KR20120078448A - Glass fiber reinforced partially aromatic polyamide/polyphenylene ether thermoplastic resin composition, and thermostat housing using the resin compositiona - Google Patents
Glass fiber reinforced partially aromatic polyamide/polyphenylene ether thermoplastic resin composition, and thermostat housing using the resin compositiona Download PDFInfo
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- KR20120078448A KR20120078448A KR1020100140750A KR20100140750A KR20120078448A KR 20120078448 A KR20120078448 A KR 20120078448A KR 1020100140750 A KR1020100140750 A KR 1020100140750A KR 20100140750 A KR20100140750 A KR 20100140750A KR 20120078448 A KR20120078448 A KR 20120078448A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
Abstract
Description
본 발명은 써모스탯 하우징의 내습성, 치수안정성, 내충격성 및 내부동액성 등과 같은 물성 및 표면특성을 개선하기 위한 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물 및 상기 수지조성물로 제조되는 써모스탯 하우징에 관한 것이다.The present invention is a glass fiber-reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition and the resin for improving the physical properties and surface properties such as moisture resistance, dimensional stability, impact resistance and internal fluid resistance of the thermostat housing It relates to a thermostat housing made of a composition.
일반적으로 폴리아미드(polyamide)/폴리페닐렌 에테르(polyphenylene ether)계 수지조성물은 우수한 기계적 물성, 내열성 및 내화학성을 갖는다.Generally, polyamide / polyphenylene ether resin compositions have excellent mechanical properties, heat resistance, and chemical resistance.
또한, 유리섬유, 탄소섬유, 탈크, 탄산칼슘, 황산바륨과 같은 다양한 무기물을 첨가함으로써 높은 강도와 내열성 및 탄성율을 얻을 수 있으며, 여타 첨가제들을 첨가하여 여러 물성 및 저항성을 증가시킬 수가 있어서, 폴리아미드와 폴리페닐렌 에테르의 합성수지는 자동차 부품, 전기전자 부품, 기계부품 등에 널리 사용되어 왔다.In addition, by adding various inorganic materials such as glass fiber, carbon fiber, talc, calcium carbonate and barium sulfate, high strength, heat resistance and elastic modulus can be obtained, and other additives can be added to increase various properties and resistances. And synthetic resins of polyphenylene ethers have been widely used in automobile parts, electrical and electronic parts, and mechanical parts.
그러나 이들 수지는 폴리아미드를 함유하기 때문에 수분을 흡수하게 되면 치수 변화, 기계적 물성이 낮아지는 문제점을 내포하고 있으며, 자동차 엔진 냉각기 계통에 사용되는 부동액 성분인 에틸렌글리콜 수용액에 대한 저항성이 문제가 되어왔다.However, since these resins contain polyamides, they absorb problems of dimensional change and lower mechanical properties when they absorb moisture, and their resistance to aqueous ethylene glycol solutions, which are antifreeze components used in automotive engine cooler systems, has been a problem. .
이는 내열성 및 내부동액성이 필수적인 자동차 엔진 냉각기 계통과 같은 응용분야에서 치명적인 결점으로 작용하며, 자동차의 엔진부품 용도로 유리섬유가 강화된 폴리아미드/폴리페닐렌 에테르계 수지조성물이 사용되기 위해서는 많은 까다로운 특성들이 요구된다.This is a fatal drawback in applications such as automotive engine cooler systems where heat resistance and internal liquidity are essential. It is difficult to use glass fiber reinforced polyamide / polyphenylene ether resin compositions for automotive engine parts. Properties are required.
그 중 대표적인 것이 내열성, 내에틸렌글리콜성이며, 특히 냉각기 제품으로 사용하기 위해서는 고온, 예를 들어 120℃ 이상의 조건하에서 제품의 성능이 발휘되어야 하기 때문에 내열성이 우수해야 하며, 또한 엔진 냉각수로 쓰이는 에틸렌글리콜에도 견딜 수 있어야 한다.The representative ones are heat resistance and ethylene glycol resistance, and in particular, in order to use the product as a cooler, the performance of the product must be exhibited under high temperature, for example, 120 ° C. or higher, so it must be excellent in heat resistance and ethylene glycol used as engine coolant. Must be able to withstand
본 발명이 해결하려는 과제는 내습성, 내충격성 및 치수안정성이 향상되고, 내에틸렌글리콜성 및 표면특성을 개선한 써모스탯 하우징 용도의 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물 및 상기 수지조성물로 제조되는 써모스탯 하우징을 제공하는 것이다.The problem to be solved by the present invention is a partially aromatic polyamide / polyphenylene ether-based thermoplastic glass fiber reinforced for use in thermostat housings improved moisture resistance, impact resistance and dimensional stability, improved ethylene glycol resistance and surface properties It is to provide a resin composition and a thermostat housing made of the resin composition.
상기 과제를 달성하기 위하여 본 발명은, 부분 방향족 폴리아미드 수지 5~95중량% 및 폴리페닐렌 에테르계 수지 5~95중량%로 구성되는 수지혼합물 100중량부; 실란 커플링제가 처리된 유리섬유 10~60중량부; 충격보강제 1~10중량부; 및 상용화제 0.1~5.0중량부;를 포함하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물을 제공한다.In order to achieve the above object, the present invention, 100 parts by weight of a resin mixture composed of 5 to 95% by weight of a partially aromatic polyamide resin and 5 to 95% by weight of a polyphenylene ether-based resin; 10 to 60 parts by weight of the glass fiber treated with the silane coupling agent; 1 to 10 parts by weight of an impact modifier; And 0.1 to 5.0 parts by weight of a compatibilizer; provides a glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition.
또한, 본 발명은 상기 부분 방향족 폴리아미드 수지, 폴리페닐렌 에테르 수지, 충격보강제 및 상용화제를 혼합하여 압출기에 투입한 다음, 압출기의 중간지점에 실란 커플링제가 처리된 유리섬유를 공급하여 제조되는 써모스탯 하우징을 제공한다.In addition, the present invention is prepared by mixing the partially aromatic polyamide resin, polyphenylene ether resin, impact modifier and compatibilizer into the extruder, and then supplying the glass fiber treated with the silane coupling agent to the intermediate point of the extruder Provides a thermostat housing.
본 발명에 따른 열가소성 수지조성물은 부분 방향족 폴리아미드 수지, 폴리페닐렌 에테르 수지 및 실란 커플링제가 처리된 유리섬유의 상용성이 개선되어, 기계적 물성, 내열성 및 내부동액성이 우수하고 사출성형성이 양호하며, 폴리아미드 66보다 수분 흡수율이 작아서 무게 및 치수안정성이 우수하다.The thermoplastic resin composition according to the present invention has improved compatibility with glass fibers treated with partially aromatic polyamide resins, polyphenylene ether resins and silane coupling agents, and thus has excellent mechanical properties, heat resistance and internal liquid resistance, and injection molding properties. It is good, and its water absorption rate is lower than that of polyamide 66, which is excellent in weight and dimensional stability.
또한, 상기 수지조성물로 제조되는 써모스탯 하우징은 자동차 엔진 냉각기 계통과 같은 응용분야에서 안정된 성능을 발휘할 수 있다.In addition, the thermostat housing made of the resin composition may exhibit stable performance in applications such as automotive engine cooler systems.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 수지조성물은 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지가 상용화제에 의하여 상용화되고 여기에 충격보강제 및 실란 커플링제가 처리된 유리섬유를 포함하여 구성된다.The resin composition according to the present invention comprises glass fibers in which a partially aromatic polyamide resin and a polyphenylene ether-based resin are commercialized by a compatibilizer and treated with an impact modifier and a silane coupling agent.
이하에서는 상기 수지조성물에 사용되는 각 성분에 대하여 설명한다.
Hereinafter, each component used for the said resin composition is demonstrated.
부분 방향족 폴리아미드 수지Partially aromatic polyamide resin
본 발명의 구성성분인 부분 방향족 폴리아미드 수지는 선형 지방족 디아민, 선형 지방족 디카르복실산 및 방향족 디카르복실산의 축중합에 의하여 제조된 중합체이다.Partly aromatic polyamide resins, which are components of the present invention, are polymers prepared by the polycondensation of linear aliphatic diamines, linear aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
상기 선형 지방족 디아민은 탄소수가 4~20인 것을 사용할 수 있으며, 예를 들어 헥사메틸렌디아민(hexamethylenediamine) 또는 테트라메틸렌디아민(tetramethylenediamine)이 바람직하다.The linear aliphatic diamine may be used having 4 to 20 carbon atoms, for example, hexamethylenediamine or tetramethylenediamine is preferable.
상기 선형 지방족 디카르복실산은 탄소수가 2~20인 것이 사용되며, 예를 들어 아디픽산(adipic acid)과 세바식산(sebacic acid)이 바람직하다.The linear aliphatic dicarboxylic acid having 2 to 20 carbon atoms is used, for example, adipic acid and sebacic acid are preferable.
상기 방향족 디카르복실산은 테레프탈산(terephthalic acid), 이소프탈산(isophthalic acid) 또는 나프탈렌 디카르복실산(naphthalene dicarboxylic acid)이 바람직하다.The aromatic dicarboxylic acid is preferably terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid.
디카르복실산에서 선형 지방족 디카르복실산 및 방향족 디카르복실산의 비율은 선형 지방족 디카르복실산 1몰(mole)에 대하여 방향족 디카르복실산 0.1~10.0몰이 바람직하다.As for the ratio of linear aliphatic dicarboxylic acid and aromatic dicarboxylic acid in dicarboxylic acid, 0.1-10.0 mol of aromatic dicarboxylic acid is preferable with respect to 1 mol of linear aliphatic dicarboxylic acids.
또한, 본 발명의 구성성분인 부분 방향족 폴리아미드 수지는 적어도 0.04㎎-equiv/g의 말단 아미노기가 요구되며, 적어도 0.05㎎-equiv/g이 바람직하다.In addition, partially aromatic polyamide resins which are components of the present invention require at least 0.04 mg-equiv / g of terminal amino groups, with at least 0.05 mg-equiv / g being preferred.
0.04㎎-equiv/g 보다 적은 함량의 말단 아미노기가 존재하는 경우, 상기 폴리페닐렌 에테르 수지와 상용성이 충분하지 않고 충격강도가 약하게 되므로 바람직하지 않다.When terminal amino groups of less than 0.04 mg-equiv / g are present, it is not preferable because the compatibility with the polyphenylene ether resin is insufficient and the impact strength becomes weak.
상기 부분 방향족 폴리아미드 수지의 비제한적 예로서는 듀퐁(DuPont)사의 상품명 Zytel HTN(high temperature nylon), 솔베이(Solvay)사의 상품명 Amodel, 미쓰이 석유화학(Mitsui Petrochemical)사의 상품명 Arlen, 에보닉(Evonik)사의 상품명 Vestamid와 같은 Modified PA6T와 쿠라레이(Kuraray)사의 상품명 Genestar와 같은 PA9T가 상업화되어 있다.
Non-limiting examples of the partially aromatic polyamide resin include DuPont trade name Zytel HTN (high temperature nylon), Solvay trade name Amodel, Mitsui Petrochemical trade name Arlen, Evonik trade name Modified PA6T such as Vestamid and PA9T such as Kuraray trade name Genestar are commercially available.
폴리페닐렌 에테르계 수지Polyphenylene Ether Resin
폴리페닐렌 에테르계 수지의 비제한적인 예로서 폴리(2,6-디메틸-1,4-페닐렌)에테르, 폴리(2,6-디에틸-1,4-페닐렌)에테르, 폴리(2,6-디프로필-1,4-페닐렌)에테르, 폴리(2-에틸-6-에틸-1,4-페닐렌)에테르, 폴리(2-메틸-6-프로필-1,4-페닐렌)에테르, 폴리(2-에틸-6-프로틸-1,4-페닐렌)에테르 또는 이들의 2종 이상 공중합체를 사용할 수 있으며, 상기 공중합체로서는 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,6-트리메틸-1,4-페닐렌)에테르의 공중합체 및 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,6-트리에틸-1,4-페닐렌)에테르와의 공중합체를 예로 들 수 있다.Non-limiting examples of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2 , 6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene ) Ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, or two or more copolymers thereof can be used, and as the copolymer, poly (2,6-dimethyl-1,4 Copolymer of -phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3) And copolymers with, 6-triethyl-1,4-phenylene) ether.
이들 중에서, 폴리(2,6-디메틸-1,4-페닐렌)에테르 및 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,6-트리메틸-1,4-페닐렌)에테르와의 공중합체가 바람직하며, 폴리(2,6-디메틸-1,4-페닐렌)에테르가 더욱 바람직하다.Among them, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4 Copolymers with -phenylene) ether are preferred, and poly (2,6-dimethyl-1,4-phenylene) ether is more preferred.
상기 폴리페닐렌 에테르계 수지의 중합도는 특별히 제한되지는 않지만, 상기 수지조성물의 열안정성이나 작업성을 고려하면, 고유점도가 25℃의 클로로포름 용매에서 측정하였을 때 0.2~0.8㎗/g인 것이 바람직하다.The degree of polymerization of the polyphenylene ether resin is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity is preferably 0.2 to 0.8 dl / g when measured in a chloroform solvent at 25 ° C. Do.
상기 폴리페닐렌 에테르계 수지는 단독으로 사용하거나 2종 이상의 화합물을 적정 비율로 혼합하여 사용하는 것도 가능하다.
The polyphenylene ether resin may be used alone or in combination of two or more compounds in an appropriate ratio.
상기 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지는 부분 방향족 폴리아미드 수지 5~95중량% 및 폴리페닐렌 에테르계 수지 5~95중량%로 혼합되는 것이 바람직하다.
It is preferable that the partially aromatic polyamide resin and the polyphenylene ether resin are mixed with 5 to 95% by weight of the partially aromatic polyamide resin and 5 to 95% by weight of the polyphenylene ether resin.
실란Silane 커플링제가Coupling agent 처리된 유리섬유 Treated fiberglass
본 발명에 따른 수지조성물은 내에틸렌글리콜성 및 기계적 물성을 강화하기 위하여 유리섬유를 포함하며, 그 예로서는 수지와의 상용성을 부여하기 위하여 실란 커플링제가 처리된 유리섬유를 사용할 수 있다.The resin composition according to the present invention includes glass fibers to enhance ethylene glycol resistance and mechanical properties, and examples thereof may include glass fibers treated with a silane coupling agent to impart compatibility with the resin.
본 발명에 사용되는 실란 커플링제가 처리된 유리섬유는 길이 3~4㎜, 지름 10~13㎛인 것이 바람직하다.It is preferable that the glass fiber to which the silane coupling agent used for this invention was processed is 3-4 mm in length, and 10-13 micrometers in diameter.
상기 실란 커플링제 처리된 유리섬유는 상기 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지가 혼합된 수지혼합물 100중량부에 대하여 10~60중량부의 함량으로 사용할 수 있다.The silane coupling agent treated glass fiber may be used in an amount of 10 to 60 parts by weight based on 100 parts by weight of the resin mixture in which the partially aromatic polyamide resin and the polyphenylene ether resin are mixed.
상기 함량이 10중량부 미만이면 내에틸렌글리콜성 및 기계적 물성 강화효과가 충분치 않고, 60중량부를 초과할 경우 작업성에 악영향을 미칠 수 있다.
If the content is less than 10 parts by weight, the effect of strengthening the ethylene glycol resistance and mechanical properties is not sufficient, and if it exceeds 60 parts by weight may adversely affect workability.
충격보강제Impact modifier
본 발명에 따른 수지조성물은 내충격성을 강화하기 위하여 충격보강제를 포함하는데, 예를 들어 스티렌계 충격보강제를 사용할 수 있다.The resin composition according to the present invention includes an impact modifier in order to enhance impact resistance, for example, a styrene-based impact modifier may be used.
상기 충격보강제는 상기 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지가 혼합된 수지혼합물 100중량부에 대하여 1~10중량부의 함량으로 사용할 수 있으며, 상기 충격보강제의 함량이 1중량부 미만이면 내충격성 개선이 불충분하고, 10중량부를 초과하는 경우 내열성이 취약해지는 문제가 있다.The impact modifier may be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the resin mixture in which the partially aromatic polyamide resin and the polyphenylene ether-based resin are mixed. Insufficient impact improvement, there is a problem that the heat resistance is weak when it exceeds 10 parts by weight.
본 발명의 수지조성물에 사용가능한 스티렌계 충격보강제는 비닐 방향족 단량체에서 유도된 것으로서, 스티렌(styrene) 블록 및 디엔(diene) 블록을 포함하는 열가소성 탄성체가 바람직하며, 예를 들어 스티렌-부타디엔-스티렌 이원 공중합체, 스티렌-에틸렌-부타디엔-스티렌 삼원 공중합체, 스티렌-에틸렌-에틸렌-프로필렌-스티렌 삼원 공중합체, 관능기가 부여된 스티렌-에틸렌-부타디엔-스티렌 삼원 공중합체, 관능기가 부여된 스티렌-에틸렌-에틸렌-프로필렌-스티렌 삼원 공중합체가 사용될 수 있고, 1종 또는 2종 이상을 조합하여 사용할 수도 있다.Styrene-based impact modifiers usable in the resin composition of the present invention are derived from vinyl aromatic monomers, preferably thermoplastic elastomers comprising styrene blocks and diene blocks, for example styrene-butadiene-styrene binary. Copolymer, styrene-ethylene-butadiene-styrene terpolymer, styrene-ethylene-ethylene-propylene-styrene terpolymer, functionalized styrene-ethylene-butadiene-styrene terpolymer, functional group styrene-ethylene- Ethylene-propylene-styrene terpolymer can be used, and can also be used 1 type or in combination of 2 or more types.
또한, 상기 스티렌계 충격보강제는 AB 또는 ABA 형태의 블록 또는 라디알(radial) 트리블록 공중합체가 사용될 수 있다.In addition, the styrene-based impact modifier may be a block or a radial triblock copolymer of the AB or ABA form.
AB 또는 ABA 형태의 블록 또는 라디알 트리블록 공중합체는 비닐 방향족 단량체와 수소첨가, 부분 수소첨가 또는 수소가 첨가되지 않은 불포화 디엔 블록으로 이루어진 공중합체를 사용할 수 있고, AB 디블록형의 블록 공중합체의 예로는 폴리스티렌-폴리부타디엔 공중합체, 폴리스티렌-폴리이소프렌 공중합체, 폴리알파메틸스티렌-폴리부타디엔 공중합체와 이들의 수소첨가 형태의 공중합체가 있다.Blocks or radial triblock copolymers in the form of AB or ABA can be copolymers composed of vinyl aromatic monomers and unsaturated diene blocks without hydrogenation, partial hydrogenation or hydrogenation, and block copolymers of AB diblock type Examples are polystyrene-polybutadiene copolymers, polystyrene-polyisoprene copolymers, polyalphamethylstyrene-polybutadiene copolymers and their hydrogenated forms.
이러한 AB 디블록형 공중합체는 상업적으로 널리 알려져 있으며, 대표적으로 필립스(PHILLIPS)사의 상품명 SOLPRENED와 K-RESIN, 쉘(SHELL)사의 상품명 KRATON D와 KRATON G 등이 있다.Such AB diblock type copolymers are widely known commercially, and are typically represented by Philips (trade names SOLPRENED and K-RESIN, SHELL's trade names KRATON D and KRATON G).
상기 ABA 트리블록형의 블록공중합체의 예로는 폴리스티렌-폴리부타디엔-폴리스티렌 공중합체, 폴리스티렌-폴리이소프렌-폴리스티렌 공중합체, 폴리알파메틸스티렌-폴리부타디엔-폴리알파메틸스티렌 공중합체 및 폴리알파메틸스티렌-폴리이소프렌-폴리알파메틸스티렌 공중합체와 이들의 수소첨가 형태의 공중합체가 있다.Examples of the ABA triblock type block copolymers include polystyrene-polybutadiene-polystyrene copolymers, polystyrene-polyisoprene-polystyrene copolymers, polyalphamethylstyrene-polybutadiene-polyalphamethylstyrene copolymers, and polyalphamethylstyrene- Polyisoprene-polyalphamethylstyrene copolymers and their hydrogenated copolymers.
이러한 ABA 트리블록형 공중합체도 상업적으로 널리 알려져 있으며, 대표적으로 쉘(SHELL)사의 상품명 CARFLEX, KRATON D, KRATON G와 쿠라레이(KURARAY)사의 상품명 SEPTON 등이 있다.
Such ABA triblock type copolymers are also widely known commercially, and examples thereof include SHF trade names CARFLEX, KRATON D, KRATON G, and KURARAY trade name SEPTON.
상용화제Compatibilizer
본 발명에 따른 수지조성물은 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지의 상용성을 부여하기 위하여 상용화제를 포함하며, 그 예로서는 페놀형 에폭시 수지를 사용할 수 있다.The resin composition according to the present invention includes a compatibilizer in order to impart compatibility between the partially aromatic polyamide resin and the polyphenylene ether resin, and an example thereof may be a phenol type epoxy resin.
본 발명의 수지조성물에 사용가능한 상용화제로서는 비제한적인 예로서 2,2'-(2-메틸프로필리덴)비스[2,4-디메틸페놀], 2,2'-메틸리덴비스(4-노닐페놀), 4,4'-(1-메틸에틸리덴)비스[2-(1-메틸에틸)페놀], 4,4'-(1-메틸에틸리덴)비스[2-(1,1-디메틸에틸)페놀], 테트라메틸비스페놀 A, 테트라메틸비스페놀 F, 4,4'-(1-메틸에틸리덴)비스[2,6-디(1,1-디메틸에틸)페놀], 4,4'-(1-메틸에틸리덴)비스[2-(2-프로페닐)페놀], 4,4'-메틸렌비스[2-(2-프로페닐)페놀], 3,3'-디메틸(1,1'-비페닐)-4,4'-디올, 3,3'-비스(2-프로페닐)-[1,1'-비페닐]-4,4'-디올, 4,4'-(1-메틸에틸리덴)비스[2-메틸-6-히드록시메틸페놀], 테트라메틸올비스페놀 A, 3,3',5,5'-테트라키스(히드록시메틸)-(1,1'-비페닐)-4,4'-디올, 4,4'-(1-메틸에틸리덴)비스[2-페닐페놀], 4,4'-(1-메틸에틸리덴)비스[2-시클로헥실페놀], 4,4'-메틸렌비스(2-시클로헥실-5-메틸페놀), 4,4'-(1-메틸프로필리덴)비스페놀, 4,4'-(1-메틸헵틸리덴)비스페놀, 4,4'-(1-메틸옥틸리덴)비스페놀, 4,4'-(1,3-디메틸부틸리덴)비스페놀, 3,3',5,5'-테트라메틸-(1,1'-비페닐)-4,4'-디올, 3,3',5,5'-테트라-t-부틸-(1,1'-비페닐)-4,4'-디올, 4,4'-(1-메틸에틸리덴)비스[2-(1-페닐에틸)페놀], 4,4'-(2-에틸헥실리덴)비스페놀, 4,4'-메틸렌비스(2-메틸페놀), 4,4'-(2-메틸프로필리덴)비스페놀, 4,4'-프로필리덴비스페놀, 4,4'-(1-에틸프로필리덴)비스페놀, 4,4'-메틸렌비스[2,6-비스(1,1-디메틸에틸)페놀], 4,4'-(3-메틸부틸리덴)비스페놀, 4,4'-(1-페닐에틸리덴)비스페놀, 4,4'-(1-메틸에틸리덴)비스[2-(1,1-메틸프로필)페놀], 4,4'-(페닐메틸렌)비스페놀, 4,4'-(디페닐메틸렌)비스페놀, 4,4'-[1-(4-니트로페닐)에틸리덴]비스페놀, 4,4'-[1-(4-아미노페닐)에틸리덴]비스페놀, 4,4'-[(4-브로모페닐)메틸렌비스페놀, 4,4'-[(4-클로로페닐)메틸렌비스페놀, 4,4'-[(4-플루오로페닐)메틸렌비스페놀, 4,4'-(2-메틸프로필리덴)비스[3-메틸-6-(1,1-디메틸에틸)페놀], 4,4'-(1-에틸프로필리덴)비스[2-메틸페놀], 4,4'-(1-페닐에틸리덴)비스[2-메틸페놀], 4,4'-(페닐메틸렌)비스-2,3,5-트리메틸페놀, 4,4'-(1-페닐에틸리덴)비스[2-(1,1-디메틸에틸)페놀], 4,4'-(1-메틸프로필리덴)비스[2-시클로헥실-5-메틸페놀], 4,4'-(1-페닐에틸리덴)비스[2-페닐페놀], 4,4'-부틸리덴비스[3-메틸-6-(1,1-디메틸에틸)페놀], 4-히드록시-α-(4-히드록시페닐-α-메틸벤젠아세틸렌메틸에스테르), 4-히드록시-α-(4-히드록시페닐-α-메틸벤젠아세틸렌에틸에스테르), 4-히드록시-α-(4-히드록시페닐)벤젠아세틸렌부틸에스테르, 테트라브로모비스페놀 A, 테트라브로모비스페놀 F, 테트라브로모비스페놀 AD, 4,4'-(1-메틸에틸렌)비스[2,6-디클로로페놀], 4,4'-(1-메틸에틸리덴)비스[2-클로로페놀], 4,4-(1-메틸에틸리덴)비스[2-클로로-6-메틸페놀], 4,4'-메틸렌비스(2-플루오로페놀), 4,4'-메틸렌비스(2,6-디플루오로페놀), 4,4'-이소프로필리덴비스(2-플루오로페놀), 3,3'-디플루오로-(1,1'-디페닐)-4,4'-디올, 3,3',5,5'-테트라플루오로-(1,1'-비페닐)-4,4'-디올, 4,4'-(페닐메틸렌)비스[2-플루오로페놀], 4,4'-[(4-플루오로페닐)메틸렌비스[2-플루오로페놀], 4,4'-(플루오로메틸렌)비스[2,6-디플루오로페놀], 4,4'-(4-플루오로페닐)메틸렌비스[2,6-디플루오로페놀], 4,4'-(디페닐메틸렌)비스[2-플루오로페놀], 4,4'-(디페닐메틸렌)비스[2,6-디플루오로페놀], 4,4'-(1-메틸에틸렌)비스[2-니트로페놀], 1,4-나프탈렌디올, 1,5-나프탈렌디올, 1,6-나프탈렌디올, 1,7-나프탈렌디올, 2,7-나프탈렌디올, 4,4'-디히드록시디페닐에테르, 비스(4-히드록시페닐)메타논, 4,4'-시클로헥실리덴비스페놀, 4,4'-시클로헥실리덴비스(2-메틸페놀), 4,4'-시클로펜틸리덴비스페놀, 4,4'-시클로펜틸리덴비스(2-메틸페놀), 4,4'-시클로헥실리덴(2,6-디메틸페놀), 4,4'-시클로헥실리덴비스[2-(1,1-디메틸에틸)페놀], 4,4'-시클로헥실리덴비스([2-시클로헥실페놀), 4,4'-(1,2-에탄디일)비스페놀, 4,4'-시클로헥실리덴비스(2-페닐페놀), 4,4'-[1,4-페닐렌비스(1-메틸에틸리덴)]비스[2-메틸페놀], 4,4'-[1,3-페닐렌비스(1-메틸에틸리덴)]비스페놀, 4,4'-[1,4-페닐렌비스(1-메틸에틸리덴)]비스페놀, 4,4'-[1,4-페닐렌비스(1-메틸에틸리덴)]비스[2-메틸-6-히드록시메틸페놀], 4-[1-[4-(4-히드록시-3-메틸페닐)-4-메틸시클로헥실]-1-메틸에틸]-2-메틸페놀, 4-[1-(4-히드록시-3,5-디메틸페닐)-4-메틸시클로헥실-1-메틸에틸]-2,6-디메틸페놀, 4,4'-(1,2-에탄디일)비스[2,6-디-(1,1-디메틸에틸)페놀], 4,4'-(디메틸실릴렌)비스페놀, 1,3-비스(p-히드록시페닐)-1,1,3,3-테트라메틸디실록산, 양 말단에 p-히드록시페닐기를 갖는 실리콘 올리고머, 2,2'-메틸리덴비스페놀, 2,2'-메틸에틸리덴비스페놀, 2,2'-에틸리덴비스페놀 등의 페놀 골격의 방향 환에 직쇄형 알킬기, 분지형 알킬기, 아릴기, 메틸올기, 알릴기 등을 도입한 것이다.Compatibilizers usable in the resin composition of the present invention include, but are not limited to, 2,2 '-(2-methylpropylidene) bis [2,4-dimethylphenol], 2,2'-methylidenebis (4-nonyl Phenol), 4,4 '-(1-methylethylidene) bis [2- (1-methylethyl) phenol], 4,4'-(1-methylethylidene) bis [2- (1,1 -Dimethylethyl) phenol], tetramethylbisphenol A, tetramethylbisphenol F, 4,4 '-(1-methylethylidene) bis [2,6-di (1,1-dimethylethyl) phenol], 4, 4 '-(1-methylethylidene) bis [2- (2-propenyl) phenol], 4,4'-methylenebis [2- (2-propenyl) phenol], 3,3'-dimethyl ( 1,1'-biphenyl) -4,4'-diol, 3,3'-bis (2-propenyl)-[1,1'-biphenyl] -4,4'-diol, 4,4 ' -(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], tetramethylolbisphenol A, 3,3 ', 5,5'-tetrakis (hydroxymethyl)-(1, 1'-biphenyl) -4,4'-diol, 4,4 '-(1-methylethylidene) bis [2-phenylphenol], 4,4'-(1-methylethylidene) bis [ 2-cyclohexylphenol], 4,4'-methylenebis (2-cyclohexyl -5-methylphenol), 4,4 '-(1-methylpropylidene) bisphenol, 4,4'-(1-methylheptylidene) bisphenol, 4,4 '-(1-methyloctylidene) bisphenol , 4,4 '-(1,3-dimethylbutylidene) bisphenol, 3,3', 5,5'-tetramethyl- (1,1'-biphenyl) -4,4'-diol, 3, 3 ', 5,5'-tetra-t-butyl- (1,1'-biphenyl) -4,4'-diol, 4,4'-(1-methylethylidene) bis [2- (1 -Phenylethyl) phenol], 4,4 '-(2-ethylhexylidene) bisphenol, 4,4'-methylenebis (2-methylphenol), 4,4'-(2-methylpropylidene) bisphenol, 4,4'-propylidenebisphenol, 4,4 '-(1-ethylpropylidene) bisphenol, 4,4'-methylenebis [2,6-bis (1,1-dimethylethyl) phenol], 4,4 '-(3-methylbutylidene) bisphenol, 4,4'-(1-phenylethylidene) bisphenol, 4,4 '-(1-methylethylidene) bis [2- (1,1-methyl Propyl) phenol], 4,4 '-(phenylmethylene) bisphenol, 4,4'-(diphenylmethylene) bisphenol, 4,4 '-[1- (4-nitrophenyl) ethylidene] bisphenol, 4,4 '-[1- (4-aminophenyl) ethylidene] bisphenol, 4,4'-[(4-bromophenyl) methylene ratio Phenol, 4,4 '-[(4-chlorophenyl) methylenebisphenol, 4,4'-[(4-fluorophenyl) methylenebisphenol, 4,4 '-(2-methylpropylidene) bis [3-methyl -6- (1,1-dimethylethyl) phenol], 4,4 '-(1-ethylpropylidene) bis [2-methylphenol], 4,4'-(1-phenylethylidene) bis [2 -Methylphenol], 4,4 '-(phenylmethylene) bis-2,3,5-trimethylphenol, 4,4'-(1-phenylethylidene) bis [2- (1,1-dimethylethyl) Phenol], 4,4 '-(1-methylpropylidene) bis [2-cyclohexyl-5-methylphenol], 4,4'-(1-phenylethylidene) bis [2-phenylphenol], 4 , 4'-butylidenebis [3-methyl-6- (1,1-dimethylethyl) phenol], 4-hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetylenemethylester), 4 -Hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetyleneethylester), 4-hydroxy-α- (4-hydroxyphenyl) benzeneacetylenebutylester, tetrabromobisphenol A, tetrabromobis Phenol F, tetrabromobisphenol AD, 4,4 '-(1-methylethylene) bis [2,6-dicle Lophenol], 4,4 '-(1-methylethylidene) bis [2-chlorophenol], 4,4- (1-methylethylidene) bis [2-chloro-6-methylphenol], 4 , 4'-methylenebis (2-fluorophenol), 4,4'-methylenebis (2,6-difluorophenol), 4,4'-isopropylidenebis (2-fluorophenol), 3 , 3'-difluoro- (1,1'-diphenyl) -4,4'-diol, 3,3 ', 5,5'-tetrafluoro- (1,1'-biphenyl) -4 , 4'-diol, 4,4 '-(phenylmethylene) bis [2-fluorophenol], 4,4'-[(4-fluorophenyl) methylenebis [2-fluorophenol], 4,4 '-(Fluoromethylene) bis [2,6-difluorophenol], 4,4'-(4-fluorophenyl) methylenebis [2,6-difluorophenol], 4,4 '-( Diphenylmethylene) bis [2-fluorophenol], 4,4 '-(diphenylmethylene) bis [2,6-difluorophenol], 4,4'-(1-methylethylene) bis [2- Nitrophenol], 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxydiphenyl ether , Bis (4-hydroxyphenyl) Tanone, 4,4'-cyclohexylidenebisphenol, 4,4'-cyclohexylidenebis (2-methylphenol), 4,4'-cyclopentylidenebisphenol, 4,4'-cyclopentylidene Bis (2-methylphenol), 4,4'-cyclohexylidene (2,6-dimethylphenol), 4,4'-cyclohexylidenebis [2- (1,1-dimethylethyl) phenol], 4,4'-cyclohexylidenebis ([2-cyclohexylphenol), 4,4 '-(1,2-ethanediyl) bisphenol, 4,4'-cyclohexylidenebis (2-phenylphenol) , 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis [2-methylphenol], 4,4'-[1,3-phenylenebis (1-methylethylli Den)] bisphenol, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4'-[1,4-phenylenebis (1-methylethylidene) ] Bis [2-methyl-6-hydroxymethylphenol], 4- [1- [4- (4-hydroxy-3-methylphenyl) -4-methylcyclohexyl] -1-methylethyl] -2-methyl Phenol, 4- [1- (4-hydroxy-3,5-dimethylphenyl) -4-methylcyclohexyl-1-methylethyl] -2,6-dimethylphenol, 4,4 '-(1,2- Ethanediyl) bis [2,6-di- (1,1-dimethylethyl) Nol], 4,4 '-(dimethylsilylene) bisphenol, 1,3-bis (p-hydroxyphenyl) -1,1,3,3-tetramethyldisiloxane, p-hydroxyphenyl groups at both ends Linear alkyl groups, branched alkyl groups, and aryl groups in aromatic rings of phenol skeletons such as silicone oligomers, 2,2'-methylidene bisphenols, 2,2'-methylethylidene bisphenols, and 2,2'-ethylidene bisphenols; , Methylol group, allyl group and the like are introduced.
구체적으로는 2,2'-메틸리덴비스(4-메틸페놀), 2,2'-에틸리덴비스(4-메틸페놀), 2,2'-메틸리덴비스(4,6-디메틸페놀), 2,2'-(1-메틸에틸리덴)비스[4,6-디메틸페놀], 2,2'-(1-메틸에틸리덴)비스[4-sec-부틸페놀], 2,2'-메틸리덴비스[6-(1,1-디메틸에틸)-4-메틸페놀], 4,4'-(1-메틸에틸리덴)비스[2-메틸페놀], 2,2'-에틸리덴비스[4,6-디(1,1-디메틸에틸)페놀], 2,2'-메틸리덴비스[3-메틸 4,6-디-(1,1-디메틸에틸)페놀], 2,2'-에틸리덴비스[4-(1,1-디메틸에틸)페놀], 2,2'-메틸리덴비스(2,4-디-t-부틸-5-메틸페놀), 2,2'-메틸리덴비스(4-페닐페놀), 2,2'-메틸리덴비스(4-메틸-6-히드록시메틸페놀), 2,2'-메틸렌비스[6-(2-프로페닐)페놀] 등이 있다.Specifically, 2,2'-methylidenebis (4-methylphenol), 2,2'-ethylidenebis (4-methylphenol), 2,2'-methylidenebis (4,6-dimethylphenol), 2,2 '-(1-methylethylidene) bis [4,6-dimethylphenol], 2,2'-(1-methylethylidene) bis [4-sec-butylphenol], 2,2 ' -Methylidenebis [6- (1,1-dimethylethyl) -4-methylphenol], 4,4 '-(1-methylethylidene) bis [2-methylphenol], 2,2'-ethylidene Bis [4,6-di (1,1-dimethylethyl) phenol], 2,2'-methylidenebis [3-methyl 4,6-di- (1,1-dimethylethyl) phenol], 2,2 '-Ethylidenebis [4- (1,1-dimethylethyl) phenol], 2,2'-methylidenebis (2,4-di-t-butyl-5-methylphenol), 2,2'-methyl Lidenebis (4-phenylphenol), 2,2'-methylidenebis (4-methyl-6-hydroxymethylphenol), 2,2'-methylenebis [6- (2-propenyl) phenol] have.
상기 페놀형 에폭시계 수지는 커플링제 역할을 나타내는 것이면 사용에 제약받지 않으나, 작업성을 고려하면 고상 또는 고상에 근접한 에폭시로서 2개 이상의 관능기를 가지고 있는 페놀형 에폭시 수지가 바람직하다.The phenolic epoxy resin is not limited to use as long as it exhibits a role of a coupling agent, but in view of workability, a phenolic epoxy resin having two or more functional groups as the solid phase or the solid phase is preferred.
상기 상용화제는 상기 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지가 혼합된 수지혼합물 100중량부에 대하여 0.1~5.0중량부의 함량으로 사용할 수 있으며, 상기 상용화제의 함량이 0.1중량부 미만이면 상기 부분 방향족 폴리아미드 수지, 폴리페닐렌 에테르계 수지 및 실란 커플링제가 처리된 유리섬유의 상용성이 충분치 않고, 5.0중량부를 초과하는 경우 기계적 물성이 저하된다.
The compatibilizer may be used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the resin mixture in which the partially aromatic polyamide resin and the polyphenylene ether-based resin are mixed, and the content of the compatibilizer is less than 0.1 part by weight. The compatibility of the glass fiber treated with the partially aromatic polyamide resin, the polyphenylene ether resin and the silane coupling agent is not sufficient, and when it exceeds 5.0 parts by weight, the mechanical properties decrease.
분산제Dispersant
본 발명의 수지조성물은 각 성분들의 분산성을 강화시키기 위하여 분산제를 더 포함할 수 있으며, 그 예로서는 탄소수가 6~30개인 지방족 폴리에스테르계 왁스 또는 탄소수 6~30개의 합성유인 터빈유 등을 사용할 수 있다.The resin composition of the present invention may further include a dispersant to enhance the dispersibility of each component, and examples thereof include aliphatic polyester waxes having 6 to 30 carbon atoms or turbine oils having 6 to 30 carbon atoms. have.
상기 분산제는 상기 부분 방향족 폴리아미드 수지와 폴리페닐렌 에테르계 수지가 혼합된 수지혼합물 100중량부에 대하여 0.1~2.0중량부의 함량으로 사용할 수 있으며, 상기 분산제의 함량이 0.1중량부 미만이면 분산성의 개선이 불충분하고, 2.0중량부를 초과하는 경우 기계적 물성이 저하되는 문제가 있어 바람직하지 않다.
The dispersant may be used in an amount of 0.1 to 2.0 parts by weight based on 100 parts by weight of the resin mixture in which the partially aromatic polyamide resin and the polyphenylene ether-based resin are mixed. When the content of the dispersant is less than 0.1 part by weight, dispersibility is improved. If this is insufficient and exceeds 2.0 parts by weight, there is a problem that the mechanical properties are lowered, which is not preferable.
첨가제additive
본 발명에 따른 수지조성물은 각종 첨가제를 더 포함할 수 있으며, 예를 들어 계면활성제, 핵제, 커플링제, 충전제, 가소제, 충격완화제, 혼화제, 착색제, 윤활제, 대전방지제, 안료, 방염제, 탈크, 산화아연, 스테아린산, 산화방지제, 왁스 등의 공지의 열가소성 수지조성물 첨가제들이 가능하고, 이들 각각은 이미 알려진 첨가량의 범위에 따라 1종 또는 2종 이상 선택하여 용이하게 조합할 수 있으므로 이들에 관한 상세한 설명은 생략한다.
The resin composition according to the present invention may further include various additives, for example, surfactants, nucleating agents, coupling agents, fillers, plasticizers, shock absorbers, admixtures, colorants, lubricants, antistatic agents, pigments, flame retardants, talc, oxidation Known thermoplastic resin additives such as zinc, stearic acid, antioxidants, and waxes are possible, and each of these can be easily selected by combining one or two or more kinds according to a range of known amounts. Omit.
본 발명의 조성물을 제조하는 방법으로는 열가소성 고분자 조성물을 혼합 제조하는 통상적인 방법이 채용될 수 있으며, 예를 들어 단축 및 이축 압출기, 슈퍼믹서(super-mixer), 밴버리 믹서(banbury-mixer), 각종 니더(kneader), 롤(roll) 등이 이용될 수 있다.As a method of preparing the composition of the present invention, a conventional method of mixing and preparing a thermoplastic polymer composition may be employed, and for example, a single screw and twin screw extruder, a super-mixer, a banbury-mixer, Various kneaders, rolls, and the like can be used.
본 발명에 따른 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 수지조성물은 사출성형 방식으로 용이하게 성형될 수 있으므로, 상기 수지조성물로 제조되는 써모스탯 하우징은 사출성형 방식으로 제조되어 생산효율이 우수하다.
Since the glass fiber-reinforced partially aromatic polyamide / polyphenylene ether-based resin composition according to the present invention can be easily molded by an injection molding method, a thermostat housing made of the resin composition is manufactured and produced by an injection molding method. The efficiency is excellent.
이하, 본 발명을 하기의 실시예, 비교예 및 시험예에 의거하여 좀더 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to the following examples, comparative examples and test examples.
단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 치환 및 균등한 타 실시예로 변경할 수 있음은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어서 명백할 것이다.
It is to be understood, however, that the invention is not to be construed as limited to the embodiments set forth herein, but is capable of modifications and equivalents within the spirit and scope of the invention. Will be apparent to those skilled in the art to which the present invention pertains.
<실시예 1~8> 및 <비교예 1~4><Examples 1-8> and <Comparative Examples 1-4>
하기 표 1의 각 성분을 균일하게 분산시키기 위하여, 먼저 폴리페닐렌 에테르 수지, 부분 방향족 폴리아미드 수지 또는 폴리아미드 수지, 스티렌계 충격보강제 및 페놀형 에폭시 수지를 혼합하고 여기에 폴리에스테르계 왁스 또는 터빈유의 분산제, 산화방지제를 첨가하여 리본믹서로 혼합하고, L/D=40, 지름 30㎜인 이축 압출기에 투입한 다음, 상기 이축 압출기의 중간 지점인 #6 zone에 실란 커플링제가 처리된 유리섬유를 측면공급(side feeding)하면서 압출온도 310~330℃, 스크류 회전수 200~250rpm으로 압출하여 펠릿으로 제조하였다.In order to uniformly disperse each component of Table 1, first, a polyphenylene ether resin, a partially aromatic polyamide resin or a polyamide resin, a styrene-based impact modifier, and a phenol-type epoxy resin are mixed and a polyester-based wax or a turbine is added thereto. Glass fiber treated with a silane coupling agent in the # 6 zone, which is the middle point of the twin screw extruder, was mixed with a ribbon mixer by adding a dispersant and an antioxidant, and then mixed with a ribbon mixer. Extruded at 310 ~ 330 ℃, screw rotation speed 200 ~ 250rpm while side feeding (side feeding) was prepared as a pellet.
상기 펠릿을 90℃에서 4시간 제습 건조한 후, 사출기에서 성형온도 310~330℃, 금형온도 150℃의 조건으로 사출하여 시편을 제조하였다.
After the pellet was dehumidified and dried at 90 ° C. for 4 hours, a specimen was prepared by injecting the pellet at a molding temperature of 310 to 330 ° C. and a mold temperature of 150 ° C.
주1) Polyphenylene ether resin
Note 1)
주2) Partially aromatic polyamide resin
Note 2)
주3) Polyamide resin
Note 3)
주4) Styrene-based impact modifier
Note 4)
주5) Phenolic Type Epoxy Resin
Note 5)
주6) Glass fiber treated with silane coupling agent
Note 6)
주1) 폴리페닐렌 에테르 수지 : A201A, 아사히 카세이사 제조, 일본Note 1) Polyphenylene ether resin: A201A, manufactured by Asahi Kasei, Japan
주2) 부분 방향족 폴리아미드 수지 : Arlen A3000, 미쓰이 석유화학사 제조, 일본 - 테레프탈산, 아디픽산 및 헥사메틸렌디아민의 축중합에 의하여 제조된 Polyamide 6T, 고유점도(intrinsic viscosity) 1.3(30℃, 진한 황산), 용융점 312℃, 유리전이온도 83℃, 말단 아미노기 함량 0.051㎎-equiv/gNote 2) Partly aromatic polyamide resin: Arlen A3000, manufactured by Mitsui Petrochemical, Japan-Polyamide 6T prepared by condensation polymerization of terephthalic acid, adipic acid and hexamethylenediamine, intrinsic viscosity 1.3 (30 ° C, concentrated sulfuric acid) ), Melting point 312 ℃, glass transition temperature 83 ℃, terminal amino group content 0.051mg-equiv / g
주3) 폴리아미드 수지 : 폴리아미드66, 로디아사 제조, 프랑스 Note 3) Polyamide resin: Polyamide 66, manufactured by Rhodia, France
주4) 스티렌계 충격보강제 : 스티렌-에틸렌-부타디엔-스티렌 공중합체(SEBS), KRATION G 1651, 쉘사 제조, 미국Note 4) Styrene-based impact modifiers: styrene-ethylene-butadiene-styrene copolymer (SEBS), KRATION G 1651, manufactured by Shell, USA
주5) 페놀형 에폭시 수지 : 상용화제, 비스페놀 A타입의 YD-011, 국도화학(주), 한국Note 5) Phenolic epoxy resin: compatibilizer, bisphenol A type YD-011, Kukdo Chemical Co., Ltd., Korea
주6) 실란 커플링제가 처리된 유리섬유 : 오웬스코닝에서 원심성형법으로 제조된 촙 스트랜드로서 10㎛의 장섬유를 사이징 처리 후 4㎜로 절단된 제품
Note 6) Glass fiber treated with silane coupling agent: 촙 strand manufactured by Owens Corning by centrifugal molding method and cut into 4mm after sizing 10μm long fiber.
<시험예 1>≪ Test Example 1 >
상기 실시예 및 비교예에서 제조된 시편에 대하여 하기의 시험방법으로 물성을 측정하고, 그 결과를 하기 표 2에 나타내었다.
Physical properties of the specimens prepared in Examples and Comparative Examples were measured by the following test methods, and the results are shown in Table 2 below.
- 인장강도 및 신율 : ASTM D638-Tensile Strength and Elongation: ASTM D638
- 굴곡강도, 굴곡탄성율 : ASTM D790-Flexural Strength, Flexural Modulus: ASTM D790
- 아이조드 충격강도(1/4 및 1/8 노치) : ASTM D256Izod impact strength (1/4 and 1/8 notch): ASTM D256
- 내부동액성 : 물:에틸렌글리콜=50:50중량비의 수용액에 상기 시편을 146℃에서 144시간 침적 후 인장강도 시험(ASTM D638) 실시
-Internal copper liquid: Tensile strength test (ASTM D638) was performed after immersing the specimen in an aqueous solution of water: ethylene glycol = 50: 50 weight ratio for 144 hours at 146 ° C.
상기 표 2에 나타낸 바와 같이, 부분 방향족 폴리아미드의 함량이 증가함에 따라 기계적 물성이 증가하고, 에폭시 수지의 함량이 증가함에 따라 기계적 물성 및 내부동액성이 증가함을 알 수 있다.As shown in Table 2, it can be seen that the mechanical properties increase as the content of the partially aromatic polyamide increases, and the mechanical properties and the internal copper property increase as the content of the epoxy resin increases.
부분 방향족 폴리아미드 대신에 폴리아미드66을 적용한 비교예에서는 실시예에 비하여 인장강도, 굴곡강도, 굴곡탄성율 및 내부동액성이 저하됨을 알 수 있다.
In the comparative example in which polyamide 66 was applied instead of the partially aromatic polyamide, it can be seen that the tensile strength, the flexural strength, the flexural modulus, and the internal copper fluid were lowered compared to the examples.
<시험예 2> 수분 흡수율 시험Test Example 2 Water Absorption Rate Test
상기 실시예 2 및 비교예 2 시편의 수분 흡수로 인한 무게증가율 및 치수변화율을 측정하여 하기 표 3에 나타내었다.Example 2 and Comparative Example 2 The weight increase rate and the dimensional change rate due to the moisture absorption of the specimen is measured and shown in Table 3 below.
측정은 ASTM 1/8-inch 시편들을 40㎜ 간격으로 표시하고, 95℃ 중탕조에 담근 후, 시간에 따라 시편을 중탕조로부터 꺼내어 표면의 물기를 제거하고 시편의 무게 및 치수를 측정하여 시험 전의 무게 및 치수와 대비하였다.
The measurement was performed by marking ASTM 1 / 8-inch specimens at 40 mm intervals, immersing them in a 95 ° C. hot water bath, and then removing the specimens from the water bath with time to remove water from the surface and measuring the weight and dimensions of the test pieces. And dimensions.
상기 표 3에서 알 수 있는 바와 같이, 실시예 2에 비하여 부분 방향족 폴리아미드 수지 대신에 폴리아미드66 수지를 적용한 비교예 2의 수분 흡수율이 더 큼을 알 수 있다.
As can be seen from Table 3, it can be seen that the water absorption rate of Comparative Example 2 in which the polyamide 66 resin is applied instead of the partially aromatic polyamide resin as compared to Example 2.
상기에서 살펴본 바와 같이, 본 발명에 따른 열가소성 수지조성물은 부분 방향족 폴리아미드 수지, 폴리페닐렌 에테르 수지 및 실란 커플링제가 처리된 유리섬유의 상용성이 개선되어 기계적 물성, 내열성 및 내부동액성이 우수하고 사출성형성이 양호하며, 폴리아미드 66 수지보다 수분 흡수율이 작아서 무게 및 치수안정성이 우수하다.As described above, the thermoplastic resin composition according to the present invention is improved in compatibility of glass fibers treated with a partially aromatic polyamide resin, a polyphenylene ether resin, and a silane coupling agent, thereby providing excellent mechanical properties, heat resistance, and internal liquid resistance. It has good injection molding and excellent water weight and dimensional stability due to its smaller water absorption than polyamide 66 resin.
또한, 상기 수지조성물로 제조된 써모스탯 하우징은 자동차 엔진 냉각기 계통과 같은 응용분야에서 안정된 성능을 발휘할 수 있다.In addition, the thermostat housing made of the resin composition can exhibit stable performance in applications such as automotive engine cooler systems.
Claims (15)
실란 커플링제가 처리된 유리섬유 10~60중량부;
충격보강제 1~10중량부; 및
상용화제 0.1~5.0중량부;를 포함하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.100 parts by weight of a resin mixture composed of 5 to 95% by weight of a partially aromatic polyamide resin and 5 to 95% by weight of a polyphenylene ether resin;
10 to 60 parts by weight of the glass fiber treated with the silane coupling agent;
1 to 10 parts by weight of an impact modifier; And
Comprising 0.1 to 5.0 parts by weight of a glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition comprising a.
상기 부분 방향족 폴리아미드 수지는 선형 지방족 디카르복실산, 방향족 디카르복실산 및 선형 지방족 디아민의 축중합에 의하여 얻어지는 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
The partially aromatic polyamide resin is obtained by condensation polymerization of linear aliphatic dicarboxylic acid, aromatic dicarboxylic acid and linear aliphatic diamine, glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic Resin composition.
상기 선형 지방족 디카르복실산은 아디픽산 또는 세바식산이고, 방향족 디카르복실산은 테레프탈산, 이소프탈산 또는 나프탈렌 디카르복실산이며, 선형 지방족 디아민은 헥사메틸렌디아민 또는 테트라메틸렌디아민인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 2,
The linear aliphatic dicarboxylic acid is adipic acid or sebacic acid, the aromatic dicarboxylic acid is terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid, the linear aliphatic diamine is hexamethylenediamine or tetramethylenediamine, glass fiber Partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition fortified.
상기 부분 방향족 폴리아미드 수지는 선형 지방족 디카르복실산 1몰당 방향족 디카르복실산 0.1~10.0몰로 구성되는 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 2,
The partially aromatic polyamide resin is a glass fiber-reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition, characterized in that composed of 0.1 to 10.0 moles of aromatic dicarboxylic acid per mole of linear aliphatic dicarboxylic acid.
상기 부분 방향족 폴리아미드 수지는 말단 아미노기 함량이 적어도 0.04㎎-equiv/g인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
The partially aromatic polyamide resin has a terminal amino group content of at least 0.04 mg-equiv / g, glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition.
상기 폴리페닐렌 에테르 수지는 폴리(2,6-디메틸-1,4-페닐렌)에테르, 폴리(2,6-디에틸-1,4-페닐렌)에테르, 폴리(2,6-디프로필-1,4-페닐렌)에테르, 폴리(2-에틸-6-에틸-1,4-페닐렌)에테르, 폴리(2-메틸-6-프로필-1,4-페닐렌)에테르, 폴리(2-에틸-6-프로틸-1,4-페닐렌)에테르, 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,6-트리메틸-1,4-페닐렌)에테르의 공중합체 및 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,6-트리에틸-1,4-페닐렌)에테르의 공중합체로 이루어진 군 중에서 선택되는 적어도 어느 하나인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
The polyphenylene ether resin may be poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl -1,4-phenylene) ether, poly (2-ethyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly ( 2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenyl Ene) ether and a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-triethyl-1,4-phenylene) ether A glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition, characterized in that at least one selected.
상기 유리섬유는 길이 3~4㎜, 지름 10~13㎛인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
The glass fiber is a partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition, characterized in that the glass fiber is 3 ~ 4mm in length, 10 ~ 13㎛ in diameter.
상기 충격보강제는 스티렌 블록 및 디엔 블록을 포함하는 열가소성 탄성체인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
Wherein the impact modifier is a thermoplastic elastomer comprising a styrene block and a diene block, glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition.
상기 스티렌 블록 및 디엔 블록을 포함하는 열가소성 탄성체는 스티렌-부타디엔-스티렌 이원 공중합체, 스티렌-에틸렌-부타디엔-스티렌 삼원 공중합체, 스티렌-에틸렌-에틸렌-프로필렌-스티렌 삼원 공중합체, 관능기가 부여된 스티렌-에틸렌-부타디엔-스티렌 삼원 공중합체 및 관능기가 부여된 스티렌-에틸렌-에틸렌-프로필렌-스티렌 삼원 공중합체로 이루어진 군 중에서 선택되는 적어도 어느 하나인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 8,
The thermoplastic elastomer including the styrene block and the diene block may be a styrene-butadiene-styrene binary copolymer, a styrene-ethylene-butadiene-styrene terpolymer, a styrene-ethylene-ethylene-propylene-styrene terpolymer, a styrene endowed with a functional group. Glass-enhanced partially aromatic polyamide, characterized in that it is at least one selected from the group consisting of -ethylene-butadiene-styrene terpolymer and styrene-ethylene-ethylene-propylene-styrene terpolymer with functional groups Polyphenylene Ether Thermoplastic Resin Composition.
상기 상용화제는 2개 이상의 관능기를 가지는 페놀형 에폭시 수지인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
The compatibilizing agent is a phenol-type epoxy resin having two or more functional groups, glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition.
상기 페놀형 에폭시 수지는 2,2'-(2-메틸프로필리덴)비스[2,4-디메틸페놀], 2,2'-메틸리덴비스(4-노닐페놀), 4,4'-(1-메틸에틸리덴)비스[2-(1-메틸에틸)페놀], 4,4'-(1-메틸에틸리덴)비스[2-(1,1-디메틸에틸)페놀], 테트라메틸비스페놀 A, 테트라메틸비스페놀 F, 4,4'-(1-메틸에틸리덴)비스[2,6-디(1,1-디메틸에틸)페놀], 4,4'-(1-메틸에틸리덴)비스[2-(2-프로페닐)페놀], 4,4'-메틸렌비스[2-(2-프로페닐)페놀], 3,3'-디메틸(1,1'-비페닐)-4,4'-디올, 3,3'-비스(2-프로페닐)-[1,1'-비페닐]-4,4'-디올, 4,4'-(1-메틸에틸리덴)비스[2-메틸-6-히드록시메틸페놀], 테트라메틸올비스페놀 A, 3,3',5,5'-테트라키스(히드록시메틸)-(1,1'-비페닐)-4,4'-디올, 4,4'-(1-메틸에틸리덴)비스[2-페닐페놀], 4,4'-(1-메틸에틸리덴)비스[2-시클로헥실페놀], 4,4'-메틸렌비스(2-시클로헥실-5-메틸페놀), 4,4'-(1-메틸프로필리덴)비스페놀, 4,4'-(1-메틸헵틸리덴)비스페놀, 4,4'-(1-메틸옥틸리덴)비스페놀, 4,4'-(1,3-디메틸부틸리덴)비스페놀, 3,3',5,5'-테트라메틸-(1,1'-비페닐)-4,4'-디올, 3,3',5,5'-테트라-t-부틸-(1,1'-비페닐)-4,4'-디올, 4,4'-(1-메틸에틸리덴)비스[2-(1-페닐에틸)페놀], 4,4'-(2-에틸헥실리덴)비스페놀, 4,4'-메틸렌비스(2-메틸페놀), 4,4'-(2-메틸프로필리덴)비스페놀, 4,4'-프로필리덴비스페놀, 4,4'-(1-에틸프로필리덴)비스페놀, 4,4'-메틸렌비스[2,6-비스(1,1-디메틸에틸)페놀], 4,4'-(3-메틸부틸리덴)비스페놀, 4,4'-(1-페닐에틸리덴)비스페놀, 4,4'-(1-메틸에틸리덴)비스[2-(1,1-메틸프로필)페놀], 4,4'-(페닐메틸렌)비스페놀, 4,4'-(디페닐메틸렌)비스페놀, 4,4'-[1-(4-니트로페닐)에틸리덴]비스페놀, 4,4'-[1-(4-아미노페닐)에틸리덴]비스페놀, 4,4'-[(4-브로모페닐)메틸렌비스페놀, 4,4'-[(4-클로로페닐)메틸렌비스페놀, 4,4'-[(4-플루오로페닐)메틸렌비스페놀, 4,4'-(2-메틸프로필리덴)비스[3-메틸-6-(1,1-디메틸에틸)페놀], 4,4'-(1-에틸프로필리덴)비스[2-메틸페놀], 4,4'-(1-페닐에틸리덴)비스[2-메틸페놀], 4,4'-(페닐메틸렌)비스-2,3,5-트리메틸페놀, 4,4'-(1-페닐에틸리덴)비스[2-(1,1-디메틸에틸)페놀], 4,4'-(1-메틸프로필리덴)비스[2-시클로헥실-5-메틸페놀], 4,4'-(1-페닐에틸리덴)비스[2-페닐페놀], 4,4'-부틸리덴비스[3-메틸-6-(1,1-디메틸에틸)페놀], 4-히드록시-α-(4-히드록시페닐-α-메틸벤젠아세틸렌메틸에스테르), 4-히드록시-α-(4-히드록시페닐-α-메틸벤젠아세틸렌에틸에스테르), 4-히드록시-α-(4-히드록시페닐)벤젠아세틸렌부틸에스테르, 테트라브로모비스페놀 A, 테트라브로모비스페놀 F, 테트라브로모비스페놀 AD, 4,4'-(1-메틸에틸렌)비스[2,6-디클로로페놀], 4,4'-(1-메틸에틸리덴)비스[2-클로로페놀], 4,4-(1-메틸에틸리덴)비스[2-클로로-6-메틸페놀], 4,4'-메틸렌비스(2-플루오로페놀), 4,4'-메틸렌비스(2,6-디플루오로페놀), 4,4'-이소프로필리덴비스(2-플루오로페놀), 3,3'-디플루오로-(1,1'-디페닐)-4,4'-디올, 3,3',5,5'-테트라플루오로-(1,1'-비페닐)-4,4'-디올, 4,4'-(페닐메틸렌)비스[2-플루오로페놀], 4,4'-[(4-플루오로페닐)메틸렌비스[2-플루오로페놀], 4,4'-(플루오로메틸렌)비스[2,6-디플루오로페놀], 4,4'-(4-플루오로페닐)메틸렌비스[2,6-디플루오로페놀], 4,4'-(디페닐메틸렌)비스[2-플루오로페놀], 4,4'-(디페닐메틸렌)비스[2,6-디플루오로페놀], 4,4'-(1-메틸에틸렌)비스[2-니트로페놀], 1,4-나프탈렌디올, 1,5-나프탈렌디올, 1,6-나프탈렌디올, 1,7-나프탈렌디올, 2,7-나프탈렌디올, 4,4'-디히드록시디페닐에테르, 비스(4-히드록시페닐)메타논, 4,4'-시클로헥실리덴비스페놀, 4,4'-시클로헥실리덴비스(2-메틸페놀), 4,4'-시클로펜틸리덴비스페놀, 4,4'-시클로펜틸리덴비스(2-메틸페놀), 4,4'-시클로헥실리덴(2,6-디메틸페놀), 4,4'-시클로헥실리덴비스[2-(1,1-디메틸에틸)페놀], 4,4'-시클로헥실리덴비스([2-시클로헥실페놀), 4,4'-(1,2-에탄디일)비스페놀, 4,4'-시클로헥실리덴비스(2-페닐페놀), 4,4'-[1,4-페닐렌비스(1-메틸에틸리덴)]비스[2-메틸페놀], 4,4'-[1,3-페닐렌비스(1-메틸에틸리덴)]비스페놀, 4,4'-[1,4-페닐렌비스(1-메틸에틸리덴)]비스페놀, 4,4'-[1,4-페닐렌비스(1-메틸에틸리덴)]비스[2-메틸-6-히드록시메틸페놀], 4-[1-[4-(4-히드록시-3-메틸페닐)-4-메틸시클로헥실]-1-메틸에틸]-2-메틸페놀, 4-[1-(4-히드록시-3,5-디메틸페닐)-4-메틸시클로헥실-1-메틸에틸]-2,6-디메틸페놀, 4,4'-(1,2-에탄디일)비스[2,6-디-(1,1-디메틸에틸)페놀], 4,4'-(디메틸실릴렌)비스페놀, 1,3-비스(p-히드록시페닐)-1,1,3,3-테트라메틸디실록산, 양 말단에 p-히드록시페닐기를 갖는 실리콘 올리고머, 2,2'-메틸리덴비스페놀, 2,2'-메틸에틸리덴비스페놀 및 2,2'-에틸리덴비스페놀로 이루어진 군 중에서 선택되는 적어도 어느 하나의 페놀 골격의 방향 환에 직쇄형 알킬기, 분지형 알킬기, 아릴기, 메틸올기 및 알릴기로 이루어진 군 중에서 선택되는 적어도 어느 하나를 도입한 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 10,
The phenolic epoxy resin is 2,2 '-(2-methylpropylidene) bis [2,4-dimethylphenol], 2,2'-methylidenebis (4-nonylphenol), 4,4'-(1 -Methylethylidene) bis [2- (1-methylethyl) phenol], 4,4 '-(1-methylethylidene) bis [2- (1,1-dimethylethyl) phenol], tetramethylbisphenol A, tetramethylbisphenol F, 4,4 '-(1-methylethylidene) bis [2,6-di (1,1-dimethylethyl) phenol], 4,4'-(1-methylethylidene ) Bis [2- (2-propenyl) phenol], 4,4'-methylenebis [2- (2-propenyl) phenol], 3,3'-dimethyl (1,1'-biphenyl) -4 , 4'-diol, 3,3'-bis (2-propenyl)-[1,1'-biphenyl] -4,4'-diol, 4,4 '-(1-methylethylidene) bis [2-Methyl-6-hydroxymethylphenol], tetramethylolbisphenol A, 3,3 ', 5,5'-tetrakis (hydroxymethyl)-(1,1'-biphenyl) -4,4 '-Diol, 4,4'-(1-methylethylidene) bis [2-phenylphenol], 4,4 '-(1-methylethylidene) bis [2-cyclohexylphenol], 4,4 '-Methylenebis (2-cyclohexyl-5-methylphenol), 4,4'-(1-methylpropylidene) bisphenol, 4,4 '-(1-methylheptylidene) bisphenol, 4,4'-(1-methyloctylidene) bisphenol, 4,4 '-(1,3-dimethylbutylidene) bisphenol, 3,3 ', 5,5'-tetramethyl- (1,1'-biphenyl) -4,4'-diol, 3,3', 5,5'-tetra-t-butyl- (1,1'-ratio Phenyl) -4,4'-diol, 4,4 '-(1-methylethylidene) bis [2- (1-phenylethyl) phenol], 4,4'-(2-ethylhexylidene) bisphenol , 4,4'-methylenebis (2-methylphenol), 4,4 '-(2-methylpropylidene) bisphenol, 4,4'-propylidenebisphenol, 4,4'-(1-ethylpropylidene) Bisphenol, 4,4'-methylenebis [2,6-bis (1,1-dimethylethyl) phenol], 4,4 '-(3-methylbutylidene) bisphenol, 4,4'-(1-phenyl Ethylidene) bisphenol, 4,4 '-(1-methylethylidene) bis [2- (1,1-methylpropyl) phenol], 4,4'-(phenylmethylene) bisphenol, 4,4'- (Diphenylmethylene) bisphenol, 4,4 '-[1- (4-nitrophenyl) ethylidene] bisphenol, 4,4'-[1- (4-aminophenyl) ethylidene] bisphenol, 4,4'- [(4-bromophenyl) methylenebisphenol, 4,4 '-[(4-chlorophenyl) methylenebisphenol, 4,4'-[ (4-fluorophenyl) methylenebisphenol, 4,4 '-(2-methylpropylidene) bis [3-methyl-6- (1,1-dimethylethyl) phenol], 4,4'-(1-ethyl Propylidene) bis [2-methylphenol], 4,4 '-(1-phenylethylidene) bis [2-methylphenol], 4,4'-(phenylmethylene) bis-2,3,5-trimethyl Phenol, 4,4 '-(1-phenylethylidene) bis [2- (1,1-dimethylethyl) phenol], 4,4'-(1-methylpropylidene) bis [2-cyclohexyl-5 -Methylphenol], 4,4 '-(1-phenylethylidene) bis [2-phenylphenol], 4,4'-butylidenebis [3-methyl-6- (1,1-dimethylethyl) Phenol], 4-hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetylenemethylester), 4-hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetyleneethylester), 4 -Hydroxy-α- (4-hydroxyphenyl) benzeneacetylenebutylester, tetrabromobisphenol A, tetrabromobisphenol F, tetrabromobisphenol AD, 4,4 '-(1-methylethylene) bis [2 , 6-dichlorophenol], 4,4 '-(1-methylethylidene) bis [2-chlorofe ], 4,4- (1-methylethylidene) bis [2-chloro-6-methylphenol], 4,4'-methylenebis (2-fluorophenol), 4,4'-methylenebis (2 , 6-difluorophenol), 4,4'-isopropylidenebis (2-fluorophenol), 3,3'-difluoro- (1,1'-diphenyl) -4,4'- Diol, 3,3 ', 5,5'-tetrafluoro- (1,1'-biphenyl) -4,4'-diol, 4,4'-(phenylmethylene) bis [2-fluorophenol] , 4,4 '-[(4-fluorophenyl) methylenebis [2-fluorophenol], 4,4'-(fluoromethylene) bis [2,6-difluorophenol], 4,4 ' -(4-fluorophenyl) methylenebis [2,6-difluorophenol], 4,4 '-(diphenylmethylene) bis [2-fluorophenol], 4,4'-(diphenylmethylene) Bis [2,6-difluorophenol], 4,4 '-(1-methylethylene) bis [2-nitrophenol], 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalene Diol, 1,7-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxydiphenylether, bis (4-hydroxyphenyl) methanone, 4,4'-cyclohexylidenebisphenol, 4,4'-cyclo Hexylidenebis (2-methylphenol), 4,4'-cyclopentylidenebisphenol, 4,4'-cyclopentylidenebis (2-methylphenol), 4,4'-cyclohexylidene (2 , 6-dimethylphenol), 4,4'-cyclohexylidenebis [2- (1,1-dimethylethyl) phenol], 4,4'-cyclohexylidenebis ([2-cyclohexylphenol), 4,4 '-(1,2-ethanediyl) bisphenol, 4,4'-cyclohexylidenebis (2-phenylphenol), 4,4'-[1,4-phenylenebis (1-methyl) Thilidene)] bis [2-methylphenol], 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4,4'-[1,4-phenylenebis ( 1-methylethylidene)] bisphenol, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis [2-methyl-6-hydroxymethylphenol], 4- [1 -[4- (4-hydroxy-3-methylphenyl) -4-methylcyclohexyl] -1-methylethyl] -2-methylphenol, 4- [1- (4-hydroxy-3,5-dimethylphenyl ) -4-methylcyclohexyl-1-methylethyl] -2,6-dimethylphenol, 4,4 '-(1,2-ethanediyl) bis [2,6-di- (1,1-dimethylethyl) Phenol], 4,4 '-(dimethylsilylene) bisphenol, 1,3-bis (p-hi Oxyphenyl) -1,1,3,3-tetramethyldisiloxane, silicone oligomers having p-hydroxyphenyl groups at both ends, 2,2'-methylidenebisphenol, 2,2'-methylethylidenebisphenol and At least one selected from the group consisting of linear alkyl groups, branched alkyl groups, aryl groups, methylol groups and allyl groups is introduced into the aromatic ring of at least one phenol skeleton selected from the group consisting of 2,2'-ethylidene bisphenol. A glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition.
상기 페놀형 에폭시 수지는 2,2'-메틸리덴비스(4-메틸페놀), 2,2'-에틸리덴비스(4-메틸페놀), 2,2'-메틸리덴비스(4,6-디메틸페놀), 2,2'-(1-메틸에틸리덴)비스[4,6-디메틸페놀], 2,2'-(1-메틸에틸리덴)비스[4-sec-부틸페놀], 2,2'-메틸리덴비스[6-(1,1-디메틸에틸)-4-메틸페놀], 4,4'-(1-메틸에틸리덴)비스[2-메틸페놀], 2,2'-에틸리덴비스[4,6-디(1,1-디메틸에틸)페놀], 2,2'-메틸리덴비스[3-메틸 4,6-디-(1,1-디메틸에틸)페놀], 2,2'-에틸리덴비스[4-(1,1-디메틸에틸)페놀], 2,2'-메틸리덴비스(2,4-디-t-부틸-5-메틸페놀), 2,2'-메틸리덴비스(4-페닐페놀), 2,2'-메틸리덴비스(4-메틸-6-히드록시메틸페놀) 및 2,2'-메틸렌비스[6-(2-프로페닐)페놀]로 이루어진 군 중에서 선택되는 적어도 어느 하나인 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 10,
The phenolic epoxy resin is 2,2'-methylidenebis (4-methylphenol), 2,2'-ethylidenebis (4-methylphenol), 2,2'-methylidenebis (4,6-dimethyl Phenol), 2,2 '-(1-methylethylidene) bis [4,6-dimethylphenol], 2,2'-(1-methylethylidene) bis [4-sec-butylphenol], 2 , 2'-methylidenebis [6- (1,1-dimethylethyl) -4-methylphenol], 4,4 '-(1-methylethylidene) bis [2-methylphenol], 2,2' -Ethylidenebis [4,6-di (1,1-dimethylethyl) phenol], 2,2'-methylidenebis [3-methyl 4,6-di- (1,1-dimethylethyl) phenol], 2,2'-ethylidenebis [4- (1,1-dimethylethyl) phenol], 2,2'-methylidenebis (2,4-di-t-butyl-5-methylphenol), 2,2 '-Methylidenebis (4-phenylphenol), 2,2'-methylidenebis (4-methyl-6-hydroxymethylphenol) and 2,2'-methylenebis [6- (2-propenyl) phenol Glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin tank, characterized in that at least one selected from the group consisting of Water.
상기 수지조성물은 분산제, 계면활성제, 핵제, 커플링제, 충전제, 가소제, 충격완화제, 혼화제, 착색제, 윤활제, 대전방지제, 안료, 방염제, 탈크, 산화아연, 스테아린산, 산화방지제 및 왁스로 이루어진 군 중에서 선택되는 적어도 어느 하나의 첨가제를 더 포함하는 것을 특징으로 하는, 유리섬유가 강화된 부분 방향족 폴리아미드/폴리페닐렌 에테르계 열가소성 수지조성물.The method according to claim 1,
The resin composition is selected from the group consisting of dispersants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, admixtures, colorants, lubricants, antistatic agents, pigments, flame retardants, talc, zinc oxide, stearic acid, antioxidants and waxes. A glass fiber reinforced partially aromatic polyamide / polyphenylene ether-based thermoplastic resin composition, characterized in that it further comprises at least one additive.
상기 써모스탯 하우징의 제조는 부분 방향족 폴리아미드 수지, 폴리페닐렌 에테르 수지, 충격보강제 및 상용화제를 혼합하여 압출기에 투입한 다음, 압출기의 중간지점에 실란 커플링제가 처리된 유리섬유를 공급하여 제조되는 것을 특징으로 하는 써모스탯 하우징.The method according to claim 14,
The thermostat housing is manufactured by mixing partially aromatic polyamide resin, polyphenylene ether resin, impact modifier, and compatibilizer into an extruder, and then supplying a glass fiber treated with a silane coupling agent to an intermediate point of the extruder. Thermostat housing, characterized in that.
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| KR1020100140750A KR20120078448A (en) | 2010-12-31 | 2010-12-31 | Glass fiber reinforced partially aromatic polyamide/polyphenylene ether thermoplastic resin composition, and thermostat housing using the resin compositiona |
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|---|---|---|---|
| KR1020100140750A KR20120078448A (en) | 2010-12-31 | 2010-12-31 | Glass fiber reinforced partially aromatic polyamide/polyphenylene ether thermoplastic resin composition, and thermostat housing using the resin compositiona |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401287A (en) * | 2018-10-22 | 2019-03-01 | 滁州吉胜新材料科技有限公司 | A kind of smooth nylon of lightweight and preparation method thereof |
| US10442927B2 (en) | 2015-08-12 | 2019-10-15 | Hyundai Motor Company | Flame-retardant polyphenylene ether resin composition having high rigidity and high impact strength |
-
2010
- 2010-12-31 KR KR1020100140750A patent/KR20120078448A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10442927B2 (en) | 2015-08-12 | 2019-10-15 | Hyundai Motor Company | Flame-retardant polyphenylene ether resin composition having high rigidity and high impact strength |
| CN109401287A (en) * | 2018-10-22 | 2019-03-01 | 滁州吉胜新材料科技有限公司 | A kind of smooth nylon of lightweight and preparation method thereof |
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