TW201100492A - Polyphenyleneether thermoplastic resin composition, method of preparing the same, and molded product using the same - Google Patents

Polyphenyleneether thermoplastic resin composition, method of preparing the same, and molded product using the same Download PDF

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TW201100492A
TW201100492A TW098145795A TW98145795A TW201100492A TW 201100492 A TW201100492 A TW 201100492A TW 098145795 A TW098145795 A TW 098145795A TW 98145795 A TW98145795 A TW 98145795A TW 201100492 A TW201100492 A TW 201100492A
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resin
polyphenylene ether
poly
copolymer
ether
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TW098145795A
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Chinese (zh)
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In-Sik Shim
Jin-Young Huh
Doo-Han Ha
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Cheil Ind Inc
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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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

Disclosed are a polyphenyleneether-based thermoplastic resin composition that includes (A) a mixed resin including (A-1) a polyphenyleneether-based resin and (A-2) a polyamide resin; (B) a styrene-based copolymer resin; (C) a conductive additive; and (D) mica, a method of preparing the same, and a molded product using the same.

Description

201100492 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種聚笨醚類 (polyphenyleneether-based)熱塑性樹脂組成物及其製備方 法以及使用此組成物的模製產品(m〇lded pr〇duct)。 【先前技術】 聚苯醚樹脂的混合物或聚苯醚樹脂與聚苯乙烯 〇 (p〇1ystyrene)樹脂由於在高溫下優異的機械與電性特性而 被廣泛地使用於各種汽車零件、電性或電子零件的領域。 然而，聚苯醚樹脂具有不佳的耐化學性(chemicalresistane 與可使用性(workability)。 聚醯胺(polyamide)樹脂具有良好的耐化學性與可使 用性，但具有不佳的耐熱性(heat resistance)與耐衝擊性 (impact resistance)。因此，聚醯胺樹脂對於工程塑膠樹脂 的應用具有限制。 夕 θ 二種樹脂的組合實現了耐化學性、可使用性與耐埶 〇 性。 …、 為了提供具有導電性的樹脂，可以使用導電添加物 (conductive additive)(例如碳黑(carb〇n black)、碳纖維、金 屬粉末、金屬塗層無機粉末(metal coating inwganiep()wde0 或金屬纖維。然而，當加入的導電添加物少於樹脂的1〇 wt/。時，可旎無法確保足夠的導電性（也血丨㈤ conductivity)，而當加入大量的導電添加物時，導電熱塑性 3 201100492 Γ的基本機械特性(例如耐衝擊性科)可能會明顯地降 添加物來^ 碳管(carb〇n nan〇tube)作為導電 用奈米碳管時提供導電度。'然而，當單獨使 且當同時使用分散’因而不易得到導電性， 導電性可能會降低。n料 【發明内容】 ^明的-觀點提供—種聚苯鍵類熱塑性樹脂 〜、具有優異的衝擊強度、硬度、導電性與抗潛變性 (creep resistance)的特性平衡。 本發月的另觀點提供一種製備聚苯醚類熱塑性樹 脂組成物的方法。 本發明的又一觀點提供一種使用聚苯醚類熱塑性樹 脂組成物製造的模製產品。 根據本發明的一觀點，提供一種聚苯醚類熱塑性樹脂 組成物’其包括(A) 1〇〇重量份(parts by weight)的包括(A-1) 5至95 wt%的聚苯醚類樹脂與(A_2) 5至95 wt%的聚醯胺 樹脂的混合樹脂；基於1〇〇重量份的混合樹脂，（B) 1至 3〇重罝份的苯乙稀類(styrene_based)共聚物樹脂；以及(C) 0.1至30重量份的導電添加物；以及(d) 1至50重量份的 雲母(mica)。 聚苯醚類樹脂包括聚苯醚樹脂、聚苯醚樹脂與乙烯基 芳族(vinyl aromatic)聚合物的混合物或經改質的(modified) 201100492 聚苯醚樹脂（反應性單體(monomer)接枝至聚苯醚樹脂 上）。聚苯醚樹脂包括聚（2,6-二甲基-1，4_伸苯基）鍵 (poly(2,6-dimettiyl-l，4-phenylene)ether)、聚(2,6-二乙基-1，‘ 伸苯基)鍵(卩〇1丫(2,6-(^出>4-1,4-卩11611)^1^>1:1^1*)、聚(2,6-二 丙 基 -1,4- 伸 苯基） 喊 (poly(2,6-dipropyl-l，4-phenylene)ether)、聚(2-甲基-6-乙基 -M- 伸 苯基） _ 0 (p〇ly(2-methyl-6-ethyl-l，4-phenylene)ether)、聚（2-甲基 _6- 丙 基 -M- 伸 苯基） 喊 (poly(2-methyl-6-propyl-l,4_phenylene)ether)、聚(2_乙基_6_ 丙 基 -1,4- 伸 苯 基 ） 喊 (poly(2-ethyl-6-propyl-l,4-phenylene)ether)、聚(2,6-二苯基 -1，4-伸苯基）醚(卩〇汐(2,6-(^1^1^1-1,4-1)1^11；716116>(1^1')、聚 (2,6-二曱基-1，4_伸苯基)醚與聚(2,3,6-三曱基-1,4-伸苯基) 醚(卩〇1丫(2,3,6-1：1111^1;1171-1，4-卩1^11}^1^)61±^1*)的共聚物、聚 (2,6-二甲基-1，4-伸苯基)醚與聚(2,3,6-三乙基-1,4-伸苯基) 〇 醚(p〇ly(2,3,6-triethyl-l，4-phenylene)ether)的共聚物或其組 合。 聚醯胺樹脂包括聚己内酸胺(polycaprolactam)(耐隆 6)、聚（11-胺基Ί —酸)(poly(l 1-aminoundecanoic acid))(耐 隆11)、聚十二内醯胺(polylauryllactam)(而才隆12)、聚伸己 基己二醯二胺(polyhexamethylene adipamide)(耐隆 66)、聚 六乙稀壬二醯胺(卩〇1丫116\&61：11>46116&261&11^6)(耐隆69)、聚 六乙烯癸二醯胺（polyhexaethylene sebacamide)(耐隆 201100492 610)、聚六乙烯十二二醯胺（polyhexaethylene dodecanodiamide)(耐隆612)、聚伸己基對醜醯胺 (polyhexamethylene terephthalamide)(而才隆 6T)、聚伸 丁基己 二酿二胺（polytetramethylene adipamide)(而才隆 46)、 polycaproamide/聚伸己基對献醯胺共聚物(对隆6/6T)、聚 伸己基己二醯二胺/聚伸己基對酞醯胺共聚物（耐隆 66/6T)、聚伸己基己二醯二胺/聚伸己基異酞醯胺 (polyhexamethylene isophthalamide)共聚物（而f 隆 66/61)、聚 伸己基對酞醯胺/聚伸己基異酞醯胺共聚物(耐隆6T/6I)、聚 伸己基對酜酿胺(polyhexamethylene terephthalamide)/ 聚十 二醢胺(polydodecaneamide)共聚物(耐隆6T/12)、聚伸己基 己二醯二胺/polyhexamethylene a terephthalamide/聚伸己基 異西大臨胺共聚物（耐隆66/6T/6I)、聚芳醯胺(polyxylene adipamide)(耐隆MXD6)、聚伸己基對酞醯胺/聚2-曱基伸 戊基對酞醯胺共聚物（poly 2-methylpentamethylene terephthalamide)(而寸隆 6T/M5T)、财隆 10T/1012、聚伸壬基 對酜醯胺(polynonamethyleneterephthalamide)(财隆 9T)、聚 伸己基對酞醯胺(polyhexamethylene terephthalamide)(耐隆 10T)、聚醯胺11T (耐隆11T)、聚醯胺12T (耐隆12T)、其 共聚物或其組合。 苯乙烯類共聚物樹脂可以包括AB型二嵌段(diblock) 共聚物、ΑΒΑ型三喪段共聚物、自由基散段(radical block) 共聚物或其組合’且亦包括乙烯基芳族單體與二烯(diene) 的共聚物，二稀包括加氮的不飽和二稀(hydrogen-added 201100492 unsaturated diene)、部分加氫的不餘和二浠（partially hydrogen-added unsaturated diene)或不力口氫的不飽和二稀。 基於100重量份的混合樹脂，可以含有0.1至10重量 份的導電添加物。導電添加物包括奈米碳管、碳黑、碳纖 維、金屬粉末或其組合，且在一實施例中，可以包括奈米 碳管與碳黑的混合物。基於奈米碳管與碳黑的混合物，奈 米碳管的含量可以為0.1至3 wt%。 0 奈米碳管具有0.5至100 nm的直徑、0.01至100 μπι 的長度’而碳黑具有20至70 μιη的平均粒徑。 雲母包括白雲母(muscovite)、絹雲母(sericite)、金雲 母(phlogopite)或其組合，且可以具有1至1〇〇 μιη的粒徑。 本發明的另一觀點提供一種製造聚苯醚類熱塑性樹 脂組成物的方法’其包括藉由混合聚苯醚樹脂與反應性單 體來得到經改質的聚苯醚樹脂(反應性單體接枝至聚苯醚 樹脂）；以及混合經改質的聚苯醚樹脂、聚醯胺樹脂、苯乙 婦類共聚物樹脂、導電添加物與雲母。 〇 反應性單體可以包括不飽和羧酸(carboxylic acid)或酐 基(anhydride group) ’且在一實施例中，可以包括檸檬酸酐 (citric anhydride)、順丁烯二酸酐(maleic anhydride)、順丁 烯二酸(maleic acid)、衣康酸酐(itaconic anhydride)、反丁 烯二酸(fiimaric acid)、（甲基)丙烯酸((meth)acrylic acid)、（曱 基)丙烯酸酯((meth)acrylic acid ester)或其組合。 可以加入0.1至10重量份的反應性單體(基於1〇〇重 量份的經改質的聚苯醚樹脂與聚醯胺樹脂）。 7 201100492 脂組供—種使用聚苯W塑性樹 以下，將會詳細說明其他實施例。 異二===熱r樹脂組成物具有優 衝擎強度硬度、導電性、抗潛變性等等， =此可制於零件材料(例如汽車的加油門(fuei d·)、 汽車的防護板(fender)等等）。 為讓本毛明之上述特徵和優點能更明顯易懂，下文特 舉實施例，並配合所_式作詳細說明如下。 【實施方式】 以下將詳細說明示例性實施例。然而，這些實施例僅 為示例性的，且本發明並不以此為限。 如文中所使用，當未提供特殊定義時，甲基)丙烯酸，， 表示“丙烯酸’’與“曱基丙烯酸，，，而“（甲基）丙烯酸酯，，表示 “丙烯酸酯”與“甲基丙烯酸酯”。 根據一實施例的聚苯醚類熱塑性樹脂組成物包括(A) 100重量份的包括(A-1) 5至95 wt%的聚苯醚類樹脂與(A_2) 5至95 wt%的聚酿胺樹脂的混合樹脂，以及基於1 〇〇重量 份的混合樹脂，聚苯醚類熱塑性樹脂組成物包括(B) 1至 30重量份的苯乙烯類共聚物樹脂；（C) 0.1至30重量份的 導電添加物；以及(D) 1至50重量份的雲母。 以下將詳細說明包含於根據實施例的聚苯醚類熱塑 性樹脂組成物中的示例性成分。 (A)混合樹脂 201100492 (A-l)聚苯醚類樹脂 根據一實施例的聚苯醚類樹脂包括聚笨醚樹脂、聚苯 謎樹月曰與乙烯基芳族聚合物的混合物或經改質的聚苯醚樹 脂（包括接枝至聚苯醚樹脂的反應性單體）。 聚苯醚樹脂包括聚(2,6_二f基从伸苯基•聚(2,6_ 二乙基_1，4_伸苯基)趟、聚(2,6·二丙基-1,4-伸苯基)醚、聚(2_ 甲基-6-乙基·1，4_伸苯基、聚(2_甲基_6_丙基_14_伸苯基) 〇 醚、聚(2_乙基丙基Κ伸苯基)_、聚(2,6-二苯基_1，4_ 伸笨基)鱗、?最(2,6-二甲基_ι，4_伸苯基)_與聚(2 3 6三甲基 Μ_伸苯基)關共聚物、聚(2,6·二甲基-1，4-伸苯基)醚與 聚(2,3,6-三乙基_1，4_伸苯基)醚的共聚物或其組合。在一實 施例中，較佳為聚(2,6-二曱基_1，4_伸苯基)醚或聚(2,6_二甲 基_1，4_伸苯基)ϋ與聚(2,3,6_三曱基]，4_伸笨基)_共聚 物，而在另一實施例中，較佳為聚(26_二甲基^ 醚。 ， 6烯基㈣聚合物包括乙烯絲族單體（例如苯乙 0 烯、α -曱基苯乙稀（α _methyl styrene)、0 _甲基苯乙烯、 4-N-丙基苯乙烯(4-N-propyl styrene)等等）的聚合產物，且 在一實施例中，較佳為苯乙烯的聚合產物與^^甲其 的聚合產物。 ι 聚笨喊樹脂與乙烯基芳族聚合物的含量可分 至 99 wt0/〇與 1 至 40 wt%。 刀 *、 反應性單體接枝至聚苯醚樹脂，以產生經改質的笮苯 鍵樹脂，且包括其不飽和紐基或肝基。反應性單體的例 201100492 夕如》毳i 子可以包括檸檬酸酐、順丁烯二酸酐、順丁烯二酸、衣康 酸肝、反丁烯二酸、（曱基）丙烯酸、（甲基)丙烯酸酯或其組 合，且在一實施例中，較佳為檸檬酸酐。檸檬酸酐可以形 成經改質的聚苯喊樹脂而不需要起始劑(丨也如沉）。 製造經改質的聚苯醚樹脂的方法並不特別地限定，但 考量到尚溫製程，較佳是在使用亞鱗酸鹽類 (phosphite-based)熱穩定劑（heat stabmzer)的熔融-捏合 (melt-kneading)下進行接枝。 基於聚苯醚類樹脂的總量，反應性單體的含量可以為 0.1至10 wt%。當反應性單體的含量在此範圍中時，聚苯 _類熱塑性樹脂組成物可以具有經提高的相容性 (compatibility)與優異的耐衝擊性。 聚苯醚類樹脂的聚合程度並不特別地限制。考量樹脂 組成物的熱穩定性與可使用性，在25°C時，在三氯甲烷 (chloroform)溶劑中所測量的固有黏度（intrinsic仏⑽办) 可以為0.2至0.8 dl/g。 基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的 總量’聚苯鍵類樹脂的含量可以為5至95 wt%，且在一實 施例中，基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂 的總量，聚苯醚類樹脂的含量可以為30至70 wt%。當聚 苯醚類樹脂的含量在此範圍中時，藉由適當地執行聚苯醚 樹脂的特性’聚苯醚類熱塑性樹脂組成物可以具 耐衝擊。 ^、，八、 (A-2)聚醯胺樹脂 201100492 根據一實施例，聚醯胺樹脂包括在聚合物主鏈以及胺 基酸(amino acid)、内醯胺(lactam)或二胺(diamine)中的酿胺 基(amide-group)，且作為主要成分的二羧酸(dicarboxylic acid)被聚合而提供聚醯胺。 胺基酸的例子包括6-胺基己酸(6-aminocaproic acid)， 11-胺基Η—酸(11-aminoundecanoic acid)、12-胺基十二酸 (12-aminododecanoic acid)、對氨曱基苯曱酸 (paraaminomethylbenzoic acid)等等。内醯胺的例子包括 ε - Ο . / 已内酿胺（ε -caprolactam)、ω -12 内醢胺（ω -laurolactam) 等等。二胺的例子包括四亞曱基二胺 (tetramethylenediamine) 、 六亞曱 基二胺 (hexamethylenediamine) 、2-曱基五亞曱基二胺 (2-methylpentamethylenediamine)、九亞甲基二胺 (nonamethylenediamine)、十一亞曱基二胺 (undecamethylenediamine)、十二亞甲基二胺 (dodecamethylenediamine)、2,2,4-三甲基六亞曱基二胺 〇 (2,2,4-trimethylhexamethylenediamine)、2,4,4-三曱基六亞曱 基二胺(2,4,4-出11^1;1134116\&11161;117161^(^111^16)、5-甲基九亞 甲基二胺（5-methylnonamethylenediamine)、間苯二甲胺 (metaxylenediamine)、對苯二曱胺(paraxylenediamine)、1,3-雙(胺曱基)環己烧(l，3-bis(aminometliyl)cycloliexane)、1,4-雙(胺甲基)環己烧(l，4-bis(aminomethyl)cyclohexane)、1-胺 基 -3- 胺曱基 -3,5,5-三曱基環己烷 (l-amino-3-aminomethyl-3,5,5-trimethylcyclohexane)、雙(4- 11 201100492 胺基環己基）曱烧(1^(4-&111丨11〇〇>^1〇1^丫1)11161:11&116)、雙(3-曱基-4-胺基環己基）曱烷 （bis (3-11161:1171-4-&11^11〇。>^1〇116乂71)11^113116)、2,2-雙(4-胺基環己 基）丙烧(2,2~bis(4_aminocyclohexyl)propane)、雙(胺基丙基) 口辰嗪（bis(aminopropyl)piperazine)、胺基乙基旅 口秦 (aminoethylpiperazine)等等的脂族（aliphatic)、脂環族 (alicyclic)或芳族(aromatic)二胺。二羧酸的例子包括脂族、 脂環族或芳族二叛酸（例如己二酸(adipic acid)、辛二酸 (suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid), dodecane2 acid、對苯二曱酸(terephthalic acid)、間苯二甲 酸(isophthalic acid)、2-氣對苯二甲酸(2-chloroterephthalic acid)、2-曱基對苯二曱酸(2-methylterephthalic acid)、5-甲 基間苯二甲酸(5-methylisophthalic acid)、5-石黃基間苯二甲 酸鈉（5-sodium sulfoisophthaate)、2,6-萘二羧酸 (2,6-naphthalenedicarboxylic acid)、六氫對苯二曱酸 (hexahydroterephthalic acid)、六氫間苯二甲酸 (hexahydroisophthalic acid)等等）。自原料(raw material)衍生 的聚酿胺均聚物(homopolymer)或共聚物可以單獨使用或 以混合物來使用。 聚醯胺樹脂包括聚己内醯胺(耐隆6)、聚（11-胺基十一 酸)(耐隆11)、聚十二内醯胺(耐隆12)、聚伸己基己二醯二 胺(耐隆66)、聚六乙烯壬二醯胺(耐隆69)、聚六乙烯癸二 醯胺(耐隆610)、聚六乙烯十二二醯胺(耐隆612)、聚伸己 基對酞醯胺（耐隆6T)、聚伸丁基己二醯二胺（耐隆46)、 12 201100492 polycaproamide/聚伸己基對酜酸胺共聚物(耐隆6/6T)、聚 伸己基己二醯二胺/聚伸己基對酜醯胺共聚物（耐隆 66/6T)、聚伸己基己二酿二胺/聚伸己基異酞酿胺共聚物(耐 隆66/61)、聚伸己基對欧醯胺/聚伸己基異g大醯胺共聚物(耐 隆6T/6I)、聚伸己基對酞醯胺/聚十二醯胺共聚物（耐隆 61V12)、聚伸己基己二醒二胺 /polyhexamethylene a terephthalamide/聚伸己基異酿醯胺共聚物（耐隆 ❹ 66/6T/6I)、聚芳醯胺(财隆MXD6)、聚伸己基對酞醯胺/聚 2-曱基伸戊基對酞醯胺共聚物（耐隆6T/M5T)、财隆 10T/1012、聚伸壬基對酞醯胺(耐隆9T)、聚伸己基對酞醯 胺(耐隆10T)、聚醯胺11T (耐隆11T)、聚醯胺〗2T (耐隆 12T)、其共聚物或其組合。其共聚物包括耐隆6/61〇、耐隆 6/66、耐隆6/12等等。 聚醯胺樹脂具有250°C或更高的熔點、2或更高的相 • 對黏度（relative viscosity)(在25 ° C下測量，間_甲齡 (m-cresol)中含有1 wt%的聚醯胺樹脂）。當熔點與相對黏度 Ο 在上述範圍中時’聚苯醚類熱塑性樹脂組成物的機械特性 與耐熱性可被提升。 基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的 總量，聚醯胺樹脂的含量可為5至95 wt%，且在一實施例 中’基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的總 量’聚醯胺樹脂的含量可為30至70 wt%。當聚醯胺樹脂 的含量在此範圍中時，可以得到優異的與聚苯醚類樹脂的 相容性。 13 201100492 (B)苯乙烯類共聚物樹脂 根據-實施例，自乙烯基芳族單體衍生的苯乙稀類共 聚物樹脂相為AB型二纽絲物、aba型三嵌段共聚 物、自由基嵌段共聚物或其組合。 欲^又/、t物可以為乙細基芳族單體與二 丘 物，二，包括加氫的不飽和二烯、部分加氫的不飽和二稀 或不加風的不飽和二稀。 乙烯基芳族單體可以包括苯乙烯、ρ_ψ基苯乙稀、α -甲基苯乙烯、4-Ν-丙基苯乙烯等等，且在一實施例中，較 佳為本乙稀、α_甲基苯乙稀等等。這些單體可以單獨使用 或以混合物來使用。 ΑΒ型二嵌段共聚物包括聚苯乙烯-聚丁二烯 (polybutadiene)共聚物、聚本乙稀-聚異戍二婦(p〇iyis〇prene) 共聚物、聚α·甲基苯乙烯(polyalphamethylstyrene)-聚丁二 烯共聚物或將氫加至共聚物的共聚物。在本領域中，AB 型二嵌段共聚物在商業上被熟知。AB型二嵌段共聚物的 例子包括由Phillips製造的Solprene與K-樹脂(K-resin)以 及由 Shell chemical 製造的 Kraton D 與 Kraton G。 ΑΒΑ型三嵌段共聚物包括聚苯乙烯-聚丁二烯-聚苯乙 烯(SBS)共聚物、聚苯乙烯-聚異戊二烯-聚苯乙烯(SIS)共聚 物、聚α-曱基苯乙烯-聚丁二烯-聚α-曱基苯乙烯共聚物、 聚α-甲基苯乙烯-聚異戊二烯-聚甲基苯乙烯共聚物或 將氫加至共聚物的共聚物。ΑΒΑ型三嵌段共聚物在商業領 域中已被熟知。ΑΒΑ型三嵌段共聚物的例子包括由Shell 14 201100492 chemical 製造的 Cariflex, Kraton D 與 Kraton G 以及由 尺1»^&丫(：〇.,1^(!.製造的86口(〇11等等。 基於100重量份的聚苯醚類樹脂與聚醯胺樹脂的混合 樹脂’苯乙烯類共聚物樹脂的含量可為1至30重量份，且 在一實施例中，基於100重量份的聚苯醚類樹脂與聚醯胺 樹脂的混合樹脂，苯乙烯類共聚物樹脂的含量可為1至1〇 重量份。當苯乙烯類共聚物樹脂的含量在此範圍中時，耐 衝擊性明顯地增加，且不降低聚苯醚類樹脂與聚醯胺樹脂 的優異相容性。 (C)導電添加物 根據一實施例，導電添加物可以包括奈米碳管、碳 黑、碳纖維、金屬粉末或其組合，且在另一實施例中，較 佳為奈米碳管與碳黑的混合物。 奈米碳管具有優異的機械強度、機械特性(例如高的揚 氏模數(Young’s Modulus)與縱橫比(aspect rati〇))、導電度與 熱穩疋性。當奈米奴官用於製造聚合物合成物時，可以得 到具有改良的機械特性、熱特性與電特性的奈米碳管_聚合 物合成物。 合成奈米奴管的方法包括電弧放電(arc_discharge)、熱 裂解(pyrolysis)、電漿化學氣相沈積(plasmachemicalvap〇r deposition ’ PECVD)、熱化學氣相沈積（chemical vapor deposition，CVD)、電解(eiectr〇iySis)等等，且在一實施例 中’不論合成的方法’所得到的奈米碳管皆可以使用。 15 201100492 —--j-— 取決於壁（wall)的數目，奈米碳管可以分為單壁 (single-walled)奈米碳管、雙壁(double-walled)奈米碳管與 多壁(multi-walled)奈米碳管。在一實施例中，較佳為多壁 奈米碳管，但並不限於此。 並不特別限定奈米碳管的尺寸，奈米碳管可具有0.5 至100 nm的直徑與0.01至100 μιη的長度，且在一實施例 中，奈米碳管可具有1至10 nm的直徑與0.5至10 μιη的 長度。當奈米碳管的直徑與長度在此範圍中時，導電度與 可使用性可被提升。 此外，由於如此大的尺寸，奈米碳管具有大的縱橫比 (L/D)。當使用具有L/D為100至1，000的奈米碳管時，導 電度可被提升。 碳黑可以為任意的導電碳黑而無限制，且包括石墨碳 (graphitized carbon)、爐黑（furnace black)、乙炔黑（acetylene black)、科琴碳黑(ketjen black)等等。 導電碳黑的平均粒徑為20至70 μιη，且吸油量(oil absorption)由 JIS K 5101 調整為 100 至 600 mWlOOg 時可作 為碳黑。當碳黑的平均粒徑在此範圍中時，可以實現優異 的導電性。 當奈米碳管與碳黑混合時，基於奈米碳管與碳黑的混 合物的總量，奈米碳管的含量可為0.1至3 wt%。當奈米 碳管的含量在此範圍中時，可以藉由此少量的添加來實現 合適的電滲滤(electrical percolation)以導電，且可以維持機 械強度(例如優異的抗拉強度(tensile strength))與耐熱性。 16 201100492 基於100重量份的包括聚苯嗎樹脂與聚醯胺樹脂的 混合樹脂，導電添加物的含量可以為〇 1至重量份，且 在一實施例中，基於100重量份的包括聚苯醚類樹=與聚 醯胺樹脂的混合樹脂，導電添加物的含量可以為〇 1至1〇 重量份。當導電添加物的含量在此範圍中時，聚笨鱗類熱 塑性樹脂組成物可以具有優異的導電性與耐衝擊性。Μ (D)雲母 根據一實施例，不論種類，雲母可以包括白雲母、絹 雲母、金雲母等等。這些雲母可以單獨使用或以其混合物 使用。 雲母的粒控可以為1至100 μη!。當使用此範圍中的雲 母時，可以得到優異的抗潛變性（creep resistance )。 基於100重量份的聚苯醚類樹脂與聚醯胺樹脂的混合 樹脂，雲母的含量可以為1至50重量份，且在一實施例中， ' 基於重量份的聚苯醚類樹脂與聚酿胺樹脂的混合樹 脂’雲母的含量可以為10至40重量份。當雲母的含量在 〇 此範圍中時，聚苯醚類熱塑性樹脂組成物可以具有優異的 硬度與财衝擊性。 根據一實施例，聚苯醚類熱塑性樹脂組成物可以進一 步包括添加劑(additive)。取決於使用目的，添加劑可以包 括抗滴落劑(anti-drip agent)、光穩定劑(light stabilizer)、顏 料(pigment)、染料(dye)或其組合。基於100重量份的聚苯 醚類樹脂與聚酿胺樹脂的混合樹脂，添加劑的含量可以為 0.1至30重量份。當添加劑的含量在此範圍中時，可以得 17 201100492 - - 1--- 到取決於目的的添加劑功效，且可以得到優異的機械特性 與、改良的表面外觀(surface appearance)。 上述的聚苯醚類熱塑性樹脂組成物可以藉由一般熟 知的方法來製造。舉例來說，將上述的成分與所選擇的添 加劑克合’且在擠壓機（extruder)中溶融擠出 (melt-extrud)，以製成顆粒物(peUet)。 在另一實施例中’聚苯醚類熱塑性樹脂組成物藉由取 得經改質的聚苯醚樹脂（混合聚苯醚樹脂與反應性單體而 將反應性單體接枝至聚苯醚樹脂）以及將經改質的聚笨醚 樹脂、聚醯胺樹脂、苯乙烯類共聚物樹脂、導電添加物與 雲母混合來製造。 ' 反應性早體可以與前述相同。 基於100重量份的經改質的聚苯醚樹脂與聚醯胺樹 脂，反應性單體的含量可以為〇丨至1〇重量份，且在一實 施例中，基於100重量份的經改質的聚苯醚樹脂，反應性 單體的含量可以為0.1至5重量份。當反應性單體的含量 在此範圍中時，聚苯醚類熱塑性樹脂組成物可以具有經改 良的相容性與優異的耐衝擊性。 考慮高操作溫度’經改質的聚苯醚樹脂可以在使用磷 酸酯類（phosphate_based)熱穩定劑的熔融-捏合 (melt-kneading)下進行製備。 根據又一實施例，提供一種使用聚苯醚類熱塑性樹脂 組成物製造的模製產品。聚苯_類熱塑性樹脂組成物可以 18 201100492 應用於極度需要衝擊強度、硬度、導電性與抗潛變性的模 製產品(例如汽車加油門、汽車防護板等零件材料）。 以下，將參考範例來更詳細地說明實施例。然而，以 下為示例性實施例，並不用於限定本發明。 (範例） 根據一實施例，聚苯醚類熱塑性樹脂組成物包括以下 0 各成分。 (A) 混合樹脂 (A-1)聚苯醚類樹脂 將作為聚苯醚樹脂的聚(2,6-二曱基·1，4_伸苯基)醚的 GE plastic ΗΡΡ-820 (由 GE plastics Ltd·製造)與作為反應性 . 單體的擰檬酸酐（由Samchun Pure Chemical Ltd.製造)混 合’且接著使用經改質的聚苯醚樹脂(藉由將反應性單體接 ' 枝至聚苯醚樹脂而得到）。基於聚苯醚類樹脂的總量，反應 性單體的含量為1 wt%。 〇 (A-2)聚醯胺樹脂 使用耐隆 66 的 VYDYNE 50BW (由 Solutia Inc.製造)。 (B) 苯乙烯類共聚物樹脂 使用聚（苯乙烯-乙烯-丁二烯）三嵌段共聚物的 G1651(由 ShellCo.，Ltd.製造） (C) 導電添加物 19 201100492 (c-l)使用直徑為10至50 nm且長度為1至25 μΐη的 多壁奈米碳管的C-tube 100 (由CNT Co.，Ltd.製造)作為奈 米碳管。 (C-2)使用 Timrex, KS 5-75TT (由 Timcal Ltd.製造)作 為炭黑。 (D) 雲母 使用 M-325 (由 KOCH Co.，Ltd.製造）。 (E) 滑石（talc) 使用 UPN HS-T 0·5 (由 HAYASHI Pure Chemical Ind.， Ltd.製造）。 (F) 石夕礦石（wollastonite)201100492 VI. Description of the Invention: [Technical Field] The present invention relates to a polyphenyleneether-based thermoplastic resin composition, a preparation method thereof, and a molded product using the same (m〇lded pr 〇duct). [Prior Art] A mixture of a polyphenylene ether resin or a polyphenylene ether resin and a polystyrene fluorene resin are widely used in various automobile parts, electrical properties, or the like because of excellent mechanical and electrical properties at high temperatures. The field of electronic parts. However, polyphenylene ether resins have poor chemical resistance (workability). Polyamide resins have good chemical resistance and workability, but have poor heat resistance (heat Resistance) and impact resistance. Therefore, polyamine resin has limitations on the application of engineering plastic resins. The combination of the two resins achieves chemical resistance, workability and stagnation resistance. In order to provide a conductive resin, a conductive additive such as carb〇n black, carbon fiber, metal powder, metal coating inwganiep (wde0 or metal fiber) may be used. When the conductive additive added is less than 1 〇wt/ of the resin, sufficient conductivity (also known as blood conductivity) cannot be ensured, and when a large amount of conductive additive is added, the conductive thermoplastic 3 201100492 Γ Basic mechanical properties (such as impact resistance) may significantly reduce the additives to provide a guide for carbon nanotubes (carb〇n nan〇tube) as a conductive carbon nanotube. Degree. 'However, when the dispersion is used separately and when it is used at the same time, it is difficult to obtain conductivity, and the conductivity may be lowered. n Materials [Invention] The viewpoint is provided - a kind of polyphenylene-based thermoplastic resin ~, excellent A balance of impact strength, hardness, electrical conductivity, and creep resistance characteristics. Another aspect of this month provides a method of preparing a polyphenylene ether-based thermoplastic resin composition. Yet another aspect of the present invention provides a use of poly A molded product produced from a phenylene ether-based thermoplastic resin composition. According to an aspect of the invention, there is provided a polyphenylene ether-based thermoplastic resin composition which comprises (A) 1 part by weight of a part (A) -1) a mixed resin of 5 to 95 wt% of a polyphenylene ether-based resin and (A_2) 5 to 95 wt% of a polyamide resin; based on 1 part by weight of the mixed resin, (B) 1 to 3 〇 a styrene-based copolymer resin; and (C) 0.1 to 30 parts by weight of a conductive additive; and (d) 1 to 50 parts by weight of mica. The polyphenylene ether resin includes a poly Phenyl ether resin, polyphenylene ether resin and vinyl Mixture of vinyl aromatic polymers or modified 201100492 polyphenylene ether resin (reactive monomer grafted onto polyphenylene ether resin). Polyphenylene ether resin including poly(2,6) -(2,6-diimettiyl-l,4-phenylene)ether, poly(2,6-diethyl-1, 'phenylene) bond (卩〇1丫(2,6-(^出>4-1,4-卩11611)^1^>1:1^1*), poly(2,6-dipropyl-1,4 - phenyl) (poly(2,6-dipropyl-l,4-phenylene)ether), poly(2-methyl-6-ethyl-M-phenylene) _ 0 (p〇ly(2) -methyl-6-ethyl-l,4-phenylene)ether), poly(2-methyl-6-propyl-M-phenylene) shouting (poly(2-methyl-6-propyl-l,4_phenylene) Ether), poly(2-ethyl-6-propyl-l,4-phenylene), poly(2,6-di) Phenyl-1,4-phenylene ether (卩〇汐(2,6-(^1^1^1-1,4-1)1^11; 716116>(1^1'), poly( 2,6-dimercapto-1,4_phenylene)ether with poly(2,3,6-trimethyl-1,4-phenylene) ether (卩〇1丫(2,3,6) -1:1111^1;1171-1,4-卩1^11}^1^)61±^1*) copolymer, poly(2,6-dimethyl-1 , 4-phenylene ether and poly(2,3,6-triethyl-1,4-phenylene) oxime ether (p〇ly(2,3,6-triethyl-l,4-phenylene) Ether copolymer or a combination thereof. Polyamine resin includes polycaprolactam (lonone 6), poly(l-aminoundecanoic acid) (endron 11), polytetradecalin Amine (polylauryllactam) (而才隆12), polyhexamethylene adipamide (Rilong 66), polyhexamethylenediamine (卩〇1丫116\&61:11>46116&261&11^6) (Nylon 69), polyhexaethylene sebacamide (Nylon 201100492 610), polyhexaethylene dodecanodiamide (Nylon 612), Polyhexamethylene terephthalamide (polychlorinated 6T), polytetramethylene adipamide (polycylylene 46), polycaproamide/polyhexyl cis-amine copolymer对6/6T), polyhexylhexamethylenediamine/polyhexyl-p-guanamine copolymer (Rilong 66/6T), polyhexamethylenediamine/polyhexylisodecylamine Polyhexamethylene isophthalamide copolymer (and f-long 66/61), poly-extension hexyl-p-amine/polyhexylisodecylamine copolymer (Tanglong 6T/6I) Polyhexamethylene terephthalamide/polydodecaneamide copolymer (Tanglong 6T/12), polyhexamethylenediamine/polyhexamethylene a terephthalamide/polyhexamethylene a terephthalamide Amine copolymer (Nylon 66/6T/6I), polyxylene adipamide (Nylon MXD6), poly(hexyl)-p-amine/poly-2-indolyl-pentyl-p-amine copolymer (poly 2-methylpentamethylene terephthalamide), Cailong 10T/M5T, Cailong 10T/1012, polynonamethyleneterephthalamide (Cailong 9T), polyhexamethylene terephthalamide (resistant) Long 10T), polyamine 11T (Rilong 11T), polyamido 12T (Rilong 12T), copolymers thereof or combinations thereof. The styrenic copolymer resin may include an AB type diblock copolymer, a ruthenium three-stage copolymer, a radical block copolymer or a combination thereof and also includes a vinyl aromatic monomer. Copolymer with diene, dilute includes hydrogen-added 201100492 unsaturated diene, partially hydrogenated hydrogen dimer or partially hydrogenated Unsaturated dilute. The conductive additive may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the mixed resin. The conductive additive includes a carbon nanotube, carbon black, carbon fiber, metal powder, or a combination thereof, and in one embodiment, may include a mixture of a carbon nanotube and carbon black. The carbon nanotubes may be present in an amount of from 0.1 to 3 wt% based on a mixture of carbon nanotubes and carbon black. The carbon nanotubes have a diameter of 0.5 to 100 nm, a length of 0.01 to 100 μm, and the carbon black has an average particle diameter of 20 to 70 μm. The mica includes muscovite, sericite, phlogopite, or a combination thereof, and may have a particle diameter of 1 to 1 μm. Another aspect of the present invention provides a method for producing a polyphenylene ether-based thermoplastic resin composition, which comprises obtaining a modified polyphenylene ether resin by mixing a polyphenylene ether resin and a reactive monomer (reactive monomer connection) Branched to polyphenylene ether resin); and mixed modified polyphenylene ether resin, polyamide resin, styrene copolymer resin, conductive additive and mica. The ruthenium reactive monomer may include an unsaturated carboxylic acid or an anhydride group 'and in one embodiment may include citric anhydride, maleic anhydride, cis Maleic acid, itaconic anhydride, fiimaric acid, (meth)acrylic acid, (meth) acrylate ((meth) Acrylic acid ester) or a combination thereof. 0.1 to 10 parts by weight of a reactive monomer (based on 1 part by weight of the modified polyphenylene ether resin and polyamine resin) may be added. 7 201100492 Lipid Group Supply - Polystyrene W Plastic Tree Hereinafter, other embodiments will be described in detail. The same two === hot r resin composition has excellent strength, hardness, conductivity, anti-potential denaturation, etc., = This can be made in parts and materials (such as the car's fuel door (fuei d ·), the car's protective plate ( Fender) and so on). In order to make the above features and advantages of the present invention more apparent, the following embodiments are described in detail with reference to the following description. [Embodiment] Hereinafter, exemplary embodiments will be described in detail. However, these examples are merely exemplary, and the invention is not limited thereto. As used herein, when no special definition is provided, methyl acrylate, means "acrylic" and "mercapto acrylate," and "(meth) acrylate, means "acrylate" and "methyl" The polyphenylene ether-based thermoplastic resin composition according to an embodiment comprises (A) 100 parts by weight of a polyphenylene ether-based resin comprising (A-1) 5 to 95 wt% and (A_2) 5 to 95 wt%. a mixed resin of a polyacrylamide resin, and a mixed resin based on 1 part by weight, the polyphenylene ether-based thermoplastic resin composition comprising (B) 1 to 30 parts by weight of a styrene-based copolymer resin; (C) 0.1 To 30 parts by weight of the conductive additive; and (D) 1 to 50 parts by weight of mica. Exemplary components contained in the polyphenylene ether-based thermoplastic resin composition according to the examples will be described in detail below. (A) Mixed resin 201100492 (Al) Polyphenylene Ether Resin The polyphenylene ether resin according to an embodiment includes a polyether ether resin, a mixture of polystyrene and a vinyl aromatic polymer, or a modified polyphenylene ether resin ( Including reactive monomers grafted to polyphenylene ether resin). Ether resins include poly(2,6-di-f-yl) from phenyl-poly(2,6-diethyl-1,4-phenylene) fluorene, poly(2,6-dipropyl-1,4- Phenyl)ether, poly(2_methyl-6-ethyl·1,4_phenylene, poly(2-methyl-6-propyl_14_phenylene) oxime ether, poly(2_ Ethyl propyl hydrazine phenyl) _, poly (2,6-diphenyl _1,4 _ stupyl) scale, ? most (2,6-dimethyl-I, 4 _ phenyl) Copolymer with poly(2 3 6 trimethylsulfonium phenylene), poly(2,6·dimethyl-1,4-phenylene) ether and poly(2,3,6-triethyl) a copolymer of _1,4_phenylene)ether or a combination thereof. In one embodiment, poly(2,6-dimercapto-1,4-phenylene)ether or poly(2, preferably, 6-Dimethyl-1,4_phenylene) fluorene and poly(2,3,6-trimethyl), 4-extended base) copolymer, and in another embodiment, preferably Poly(26-dimethyl ether). 6 alkenyl (tetra) polymer includes a vinyl group monomer (for example, phenethyl ene, α _methyl styrene, 0 _ methyl styrene, A polymerization product of 4-N-propyl styrene or the like, and in one embodiment, is preferably a polymerization product of styrene and a polymerization product thereof. The content of polystyrene resin and vinyl aromatic polymer can be divided into 99 wt0 / 〇 and 1 to 40 wt%. Knife *, reactive monomer grafted to polyphenylene ether resin to produce modified terpene Key resin, and including its unsaturated neokyl group or hepatic group. Examples of reactive monomers 201100492 如如毳 子i can include citric anhydride, maleic anhydride, maleic acid, itaconic acid liver, anti Butylene acid, (mercapto)acrylic acid, (meth) acrylate or a combination thereof, and in one embodiment, is preferably citric anhydride. The citric anhydride can form a modified polystyrene resin without the need for an initiator (as well as sinking). The method for producing the modified polyphenylene ether resin is not particularly limited, but it is considered to be a warm-temperature process, preferably a melt-kneading using a phosphite-based heat stabmzer. Grafting was carried out under (melt-kneading). The content of the reactive monomer may be from 0.1 to 10% by weight based on the total amount of the polyphenylene ether-based resin. When the content of the reactive monomer is in this range, the polyphenylene-based thermoplastic resin composition may have improved compatibility and excellent impact resistance. The degree of polymerization of the polyphenylene ether-based resin is not particularly limited. Considering the thermal stability and workability of the resin composition, the intrinsic viscosity (intrinsic(10)) measured in chloroform solvent at 25 ° C can be 0.2 to 0.8 dl / g. The content of the polyphenylene-based resin based on the total amount of the mixed resin including the polyphenylene ether resin and the polyamide resin may be 5 to 95% by weight, and in one embodiment, based on the polyphenylene ether-based resin and the poly The total amount of the mixed resin of the guanamine resin may be from 30 to 70% by weight based on the content of the polyphenylene ether-based resin. When the content of the polyphenylene ether-based resin is in this range, the polyphenylene ether-based thermoplastic resin composition can be impact-resistant by appropriately performing the properties of the polyphenylene ether resin. ^,, VIII, (A-2) Polyamide resin 201100492 According to an embodiment, the polyamide resin is included in the polymer backbone and an amino acid, a lactam or a diamine. The amide-group in the amide-group, and the dicarboxylic acid as a main component is polymerized to provide polyamine. Examples of the amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and aminoguanidine. Paraaminomethylbenzoic acid and the like. Examples of the intrinsic amine include ε - Ο . / endo-amine (ε - caprolactam), ω -12 indoleamine (ω - laurolactam) and the like. Examples of the diamine include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, and nonamethylenediamine. , undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2 , 4,4-tridecylhexamethylenediamine (2,4,4-out 11^1; 1134116\&11161;117161^(^111^16), 5-methylnonamethylene Amine (5-methylnonamethylenediamine), metaxylenediamine, paraxylenediamine, 1,3-bis(aminometliyl)cycloliexane, 1,4-Bis(aminomethyl)cyclohexane, 1-amino-3-aminoindolyl-3,5,5-trimethylcyclohexane (l -amino-3-aminomethyl-3,5,5-trimethylcyclohexane), bis(4- 11 201100492 aminocyclohexyl) oxime (1^(4-&111丨11〇〇>^1〇1^丫) 1) 11161: 11 & 116), bis(3-indolyl-4-aminocyclohexyl)decane Bis (3-11161:1171-4-&11^11〇.>^1〇116乂71)11^113116), 2,2-bis(4-aminocyclohexyl)propane (2,2 ~bis(4_aminocyclohexyl)propane), bis(aminopropyl)piperazine, aminoethylpiperazine, etc.,aliphatic,alicyclic Or an aromatic diamine. Examples of dicarboxylic acids include aliphatic, alicyclic or aromatic diremediation acids (eg, adipic acid, suberic acid, azelaic acid ( Azelaic acid), sebacic acid, dodecane2 acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2- 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthaate, 2,6-naphthalene 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and the like. A homopolymer or a homopolymer derived from a raw material may be used singly or as a mixture. Polyamine resin includes polycaprolactam (Rilong 6), poly(11-aminoundecanoic acid) (Rilong 11), polydodecanamide (Rilong 12), and polyhexylhexanide Diamine (Rilong 66), polyhexaethylene quinone diamine (Rilong 69), polyhexaethylene quinone diamine (Rilong 610), polyhexaethylene dodecylamine (Rilong 612), poly-stretching Hexyl-p-amine (Rilong 6T), poly(butylene hexamethylenediamine), 12 201100492 polycaproamide/polyhexyl phthalic acid amine copolymer (Nellon 6/6T), polyhexyl Hexamethylenediamine/polyhexyl-p-guanamine copolymer (Rilong 66/6T), polyhexamethylenediamine/polyhexylisobutylamine copolymer (Nylon 66/61), poly己 基 对 醯 对 对 对 对 对 对 对 对 对 对 对 对 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Dioxamethylenediamine/polyhexamethylene a terephthalamide/polyhexylisomeric ruthenium amide copolymer (resistant ❹66/6T/6I), polyarylamine (Cailong MXD6), polyhexylamine phthalamide/poly 2 Indole-based pentyl-p-amine copolymer (Nylon 6T/M5T), Cailong 10T/1012, poly-stretching Base-p-amine (Rilong 9T), polyhexyl-p-guanamine (Rilong 10T), polyamido 11T (Rilong 11T), polyamidamine 2T (Rilong 12T), copolymer or combination. The copolymers include Nylon 6/61 耐, Nylon 6/66, Nylon 6/12 and the like. Polyamide resin has a melting point of 250 ° C or higher, a relative viscosity of 2 or higher (measured at 25 ° C, 1 wt% in m-cresol) Polyamide resin). When the melting point and the relative viscosity Ο are in the above range, the mechanical properties and heat resistance of the polyphenylene ether-based thermoplastic resin composition can be improved. The content of the polyamide resin may be from 5 to 95% by weight based on the total amount of the mixed resin including the polyphenylene ether resin and the polyamide resin, and in one embodiment is based on the inclusion of the polyphenylene ether resin and the polyfluorene. The total amount of the mixed resin of the amine resin 'polyamide resin' may be from 30 to 70% by weight. When the content of the polyamide resin is in this range, excellent compatibility with the polyphenylene ether resin can be obtained. 13 201100492 (B) Styrene-based copolymer resin According to the embodiment, the styrene-based copolymer resin phase derived from the vinyl aromatic monomer is AB type dioxane, aba type triblock copolymer, free Base block copolymer or combination thereof. The product may be an ethylenic aromatic monomer and a mound, and a hydrogenated unsaturated diene, a partially hydrogenated unsaturated dilute or an unsaturated unsaturated dilute. The vinyl aromatic monomer may include styrene, ρ-mercaptostyrene, α-methylstyrene, 4-anthracyl styrene, and the like, and in one embodiment, preferably ethylene, α _Methyl styrene and so on. These monomers may be used singly or as a mixture. ΑΒ-type diblock copolymers include polybutadiene-polybutadiene copolymers, polyethylene-polyisophthalide (p〇iyis〇prene) copolymers, and poly-α-methylstyrene ( Polyalphamethylstyrene) - a polybutadiene copolymer or a copolymer of hydrogen added to a copolymer. Type AB diblock copolymers are well known in the art. Examples of the AB type diblock copolymer include Solprene and K-resin manufactured by Phillips and Kraton D and Kraton G manufactured by Shell Chemical. ΑΒΑ-type triblock copolymers include polystyrene-polybutadiene-polystyrene (SBS) copolymers, polystyrene-polyisoprene-polystyrene (SIS) copolymers, poly-α-fluorenyl groups A styrene-polybutadiene-poly-α-mercaptostyrene copolymer, a poly-α-methylstyrene-polyisoprene-polymethylstyrene copolymer or a copolymer of hydrogen added to a copolymer. Anthracene triblock copolymers are well known in the commercial art. Examples of the quinoid type triblock copolymer include Cariflex, Kraton D and Kraton G manufactured by Shell 14 201100492 chemical, and 86 mouthpieces manufactured by Ruler 1»^&丫(:〇.,1^(!. The content of the mixed resin 'styrene-based copolymer resin based on 100 parts by weight of the polyphenylene ether-based resin and the polyamide resin may be 1 to 30 parts by weight, and in one embodiment, based on 100 parts by weight The mixed resin of the polyphenylene ether resin and the polyamide resin may have a content of the styrene copolymer resin of 1 to 1 part by weight. When the content of the styrene copolymer resin is in this range, the impact resistance is remarkable. It is increased without degrading the excellent compatibility of the polyphenylene ether resin with the polyamide resin. (C) Conductive Additive According to an embodiment, the conductive additive may include carbon nanotubes, carbon black, carbon fiber, metal powder. Or a combination thereof, and in another embodiment, preferably a mixture of carbon nanotubes and carbon black. The carbon nanotubes have excellent mechanical strength and mechanical properties (for example, high Young's Modulus and Aspect rati〇), conductivity and heat疋. When a nano slave is used to make a polymer composition, a carbon nanotube-polymer composite with improved mechanical, thermal and electrical properties can be obtained. The method for synthesizing the nanotubes includes arcing. Discharge (arc_discharge), pyrolysis (pyrolysis), plasma chemical vapor deposition (PECVD), thermal chemical vapor deposition (CVD), electrolysis (eiectr〇iySis), etc. In one embodiment, the carbon nanotubes obtained by the 'method of synthesis' can be used. 15 201100492 —--j-— Depending on the number of walls, the carbon nanotubes can be divided into single walls (single- Walled) a carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. In one embodiment, a multi-walled carbon nanotube is preferred, but not The size of the carbon nanotubes is not particularly limited, and the carbon nanotubes may have a diameter of 0.5 to 100 nm and a length of 0.01 to 100 μm, and in one embodiment, the carbon nanotubes may have 1 to 10 The diameter of nm is 0.5 to 10 μηη. When the carbon nanotube is straight When the diameter and length are in this range, the conductivity and workability can be improved. Furthermore, due to such a large size, the carbon nanotubes have a large aspect ratio (L/D). When used, the L/D is 100. Conductivity can be increased up to 1,000 carbon nanotubes. Carbon black can be any conductive carbon black without limitation, and includes graphitized carbon, furnace black, acetylene black (acetylene) Black), ketjen black, etc. The conductive carbon black has an average particle diameter of 20 to 70 μm, and the oil absorption can be regarded as carbon black when it is adjusted from JIS K 5101 to 100 to 600 mW100g. When the average particle diameter of the carbon black is in this range, excellent conductivity can be achieved. When the carbon nanotubes are mixed with carbon black, the content of the carbon nanotubes may be 0.1 to 3 wt% based on the total amount of the mixture of the carbon nanotubes and the carbon black. When the content of the carbon nanotubes is in this range, a suitable electro-percolation can be achieved by this small amount of addition to conduct electricity, and mechanical strength (for example, excellent tensile strength) can be maintained. ) with heat resistance. 16 201100492 The content of the conductive additive may be from 1 to parts by weight based on 100 parts by weight of the mixed resin comprising polyphenylene resin and polyamine resin, and in one embodiment, based on 100 parts by weight including polyphenylene ether Tree-like = mixed resin with polyamine resin, the content of the conductive additive may be from 1 to 1 part by weight. When the content of the conductive additive is in this range, the polystyrene-based thermoplastic resin composition can have excellent electrical conductivity and impact resistance. Μ (D) Mica According to an embodiment, mica may include muscovite, sericite, phlogopite and the like regardless of the species. These mica can be used alone or in a mixture thereof. Mica can have a particle size of 1 to 100 μη!. When the mica in this range is used, excellent creep resistance can be obtained. The mica content may be 1 to 50 parts by weight based on 100 parts by weight of the mixed resin of the polyphenylene ether resin and the polyamide resin, and in one embodiment, 'parts by weight of the polyphenylene ether resin and the polystyrene The content of the mixed resin 'mica of the amine resin may be 10 to 40 parts by weight. When the content of mica is in this range, the polyphenylene ether-based thermoplastic resin composition can have excellent hardness and impact resistance. According to an embodiment, the polyphenylene ether-based thermoplastic resin composition may further include an additive. The additive may include an anti-drip agent, a light stabilizer, a pigment, a dye, or a combination thereof, depending on the purpose of use. The content of the additive may be from 0.1 to 30 parts by weight based on 100 parts by weight of the mixed resin of the polyphenylene ether resin and the polyacrylamide resin. When the content of the additive is in this range, it is possible to obtain an effect depending on the purpose of the additive, and excellent mechanical properties and an improved surface appearance can be obtained. The above polyphenylene ether-based thermoplastic resin composition can be produced by a generally known method. For example, the above ingredients are combined with the selected additive and melt-extruded in an extruder to form a granule (peUet). In another embodiment, the polyphenylene ether-based thermoplastic resin composition is obtained by grafting a reactive monomer to a polyphenylene ether resin by obtaining a modified polyphenylene ether resin (mixing a polyphenylene ether resin and a reactive monomer). And a modified polyphenyl ether resin, a polyamide resin, a styrene copolymer resin, and a conductive additive are mixed with mica. 'Reactive early body can be the same as previously described. The content of the reactive monomer may be from 〇丨 to 1 〇 by weight based on 100 parts by weight of the modified polyphenylene ether resin and the polyamide resin, and in one embodiment, based on 100 parts by weight of the modified The polyphenylene ether resin may have a reactive monomer content of 0.1 to 5 parts by weight. When the content of the reactive monomer is in this range, the polyphenylene ether-based thermoplastic resin composition can have improved compatibility and excellent impact resistance. Considering high operating temperatures, the modified polyphenylene ether resin can be prepared by melt-kneading using a phosphate-based heat stabilizer. According to still another embodiment, there is provided a molded product produced using a polyphenylene ether-based thermoplastic resin composition. Polyphenylene-based thermoplastic resin composition can be applied to molded products that require extreme impact strength, hardness, electrical conductivity and resistance to latent denaturation (such as automotive fuel fillers, automotive fenders, etc.). Hereinafter, embodiments will be described in more detail with reference to examples. However, the following is an exemplary embodiment and is not intended to limit the invention. (Example) According to an embodiment, the polyphenylene ether-based thermoplastic resin composition includes the following 0 components. (A) Mixed resin (A-1) polyphenylene ether resin GE plastic ΗΡΡ-820 (poly(2,6-dimercapto·1,4_phenylene) ether) as a polyphenylene ether resin Plastics Ltd. manufactured) mixed with a monomeric citric acid anhydride (manufactured by Samchun Pure Chemical Ltd.) and then a modified polyphenylene ether resin (by ligating the reactive monomer to Obtained from polyphenylene ether resin). The content of the reactive monomer was 1 wt% based on the total amount of the polyphenylene ether resin. 〇 (A-2) Polyamide resin VYDYNE 50BW (manufactured by Solutia Inc.) of Nylon 66 was used. (B) Styrene-based copolymer resin G1651 (manufactured by Shell Co., Ltd.) using a poly(styrene-ethylene-butadiene) triblock copolymer (C) Conductive additive 19 201100492 (cl) Diameter used A C-tube 100 (manufactured by CNT Co., Ltd.) of a multi-walled carbon nanotube of 10 to 50 nm and having a length of 1 to 25 μM was used as a carbon nanotube. (C-2) Timrex, KS 5-75TT (manufactured by Timcal Ltd.) was used as carbon black. (D) Mica Using M-325 (manufactured by KOCH Co., Ltd.). (E) Talc (talc) UPN HS-T 0·5 (manufactured by HAYASHI Pure Chemical Ind., Ltd.) was used. (F) Shixistonite (wollastonite)

Nygl〇s-8 (由 NYCO Minerals Inc.製造）。 範例1至6以及比較範例1至4 表一顯示根據組成物含量的所使用的每一個上述成 分。將聚苯醚樹脂與反應性單體混合，且混合剩餘的成分， 以製備聚苯喊類樹脂組成物。然後，使用在28〇至3〇〇。〇 下加熱的雙螺桿溶融擠出機(twin screw melt-extruder)將每 一個組成物熔融揉合(melt_kneaded),以製成薄片（chip)。 將薄片在130°C下乾燥5小時或更久，且接著在80至1〇〇 C的模製溫度(m〇iding temperature)下，使用加熱至28〇 至300 C的螺旋型注入器（screw type injecter)來製造1〇 cm 寬xlO cm 高 x〇.3 cm 厚的平坦樣本(flat specimen)。 表一 20 201100492 ——------- 範例 比較範例 1 2 3 4 5 6 1 2 3 4 (A)混合樹脂 (A-1)聚笨醚類樹脂 (wt%) 50 50 50 50 50 50 50 50 50 50 (A-2)聚醯胺樹脂 (wt%) 50 50 50 50 50 50 50 50 50 50 (B)苯乙烯類共聚物樹脂(重量份*) 5 5 5 5 5 5 5 5 5 5 (C)導電添加物(重量份Ί (C-1)奈米碳管 0.2 0.3 0.3 - 0.5 - 0.2 0.2 0.3 0.3 (C-2)碳黑 2 1 3 2 - 10 2 2 3 3 (D)雲母(重量份*) 30 30 30 30 30 30 - 60 - - (E)滑石（重量份*) 30 - (F)矽礦石（重量份*) - 30Nygl〇s-8 (manufactured by NYCO Minerals Inc.). Examples 1 to 6 and Comparative Examples 1 to 4 Table 1 shows each of the above components used in accordance with the content of the composition. The polyphenylene ether resin is mixed with a reactive monomer, and the remaining components are mixed to prepare a polyphenylene resin composition. Then, use at 28〇 to 3〇〇. Each of the compositions was melt-kneaded by a twin screw melt-extruder to form a chip. The sheet was dried at 130 ° C for 5 hours or longer, and then at a molding temperature of 80 to 1 ° C, a spiral type injector (screw) heated to 28 〇 to 300 C was used. Type injecter) to make a flat specimen of 1〇cm wide xlO cm high x〇.3 cm thick. Table 1 20 201100492 ——------- Example Comparison Example 1 2 3 4 5 6 1 2 3 4 (A) Mixed Resin (A-1) Polyetherether Resin (wt%) 50 50 50 50 50 50 50 50 50 50 (A-2) Polyamide resin (wt%) 50 50 50 50 50 50 50 50 50 50 (B) Styrene copolymer resin (parts by weight *) 5 5 5 5 5 5 5 5 5 5 (C) Conductive additive (parts by weight Ί (C-1) carbon nanotubes 0.2 0.3 0.3 - 0.5 - 0.2 0.2 0.3 0.3 (C-2) carbon black 2 1 3 2 - 10 2 2 3 3 (D ) Mica (parts by weight *) 30 30 30 30 30 30 - 60 - - (E) talc (parts by weight *) 30 - (F) 矽 ore (parts by weight *) - 30

*重量份：表示含量單位，基於100重量份的混合樹脂A。 (實驗範例） 在以下方法中’根據特性，對範例1至6與比較範例 1至4的樣本進行評價。評價結果提供於表二中。 ⑴缺口衝擊強度(Notch Izod Impact strength):根據 ASTMD256來對1/8”厚的樣本進行評價。 ▲ (2)彎曲模數(flexuralm〇dulus):使用 ASTMd79〇，根 據彎曲模數來對1/4”厚的樣本進行評價。 21 201100492 ⑶片電阻(sheet resistance):藉由施加1 〇〇 v的電壓以 及使用4-探針法(4-probe method)來對樣本進行評價。 (4)潛變伸長量(creep displacement):根據 ASTM 2990 ’驚曲潛變測量標準(flexural creep measuring standard)，在 9〇°C的溫度下50小時，根據伸長量來對i/4”厚的樣本進 行評價。 表二 範例 比較範例 1 2 3 4 5 6 1 2 「3 「4 衝擊強度 (kgf · cm/cm) 7.2 6.5 6.3 12.2 7.6 12.8 18.2 3.5 5.5 5.4 彎曲模數 (kgf/cm2) 36,500 41,200 42,100 36,200 36,500 43,600 22,100 50,100 35,400 34,800 片電阻 (Ω/sq.) 1011 1011 1011 1011 1011 1010 1010 1010 1012 1011 潛變伸長量 (mm) 1.7 1.7 1.8 1.7 1.8 1.6 4.2 1.6 2.4 3.2* Parts by weight: indicates a content unit based on 100 parts by weight of the mixed resin A. (Experimental Example) Samples of Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated according to characteristics in the following methods. The evaluation results are provided in Table 2. (1) Notch Izod Impact strength: A 1/8" thick sample was evaluated according to ASTM D256. ▲ (2) Flexural modulus (flexuralm〇dulus): using ASTMd79〇, 1/1 according to the bending modulus 4" thick samples were evaluated. 21 201100492 (3) Sheet resistance: The sample was evaluated by applying a voltage of 1 〇〇 v and using a 4-probe method. (4) creep displacement: according to ASTM 2990 'flexural creep measuring standard, 50 ° at a temperature of 9 ° C, according to the amount of elongation to i / 4" thick The sample is evaluated. Table 2 Example comparison example 1 2 3 4 5 6 1 2 "3 "4 impact strength (kgf · cm / cm) 7.2 6.5 6.3 12.2 7.6 12.8 18.2 3.5 5.5 5.4 bending modulus (kgf / cm2) 36,500 41,200 42,100 36,200 36,500 43,600 22,100 50,100 35,400 34,800 Piece resistance (Ω/sq.) 1011 1011 1011 1011 1011 1010 1010 1010 1012 1011 Elongation at creep (mm) 1.7 1.7 1.8 1.7 1.8 1.6 4.2 1.6 2.4 3.2

〇 22 201100492 根據表一與表二，根據一實施例’與無雲母的比較範 例1、包括雲母但在實施例的範圍外的比較範例2以及包 括滑石或矽礦石而非雲母的比較範例3、4相比’範例1 至6具有優異的特性平衡(；例如衝擊強度、硬度、導電性與 抗潛變性）。 特別地，無雲母的比較範例1顯示降低的硬度與抗潛 變性’且使用雲母但在實施例的範圍外的比較範例2顯示〇22 201100492 According to Table 1 and Table 2, a comparative example with no mica according to an embodiment, a comparative example 2 including mica but outside the scope of the embodiment, and a comparative example including talc or strontium ore rather than mica 3 4 Compared to 'Examples 1 to 6, there is an excellent balance of properties (for example, impact strength, hardness, electrical conductivity and resistance to latent denaturation). In particular, Comparative Example 1 without mica showed reduced hardness and anti-submergence' and Comparative Example 2 showing the use of mica but outside the scope of the examples

降低的衝擊強度。此外，使用滑石或矽礦石而非雲母的比 較範例3、4顯示降低的衝擊強度與抗潛變性。 因此’使用與苯乙烯類共聚物樹脂、導電添加物以及 雲母混合的聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的實施 例可以具有優異的特性(例如衝擊強度、硬度、導電性鱼抗 潛變性等等）。 〃 當本揭露已根據當前考量而描述為實際示例性實施 =時’其被理解為本發明不限於所揭露的實施例，相反地， 以下的申請專利範_精神與觀財預期各種修改盘相 =的配置。因此，前述實施例應被理解為賴 任何方式來限定本發明。 【圖式簡單說明】 無 【主要元件符號說明】 無 23Reduced impact strength. In addition, Comparative Examples 3 and 4 using talc or strontium ore rather than mica showed reduced impact strength and resistance to latent denaturation. Therefore, the embodiment using a mixed resin of a polyphenylene ether-based resin and a polyamide resin mixed with a styrene-based copolymer resin, a conductive additive, and mica can have excellent characteristics (for example, impact strength, hardness, and conductive fish resistance). Stagnation, etc.). 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 = configuration. Therefore, the foregoing embodiments are to be considered in all respects as illustrative. [Simple description of the diagram] None [Key component symbol description] None 23

Claims (1)

201100492 七、申請專利範圍： 1· 一種聚笨醚類熱塑性樹脂組成物’包括： (A) 100重量份的混合樹脂，所述混合樹脂包括(A-1) 5 至95 wt%的聚笨醚類樹脂與(A_2) 5至95 wt%的聚醯胺樹 基於100重量份的所述混合樹脂， (B) 1至30重量份的苯乙烯類共聚物樹脂； (C) 0.1至30重量份的導電添加物；以及 (D) 1至50重量份的雲母。 2. 如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物’其中所述聚苯醚類樹脂包括聚苯醚樹脂、聚笨 醚樹脂與乙烯基芳族聚合物的混合物或反應性單體接枝至 聚苯醚樹脂的經改質的聚苯醚樹脂。 3. 如申請專利範圍第2項所述之聚苯醚類熱塑性樹 脂組成物，其中所述聚苯醚樹脂包括聚(2,6-二曱基-1，4-伸 苯基)醚、聚(2,6·二乙基-I，4·伸苯基)醚、聚(2,6-二丙基-i,4_ 伸苯基)醚、聚(2-甲基-6-乙基-1,4-伸苯基)醚、聚(2_甲基_6_ 丙基-1,4-伸苯基)謎、聚(2-乙基-6-丙基_i，4_伸苯基)越、聚 (2,6-二苯基-1，4-伸苯基)醚、聚(2,6-二曱基_ι，4_伸苯基)醚與 聚(2,3,6-三曱基-1,4-伸苯基）醚的共聚物、聚(2,6_二甲基 -1,4-伸苯基)¾與聚(2,3,6-二乙基-1，4-伸苯基)鱗的共聚物 或其組合。 4. 如申請專利範圍第11項所述之聚苯醚類熱塑性樹 脂組成物’其中所述聚醯胺樹脂包括聚己内醯胺(财隆6)、 24 201100492 聚(11-胺基十一酸)(耐隆u)、聚十二内醯胺(耐隆12)、聚 伸己基己二醯二胺（财隆66)、聚六乙烯壬二醯胺（耐隆 69)、聚六乙烯癸二醯胺(耐隆610)、聚六乙烯十二二醯胺 (耐隆612)、聚伸己基對酞醯胺(耐隆6T)、聚伸丁基己二 酿二胺(财隆46)、polycaproamide/聚伸己基對欧醯胺共聚 物(耐隆6/6T)、聚伸己基己二醯二胺/聚伸己基對酞醯胺共 聚物(耐隆66/6T)、聚伸己基己二醯二胺/聚伸己基異酞醯 胺共聚物（耐隆66/61)、聚伸己基對酞醯胺/聚伸己基異酞 〇 醯胺共聚物（耐隆6T/6I)、聚伸己基對酞醯胺/聚十二醯胺 共聚物（耐隆6T/12)、聚伸己基己二醯二胺 /polyhexamethylene a terephthalamide/聚伸己基異敌酿胺 共聚物(耐隆66/6T/6I)、聚芳醯胺(耐隆MXD6)、聚伸己基 對酞醯胺/聚2-甲基伸戊基對酞醯胺共聚物（耐隆 6T/M5T)、耐隆10T/1012、聚伸壬基對酞醯胺(耐隆9T)、 1 聚伸己基對酞醯胺(耐隆10T)、聚醯胺11T (耐隆11T)、 聚醯胺12T (耐隆12T)、其共聚物或其組合。 Ο 5.如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物，其中所述苯乙烯類共聚物樹脂包括AB型二嵌 段共聚物、ΑΒΑ型三嵌段共聚物、自由基嵌段共聚物或其 組合。 6.如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物，其中所述苯乙烯類共聚物樹脂包括乙烯基芳族 早體與二稀的共聚物，所述二卸包括加氣的不餘和二婦、 部分加氫的不飽和二稀或不加氫的不飽和二烯。 25 201100492 Λ如甲睛專利範圍第丨 脂組成物，1中臭於咖舌峻頰熱塑性樹 乂 W 基於100重量份的所述混合樹月旨 電添加物的含量為〇丨至1〇重量份。 述導 8.如申請專利範圍第1 脂組成物，其中所料魏加物包括奈米碳管性樹 纖維、金屬粉末或其組合。 “、、蚊 9·如申請專·_ χ項所狀料__ ^成物’其巾所料餘加純括奈米料料黑的】 瓜如申請專利第9項所述之聚笨_執塑 脂組成物’其巾基於所述奈米碳管與所述碳黑的混 總量’所述奈米碳管的含量為〇 1至3 wt〇/。。 、 11.如申請專利範園第8項所述之聚笨喊類熱塑 脂組成物，其中所述奈米碳管的直徑為0.5至1〇〇 nm，長 度為0.01至1〇〇 μιη ° 12. 如申清專利範園第8項所述之聚笨峻類熱塑性樹 脂組成物’其中所述碳黑的平均粒徑為20至70 μιη。 13. 如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物，其十所述雲母包括白雲母、絹雲母、金雲母或 其組合，且所述雲母的粗徑為1至1〇〇 μιη。 14. 一種聚苯醚類熱塑性樹脂組成物的製造方法，包 括： 26 201100492 '£--- 藉由«苯_酿反舰單體混合，取得所述反應 ’早體接枝至所述聚苯鍵樹脂的經改質的聚苯輯脂 及 ;以 將所述經改質的聚苯驗樹脂、聚醯胺樹脂、苯乙烯類 共聚物樹脂、導電添加物與雲母混合。 、 15.如申請專利範圍第14項所述之聚苯醚類熱塑性201100492 VII. Patent application scope: 1. A polyether ether type thermoplastic resin composition 'comprises: (A) 100 parts by weight of a mixed resin including (A-1) 5 to 95 wt% of polyether ether Resin-like resin and (A_2) 5 to 95 wt% of polyamido tree based on 100 parts by weight of the mixed resin, (B) 1 to 30 parts by weight of a styrene-based copolymer resin; (C) 0.1 to 30 parts by weight a conductive additive; and (D) 1 to 50 parts by weight of mica. 2. The polyphenylene ether-based thermoplastic resin composition as described in claim 1, wherein the polyphenylene ether resin comprises a polyphenylene ether resin, a mixture or reaction of a polyphenylene ether resin and a vinyl aromatic polymer. The modified monomer is grafted to a modified polyphenylene ether resin of a polyphenylene ether resin. 3. The polyphenylene ether-based thermoplastic resin composition according to claim 2, wherein the polyphenylene ether resin comprises poly(2,6-dimercapto-1,4-phenylene) ether, poly (2,6·Diethyl-I,4·phenylene)ether, poly(2,6-dipropyl-i,4_phenylene)ether, poly(2-methyl-6-ethyl- 1,4-phenylene ether, poly(2-methyl-6-propyl-1,4-phenylene), poly(2-ethyl-6-propyl-i, 4-phenylene) ), poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-diindenyl), and poly(2,3,6) - a copolymer of tris-yl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) 3⁄4 and poly(2,3,6-diethyl- a copolymer of 1,4-phenylene) scales or a combination thereof. 4. The polyphenylene ether-based thermoplastic resin composition as described in claim 11, wherein the polyamine resin comprises polycaprolactam (Cai Lung 6), 24 201100492 poly (11-aminol eleven) Acid) (Rilong u), polydodecanamide (Rilong 12), polyhexamethylenediamine (Cailong 66), polyhexamethylenediamine (Rilong 69), polyhexaethylene Indoleamine (Rilong 610), polyhexaethylene dodecylamine (Rilong 612), polyhexyl-p-guanamine (Rilong 6T), and polybutylene hexamethylenediamine (Cailong 46) ), polycaproamide/polyhexyl-p-acetamide copolymer (Rilong 6/6T), polyhexylhexamethylenediamine/polyhexamethylene-p-amine copolymer (Rilong 66/6T), polyhexyl Hexamethylenediamine/polyhexylisodecylamine copolymer (Rilong 66/61), poly(hexyl)-p-amine/polyhexylisodecylamine copolymer (Tanglong 6T/6I), poly己 基 酞醯 酞醯 / / 聚 / / / / / / / / / / / / / / / / / / 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 /6I), polyarylamine (Nylon MXD6), poly-extension Indoleamine/poly-2-methyl-amyl-p-nonylamine copolymer (Rilong 6T/M5T), Nylon 10T/1012, poly-anthracene-p-guanamine (Rilong 9T), 1 polyhexyl group Indoleamine (Rilong 10T), Polyamido 11T (Rilong 11T), Polyamido 12T (Rilong 12T), copolymers thereof or combinations thereof. 5. The polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the styrene-based copolymer resin comprises an AB type diblock copolymer, a fluorene type triblock copolymer, and a radical. Block copolymer or a combination thereof. 6. The polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the styrene-based copolymer resin comprises a copolymer of a vinyl aromatic precursor and a dilute, and the second unloading includes No more gas and two women, partially hydrogenated unsaturated dilute or non-hydrogenated unsaturated diene. 25 201100492 For example, the scent of the scorpion patent range, the scent of the scent of the scent of the scent of the scent of the scent of the scent of the squid . Description 8. The pharmaceutical composition of claim 1, wherein the Wei additive comprises a carbon nanotube fiber, a metal powder or a combination thereof. ",, mosquitoes 9 · If you apply for special _ χ 所 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The plastic fat composition 'the towel is based on the total amount of the carbon nanotubes mixed with the carbon black', the content of the carbon nanotubes is 〇1 to 3 wt〇/. 11. The polystyrene-like thermoplastic resin composition according to the eighth item, wherein the carbon nanotube has a diameter of 0.5 to 1 〇〇 nm and a length of 0.01 to 1 〇〇 μιη ° 12. The polystyrene-like thermoplastic resin composition described in the above item 8 wherein the carbon black has an average particle diameter of 20 to 70 μm. 13. The polyphenylene ether-based thermoplastic resin composition as described in claim 1 The mica includes mica, sericite, phlogopite or a combination thereof, and the mica has a diameter of 1 to 1 μm η. 14. A method for producing a polyphenylene ether-based thermoplastic resin composition, Including: 26 201100492 '£--- By the «benzene-brewed anti-ship monomer mixing, the reaction was obtained, the early grafting of the polyphenylene bond resin was changed. And polystyrene resin; and the modified polyphenylene resin, polyamine resin, styrene copolymer resin, conductive additive and mica are mixed; 15. as claimed in claim 14 Polyphenylene ether thermoplastic 樹脂組成物的製造絲，其情述反舰單體包括不飽和 鲮酸或其酐基。 16.如申請專利範圍第14項所述之聚苯醚類熱塑性 樹脂組成物的製造方法，其中所述反應性單體包括擰檬酸 酐、順丁烯二酸酐、順丁烯二酸、衣康酸酐、反丁烯二酸、 (甲基)丙烯酸、（曱基)丙烯酸酯或其組合。 Π.如申請專利範圍第14項所述之聚苯醚類熱塑性 樹脂組成物的製造方法，其中基於1〇〇重量份的所述經改 質的聚苯鱗樹脂與所述聚醯胺樹脂，所述反應性單體的添 加量為0.1至10重量份。 18. —種使用如申請專利範圍第1至13項中任一項所 述之聚苯醚類熱塑性樹脂組成物製造的模製產品。 27 201100492 Γ A y ^l.L· 四、 指定代表圖： (一） 本案之指定代表圖：無 (二） 本代表圖之元件符號簡單說明： 無 五、 本案若有化學式時，請揭示最能顯示發明特徵 的化學式： 益 V?* 201100492 334iypitl 修正曰期·. 99年4月27日 爲第98145795號中文專利說明書無割線修正本 發明專利說明書 ※記號部分請勿填寫） (本說明書格式、順序，請勿任意更動 ※申請案號： s.i〇06,ap ※申請日： ※工卩匸分類：(Ti0L % 一、發明名稱：（中文/英文） 〇2L % 聚苯醚熱塑性樹脂組成物、製備此組成物的方法以及 使用此組成物的模製產品 丨The manufacture of a resin composition, the anti-ship monomer includes unsaturated decanoic acid or its anhydride group. 16. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 14, wherein the reactive monomer comprises citric acid anhydride, maleic anhydride, maleic acid, and itaconic acid. Anhydride, fumaric acid, (meth)acrylic acid, (mercapto) acrylate or a combination thereof. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 14, wherein the modified polystyrene resin and the polyamide resin are used in an amount of 1 part by weight, The reactive monomer is added in an amount of 0.1 to 10 parts by weight. A molded product produced by using the polyphenylene ether-based thermoplastic resin composition as described in any one of claims 1 to 13. 27 201100492 Γ A y ^lL· IV. Designated representative map: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: Benefit V?* 201100492 334iypitl Correction period.. April 27, 1999 is the Chinese patent specification No. 98145795. There is no secant correction. The patent specification of the present invention ※ Do not fill in the mark) (The format, order of this manual, Please do not change arbitrarily. ※Application number: si〇06, ap ※Application date: ※Work classification: (Ti0L % I. Invention name: (Chinese / English) 〇 2L % Polyphenylene ether thermoplastic resin composition, preparation Method of composition and molded product using the same 〇 POLYPHENYLENEETHER THERMOPLASTIC RESIN COMPOSITION, METHOD OF PREPARING THE SAME, AND MOLDED PRODUCT USING THE SAME. 嫌ή 二、 中文發明摘要： 岣从 ，M,on 一種聚苯醚類熱塑性樹脂組成物，其包括(A)混合樹 脂，其包括(A_l)聚苯醚類樹脂與(A-2)聚醯胺樹脂；（B)苯 乙烯類共聚物樹脂；（C)導電添加物；以及(D)雲母。一種 製備此聚苯醚類熱塑性樹脂組成物的方法以及使用此聚苯 醚類熱塑性樹脂組成物的模製產品。 三、英文發明摘要： Disclosed are a polyphenyleneether-based thermoplastic resin composition that includes (A) a mixed resin including (A-l) a polyphenyleneether-based resin and (A-2) a polyamide resin; (B) a styrene-based copolymer resin; (C) a conductive additive; and (D) mica, a method of preparing the same, and a molded product using the same. 201100492 1 ^uili 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種聚苯醚類 (polyphenyleneether-based)熱塑性樹脂組成物及其製備方 法以及使用此組成物的模製產品(molded product)。 【先前技術】 聚本鍵樹脂或聚苯鍵樹脂與聚苯乙晞(P〇lystyreneWf ◎ 脂的混合物由於在高溫下優異的機械與電性特性而被廣泛 地使用於各種汽車零件、電性或電子零件的領域。然而， 聚苯醚樹脂具有不佳的财化學性(chemical resistance)與可 使用性(workability)。 聚醯胺(polyamide)樹脂具有良好的耐化學性與可使 . 用性，但具有不佳的对熱性(heat resistance)與耐衝擊性 气 （impact resistance)。因此，聚醯胺樹脂對於工程塑膠樹脂 ^ 的應用具有限制。 二種樹脂的組合實現了财化學性、可使用性與财熱 十生。 為了提供具有導電性的樹脂，可以使用導電添加物 (conductive additive)(例如碳黑(carbon black)、碳纖維、金 屬粉末、金屬塗層無機粉末(metal coating inorganic p0Wder) 或金屬纖維。然而，當加入的導電添加物少於樹脂的1〇 wt%時，可能無法確保足夠的導電性（dectrical conductivity)，而當加入大量的導電添加物時，導電熱塑性 201100492 33419pifl 樹月曰的基本機械特性(例如耐衝擊性等等)可能會明顯地降 低。 ’’ 藉由添加少I的奈米碳管(carbon nanotube)作為導電 添加物來試圖對熱塑性樹脂提供導電度。然而，當單獨使 用^米1管時，由於不良的分散，因而不易得到導電性， 且田同日守使用奈米碳管與無機填充物(filler)時，衝擊強度 (impact strength)與導電性可能會降低。 【發明内容】 本發明的一觀點提供一種聚苯醚類熱塑性樹脂組成 物，其具有優異的衝擊強度、硬度、導電性與抗潛變性 (creep resistance)的特性平衡。 本發明的另一觀點提供一種製備聚苯醚類熱塑性樹 脂組成物的方法。 本發明的又一觀點提供一種使用聚苯醚類熱塑性樹 脂組成物製造的模製產品。 根據本發明的一觀點，提供一種聚苯醚類熱塑性樹脂 組成物，其包括(A) 100重量份(parts by weight)的包括(Α]) 5至95 wt%的聚笨醚類樹脂與(A_2) 5至95 wt%的聚醯胺 樹脂的混合樹脂；基於100重量份的混合樹脂，（B) 1至 30重量份的苯乙烯類(styrene-based)共聚物樹脂；以及(〇 0.1至30重量份的導電添加物；以及(D)】至5〇重量份的 雲母(mica)。 聚笨醚類樹脂包括聚笨醚樹脂、聚苯醚樹脂與乙烯基 方族(vinyl aromatic) t合物的混合物或經改質的 201100492 聚苯趟樹脂（反應性單體（monomer)接枝至聚苯醚樹脂 上）。聚苯醚樹脂包括聚（2,6-二曱基-1,4-伸苯基）醚 (poly(2,6-dimethyl-l,4-phenylene)ether)、聚(2,6-二乙基-1,4-伸苯基)趟(卩〇1丫(2,6-出6&71-1,4-卩116115^1^^1^1*)、聚(2,6_二 丙 基 -1,4- 伸苯基 ） 醚 (poly(2,6-dipropyl-l，4-phenylene)ether)、聚(2-曱基-6-乙基 -1,4- 伸苯基 ） 醚 0 (p〇ly(2-methyl-6_ethyl-l，4-phenylene)ether)、聚（2-甲基-6· 丙 基 -1,4- 伸 苯 基 ） 醚 (poly(2-methyl-6-propyl-l,4-phenylene)ether)、聚(2-乙基-6-丙 基 伸苯基 ） 醚 (poly(2-ethyl-6-propyl-l,4-phenylene)ether)、聚(2,6-二苯基 -1，4-伸苯基）醚(p〇ly(2,6-diphenyl-1，4-plienylene)etlier)、聚 (2,6-二曱基-1，4·伸苯基)醚與聚(2,3,6-三曱基-1，4-伸笨基) 醚(poly(2,3,6-trimethyl-l,4-plienyleiie)ether)的共聚物、聚 (2,6-二曱基-1,4-伸苯基)醚與聚(2,3,6-三乙基-1，4-伸苯基) ❹ 醚(p〇ly(2,3,6-triethyl-l，4-phenylene)ether)的共聚物或其組 合。 聚醢胺樹脂包括聚己内酿胺(polycaprolactam)(耐隆 6)、聚（11-胺基—酸)(p〇ly(l 1-aminoundecanoic acid))(耐 隆11)、聚十二内龜胺(polylauryllactam)(财隆12)、聚伸己 基己二酿二胺(polyhexamethylene adipamide)(财隆 66)、聚 六乙烯壬二酿胺(p〇lyhexaethyleneazelamide)(而寸隆 69)、聚 六乙浠癸二醯胺（polyhexaethylene sebacamide)(耐隆 201100492 33419pifl 610)、聚六乙稀十二二醯胺（polyhexaethylene dodecanodiamide)(耐隆612)、聚伸己基對酞醯胺 (polyhexamethylene terephthalamide)(耐隆 6T)、聚伸 丁基己 二醯二胺(polytetramethylene adipamide)(财隆 46)、聚己内 醯胺/聚伸己基對酞醯胺共聚物(耐隆6/6T)、聚伸己基己二 醯二胺/聚伸己基對酞醯胺共聚物(耐隆66/6T)、聚伸己基 己二酿二胺/聚伸己基異献酿胺（polyhexamethylene isophthalamide)共聚物(耐隆66/61)、聚伸己基對酞醯胺/聚 伸己基異酞醯胺共聚物（耐隆6T/6I)、聚伸己基對酞醯胺 (polyhexamethylene terephthalamide)/ 聚十二酿胺 (polydodecaneamide)共聚物（耐隆6T/12)、聚伸己基己二酿 二胺/聚伸己基對酞醯胺/聚伸己基異酞醯胺共聚物（耐隆 66/6T/6I)、聚芳酿胺(polyxylene adipamide)(耐隆 MXD6)、 聚伸己基對酞醯胺/聚2-曱基伸戊基對酞醯胺共聚物(poly 2-methylpentamethylene terephthalamide)(财隆 6T/M5T)、而才 隆10T/1012、聚伸壬基對駄醢胺（polynonamethylene terephthalamide)(财隆 9T)、聚伸癸基對酜醯胺 (polydecamethyleneterephthalamide)(财隆 10T)、聚醯胺 11T (耐隆11T)、聚醯胺12T (耐隆12T)、其共聚物或其組合。 苯乙烯類共聚物樹脂可以包括AB型二嵌段(diblock) 共聚物、ΑΒΑ型三喪段共聚物、自由基欲段(radical block) 共聚物或其組合，且亦包括乙烯基芳族單體與二烯(diene) 的共聚物，二烯包括加氫的不飽和二稀(hydrogen-added 201100492 unsaturated diene)、部分加氫的不飽和二烯（partially hydrogen-added unsaturated diene)或不加氫的不飽和二婦。 基於100重量份的混合樹脂，可以含有0.1至10重量 份的導電添加物。導電添加物包括奈米碳管、碳黑、碳纖 維、金屬粉末或其組合，且在一實施例中，可以包括奈米 碳管與碳黑的混合物。基於奈米碳管與碳黑的混合物，奈 米碳管的含量可以為0.1至3 wt%。 奈米碳管具有0.5至100 nm的直徑、0.01至100 pm 的長度，而碳黑具有20至70 μιη的平均粒徑。 雲母包括白雲母(muscovite)、絹雲母(sericite)、金雲 母(phlogopite)或其組合，且可以具有1至1〇〇 μπι的粒徑。 本發明的另一觀點提供一種製造聚苯醚類熱塑性樹 脂組成物的方法，其包括藉由混合聚苯醚樹脂與反應性單 體來得到經改質的聚苯醚樹脂（反應性單體接枝至聚笨醚 樹脂）；以及混合經改質的聚笨醚樹脂、聚醢胺樹脂、苯乙 烯類共聚物樹脂、導電添加物與雲母。 反應性單體可以包括不飽和羧酸(carboxylic acid)或肝 基(anhydride group)，且在一實施例中，可以包括檸檬酸酐 (citric anhydride)、順丁烯二酸酐(maleic anhydride)、順丁 稀二酸(maleic acid)、衣康酸酐(itaconic anhydride)、反丁 烯二酸(fumaric acid)、（曱基)丙稀酸((metli)acrylic acid)、（曱 基)丙烯酸酯((meth)acrylic acid ester)或其組合。 可以加入0,1至10重量份的反應性單體(基於1〇〇重 量份的經改質的聚苯醚樹脂與聚醯胺樹脂）。 201100492 33419pifl 脂組=的又模= 广種使用聚苯_塑性樹 以下，將會詳細說明其他實施例。 里的:匕例的聚苯醚類熱塑性樹脂組成物具有優 、、’歹’衝擊強度、硬度、導電性、抗潛變性等等， =此可應祕零件材料(例如汽車的加油門㈣d〇〇r)、 A車的防5蔓板(fender)等等）。 為讓本發明之上述特徵和優點能更明顯易懂，下文特 舉實施例，並配合所附圖式作詳細說明如下。 【實施方式】 以下將詳細說明示例性實施例。然而，這些實施例僅 為示例性的’且本發明並不以此為限。 如文中所使用，當未提供特殊定義時，“(曱基)丙烯酸” 表示“丙烯酸’’與“曱基丙烯酸”，而“（曱基）丙烯酸酯，，表示 丙細酸S旨”與“曱基丙烤酸g旨”。 根據一實施例的聚苯醚類熱塑性樹脂組成物包括(A) 100重量份的包括(A-1) 5至95 wt%的聚苯謎類樹脂與(a_2) 5至95 wt%的聚醯胺樹脂的混合樹脂；以及基於1〇〇重量 份的混合樹脂，聚苯醚類熱塑性樹脂組成物包括(B) 1至 3〇重量份的苯乙烯類共聚物樹脂；（C) 0.1至30重量份的 導電添加物；以及(D) 1至50重量份的雲母。 以下將詳細說明包含於根據實施例的聚苯醚類熱塑 性樹脂組成物中的示例性成分。 (A)混合樹脂 201100492 -/-/ ~r i (A-l)聚苯醚類樹脂 根據一實施例的聚苯醚類樹脂包括聚笨醚樹脂、聚苯 醚樹脂與乙烯基芳族聚合物的混合物或經改質的聚苯醚樹 脂（包括接枝至聚苯醚樹脂的反應性單體）。 聚苯醚樹脂包括聚(2,6-二曱基-1,4-伸苯基)醚、聚(2,6_ 一乙基-1，4-伸本基)醚、聚(2,6-二丙基-l，4-伸苯基)謎、聚(2_ 曱基-6-乙基-1，4-伸苯基)醚、聚(2-曱基_6•丙基4，4_伸苯基) 〇 醚、聚(2_乙基冬丙基-I，4·伸苯基)醚、聚(2,6-二苯基-Μ-伸苯基)¾、聚(2,6-二曱基-1,4·伸苯基)驗與聚(2,3,6_三曱基 -Μ-伸苯基)醚的共聚物、聚(2,6_二甲基^，冬伸苯基)醚與 1(2,3,6_二乙基-1，4_伸苯基)醚的共聚物或其組合。在一實 施例中，較佳為聚(2,6-二曱基_1，4_伸苯基)醚或聚(2,6_二曱 ' 基_1，4_伸苯基)鱗與聚(2,3,6-三甲基-I，4-伸苯基)醚的共聚 物，而在另一實施例中，較佳為聚(2,6-二曱基_Μ_伸苯基) 鍵。 乙烯基芳族聚合物包括乙烯基芳族單體（例如苯乙 烯、α -曱基苯乙烯（〇；-methyl styrene)、ρ -曱基苯乙烯、 4-N-丙基苯乙烯(4-N-propyl styrene)等等）的聚合產物，且 在一實施例中，較佳為苯乙烯的聚合產物與^^曱基苯乙烯 的聚合產物。 聚苯謎樹脂與乙烯基芳族聚合物的含量可分別為6〇 至 99 wt%與 1 至 40 wt%。 反應性單體接枝至聚苯謎樹脂，以產生經改質的聚苯 趟樹脂’且包括其不飽和羧酸基或酐基。反應性單體的例 9 201100492 子可以包括檸檬酸酐、順丁稀二酸肝、順丁稀二酸、衣康 酸酐、反丁烯二酸、（甲基)丙烯酸、（甲基)丙烯酸醋或其組 合’且在-實加例中，較佳為檸檬酸酐。捧樣酸針可以形 成經改質的聚苯_封脂而不需要起始劑(initiat〇r)。 製造經改質的聚笨醚樹脂的方法並不特別地限定’但 考董到南溫製程’較佳是在使用亞磷酸鹽類 (phosphite-based)熱穩定劑（heat stabiHzer)的熔融捏合 (melt-kneading)下進行接枝。 基於聚笨趟類樹脂的總量，反應性單體的含量可以為 0.1至10 wt%。當反應性單體的含量在此範圍中時，聚苯 醚類熱塑性樹脂組成物可以具有經提高的相容性 (compatibility)與優異的耐衝擊性。 聚苯醚類樹脂的聚合程度並不特別地限制。考量樹脂 組成物的熱穩定性與可使用性，在25°C時，在三氯曱烷 (chloroform)溶劑中所測量的固有黏度(intrinsic visc〇sity) 可以為0.2至0.8 dl/g。 基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的 總量’聚苯醚類樹脂的含量可以為5至95 wt%，且在一實 施例中，基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂 的總量，聚苯醚類樹脂的含量可以為30至70 wt%。當聚 笨醚類樹脂的含量在此範圍中時，藉由適當地執行聚苯喊 樹脂的特性，聚苯醚類熱塑性樹脂組成物可以具有優異的 耐衝擊。 (A-2)聚醯胺樹脂 201100492 -5^4iypiIX 根據一實施例，聚醯胺樹脂包括在聚合物主鏈以及胺 基酸(amino acid)、内醯胺(lactam)或二胺(diamine)中的醯胺 基(amide-group)，且作為主要成分的二羧酸(dicarboxylic acid)被聚合而提供聚醯胺。 胺基酸的例子包括6-胺基己酸(6-aminocaproic acid), 11-胺基~)—酸(11-aminoundecanoic acid)、12-胺基十二酸 (12-aminododecanoic acid)、對氨曱基苯曱酸 (paraaminomethylbenzoic acid)等等。内酸胺的例子包括 ε -已内酿胺（ε -caprolactam)、ω -12 内酿胺（ω -laurolactam) 等等。二胺的例子包括四亞曱基二胺 (tetramethylenediamine) 、 六亞曱 基二胺 (hexamethylenediamine)、2-曱基五亞甲基二胺 (2-methylpentamethylenediamine)、九亞曱基二胺 (nonamethylenediamine)、十一亞甲基二胺 (undecamethylenediamine)、十二亞曱基二胺 (dodecamethylenediamine)、2,2,4-三曱基六亞曱基二胺 (2,2,4-trimethylhexamethylenediamine)、2,4,4-三曱基六亞曱 基二胺(2,4,4-trimethylhexamethylenediamine)、5-甲基九亞 甲基二胺（5-methylnonamethylenediamine)、間苯二曱胺 (metaxylenediamine)、對苯二甲胺(paraxylenediamine)、1,3-雙（胺甲基)環己烧(1,3~1^(&111^1011161；1171)。>^1〇116\3116)、1,4-雙(胺曱基)環己烧(1，4-1^(&111^1〇11^11丫1)〇7〇1〇1^又&116)、1-胺 基-3-胺曱基-3,5,5-三曱基環己烷 (l-amino_3-aminomethyl-3,5,5-trimethylcyclohexane)、雙(4- 201100492 33419pifl 胺基環己基）甲烧(bis(4-aminocyclohexyl)methane)、雙(3-曱基 -4- 胺基環己基）曱烷 （bis (3-methyl-4-aminocyclohexyl)methane)、2,2-雙(4-胺基環己 基）丙烧(2,2-bis(4-aminocyclohexyl)propane)、雙(胺基丙基) α底嗓（bis(aminopropyl)piperazine)、胺基乙基派 °秦 (aminoethylpiperazine)等等的脂族（aliphatic)、脂環族 (alicyclic)或芳族(aromatic)二胺。二羧酸的例子包括脂族、 脂環族或芳族二叛酸(例如己二酸(adipic acid)、辛二酸 (suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、 十二烧二酸(dodecane diacid)、對苯二甲酸(terephthalic acid)、間苯二曱酸(isophthalic acid)、2-氯對苯二曱酸 (2-chloroterephthalic acid)、2-曱基對苯二甲酸 (2-methylterephthalic acid)、5-曱基間苯二曱酸 (5-methylisophthalic acid)、5-石黃基間苯二甲酸鈉(5-sodium sulfoisophthalate) 、 2,6- 萘 二竣酸 (2,6-naphthalenedicarboxylic acid)、六氫對苯二曱酸 (hexahydroterephthalic acid)、六氫間苯二甲酸 (hexahydroisophrtialic acid)等等）。自原料(raw material)衍生 的聚醯胺均聚物(homopolymer)或共聚物可以單獨使用或 以混合物來使用。 聚醯胺樹脂包括聚己内醯胺(耐隆6)、聚（11-胺基十一 酸)(耐隆11)、聚十二内醯胺(耐隆12)、聚伸己基己二醯二 胺(耐隆66)、聚六乙烯壬二醯胺(耐隆69)、聚六乙烯癸二 酿胺(财隆610)、1/、乙刘ϊ十 --酿胺(财隆612)、聚伸己 12 201100492 jJH-xypui 基對酞醯胺(耐隆6T)、聚伸丁基己二醯二胺(耐隆46)、聚 己内醯胺/聚伸己基對酞醯胺共聚物(耐隆6/6Τ)、聚伸己基 己二醯二胺/聚伸己基對酞醯胺共聚物(耐隆66/6Τ)、聚伸 己基己一酸一胺/聚伸己基異駄酿胺共聚物(财隆66/61)、聚 伸己基對酞醯胺/聚伸己基異酞醯胺共聚物(耐隆6Τ/6Ι)、聚 伸己基對酞醯胺/聚十二醯胺共聚物(耐隆6Τ/12)、聚伸己 基己二醯二胺/聚伸己基對酞醯胺/聚伸己基異酞醯胺共聚 0 物(耐隆66/6Τ/6Ι)、聚芳醯胺(耐隆MXD6)、聚伸己基對酞 醯胺/聚2-曱基伸戊基對酞醯胺共聚物(耐隆6Τ/Μ5Τ)、耐 隆10Τ/1012、聚伸壬基對酞醯胺(耐隆9Τ)、聚伸癸基對酞 醯胺(耐隆10Τ)、聚醯胺11Τ (耐隆11Τ)、聚醯胺12Τ (耐 隆12Τ)、其共聚物或其組合。其共聚物包括财隆6/610、 耐隆6/66、耐隆6/12等等。 聚醯胺樹脂具有250°C或更高的熔點、2或更高的相 ^ 對黏度（relative viscosity)(在25。C下測量，間-甲盼 (m-cresol)中含有1 wt%的聚醯胺樹脂）。當熔點與相對黏度 〇 在上述範圍中時，聚苯醚類熱塑性樹脂組成物的機械特性 與耐熱性可被提升。 基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的 總量，聚醯胺樹脂的含量可為5至95 wt%，且在一實施例 中，基於包括聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的總 量，聚醯胺樹脂的含量可為30至70 wt%。當聚醢胺樹脂 的含量在此範圍中時，可以得到優異的與聚苯醚類樹脂的 相容性。 13 201100492 33419pifl (B)苯乙烯類共聚物樹脂 ，據實施例，自乙稀基芳族單體衍生的苯乙婦類共 聚物树脂可以為AB ^二狀絲物、aba狂嵌段共聚 物、自由基嵌段共聚物或其組合。 嵌&共名物可以為乙烯基芳族單體與二烯的共聚 物，二烯包括加氫的不飽和二烯、部分加氫的不飽和二稀 或不加風的不飽和二稀。 乙烯基芳族單體可以包括苯乙烯、p_甲基苯乙婦、α -甲基苯乙烯、4-Ν-丙基苯乙烯等等，且在一實施例中，較 佳為笨乙烯、α-甲基苯乙烯等等。這些單體可以單獨使用 或以混合物來使用。 ΑΒ型二嵌段共聚物包括聚苯乙烯-聚丁二烯 (polybutadiene)共聚物、聚本乙細-聚異戊二婦(p〇iyjs〇prene) 共 ^^物、t CK -甲基本乙稀(polyalphamethylstyrene)-聚丁 二 烯共聚物或將氫加至共聚物的共聚物。在本領域中，AB 型二嵌段共聚物在商業上被熟知。AB型二嵌段共聚物的 例子包括由Phillips製造的Solprene與K-樹脂(K-resin)以 及由 Shell chemical 製造的 Kraton D 與 Kraton G。 ΑΒΑ型三嵌段共聚物包括聚苯乙烯-聚丁二烯_聚苯乙 烯(SBS)共聚物、聚苯乙烯·聚異戊二烯-聚苯乙烯(SIS)共聚 物、聚曱基苯乙稀·聚丁二細-聚α-甲基苯乙烯共聚物、 聚曱基苯乙烯-聚異戍二烯-聚α -曱基笨乙烯共聚物或 將氫加至共聚物的共聚物。ΑΒΑ型三嵌段共聚物在商業領 域中已被熟知。ΑΒΑ变二篏段共聚物的例子包括由Shell 14 201100492 chemical 製造的 Cariflex, Kraton D 與 Kraton G 以及由 Kuraray Co.，Ltd.製造的 Septon 等等。 基於100重量份的聚苯醚類樹脂與聚醯胺樹脂的混合 樹脂，苯乙烯類共聚物樹脂的含量可為1至30重量份，且 在一實施例中，基於100重量份的聚苯醚類樹脂與聚醯胺 樹脂的混合樹脂，苯乙烯類共聚物樹脂的含量可為1至1〇 重量份。當苯乙烯類共聚物樹脂的含量在此範圍中時，耐 衝擊性明顯地增加’且不降低聚苯醚類樹脂與聚醯胺樹脂 的優異相容性。 (C)導電添加物 根據一實施例，導電添加物可以包括奈米碳管、碳 黑、碳纖維、金屬粉末或其組合，且在另一實施例中，較 佳為奈米碳管與碳黑的混合物。 奈米碳管具有優異的機械強度、機械特性(例如高的揚 氏模數(Young’s Modulus)與縱橫比(aspect ratio))、導電度與 熱穩疋性。當奈米破管用於製造聚合物合成物時，可以得 到具有改良的機械特性、熱特性與電特性的奈米碳管-聚合 物合成物。 合成奈米碳管的方法包括電弧放電(arc_discharge)、熱 裂解（pyrolysis)、電漿增強型化學氣相沈積（plas=a enhanced chemical vapor deposition，PECVD)、熱化學氣相 沈積(chemical vapor deposition，CVD)、電解(eiectrolysis) 等等，且在一實施例中，不論合成的方法，所得到的奈米 碳管皆可以使用。 ' 15 201100492 33419pifl 取決於壁（wall)的數目，奈米碳管可以分為單壁 (single-walled)奈米碳管、雙壁(double-walled)奈米;ε炭管與 多壁(multi-walled)奈米碳管。在一實施例中，較佳為多壁 奈米碳管，但並不限於此。 並不特別限定奈米碳管的尺寸，奈米碳管可具有〇.5 至100 nm的直徑與0.01至100 μιη的長度，且在一實施例 中，奈米碳管可具有1至10 nm的直徑與0.5至1〇 μιη的 長度。當奈米碳管的直徑與長度在此範圍中時，導電度與 可使用性可被提升。 此外，由於如此大的尺寸，奈米碳管具有大的縱橫比 (L/D)。當使用具有L/D為100至1,000的奈米碳管時，導 電度可被提升。 碳黑可以為任意的導電碳黑而無限制，且包括石墨碳 (graphitized carbon)、爐黑（furnace black)、乙炔黑（acetylene black)、科琴碳黑(ketjen black)等等。 導電碳黑的平均粒徑為20至70 μπι，且吸油量(〇il absorption)由 JIS K 5101 調整為 100 至 600 mOlOOg 時可作 為碳黑。當破黑的平均粒徑在此範圍中時，可以實現優異 的導電性。 當奈米碳管與碳黑混合時，基於奈米碳管與碳黑的混 合物的總量，奈米碳管的含量可為0.1至3 wt°/。。當奈米 碳管的含量在此範圍中時，可以藉由此少量的添加來實現 合適的電滲滤(electrical percolation)以導電，且可以維持機 械強度(例如優異的抗拉強度(tensile strength))與耐熱性。 16 201100492 基於100重量份的包括聚苯醚類樹脂與聚醯胺樹脂的 混合樹脂，導電添加物的含量可以為〇1至3〇重量份，且 在一實施例中，基於1〇〇重量份的包括聚苯醚類樹脂與聚 醯胺樹脂的混合樹脂，導電添加物的含量可以為〇丨至1〇 重量份。當導電添加物的含量在此範圍中時，聚苯醚類熱 塑性樹脂組成物可以具有優異的導電性與财衝擊性。 (D)雲母 0 根據一實施例，不論種類，雲母可以包括白雲母、絹 雲母、金雲母等等。這些雲母可以單獨使用或以其混合物 使用。 雲母的粒徑可以為1至100 μιη。當使用此範圍中的雲 母時，可以得到優異的抗潛變性（creepresistance)。 基於100重量份的聚笨驗類樹脂與聚醯胺樹脂的混合 樹脂，雲母的含量可以為1至50重量份，且在一實施例中， 基於100重量份的聚苯醚類樹脂與聚醯胺樹脂的混合樹 脂，雲母的含量可以為10至40重量份。當雲母的含量在 〇 此範圍中時，聚苯醚類熱塑性樹脂組成物可以具有優異的 硬度與耐衝擊性。 根據一實施例’聚苯醚類熱塑性樹脂組成物可以進一 步包括添加劑(additive)。取決於使用目的，添加劑可以包 括抗滴落劑(anti-drip agent)、光穩定劑(light stabilizer)、顏 料(pigment)、染料(dye)或其組合。基於1〇〇重量份的聚苯 醚類樹脂與聚醯胺樹脂的混合樹脂，添加劑的含量可以為 0.1至30重量份。當添加劑的含量在此範圍中時，可以得 17 201100492 33419pifl 到取決於目的的添加劑功效，且可以得到優異的機械特性 與、C改良的表面外觀(surface appearance)。 上述的聚苯醚類熱塑性樹脂組成物可以藉由一般熟 知的方法來製造。舉例來說’將上述的成分與所選擇的添 加劑混合’且在擠壓機（extruder)中溶融擠出 (melt-extrud)，以製成顆粒物(pellet)。 在另一實施例中，聚笨醚類熱塑性樹脂組成物藉由取 知經改質的聚苯醚樹脂（混合聚苯醚樹脂與反應性單體而 將反應性單體接枝至聚苯醚樹脂）以及將經改質的聚笨醚 〇 樹脂、聚醯胺樹脂、笨乙烯類共聚物樹脂、導電添加物與 雲母混合來製造。 〃 反應性單體可以與前述相同。 基於100重量份的經改質的聚苯醚樹脂與聚醯胺樹 脂，反應性單體的含量可以為〇丨至1〇重量份，且在—實 施例中，基於100重量份的經改質的聚笨醚樹脂與聚醯胺 - 樹脂，反應性單體的含量可以為0 1至5重量份。當反應 性單體的含量在此範圍中時，聚苯醚類熱塑性樹脂組成物 ❹ 可以具有經改良的相容性與優異的耐衝擊性。 考慮高操作溫度，經改質的聚苯醚樹脂可以在使用麟 酸醋類（phosphate-based)熱穩定劑的熔融-捏合 (melt-kneading)下進行製備。 根據又一實施例’提供一種使用聚苯醚類熱塑性樹脂 組成物製造的模製產品。聚苯醚類熱塑性樹脂組成物可以 18 201100492 應用於極度需要衝擊強度、硬度、導電性與抗潛變性的模 製產品(例如汽車加油門、汽車防護板等零件材料）。 以下，將參考範例來更詳細地說明實施例。然而，以 下為示例性實施例，並不用於限定本發明。 (範例） 根據一實施例，聚苯醚類熱塑性樹脂組成物包括以下 0 各成分。 (A) 混合樹脂 (A-1)聚苯醚類樹脂 將作為聚本鍵樹脂的聚(2,6-二甲基-1,4-伸苯基)趟的 GE plastic HPP-820 (由 GE plastics Ltd·製造)與作為反應性 單體的檸檬酸酐（由Samchun Pure Chemical Ltd.製造)混 . 合，且接著使用經改質的聚苯醚樹脂(藉由將反應性單體接 枝至聚苯醚樹脂而得到）。基於聚苯醚類樹脂的總量，反應 性單體的含量為lwt%。 ® (A_2)聚醯胺樹脂 使用耐隆 66 的 VYDYNE 50BW (由 Solutia Inc.製造）。 (B) 苯乙烯類共聚物樹脂 使用聚（苯乙烯-乙烯-丁二烯）三嵌段共聚物的 G1651(由 ShellCo.，Ltd.製造） (C) 導電添加物 19 201100492 33419pifl (C-l)使用直徑為10至50 nm且長度為1至25 μιη的 多壁奈米碳管的C-tube 100 (由CNT Co., Ltd.製造)作為奈 米碳管。 (C-2)使用 Timrex, KS 5-75TT (由 Timcal Ltd.製造)作 為礙黑^ (D) 雲母 使用 M-325 (由 KOCH Co·，Ltd.製造）。 (E) 滑石（talc) 使用 UPN HS_T 0.5 (由 HAYASHI Pure Chemical Ind., Ltd.製造）。 (F) 石夕礙石（wollastonite) Nygl〇s-8 (由 NYCO Minerals Inc.製造）。 範例1至6以及比較範例1至4 表一顯示根據組成物含量的所使用的每一個上述成 分。將聚苯醚樹脂與反應性單體混合，且混合剩餘的成分， 以製備聚苯趟類樹脂組成物。然後，使用在280至3〇〇°c 下加熱的雙螺桿炫融擠出機(twin screw meit_extru(jer)將每 一個組成物熔融揉合(melt-kneaded)，以製成薄片（Chip)。 將薄片在13(TC下乾燥5小時或更久，且接著在8〇至1〇〇 C的模製溫度(m〇iding temperature)下’使用加熱至細 至3〇〇 C的螺旋型注入器（screw type injector)來製造1〇 cm 寬><1〇(^1高\〇.3〇111厚的平坦樣本卬沾叩沈1111邱）〇 表一 20 201100492 jj^xypxii 範例 比較範例 1 2 3 4 5 6 1 2 3 4 (A-1)聚苯酿類樹脂 50 50 50 50 50 50 50 50 50 50 (A)混合樹脂 (wt%) (A-2)聚醯胺樹脂 (wt%) 50 50 50 50 50 50 50 50 50 50 (B)苯乙烯類共聚物樹脂(重量份*) 5 5 5 5 5 5 5 5 5 5 (C)導電添加物(重量份*) (C-1)奈米碳管 0.2 0.3 0.3 - 0.5 - 0.2 0.2 0.3 0.3 (C-2)碳黑 2 1 3 2 - 10 2 2 3 3 (D)雲母(重量份 30 30 30 30 30 30 - 60 - - (E)滑石（重量份*) 30 - (F)矽礦石（重量份*) - - - 30〇 POLYPHENYLENEETHER THERMOPLASTIC RESIN COMPOSITION, METHOD OF PREPARING THE SAME, AND MOLDED PRODUCT USING THE SAME. II. Chinese Abstract: 岣, M,on A polyphenylene ether thermoplastic resin composition comprising (A) mixed resin It comprises (A-1) a polyphenylene ether resin and (A-2) a polyamide resin; (B) a styrene copolymer resin; (C) a conductive additive; and (D) mica. A method of preparing the polyphenylene ether-based thermoplastic resin composition and a molded product using the polyphenylene ether-based thermoplastic resin composition. III. English Abstract: Disclosed are a polyphenyleneether-based thermoplastic resin composition that includes (A) a mixed resin including (Al) a polyphenyleneether-based resin and (A-2) a polyamide resin; (B) a styrene-based copolymer (C) a conductive additive; and (D) mica, a method of preparing the same, and a molded product using the same. 201100492 1 ^uili VI. Description of the invention: [Technical field to which the invention pertains] The present invention is A polyphenyleneether-based thermoplastic resin composition, a process for producing the same, and a molded product using the composition. [Prior Art] A mixture of a poly-bond resin or a polyphenylene bond resin and a polystyrene resin (P〇lystyrene Wf ◎ grease) is widely used in various automobile parts, electrical properties, or the like due to excellent mechanical and electrical properties at high temperatures. The field of electronic parts. However, polyphenylene ether resin has poor chemical resistance and workability. Polyamide resin has good chemical resistance and usability. However, it has poor heat resistance and impact resistance. Therefore, polyamine resin has limitations on the application of engineering plastic resin. The combination of two resins enables chemical and chemical use. In order to provide a conductive resin, a conductive additive (for example, carbon black, carbon fiber, metal powder, metal coating inorganic p0Wder or Metal fiber. However, when the conductive additive added is less than 1% by weight of the resin, sufficient conductivity may not be ensured (dectrical condu) Ctivity), and when a large amount of conductive additive is added, the basic mechanical properties (eg, impact resistance, etc.) of the conductive thermoplastic 201100492 33419pifl can be significantly reduced. '' By adding a carbon nanotube with less I (carbon nanotube) is used as a conductive additive to attempt to provide conductivity to a thermoplastic resin. However, when a single tube is used alone, conductivity is not easily obtained due to poor dispersion, and the same carbon nanotubes and inorganic are used in the same day. In the case of a filler, the impact strength and the electrical conductivity may be lowered. SUMMARY OF THE INVENTION An aspect of the present invention provides a polyphenylene ether-based thermoplastic resin composition which has excellent impact strength, hardness, and electrical conductivity. A balance of properties and creep resistance characteristics. Another aspect of the present invention provides a method for producing a polyphenylene ether-based thermoplastic resin composition. Still another aspect of the present invention provides a polyphenylene ether-based thermoplastic resin composition. A molded product produced. According to an aspect of the invention, a polyphenylene ether-based thermoplastic resin composition is provided, It comprises (A) 100 parts by weight of a mixed resin comprising (Α)) 5 to 95 wt% of a polyether ether resin and (A_2) 5 to 95 wt% of a polyamide resin; Parts by weight of the mixed resin, (B) 1 to 30 parts by weight of a styrene-based copolymer resin; and (〇 0.1 to 30 parts by weight of a conductive additive; and (D)) to 5 parts by weight Mica (mica). The polyether ether resin comprises a polyether ether resin, a mixture of a polyphenylene ether resin and a vinyl aromatic t compound or a modified 201100492 polyphenylene resin (reactive monomer grafted to the monomer) Polyphenylene ether resin). Polyphenylene ether resin includes poly(2,6-dimethyl-l,4-phenylene)ether, poly(2,6-diethyl) --1,4-phenylene) 趟(卩〇1丫(2,6-出6&71-1,4-卩116115^1^^1^1*), poly(2,6_di-propyl) Poly(2,6-dipropyl-l,4-phenylene)ether, poly(2-mercapto-6-ethyl-1,4-phenylene) ether 0 (p〇ly(2-methyl-6_ethyl-l,4-phenylene)ether), poly(2-methyl-6-propyl-1,4-phenylene) ether (poly(2-methyl-6) -propyl-l,4-phenylene)ether, poly(2-ethyl-6-propyl-l,4-phenylene)ether, poly(2) ,6-diphenyl-1,4-phenylene ether (p〇ly(2,6-diphenyl-1,4-plienylene) etlier), poly(2,6-dimercapto-1,4· a copolymer of phenyl)ether and poly(2,3,6-trimethyl-l,4-plienyleiieether), Poly(2,6-diamidino-1,4-phenylene) ether and poly(2,3,6-triethyl-1,4-phenylene) oxime ether (p〇ly(2,3) a copolymer of 6-triethyl-l, 4-phenylene) or a combination thereof. Polyamine resin including polycaprolactam (polycapr) Olactam), poly (l-aminoundecanoic acid) (endo 11), polyduronic acid (polylauryllactam) (Qilong 12), Polyhexamethylene adipamide (Cilong 66), p〇lyhexaethyleneazelamide (and Inchong 69), polyhexaethylene sebacamide (polyhexaethylene sebacamide) Nylon 201100492 33419pifl 610), polyhexaethylene dodecanodiamide (Rilong 612), polyhexamethylene terephthalamide (Tanglong 6T), polybutylene bismuth Polytetramethylene adipamide (Cailong 46), polycaprolactam/polyhexyl-p-guanamine copolymer (Rilong 6/6T), polyhexamethylenediamine/polyhexamethylene Amine copolymer (Rilong 66/6T), polyhexamethylene isophthalamide copolymer (Rilong 66/61), polyhexylamine-p-amine/poly Hexylisodecylamine copolymer (Nylon 6T/6I), polyhexamethylene terephthalamide / poly Polydodecaneamide Copolymer (Nylon 6T/12), Polyhexylhexylenediamine/Polyhexanyl-p-Amine/Polyhexylisodecylamine Copolymer (Nellon 66/6T/6I ), polyxylene adipamide (Nylon MXD6), polyethylene-p-nonylamine/poly-2-methylpentamethylene terephthalamide (Cailong 6T/M5T) ), 才隆10T/1012, polynonamethylene terephthalamide (Cailong 9T), polydecamethylene terephthalamide (Cailong 10T), polyamine 11T (resistant Long 11T), polyamine 12T (Rilong 12T), its copolymer or a combination thereof. The styrenic copolymer resin may include an AB type diblock copolymer, a ruthenium type three-segment copolymer, a radical block copolymer or a combination thereof, and also includes a vinyl aromatic monomer. Copolymer with diene, including hydrogen-added 201100492 unsaturated diene, partially hydrogen-added unsaturated diene or non-hydrogenated Unsaturated two women. The conductive additive may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the mixed resin. The conductive additive includes a carbon nanotube, carbon black, carbon fiber, metal powder, or a combination thereof, and in one embodiment, may include a mixture of a carbon nanotube and carbon black. The carbon nanotubes may be present in an amount of from 0.1 to 3 wt% based on a mixture of carbon nanotubes and carbon black. The carbon nanotubes have a diameter of 0.5 to 100 nm and a length of 0.01 to 100 pm, and the carbon black has an average particle diameter of 20 to 70 μm. The mica includes muscovite, sericite, phlogopite, or a combination thereof, and may have a particle diameter of 1 to 1 μm. Another aspect of the present invention provides a method for producing a polyphenylene ether-based thermoplastic resin composition comprising: obtaining a modified polyphenylene ether resin by mixing a polyphenylene ether resin and a reactive monomer (reactive monomer connection) Branched to polyether ether resin; and mixed modified polyether ether resin, polyamide resin, styrene copolymer resin, conductive additive and mica. The reactive monomer may include an unsaturated carboxylic acid or an anhydride group, and in one embodiment may include citric anhydride, maleic anhydride, and cis-butane. Maleic acid, itaconic anhydride, fumaric acid, (metli)acrylic acid, (meth) acrylate ((meth) )acrylic acid ester) or a combination thereof. 0, 1 to 10 parts by weight of a reactive monomer (based on 1 part by weight of the modified polyphenylene ether resin and polyamine resin) may be added. 201100492 33419pifl Lipid = Remodeling = Widely used polystyrene_Plastic tree Hereinafter, other embodiments will be described in detail. In the case: the polyphenylene ether thermoplastic resin composition of the example has excellent, '歹' impact strength, hardness, electrical conductivity, anti-potential denaturation, etc., = this can be used for the parts of the body (such as the car's fuel door (four) d〇 〇r), A car's anti-fence (fender), etc.). The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] Hereinafter, exemplary embodiments will be described in detail. However, these examples are merely exemplary 'and the invention is not limited thereto. As used herein, when a special definition is not provided, "(indenyl)acrylic" means "acrylic" and "mercaptoacrylic", and "(indenyl)acrylate means "acrylic acid" and " The polyphenylene ether-based thermoplastic resin composition according to an embodiment comprises (A) 100 parts by weight of a polyphenyl mystery resin comprising (A-1) 5 to 95 wt% and (a_2) a mixed resin of 5 to 95 wt% of a polyamide resin; and a polyphenylene ether-based thermoplastic resin composition comprising (B) 1 to 3 parts by weight of a styrene copolymer based on 1 part by weight of the mixed resin (C) 0.1 to 30 parts by weight of a conductive additive; and (D) 1 to 50 parts by weight of mica. Exemplary components contained in the polyphenylene ether-based thermoplastic resin composition according to the examples will be described in detail below. (A) Mixed Resin 201100492 -/-/ ~ ri (Al) Polyphenylene Ether Resin The polyphenylene ether resin according to an embodiment includes a polyether ether resin, a mixture of a polyphenylene ether resin and a vinyl aromatic polymer. Or modified polyphenylene ether resin (including reactive sheets grafted to polyphenylene ether resin) Polyphenylene ether resin includes poly(2,6-dimercapto-1,4-phenylene) ether, poly(2,6-ethylidene-1,4-extension) ether, poly(2, 6-dipropyl-l,4-phenylene) mystery, poly(2_fluorenyl-6-ethyl-1,4-phenylene) ether, poly(2-mercapto-6-propyl 4, 4_Extended phenyl) anthracene ether, poly(2-ethylidene-I,4·phenylene)ether, poly(2,6-diphenyl-fluorene-phenylene) 3⁄4, poly(2) , 6-dimercapto-1,4·phenylene) and copolymer of poly(2,3,6-tridecyl-fluorene-phenylene) ether, poly(2,6-dimethyl^ a copolymer of phenyl phenyl ether and 1 (2,3,6-diethyl-1,4-phenylene) ether or a combination thereof. In one embodiment, preferably poly(2,6) - Dimercapto-1,4_phenylene)ether or poly(2,6-dioxanyl-1,4-phenylene) scale with poly(2,3,6-trimethyl-I, a copolymer of 4-phenylene ether, and in another embodiment, preferably a poly(2,6-diindenyl)-phenylene bond. Vinyl aromatic polymers include vinyl aromatic Polymerization of a monomer (for example, styrene, α-methylstyrene, ρ-mercaptostyrene, 4-N-propyl styrene, etc.) Product, and in an embodiment Preferably, the polymerization product of styrene and the polymerization product of styrene-based styrene. The content of the polyphenylene resin and the vinyl aromatic polymer may be 6 〇 to 99 wt% and 1 to 40 wt%, respectively. The monomer is grafted to the polyphenylene resin to produce a modified polyphenylene resin 'and includes its unsaturated carboxylic acid or anhydride group. Example 9 of the reactive monomer 201100492 may include citrate, cis-succinate, cis-succinic acid, itaconic anhydride, fumaric acid, (meth)acrylic acid, (meth)acrylic acid vinegar or In the combination 'and in the actual addition, citric anhydride is preferred. The acid needle can be used to form a modified polyphenylene-blocking grease without the need for an initiator (initiat〇r). The method of producing the modified polyphenyl ether resin is not particularly limited to 'but the test to the south temperature process' is preferably a melt kneading using a phosphite-based heat stabiHzer ( Grafting under melt-kneading). The content of the reactive monomer may be from 0.1 to 10% by weight based on the total amount of the poly-anthraquinone-based resin. When the content of the reactive monomer is in this range, the polyphenylene ether-based thermoplastic resin composition can have improved compatibility and excellent impact resistance. The degree of polymerization of the polyphenylene ether-based resin is not particularly limited. Considering the thermal stability and workability of the resin composition, the intrinsic viscsity measured in a chloroform solvent at 25 ° C may be 0.2 to 0.8 dl / g. The content of the polyphenylene ether-based resin based on the total amount of the mixed resin including the polyphenylene ether resin and the polyamide resin may be 5 to 95% by weight, and in one embodiment, based on the polyphenylene ether-based resin and the poly The total amount of the mixed resin of the guanamine resin may be from 30 to 70% by weight based on the content of the polyphenylene ether-based resin. When the content of the polyether-based resin is in this range, the polyphenylene ether-based thermoplastic resin composition can have excellent impact resistance by appropriately performing the properties of the polyphenylene resin. (A-2) Polyamide resin 201100492 - 5^4iypiIX According to an embodiment, the polyamide resin is included in the polymer main chain and an amino acid, a lactam or a diamine. The amide-group in the diol-group, and the dicarboxylic acid as a main component is polymerized to provide polyamine. Examples of the amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and ammonia. Paraaminomethylbenzoic acid and the like. Examples of the lactams include ε-caprolactam, ω-12 laurolactam and the like. Examples of the diamine include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, and nonamethylenediamine. , undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2, 4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, para-benzoic acid Paraxylenediamine, 1,3-bis(aminomethyl)cyclohexene (1,3~1^(&111^1011161;1171).>^1〇116\3116), 1,4 - bis(amine oxime) cyclohexane (1,4-1^(&111^1〇11^11丫1)〇7〇1〇1^又&116), 1-amino-3- Aminomethyl-3,5,5-trimethylcyclohexane (1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane), bis(4-201100492 33419pifl Aminocyclohexyl)methyst (bis(4- Aminocyclohexyl)methane), bis(3-indolyl-4-aminocyclohexyl)anthracene (bis (3-methyl-4-aminocyclohexyl)methane), 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl) Aliphatic, alicyclic or aromatic diamines of bis (aminopropyl) piperazine, aminoethylpiperazine and the like. Examples of the dicarboxylic acid include aliphatic, alicyclic or aromatic di-tagacids (e.g., adipic acid, suberic acid, azelic acid, sebacic acid). ), dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-mercapto 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalate, 2,6-naphthalene dioxime Acid (2,6-naphthalenedicarboxylic acid), hexahydroterephthalic acid, hexahydroisophrtialic acid, and the like. A homopolymer or a homopolymer derived from a raw material may be used singly or as a mixture. Polyamine resin includes polycaprolactam (Rilong 6), poly(11-aminoundecanoic acid) (Rilong 11), polydodecanamide (Rilong 12), and polyhexylhexanide Diamine (Rilong 66), Polyhexaethylene decylamine (Rilong 69), Polyhexaethylene quinone II (Cailong 610), 1/, B Liu Yi Shi---------------------------------- ,聚伸己12 201100492 jJH-xypui carbamide (Rilong 6T), poly(butylene hexamethylenediamine (Rilong 46), polycaprolactam/polyhexyl-p-amine copolymer (Nallon 6/6Τ), poly-extension hexamethylenediamine/polyhexyl-p-amine copolymer (Nylon 66/6Τ), polyhexylhexanic acid monoamine/polyhexylisomeric amine Copolymer (Cailong 66/61), poly(hexamethylene)-p-amine/polyhexylisodecylamine copolymer (Nylon 6Τ/6Ι), polyhexyl-p-guanamine/polydodecylamine copolymer (Nallon 6Τ/12), polyhexylhexamethylenediamine/polyhexyl-p-amine/polyamine-isohexylamine copolymer (Hylon 66/6Τ/6Ι), polyarylamine ( Nylon MXD6), poly(extension)-p-amine/poly-2-indolyl-pentyl-p-amine copolymer (Nylon 6Τ/Μ5Τ), Nylon 10Τ/1012, poly-extension酞醯 酞醯 ( 耐 耐 耐, 聚 酞醯 酞醯 酞醯 ( ( 耐 耐 耐 耐 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 、 、 、 、 、 、 、 、 、 、 、 . The copolymers include Cailong 6/610, Nylon 6/66, Nylon 6/12 and the like. The polyamide resin has a melting point of 250 ° C or higher, a relative viscosity of 2 or higher (measured at 25 ° C, and 1 wt% in m-cresol) Polyamide resin). When the melting point and the relative viscosity 〇 are in the above range, the mechanical properties and heat resistance of the polyphenylene ether-based thermoplastic resin composition can be improved. The content of the polyamide resin may be 5 to 95% by weight based on the total amount of the mixed resin including the polyphenylene ether resin and the polyamide resin, and in one embodiment, based on the polyphenylene ether resin and polyfluorene. The total amount of the mixed resin of the amine resin, the content of the polyamide resin may be from 30 to 70% by weight. When the content of the polyamide resin is in this range, excellent compatibility with the polyphenylene ether resin can be obtained. 13 201100492 33419pifl (B) Styrene-based copolymer resin, according to the examples, the styrene-based copolymer resin derived from the ethylene-based aromatic monomer may be AB ^ difilament, aba mad block copolymer, Free radical block copolymer or a combination thereof. The inlaid & co-named material may be a copolymer of a vinyl aromatic monomer and a diene comprising a hydrogenated unsaturated diene, a partially hydrogenated unsaturated dilute or an unsaturated unsaturated dilute. The vinyl aromatic monomer may include styrene, p-methyl phenyl ethene, α-methyl styrene, 4-fluorenyl propyl styrene, and the like, and in one embodiment, is preferably stupid ethylene, Α-methyl styrene and the like. These monomers may be used singly or as a mixture. ΑΒ-type diblock copolymers include polybutadiene-polybutadiene copolymers, poly-benzidine-pyrene (p〇iyjs〇prene), t CK-methyl-B A polyalphamethylstyrene-polybutadiene copolymer or a copolymer of hydrogen added to a copolymer. Type AB diblock copolymers are well known in the art. Examples of the AB type diblock copolymer include Solprene and K-resin manufactured by Phillips and Kraton D and Kraton G manufactured by Shell Chemical. ΑΒΑ-type triblock copolymers include polystyrene-polybutadiene-polystyrene (SBS) copolymers, polystyrene-polyisoprene-polystyrene (SIS) copolymers, poly(fluorenyl phenyl) A dilute polybutylene-poly-α-methylstyrene copolymer, a polydecylstyrene-polyisoprene-poly-α-mercapto ethylene copolymer or a copolymer of hydrogen added to a copolymer. Anthracene triblock copolymers are well known in the commercial art. Examples of the metamorphic two-stage copolymer include Cariflex, Kraton D and Kraton G manufactured by Shell 14 201100492 chemical, Septon manufactured by Kuraray Co., Ltd., and the like. The content of the styrene-based copolymer resin may be 1 to 30 parts by weight based on 100 parts by weight of the mixed resin of the polyphenylene ether-based resin and the polyamide resin, and in one embodiment, based on 100 parts by weight of the polyphenylene ether The mixed resin of the resin-like resin and the polyamide resin may be contained in an amount of from 1 to 1 part by weight based on the styrene-based copolymer resin. When the content of the styrene-based copolymer resin is in this range, the impact resistance is remarkably increased 'and the excellent compatibility of the polyphenylene ether-based resin with the polyamide resin is not lowered. (C) Conductive Additive According to an embodiment, the conductive additive may comprise a carbon nanotube, carbon black, carbon fiber, metal powder or a combination thereof, and in another embodiment, preferably a carbon nanotube and carbon black mixture. The carbon nanotubes have excellent mechanical strength and mechanical properties (such as high Young's Modulus and aspect ratio), electrical conductivity and thermal stability. When a nanotube tube is used to make a polymer composition, a carbon nanotube-polymer composition having improved mechanical, thermal and electrical properties can be obtained. Methods for synthesizing carbon nanotubes include arc discharge (disclysis), pyrolysis, plasma enhanced chemical vapor deposition (PECVD), and chemical vapor deposition (chemical vapor deposition). CVD), eiectrolysis, etc., and in one embodiment, the resulting carbon nanotubes can be used regardless of the method of synthesis. ' 15 201100492 33419pifl Depending on the number of walls, the carbon nanotubes can be divided into single-walled carbon nanotubes, double-walled nanoparticles, ε carbon tubes and multi-walls (multi -walled) carbon nanotubes. In one embodiment, a multi-walled carbon nanotube is preferred, but is not limited thereto. The size of the carbon nanotubes is not particularly limited, and the carbon nanotubes may have a diameter of 〇.5 to 100 nm and a length of 0.01 to 100 μm, and in one embodiment, the carbon nanotubes may have 1 to 10 nm. The diameter is 0.5 to 1 〇 μιη length. When the diameter and length of the carbon nanotubes are in this range, the conductivity and workability can be improved. In addition, due to such a large size, the carbon nanotubes have a large aspect ratio (L/D). When a carbon nanotube having an L/D of 100 to 1,000 is used, the conductivity can be improved. The carbon black may be any conductive carbon black without limitation, and includes graphitized carbon, furnace black, acetylene black, ketjen black, and the like. The conductive carbon black has an average particle diameter of 20 to 70 μm, and the oil absorption can be regarded as carbon black when it is adjusted from JIS K 5101 to 100 to 600 mO100g. When the average particle diameter of the black is in this range, excellent conductivity can be achieved. When the carbon nanotubes are mixed with carbon black, the content of the carbon nanotubes may be from 0.1 to 3 wt% based on the total amount of the mixture of the carbon nanotubes and the carbon black. . When the content of the carbon nanotubes is in this range, a suitable electro-percolation can be achieved by this small amount of addition to conduct electricity, and mechanical strength (for example, excellent tensile strength) can be maintained. ) with heat resistance. 16 201100492 The content of the conductive additive may be from 1 to 3 parts by weight based on 100 parts by weight of the mixed resin including the polyphenylene ether resin and the polyamide resin, and in one embodiment, based on 1 part by weight The mixture includes a mixed resin of a polyphenylene ether resin and a polyamide resin, and the conductive additive may be contained in an amount of from 〇丨 to 1 part by weight. When the content of the conductive additive is in this range, the polyphenylene ether-based thermoplastic resin composition can have excellent electrical conductivity and financial impact resistance. (D) Mica 0 According to an embodiment, mica may include muscovite, sericite, phlogopite and the like regardless of the species. These mica can be used alone or in a mixture thereof. The mica may have a particle diameter of 1 to 100 μm. When using mica in this range, excellent creep resistance can be obtained. The mica may be contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the mixed resin of the polystyrene resin and the polyamide resin, and in one embodiment, based on 100 parts by weight of the polyphenylene ether resin and the polyfluorene The mixed resin of the amine resin may have a mica content of 10 to 40 parts by weight. When the content of mica is in this range, the polyphenylene ether-based thermoplastic resin composition can have excellent hardness and impact resistance. According to an embodiment, the polyphenylene ether-based thermoplastic resin composition may further include an additive. The additive may include an anti-drip agent, a light stabilizer, a pigment, a dye, or a combination thereof, depending on the purpose of use. The content of the additive may be 0.1 to 30 parts by weight based on 1 part by weight of the mixed resin of the polyphenylene ether resin and the polyamide resin. When the content of the additive is in this range, 17 201100492 33419pifl can be obtained to the effect of the additive depending on the purpose, and excellent mechanical properties and C surface appearance can be obtained. The above polyphenylene ether-based thermoplastic resin composition can be produced by a generally known method. For example, the above ingredients are mixed with the selected additive and melt-extruded in an extruder to form a pellet. In another embodiment, the polystyrene-based thermoplastic resin composition grafts the reactive monomer to the polyphenylene ether by knowing the modified polyphenylene ether resin (mixing the polyphenylene ether resin and the reactive monomer) Resin) and a modified polyether ether oxime resin, a polyamide resin, a stray ethylene copolymer resin, and a conductive additive are mixed with mica. 〃 The reactive monomer can be the same as described above. The content of the reactive monomer may be from 〇丨 to 1 〇 by weight based on 100 parts by weight of the modified polyphenylene ether resin and the polyamide resin, and in the embodiment, based on 100 parts by weight of the modified The polystyrene resin and the polyamine-resin may have a reactive monomer content of from 0.1 to 5 parts by weight. When the content of the reactive monomer is in this range, the polyphenylene ether-based thermoplastic resin composition ❹ can have improved compatibility and excellent impact resistance. The modified polyphenylene ether resin can be prepared by melt-kneading using a phosphate-based heat stabilizer in consideration of a high operating temperature. According to still another embodiment, a molded product produced using a polyphenylene ether-based thermoplastic resin composition is provided. The polyphenylene ether thermoplastic resin composition can be applied to molded products (such as automobile fuel fillers, automobile protective sheets, etc.) that are extremely in need of impact strength, hardness, electrical conductivity, and resistance to latent denaturation. Hereinafter, embodiments will be described in more detail with reference to examples. However, the following is an exemplary embodiment and is not intended to limit the invention. (Example) According to an embodiment, the polyphenylene ether-based thermoplastic resin composition includes the following 0 components. (A) Mixed resin (A-1) polyphenylene ether resin GE plastic HPP-820 (poly(2,6-dimethyl-1,4-phenylene)) which is a poly-bond resin (manufactured by Plastics Ltd.) mixed with citric anhydride (manufactured by Samchun Pure Chemical Ltd.) as a reactive monomer, and then using a modified polyphenylene ether resin (by grafting a reactive monomer to poly Obtained from phenyl ether resin). The content of the reactive monomer is 1 wt% based on the total amount of the polyphenylene ether resin. ® (A_2) Polyamide Resin Resin 66 VYDYNE 50BW (manufactured by Solutia Inc.) was used. (B) Styrene-based copolymer resin G1651 (manufactured by Shell Co., Ltd.) using a poly(styrene-ethylene-butadiene) triblock copolymer (C) Conductive additive 19 201100492 33419pifl (Cl) use A C-tube 100 (manufactured by CNT Co., Ltd.) of a multi-walled carbon nanotube having a diameter of 10 to 50 nm and a length of 1 to 25 μm was used as a carbon nanotube. (C-2) Using Timrex, KS 5-75TT (manufactured by Timcal Ltd.) as the black (D) mica, M-325 (manufactured by KOCH Co., Ltd.) was used. (E) Talc (talc) UPN HS_T 0.5 (manufactured by HAYASHI Pure Chemical Ind., Ltd.) was used. (F) Wollastonite Nygl〇s-8 (manufactured by NYCO Minerals Inc.). Examples 1 to 6 and Comparative Examples 1 to 4 Table 1 shows each of the above components used in accordance with the content of the composition. The polyphenylene ether resin is mixed with a reactive monomer, and the remaining components are mixed to prepare a polyphenylene-based resin composition. Then, each of the compositions was melt-kneaded using a twin screw meit_extru (jer) heated at 280 to 3 ° C to form a chip. The sheet was dried at 13 (TC for 5 hours or longer, and then at a molding temperature of 8 Torr to 1 〇〇C) using a spiral type injector heated to a fineness of 3 〇〇C (screw type injector) to make 1〇cm width><1〇(^1高\〇.3〇111 thick flat sample 卬 叩 11 1111 Qiu) 〇表一20 201100492 jj^xypxii Example comparison example 1 2 3 4 5 6 1 2 3 4 (A-1) Polyphenylene-based resin 50 50 50 50 50 50 50 50 50 50 (A) Mixed resin (wt%) (A-2) Polyamide resin (wt% 50 50 50 50 50 50 50 50 50 50 (B) Styrene-based copolymer resin (parts by weight *) 5 5 5 5 5 5 5 5 5 5 (C) Conductive additive (parts by weight *) (C-1 ) Carbon nanotubes 0.2 0.3 0.3 - 0.5 - 0.2 0.2 0.3 0.3 (C-2) Carbon black 2 1 3 2 - 10 2 2 3 3 (D) Mica (parts by weight 30 30 30 30 30 30 - 60 - - ( E) talc (parts by weight *) 30 - (F) bismuth ore (parts by weight *) - - - 30 Ο *重量份：表示含量單位，基於10〇重量份的混合樹脂A。 (實驗範例） 在以下方法中’根據特性’對範例1至6與比較範例 1至4的樣本進行評價。評價結果提供於表二中。 ⑴缺口衝擊強度(Notch IZ0d Impact strength) ASTMI^256來對1/8，，厚的樣本進行評價。 撼料!η曲拉數(fiexurai _uius):使用 as™ D79〇，根 據号曲拉數來對1/4”厚的樣本進行評價。 21 201100492 33419pifl ⑺片電阻(sheet resistance):藉由施加loo v的電壓以 及使用4-探針法(4-probe method)來對樣本進行評價。 (4)潛變伸長量(creep displacement):根據 ASTM 2990 聋曲潛變測量標準(flexural creep measuring standard)，在 90 C的溫度下5〇小時，根據伸長量來對i/4”厚的樣本進 行評價。 表二 範例 比較範例 1 2 3 4 5 6 1 2 3 4 衝擊強度 (kgf · cm/cm) 7.2 6.5 6.3 12.2 7.6 12.8 18.2 3.5 5.5 5.4 彎曲模數 (kgfi^cm2) 36,500 41,200 42,100 36,200 36,500 43,600 22,100 50,100 35,400 34,800 片電阻 (Ω/sq.) 1011 1011 1011 1011 1011 1010 1010 1010 1012 1011 潛變伸長量 (mm) 1.7 1.7 1.8 1.7 1.8 1.6 4.2 1.6 2.4 3.2 22 201100492 33419pifl 根據表一與表二，根據一實施例，與無雲母的比較靶 例1、包括雲母但在實施例的範圍外的比較範例2以及包 括滑石或矽礦石而非雲母的比較範例3、4相比，範例1 至6具有優異的特性平衡(例如衝擊強度、硬度、導電性與 抗潛變性；）。 特別地，無雲母的比較範例1顯示降低的硬度與抗潛 變性’且使用雲母但在實施例的範圍外的比較範例2顯示Ο *parts by weight: indicates a content unit based on 10 parts by weight of the mixed resin A. (Experimental Example) The samples of Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated 'by characteristics' in the following methods. The evaluation results are provided in Table 2. (1) Notch IZ0d Impact strength ASTMI^256 was used to evaluate a 1/8, thick sample. !!! ex曲拉数(fiexurai _uius): Use asTM D79〇 to evaluate 1/4” thick samples according to the number of tens. 21 201100492 33419pifl (7) sheet resistance: by applying loo The voltage of v and the 4-probe method are used to evaluate the sample. (4) creep displacement: according to ASTM 2990 flexural creep measuring standard, At a temperature of 90 C for 5 hours, an i/4" thick sample was evaluated based on the amount of elongation. Table 2 Example comparison example 1 2 3 4 5 6 1 2 3 4 Impact strength (kgf · cm/cm) 7.2 6.5 6.3 12.2 7.6 12.8 18.2 3.5 5.5 5.4 Flexural modulus (kgfi^cm2) 36,500 41,200 42,100 36,200 36,500 43,600 22,100 50,100 35,400 34,800 piece resistance (Ω/sq.) 1011 1011 1011 1011 1011 1010 1010 1010 1012 1011 creep elongation (mm) 1.7 1.7 1.8 1.7 1.8 1.6 4.2 1.6 2.4 3.2 22 201100492 33419pifl According to Table 1 and Table 2, according to one implementation For example, examples 1 to 6 have superior characteristics compared to non-mica comparison target 1, comparative example 2 including mica but outside the scope of the examples, and comparative examples 3 and 4 including talc or strontium ore rather than mica. Equilibrium (eg impact strength, hardness, electrical conductivity and anti-potential denaturation;). In particular, Comparative Example 1 without mica showed reduced hardness and anti-submergence' and Comparative Example 2 showing the use of mica but outside the scope of the examples 降低的衝擊強度。此外，使用滑石或矽礦石而非雲母的比 較範例3、4顯示降低的衝擊強度與抗潛變性。 帝因此，使用與苯乙烯類共聚物樹脂、導電添加物以及 π,混合的聚苯醚類樹脂與聚醯胺樹脂的混合樹脂的實施 ϋΙΖί優異的特性(例如衝擊強度、硬度、導電性與抗 潛變性等等）。 例時，其被理解示例性實施 在以下的”/所揭露的實關，相反地， 同的配置3 精神與觀點中翻各種修改與相 任何4二本;:實施例應被理解為示例_^ 【圖式簡單說明】 #、、、 【主要元件符號說明】 益 23 V?* 201100492 334iypitl 修正曰期·. 99年4月27日 爲第98145795號中文專利說明書無割線修正本 發明專利說明書 ※記號部分請勿填寫） (本說明書格式、順序，請勿任意更動 ※申請案號： s.i〇06,ap ※申請日： ※工卩匸分類：(Ti0L % 一、發明名稱：（中文/英文） 〇2L % 聚苯醚熱塑性樹脂組成物、製備此組成物的方法以及 使用此組成物的模製產品 丨Reduced impact strength. In addition, Comparative Examples 3 and 4 using talc or strontium ore rather than mica showed reduced impact strength and resistance to latent denaturation. Therefore, the use of a mixed resin of a polyphenylene ether resin and a polyamide resin mixed with a styrene copolymer resin, a conductive additive, and π is excellent in properties (for example, impact strength, hardness, electrical conductivity, and resistance). Stagnation, etc.). For example, it is understood that the exemplary implementation is implemented in the following "/ disclosed, and conversely, the same configuration 3 spirit and viewpoints are various modifications and any four copies; the embodiment should be understood as an example _ ^ [Simple diagram description] #,,, [Description of main component symbols] 益23 V?* 201100492 334iypitl Revision period. Do not fill in the mark part. (The format and order of this manual should not be changed. ※Application number: si〇06,ap ※Application date: ※Work classification: (Ti0L % I. Invention name: (Chinese / English) 〇 2L % polyphenylene ether thermoplastic resin composition, method of preparing the same, and molded product using the same 〇 POLYPHENYLENEETHER THERMOPLASTIC RESIN COMPOSITION, METHOD OF PREPARING THE SAME, AND MOLDED PRODUCT USING THE SAME. 嫌ή 二、 中文發明摘要： 岣从 ，M,on 一種聚苯醚類熱塑性樹脂組成物，其包括(A)混合樹 脂，其包括(A_l)聚苯醚類樹脂與(A-2)聚醯胺樹脂；（B)苯 乙烯類共聚物樹脂；（C)導電添加物；以及(D)雲母。一種 製備此聚苯醚類熱塑性樹脂組成物的方法以及使用此聚苯 醚類熱塑性樹脂組成物的模製產品。 三、英文發明摘要： Disclosed are a polyphenyleneether-based thermoplastic resin composition that includes (A) a mixed resin including (A-l) a polyphenyleneether-based resin and (A-2) a polyamide resin; (B) a styrene-based copolymer resin; (C) a conductive additive; and (D) mica, a method of preparing the same, and a molded product using the same. 201100492 33419ρίΩ 七、申請專利範圍： 1‘一種聚笨醚類熱塑性樹脂組成物’包括： (Α) 100重量份的混合樹脂，所述混合樹脂包括(Α-1) 5 至95 wt%的聚苯醚類樹脂與(Α_2) 5至95 wt%的聚醯胺樹 脂； 基於100重量份的所述混合樹脂， (B) 1至30重量份的苯乙烯類共聚物樹脂； (C) 0,1至30重量份的導電添加物；以及 (D) 1至50重量份的雲母。 2. 如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物，其中所述聚苯醚類樹脂包括聚苯醚樹脂、聚苯 醚樹脂與乙烯基芳族聚合物的混合物或反應性單體接枝至 聚苯it樹脂的經改質的聚苯醚樹脂。 3. 如申請專利範圍第2項所述之聚苯醚類熱塑性樹 脂組成物，其中所述聚苯醚樹脂包括聚(2,6-二曱基-1，4-伸 苯基)醚、聚(2,6-二乙基-1，4-伸苯基)醚、聚(2,6-二丙基-1，4. 伸苯基)醚、聚(2-曱基-6-乙基-1，4-伸苯基)醚、聚(2-甲基_6_ 丙基-1,4-伸苯基)醚、聚(2-乙基-6-丙基-1,4-伸苯基)醚、聚 (2,6-二苯基-I，4·伸苯基)謎、聚(2,6·二曱基-I，4-伸苯基)鲢與 聚(2,3,6-三曱基-1，4-伸苯基）醚的共聚物、聚(2,6-二甲基 -1,4-伸苯基)醚與聚(2,3,6-三乙基-1,4-伸苯基)醚的共聚物 或其組合。 4·如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物，其中所述聚醯胺樹脂包括聚己内醯胺(耐隆6)、 24 201100492 33419pifl 聚(11·胺基十一酸)(耐隆11)、聚十二内醯胺(耐隆12)、聚 伸，己基己二醯二胺（耐隆66)、聚六乙烯壬二醯胺（耐隆 69)、聚六乙稀癸二醯胺(耐隆610)、聚六乙稀十二二酿胺 (耐隆612)、聚伸己基對酞醯胺(耐隆6Τ)、聚伸丁基己二 醯二胺（耐隆46)、聚己内醯胺/聚伸己基對酞醯胺共聚物 (耐隆6/6Τ)、聚伸己基己二醯二胺/聚伸己基對酞醯胺共聚 物(耐隆66/6Τ)、聚伸己基己二醯二胺/聚伸己基異酞醯胺 〇 共聚物（耐隆66/61)、聚伸己基對酞醯胺/聚伸己基異酞醯 胺共聚物(财隆6Τ/6Ι)、聚伸己基對駄醯胺/聚十二醯胺共 聚物(财隆6Τ/12)、聚伸己基己二醯二胺/聚伸己基對敌醯 胺/聚伸己基異酞醯胺共聚物（耐隆66/6Τ/6Ι)、聚芳醯胺 (耐隆MXD6)、聚伸己基對酞醯胺/聚2-曱基伸戊基對酞醯 ' 胺共聚物(耐隆6Τ/Μ5Τ)、耐隆10Τ/1012、聚伸壬基對酞 、 酿胺(对隆9Τ)、聚伸癸基對敌酿胺(耐隆10Τ)、聚醯胺11Τ (耐隆11Τ)、聚醢胺12Τ (耐隆12Τ)、其共聚物或其組合。 〇 5.如申請專利範圍第1項所述之聚苯醚類熱塑性樹 脂組成物’其中所述苯乙烯類共聚物樹脂包括ΑΒ型二嵌 段共聚物、ΑΒΑ型三嵌段共聚物、自由基嵌段共聚物或其 多且合。 6.如申睛專利範圍第丨項所述之聚苯醚類熱塑性樹 ，組成物，其中所述苯乙烯類共聚物樹脂包括乙烯基芳族 單體與二烯的共聚物，所述二烯包括加氫的不飽和二烯、 部分加氫的不飽和二烯或不加氫的不飽和二烯。 25 201100492 33419pifl 7·如申請專利範圍第1項所述之聚苯醚類熱塑性樹 月㈢組成物，其中基於1〇〇重量份的所述混合樹脂，所述導 電添加物的含量為0.1至1〇重量份。 8_如申請專利範圍第i項所述之聚苯醚類熱塑性樹 月曰組成物’其中所述導電添加物包括奈米碳管、破黑、石展 織維、金屬粉末或其組合。 9. 如申請專利範圍第1項所述之聚苯醚類熱塑性樹 月曰組成物，其中所述導電添加物包括奈米碳管與破黑的滿 合物。 10. 如申明專利範圍弟9項所述之聚苯鱗類熱塑性樹 脂組成物，其中基於所述奈米碳管與所述碳黑的混合物的 總量，所述奈米碳管的含量為αι至3 wt%。 11. 如申請專利範圍第8項所述之聚苯醚類熱塑性樹 月曰組成物，其中所述奈米碳管的直徑為〇 5至^⑻，長 度為 0.01 至 100 μιη。 I2·如申5Η專利8項所述之聚笨謎類熱塑性樹 脂組成物，其中所述碳黑的平均粒徑為20至70卜111。 13. 如申$專利範圍第丨項所述之聚苯剛貞熱塑性樹 脂組成物，其中所述雲母包括白雲母、竭雲母、金雲母或 其組合，且所述雲母的粒徑為丨至1〇〇 μιη。 14. -種聚苯咱熱塑性樹驗成物的製造方法，包 括： 26 201100492 33419pifl 藉由將聚苯醚樹脂與反應性單體混合，取得所述反應 性單體接枝至所述聚苯醚樹脂的經改質的聚苯醚樹脂；以 及 將所述經改質的聚苯醚樹脂、聚醯胺樹脂、苯乙烯類 共聚物樹脂、導電添加物與雲母混合。 15.如申請專利範圍第14項所述之聚苯醚類熱塑性 樹脂組成物的製造方法’其中所述反應性單體包括不飽和 〇 羧酸或其酐基。 16·如申請專利範圍第14項所述之聚苯醚類熱塑性 樹脂組成物的製造方法，其中所述反應性單體包括檸檬酸 酐、順丁烯二酸酐、順丁烯二酸、衣康酸酐、反丁烯二酸、 (曱基)丙烯酸、（甲基)丙烯酸酯或其組合。 ' 丨7.如申請專利範圍第14項所述之聚苯醚類熱塑性 ‘ 树知組成物的製造方法，其中基於100重量份的所述經改 貝的聚苯醚樹脂與所述聚醯胺樹脂，所述反應性單體的添 加量為0.1至10重量份。 〇 18. —種使用如申請專利範圍第1至13項中任一項所 述之聚苯醚類熱塑性樹脂組成物製造的模製產品。 27 201100492 33419pifl 四、指定代表圖： (一） 本案之指定代表圖：無 (二） 本代表圖之元件符號簡單說明： 無 五、本案若有化學式時，請揭示最能顯示發明特徵 的化學式： 無〇 POLYPHENYLENEETHER THERMOPLASTIC RESIN COMPOSITION, METHOD OF PREPARING THE SAME, AND MOLDED PRODUCT USING THE SAME. II. Chinese Abstract: 岣, M,on A polyphenylene ether thermoplastic resin composition comprising (A) mixed resin It comprises (A-1) a polyphenylene ether resin and (A-2) a polyamide resin; (B) a styrene copolymer resin; (C) a conductive additive; and (D) mica. A method of preparing the polyphenylene ether-based thermoplastic resin composition and a molded product using the polyphenylene ether-based thermoplastic resin composition. III. English Abstract: Disclosed are a polyphenyleneether-based thermoplastic resin composition that includes (A) a mixed resin including (Al) a polyphenyleneether-based resin and (A-2) a polyamide resin; (B) a styrene-based copolymer (C) a conductive additive; and (D) mica, a method of preparing the same, and a molded product using the same. 201100492 33419ρίΩ VII. Patent application scope: 1 'a polyether ether type thermoplastic resin composition' The method comprises: (Α) 100 parts by weight of a mixed resin comprising (Α-1) 5 to 95 wt% of a polyphenylene ether resin and (Α_2) 5 to 95 wt% of a polyamide resin; Parts by weight of the mixed resin, (B) 1 to 30 parts by weight of a styrenic copolymer resin; (C) 0, 1 to 30 parts by weight of a conductive additive; and (D) 1 to 50 parts by weight of mica . 2. The polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the polyphenylene ether resin comprises a polyphenylene ether resin, a mixture or reaction of a polyphenylene ether resin and a vinyl aromatic polymer. The modified monomer is grafted to a modified polyphenylene ether resin of polyphenylene resin. 3. The polyphenylene ether-based thermoplastic resin composition according to claim 2, wherein the polyphenylene ether resin comprises poly(2,6-dimercapto-1,4-phenylene) ether, poly (2,6-Diethyl-1,4-phenylene)ether, poly(2,6-dipropyl-1,4.phenylene)ether, poly(2-mercapto-6-ethyl) -1,4-phenylene ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-benzene) Ether, poly(2,6-diphenyl-I,4·phenylene) mystery, poly(2,6·didecyl-I,4-phenylene)anthracene and poly(2,3, Copolymer of 6-trimethyl-1,4-phenylene ether, poly(2,6-dimethyl-1,4-phenylene) ether and poly(2,3,6-triethyl) a copolymer of -1,4-phenylene)ether or a combination thereof. 4. The polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the polyamidamide resin comprises polycaprolactam (Rilong 6), 24 201100492 33419pifl poly(11. Amino-10) Monoacid) (Rilong 11), polydodecanamide (Rilong 12), poly-stretching, hexylhexamethylenediamine (Rilong 66), polyhexamethylenediamine (Rilong 69), poly Hexaethylene diamine (Rilong 610), polyhexaethylene diuret (Rilong 612), polyhexylamine phthalamide (Rilong 6Τ), poly(butylene hexamethylenediamine) (Rilong 46), polycaprolactam/polyhexyl-p-amine copolymer (Nylon 6/6Τ), polyhexylhexamethylenediamine/polyhexyl-p-amine copolymer (Nylon 66/6Τ), polyhexylhexamethylenediamine/polyhexylisodecylamine copolymer (Rilong 66/61), polyhexyl-p-guanamine/polyhexylisodecylamine copolymer (财隆6Τ/6Ι), poly-extension-p-amine/poly-dodecylamine copolymer (Cailong 6Τ/12), poly-extension hexamethylenediamine/polyhexyl group to carbamide/polyhexyl Isodecylamine copolymer (Nylon 66/6Τ/6Ι), polyarylamine (Nylon MXD6), and stretching Hexyl-p-amine/poly-2-indenyl-pentyl-p-anthracene amine copolymer (Nylon 6Τ/Μ5Τ), Nylon 10Τ/1012, polythene-based ruthenium, lanthanide (on-column 9Τ), poly癸 癸 对 敌 敌 敌 敌 敌 耐 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 敌 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The polyphenylene ether-based thermoplastic resin composition as described in claim 1, wherein the styrene-based copolymer resin comprises a fluorene-type diblock copolymer, a hydrazine-type triblock copolymer, and a radical Block copolymers or multiple combinations thereof. 6. The polyphenylene ether-based thermoplastic tree according to the above aspect of the invention, wherein the styrene-based copolymer resin comprises a copolymer of a vinyl aromatic monomer and a diene, the diene These include hydrogenated unsaturated dienes, partially hydrogenated unsaturated dienes or non-hydrogenated unsaturated dienes. The polyphenylene ether-based thermoplastic tree (III) composition according to claim 1, wherein the conductive additive is contained in an amount of 0.1 to 1 based on 1 part by weight of the mixed resin. 〇 by weight. 8_ The polyphenylene ether-based thermoplastic tree of the invention of claim i wherein the conductive additive comprises a carbon nanotube, a blackened stone, a stone-stretched metal, a metal powder or a combination thereof. 9. The polyphenylene ether thermoplastic tree composition according to claim 1, wherein the conductive additive comprises a carbon nanotube and a blackened solid. 10. The polyphenylene-based thermoplastic resin composition according to claim 9, wherein the content of the carbon nanotubes is α1 based on the total amount of the mixture of the carbon nanotubes and the carbon black. Up to 3 wt%. 11. The polyphenylene ether thermoplastic tree composition according to claim 8, wherein the carbon nanotubes have a diameter of from 5 to (8) and a length of from 0.01 to 100 μm. The poly-mystery thermoplastic resin composition of claim 8, wherein the carbon black has an average particle diameter of 20 to 70 bl 111. 13. The polyphenylanthracene thermoplastic resin composition according to the above aspect of the invention, wherein the mica comprises muscovite, eutropha, phlogopite or a combination thereof, and the mica has a particle size of 丨1 to 1 〇〇μιη. 14. A method for producing a polyphenylene hydrazine thermoplastic tree test comprising: 26 201100492 33419pifl by grafting a polyphenylene ether resin with a reactive monomer to obtain grafting of the reactive monomer to the polyphenylene ether a modified polyphenylene ether resin of a resin; and mixing the modified polyphenylene ether resin, a polyamide resin, a styrene copolymer resin, and a conductive additive with mica. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 14, wherein the reactive monomer comprises an unsaturated hydrazine carboxylic acid or an anhydride group thereof. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 14, wherein the reactive monomer comprises citric anhydride, maleic anhydride, maleic acid, itaconic anhydride , fumaric acid, (meth)acrylic acid, (meth) acrylate or a combination thereof. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 14, wherein 100 parts by weight of the modified polyphenylene ether resin and the polyamine are used. The resin, the reactive monomer is added in an amount of 0.1 to 10 parts by weight. A molded product produced by using a polyphenylene ether-based thermoplastic resin composition as described in any one of claims 1 to 13. 27 201100492 33419pifl IV. Designated representative map: (1) The designated representative figure of the case: None (2) The symbolic symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: no
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