CN100357351C - 模塑材料和用于激光熔合的模塑制品 - Google Patents

模塑材料和用于激光熔合的模塑制品 Download PDF

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CN100357351C
CN100357351C CNB2004800035537A CN200480003553A CN100357351C CN 100357351 C CN100357351 C CN 100357351C CN B2004800035537 A CNB2004800035537 A CN B2004800035537A CN 200480003553 A CN200480003553 A CN 200480003553A CN 100357351 C CN100357351 C CN 100357351C
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vinyl
compound
laser
rubber
resin
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CN1748002A (zh
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元重良一
加来野涉
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Denko Nitsubishi Corp
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TAKANON RESIN CO Ltd
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    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract

提供一种模塑材料和用于激光焊接的模塑制品，它包括热塑性树脂(A)，所述热塑性树脂(A)包括在橡胶状聚合物(a)存在下聚合乙烯基单体而获得的橡胶增强的树脂(A1)，或者含该橡胶增强的树脂(A1)与乙烯基单体的(共)聚合物(b)的组合物(A2)，和其中当所述模塑材料被模塑成4mm厚的样片时，它在808纳米的波长下的透光率范围为5%或更高。分散在热塑性树脂(A)内的橡胶状聚合物(a)的重均粒度优选为50-220纳米，和优选相对于100wt%的组分(a)包括用量为0-20wt%的直径为300纳米或更大的颗粒。激光可透过该模塑材料和模塑制品，并允许用各种树脂模塑技术激光焊接模塑材料和模塑制品。

Description

模塑材料和用于激光熔合的模塑制品
技术领域
本发明涉及模塑材料和适于通过激光焊接连接的模塑制品，和尤其涉及模塑材料和含有橡胶增强的树脂的模塑制品。
背景技术
作为一起连接由热塑性树脂组成的模塑制品的方法，除了使用紧固部件(螺栓、螺纹、夹子和类似物)或粘合剂以外，还常规地已知焊接技术，其中包括热板焊接、振动焊接、超声焊接和激光焊接。热板焊接是其中使模塑制品的待焊接的区域与热板接触，以便熔融，和在冷却与固结之前，使熔融区域彼此相对压制的技术。然而，当待焊接的区域从热板上分离时，该技术常常形成线状物，从而影响模塑制品的外观。振动焊接和超声焊接是其中固定一种制品，和在其上压制另一制品，同时施加振动或超声波，以便待焊接的区域熔融并通过摩擦能量焊接的技术。然而，这些技术在焊接区域内常常引起灰尘和线状毛边(flash)或引起弯曲毛边或其它问题。结果，取决于制品形状，模塑制品的外观常常劣化并变得无用。
激光焊接是其中待焊接的制品之一由激光吸收材料形成，而另一种由激光透射材料形成，和将它们层叠在一起，然后用激光在激光透射材料的一侧上进行辐照的方法。因此，穿过透射材料的激光加热并熔化激光吸收材料的表面，且还通过传热熔化激光透射材料，以便将两种树脂焊接在一起(参见，日本专利特开公布No.2001-71384)。该技术的优点在于，没有形成线状物、灰尘或毛边，所得焊接区域具有良好的外观，和它可用于焊接各种形状的模塑制品。尽管如此，该技术的局限在于待焊接的制品之一必须由激光透射模塑材料形成。
以丙烯腈-丁二烯-苯乙烯(ABS)树脂、高抗冲聚苯乙烯等为代表的橡胶增强的苯乙烯树脂的机械性能、物理性能、电性能等优良，因此用于宽范围的领域如电子或电器、办公自动化或家用电器、机动车和卫生用具上。然而，这些树脂的激光透射率低，因此不可能在激光焊接中使用，除非用由激光透射的材料制造的制品来焊接它们。
发明公开
因此，本发明的目的是提供模塑材料和模塑制品，它包括含橡胶增强的树脂的热塑性树脂且可透射激光，因此可以激光焊接到各种含树脂的模塑制品上。
本发明人就在树脂内分散的橡胶状聚合物的粒度及其分布方面深入地研究了橡胶改性的树脂，结果发现，当其粒度及其分布落在特定的范围内时，橡胶增强的树脂透射足以进行激光焊接的激光，从而完成本发明。
具体地说，根据本发明的一个方面，提供一种用于激光焊接的模塑材料，它包括热塑性树脂(A)，所述热塑性树脂(A)包括：
在橡胶状聚合物(a)存在下聚合乙烯基单体而获得的橡胶增强的树脂(A1)，
或者含所述橡胶增强的树脂(A1)和乙烯基单体的(共)聚合物(b)的组合物(A2)，
其中当所述模塑材料被模塑成4mm厚的样片时，该材料在808纳米的波长下的透光率范围为5％或更高。从可激光焊接性的角度考虑，上述透光率优选7％或更高，更优选10％或更高，和特别优选12％或更高。同时，在本发明的说明书中，术语“(共)聚合物”是指均聚物和/或共聚物。
根据本发明另一方面，提供一种用于激光焊接的包含热塑性树脂(A)的模塑材料，所述模塑材料包括：
在橡胶状聚合物(a)存在下，通过聚合乙烯基单体而获得的橡胶增强的树脂(A1)，
或者含所述橡胶增强的树脂(A1)和乙烯基单体的(共)聚合物(b)的组合物(A2)，
其中分散在所述热塑性树脂内的橡胶状聚合物(a)的重均粒度为50-220纳米。优选地，包含在该模塑材料内的橡胶状聚合物(a)包括相对于100wt％的组分(a)，用量为0-20wt％的直径为300纳米或更大的颗粒。
根据本发明又一方面，提供一种用于激光焊接的模塑制品，它由以上所述的用于激光焊接的模塑材料形成。
实施本发明的最佳模式
本发明中使用的热塑性树脂(A)含有或者在橡胶状聚合物(a)存在下，通过聚合乙烯基单体而获得的橡胶增强的树脂(A1)，或者含该橡胶增强的树脂(A1)和乙烯基单体的(共)聚合物(b)的组合物(A2)。
本发明中使用的组分(A1)优选是在5-70wt％的橡胶状聚合物(a)存在下，通过聚合95-30wt％的乙烯基单体而获得的橡胶增强的乙烯基树脂(在此情况下，橡胶状聚合物(a)和乙烯基单体之和为100wt％)。
橡胶状聚合物(a)的实例包括二烯(共)聚合物，如聚丁二烯、丁二烯-苯乙烯共聚物、丁二烯-丙烯腈共聚物、丁二烯-丙烯酰基共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物，和异丁烯-异戊二烯共聚物，这些二烯烃(共)聚合物的氢化产物、乙烯-α-烯烃或乙烯-α-烯烃-非共轭二烯共聚物(例如，乙烯-丙烯共聚物、乙烯-丙烯-非共轭二烯共聚物、乙烯-丁烯-1-共聚物、乙烯-丁烯-1-非共轭二烯共聚物)、聚氨酯橡胶、丙烯酰基橡胶和硅橡胶。可单独或结合两种或多种使用这些。在这些橡胶状聚合物当中，优选二烯(共)聚合物、二烯(共)聚合物的氢化产物、乙烯-α-烯烃或乙烯-α-烯烃-非共轭二烯共聚物、丙烯酰基橡胶和硅橡胶，和尤其优选二烯(共)聚合物。
橡胶状聚合物(a)以5-70wt％的用量，优选5-65wt％的用量存在于本发明的橡胶增强的树脂(A1)内。若橡胶状聚合物(a)的用量小于5wt％，则抗冲性下降。若它大于70wt％，则模塑制品的外观劣化。
分散在本发明的橡胶增强的树脂(A1)内的橡胶状聚合物(a)的重均粒度范围典型地为50-220纳米，优选80-210纳米，更优选100-200纳米，和尤其优选150-190纳米。若重均粒度大于220纳米，则模塑制品的激光透过率下降。结果模塑制品难以透过用于激光焊接的激光。若重均粒度小于50纳米，则抗冲性下降。为了确保均匀的激光透过率，优选橡胶状聚合物(a)包括相对于100wt％的组分(a)，用量为0-20wt％的直径为300纳米或更大的颗粒。
本发明中使用的橡胶状聚合物(a)优选是通过乳液聚合获得的聚合物。可例如通过合适地设定聚合条件，以便在橡胶状聚合物(a)的乳液聚合过程中生产的胶乳满足以上所述的粒度要求，从而生产满足以上所述粒度要求的模塑材料。或者，可通过合适地混合由重均粒度小的胶乳组成的橡胶状聚合物和由重均粒度大的胶乳组成的橡胶状聚合物，从而获得满足上述粒度要求的橡胶状聚合物。
在本发明的组分(A1)中使用的乙烯基单体优选包括选自芳族乙烯基化合物、乙烯基氰化物和可与这些化合物共聚的其它乙烯基化合物中的至少一种单体。
芳族乙烯基化合物的实例包括苯乙烯、α-甲基苯乙烯、邻甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、甲基-α-甲基苯乙烯、苯乙烯溴和羟基苯乙烯。在这些当中，优选苯乙烯和α-甲基苯乙烯。
乙烯基氰化物的实例包括丙烯腈和甲基丙烯腈。在这些当中，优选丙烯腈。
可与芳族乙烯基化合物或乙烯基氰化物化合物共聚的其它乙烯基单体的实例包括例如，(甲基)丙烯酸酯和马来酰亚胺化合物，以及含有各种官能团的不饱和化合物，如含酸酐基的不饱和化合物，含羟基的不饱和化合物，含羧基的不饱和化合物，含环氧基的不饱和化合物，和含噁唑啉的不饱和化合物。此处所使用的术语“(甲基)丙烯酸”是指丙烯酸和/或甲基丙烯酸。
(甲基)丙烯酸酯的实例包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯和甲基丙烯酸丁酯。
马来酰亚胺化合物的实例包括N-甲基马来酰亚胺、N-丁基马来酰亚胺、N-苯基马来酰亚胺、N-(4-羟苯基)马来酰亚胺和N-环己基马来酰亚胺。可通过其中共聚马来酸酐，接着酰亚胺化的方法，从而引入这些马来酰亚胺化合物。
含酸酐基的不饱和化合物的实例包括马来酸酐、衣康酸酐和柠康酸酐。
含羟基的不饱和化合物的实例包括3-羟基1-丙烯、4-羟基-1-丁烯、顺式-4-羟基-2-丁烯、反式-4-羟基-2-丁烯、3-羟基-2-甲基-1-丙烯、丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、羟基苯乙烯和N-(4-羟苯基)马来酰亚胺。
含羧基的不饱和化合物的实例包括丙烯酸和甲基丙烯酸。
含环氧基的不饱和化合物的实例包括丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯和烯丙基缩水甘油醚。
含唑啉基的不饱和化合物的实例包括乙烯基唑啉。
以上所述的乙烯基单体可单独或结合两种或多种使用。
优选的乙烯基单体是含有芳族乙烯基化合物作为基本组分的那些。实例包括苯乙烯，苯乙烯与丙烯腈的结合，α-甲基苯乙烯、丙烯腈和甲基丙烯酸甲酯的结合，和苯乙烯与甲基丙烯酸甲酯的结合。尤其优选芳族乙烯基化合物和乙烯基氰化物的结合，尤其苯乙烯与丙烯腈的结合。
芳族乙烯基化合物对乙烯基氰化物化合物的共混比例优选为100-50/0-50wt％作为芳族乙烯基化合物/乙烯基氰化物化合物，更优选95-50/5-50wt％，和尤其优选75-65/25-35wt％。其它可共聚单体的共混比例相对于组分(A1)为0-50wt％，优选0-40wt％。
相对于本发明的组分(A1)，乙烯基单体的含量为30-95wt％，优选35-95wt％。若该含量大于95wt％，则抗冲性下降。若它小于30wt％，则模塑制品的外观劣化。
可通过使用已知的聚合工艺，如乳液聚合、本体聚合、溶液聚合、悬浮聚合及其结合，聚合本发明的组分(A1)。为了实现本发明的目的，尤其优选通过乳液聚合获得的聚合物。
当通过乳液聚合生产时，使用聚合引发剂、链转移剂、乳化剂和水。这些可以是任何已知的一种。可通过全部、间歇或连续地将乙烯基单体加入到全部含量的橡胶状聚合物(a)中，从而进行在橡胶状聚合物(a)存在下乙烯基单体的聚合，或者可结合使用添加技术。或者，在聚合工艺过程中可添加并聚合全部或部分橡胶状聚合物(a)。
聚合引发剂的实例包括例如氢过氧化枯烯、氢过氧化二异丙基苯、过硫酸钾、偶氮二异丁腈、过氧化苯甲酰、过氧化月桂酰、过月桂酸叔丁酯和过单碳酸叔丁酯。
链转移剂的实例包括辛基硫醇、正十二烷基硫醇、叔十二烷基硫醇、正己基硫醇、二硫化四乙基秋兰姆、丙烯醛、甲基丙烯醛、烯丙醇和2-乙基己基硫代二醇。
在乳液聚合工艺中所使用的乳化剂的实例包括例如高级醇的硫酸酯，烷基苯磺酸盐如十二烷基苯磺酸钠，脂族磺酸盐如硫酸月桂酯钠，阴离子表面活性剂如高级脂族羧酸的盐、松香酸的盐，和磷酸的盐，和已知的非离子表面活性剂。
在乳液聚合工艺中，通常使用混凝剂获得粉末，然后用水洗涤所述粉末，并干燥，得到粉化的橡胶增强的树脂。为此目的而使用的混凝剂可以是无机盐如氯化钙、硫酸镁和氯化镁，或酸如硫酸、盐酸和乙酸。
在本体聚合、溶液聚合和悬浮聚合工艺中，使用各种溶剂、悬浮剂、聚合引发剂、链转移剂和其它试剂、这些可以是任何已知的试剂。
当通过乳液聚合获得本发明的组分(A1)时，在大多数情况下橡胶状聚合物是通过乳液聚合获得的聚合物。在这一情况下，橡胶状聚合物的凝胶含量典型地为98wt％或更低，优选40-98wt％，更优选50-95wt％，和尤其优选60-90wt％。当凝胶含量为40-98wt％时，可获得提供模塑制品尤其优良的抗冲性和表面外观的热塑性树脂组合物。
在如上所述的凝胶含量的测定中，将1g橡胶状聚合物加入到100ml甲苯中。使混合物在室温下静置48小时，然后通过100目的筛网过滤(重量＝W1)。在80℃下真空干燥在甲苯内的不溶物和筛余物6小时并称重(重量＝W2)。然后可通过下述方程式测定凝胶含量：
凝胶含量(％)＝[{W2(g)-W1(g)}/1(g)]×100
当生产橡胶状聚合物时，可通过设定分子量调节剂的类型与用量、聚合时间与温度，和聚合转化速度来调节凝胶含量。
本发明的组分(A1)的接枝比优选20-200wt％，更优选30-150wt％，和尤其优选40-120wt％。可用下述方程式获得接枝比(％)：
接枝比(％)＝{(T-S)/S}×100
在上述方程式中，如下所述测定T：将1g组分(A1)加入到20ml丙酮中。藉助振摇器摇动混合物2小时，然后离心60分钟(23000rpm)，分离可溶和不溶物。然后T表示不溶物的重量(g)，S是在1g组分(A1)内存在的橡胶状聚合物的重量(g)。
组分(A1)的丙酮可溶物的特性粘度[η](使用甲乙酮作为溶剂在30℃下测定)优选0.2-1.2dl/g，更优选0.2-1dl/g，和尤其优选0.3-0.8dl/g。
本发明的组分(A2)是通过共混以上所述的橡胶增强的树脂(A1)与乙烯基单体的(共)聚合物(b)而获得的组合物。
在本发明的组分(b)中使用的乙烯基单体优选包括选自芳族乙烯基化合物、乙烯基氰化物和可与这些化合物共聚的其它乙烯基化合物中的至少一种单体。
芳族化合物和乙烯基氰化物化合物可以是相对于组分(A1)描述的任何一种。
可与芳族化合物或乙烯基氰化物化合物共聚的其它乙烯基化合物可以是相对于组分(A1)描述的任何一种。
这些乙烯基单体可单独或结合两种或多种使用。
在本发明的组分(A2)中使用的优选的(共)聚合物(b)是含有芳族乙烯基化合物作为基本组分的那些。优选的(共)聚合物的实例包括例如芳族乙烯基化合物的均聚物，和芳族乙烯基化合物与至少一种选自乙烯基氰化物化合物、(甲基)丙烯酸酯、马来酰亚胺化合物和含酸酐的不饱和化合物中的乙烯基单体的共聚物。在这些当中，特别优选由含芳族乙烯基化合物和乙烯基氰化物化合物作为基本组分的单体组成的共聚物，尤其苯乙烯-丙烯腈共聚物、苯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物和苯乙烯-丙烯腈-马来酰亚胺化合物的共聚物。
从性能与可加工性之间的平衡的角度考虑，在组分(b)中使用的芳族乙烯基化合物对乙烯基氰化物化合物的共混比例优选95-50/5-50wt％作为芳族乙烯基化合物/乙烯基氰化物化合物，和更优选75-65/25-35wt％。
在本发明中，将乙烯基(共)聚合物(b)以预定用量加入到组分(A2)中，以便相对于100wt％的组分(A2)，来自于组分(A1)的橡胶状聚合物(a)的含量优选5-40wt％，更优选5-35wt％，和尤其优选7-30wt％。若橡胶状聚合物(a)的含量小于以上所述的范围，则抗冲性劣化。若含量大于以上所述的范围，则模塑制品表面的外观劣化。
可通过使用已知的聚合工艺如乳液聚合、本体聚合、溶液聚合、悬浮聚合及其结合，生产本发明的组分(b)。
当通过溶液聚合生产组分(b)时，可使用相对于组分(A1)描述的工艺。
在溶液聚合中使用的溶剂可以是在常见的自由基聚合中使用的惰性聚合溶剂。实例包括芳烃如乙基苯和甲苯，酮如甲乙酮和丙酮，卤代烃如二氯甲烷和四氯化碳，乙腈，二甲基甲酰胺和N-甲基吡咯烷酮。聚合温度优选80-140℃，更优选85-130℃，和尤其优选90-120℃。
可在没有使用聚合引发剂的情况下通过热聚合技术进行聚合，或者可通过使用聚合引发剂进行聚合。作为聚合引发剂，优选使用有机过氧化物如过氧化酮、二烷基过氧化物、二酰基过氧化物、过酯和过氧化氢。链转移剂的实例包括硫醇和α-甲基苯乙烯二聚体。
在本体聚合中，可使用相对于溶液聚合所描述的所有聚合引发剂和链转移剂。
组分(b)的特性粘度[η](使用甲乙酮作为溶剂在30℃下测定)优选0.2-1.2dl/g，更优选0.2-1dl/g，和尤其优选0.3-0.8dl/g。
可合适地通过混合组分(b)与组分(A1)生产本发明的组分(A2)。
最终残留在组分(A1)与组分(A2)内的单体含量优选10000ppm或更低，和更优选5000ppm或更低。
在本发明中，在组分(A)内的橡胶状聚合物(a)的含量相对于100wt％的组分(A)，优选5-40wt％，更优选5-35wt％，和尤其优选7-30wt％。若含量小于以上所述的范围，则抗冲性下降。若含量大于以上所述的范围，则模塑制品的可成型性和表面外观劣化。
取决于所打算的目的和应用，可向本发明的热塑性树脂(A)中进一步添加添加剂如无机填料、金属粉末、增强剂、增塑剂、相容剂、热稳定剂、光稳定剂、抗氧剂、UV吸收剂、染料、颜料、抗静电剂、润滑剂和阻燃剂，只要不影响透光率即可。
可在没有脱离本发明目的的情况下，向本发明的热塑性树脂(A)中进一步添加其它聚合物(B)，所述其它聚合物(B)包括例如聚碳酸酯树脂、聚酯树脂、聚酰胺树脂、聚酰胺弹性体、聚酯弹性体、聚乙烯、聚丙烯、聚苯醚、聚芳醚、POM(聚缩醛)、酚醛树脂、环氧树脂和LCP(液晶聚合物)。
可通过各种挤塑机、亨舍尔混合机、本伯里密炼机、捏合机、辊、热炼机ruder或类似机器，通过熔融并一起捏合各组分，从而生产本发明的模塑材料。可优选使用挤塑机、亨舍尔混合机或本伯里密炼机的生产工艺。
此外，当捏合各组分时，可一次捏合所有组分，或者可以使用挤塑机、亨舍尔混合机或本伯里密炼机，在多步中逐渐供入各组分并捏合。
在亨舍尔混合机、本伯里密炼机、捏合机或类似机器中捏合的产物可在挤塑机中进一步制成粒料。
可通过任何已知的模塑技术，其中包括注塑、压模、片材挤塑、真空模塑、异形挤塑和发泡成形，将本发明的模塑材料模塑成模塑制品。
可通过在激光吸收树脂模塑制品上层叠本发明的模塑制品，并用激光辐照本发明的模塑制品，将本发明的模塑制品与另一树脂模塑制品一起激光焊接。可使用的激光包括玻璃：钕3+激光器，YAG：钕3+激光器，红宝石激光器、氦氖激光器、氪激光器、氩激光器、H2激光器、N2激光器和半导体激光器的激光。在这些当中，优选半导体激光器。激光的波长优选1060纳米或更短，但它可随树脂模塑制品而变化。若激光波长长于1060纳米，则难以熔化待焊接的表面。激光器的功率优选5-100W。低于5W的激光器功率太低，以致于不可能熔化树脂模塑制品的待焊接的表面。高于100W的功率过高和可蒸发或分解模塑材料。
附图简述
图1是显示评价可焊接性的方法的示意图。
实施例
下文参考实施例将更详细地描述本发明。应当理解本发明不限于下述实施例。
在下述实施例中，分数和百分数以重量为基础，除非另有说明。在实施例中，基于下述方式进行评价。
(1)评价方法
(1-1)测量透光率
在240℃下压制已生产的粒料5分钟，形成4mm厚、10mm宽的样片。使用分光光度计(MPS-2000，Shimadzu Corporation)，在808纳米的波长下测量样片的透光率。
(1-2)橡胶状聚合物中尺寸为300纳米或更大的颗粒的重均粒度和比例
使用由Nikkiso Co.，Ltd.制造的粒度分析仪UPA 150(商品名)，通过测量所生产的乳液状态的胶乳的粒度，获得橡胶状聚合物的粒度。事先已通过电子显微镜证明，所测量的粒度相当于在树脂内分散的颗粒的粒度。相对于100％全部的橡胶状聚合物，测定橡胶状聚合物中尺寸为300纳米或更大的颗粒的比例。
(1-3)组分(A)(橡胶增强的树脂)的接枝比
以与以上所述的方式测量组分(A)的接枝比。
(1-4)评价可焊接性
如图1所示，将与(1-1)中相同的方式制造的样片2层叠在待焊接的样片1上。样片1具有与样片2相同的尺寸。使用由Leister制造的激光焊接器NOVOLAS-C，在下述条件下在样片2上辐照激光，使样片2焊接到样片1上。
<激光焊接的条件>
激光功率＝16A
速度＝30mm/sec
焊接宽度＝2mm
焊接长度＝10mm
压力＝7kg/cm2
采用拉伸测试仪，在2mm/min的速度下，以与图1中箭头所示的方向牵拉焊接样片1和样片2之一，同时固定另一样片。观察焊接区域3的破坏状态并根据下述标准评价可焊接性：
○：焊接强度足够高到使样片主体破坏；
△：在样片的界面处发生剥离，和样片主体也破坏；
×：在样片的界面处发生剥离。
(2)热塑性树脂组合物的各组分
生产实施例a-1(橡胶状聚合物1的生产)
提供配有回流冷凝器、搅拌器、加料器、温度计等的5升不锈钢高压釜。将150份去离子水、4.0份高级脂肪酸皂(主要由18个碳原子的脂肪酸组成的脂肪酸的钠盐)和0.075份氢氧化钠放置在高压釜中。在高压釜内的氛围用氮气替换，且在搅拌的同时加热该混合物到68℃。最后，添加由100份1，3-丁二烯(BD)和0.3份叔十二烷基硫醇(TDM)组成的20％单体混合物，接着添加0.135份过硫酸钾。在数分钟之后，混合物产生热量，表明聚合引发。在添加过硫酸钾之后1小时，开始继续添加其余80％的单体混合物。在6小时内添加单体混合物。在连续添加单体混合物之后，内部温度升高到80℃，并使反应在该温度下进行1小时，然后终止聚合反应。所得橡胶状聚合物胶乳的重均粒度为180纳米。2.0％的颗粒尺寸为300纳米或更大。
生产实施例a-2(橡胶状聚合物2的生产)
以与生产实施例a-1相同的方式进行聚合反应，所不同的是在反应开始时添加0.5份碳酸钠。所得橡胶状聚合物胶乳的重均粒度为500纳米。80％颗粒的尺寸为300纳米或更大。
生产实施例A-1到A-4(橡胶增强的树脂的生产)
使用根据表1所示比例的橡胶状聚合物、苯乙烯聚合物和丙烯腈单体进行乳液聚合。随后添加硫酸镁，使反应混合物聚结，和洗涤固体产物并干燥，得到橡胶增强的树脂(在表中表示为ABS 1-4)。表1示出了每一橡胶增强的树脂的接枝比。
生产实施例A-5(苯乙烯-丙烯腈共聚物的生产)
使用根据表1所示比例的苯乙烯单体和丙烯腈单体，进行溶液聚合，得到苯乙烯-丙烯腈共聚物(在表1中表示为AS1)。
表1
  ABS1(重量份)   ABS2(重量份)   ABS3(重量份)   ABS4(重量份)   AS1(重量份)   AS2(重量份)
橡胶状聚合物1*1 40 38 36 24 - -
橡胶状聚合物2*2     - 2 4 16 - -
    苯乙烯单体     42     42     42     42     70     43
    丙烯腈单体     18     18     18     18     30     -
    N-苯基马来酰亚胺     -     -     -     -     -     55
    马来酸酐单体     -     -     -     -     -     2
    橡胶状聚合物的重均粒度(nm)     180     196     212     308     -     -
    在橡胶状聚合物的颗粒中尺寸为300nm或更大的颗粒的比例(％)     2.0     5.9     9.8     33.2     -     -
    接枝比(％)     90     80     70     60     -     -
*1重均粒度＝180nm
*2重均粒度＝500nm
实施例1-3和对比例1
将各组分根据表2所示的比例与0.2份润滑剂和0.3份抗氧剂一起装载在亨舍尔混合机内。在混合之后，熔化混合物并通过双螺杆挤出机(TEM50A，Toshiba Machine Co.，Ltd.)在220-250℃下捏合，获得粒料形式的树脂组合物。然后使该树脂组合物进行透射率测量，并以如上所述的方式评价可焊接性。当评价可焊接性时，如下所述制备待焊接的样片：通过以如上所述的相同方式制备树脂组合物，所不同的是100份商购的ABS树脂(商品名：Techno ABS130)与0.2份润滑剂和0.3份抗氧剂一起使用，然后以与以上(1-1)中相同的方式模塑所得树脂组合物，从而获得模塑制品(透光率＝低于1％)。结果见表2。
实施例4
以与实施例1相同的方式获得树脂组合物，所不同的是使用苯乙烯-N-苯基马来酰亚胺-马来酸酐共聚物(Malecca MS-N(商品名)，Denki Kagaku Kogyo K.K.，在表中表示为AS2)替代苯乙烯-丙烯腈共聚物。以与实施例1相同的方式对该树脂组合物进行透光率的测量并评价可焊接性。结果见下表2。
表2
  实施例1   实施例2   实施例3   实施例4   对比例1
  ABS1(重量份)     50     -     -     50     -
  ABS2(重量份)     -     50     -     -     -
  ABS3(重量份)     -     -     50     -     -
  ABS4(重量份)     -     -     -     -     50
  AS1(重量份)     50     50     50     -     50
  AS2(重量份)     -     -     -     50     -
  透光率(％)     32     17     10     29     3
  可焊接性评价     0     0     △     0     ×
表1-4的树脂组合物各自显示出5％或过高的透光率，全部具有良好的可焊接性。相反，透光率低于5％的对比例1的树脂组合物没有透射足够的激光以实现激光焊接。实施例2和实施例3之间的可焊接性的比较表明，当透光率为10％或更高时，实现优良的激光可焊接性。
工业实用性
根据本发明具有高的激光透光率的橡胶增强的树脂使得可能将由橡胶增强的树脂模塑的模塑制品激光焊接成由激光吸收树脂模塑的模塑制品。

Claims (3)

1.一种用于激光焊接的模塑材料，它包括热塑性树脂(A)，所述热塑性树脂(A)包括：
在橡胶状聚合物(a)存在下聚合乙烯基单体而获得的橡胶增强的树脂(A1)，所述橡胶状聚合物(a)是选自如下的至少一种：二烯(共)聚合物，这些二烯(共)聚合物的氢化产物，乙烯-α-烯烃或乙烯-α-烯烃非共轭二烯共聚物，聚氨酯橡胶，丙烯酰基橡胶和硅氧烷橡胶；并且所述乙烯基单体是选自如下的至少一种单体：芳族乙烯基化合物，乙烯基氰化物化合物和能与这些化合物共聚的其它乙烯基化合物，
或者含该橡胶增强的树脂(A1)和乙烯基单体的(共)聚合物(b)的组合物(A2)，所述乙烯基单体是选自如下的至少一种单体：芳族乙烯基化合物，乙烯基氰化物化合物和能与这些化合物共聚的其它乙烯基化合物，
其中分散在所述热塑性树脂中的所述橡胶状聚合物(a)具有50-220纳米的重均粒度，和
其中当所述热塑性材料被模塑成4毫米厚的样片时，该材料在808纳米的波长下的透光率范围为5％或更高。
2.权利要求1的用于激光焊接的模塑材料，其中所述橡胶状聚合物(a)包括，相对于100wt％的组分(a)，用量为0-20wt％的直径为300纳米或更大的颗粒。
3.一种用于激光焊接的模塑制品，它由权利要求1或2定义的用于激光焊接的模塑材料形成。
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