has high heat resistance and relatively high price competitiveness.
- this PCT is the polymer having the highest melting point in the existing polyester polymers, except for the liquid crystal polymer, and is known to have a low water absorption rate and excellent heat discoloration resistance compared to PA polymers.
- thermoplastic resins such as polycyclonuclear silane dimethylene terephthalate resins have been applied to many products because of their excellent processability and mechanical properties.
- thermoplastic resin itself is not resistant to fire, it is regulated by law to use only polymer resin satisfying the flame retardant standard in the world.
- a method of mixing a halogen-based flame retardant and antimony oxide in a thermoplastic resin has been widely used as a technique for imparting flame retardancy to a resin.
- halogen-based flame retardants have a fatal effect on the human body and the environment, the flame retardant technology using environmentally friendly non-halogen compounds is required.
- Japanese Patent Laid-Open No. 10-204276 discloses a method of imparting flame retardancy to a resin by adding aluminum hydroxide (ATH), at least one nitrogen compound, and an enemy to an unsaturated polyester resin.
- ATH aluminum hydroxide
- Korean Patent Publication No. 10-204276 discloses a method of imparting flame retardancy to a resin by adding aluminum hydroxide (ATH), at least one nitrogen compound, and an enemy to an unsaturated polyester resin.
- ATH aluminum hydroxide
- the mechanical properties of the resin composition are lowered.
- 2007-0064924 discloses a flame retardant technology of acrylonitrile-butadiene-styrene copolymer resin (ABS resin), but there is a problem that the flame retardant used is a bromine-based organic compound, which is not environmentally friendly.
- ABS resin acrylonitrile-butadiene-styrene copolymer resin
- the present invention is a polymer having the highest melting point among polyester polymers except liquid crystal polymers, and has a low water absorption rate and excellent heat resistance and discoloration resistance as compared with PA polymers, and a non-halogen flame retardant. It is an environment-friendly and excellent flame retardant containing a phosphorus-based flame retardant having excellent flame retardant performance compared to the existing inorganic compound, and to provide a flame retardant polycyclonuclear dimethyl dimethylene terephthalate resin composition excellent in heat resistance and discoloration resistance. [Measures of problem]
- the flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to an aspect of the present invention includes a polycyclonuclear silane dimethylene terephthalate resin composed of a repeating unit represented by the following formula (1), and a flame retardant represented by the following formula (2) and the content of the flame retardant represented by the above formula (2) is 8 to 13 wt. 0/0.
- m is an integer of 1 or more
- n is an integer of 1 to 4
- R 2 is the same or different alkyl group, alkoxy group, aryl group, or aryloxy group
- M is alkaline earth metal, alkali metal, Zinc, aluminum, or iron.
- R ! And R 2 may be selected from the group consisting of methyl, ethyl, propyl, isopropyl butyl, nucleus, phenyl, methoxy, ethoxy, propoxy, isopropoxy, side effects, nucleosiloxy groups, and phenoxy groups.
- the flame-retardant polycyclonuclear silane dimethylene terephthalate resin ancestor may further include a glass fiber, the glass fiber 100 parts by weight of polycyclonuclear silane dimethylene terephthalate resin composed of a repeating unit of Formula 1 It may be included in 1 to 60 parts by weight relative to.
- a molded article made of the polycyclonuclear dimethyl dimethylene terephthalate resin composition.
- a molded article having a flame retardancy of at least V-1 at a thickness of 1/8 "according to the UL 94 VB flame retardant specification may be provided.
- an engineering plastic made of the polycyclonuclear dimethyldimethylene terephthalate resin composition may be provided.
- the flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to the present invention is excellent in flame retardancy, heat resistance and discoloration resistance, and is environmentally friendly because it does not contain a halogen compound that causes environmental pollution during combustion.
- Flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to an aspect of the present invention, polycyclohexylene dimethylene terephthalate resin composed of a repeating unit of the formula (1), and To include a flame retardant represented by the formula (2), the content of the flame retardant represented by the formula (2) is 8 to 13% by weight.
- n is an integer of 1 to 4
- R 2 is the same or different alkyl group, alkoxy group, aryl group, or aryloxy group
- M is alkaline earth metal, alkali metal, Zinc, aluminum, or iron.
- Flame retardant polycyclonuclear silane dimethylene terephthalate resin according to an embodiment of the present invention : comprises a polycyclonuclear silane dimethylene terephthalate resin consisting of a repeating unit of the formula (1).
- Polycyclonuclear silane dimethylene terephthalate resin is slower than PBT but crystallization rate is much faster than PET, and it is possible to injection molding, but it has high heat resistance and relatively high price competitiveness. It is the polymer having the highest melting point among polyester-based polymers, has a lower water absorption than PA-based polymers, and is very excellent in heat discoloration resistance.
- the flame-retardant polycyclonucleosilane di methylene terephthalate resin according to an embodiment of the present invention, comprises a flame retardant represented by the formula (2).
- Compound represented by the formula (2) is a phosphinic acid metal salt, serves as a flame retardant, and is used to prevent the decrease in tensile strength.
- R 2 is methyl, ethyl, propyl, isopropyl, butyl, nuclear chamber, phenyl, methoxy, ethoxy, propoxy, isopropoxy, appendix, nucleosiloxy group, and It may be selected from the group consisting of phenoxy group.
- M in Chemical Formula 2 may be selected from the group consisting of alkaline earth metals, alkali metals, zinc, aluminum, and iron.
- the flame retardant is first grade ammonium phosphate (Primaryammoniumphospate), 2 ammonium phosphate ⁇ (Secondary ammoniumphospate), ammonium phosphite (Ammoniumphospite), amine / amide phosphate (Amine / Amidephophate), amine seolpe byte (Aminesulfate), melamine phosphate (Melaminephosphate) , Dimelaminephosphate, melaminepyrophosphate, melaminepolyphosphate, tricrecyl phosphate, and trichloroalkylphosphate It can be selected from the group consisting of an organic compound which is a non-halogen flame retardant containing one or more, and inorganic compounds such as magnesium hydroxide and aluminum hydroxide.
- the flame retardant may be contained in an 8 to 13 weight 0/0 of the total resin composition. If the flame retardant is included in less than 8% by weight, there is a problem that the flame retardancy is lowered, and when it is included in excess of 13% by weight, the tensile strength is lowered to 20MPa or less as engineering plastics such as automobile parts and materials. This is because it is difficult to apply.
- the flame-retardant polycyclonuclearenediethylene methylene terephthalate resin may further include glass fiber.
- the diameter of the fiberglass cross section may be 10-100 mm and the length may be 1-20 mm.
- the glass fiber may be included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the polycyclonucleosilane dimethylene terephthalate resin composed of the repeating unit of Formula 1.
- the flame retardant polycyclonucleosilenedi methylene terephthalate resin composition according to the present invention may be prepared by compounding a polycyclonuclearenedi methylene terephthalate resin and a flame retardant represented by Chemical Formula 2 as described above.
- a molded article made of the polycyclonuclearenediethylene methylene terephthalate resin composition may be provided, and the molded article may have a flame retardancy of 1/8 according to UL 94 VB flame retardant regulations. May be greater than or equal to V-1.
- an engineering plastic made of the polycyclonucleosilenedi methylene terephthalate resin composition may be provided.
- preferred embodiments of the present invention will be described in detail. However, these examples are only to illustrate the invention, it will not be construed that the scope of the present invention is limited by these examples.
- the components of the polycyclonuclearenedi methylene terephthalate resin composition were prepared as follows.
- Clariant Organic phosphinate (trade name Exolit OP 1240) was used.
- Non-halogen flame retardant was prepared by compounding at a temperature range of 280 to 300 o C using HAAKE PolyDrive R600 of Thermo Electron Corporation at the composition ratio shown in Table 1.
- Example 5
- the (C) polycycloolefin nuclear xylene dimethylene terephthalate Te LES -GF (Glass fiber) composite resin 90 parts by weight 0/0 and (B) a non-halogen flame retardant 10 parts by weight 0/0 using a HAAKE PolyDrive R600 of Thermo Electron Corporation 280 Specimens were prepared by compounding in the temperature range of 300 ° C. Examples 6-8
- Specimens were prepared by compounding at a temperature range of 280 to 300 o C using a HAAKE PolyDrive R600 from Thermo Electron Corporation.
- the (C) polycycloolefin nuclear xylene dimethylene terephthalate Te LES -GF (Glass fiber) composite resin 100 parts by weight 0/0 by using a HAAKE PolyDrive R600 of Thermo Electron Corporation compounding at a temperature of 280 to 300 o C samples was prepared.
Abstract
The present invention relates to a polycyclohexylenedimethylene terephthalate resin composition having excellent flame retardant properties, and excellent heat resistance and discoloration resistance. The polycyclohexylenedimethylene terephthalate resin composition, according to one embodiment of the presenet invention, comprises: a polycyclohexylenedimethylene terephthalate resin comprising a repeating unit represented by chemical formula 1; and a flame retardant agent represented by chemical formula 2, wherein the content of the flame retardant agent represented by chemical formula 2 is 8 to 13 wt.%.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
비할로겐 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물 Non-halogen flame retardant polycyclonuclear silane dimethylene terephthalate resin composition
【기술분야】 Technical Field
본 발명은 비할로겐 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물에 관한 것으로, 더욱 구체적으로는 난연성이 우수하고, 내열성 및 내변색성이 우수한 비할로겐 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물에 관한 것이다. The present invention relates to a non-halogen flame-retardant polycyclonuclear silane dimethylene terephthalate resin composition, and more particularly to a non-halogen flame-retardant polycyclonuclear silane dimethylene terephthalate resin composition excellent in flame retardancy and excellent in heat resistance and discoloration resistance. It is about.
【배경기술】 Background Art
최근 재료들의 고내열성에 대한 요구가 높아짐에 따라 연속사용온도 270 °C 이상의 내열성과 복잡한 형상의 전자 재료 및 자동차 부품 제조에 적합한 성형성을 동시에 만족시키는 수퍼 엔지니어링 플라스틱의 필요성이 증대되고 있다. 특히， 고내열 고분자 소재는 디스플레이， 태양전지， 전자종이용 플렉시블 플라스틱 소재， 우주산업용 소재， 기타 전자 /반도체 등의 차세대 첨단산업의 핵심부품소재로서 사용된다. 디스플레이 및 태양전지용 플렉시블 플라스틱 소재로사용되기 위해서는 유리전이온도 330 °C 이상의 높은 내열성과 함께 고투명성， 저흡습성. 저수축 특성을 보유한 고분자 소재가 요구되나 아직까지 개발되고 있지 않은 상황이다. In recent years, as the demand for high heat resistance of materials increases, the necessity of a super engineering plastic that satisfies heat resistance of continuous use temperature of 270 ° C. or higher and moldability suitable for manufacturing complex-shaped electronic materials and automobile parts is increasing. In particular, high heat-resistant polymer materials are used as core component materials of next-generation high-tech industries such as displays, solar cells, flexible plastic materials for electronic paper, space industry materials, and other electronics and semiconductors. To be used as flexible plastic material for display and solar cell, high transparency and low hygroscopicity with high heat resistance over glass transition temperature of 330 ° C. Polymer materials with low shrinkage are required, but they are not being developed yet.
고분자의 내열성을 확보하기 위해서는 방향족 도입을 통해 열에 매우 안정한 분자구조를 가져야 한다. 하지만， 방향족 고분자 사슬 사이의 상호 작용에 의한 낮은 투명성， 광학적 이방성 및 유기 고분자 자체가 가지는 높은 열팽창 계수 등이 개발에 장애가 되고 있다. In order to secure the heat resistance of the polymer it must have a very stable molecular structure to heat through the introduction of aromatics. However, low transparency due to interactions between aromatic polymer chains, optical anisotropy, and high coefficient of thermal expansion of organic polymers themselves are obstacles to development.
최근 내열성은 만족하나 성형성이 나쁜 PEEK(Poly (Ether Ether Ketone))을 대체할 새로운 수퍼 엔지니어링 플라스틱이 속속 개발되고 있다. 대표적 고분자로는 OPA 계통의 PA46(Stanyl®, DSM), PPA ( Po lypht ha 1 amide 혹은 PACT 흑은 NylonOT; 대표적 상품으로는 Zytel HTN, Amodel 및 Grivory)와 PA9T (흑은 NylonOT; Genestar®), ii)전방향족 홀리에스테르계 액정고분자 (Liquid crystalline polymer; 이하 LCP; 대표적 상품으로는 Xydar 및 Sumikasuper)， 및 iii)지방족 고리 화합물 단량체로부터 출발한
폴리에스테르계 PCT(Poly(Cyclohexylene dimethyl ene terephthalate)； 대표적 상품으로 DuPont의 Thermx)가 있다. Recently, new super engineering plastics are being developed to replace PEEK (Poly (Ether Ether Ketone)) which satisfies heat resistance but is poor in formability. Typical polymers include OPA-based PA46 (Stanyl®, DSM), PPA (Polypht ha 1 amide or PACT black NylonOT; typical products include Zytel HTN, Amodel and Grivory) and PA9T (Black NylonOT; Genestar®), ii) a wholly aromatic holester-based liquid crystalline polymer (Liquid crystalline polymer; LCP; representative products Xydar and Sumikasuper), and iii) aliphatic ring compound monomers Polyester-based PCT (Poly (Cyclohexylene dimethyl ene terephthalate); DuPont's Thermx) is a representative product.
이 중 PCT는 결정화 속도가 PBT보다는 늦지만 PET보다는 월등히 빠르고 사출 성형이 가능하면서도 높은 내열성을 가지고 상대적으로 가격 경쟁력이 높아 잠재적 용도 가능성이 매우 높다. 또한， 이 PCT는 액정 폴리머를 제외하고 현존하는 폴리에스테르계 고분자 증에서 가장 높은 용융점을 갖는 고분자이며， PA계 고분자 대비 수분 흡수율이 낮고 열에 의한 내변색성이 매우 우수한 것으로 알려져 있다. Among them, PCT has a slower crystallization rate than PBT, but is much faster than PET and can be injection molded, but has high heat resistance and relatively high price competitiveness. In addition, this PCT is the polymer having the highest melting point in the existing polyester polymers, except for the liquid crystal polymer, and is known to have a low water absorption rate and excellent heat discoloration resistance compared to PA polymers.
일반적으로 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 등의 열가소성 수지는 우수한 가공성 및 기계적 특성으로 인하여 많은 제품에 적용되고 있다. 한편， 열가소성 수지 자체는 화재에 대하여 저항성이 없으므로 세계 각 국에서는 난연규격을 만족하는 고분자 수지만을 사용하도록 법으로 규제하고 있다. 종래에는 수지에 난연성을 부여하기 위한 기술로 할로겐계 난연제와 산화 안티몬을 열가소성 수지에 흔합하는 방법이 많이 사용되어 왔다. 그러나, 할로겐계 난연제는 연소 시 발생하는 가스가 인체 및 환경에 치명적인 영향을 미치기 때문에 친환경적인 비할로겐계 화합물을 이용한 난연화 기술이 요구되고 있다. In general, thermoplastic resins such as polycyclonuclear silane dimethylene terephthalate resins have been applied to many products because of their excellent processability and mechanical properties. On the other hand, since the thermoplastic resin itself is not resistant to fire, it is regulated by law to use only polymer resin satisfying the flame retardant standard in the world. Conventionally, a method of mixing a halogen-based flame retardant and antimony oxide in a thermoplastic resin has been widely used as a technique for imparting flame retardancy to a resin. However, since halogen-based flame retardants have a fatal effect on the human body and the environment, the flame retardant technology using environmentally friendly non-halogen compounds is required.
한편， 비할로겐계 화합물을 이용한 난연제로서 수산화 마그네슘， 수산화 알루미늄 등의 무기 화합물을 이용한 고분자 수지 난연화 기술이 제안되었다. 일본 특개평 10-204276호는 불포화 폴리에스테르 수지에 수산화알루미늄 (ATH)과 하나이상의 질소 화합물 및 적인을 흔합하여 첨가함으로써， 수지에 난연성을 부여하는 방법을 제시하고 있다. 그러나， 다량의 수산화알루미늄을 사용하여야 하므로 수지 조성물의 기계적 물성이 저하되는 단점이 있었다. 또한， 한국공개특허 제 2007-0064924호에서는 아크릴로니트릴 -부타디엔-스티렌 공중합체수지 (ABS수지)의 난연화 기술이 명시되어 있는데 이때 사용되는 난연제가 브롬계 유기화합물이므로 친환경적이지 않다는 문제점이 있었다. On the other hand, as a flame retardant using a non-halogen compound, a polymer resin flame retardant technology using inorganic compounds such as magnesium hydroxide and aluminum hydroxide has been proposed. Japanese Patent Laid-Open No. 10-204276 discloses a method of imparting flame retardancy to a resin by adding aluminum hydroxide (ATH), at least one nitrogen compound, and an enemy to an unsaturated polyester resin. However, since a large amount of aluminum hydroxide must be used, there is a disadvantage in that the mechanical properties of the resin composition are lowered. In addition, Korean Patent Publication No. 2007-0064924 discloses a flame retardant technology of acrylonitrile-butadiene-styrene copolymer resin (ABS resin), but there is a problem that the flame retardant used is a bromine-based organic compound, which is not environmentally friendly.
【발명의 내용】 [Content of invention]
【해결하려는 과제】
본 발명은 액정폴리머를 제외한 폴리에스테르계 고분자 중에서 가장 높은 용융점을 갖는 고분자이며 PA 계 고분자 대비 수분 흡수율이 낮고 내열성 및 내변색성이 매우 우수한 폴리시클로핵실렌디메틸렌테레프탈레이트 수지， 및 비할로겐 난연제로서 친환경적이며 사용시 기존 무기화합물에 비해 뛰어난 난연성능을 갖는 인계 난연제를 함유한 난연성이 우수하고， 내열성 및 내변색성이 우수한 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지조성물을 제공하는 것이다. 【과제의 해결 수단】 [Problem to solve] The present invention is a polymer having the highest melting point among polyester polymers except liquid crystal polymers, and has a low water absorption rate and excellent heat resistance and discoloration resistance as compared with PA polymers, and a non-halogen flame retardant. It is an environment-friendly and excellent flame retardant containing a phosphorus-based flame retardant having excellent flame retardant performance compared to the existing inorganic compound, and to provide a flame retardant polycyclonuclear dimethyl dimethylene terephthalate resin composition excellent in heat resistance and discoloration resistance. [Measures of problem]
본 발명의 일 측면에 따른 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물은, 하기 화학식 1 의 반복단위로 구성되는 플리시클로핵실렌디메틸렌 테레프탈레이트 수지, 및 하기 화학식 2 로 표시되는 난연제를 포함하고, 상기 화학식 2 로 표시되는 난연제의 함량은 8 내지 13중량0 /0 이다. The flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to an aspect of the present invention includes a polycyclonuclear silane dimethylene terephthalate resin composed of a repeating unit represented by the following formula (1), and a flame retardant represented by the following formula (2) and the content of the flame retardant represented by the above formula (2) is 8 to 13 wt. 0/0.
[화학식 1] [Formula 1]
[화학식 2] [Formula 2]
상기에서， m은 1 이상의 정수이고, n은 1 내지 4 의 정수이며， 및 R2 는 서로 같거나 다른 알킬기, 알콕시기， 아릴기, 또는 아릴록시기 이고, M은 알칼리토류금속， 알칼리금속， 아연， 알루미늄， 또는 철이다.
그리고， 상기 화학식 2의 R! 및 R2 는 메틸, 에틸, 프로필， 이소프로필 부틸， 핵실, 페닐， 메록시， 에록시, 프로폭시， 이소프로폭시, 부특시, 핵실록시기, 및 페녹시기로 이루어지는 군으로부터 선택될 수 있다. In the above, m is an integer of 1 or more, n is an integer of 1 to 4, and R 2 is the same or different alkyl group, alkoxy group, aryl group, or aryloxy group, M is alkaline earth metal, alkali metal, Zinc, aluminum, or iron. And, R ! And R 2 may be selected from the group consisting of methyl, ethyl, propyl, isopropyl butyl, nucleus, phenyl, methoxy, ethoxy, propoxy, isopropoxy, side effects, nucleosiloxy groups, and phenoxy groups.
아울러, 상기 난연성 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지 조상물은 유리섬유를 더 포함할 수 있으며， 상기 유리섬유는 상기 화학식 1 의 반복단위로 구성되는 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지 100 중량부에 대하여 1 내지 60 중량부로 포함될 수 있다. In addition, the flame-retardant polycyclonuclear silane dimethylene terephthalate resin ancestor may further include a glass fiber, the glass fiber 100 parts by weight of polycyclonuclear silane dimethylene terephthalate resin composed of a repeating unit of Formula 1 It may be included in 1 to 60 parts by weight relative to.
본 발명의 다른 측면에 따르면， 상기 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지 조성물로 제조된 성형품이 제공될 수 있다. According to another aspect of the present invention, there may be provided a molded article made of the polycyclonuclear dimethyl dimethylene terephthalate resin composition.
또한， UL 94 VB 난연 규정에 따른 난연도가 1/8"의 두께에서 V-1 이상인 성형품이 제공될 수 있다. In addition, a molded article having a flame retardancy of at least V-1 at a thickness of 1/8 "according to the UL 94 VB flame retardant specification may be provided.
본 발명의 또 다른 측면에 따르면, 상기 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지 조성물로 제조된 엔지니어링 플라스틱이 제공될 수 있다. According to another aspect of the present invention, an engineering plastic made of the polycyclonuclear dimethyldimethylene terephthalate resin composition may be provided.
【발명의 효과】 【Effects of the Invention】
본 발명에 따른 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물은 난연성， 내열성 및 내변색성이 우수하며, 연소 시에 환경오염을 야기시키는 할로겐 화합물이 함유되어 있지 않아 환경친화적이다. The flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to the present invention is excellent in flame retardancy, heat resistance and discoloration resistance, and is environmentally friendly because it does not contain a halogen compound that causes environmental pollution during combustion.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 상세한 설명에 상세하게 설명하고자 한다. 그러나， 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며， 본 발명의 사상 및 기술 범위에 포함되는 모든 변환， 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다. As the invention allows for various changes and numerous embodiments, particular embodiments will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.
본 발명의 일 측면에 따른 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물은, 하기 화학식 1 의 반복단위로 구성되는 폴리시클로헥실렌디메틸렌 테레프탈레이트 수지, 및
하기 화학식 2 로 표시되는 난연제를 포함하고, 상기 화학식 2 로 표시되 난연제의 함량은 8 내지 13중량 % 이다. Flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to an aspect of the present invention, polycyclohexylene dimethylene terephthalate resin composed of a repeating unit of the formula (1), and To include a flame retardant represented by the formula (2), the content of the flame retardant represented by the formula (2) is 8 to 13% by weight.
[화학식 1]
[Formula 1]
[화학식 2] [Formula 2]
상기에서， m은 1 이상의 정수이고, n은 1 내지 4의 정수이며， 및 R2 는 서로 같거나 다른 알킬기， 알콕시기， 아릴기, 또는 아릴록시기 이고， M은 알칼리토류금속, 알칼리금속, 아연， 알루미늄， 또는 철이다. In the above, m is an integer of 1 or more, n is an integer of 1 to 4, and R 2 is the same or different alkyl group, alkoxy group, aryl group, or aryloxy group, M is alkaline earth metal, alkali metal, Zinc, aluminum, or iron.
이하 본 발명의 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물의 구성성분에 대하여 상세히 설명하기로 한다. Hereinafter, the components of the flame retardant polycyclonuclear silane dimethylene terephthalate resin composition of the present invention will be described in detail.
본 발명의 일 구현예에 따른 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지는: 상기 화학식 1 의 반복단위로 구성되는 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지를 포함한다. Flame retardant polycyclonuclear silane dimethylene terephthalate resin according to an embodiment of the present invention : comprises a polycyclonuclear silane dimethylene terephthalate resin consisting of a repeating unit of the formula (1).
폴리시클로핵실렌디메틸렌 테레프탈레이트 수지는 결정화 속도가 PBT 보다는 늦지만 PET 보다는 월등히 빠르고 사출 성형이 가능하면서도 높은 내열성을 가지고 상대적으로 가격 경쟁력이 높아 잠재적 용도 가능성이 매우 높고， 액정 폴리머를 제외하고 현존하는 폴리에스테르계 고분자 중에서 가장 높은 용융점을 갖는 고분자이며, PA 계 고분자 대비 수분 흡수율이 낮고 열에 의한 내변색성이 매우 우수하다.
아울러， 본 발명 의 일 구현예에 따른 난연성 폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지는， 상기 화학식 2 로 표시되는 난연제를 포함한다. Polycyclonuclear silane dimethylene terephthalate resin is slower than PBT but crystallization rate is much faster than PET, and it is possible to injection molding, but it has high heat resistance and relatively high price competitiveness. It is the polymer having the highest melting point among polyester-based polymers, has a lower water absorption than PA-based polymers, and is very excellent in heat discoloration resistance. In addition, the flame-retardant polycyclonucleosilane di methylene terephthalate resin according to an embodiment of the present invention, comprises a flame retardant represented by the formula (2).
상기 화학식 2 로 표시 되는 화합물은 포스핀산 금속염으로, 난연제 역할을 하며 , 아울러 인장강도 저하 방지를 위해 사용된다. Compound represented by the formula (2) is a phosphinic acid metal salt, serves as a flame retardant, and is used to prevent the decrease in tensile strength.
바람직하게는, 상기 화학식 2 의 및 R2 는 메틸， 에 틸， 프로필， 이소프로필， 부틸, 핵실, 페닐， 메록시 , 에록시 , 프로폭시， 이소프로폭시， 부록시 , 핵실록시 기， 및 페녹시기로 이루어지는 군으로부터 선택될 수 있다. 상기 화학식 2 의 M 은 알칼리토류금속， 알칼리금속， 아연, 알루미늄， 및 철로 이루어지는 군으로부터 선택될 수 있다. 상기 난연제는 1 급 암모늄 포스페이트 (Primaryammoniumphospate), 2 급 암모늄포스페이트■ (Secondary ammoniumphospate), 암모늄포스파이트 (Ammoniumphospite), 아민 /아마이드포스페이트 (Amine/Amidephophate), 아민설페 이트 (Aminesulfate), 멜라민포스페이트 (Melaminephosphate), 디 멜라민포스페 이트 (Dimelaminephosphate), 멜라민파이로포스페이트 (Melaminepyrophosphate), 멜라민폴리포스페 이트 (Melaminepolyphosphate), 트리크레실포스페이트 (Tricrecyl phosphate), 및 트리클로로알킬포스페 이트 (TricWoro alkylphosphate) 중에 선택되는 1 종 이상을 함유하는 비 할로겐 난연제인 유기화합물， 및 수산화 마그네슴, 수산화 알루미늄 등의 무기 화합물로 이루어지는 군으로부터 선택될 수 있다. Preferably, in Formula 2 and R 2 is methyl, ethyl, propyl, isopropyl, butyl, nuclear chamber, phenyl, methoxy, ethoxy, propoxy, isopropoxy, appendix, nucleosiloxy group, and It may be selected from the group consisting of phenoxy group. M in Chemical Formula 2 may be selected from the group consisting of alkaline earth metals, alkali metals, zinc, aluminum, and iron. The flame retardant is first grade ammonium phosphate (Primaryammoniumphospate), 2 ammonium phosphate ■ (Secondary ammoniumphospate), ammonium phosphite (Ammoniumphospite), amine / amide phosphate (Amine / Amidephophate), amine seolpe byte (Aminesulfate), melamine phosphate (Melaminephosphate) , Dimelaminephosphate, melaminepyrophosphate, melaminepolyphosphate, tricrecyl phosphate, and trichloroalkylphosphate It can be selected from the group consisting of an organic compound which is a non-halogen flame retardant containing one or more, and inorganic compounds such as magnesium hydroxide and aluminum hydroxide.
그리고, 상기 난연제는 전체 수지 조성물 중 8 내지 13 중량0 /0로 포함될 수 있다'. 이는 난연제가 8 중량% 미만으호 포함될 경우 난연성 이 저하되는 문제가 있고, 13 중량 %를 초과하여 포함될 경우 인장강도 (tensile strength)가 20MPa 이하로 떨어지 게 되어 자동차부품소재 등의 엔지 니 어 링 플라스틱으로서의 적용이 어 려운 문제점 이 있기 때문이다. In addition, the flame retardant may be contained in an 8 to 13 weight 0/0 of the total resin composition. If the flame retardant is included in less than 8% by weight, there is a problem that the flame retardancy is lowered, and when it is included in excess of 13% by weight, the tensile strength is lowered to 20MPa or less as engineering plastics such as automobile parts and materials. This is because it is difficult to apply.
아을러， 본 발명 의 일 구현예에 따르면 상기 난연성 폴리시클로핵실렌디 메틸렌 테 레프탈레이트 수지는 유리섬유 (Glass fiber)를 더 포함할 수 있다. 유리섬유 단면의 직 경은 10-100輝 m 일 수 있고， 길이는 1- 20mm 일 수 있다.
상기 유리섬유는 상기 화학식 1 의 반복단위로 구성되는 폴리시클로핵실렌디 메틸렌 테 레프탈레이트 수지 100 중량부에 대하여 1 내지 60 중량부로 포함될 수 있다. In addition, according to one embodiment of the present invention, the flame-retardant polycyclonuclearenediethylene methylene terephthalate resin may further include glass fiber. The diameter of the fiberglass cross section may be 10-100 mm and the length may be 1-20 mm. The glass fiber may be included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the polycyclonucleosilane dimethylene terephthalate resin composed of the repeating unit of Formula 1.
본 발명에 따른 난연성 폴리시클로핵실렌디 메틸렌테레프탈레이트 수지 조성물은 상기와 같이 폴리시클로핵실렌디 메틸렌 테 레프탈레 이트 수지와 화학식 2 로 표시 되는 난연제를 컴파운딩하여 제조될 수 있다. The flame retardant polycyclonucleosilenedi methylene terephthalate resin composition according to the present invention may be prepared by compounding a polycyclonuclearenedi methylene terephthalate resin and a flame retardant represented by Chemical Formula 2 as described above.
본 발명의 다른 측면에 따르면, 상기 폴리시클로핵실렌디 메틸렌 테 레프탈레이트 수지 조성물로 제조된 성 형품이 제공될 수 있으며 , 이 러 한 성 형품은 UL 94 VB 난연 규정 에 따른 난연도가 1/8"의 두께에서 V-1 이상일 수 있다. According to another aspect of the present invention, a molded article made of the polycyclonuclearenediethylene methylene terephthalate resin composition may be provided, and the molded article may have a flame retardancy of 1/8 according to UL 94 VB flame retardant regulations. May be greater than or equal to V-1.
본 발명의 또 다른 측면에 따르면， 상기 폴리시클로핵실렌디 메틸렌 테 레프탈레이트 수지 조성물로 제조된 엔지 니 어 링 플라스틱 이 제공될 수 있다. 이하， 본 발명의 바람직 한 실시 예를 상세히 설명하기로 한다. 다만， 이들 실시 예는 오로지 본 발명을 예시하기 위 한 것으로서， 본 발명의 범위가 이들 실시 예에 의해 제한되는 것으로 해석되지는 않는다 할 것 이다. According to another aspect of the present invention, an engineering plastic made of the polycyclonucleosilenedi methylene terephthalate resin composition may be provided. Hereinafter, preferred embodiments of the present invention will be described in detail. However, these examples are only to illustrate the invention, it will not be construed that the scope of the present invention is limited by these examples.
하기와 같이 폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지 조성물의 성분들을 준비하였다. The components of the polycyclonuclearenedi methylene terephthalate resin composition were prepared as follows.
(A) 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 (A) polycyclonuclear silane dimethylene terephthalate resin
SK 케미칼 사의 폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지 (상품명： Puratan®)를 사용하였다. (B) 비할로겐 난연제 Organic phosphinate SK Chemicals Corp. polycycloolefin nuclear xylene dimethylene Te LES phthalate resin: (trade name Puratan ®) was used. (B) Non-halogen flame retardant Organic phosphinate
Clariant 사의 Organic phosphinate (상품명 Exolit OP 1240)을 사용하였다. Clariant Organic phosphinate (trade name Exolit OP 1240) was used.
(C) 폴리시클로핵실렌디메틸렌테레프탈레이트 -GF(Glass fiber) 복합수지
상기 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 100 중량0 /。에 대하여 GF(Glass fiber) 1 ~60 중량 %를 컴파운딩하였다. (C) Polycyclonuclear silane dimethylene terephthalate -GF (Glass fiber) composite resin 1 to 60% by weight of GF (Glass fiber) was compounded based on 100% by weight of 0 /. Of polycyclonuclear silane dimethylene terephthalate resin.
(D) 폴리부틸렌테레프탈레이트 수지 (D) polybutylene terephthalate resin
제일모직 사의 폴리부틸렌 테 레프타레이트 (Polybutylene terephthalate) 수지 (상품명 VB-5150G)를 사용하였다. 실시 예 1 Cheil Industries' polybutylene terephthalate resin (trade name VB-5150G) was used. Example 1
상기 (A)폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지 90 증량%와 (B)비할로겐 난연제 10 중량 %를 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위 에서 컴파운딩하여 시편을 제조하였다. 실시 예 2 내지 4 90% by weight of the (A) polycyclohexylenedi methylene terephthalate resin and 10% by weight of (B) non-halogen flame retardant were compounded at a temperature range of 280 to 300 o C using HAAKE PolyDrive R600 of Thermo Electron Corporation. Specimen was prepared. Examples 2-4
상기 (A)폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지와 With the said (A) polycyclo nucleosilane di methylene terephthalate resin
(B)비할로겐 난연제를 표 1 에 나타난 조성비로 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위 에서 컴파운딩하여 시편을 제조하였다. 실시 예 5 (B) Non-halogen flame retardant was prepared by compounding at a temperature range of 280 to 300 o C using HAAKE PolyDrive R600 of Thermo Electron Corporation at the composition ratio shown in Table 1. Example 5
상기 (C)폴리시클로핵실렌디 메틸렌테 레프탈레이트 -GF(Glass fiber) 복합수지 90 중량0 /0와 (B)비할로겐 난연제 10 중량0 /0를 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300°C 의 온도범위에서 컴파운딩 하여 시편을 제조하였다. 실시예 6 내지 8 The (C) polycycloolefin nuclear xylene dimethylene terephthalate Te LES -GF (Glass fiber) composite resin 90 parts by weight 0/0 and (B) a non-halogen flame retardant 10 parts by weight 0/0 using a HAAKE PolyDrive R600 of Thermo Electron Corporation 280 Specimens were prepared by compounding in the temperature range of 300 ° C. Examples 6-8
상기 (C)폴리시클로핵실렌디 메틸렌테 레프탈레이트 -GF(Glass fiber) 복합수지와 (B)비할로겐 난연제를 표 2 에 나타난 조성 비로 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위에서 컴 파운딩 하여 시편을 제조하였다.
비교예 1 The (C) polycyclonuclearenedi methylene terephthalate -GF (Glass fiber) composite resin and (B) non-halogen flame retardant using a HAAKE PolyDrive R600 of Thermo Electron Corporation at a composition ratio shown in Table 2 280 to 300 o C Compounds were prepared by compounding at a temperature range of. Comparative Example 1
상기 (A)폴리시클로핵실렌디 메틸렌테레프탈레이트 수지 100 증량 %를 (A) 100% by weight of polycyclonuclearenedi methylene terephthalate resin
Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위 에서 컴 파운딩하여 시편을 제조하였다. Specimens were prepared by compounding at a temperature range of 280 to 300 o C using a HAAKE PolyDrive R600 from Thermo Electron Corporation.
비교예 2 Comparative Example 2
상기 (D)폴리부틸렌테레프탈레이트 (PBT) 수지 90 중량 %와 90% by weight of the (D) polybutylene terephthalate (PBT) resin
(B)비할로겐 난연제 10 중량0 /0 조성으로 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 220 내지 250°C 의 온도범위에서 컴파운딩하여 시편을 제조하였다. (B) using a HAAKE PolyDrive R600 of the non-halogen flame retardant 10 parts by weight 0/0 composition as Thermo Electron Corporation to prepare a specimen by compounding at a temperature of 220 to 250 ° C.
비교예 3 Comparative Example 3
상기 (A)폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지 95 중량0 /。와 (B)비할로겐 난연제 5 중량0 /0를 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위에서 컴파운딩하여 시편을 제조하였다. The (A) polycycloolefin nuclear xylene dimethylene Te LES phthalate resin 95 parts by weight 0 /., And (B) a non-halogen flame retardant agent 5 parts by weight 0/0 to Thermo Electron Corporation of HAAKE using PolyDrive R600 280 to 300 o temperature range of C Compounds were prepared by compounding at.
비교예 4 Comparative Example 4
상기 (A)폴리시클로핵실렌디 메틸렌테 레프탈레이트 수지 93 중량 %와 93% by weight of the (A) polycyclonucleosilane di methylene terephthalate resin
(B)비할로겐 난연제 7 중량0 /0를 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위 에서 컴파운딩하여 시편을 제조하였다. (B) A specimen was prepared by compounding at a temperature in the range of non-halogen flame retardant agent 7 weight 0/0 of the Thermo Electron Corporation HAAKE PolyDrive using R600 280 to 300 o C.
비교예 5 Comparative Example 5
상기 (A)폴리시클로핵실펜디 메틸렌테레프탈레이트 수지 86 중량 %와 (B)비할로겐 난연제 14 중량0 /0를 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 은도범위에서 컴 파운딩 하여 시편을 제조하였다.
비교예 6 The (A) by compounding in a polycycloolefin haeksil Fendi terephthalate silver is the range of resin 86% by weight and (B) a non-halogen flame retardant 14 parts by weight 0/0 to Thermo Electron Corporation of HAAKE PolyDrive using R600 280 to 300 o C Specimen was prepared. Comparative Example 6
상기 (C)폴리시클로핵실렌디 메틸렌테 레프탈레이트 -GF(Glass fiber) 복합수지 100 중량0 /0를 Thermo Electron Corporation 의 HAAKE PolyDrive R600 을 이용하여 280 내지 300oC 의 온도범위에서 컴파운딩 하여 시편을 제조하였다. The (C) polycycloolefin nuclear xylene dimethylene terephthalate Te LES -GF (Glass fiber) composite resin 100 parts by weight 0/0 by using a HAAKE PolyDrive R600 of Thermo Electron Corporation compounding at a temperature of 280 to 300 o C samples Was prepared.
【표 1] [Table 1]
[표 2] TABLE 2
상기 실시예 및 비교예에 나타낸 조성을 지닌 수지 조성물을 이용한 시편들 각각을 UL 94 VB 난연 규정에 따라 1/8"의 두께에서 난연도를 측정하였고， 각각 시편들의 인장강도를 측정하였다. 측정된 난연성, 및 인장강도는 상기 표 1 및 2에 나타내었다. Each of the specimens using the resin composition having the composition shown in the above Examples and Comparative Examples was measured for flame retardancy at a thickness of 1/8 "according to the UL 94 VB flame retardant specification, and the tensile strength of each specimen was measured. , And tensile strengths are shown in Tables 1 and 2 above.
상기 난연성 및 인장강도 측정 결과에서 나타나듯이， 난연제 함량이 8 중량 % 미만인 비교예 3 및 4 의 경우 난연도가 떨어짐을 알 수 있었고， 난연제 함량이 13 중량 % 초과인 비교예 5 의 경우는 인장강도가 저하된다는 점을 알 수 있었다. 본 발명에 따른 난연성 폴리시클로핵실렌디메틸렌테레프탈레이트 수지 조성물은 난연성이 우수하며， 연소 시에 환경오염을 야기시키는 할로겐 화합물이 함유되어 있지 않아 환경친화적인 장점이 있음을 알 수 있었다. 이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며， 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. As shown in the flame retardancy and tensile strength measurement results, it can be seen that the flame retardancy is reduced in Comparative Examples 3 and 4 having a flame retardant content of less than 8% by weight, tensile strength in Comparative Example 5 having a flame retardant content of more than 13% by weight It can be seen that the lowering. The flame retardant polycyclonuclear silane dimethylene terephthalate resin composition according to the present invention was excellent in flame retardancy, and did not contain a halogen compound that causes environmental pollution during combustion. The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
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Claims
[화학식 1] [Formula 1]
[화학식 2] [Formula 2]
MM
상기에서, m은 1 이상의 정수이고, n은 1 내지 4 의 정수이며， 및 R2 는 서로 같거나 다른 알킬기， 알콕시기, 아릴기, 또는 아릴록시기 이고, M은 알칼리토류금속, 알칼리금속, 아연， 알루미늄, 또는 철이다. Wherein m is an integer of 1 or more, n is an integer of 1 to 4, and R 2 is the same or different alkyl group, alkoxy group, aryl group, or aryloxy group, M is an alkaline earth metal, an alkali metal, Zinc, aluminum, or iron.
【청구항 2】 [Claim 2]
제 1 항에 있어서, 상기 화학식 2 의 Ri 및 R2 는 메틸, 에틸, 프로필, 이소프로필, 부틸, 핵실， 페닐, 메록시， 에톡시, 프로폭시, 이소프로폭시， 부록시, 핵실록시기, 및 페녹시기로 이루어지는 군으로부터 선택되는 난연성 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지 조성물. The method of claim 1, wherein, when Ri and R 2 in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, haeksil, phenyl, methoxy, hydroxy, ethoxy, propoxy, isopropoxy, appendix, nuclear siloxy, And a flame retardant polycyclonuclear silane dimethylene terephthalate resin composition selected from the group consisting of phenoxy groups.
【청구항 3】 [Claim 3]
제 1 항에 있어서, 유리섬유를 더 포함하는. 난연성 폴리시클로핵실렌디메틸렌 테레프탈레이트 수지 조성물.
The method of claim 1, further comprising glass fibers. Flame retardant polycyclonuclear silane dimethylene terephthalate resin composition.
【청구항 4] [Claim 4]
제 3 항에 있어서， 상기 유리섬유는 상기 화학식 1 의 반복단위로 구성되는 폴리시클로핵실렌디 메틸렌 테 레프탈레이트 수지 100 중량부에 대하여 1 내지 60 중량부로 포함되는 난연성 폴리시클로핵실렌디 메틸렌 테 레프탈레이트 수지 조성물. According to claim 3, wherein the glass fiber is 1 to 60 parts by weight based on 100 parts by weight of polycyclonuclear ethylene di methylene terephthalate resin composed of a repeating unit of the formula (1) Phthalate resin composition.
【청구홧 5】 [Bill 홧 5]
제 1 항 내지 제 4 항 중 어느 한 항의 풀리시클로핵실렌디 메틸렌 테 레프탈레이트 수지 조성물로 제조된 성 형품. A molded article made of the pulley cyclonuxylenedi methylene terephthalate resin composition according to any one of claims 1 to 4.
【청구항 6】 [Claim 6]
제 5 항에 있어서, UL 94 VB 난연 규정에 따른 난연도가 1/8' '의 두께에서 V-1 이상인 성 형품. The molded article according to claim 5, wherein the flame retardancy according to the UL 94 VB flame retardant specification is V-1 or more at a thickness of 1/8 '' '.
【청구항 7] [Claim 7]
제 1 항 내지 제 4 항 중 어느 한 항의 폴리시클로핵실렌디 메틸 렌 테 레프탈레이트 수지 조성물로 제조된 엔지 니어 링 플라스틱 .
An engineered plastic made from the polycyclonuclear silane dimethylene terephthalate resin composition according to claim 1.
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| US5233016A (en) * | 1990-12-28 | 1993-08-03 | Polyplastics Co., Ltd. | Melt-stable copolyester molding resins, process for making same, and molded articles formed thereof |
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| KR19980074179A (en) * | 1997-03-21 | 1998-11-05 | 성재갑 | Non-halogen flame retardant thermoplastic resin composition excellent in heat resistance and processability |
| KR20070003786A (en) * | 2003-12-17 | 2007-01-05 | 제너럴 일렉트릭 캄파니 | Flame-retardant polyester composition |
| KR20090080104A (en) * | 2007-03-30 | 2009-07-23 | 미쓰이 가가쿠 가부시키가이샤 | Flame-retardant polyamide composition |
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| US5233016A (en) * | 1990-12-28 | 1993-08-03 | Polyplastics Co., Ltd. | Melt-stable copolyester molding resins, process for making same, and molded articles formed thereof |
| JPH07188521A (en) * | 1993-12-27 | 1995-07-25 | Polyplastics Co | Modified polyester resin composition |
| KR19980074179A (en) * | 1997-03-21 | 1998-11-05 | 성재갑 | Non-halogen flame retardant thermoplastic resin composition excellent in heat resistance and processability |
| KR20070003786A (en) * | 2003-12-17 | 2007-01-05 | 제너럴 일렉트릭 캄파니 | Flame-retardant polyester composition |
| KR20090080104A (en) * | 2007-03-30 | 2009-07-23 | 미쓰이 가가쿠 가부시키가이샤 | Flame-retardant polyamide composition |
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| CN109880317A (en) * | 2019-03-11 | 2019-06-14 | 东莞市东翔塑胶有限公司 | A kind of fiber glass reinforced halogen-free flame retardant PCT material and preparation method thereof |
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