CN1116357C - 聚碳酸酯树脂组合物及用它做的仪器外壳 - Google Patents
聚碳酸酯树脂组合物及用它做的仪器外壳 Download PDFInfo
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- CN1116357C CN1116357C CN99105139A CN99105139A CN1116357C CN 1116357 C CN1116357 C CN 1116357C CN 99105139 A CN99105139 A CN 99105139A CN 99105139 A CN99105139 A CN 99105139A CN 1116357 C CN1116357 C CN 1116357C
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
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- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
提供了聚碳酸酯树脂组合物及用该组合物成形的仪器外壳。这种聚碳酸酯树脂组合物的特征在于,它对环境无不良影响,具有高的阻燃性,同时,即使进行薄壁成形,也具有足够的刚性和耐冲击性,而且,流动性好,能制成外观漂亮的成形制品。将纤维状填料、萜烯树脂、复合橡胶类接枝共聚物、不含卤素的磷酸酯化合物及聚四氟乙烯各组分,分别以特定的比例与聚碳酸酯树脂混合,使之均匀分散,得到聚碳酸酯树脂组合物,用该组合物成形,制成电器、电子仪器等的外壳。
Description
发明领域
本发明涉及聚碳酸酯树脂组合物及用它做的电器、电子仪器等的外壳。更详细地说,是涉及具有优良阻燃性和刚性以及冲击强度、而且成形性好,可制得外观漂亮的成形制品的聚碳酸酯树脂组合物以及用该组合物成形制得的电器、电子仪器等的外壳。
发明背景
聚碳酸酯树脂的机械强度、电性能及光学性质非常好,所以,被广泛用在电器、电子仪器、汽车零件、办公设备、建筑材料等各个领域。
近年来,在这些应用领域中,伴随着制品向小型化和轻型化方向的发展,对成形材料的性能提出了更高的要求。例如,制造便携式电器、电子仪器和便携式办公设备等的外壳时,要求其壁厚尽量地薄。但成形制品如此薄壁化,使得成形制品的刚性和冲击强度不足。另外,要薄壁化的话,除了阻燃性要提高外,成形加工时,需要高的流动性。
通过开发使用各种添加剂的聚碳酸酯树脂组合物,使得伴随各种制品小型化和轻型化的发展而带来的技术问题正在逐步得到解决。然而,制成薄壁成形制品时,具有足够的刚性和耐冲击性而且成形制品的外观漂亮,废弃时对环境无坏影响的成形材料目前还不能制造。
为了赋予这些成形制品的阻燃性而混入的含卤素的阻燃剂是造成有害物质产生的原因,为此围绕树脂制品的废弃时对环境的影响,特别是对不使用含卤素的阻燃剂就可以达到阻燃目的的方法进行了研究。例如,特开昭62-4746号公报提出了将不含丁二烯的聚苯乙烯和聚碳酸酯树脂合金化,制得不含卤素的阻燃性聚碳酸酯树脂的方法,然而,这样得到的产品,冲击强度下降很大,所以,缺乏实用性。另外,特开平2-32154号公报提出了将丙烯腈-丁二烯-苯乙烯树脂等含苯乙烯的接枝共聚物与聚碳酸酯树脂合金化的方法。但是,通过这样的合金化,虽然流动性提高了,得到了成形加工性优异的物质,可是,聚碳酸酯树脂原来具有的高的刚性和冲击强度不可避免地会下降。
还有,为了进一步提高聚碳酸酯树脂的机械强度,混入了玻璃纤维和碳纤维等纤维状的填料。通过这些纤维状填料的混入,虽然可以大大提高刚性、拉伸强度和冲击强度等机械强度,但是,为了充分提高机械强度而增加其配入量时,成形加工性会下降,与此同时,用其做的成形制品的外观也受到损害,还需进行涂装等表面处理。发明目的
本发明的目的是,提供具有优异的阻燃性、刚性及冲击强度而且成形性好,可制得外观漂亮的成形制品的聚碳酸酯树脂组合物以及用该组合物成形制得的电器、电子仪器的外壳。
发明概述
为了解决上述的问题,本发明人经过反复研究,结果发现,通过使用在聚碳酸酯树脂中分别以特定的比例混入纤维状填料、萜烯树脂、复合橡胶系接枝共聚物、不含卤素的磷酸酯化合物及聚四氟乙烯各组分而得到的聚碳酸酯树脂组合物,就可达到上述目的,以这些知识为基础完成了本发明。
即,本发明的要点如下所述。[1]聚碳酸酯树脂组合物,其特征是,相对于由(a)14.8~91.5重量%的聚碳酸酯树脂、(b)1~50重量%的纤维状填料、(c)2~8重量%的萜烯树脂、(d)2~8重量%的复合橡胶系接枝共聚物和(e)该萜烯树脂与复合橡胶系接枝共聚物总量的0.8~1.2倍的不含卤素的磷酸酯化合物构成的成分100份重量,配入(f)0.05~1.0重量份的聚四氟乙烯而制得。[2]上述[1]的聚碳酸酯树脂组合物,其特征在于,所述的复合橡胶系接枝共聚物具有1~99重量%的聚有机硅氧烷橡胶成分和99~1重量%的聚丙烯酸烷基酯橡胶成分呈不可分离的、互相缠结的结构,是在平均粒径0.01~0.6μm的复合橡胶上接枝聚合1种或2种以上的乙烯系单体而形成的。[3]用上述[1]或[2]中的聚碳酸酯树脂组合物成形制得的电器、电子仪器或OA设备的外壳。发明的实施方式
本发明的聚碳酸酯树脂组合物中所使用的(a)组分-聚碳酸酯树脂可以使用按常规方法制备的树脂,即由二元酚与光气或碳酸酯化合物等聚碳酸酯的前体反应制备的聚碳酸酯树脂。
更具体地说,优先选用按下法制得的树脂,即,在二氯甲烷等溶剂中,在酸受体和分子量调节剂的存在下,按照需要,加入支链剂等添加剂,使二元酚与光气反应或使二元酚与二苯基碳酸酯等进行酯交换反应制得的树脂。
而且,作为上述的二元酚可以举出:双(4-羟基苯基)甲烷、1,1-二(4-羟基苯基)乙烷、2,2-二(4-羟基苯基)丙烷、双(4-羟基苯基)萘基甲烷、1,1-二(4-羟基-叔丁基苯基)丙烷、2,2-二(4-羟基-3,5-二甲基苯基)丙烷等双(羟基芳基)链烷烃类;1,1-二(4-羟基苯基)环戊烷、1,1-二(4-羟基苯基)环己烷、1,1-二(4-羟基苯基)3,5,5-三甲基环己烷等双(羟基芳基)环烷烃类;4,4′-二羟基二苯醚、4,4′-二羟基-3,3′-二甲基二苯醚等二羟基二芳基醚类;4,4′-二羟基二苯硫醚、4,4′-二羟基-3,3′-二甲基二苯硫醚等二羟基二芳基硫醚类;4,4′-二羟基二苯亚砜、4,4′-二羟基-3,3′-二甲基二苯亚砜等二羟基二芳基亚砜类;4,4′-二羟基二苯基砜、4,4′-二羟基-3,3′-二甲基二苯基砜等二羟基二芳基砜类;4,4′-二羟基联苯等二羟基联苯类等。在这些二元酚中,优先选用2,2-二(4-羟基苯基)丙烷。这些二元酚既可以单独使用1种,也可以2种以上混合使用。
另外,作为上述的碳酸酯化合物可列举如:碳酸二苯酯等碳酸二芳基酯、碳酸二甲酯、碳酸二乙酯等碳酸二烷基酯等。
而且,作为上述的分子量调节剂,优选选用一元酚。这样的一元酚例如有:苯酚、邻-正丁基苯酚、间-正丁基苯酚、对-正丁基苯酚、邻-异丁基苯酚、间-异丁基苯酚、对-异丁基苯酚、邻-叔丁基苯酚、间-叔丁基苯酚、对-叔丁基苯酚、邻-正戊基苯酚、间-正戊基苯酚、对-正戊基苯酚、邻-正己基苯酚、间-正己基苯酚、对-正己基苯酚、对-正辛基苯酚、邻-环己基苯酚、间-环己基苯酚、对-环己基苯酚、邻-苯基苯酚、间-苯基苯酚、对-苯基苯酚、邻-正壬基苯酚、间-正壬基苯酚、对-正壬基苯酚、邻-异丙苯基苯酚、间-异丙苯基苯酚、对 异丙苯基苯酚、邻-萘基苯酚、间-萘基苯酚、对-萘基苯酚、2,5-二-叔丁基苯酚、2,4-二-叔丁基苯酚、3,5-二-叔丁基苯酚、2,5-二异丙苯基苯酚、3,5-二异丙苯基苯酚、对甲酚等。在这些一元酚中,优先选用对-叔丁基苯酚、对-异丙苯基苯酚、对-苯基苯酚。
再有,作为前述的支链剂,适宜使用如:1,1,1-三(4-羟基苯基)乙烷、α,α′,α″-三(4-羟基苯基)1,3,5-三异丙基苯、1-[α-甲基-α-(4′-羟基苯基)乙烷]-4-[α′,α′-二(4″-羟基苯基)乙基]苯、间苯三酚、偏苯三酸、吲哚满二酮二(邻甲酚)等。
作为本发明的聚碳酸酯树脂组合物的(a)成分使用的聚碳酸酯树脂,可以使用由上述二元酚与光气或上述碳酸酯化合物等聚碳酸酯的前体反应得到的产物,其粘均分子量10,000~100,000为宜,最好是14,000~40,000。
还有,作为本发明的聚碳酸酯树脂组合物的(b)成分使用的纤维状填料,可列举如:玻璃纤维、碳纤维、钛酸钾、硼酸铝、硼纤维、氮化硅晶须、矿物纤维。这些纤维状填料中,优先使用玻璃纤维、碳纤维。
上述的玻璃纤维,以含碱玻璃、低碱玻璃、无碱玻璃为原料者比较好,其纤维长度为0.01~2mm、最好为0.05~1mm。将该玻璃纤维加入聚碳酸酯树脂中进行混炼时,玻璃纤维常常破断,所以,原料玻璃纤维的长度采用1~6mm为宜。另外,该玻璃纤维的直径以1~20μm为宜。玻璃纤维的形态,可以是粗纱、磨断纤维或短纤维粗纱中的任一种。而且,为了提高该玻璃纤维与聚碳酸酯树脂的粘结性,最好使用经表面处理剂处理过的玻璃纤维。该表面处理后,希望用集束剂进行集束处理过的玻璃纤维来混合。
这里所用的表面处理剂可列举如:氨基硅烷系、环氧硅烷系、乙烯基硅烷系、丙烯酸硅烷系等硅烷类偶联剂、酞酸酯类偶联剂、铝类偶联剂、铬类偶联剂、锆类偶联剂、硼类偶联剂。其中,优选选用硅烷类偶联剂。上述的进行表面处理的方法,无论采用常规的水溶液法,还是有机溶剂法以及喷涂法都可以。
另外,上述的集束剂,可以使用氨基甲酸酯类、丙烯酸类、丙烯腈-苯乙烯共聚物类及环氧类中的任一种。使用这些集束剂对玻璃纤维进行集束处理时,可以采用常规的浸涂、辊涂、喷镀、浇涂或喷涂等任一种方法。
并且,作为本发明的聚碳酸酯树脂组合物的(b)成分而使用的纤维状填料,既可以单独使用上述纤维状填料,也可将这种纤维状填料与板状填料或球状填料合并使用。
作为板状填料,例如可以使用如玻璃片、云母和滑石等。这些板状填料,最大径在2000μm以内,最好为0.5~1000μm,而且,纵横比(最大径与厚度之比)为5以上,最好在10以上。这种板状填料的最大径超过2000μm时,与聚碳酸酯树脂的均匀混炼比较困难,另外,在成形制品上可能产生斑点。其次,如果上述的纵横比不到5时,可能会引起成形制品尺寸稳定性和耐冲击性下降,也不可取。
再有,作为球状填料,例如可以使用玻璃珠、玻璃球和碳酸钙等,这些球状填料的粒径为0.5~200μm,最好为1~100μm。
还有,作为本发明的聚碳酸酯树脂组合物的(c)成分而使用的萜烯树脂,可以使用萜烯单体的均聚物、萜烯单体与芳香族化合物的共聚物或将它们加氢处理后的加氢萜烯树脂。
作为这种萜烯单体,可以举出α-蒎烯、β-蒎烯、二戊烯、d-柠檬烯等。另外,作为上述的芳香族化合物可以举出苯乙烯、α-甲基苯乙烯、甲基苯乙烯等含乙烯基的芳香族化合物和苯酚、甲酚、2,2-二(4-羟基苯基)丙烷等酚类。优先选用将这些萜烯单体单独或与上述芳香族化合物一起,在有机溶剂中,在弗里德尔-克拉夫特催化剂的存在下,经聚合或共聚反应制得的聚合物。
还有,作为本发明的聚碳酸酯树脂组合物的(d)成分而使用的复合橡胶类接枝共聚物,可以使用将1种或2种以上的乙烯类单体与复合橡胶接枝共聚制得的共聚物。
本发明中使用的(d)成分复合橡胶类接枝共聚物的理想形态例如可以举出,具有由1~99重量%的聚有机硅氧烷橡胶成分和99~1重量%的聚丙烯酸烷基酯橡胶成分所形成的不可分离的互相缠绕的结构,而且,是在平均粒径为0.01~0.6μm的复合橡胶上接枝聚合1种或2种以上的乙烯类单体而得到的复合橡胶类接枝共聚物。
这样的复合橡胶类接枝共聚物可用各种方法制得。例如,可以采用将合成丙烯酸烷基酯橡胶用的单体浸渍在聚有机硅氧烷橡胶胶乳中的橡胶粒子上,使合成丙烯酸烷基酯橡胶用的单体发生聚合的方法。
上述的聚有机硅氧烷橡胶可以通过将0.1~30重量%的三甲氧基甲基硅烷和四乙氧基硅烷等多官能硅烷类交联剂混入二甲基硅氧烷等链状有机硅氧烷中,经乳液聚合制得。乳液聚合时,用烷基苯磺酸和烷基磺酸等磺酸类乳化剂,使用匀浆器,经与水混合可有效地制备上述橡胶。
在这样制得的聚有机硅氧烷橡胶的乳胶中,加入氢氧化钠等碱水溶液进行中和,接着,在其中添加丙烯酸甲酯和丙烯酸正丁酯等丙烯酸的烷基酯、二甲基丙烯酸乙二醇酯等交联剂以及甲基丙烯酸烯丙酯等接枝反应促进剂,将它们浸渍在前述的聚有机硅氧烷橡胶的粒子上。接着,加入自由基聚合引发剂,经聚合反应,使聚有机硅氧烷橡胶缠绕在交联的网上,形成聚丙烯酸烷基酯橡胶交联的网,制得该两种橡胶成分完全不可分离的复合橡胶胶乳。
在该复合橡胶中加入前述乙烯类单体,进行自由基聚合,在制得的乳液中投入氯化钙等使之盐析,可制得复合橡胶接枝共聚物。这里所用的乙烯类单体例如可用苯乙烯等链烯基芳香族化合物、丙烯酸甲酯和丙烯酸乙酯等丙烯酸酯、甲基丙烯酸甲酯和甲基丙烯酸乙酯等甲基丙烯酸酯、丙烯腈等氰基化乙烯系化合物等。
其次,作为本发明的聚碳酸酯树脂组合物的(e)成分而使用的不含卤素的磷酸酯化合物,例如可以举出用下述通式(I)表示的一磷酸酯或多磷酸酯。
上述(I)式中的R1~R4表示可以分别独立地具有取代基的芳基,X表示可以具有取代基的丙炔基、a,b,c及d分别表示0或1,p表示0~5的数值。
上述芳基及丙炔基中的取代基可以是碳原子数为1~10的烷基、碳原子数为1~10的烷氧基、苯基和甲苯基等芳基,它们也可为1个或2个以上。另外,上述p的数值,当2种以上的磷酸酯混合使用的时候,用各磷酸酯的p值的平均值表示。
如果要列举由通式(I)所表示的不含卤素的磷酸酯化合物的具体例子的话,则有磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、磷酸三联苯酯等一磷酸酯;苯·间苯二酚的多磷酸酯、苯·对苯二酚的多磷酸酯、苯·甲酚·间苯二酚的多磷酸酯、苯·甲酚·对苯二酚的多磷酸酯、四苯·间苯二酚二磷酸酯、四苯·对苯二酚二磷酸酯、苯·三甲酚·间苯二酚二磷酸酯、苯·三甲酚·对苯二酚二磷酸酯、四联苯·间苯二酚二磷酸酯、四联苯·对苯二酚二磷酸酯等多磷酸酯。这些磷酸酯既可以单独使用一种,也可以2种以上合并使用。
再有,作为本发明的聚碳酸酯树脂组合物的(f)成分而使用的聚四氟乙烯没有特殊的限制,采用通常使用的就可以,优先选用照ASTM标准被分类为3型的。这种聚四氟乙烯属于当受到塑化剪切应力时具有原纤化性质的类型,由于它防止上述聚碳酸酯树脂组合物熔融滴下的效果好,所以对提高阻燃性非常有用。
作为制备具有这种形成原纤化性能的聚四氟乙烯的方法,例如可采用如下方法。即在水性溶剂中,在钠、钾或铵的过氧化二硫化物存在下,1~100psi的压力、0~200℃、最好在20~100℃的温度下,使四氟乙烯聚合的方法。
另外,关于构成本发明的聚碳酸酯树脂组合物的(a)~(f)各组分的配合比例,如前所述,相对于由(a)聚碳酸酯树脂为14.8~91.5重量%、(b)纤维状填料为1~50重量%、(c)萜烯树脂为2~8重量%、(d)复合橡胶类接枝共聚物为2~8重量%及(e)相对该萜烯树脂和该复合橡胶类接枝共聚物总量的0.8~1.2倍的不含卤素的磷酸酯化合物组成的成分合计100重量份来说,(f)聚四氟乙烯为0.05~1.0重量份。
(a)组分聚碳酸酯树脂的含量比例为14.8~91.5重量%,最好为50~80重量%。如果(a)组分的比例在此范围以外的话,则制得的聚碳酸酯树脂组合物就不能达到本发明的要求。
另外,(b)组分的纤维状填料的含有比例为1~50重量%,最好为5~30重量%。关于含该纤维状填料的比例,在将板状填料和球状填料并用时,这两种填料的总量即为上述的比例。如果这种纤维状填料所含的比例不到1重量%的话,就得不到充分提高聚碳酸酯树脂组合物机械强度的效果,反之,如果该纤维状填料所含的比例超过50重量%的话,则使用所得到的聚碳酸酯树脂组合物成形的成形制品的外观就会受损。
上述(c)组分萜烯树脂的含有比例为2~8重量%,最好为4~6重量%。如果该萜烯树脂所含的比例不到2重量%的话,就得不到充分提高聚碳酸酯树脂组合物流动性的效果,如果所含比例超过8重量%的话,就会引起聚碳酸酯树脂组合物的阻燃性及耐热性的下降。
(d)组分的复合橡胶类接枝共聚物所含比例为2~8重量%,最好为4~6重量%。如果该复合橡胶类接枝共聚物的含有比例不到2重量%的话,就不能充分得到提高聚碳酸酯树脂组合物耐冲击性的效果,如果所含的比例超过8重量%的话,则制得的聚碳酸酯树脂组合物的阻燃性就会下降。
另外,(e)组分不含卤素的磷酸酯化合物的含有比例相当于(c)组分萜烯树脂和(d)组分复合橡胶类接枝共聚物总量的0.8~1.2倍。如果该不含卤素的磷酸酯化合物的含有比例不到(c)组分和(d)组分的总量的0.8倍的话,则成形为薄壁成形制品时,就得不到足够的阻燃性,如果其配入量超过上述总量的1.2倍的话,则阻燃性虽可满足,但是会引起耐热性和耐冲击性的下降。
再有,关于(f)组分聚四氟乙烯,其配合比例相对于上述(a)~(e)组分的总量100重量份而言为0.05~1.0重量份,最好为0.1~0.5重量份。如果该(f)组分的配合比例不到0.05重量份的话,就不能赋予聚碳酸酯树脂组合物充分的抑制熔融滴下的性能,反之,如果该配合比例超过1.0重量份的话,则用所得到的聚碳酸酯树脂组合物制得的成形制品的外观就会受损,也不可取。
本发明的聚碳酸酯树脂组合物是将上述(a)~(f)各组分按上述配比混合而组成的,在不损害本发明目的的范围内,除了这些组分以外,根据需要,还可配入各种无机填料、添加剂和聚碳酸酯树脂以外的合成树脂等。
这样的无机填料可以举出:碳素片、碳黑、硫酸钙、硅酸钙、氧化钛、氧化铝、二氧化硅、石棉、粘土、石英粉等。另外,上述的添加剂例如可以举出:受阻酚类、磷酸酯类、亚磷酸酯类、胺类的防氧化剂、苯并三唑类和二苯甲酮类的紫外吸收剂、脂肪族羧酸酯类、石蜡类、硅油、聚乙烯蜡等外部润滑剂、脱模剂、防静电剂、着色剂等。上述的合成树脂可以举出:聚乙烯、聚丙烯、聚苯乙烯、丙烯腈-苯乙烯共聚树脂、丙烯腈-丁二烯-苯乙烯共聚树脂、聚甲基丙烯酸甲酯等。
至于由前述的(a)~(f)各组分配合而成的聚碳酸酯树脂组合物的制备方法,并无特殊限制,采用常规的方法就可以了。即,使用如:螺带式掺混机、享舍尔混合机、班伯里混炼机、筒式转鼓、单螺杆挤出机、双螺杆挤出机、蜗杆捏合机、多螺杆挤出机等制备的方法。这时的混炼温度,以240~280℃的范围为宜。
这样制得的聚碳酸酯树脂组合物,由于流动性高,成形加工性好,所以,很容易用各种成形方法进行成形。作为具体的成形方法,例如可以采用注塑成形法、中空吹塑成形法、挤出成形法、压缩成形法、压延成形法、旋转成形法等。
用本发明的聚碳酸酯树脂组合物成形制得的成形制品可做成各种各样的形态,特别是在形成薄壁的电器、电子仪器的外壳和OA设备的外壳的领域中,可制得质轻且具有高刚性和冲击强度、高阻燃性的制品,同时,成形后无需涂装,就呈现漂亮外观和优良的实用性。
在小型化、轻量化的应用领域中,作为这些电器、电子仪器和OA设备,适用的有如笔记本型个人计算机、移动电话等通信设备中的电池箱等各种各样的仪器。
再有,在这些成形制品废弃处理时,由于没有往成形制品的原材料中引入溴和氯就被赋予了阻燃性,所以几乎不用担心有三喹啉等有害物的生成。
实施例下面,通过实施例进一步详细地说明本发明。[实施例1]
作为(a)组分的聚碳酸酯树脂,使用以2,2-二(4-羟基苯基)丙烷作原料合成的粘均分子量为21,000的聚碳酸酯树脂[出光石油化学社制;タフロンFN2200A]、作为(b)组分的纤维状填料,使用直径为13μm的玻璃纤维[旭フアイバ一グラス社制;MA409C]。另外,作为(c)组分的萜烯树脂,使用芳香族改性的萜烯树脂[ヤスハラケミカル社制;YSレジンTR-105],作为(d)组分的复合橡胶类接枝共聚物使用甲基丙烯酸甲酯与丙烯酸烷基酯及二甲基硅氧烷的共聚物[三菱レ一ヨン社制;メタプレンS-2001],作为(e)组分的不含卤素的磷酸酯化合物使用苯·间苯二酚多磷酸酯(磷含量:9.0重量%)[旭电化工业社制;アデカスタブPFR]。
各组分的配比(a)∶(b)∶(c)∶(d)∶(e)为70∶10∶5∶5∶10(重量%)。这时,(e)组分的配合比例相当于(c)组分和(d)组分总量的1倍。
另外,作为(f)组分使用聚四氟乙烯[ダイキン工业社制;ポリフロンTFEF201L],其配合比例,相对上述(a)~(e)组分的总量100重量份而言,为0.3重量份。
将这些(a)~(f)组分的混合物供入内径为35mm的双螺杆挤出机,在机筒温度为260℃、螺杆转速为300rpm的条件下,熔融混炼挤出后,切断,制得聚碳酸酯树脂组合物的颗粒。将一部分制得的颗粒,在80℃下干燥处理5小时后,供给注塑成形机,在280℃的成形温度下成形,制成物性测定用的试片。
接着,用上述试片测定聚碳酸酯树脂组合物的各种物性。至于物性的测定方法,弯曲弹性模数按JISK 7203标准,在常温下进行测定。负荷挠曲温度,按JISK 7207标准进行测定。艾佐德冲击强度按JISK 7110标准,在常温下进行测定。流动性按JISK 7210标准,在测定温度为280℃、载荷为160kg/cm2的条件下进行测定。阻燃性按照UL标准アンダ一ライタ一ズラボラトリ一·サブジエクト94进行垂直燃烧试验。关于成形制品的表面外观,是用目测法对在280℃下注塑成形制得的边长为140mm、厚为2mm的平板状成形制品的外观进行评价。在目测评价时,成形制品表面无熔合线缺陷、模具的转印性好、设计优良者记作优(表1中用◎表示)、稍差一些的记作良(表1中用△表示)、能看到缺陷的记作可(表1中用×表示)。同时,按JISK 7105标准测定与模具镜面部分相对应的成形面的60°光泽度(相对树脂流动的方向呈垂直的方向上)。
将这些评价结果归纳,列于表1中。还有,表1中,PTFE1是表示上述的聚四氟乙烯。[实施例2]
所用原料中的(a)~(e)各组分与实施例1相同。配合比例除(a)组分变为60重量%、(b)组分变为20重量%以外,其它与实施例1相同。另外,(f)组分使用0.3重量份的聚四氟乙烯[旭硝子社制;フルオンフアインパウダ一CD076]。并且,除了原料组分按上述那样以外,与实施例1同样操作,制备聚碳酸酯树脂组合物,评价其各种物性。
它们的评价结果列于表1中。表1中,PTFE2表示的是实施例2中用的聚四氟乙烯。[实施例3]
所用原料中(a)~(e)各组分与实施例1相同,它们的配合比例变为(a)∶(b)∶(c)∶(d)∶(e)=58∶20∶7∶4∶11(重量%),除此以外与实施例1一样。另外,(f)组分用的与实施例1一样,且用同一个比例。除了原料组分按上述那样以外,与实施例1同样操作,制备聚碳酸酯树脂组合物,评价其各种物性。
它们的评价结果列于表1中。[实施例4]
在原料(a)~(e)各组分中,除了用纤径为6μm的碳纤维[东邦レ一ヨン社制;HTA-C6-SR]代替玻璃纤维作为(b)组分外,其它与实施例1一样,它们的配合比例变为(a)∶(b)∶(c)∶(d)∶(e)=65∶10∶7∶6∶12(重量%),除此以外与实施例1一样。这时(e)组分的配合比例相当于(c)组分和(d)组分总量的0.92倍。另外,(f)组分与实施例1的相同,且用同一比例。并且,除了原料组分按上面所述外,其它与实施例1一样制备聚碳酸酯树脂组合物,评价其各种物性。它们的评价结果列于表1中。[比较例1]
作为原料组分,除了不使用(b)组分的纤维状填料及聚碳酸酯树脂的配合比例改为80重量%以外,其它与实施例1一样。
对制得的聚碳酸酯树脂组合物与实施例1一样评价各种物性,结果表明,它不宜用于制作弯曲弹性模数低、薄壁的笔记本型个人计算机等OA设备和携带式的通信设备等的外壳。
它们的评价结果列于表2中。[比较例2]
除了原料的(a)~(e)各组分的配合比例变为(a)∶(b)∶(c)∶(d)∶(e)=74∶10∶5∶5∶6(重量%)以外,其它与实施例1一样。这时(e)组分的配合比例相当于(c)组分和(d)组分总量的0.6倍。
对制得的聚碳酸酯树脂组合物与实施例1一样评价各种物性,结果表明阻燃性不够。另外,成形制品的外观也不好,若不涂装就不能用作上述设备的外壳。
这些评价结果列于表2中。[比较例3]
除了原料的(a)~(e)各组分的配合比例改为(a)∶(b)∶(c)∶(d)∶(e)=56∶20∶5∶5∶14(重量%)以外,其它与实施例1一样。这时(e)组分的配合比例为(c)组分和(d)组分总量的1.4倍。
对制得的聚碳酸酯树脂组合物与实施例1一样评价各种物性,结果阻燃性不足、耐热性也不好。
这些评价结果列于表2中。[比较例4]
作为原料组分,除了不使用(c)组分的萜烯树脂,并且其它组分的配合比例改为(a)∶(b)∶(d)∶(e)=75∶10∶5∶10(重量%)以外,与实施例1相同。
对制得的聚碳酸酯树脂组合物与实施例1一样评价各种物性,结果表明流动性低,难以成形为壁厚1mm以下的成形制品,另外,成形制品的表面外观差,若不涂装就不能用作上述设备的外壳。
这些评价结果列于表2中。[比例例5]
除了将原料的(a)~(e)各组分的配合比例改为(a)∶(b)∶(c)∶(d)∶(e)=74∶10∶5∶1∶10(重量%)以外,其它与实施例1一样。这时(e)组分的配合比例相当于(c)组分和(d)组分总量的1.67倍。
对制得的聚碳酸酯树脂组合物与实施例1一样评价其各种物性,冲击强度低,不宜用作上述设备外壳的材料。
这些评价结果列于表2中。[比较例6]
除了将原料的(a)~(e)各组分的配合比例改为(a)∶(b)∶(c)∶(d)∶(e)=55∶20∶10∶5∶10(重量%)以外,其它与实施例1一样。这时(e)组分的配合比例相当于(c)组分和(d)组分总量的0.67倍。
对制得的聚碳酸酯树脂组合物与实施例1一样评价其各种物性,阻燃性不够好。
这些评价结果列于表2中。[比较例7]
除了原料的(a)~(e)各组分的配合比例改为(a)∶(b)∶(c)∶(d)∶(e)=51∶20∶10∶5∶14(重量%)以外,其它与实施例1一样。这时(e)组分的配合比例相当于(c)组分和(d)组分总量的0.93倍。
对制得的聚碳酸酯树脂组合物与实施例1一样评价其各种物性,冲击强度低,在负荷挠曲温度(℃)下评价的耐热性不够好。
这些评价结果列于表2中。[比较例8]
除了用聚己酸内酯树脂(ダイヤル化学工业(株)社制プラクヤルH4)代替实施例1中的(c)组分芳香族改性的萜烯树脂以外,与实施例1一样。对制得的聚碳酸酯树脂组合物与实施例1一样评价其各种物性,冲击强度低,在负荷挠曲温度(℃)下评价的耐热性不够好。
这些评价结果列于表2中。表1
表2
实施例1 | 实施例2 | 实施例3 | 实施例4 | ||
(a) | 聚碳酸酯树脂(重量%) | 70 | 60 | 58 | 65 |
(b) | 玻璃纤维(重量%) | 10 | 20 | 20 | |
碳纤维(重量%) | 10 | ||||
(c) | 萜烯树脂(重量%) | 5 | 5 | 7 | 7 |
(d) | 复合橡胶组分(重量%) | 5 | 5 | 4 | 6 |
(e) | 磷酸酯(重量%) | 10 | 10 | 11 | 12 |
(f) | PTFE1(重量份) | 0.3 | 0.3 | 0.3 | |
PTFE2(重量份) | 0.3 | ||||
弯曲弹性模数(MPa) | 4,300 | 6,800 | 7,000 | 5,500 | |
负荷挠曲温度(℃) | 101 | 102 | 100 | 101 | |
冲击强度(kJ/m2) | 13 | 11 | 10 | 12 | |
流动性(×10-2ml/s) | 36 | 24 | 30 | 40 | |
阻燃性[UL-94](判定) | 0.8mmV-0(合格) | 0.8mmV-0(合格) | 1.0mmV-0(合格) | 1.0mmV-0(合格) | |
表面外观评价 | ◎ | ◎ | ◎ | ◎ | |
60°光泽度 | 90 | 87 | 89 | 86 |
比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | 比较例6 | 比较例7 | 比较例8 | ||
(a) | 聚碳酸酯树脂(重量%) | 80 | 74 | 56 | 75 | 74 | 55 | 51 | 70 |
(b) | 玻璃纤维(重量%) | 10 | 20 | 10 | 10 | 20 | 20 | 10 | |
碳纤维(重量%) | |||||||||
(c) | 萜烯树脂(重量%) | 5 | 5 | 5 | 5 | 10 | 10 | ||
聚己酸内酯(重量%) | 5 | ||||||||
(d) | 复合橡胶组分(重量%) | 5 | 5 | 5 | 5 | 1 | 5 | 5 | 5 |
(e) | 磷酸酯(重量%) | 10 | 6 | 14 | 10 | 10 | 10 | 14 | 10 |
(f) | PTFE1(重量份) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
PTFE2(重量份) | 0.3 | ||||||||
弯曲弹性模数(MPa) | 2,500 | 4,200 | 7,000 | 4,200 | 4,100 | 6,800 | 6,500 | 4,300 | |
负荷挠曲温度(℃) | 92 | 115 | 88 | 106 | 101 | 91 | 82 | 88 | |
冲击强度(kJ/m2) | 52 | 13 | 9 | 14 | 5 | 9 | 6 | 8 | |
流动性(×10-2ml/s) | 45 | 21 | 34 | 18 | 37 | 32 | 46 | 42 | |
阻燃性[UL-94](判定) | 1.0mmV-0(合格) | 1.0mmV-0(不合格) | 1.0mmV-0(不合格) | 1.0mmV-0(合格) | 1.0mmV-0(合格) | 1.0mmV-0(不合格) | 1.0mmV-0(合格) | 1.0mmV-0(合格) | |
表面外观评价 | ◎ | △~× | ◎ | △ | △ | ◎ | ◎ | ◎ | |
60°光泽度 | 94 | 56 | 89 | 68 | 72 | 85 | 89 | 90 |
Claims (3)
1.聚碳酸酯树脂组合物,其特征是,相对于由(a)50~80重量%的粘均分子量为14000~40000的聚碳酸酯树脂、(b)1~50重量%的纤维状填料、(c)2~8重量%的萜烯树脂、(d)2~8重量%的复合橡胶系接枝共聚物和(e)该萜烯树脂与复合橡胶系接枝共聚物合计重量的0.8~1.2倍的不含卤素的磷酸酯化合物构成的成分100重量份,配入(f)0.05~1.0重量份的聚四氟乙烯而制得。
2.权利要求1所述的聚碳酸酯树脂组合物,其特征在于,所述的复合橡胶系接枝共聚物具有1~99重量%的聚有机硅氧烷橡胶成分和99~1重量%的聚丙烯酸烷基酯橡胶成分呈不可分离的、互相缠结的结构,是在平均粒径为0.01~0.6/μm的复合橡胶上接枝聚合1种或2种以上的乙烯系单体而形成的。
3.用权利要求1或2所述的聚碳酸酯树脂组合物成形制得的电器、电子仪器或OA设备的外壳。
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-
1998
- 1998-05-20 JP JP13870098A patent/JP3398595B2/ja not_active Expired - Fee Related
-
1999
- 1999-02-23 TW TW088102659A patent/TW530080B/zh not_active IP Right Cessation
- 1999-03-30 US US09/280,723 patent/US6174944B1/en not_active Expired - Lifetime
- 1999-04-13 EP EP99107144A patent/EP0959103B1/en not_active Expired - Lifetime
- 1999-04-13 DE DE69927634T patent/DE69927634T2/de not_active Expired - Lifetime
- 1999-04-20 CN CN99105139A patent/CN1116357C/zh not_active Expired - Fee Related
- 1999-05-18 KR KR1019990017739A patent/KR100572455B1/ko not_active IP Right Cessation
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JPH11323119A (ja) | 1999-11-26 |
TW530080B (en) | 2003-05-01 |
KR19990088356A (ko) | 1999-12-27 |
US6174944B1 (en) | 2001-01-16 |
DE69927634T2 (de) | 2006-05-04 |
KR100572455B1 (ko) | 2006-04-18 |
CN1235991A (zh) | 1999-11-24 |
DE69927634D1 (de) | 2006-02-23 |
EP0959103A2 (en) | 1999-11-24 |
JP3398595B2 (ja) | 2003-04-21 |
EP0959103A3 (en) | 2001-04-04 |
EP0959103B1 (en) | 2005-10-12 |
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