TW201331287A - Thermoplastic resin composition and thermoplastic molded article thereof - Google Patents
Thermoplastic resin composition and thermoplastic molded article thereof Download PDFInfo
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Abstract
Description
本發明是有關於一種熱塑性樹脂組成物(thermoplastic resin composition),其可具有極佳的阻燃性(flame retardancy)、染色性(colorability)以及熱穩定性(thermal stability)。 The present invention relates to a thermoplastic resin composition which has excellent flame retardancy, colorability, and thermal stability.
一般而言,橡膠改質苯乙烯系共聚物樹脂可具有好的機械強度(mechanical strength)、加工性(processability)、極佳的耐衝擊強度(impact strength)以及好的外觀(appearance),並且因此廣泛地用於電器以及電子商品的製造。然而,橡膠改質苯乙烯系共聚物樹脂不具有抗燃燒性(combustion resistance),並且如果其被點燃,則橡膠改質苯乙烯系共聚物樹脂可能導致火焰蔓延。 In general, the rubber-modified styrenic copolymer resin can have good mechanical strength, processability, excellent impact strength, and good appearance, and thus Widely used in the manufacture of electrical appliances and electronic goods. However, the rubber-modified styrene-based copolymer resin does not have a combustion resistance, and if it is ignited, the rubber-modified styrene-based copolymer resin may cause flame spread.
因此,多個國家,例如美國、日本以及許多歐洲的國家,已通過要求聚合物樹脂去滿足耐燃性(flame resistance)標準以保證於火焰存在下的安定性的法律。 Therefore, many countries, such as the United States, Japan, and many European countries, have passed laws that require polymer resins to meet flame resistance standards to ensure stability in the presence of flame.
各種各樣的技術可給予聚合物阻燃性。例如,許多傳統上使用的以及廣為人知的阻燃的方法為加入阻燃劑(flame retardant)至聚合物樹脂。這些添加劑型阻燃劑可依照其組成成分而分類,而且包括含鹵素、含磷、含氮、含矽酮(silicone)、含無機材料阻燃劑及其類似阻燃劑。 A wide variety of techniques can impart flame retardancy to the polymer. For example, many conventionally used and well known flame retardant methods involve the addition of a flame retardant to a polymeric resin. These additive type flame retardants can be classified according to their constituents, and include halogen-containing, phosphorus-containing, nitrogen-containing, silicone-containing, inorganic-containing flame retardants, and the like.
用於給予橡膠改質苯乙烯系共聚物樹脂耐燃性的廣泛使用的方法為加入含鹵素阻燃劑以及銻化合物(antimony compound)至樹脂。例如,一種如此的方法藉由以2.5:1至4:1的重量比加入含鹵素阻燃劑以及銻化合物而給予丙烯腈-丁二烯-苯乙烯(acrylonitrile-butadiene-styrene,ABS)樹脂或耐衝擊性聚苯乙烯(high impact polystyrene,HIPS)樹脂阻燃性。 A widely used method for imparting flame resistance to a rubber-modified styrene-based copolymer resin is to add a halogen-containing flame retardant and an antimony compound to the resin. For example, one such method imparts acrylonitrile-butadiene-styrene (ABS) resin by adding a halogen-containing flame retardant and a cerium compound in a weight ratio of from 2.5:1 to 4:1. High impact polystyrene (HIPS) resin flame retardant.
當使用三氧化二銻作為銻化合物時,則白色無機材料的三氧化二銻劣化樹脂組成物的染色性。尤其,提供最後產品(end product)黑色外觀會是困難的。而且,由於與含鹵素阻燃劑反應,因此於高注射溫度使用銻化合物可能產生褪色(discoloration)以及脫氣(out-gas)。 When antimony trioxide is used as the antimony compound, the antimony trioxide of the white inorganic material deteriorates the dyeability of the resin composition. In particular, it can be difficult to provide a black appearance of the end product. Moreover, the use of ruthenium compounds at high injection temperatures may result in discoloration and out-gas due to reaction with halogen-containing flame retardants.
然而,當未使用銻化合物時,與用於與銻化合物結合的含鹵素阻燃劑的量相比,使用2倍至3倍的量的含鹵素阻燃劑。因此,當僅使用含鹵素阻燃劑,樹脂組成物的機械特性以及熱特性可能劣化,從而,如此的樹脂組成物的使用限制於電器以及電子商品的製造,上述機械特性例如耐衝擊強度、抗張強度(tensile strength)、抗撓強度(flexural strength)及其類似特性,上述熱特性(thermal property)例如耐熱性(heat resistance)、熱變形溫度(heat distortion temperature)及其類似特性。 However, when the antimony compound is not used, a halogen-containing flame retardant is used in an amount of 2 to 3 times as compared with the amount of the halogen-containing flame retardant used for bonding with the antimony compound. Therefore, when only a halogen-containing flame retardant is used, the mechanical properties and thermal properties of the resin composition may be deteriorated, and thus the use of such a resin composition is limited to the manufacture of electrical appliances and electronic commodities such as impact strength and resistance. Tensile strength, flexural strength, and the like, the above thermal properties such as heat resistance, heat distortion temperature, and the like.
用於給予橡膠改質苯乙烯系共聚物樹脂耐燃性的另一種廣泛使用的方法為加入抗滴垂劑(anti-dripping agent),上述抗滴垂劑可幫助減少所需的銻化合物的量。一般而言,所需的銻化合物的量可藉由使用小量的抗滴垂劑而減少,例如:基於100重量份的樹脂組成物,0.05重量份至1重量份的抗滴垂劑。聚四氟乙烯(polytetrafluoroethylene,PTFE)被典型地用作抗滴垂劑。然而,抗滴垂劑的加入,沒有消除對於銻化合物的需求。 Another widely used method for imparting flame resistance to rubber modified styrenic copolymer resins is the addition of an anti-dripping agent which helps reduce the amount of cerium compound required. In general, the amount of the cerium compound required can be reduced by using a small amount of the anti-dripping agent, for example, 0.05 parts by weight to 1 part by weight of the anti-dripping agent based on 100 parts by weight of the resin composition. Polytetrafluoroethylene (PTFE) is typically used as an anti-dripping agent. However, the addition of an anti-drip agent did not eliminate the need for a ruthenium compound.
本發明提供一種熱塑性樹脂組成物,可具有好的阻燃性。本發明又提供一種熱塑性樹脂組成物,可具有好的染色性。本發明更提供一種熱塑性樹脂組成物,可具有好的熱穩定性。 The present invention provides a thermoplastic resin composition which can have good flame retardancy. The present invention further provides a thermoplastic resin composition which can have good dyeability. The present invention further provides a thermoplastic resin composition which can have good thermal stability.
本發明的熱塑性樹脂組成物可包括(A)45重量%至95重量%的芳香族共聚物(aromatic copolymer)、(B)5重量%至55重量%的聚碳酸酯樹脂(polycarbonate resin)、(C)基於100重量份的芳香族共聚物(A)與聚碳酸酯樹脂(B)之1重量份至30重量份的含鹵素化合物、以及(D)基於100重量份的芳香族共聚物(A)與聚碳酸酯樹脂(B)之0重量份至1重量份的銻化合物。 The thermoplastic resin composition of the present invention may comprise (A) 45% by weight to 95% by weight of an aromatic copolymer, (B) 5% by weight to 55% by weight of a polycarbonate resin, ( C) 1 part by weight to 30 parts by weight of the halogen-containing compound based on 100 parts by weight of the aromatic copolymer (A) and the polycarbonate resin (B), and (D) based on 100 parts by weight of the aromatic copolymer (A) And 0 parts by weight to 1 part by weight of the hydrazine compound of the polycarbonate resin (B).
芳香族共聚物(A)可包括(a1)橡膠改質芳香族乙烯系接枝共聚物(graft copolymer)以及(a2)芳香族乙烯系共聚物。基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),可以10重量%至40重量%的量使用橡膠改質芳香族乙烯系接枝共聚物(a1)。基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),可以5重量%至85重量%的量使用芳香族乙烯系共聚物(a2)。 The aromatic copolymer (A) may include (a1) a rubber-modified aromatic vinyl-based graft copolymer and (a2) an aromatic vinyl-based copolymer. The rubber-modified aromatic vinyl-based graft copolymer (a1) can be used in an amount of 10% by weight to 40% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B). The aromatic vinyl-based copolymer (a2) can be used in an amount of 5 to 85% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B).
橡膠改質芳香族乙烯系接枝共聚物(a1)可包括5重量%至65重量%的橡膠聚合物(rubbery polymer)、20重量%至94重量%的芳香族乙烯單體、以及1重量%至40重量%的與芳香族乙烯單體可共聚合的單體。 The rubber-modified aromatic vinyl-based graft copolymer (a1) may include 5 to 65% by weight of a rubbery polymer, 20 to 94% by weight of an aromatic vinyl monomer, and 1% by weight. Up to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer.
橡膠聚合物可包括二烯橡膠(diene rubber)、藉由二烯橡膠添加氫而獲得的飽和橡膠(saturated rubber)、丙烯酸橡膠(acrylic rubber)、乙烯-丙烯橡膠(ethylene-propylene rubber)、乙烯-丙烯-二烯三元共聚物(ethylene-propylene-diene terpolymer,EPDM)、矽酮橡膠(silicone rubber)、或其組合。 The rubber polymer may include a diene rubber, a saturated rubber obtained by adding hydrogen to a diene rubber, an acrylic rubber, an ethylene-propylene rubber, an ethylene- An ethylene-propylene-diene terpolymer (EPDM), a silicone rubber, or a combination thereof.
芳香族乙烯單體可包括苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、對甲基苯乙烯、對(三級丁基)苯乙烯、乙基苯乙烯、乙烯基二甲苯(vinylxylene)、單氯苯乙烯、二氯苯乙烯、二溴苯乙烯、乙烯萘(vinylnaphthalene)、或其組合。 The aromatic vinyl monomer may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-(tert-butyl)styrene, ethylstyrene, vinylxylene ( Vinylxylene), monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, or a combination thereof.
與芳香族乙烯單體可共聚合的單體可包括不飽和腈(unsaturated nitrile)單體、丙烯酸單體、或其組合。 The monomer copolymerizable with the aromatic vinyl monomer may include an unsaturated nitrile monomer, an acrylic monomer, or a combination thereof.
芳香族乙烯系共聚物(a2)可包括60重量%至90重量%芳香族乙烯單體、以及10重量%至40重量%的與芳香族乙烯單體可共聚合的單體。 The aromatic vinyl copolymer (a2) may include 60% by weight to 90% by weight of the aromatic vinyl monomer, and 10% by weight to 40% by weight of the monomer copolymerizable with the aromatic vinyl monomer.
芳香族乙烯單體可包括苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、對甲基苯乙烯、對(三級丁基)苯乙烯、乙基苯乙烯、乙烯基二甲苯、單氯苯乙烯、二氯苯乙烯、二溴苯乙烯、乙烯萘、或其組合。 The aromatic vinyl monomer may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-(tert-butyl)styrene, ethylstyrene, vinylxylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, or a combination thereof.
與芳香族乙烯單體可共聚合的單體可包括不飽和腈單體、丙烯酸單體、或其組合。 The monomer copolymerizable with the aromatic vinyl monomer may include an unsaturated nitrile monomer, an acrylic monomer, or a combination thereof.
基於100重量%的芳香族乙烯系共聚物(a2),芳香族乙烯系共聚物(a2)可更包括0重量%至30重量%的包含不飽和羧酸、不飽和羧酸酐、馬來醯亞胺單體、或其組合的單體。 The aromatic vinyl-based copolymer (a2) may further comprise 0% by weight to 30% by weight, based on 100% by weight of the aromatic vinyl-based copolymer (a2), of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and a Malayan A monomer of an amine monomer, or a combination thereof.
依據本發明,聚碳酸酯樹脂(B)可具有10,000 g/mol至200,000 g/mol的重量平均分子量(weight average molecular weight,Mw)。 According to the present invention, the polycarbonate resin (B) may have a weight average molecular weight (Mw) of from 10,000 g/mol to 200,000 g/mol.
依據本發明,聚碳酸酯樹脂(B)可為雙酚A系聚碳酸酯。 According to the invention, the polycarbonate resin (B) may be a bisphenol A-based polycarbonate.
含鹵素化合物(C)可包括十溴二苯基乙烷、十溴二苯基醚(decabromodiphenyl ether)、四溴雙酚A、四溴雙酚A環氧寡聚物、八溴三甲基苯基二氫茚(octabromotrimethylphenylindane)、乙烯-雙-四溴鄰苯二甲醯亞胺(ethylene-bis-tetrabromophthalimide)、三(三溴苯酚)三嗪(tris(tribromophenol)triazine)、溴化聚苯乙烯、氧化十溴二苯、或其組合。 The halogen-containing compound (C) may include decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A epoxy oligomer, octabromotrimethylbenzene Octabromotrimethylphenylindane, ethylene-bis-tetrabromophthalimide, tris(tribromophenol) triazine, brominated polystyrene , oxidized decabromobiphenyl, or a combination thereof.
含鹵素化合物(C)可包括50重量%至90重量%的鹵素。 The halogen-containing compound (C) may include 50% by weight to 90% by weight of a halogen.
銻化合物(D)可包括三氧化二銻(antimony trioxide)、五氧化二銻、或其組合。 The hydrazine compound (D) may include antimony trioxide, antimony pentoxide, or a combination thereof.
熱塑性樹脂組成物可更包括添加劑,上述添加劑包括抗衝擊改質劑(impact modifier)、抗滴垂劑(anti-dripping agent)、抗氧化劑(antioxidant)、可塑劑(plasticizer)、熱穩定劑(heat stabilizer)、光安定劑(light stabilizer)、相容劑(compatibilizer)、耐候劑(weather resistant agent)、染料(dye)、顏料(pigment)、著色劑(coloring agent)、無機充填劑(inorganic filler)、或其組合。 The thermoplastic resin composition may further include an additive including an impact modifier, an anti-dripping agent, an antioxidant, a plasticizer, and a heat stabilizer (heat) Stabilizer), light stabilizer, compatibilizer, weather resistant agent, dye, pigment, coloring agent, inorganic filler Or a combination thereof.
本發明的熱塑性樹脂組成物可具有使用1.5 mm的厚度的樣本依照UL 94測量為V0的阻燃性。 The thermoplastic resin composition of the present invention may have a flame retardancy of V0 measured in accordance with UL 94 using a sample having a thickness of 1.5 mm.
本發明的熱塑性樹脂組成物可具有使用分光光度計(spectrophotometer)依照ASTM D1925測量為26至27的L的值。 The thermoplastic resin composition of the present invention may have a value of L of 26 to 27 measured in accordance with ASTM D1925 using a spectrophotometer.
就10個射出成型樣本而言,當經受例如250℃的氣缸溫度(cylinder temperature)以及10分鐘的滯留時間(residence time)的射出成型條件時,本發明的熱塑性樹脂組成物還可具有0至5個的由於脫氣(out-gas)的焦痕(burst mark)的個數。 For the ten injection molded samples, the thermoplastic resin composition of the present invention may have 0 to 5 when subjected to injection molding conditions such as a cylinder temperature of 250 ° C and a residence time of 10 minutes. The number of burst marks due to out-gas.
本發明又提供一種熱塑性模製品,其使用本發明的熱塑性樹脂組成物來製備。 The present invention further provides a thermoplastic molded article which is prepared using the thermoplastic resin composition of the present invention.
本發明將更完整地描述於以下的本發明的詳細描述,其中描述一些但非全部本發明的實施例。事實上,此發明可以許多不同形式實施而且不應解釋為侷限於文中所提出的實施例;更確切地說,這些實施例的提供使得本公開內容將滿足合用的法律上需求。 The invention will be described more fully hereinafter in the following detailed description of the invention, in which <RTIgt; In fact, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, the embodiments are provided so that this disclosure will satisfy the legal requirements of the combination.
本發明是有關於一種熱塑性樹脂組成物,其可具有極佳的阻燃性、染色性以及熱穩定性。 The present invention relates to a thermoplastic resin composition which can have excellent flame retardancy, dyeability and thermal stability.
本發明的熱塑性樹脂組成物可包括(A)45重量%至95重量%的芳香族共聚物、(B)5重量%至55重量%的聚碳酸酯樹脂、(C)基於100重量份的芳香族共聚物(A)與聚碳酸酯樹脂(B)之1重量份至30重量份的含鹵素化合物、以及(D)基於100重量份的芳香族 共聚物(A)與聚碳酸酯樹脂(B)之0重量份至2重量份的銻化合物。 The thermoplastic resin composition of the present invention may comprise (A) 45% by weight to 95% by weight of an aromatic copolymer, (B) 5% by weight to 55% by weight of a polycarbonate resin, (C) based on 100 parts by weight of aroma 1 part by weight to 30 parts by weight of the halogen-containing compound of the family copolymer (A) and the polycarbonate resin (B), and (D) based on 100 parts by weight of the aromatic compound From 0 part by weight to 2 parts by weight of the ruthenium compound of the copolymer (A) and the polycarbonate resin (B).
(A)芳香族共聚物 (A) aromatic copolymer
本發明的芳香族共聚物(A)可為芳香族乙烯單體以及與芳香族乙烯單體可聚合的單體的共聚物。 The aromatic copolymer (A) of the present invention may be a copolymer of an aromatic vinyl monomer and a monomer polymerizable with an aromatic vinyl monomer.
基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),熱塑性樹脂組成物可以45重量%至95重量%的量包括芳香族共聚物(A)。 The thermoplastic resin composition may include the aromatic copolymer (A) in an amount of from 45% by weight to 95% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B).
芳香族共聚物(A)可包括(a1)橡膠改質芳香族乙烯系接枝共聚物以及(a2)芳香族乙烯系共聚物。 The aromatic copolymer (A) may include (a1) a rubber-modified aromatic vinyl-based graft copolymer and (a2) an aromatic vinyl-based copolymer.
基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),芳香族共聚物(A)可以10重量%至40重量%的量包括橡膠改質芳香族乙烯系接枝共聚物(a1)。 The aromatic copolymer (A) may include a rubber-modified aromatic vinyl-based graft copolymer in an amount of 10% by weight to 40% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B). (a1).
基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),芳香族共聚物(A)可以5重量%至85重量%的量包括芳香族乙烯系共聚物(a2)。 The aromatic copolymer (A) may include the aromatic vinyl-based copolymer (a2) in an amount of from 5 to 85% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B).
(a1)橡膠改質芳香族乙烯系接枝共聚物 (a1) Rubber modified aromatic vinyl graft copolymer
橡膠改質芳香族乙烯系接枝共聚物(a1)可藉由共聚橡膠聚合物、芳香族乙烯單體、任選的與芳香族乙烯單體可共聚合的單體、以及任選的給予加工性與耐熱性的單體來製備。 The rubber-modified aromatic vinyl-based graft copolymer (a1) can be copolymerized by a copolymerized rubber polymer, an aromatic vinyl monomer, optionally a monomer copolymerizable with an aromatic vinyl monomer, and optionally subjected to processing. Preparation of monomers with heat and heat resistance.
橡膠改質芳香族乙烯系接枝共聚物(a1)可包括5重量%至65重量%的橡膠聚合物、20重量%至94重量%的芳香族乙烯單體、以及1重量%至40重量%的與芳香族乙烯單體可共聚合的單 體,其各自基於橡膠改質芳香族乙烯系接枝共聚物(a1)的總重量(100重量%)。 The rubber-modified aromatic vinyl-based graft copolymer (a1) may include 5 wt% to 65 wt% of a rubber polymer, 20 wt% to 94 wt% of an aromatic vinyl monomer, and 1 wt% to 40 wt% Single copolymerizable with aromatic vinyl monomer Each of the bodies was based on the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer (a1).
適用於製備接枝共聚物樹脂的橡膠聚合物的實例可包括但不限於:二烯橡膠、藉由二烯橡膠添加氫而獲得的飽和橡膠、丙烯酸橡膠、乙烯-丙烯橡膠、乙烯-丙烯-二烯三元共聚物(EPDM)、矽酮橡膠、及其類似橡膠聚合物,以及其組合。 Examples of the rubber polymer suitable for the preparation of the graft copolymer resin may include, but are not limited to, a diene rubber, a saturated rubber obtained by adding hydrogen to a diene rubber, an acrylic rubber, an ethylene-propylene rubber, an ethylene-propylene-two Alkene terpolymer (EPDM), anthrone rubber, and similar rubber polymers, and combinations thereof.
二烯橡膠的實例包括但不限於:聚丁二烯、聚(苯乙烯-丁二烯)、聚(丙烯腈-丁二烯)、聚異戊二烯(polyisoprene)、及其類似物,以及其組合。 Examples of diene rubbers include, but are not limited to, polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), polyisoprene, and the like, and Its combination.
丙烯酸橡膠的實例包括但不限於:聚(丙烯酸甲酯)(poly(methyl acrylate))、聚(丙烯酸乙酯)、聚(丙烯酸正丙酯)、聚(丙烯酸正丁酯)、聚(丙烯酸-2-乙基己酯)、聚(甲基丙烯酸己酯)、聚(甲基丙烯酸-2-乙基己酯)、及其類似物,以及其組合。 Examples of acrylic rubber include, but are not limited to, poly(methyl acrylate), poly(ethyl acrylate), poly(n-propyl acrylate), poly(n-butyl acrylate), poly(acrylic acid- 2-ethylhexyl ester), poly(hexyl methacrylate), poly(2-ethylhexyl methacrylate), and the like, and combinations thereof.
矽酮橡膠的實例包括但不限於:聚六甲基環三矽氧烷(polyhexamethyl cyclotrisiloxane)、聚八甲基環矽氧烷、聚十甲基環矽氧烷、聚十二甲基環矽氧烷、聚三甲基三苯基環矽氧烷、聚四甲基四苯基環四矽氧烷、聚八苯基環四矽氧烷、及其類似物,以及其組合。 Examples of the fluorenone rubber include, but are not limited to, polyhexamethyl cyclotrisiloxane, polyoctamethylcyclodecane, polydecamethylcyclodecane, polydodecamethylcyclononoxide Alkane, polytrimethyltriphenylcyclodecane, polytetramethyltetraphenylcyclotetraoxane, polyoctaphenylcyclotetraoxane, and the like, and combinations thereof.
用於本發明的橡膠改質芳香族乙烯系接枝共聚物(a1)的適合的橡膠聚合物可為二烯橡膠,例如聚丁二烯橡膠。 A suitable rubber polymer used in the rubber-modified aromatic vinyl-based graft copolymer (a1) of the present invention may be a diene rubber such as a polybutadiene rubber.
基於橡膠改質芳香族乙烯系接枝共聚物(a1)的總重量(100重量%),橡膠改質芳香族乙烯系接枝共聚物(a1)可包括5重量%至65重量%的橡膠聚合物。 The rubber-modified aromatic vinyl-based graft copolymer (a1) may include 5 to 65% by weight of rubber polymerization based on the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer (a1). Things.
於橡膠改質芳香族乙烯系接枝共聚物中的橡膠聚合物的 Z-平均粒徑可在0.05 μm至4.0 μm的範圍內變動,例如0.1 μm至3.0 μm。當橡膠聚合物的Z-平均粒徑為上述範圍內時,則可提升本發明的熱塑性樹脂組成物的耐衝擊強度以及外觀。 Rubber polymer in rubber modified aromatic vinyl graft copolymer The Z-average particle diameter may vary from 0.05 μm to 4.0 μm, for example from 0.1 μm to 3.0 μm. When the Z-average particle diameter of the rubber polymer is within the above range, the impact strength and appearance of the thermoplastic resin composition of the present invention can be improved.
芳香族乙烯單體的實例可包括但不限於:苯乙烯單體,例如苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、對甲基苯乙烯、對(三級丁基)苯乙烯、乙基苯乙烯、單氯苯乙烯、二氯苯乙烯、二溴苯乙烯、乙烯基二甲苯、乙烯萘及其類似物,以及其組合。 Examples of the aromatic vinyl monomer may include, but are not limited to, a styrene monomer such as styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-(tert-butyl)benzene. Ethylene, ethyl styrene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl xylene, vinyl naphthalene and the like, and combinations thereof.
基於橡膠改質芳香族乙烯系接枝共聚物(a1)的總重量(100重量%),芳香族乙烯單體可以20重量%至94重量%的量使用。 The aromatic vinyl monomer may be used in an amount of from 20% by weight to 94% by weight based on the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer (a1).
亦可包括一或多種的與芳香族乙烯單體可共聚合的單體。與芳香族乙烯單體可共聚合的單體的實例可包括但不限於:不飽和腈單體、丙烯酸單體、及其類似物,以及其組合。 One or more monomers copolymerizable with the aromatic vinyl monomer may also be included. Examples of the monomer copolymerizable with the aromatic vinyl monomer may include, but are not limited to, an unsaturated nitrile monomer, an acrylic monomer, and the like, and combinations thereof.
不飽和腈單體的實例可包括但不限於:丙烯腈、甲基丙烯腈等丙烯腈、及其類似物,以及其組合。 Examples of the unsaturated nitrile monomer may include, but are not limited to, acrylonitrile such as acrylonitrile, methacrylonitrile, and the like, and combinations thereof.
丙烯酸單體的實例包括但不限於:丙烯酸甲酯、甲基丙烯酸甲酯及其類似物,以及其組合。 Examples of acrylic monomers include, but are not limited to, methyl acrylate, methyl methacrylate, and the like, and combinations thereof.
基於橡膠改質芳香族乙烯系接枝共聚物(a1)的總重量(100重量%),橡膠改質芳香族乙烯系接枝共聚物(a1)可以1重量%至40重量%的量包括與芳香族乙烯單體可共聚合的單體。 The rubber-modified aromatic vinyl-based graft copolymer (a1) may be included in an amount of from 1% by weight to 40% by weight based on the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer (a1). A monomer in which an aromatic vinyl monomer can be copolymerized.
橡膠改質芳香族乙烯系接枝共聚物(a1)可更包括單體以給予加工性與耐熱性。給予加工性與耐熱性的單體的實例可包括但不限於:不飽和羧酸、不飽和羧酸酐、馬來醯亞胺單體、及其類似物,以及其組合。不飽和羧酸的實例可包括但不限於:丙烯酸、甲基丙烯酸、及其類似物,以及其組合。不飽和羧酸酐的實 例可包括但不限於:馬來酸酐(maleic anhydride)。馬來醯亞胺單體的實例可包括但不限於:C1-C10烷基或苯基N-取代馬來醯亞胺、及其類似物,以及其組合。 The rubber-modified aromatic vinyl-based graft copolymer (a1) may further include a monomer to impart workability and heat resistance. Examples of the monomer which imparts processability and heat resistance may include, but are not limited to, an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, and the like, and combinations thereof. Examples of the unsaturated carboxylic acid may include, but are not limited to, acrylic acid, methacrylic acid, and the like, and combinations thereof. Examples of the unsaturated carboxylic anhydride may include, but are not limited to, maleic anhydride. Examples of the maleimide monomer may include, but are not limited to, a C 1 -C 10 alkyl group or a phenyl N-substituted maleimide, and the like, and combinations thereof.
基於橡膠改質芳香族乙烯系接枝共聚物(a1)的總重量(100重量%),橡膠改質芳香族乙烯系接枝共聚物(a1)可以0重量%至15重量%的量更包括給予加工性與耐熱性的單體。 The rubber-modified aromatic vinyl-based graft copolymer (a1) may be further included in an amount of from 0% by weight to 15% by weight based on the total weight (100% by weight) of the rubber-modified aromatic vinyl-based graft copolymer (a1). A monomer that imparts processability and heat resistance.
基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),芳香族共聚物(A)可以10重量%至40重量%的量包括橡膠改質芳香族乙烯系接枝共聚物(a1),例如15重量%至40重量%、以及作為另一實例之15重量%至35重量%。 The aromatic copolymer (A) may include a rubber-modified aromatic vinyl-based graft copolymer in an amount of 10% by weight to 40% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B). (a1), for example, 15% by weight to 40% by weight, and 15% by weight to 35% by weight as another example.
(a2)芳香族乙烯系共聚物 (a2) aromatic vinyl copolymer
芳香族乙烯系共聚物(a2)可藉由共聚芳香族乙烯單體、與芳香族乙烯單體可共聚合的單體、以及任選的給予加工性與耐熱性的單體來製備。芳香族乙烯系共聚物(a2)不包括橡膠聚合物,而與橡膠改質芳香族乙烯系接枝共聚物(a1)形成對照。 The aromatic vinyl copolymer (a2) can be produced by copolymerizing an aromatic vinyl monomer, a monomer copolymerizable with an aromatic vinyl monomer, and optionally a monomer which imparts workability and heat resistance. The aromatic vinyl-based copolymer (a2) does not include a rubber polymer, but is in contrast to the rubber-modified aromatic vinyl-based graft copolymer (a1).
基於芳香族乙烯系共聚物(a2)的總重量(100重量%),芳香族乙烯系共聚物(a2)可包括60重量%至90重量%的芳香族乙烯單體以及10重量%至40重量%的與芳香族乙烯單體可共聚合的單體。 The aromatic vinyl-based copolymer (a2) may include 60% by weight to 90% by weight of the aromatic vinyl monomer and 10% by weight to 40% by weight based on the total weight (100% by weight) of the aromatic vinyl-based copolymer (a2). % of a monomer copolymerizable with an aromatic vinyl monomer.
芳香族乙烯單體的實例可包括但不限於:苯乙烯單體,例如苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、對甲基苯乙烯、對(三級丁基)苯乙烯、乙基苯乙烯、單氯苯乙烯、二氯苯乙烯、二溴苯乙烯、乙烯基二甲苯、乙烯萘、及其類似物,以及其組合。 Examples of the aromatic vinyl monomer may include, but are not limited to, a styrene monomer such as styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-(tert-butyl)benzene. Ethylene, ethyl styrene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl xylene, vinyl naphthalene, and the like, and combinations thereof.
亦可包括一或多種的與芳香族乙烯單體可共聚合的單 體。與芳香族乙烯單體可共聚合的單體的實例可包括但不限於:不飽和腈單體、丙烯酸單體、及其類似物,以及其組合。 Also may include one or more single sheets copolymerizable with the aromatic vinyl monomer body. Examples of the monomer copolymerizable with the aromatic vinyl monomer may include, but are not limited to, an unsaturated nitrile monomer, an acrylic monomer, and the like, and combinations thereof.
不飽和腈單體實例可包括但不限於:丙烯腈、甲基丙烯腈、乙基丙烯腈、及其類似物,以及其組合。 Examples of the unsaturated nitrile monomer may include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and combinations thereof.
丙烯酸單體的實例可包括但不限於:丙烯酸甲酯、甲基丙烯酸甲酯及其類似物,以及其組合。 Examples of the acrylic monomer may include, but are not limited to, methyl acrylate, methyl methacrylate, and the like, and combinations thereof.
芳香族乙烯系共聚物(a2)可更包括單體以給予加工性與耐熱性。給予加工性與耐熱性的單體的實例可包括但不限於:不飽和羧酸、不飽和羧酸酐、馬來醯亞胺單體、及其類似物,以及其組合。 The aromatic vinyl copolymer (a2) may further include a monomer to impart workability and heat resistance. Examples of the monomer which imparts processability and heat resistance may include, but are not limited to, an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide monomer, and the like, and combinations thereof.
不飽和羧酸的實例可包括但不限於:丙烯酸、甲基丙烯酸、及其類似物,以及其組合。 Examples of the unsaturated carboxylic acid may include, but are not limited to, acrylic acid, methacrylic acid, and the like, and combinations thereof.
不飽和羧酸酐的實例可包括但不限於:馬來酸酐。 Examples of the unsaturated carboxylic anhydride may include, but are not limited to, maleic anhydride.
馬來醯亞胺單體的實例可包括但不限於:C1-C10烷基或苯基N-取代馬來醯亞胺、及其類似物,以及其組合。 Examples of the maleimide monomer may include, but are not limited to, a C 1 -C 10 alkyl group or a phenyl N-substituted maleimide, and the like, and combinations thereof.
基於芳香族乙烯系共聚物(a2)的總重量(100重量%),芳香族乙烯系共聚物(a2)可以0重量%至30重量%的量包括給予加工性與耐熱性的單體。 The aromatic vinyl-based copolymer (a2) may include a monomer which imparts workability and heat resistance in an amount of from 0% by weight to 30% by weight based on the total weight (100% by weight) of the aromatic vinyl-based copolymer (a2).
基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),芳香族共聚物(A)可以5重量%至85重量%的量包括芳香族乙烯系共聚物(a2),例如5重量%至80重量%、以及作為另一實例10重量%至80重量%。 The aromatic copolymer (A) may include the aromatic vinyl-based copolymer (a2) in an amount of from 5 to 85% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B), for example 5 wt% to 80 wt%, and as another example 10 wt% to 80 wt%.
(B)聚碳酸酯樹脂 (B) Polycarbonate resin
本發明的聚碳酸酯樹脂(B)可藉由使由化學式1所表示的一或多個二酚與二氯化羰(phosgene)、鹵甲酸酯、碳酸二酯及其組合反應而被製備。 The polycarbonate resin (B) of the present invention can be produced by reacting one or more diphenols represented by Chemical Formula 1 with phosgene, a haloformate, a carbonic acid diester, and a combination thereof. .
其中A為單鍵、C1至C5伸烷基(alkylene)、C1至C5烷叉基(alkylidene)、C5至C6環烷叉基、-S-或-SO2-。 Wherein A is a single bond, C 1 to C 5 alkylene, C 1 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -S- or -SO 2 -.
化學式1的二酚的實例可包括但不限於:4,4'-二羥基二苯醚(4,4'-dihydroxy diphenyl)、2,2-雙-(4-羥苯基)-丙烷、2,4-雙-(4-羥苯基)-2-甲基丁烷、1,1-雙-(4-羥苯基)-環己烷、2,2-雙-(3-氯-4-羥苯基)-丙烷、2,2-雙-(3,5-二氯-4-羥苯基)-丙烷、及其類似物,以及其組合。於例示實施例中,二酚可包括2,2-雙-(4-羥苯基)-丙烷(亦被稱為雙酚A或BPA(bisphenol A))、2,2-雙-(3,5-二氯-4-羥苯基)-丙烷、1,1-雙-(4-羥苯基)-環己烷、及其類似物。於其他例示實施例中,二酚可包括2,2-雙-(4-羥苯基)-丙烷。 Examples of the diphenol of Chemical Formula 1 may include, but are not limited to, 4,4'-dihydroxy diphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2 ,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3-chloro-4 -Hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, and analogs thereof, and combinations thereof. In the illustrated embodiment, the diphenol may include 2,2-bis-(4-hydroxyphenyl)-propane (also known as bisphenol A or BPA (bisphenol A)), 2,2-bis-(3, 5-Dichloro-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, and the like. In other exemplary embodiments, the diphenol may comprise 2,2-bis-(4-hydroxyphenyl)-propane.
依據本發明,聚碳酸酯樹脂(B)可具有10,000 g/mol至200,000 g/mol的重量平均分子量(Mw),例如15,000 g/mol至80,000 g/mol。 According to the invention, the polycarbonate resin (B) may have a weight average molecular weight (Mw) of from 10,000 g/mol to 200,000 g/mol, for example from 15,000 g/mol to 80,000 g/mol.
依照各種各樣的本發明的實施例,用於本發明的熱塑性樹脂組成物的適合的聚碳酸酯樹脂(B)可包括但不限於:線性聚碳酸酯樹脂、分支聚碳酸酯樹脂、聚酯-碳酸酯樹脂、及其類似物,以及其組合。用於本發明的熱塑性樹脂組成物的適合的聚碳酸酯樹脂亦可包括但不限於:均聚碳酸酯、共聚碳酸酯,以及其組合。 Suitable polycarbonate resins (B) for use in the thermoplastic resin composition of the present invention may include, but are not limited to, linear polycarbonate resins, branched polycarbonate resins, polyesters according to various embodiments of the present invention. - carbonate resins, and the like, and combinations thereof. Suitable polycarbonate resins for use in the thermoplastic resin compositions of the present invention may also include, but are not limited to, homopolycarbonates, copolycarbonates, and combinations thereof.
聚碳酸酯樹脂(B)可使用本領域中已知的方法來製備。例如,聚碳酸酯樹脂可為例如雙酚A系聚碳酸酯樹脂的線性聚碳酸酯。作為另一實例,分支聚碳酸酯樹脂可以已知的方式來製備,例如藉由基於所使用的二酚的總量併入0.05 mol%至2 mol%的三或更高官能基化合物(例如具有三或更多個酚基(phenolic group)者)。作為又一實例,聚碳酸酯樹脂可使用已知技術經酯前驅物(ester precursor)全部或部分取代,例如藉由於二官能基羧酸存在下聚合來製備的芳香族聚酯-碳酸酯樹脂。 The polycarbonate resin (B) can be produced using a method known in the art. For example, the polycarbonate resin may be a linear polycarbonate such as a bisphenol A-based polycarbonate resin. As another example, a branched polycarbonate resin can be prepared in a known manner, for example by incorporating 0.05 mol% to 2 mol% of a tri- or higher-functional compound based on the total amount of diphenol used (for example, Three or more phenolic groups). As a further example, the polycarbonate resin may be substituted, in whole or in part, with an ester precursor using known techniques, for example, an aromatic polyester-carbonate resin prepared by polymerization in the presence of a difunctional carboxylic acid.
基於100重量%的芳香族共聚物(A)與聚碳酸酯樹脂(B),熱塑性樹脂組成物可以5重量%至55重量%的量包括聚碳酸酯樹脂(B)。 The thermoplastic resin composition may include the polycarbonate resin (B) in an amount of 5 to 55% by weight based on 100% by weight of the aromatic copolymer (A) and the polycarbonate resin (B).
當聚碳酸酯樹脂(B)的量小於5重量%時,則可能劣化熱塑性樹脂組成物的阻燃性以及耐衝擊強度。另一方面,當聚碳酸酯樹脂(B)的量多於55重量%時,則可能劣化流動性(flowability)以及熱穩定性。 When the amount of the polycarbonate resin (B) is less than 5% by weight, the flame retardancy and impact strength of the thermoplastic resin composition may be deteriorated. On the other hand, when the amount of the polycarbonate resin (B) is more than 55% by weight, flowability and thermal stability may be deteriorated.
(C)含鹵素化合物 (C) Halogen-containing compounds
本發明的含鹵素化合物可用作阻燃劑。用於本發明的熱塑性樹脂組成物的適合的含鹵素化合物可包括溴系化合物、氯系化合物、及其類似物,以及其組合。 The halogen-containing compound of the present invention can be used as a flame retardant. Suitable halogen-containing compounds for use in the thermoplastic resin composition of the present invention may include bromine-based compounds, chlorine-based compounds, and the like, and combinations thereof.
適用於製備熱塑性樹脂組成物的含鹵素化合物(C)的實例可包括但不限於:十溴二苯基乙烷、十溴二苯基醚、四溴雙酚A、四溴雙酚A環氧寡聚物、八溴三甲基苯基二氫茚、乙烯-雙-四溴鄰苯二甲醯亞胺、三(三溴苯酚)三嗪、溴化聚苯乙烯、氧化十溴二 苯及其類似物,以及其組合。 Examples of the halogen-containing compound (C) suitable for the preparation of the thermoplastic resin composition may include, but are not limited to, decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A epoxy Oligomer, octabromotrimethylphenyl dihydroanthracene, ethylene-bis-tetrabromophthalimide, tris(tribromophenol)triazine, brominated polystyrene, decyl bromide Benzene and its analogs, as well as combinations thereof.
含鹵素化合物可於製程溫度下被熔化,例如,含鹵素化合物可具有小於250℃的熔點或軟化點(softening point)。 The halogen-containing compound can be melted at the process temperature. For example, the halogen-containing compound can have a melting point or a softening point of less than 250 °C.
含鹵素化合物(C)可包括多於50重量%的鹵素,例如50重量%至90重量%的鹵素。 The halogen-containing compound (C) may include more than 50% by weight of a halogen, for example, 50% by weight to 90% by weight of a halogen.
基於100重量份的芳香族共聚物(A)與聚碳酸酯樹脂(B),熱塑性樹脂組成物可以1重量份至30重量份的量包括含鹵素化合物(C)。 The thermoplastic resin composition may include the halogen-containing compound (C) in an amount of from 1 part by weight to 30 parts by weight based on 100 parts by weight of the aromatic copolymer (A) and the polycarbonate resin (B).
當含鹵素化合物(C)的量小於1重量份時,則可能劣化熱塑性樹脂組成物的阻燃性。另一方面,當含鹵素化合物(C)的量多於30重量份時,則可能劣化熱塑性樹脂組成物的耐衝擊強度。 When the amount of the halogen-containing compound (C) is less than 1 part by weight, the flame retardancy of the thermoplastic resin composition may be deteriorated. On the other hand, when the amount of the halogen-containing compound (C) is more than 30 parts by weight, the impact strength of the thermoplastic resin composition may be deteriorated.
(D)銻化合物 (D) bismuth compound
基於100重量份的芳香族共聚物(A)與聚碳酸酯樹脂(B),本發明的熱塑性樹脂組成物可包括0重量份至2重量份的銻化合物(D)。當銻化合物的量多於2重量份時,則可能劣化熱塑性樹脂組成物的染色性以及熱穩定性。 The thermoplastic resin composition of the present invention may include 0 parts by weight to 2 parts by weight of the cerium compound (D) based on 100 parts by weight of the aromatic copolymer (A) and the polycarbonate resin (B). When the amount of the cerium compound is more than 2 parts by weight, the dyeability and thermal stability of the thermoplastic resin composition may be deteriorated.
適用於製備熱塑性樹脂組成物的銻化合物(D)的實例可包括但不限於:三氧化二銻、五氧化二銻、及其類似物,以及其組合。 Examples of the ruthenium compound (D) suitable for the preparation of the thermoplastic resin composition may include, but are not limited to, antimony trioxide, antimony pentoxide, and the like, and combinations thereof.
(E)添加劑 (E) additive
熱塑性樹脂組成物可包括任選的一或多種添加劑,視熱塑性樹脂組成物各自的使用以及額外的所需特性而定。如此的添 加劑的實例可包括但不限於:抗衝擊改質劑、抗滴垂劑、抗氧化劑、可塑劑、熱穩定劑、光安定劑、相容劑、耐候劑、染料、顏料、著色劑、無機充填劑、及其類似物,以及其組合。 The thermoplastic resin composition may include optional one or more additives depending on the respective use of the thermoplastic resin composition and additional desired characteristics. Such a Tim Examples of additives may include, but are not limited to, impact modifiers, anti-dripping agents, antioxidants, plasticizers, heat stabilizers, light stabilizers, compatibilizers, weathering agents, dyes, pigments, colorants, inorganics Fillers, and the like, and combinations thereof.
基於100重量份的芳香族共聚物(A)與聚碳酸酯樹脂(B),添加劑(E)可以小於30重量份的量使用,例如0.0001重量份至30重量份。 The additive (E) may be used in an amount of less than 30 parts by weight, for example, 0.0001 part by weight to 30 parts by weight based on 100 parts by weight of the aromatic copolymer (A) and the polycarbonate resin (B).
依據本發明,熱塑性樹脂組成物可藉由常見的方法來製備。例如,組成成分以及任選的添加劑可混合在一起且透過擠壓機擠壓,並且可以顆粒(pellet)或屑片(chip)的形狀而製備。 According to the present invention, the thermoplastic resin composition can be produced by a usual method. For example, the constituents and optional additives can be mixed together and extruded through an extruder, and can be prepared in the form of pellets or chips.
本發明的熱塑性樹脂組成物可具有使用1.5 mm的厚度的樣本依照UL 94測量為V0的阻燃性。 The thermoplastic resin composition of the present invention may have a flame retardancy of V0 measured in accordance with UL 94 using a sample having a thickness of 1.5 mm.
本發明的熱塑性樹脂組成物可具有使用分光光度計依照ASTM D1925測量為26至27的L的值。 The thermoplastic resin composition of the present invention may have a value of L of 26 to 27 measured in accordance with ASTM D1925 using a spectrophotometer.
就10個射出成型樣本而言,當經受例如250℃的氣缸溫度以及10分鐘的滯留時間的射出成型條件時,本發明的熱塑性樹脂組成物可具有0至5個的由於脫氣的焦痕的個數。本發明的熱塑性樹脂組成物可具有極佳的阻燃性、染色性以及熱穩定性,而且可用於各種各樣的產品的生產。上述各種各樣的產品包括但不限於:用於電器以及電子商品的外殼(housing),上述電器以及電子商品例如電視(television,TV)、音響裝置(audio device)、行動電話(cellular phone)、數位相機、導航系統、洗衣機、電腦、監視器(monitor)、MP3播放器、電視播放器(video player)、光碟播放機(CD(Compact Disc)player)、及其類似物;以及大型模製產品。 For the ten injection molded samples, the thermoplastic resin composition of the present invention may have 0 to 5 due to degassing of scorch marks when subjected to injection molding conditions such as a cylinder temperature of 250 ° C and a residence time of 10 minutes. Number. The thermoplastic resin composition of the present invention can have excellent flame retardancy, dyeability, and thermal stability, and can be used for production of various products. The above various products include, but are not limited to, housings for electric appliances and electronic goods, such as electric appliances, such as televisions, televisions, cellular phones, cellular phones, Digital camera, navigation system, washing machine, computer, monitor, MP3 player, video player, CD (Compact Disc) player, and the like; and large molded products .
本發明的熱塑性模製品藉由本發明的熱塑性樹脂組成物 來製備。用於製備使用本發明的熱塑性樹脂組成物的熱塑性模製品的方法不受限制,而且例如可採用擠壓成型、射出成型、吹氣成型、壓縮成型或澆注成型(casting)的方法。如此的方法於本領域中是為人所知的,並且容易地被本領域中之技藝者所實行。 Thermoplastic molded article of the present invention by the thermoplastic resin composition of the present invention To prepare. The method for preparing the thermoplastic molded article using the thermoplastic resin composition of the present invention is not limited, and for example, a method of extrusion molding, injection molding, air blowing molding, compression molding or casting can be employed. Such methods are well known in the art and are readily practiced by those skilled in the art.
藉由參照以下的實例,可更好地理解本發明,這些實例的本意是說明的目的並且將不被解釋為於任何方面限制本發明的範圍,而本發明的範圍定義於之後所附的申請專利範圍中。 The invention may be better understood by reference to the following examples, which are intended to be illustrative and not to limit the scope of the invention in any way, and the scope of the invention is defined in the appended claims In the scope of patents.
實例 Instance
以下的實例以及比較例中的各組成成分的詳細敘述提供如下。 The detailed description of each of the following examples and comparative examples is provided below.
(A)芳香族共聚物 (A) aromatic copolymer
(a1)橡膠改質芳香族乙烯系接枝共聚物 (a1) Rubber modified aromatic vinyl graft copolymer
使用由韓國的第一毛織株式會社(Cheil Industries,Inc.)製造的接枝-丙烯腈-丁二烯-苯乙烯共聚物(grafted-acrylonitrile-butadiene-styrene,g-ABS),此接枝-丙烯腈-丁二烯-苯乙烯共聚物具有58重量%的聚丁二烯橡膠。 A graft-acrylonitrile-butadiene-styrene (g-ABS) manufactured by Cheil Industries, Inc. of Korea was used, and this graft- The acrylonitrile-butadiene-styrene copolymer had 58% by weight of a polybutadiene rubber.
(a2)芳香族乙烯系共聚物 (a2) aromatic vinyl copolymer
使用由韓國的第一毛織株式會社製造的苯乙烯-丙烯腈共聚物(SAN),此苯乙烯-丙烯腈共聚物具有28重量%的丙烯腈。 A styrene-acrylonitrile copolymer (SAN) manufactured by First Wool Co., Ltd. of Korea was used, and this styrene-acrylonitrile copolymer had 28% by weight of acrylonitrile.
(B)聚碳酸酯樹脂 (B) Polycarbonate resin
使用由日本的帝人有限公司(Teijin Company)製造的雙酚A型聚碳酸酯樹脂(產品名稱:PANLITE L-1250)。 A bisphenol A type polycarbonate resin (product name: PANLITE L-1250) manufactured by Teijin Company of Japan was used.
(C)含鹵素化合物 (C) Halogen-containing compounds
使用由美國的艾比馬爾公司(Albemarle Company)製造的含鹵素化合物(產品名稱:Saytex 4010)。 A halogen-containing compound (product name: Saytex 4010) manufactured by Albemarle Company of the United States was used.
(C’)含磷化合物 (C') phosphorus-containing compound
使用由日本的大八化工股份有限公司(Daihachi Chemical Company)製造的雙酚A二磷酸酯(產品名稱:CR-741)。 A bisphenol A diphosphate (product name: CR-741) manufactured by Daihachi Chemical Company of Japan was used.
(D)銻化合物 (D) bismuth compound
使用由韓國的Ilsung銻公司(Ilsung Antimony Company)製造的銻化合物(產品名稱:ANTIS-W)。 A hydrazine compound (product name: ANTIS-W) manufactured by Ilsung Antimony Company of Korea was used.
物理特性為藉由以下的方法所測量: Physical properties are measured by the following methods:
(1)阻燃性:使用具有1.5 mm的厚度的樣本依照UL 94測量阻燃性。 (1) Flame retardancy: Flame retardancy was measured in accordance with UL 94 using a sample having a thickness of 1.5 mm.
不合格:總燃燒時間(burning time)多於50秒或各自燃燒時間多於10秒 Failed: total burning time is more than 50 seconds or each burning time is more than 10 seconds
(2)染色性:使用柯尼卡美能達公司(Konica Minolta Company)的CM-3600D分光光度計依照ASTM D1925測量L的值。 (2) Dyeability: The value of L was measured in accordance with ASTM D1925 using a CM-3600D spectrophotometer of Konica Minolta Company.
(3)熱穩定性:就10個射出成型樣本而言,於250℃的氣缸溫度以及10分鐘的滯留時間之射出成型的期間,測量由於脫氣的焦痕的個數。 (3) Thermal stability: For the ten injection molded samples, the number of scorch marks due to degassing was measured during the injection molding at a cylinder temperature of 250 ° C and a residence time of 10 minutes.
佳:無由於脫氣的焦痕;一般:產生少的由於脫氣的焦痕的個數(小於5);差:產生多的由於脫氣的焦痕的個數(多於5) Good: no scorch due to degassing; general: the number of scorch marks due to degassing (less than 5); poor: the number of scorch marks due to degassing (more than 5)
(4)流動性(螺旋流動長度(spiral flow length),mm):藉由20盎司射出成型機,於220℃的氣缸溫度以及60℃的模溫度下測量螺旋流動長度,上述射出成型機使用具有螺旋形模穴(cavity)的金屬模具,上述螺旋形模穴具有5 mm×0.5 mm的尺寸。測定螺 旋流動長度作為模製產品的長度。 (4) Flowability (spiral flow length, mm): The spiral flow length is measured by a 20 ounce injection molding machine at a cylinder temperature of 220 ° C and a mold temperature of 60 ° C. The above injection molding machine has A metal mold of a spiral cavity having a size of 5 mm × 0.5 mm. Measuring snail The swirl flow length is used as the length of the molded product.
熱塑性樹脂組成物的製備 Preparation of thermoplastic resin composition
包括以下的表1以及表2所示之量的組成成分、0.5重量份的炭黑(carbon black)、1.5重量份的抗氧化劑、以及1.0重量份的熱穩定劑的組成物透過常見的擠壓機來擠壓,並且使用雙螺桿擠壓機(twin screw extruder)(L/D=35,Φ=45 mm)來製備顆粒。使用15盎司射出成型機,於220℃至240℃的模溫度的條件下,射出成型所製備的顆粒以形成樣本。於23℃的溫度以及50%的相對溼度下乾燥樣本持續2小時後,製備試樣。 The composition including the components shown in Table 1 and Table 2 below, 0.5 parts by weight of carbon black, 1.5 parts by weight of an antioxidant, and 1.0 part by weight of a heat stabilizer were passed through a common extrusion. The machine was extruded and a pellet was prepared using a twin screw extruder (L/D = 35, Φ = 45 mm). The prepared particles were injection molded to form a sample using a 15 oz injection molding machine at a mold temperature of 220 ° C to 240 ° C. A sample was prepared after drying the sample at a temperature of 23 ° C and a relative humidity of 50% for 2 hours.
於以下的表1以及表2中,(a1)、(a2)以及(B)的量是基於100重量%的(a1)、(a2)以及(B),並且(C)、(C’)以及(D)的量是基於100重量份的(a1)、(a2)以及(B)。 In Tables 1 and 2 below, the amounts of (a1), (a2), and (B) are based on 100% by weight of (a1), (a2), and (B), and (C), (C') And the amount of (D) is based on 100 parts by weight of (a1), (a2), and (B).
如表1以及表2中所示,於以本發明的範圍之外的量包括聚碳酸酯樹脂的比較例1中,流動性劣化。而且,於以本發明的範圍之外的量包括聚碳酸酯樹脂的比較例2中,阻燃性劣化。於使用不具聚碳酸酯樹脂的銻化合物的比較例4中,染色性以及熱穩定性劣化。於使用較比較例4少量的銻化合物的比較例3中, 阻燃性劣化。於比較例5中,染色性以及熱穩定性劣化。於以本發明的範圍之外的量使用銻化合物的比較例6中,染色性以及熱穩定性劣化。於使用含磷化合物而非使用含鹵素化合物的比較例7中,阻燃性以及流動性劣化。 As shown in Table 1 and Table 2, in Comparative Example 1 including a polycarbonate resin in an amount outside the range of the present invention, fluidity was deteriorated. Further, in Comparative Example 2 including a polycarbonate resin in an amount outside the scope of the present invention, the flame retardancy was deteriorated. In Comparative Example 4 using a ruthenium compound having no polycarbonate resin, dyeability and thermal stability were deteriorated. In Comparative Example 3 using a smaller amount of a ruthenium compound than Comparative Example 4, The flame retardancy is deteriorated. In Comparative Example 5, dyeability and thermal stability were deteriorated. In Comparative Example 6 in which a ruthenium compound was used in an amount outside the range of the present invention, dyeability and thermal stability were deteriorated. In Comparative Example 7 in which a phosphorus-containing compound was used instead of using a halogen-containing compound, flame retardancy and fluidity were deteriorated.
本發明的許多變型以及其他實施例對於一個此發明相關領域中的技藝者而言,將具有呈現於前面的描述中的教示的利益。因此,可理解本發明不被限制於所揭露的特定實施例及其變型,而且其他實施例將被包括於所附的申請專利的範圍中。儘管文中採用了特定的術語,但它們僅以一般性以及描述性的意義來使用,而不是出於限制的目的,本發明的範圍定義於申請專利範圍中。 Many variations of the invention, as well as other embodiments, will be apparent to those of ordinary skill in the art of the invention. Therefore, it is to be understood that the invention is not limited to the particular embodiment disclosed and the modifications thereof, and other embodiments are included in the scope of the appended claims. The specific terms are used herein, and are used in a generic and descriptive sense only, and are not intended to limit the scope of the invention.
Claims (20)
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KR20110147438 | 2011-12-30 | ||
KR1020120149275A KR20130079175A (en) | 2011-12-30 | 2012-12-20 | Thermoplastic resin composition having excellent flame retardancy, colorability and thermal stability |
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TW201331287A true TW201331287A (en) | 2013-08-01 |
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TW101150778A TW201331287A (en) | 2011-12-30 | 2012-12-28 | Thermoplastic resin composition and thermoplastic molded article thereof |
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KR (1) | KR20130079175A (en) |
TW (1) | TW201331287A (en) |
Families Citing this family (1)
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KR101875999B1 (en) * | 2015-10-23 | 2018-08-02 | 주식회사 엘지화학 | Flame retardant thermoplastic resin composition having excellent thermal stability, method of preparing the same and molded product using the same |
-
2012
- 2012-12-20 KR KR1020120149275A patent/KR20130079175A/en not_active Application Discontinuation
- 2012-12-28 TW TW101150778A patent/TW201331287A/en unknown
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KR20130079175A (en) | 2013-07-10 |
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