CN104755553A - 用于电子装置的模塑和重叠模塑组合物 - Google Patents
用于电子装置的模塑和重叠模塑组合物 Download PDFInfo
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- CN104755553A CN104755553A CN201380056404.6A CN201380056404A CN104755553A CN 104755553 A CN104755553 A CN 104755553A CN 201380056404 A CN201380056404 A CN 201380056404A CN 104755553 A CN104755553 A CN 104755553A
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Abstract
本发明涉及用于精密组件的模塑和重叠模塑组合物。更具体地,本发明涉及用于低压模塑和重叠模塑的组合物,从而使得这些组合物特别适合电子装置。所述模塑和重叠模塑组合物适合于低压注塑方法,特别是在0.5-200巴和70℃-240℃的低压注塑方法。
Description
技术领域
本发明涉及用于电子装置的模塑(molding)和重叠模塑(overmolding)组合物。更具体地,本发明涉及用于在低压下模塑和重叠模塑的组合物,从而使得这些组合物特别适合与电子装置一起使用。
背景技术
模塑是通过将塑料或金属材料液化到模腔中并将材料冷却和硬化成空腔的结构来制造成形制品的制造方法。在重叠模塑中,可以将预先模塑的部件再插入新的模具中,以在所述预先模塑的部件周围形成新的模塑层,并且成为新制品的组成部分。重叠模塑可以在不使用任何粘合剂或底漆的情况下将两个不同的组件结合在一起。两个不同的组件的这种组合允许产生具有人体工程学舒适性和安抚显示(appeasing display)的坚固的结构产品。
典型的注塑在250℃或更高温度下所需的压力大于200巴,因为模塑材料具有高的粘度和高的软化温度。尽管坚固的组件适合以较高的压力注塑,但精密组件无法承受高压和高温。典型的注塑方法的替代是低压注塑。这两种方法实质上相同,只是低压注塑需要在0.5-200巴和70℃-240℃进行注射。
照明或电子装置包含易碎组件,因此,低压注塑优于传统的高压注塑。电子装置包含例如LED(发光二极管)、连接器、传感器、电容器、微型开关、印刷电路板、电缆束、转发器等的组件。LED是半导体二极管,其消耗很少的能量(例如,小于5伏的电压或小于20毫安的电流),但所发射光的亮度超过远远更大的白炽灯泡发射的光的亮度。无论是灯类型或是表面安装装置(SMD)类型,LED通常包含LED芯片,所述芯片由光学透明和热稳定的材料封装到用于适当接线、安装和运行的装置中。
存在各种LED模塑和重叠模塑材料。WO 2010138221描述氨基甲酸酯、聚硅氧烷和丙烯酸类的两部分液体模塑系统。尽管所述两部分液体系统的性能是可接受的,但液体形式通常导致使用例如灌封(potting)或流延的特殊技术来制造聚硅氧烷主体以及延长的固化时间(例如超过几个小时到几天),从而导致较低的生产力。延长的固化时间又可导致尤其是用较厚的模具时缺乏表面均匀性,并且转化成所得LED的低光学质量。
环氧树脂也被广泛地用作模塑和重叠模塑组合物。然而,环氧树脂往往表现出较差的光稳定性,因为它们在暴露于紫外(UV)光或升高的热条件(例如,超过(>)110℃的温度>1000小时的时间)后随着时间的推移而泛黄。泛黄又导致随着时间的推移从LED的光输出降低。此外,固化通常进行较长的时间(例如,3小时),以最小化固化的环氧树脂的等分试样(aliquot)内的残余应力。“残余应力”是指在不施加外部负载(例如外加力或热梯度的位移)下存在于块状材料中的拉紧(tension)或压缩。随着LED材料内的残余应力增大,在LED的使用寿命中往往会发生不利效果,例如尺寸变化或开裂。
聚酰胺由于其低粘度而广泛地用于低压注塑。尽管非常适合作为模塑和重叠模塑材料,但聚酰胺通常为琥珀色的,这对于光学应用是不希望的。
美国公开第2011/0133245号教导用于LED封装材料和重叠模塑应用的氢化苯乙烯/丁二烯三嵌段聚合物组合物;然而,所述组合物的粘度对于低压注塑方法而言太高。
WO200954553A2教导丙烯酸嵌段共聚物具有出色的透明度、低色度和可用于光学应用的稳定性。颁予Kato的美国专利第6894114号进一步教导,丙烯酸嵌段共聚物可用于模塑制品;然而,所述材料局限于传统的高压注塑方法。
更通常地,将丙烯酸嵌段共聚物与增粘剂组合作为压敏材料。压敏材料表现出“强烈且持久的粘性”或者在活化温度下表现出粘性(可热活化),并且在环境温度下具有小于3×106达因/厘米2的模量值。颁予Everaerts等人的美国专利第6,734,256号教导使用丙烯酸嵌段和大量的增粘剂(>28.5%)以获得可热熔加工的粘合剂,例如压敏粘合剂(PSA)或可热活化的粘合剂组合物。此外,颁予Everaerts等人的美国专利第7,084,209号教导使用丙烯酸嵌段共聚物和大量的增粘剂用于压敏粘合剂带。
本领域需要用于低压注塑的非粘性模塑和重叠模塑组合物,其具有快速生产能力和透明度,而不会损坏待重叠模塑的制品的精密电气或电子组件。本发明满足这种需要。
发明内容
本发明涉及适合在制备电子装置中用作在低压下模塑或重叠模塑材料的组合物,以及所得模塑和重叠模塑的装置。
本发明的一个方面涉及重叠模塑组合物,其包含:(1)[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的[A]单体,以及(2)增粘树脂。所述重叠模塑组合物在210℃根据ASTM D3236测量的粘度小于75,000cP,并且在25℃模量大于1×107达因/厘米2。
本发明的另一个方面涉及包含电子组件和重叠模塑组合物的制品。所述重叠模塑组合物包含(1)[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的[A]单体,(2)增粘树脂,以及(3)约0.05-约5重量%的选自苯并三唑、三嗪和二苯甲酮的紫外线吸收剂。所述重叠模塑组合物的根据ASTMD6090测量的软化点大于135℃。
本发明的再一个方面涉及在电子组件上形成重叠模塑件的方法,其包括:(a)制备重叠模塑组合物,其包含:[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的[A]单体;增粘树脂;以及0.05-约5重量%的选自苯并三唑、三嗪和二苯甲酮的紫外线吸收剂;(b)将所述重叠模塑组合物在小于150巴的压力下施加在所述电子组件上;以及(c)冷却所述重叠模塑组合物。
具体实施方式
本文引用的所有文件的全部内容都通过引用并入本文。
除非另有说明,否则重量百分比(重量%)都是基于组合物的总重量的。
术语“模塑”和“重叠模塑”可互换使用以表示单材料模塑或多材料模塑。
本发明涉及适于重叠模塑精密组件的组合物,所述精密组件优选电子组件,更优选要求高透明度的电子组件。
所述重叠模塑组合物包含(1)[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的[A]单体;以及(2)增粘树脂。本发明的重叠模塑组合物表现出独特的特征,从而使其可用于电子组件的低压模塑。例如高透射率、低色度、UV稳定性和耐热循环性的特征使得模塑和重叠模塑组合物非常适合于包含易碎组件的照明或电子装置。
在一个实施方案中,按重叠模塑组合物的重量计,嵌段共聚物组分以等于或大于50%的水平存在。
如本文所用,丙烯酸类聚合物意欲包括含有至少一种丙烯酸或甲基丙烯酸烷基酯单体的那些聚合物。可在本发明的实践中使用的嵌段共聚物通常是其中大于约35重量%的聚合物包含至少2种硬嵌段的多嵌段聚合物。有用的嵌段共聚物的实例包括式-A-B-A-和(-A-B-)n-Xm的那些。特别优选式-[A1]-[B]-[A2]-的嵌段共聚物。在上述代表性的式中,A、A1和A2各自表示通过差示扫描量热法(DSC)所测定的玻璃化转变温度(Tg)大于约30℃,优选大于80℃,最优选大于110℃的聚合物嵌段,B表示通过DSC所测定的Tg小于约20℃,优选小于0℃,最优选小于-20℃的聚合物嵌段,并且X表示多官能偶联剂,例如四氯化硅、二溴乙烷和亚磷酸三(壬基苯基)酯。
丙烯酸类嵌段的Tg可通过以20℃/分钟的加热速率用5mg或更少的样品进行的差示扫描量热法(DSC)测定。Tg计算为DSC热容加热曲线上对应于玻璃化转变的热流变化的起点和终点之间的中点。使用DSC来测定Tg在本领域熟知,并且由B.Cassel和M.P.DiVito在“Use of DSC To Obtain AccurateThermodynamic and Kinetic Data”,American Laboratory,1994年1月,第14-19页中以及由B.Wunderlich在Thermal Analysis,Academic Press公司,1990年中描述。
合适的A1和A2聚合物嵌段包括衍生自丙烯酸或甲基丙烯酸烷基酯单体的聚合物或共聚物,所述丙烯酸或甲基丙烯酸烷基酯单体例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丁酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸环己酯和它们的组合。优选的A1和A2聚合物嵌段是甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、甲基丙烯酸环己酯和它们的组合。
合适的B聚合物嵌段包括衍生自丙烯酸或甲基丙烯酸烷基酯单体的聚合物或共聚物,所述丙烯酸或甲基丙烯酸烷基酯单体例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丁酯、丙烯酸正丁酯、丙烯酸正丙酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸戊酯、丙烯酸异戊酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸月桂酯、丙烯酸异辛酯、甲基丙烯酸癸酯和它们的组合。优选的B聚合物嵌段是丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸异辛酯和它们的组合。
应理解,硬嵌段和软嵌段中可包含相同的丙烯酸类单体,并且在聚合物嵌段的制备中可使用一种或多种其它可共聚单体。可共聚单体包括但不限于丙烯酸、甲基丙烯酸、乙烯基酯、乙烯基醚、苯乙烯单体,以及丙烯酰胺和甲基丙烯酰胺。其它共聚单体可以各嵌段的不超过约25%,优选小于10%的量存在,前提是它们不干扰冷却后硬嵌段和软嵌段之间的干净的相分离。
[A]单体按重量计以大于约35%,优选大于45%的聚合物存在。
在一个特别优选的实施方案中,A1和A2是甲基丙烯酸甲酯,并且B是丙烯酸正丁酯。合适的嵌段共聚物可以商品名KURARITYTM从Kuraray购得。一种例示性嵌段共聚物是具有聚(甲基丙烯酸甲酯)末端嵌段和聚(丙烯酸正丁酯)中间嵌段的LA4285三嵌段共聚物。可加入其它嵌段共聚物,例如具有聚(甲基丙烯酸甲酯)末端嵌段和聚(丙烯酸正丁酯)中间嵌段的LA2250、LA2140e和LA2330三嵌段共聚物,以改性组合物的性质和加工条件。
丙烯酸嵌段共聚物的分子量没有特别的限制,但从本发明的光学组件的模塑性的观点来看,通过凝胶渗透色谱法(GPC)测量所测定并且以聚苯乙烯换算的共聚物的重均分子量优选10,000-500,000Da,更优选20,000-300,000Da。
制备丙烯酸嵌段共聚物的方法在本领域已知。用于本发明的实践的嵌段共聚物可通过以下方式制备:如日本专利公开11-302617中所述的阴离子聚合、如P.Mancinelli,Materiaux et Techniques,1990年3-4月,第41-46页所述的自由基聚合、由例如美国专利第5,679,762号描述的多官能链转移剂、如EP0 349 270 B1中所述的引发转移终止剂聚合和/或如共同待审查的共同受让的美国申请第10/045,881号中所述的自由基反向(retrograde)沉淀。特别优选通过阴离子聚合制备的丙烯酸类嵌段共聚物。
所述重叠模塑组合物还包含增粘树脂。增粘树脂以基于总组合物至少约10重量%,优选至少约15重量%,更优选至少约20重量%存在。
如通过ASTM方法E28测定的,典型的增粘剂具有约70℃-约150℃的环球软化点。
有用的增粘树脂可包括任何相容的树脂或它们的混合物,例如天然和改性松香,包括例如脂松香、木松香、妥尔油松香、蒸馏松香、氢化松香、二聚松香、树脂酸盐和聚合松香;天然和改性松香的甘油酯和季戊四醇酯,包括例如灰木松香的甘油酯、氢化松香的甘油酯、聚合松香的甘油酯、氢化松香的季戊四醇酯以及酚醛改性的松香季戊四醇酯;天然萜烯的共聚物和三元共聚物,包括例如苯乙烯/萜烯和α-甲基苯乙烯/萜烯;通过ASTM方法E28-58T所测定的软化点为约70℃-150℃的聚萜烯树脂;酚醛改性的萜烯树脂和其氢化衍生物,包括例如由二环萜烯和酚在酸性介质中缩合产生的树脂产物;具有约70℃-135℃的环球软化点的脂族石油烃树脂;芳族石油烃树脂和其氢化衍生物;以及脂环族石油烃树脂和其氢化衍生物。
在一个实施方案中,增粘剂是合成烃树脂。包括脂族或脂环族烃、芳烃、芳族改性的脂族或脂环族烃以及其混合物。非限制性实例包括衍生自脂族烯烃的树脂。
也可使用芳烃树脂,其衍生自C9芳族/脂族烯烃,并且可以相同的商品名Norsolene从Sartomer和Cray Valley购得,以及购自TK芳烃树脂的Rutgers系列。
α-甲基苯乙烯例如来自Eastman Chemical的Kristalex 3085和3100、来自Arizona Chemical的Sylvares SA 100也可在本发明中用作增粘剂。
对于一些重叠模塑组合物,可能需要两种或更多种所述增粘树脂的混合物。
本发明的重叠模塑组合物中的例示性增粘树脂包括α-甲基苯乙烯、松香酯、歧化和/或氢化松香酯、苯乙烯化萜烯、萜烯酚、脂族改性的芳族树脂和它们的混合物。
在另一个实施方案中,所述重叠模塑组合物还包含低分子量的末端嵌段增粘剂。低分子量是指平均分子量小于20,000Da。末端嵌段增粘剂是加强硬的A嵌段相而不是软的B嵌段相的那些。合适的末端嵌段增粘剂包括基于丙烯酸酯的末端嵌段增粘树脂。一种特别优选的末端嵌段增粘树脂是分子量小于20,000Da的聚(甲基丙烯酸甲酯)树脂。
所述重叠模塑组合物还可以包含约0.05-约5重量%的紫外线吸收剂。紫外线吸收剂是苯并三唑、三嗪、二苯甲酮、氰基丙烯酸酯、草酰替苯胺等。此类紫外线吸收剂的实例包括Tinuvin 328、Tinuvin 329、Tinuvin 384-2、Tinuvin400、Tinuvin 479、Tinuvin 900、Tinuvin 928、Tinuvin 1130,以及以Tinuvin和Chimassorb商品名购自BASF和以BLS商品名购自Mayzo的其它紫外线吸收剂。
在一个优选实施方案中,苯并三唑是具有以下结构的羟基苯基苯并三唑:
其中R1、R2、R4=H、C1-C20脂族、脂环族或芳族基,并且其中,R3不为H。在一个优选实施方案中,R3是C1-C20脂族、脂环族或芳族基。
包含上述紫外线吸收剂的重叠模塑组合物随着时间的推移具有长期UV稳定性和高透明度。在一些实施方案中,甚至在UV老化至少3000小时后,根据ASTM G154测量,UV稳定性和色度(b值)小于8,优选小于5。
在另一个实施方案中,所述重叠模塑组合物还包含约0.05-约5重量%的受阻胺光稳定剂。例示性受阻胺光稳定剂是可从BASF购得的Tinuvin 152、Tinuvin 292、Tinuvin 622、Tinuvin 770和Tinuvin 783,以及可从Mayzo购得的BLS 1944和BLS 123。
本文所述的重叠模塑组合物还可以包含不超过约3重量%的量,更通常约0.5重量%的量的抗氧化剂或稳定剂。可用于本发明的稳定剂或抗氧化剂包括受阻酚或与辅助抗氧化剂例如硫代二丙酸二硬脂酯(“DSTDP”)或硫代二丙酸二月桂酯(“DLTDP”)组合的受阻酚。代表性抗氧化剂包括:1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯;季戊四醇四-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯;季戊四醇四(3-月桂基硫代二丙酸酯);正十八烷基-3,5-二叔丁基-4-羟基苯酚)丙酸酯;4,4′-亚甲基双(2,6-叔丁基苯酚);4,4′-硫代双(6-叔丁基-邻-甲酚);2,6-二叔丁基苯酚;6-(4-羟基苯氧基)-2,4-双(正辛基-4-硫代)-1,3,5-三嗪;3,5-二叔丁基-4-羟基苄基膦酸二-正十八烷基酯;3,5-二叔丁基-4-羟基-苯甲酸2-(正辛基硫代)乙酯;以及山梨醇六[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。优选IRGAFOS 168(从BASF购得的辅助抗氧化剂)和IRGANOX 1010(从BASF购得的受阻酚主抗氧化剂)。其它抗氧化剂包括ETHANOX 330(来自Albermarle的受阻酚);SANTOVAR A(来自Monsanto的2,5-二叔戊基氢醌);以及NAUGARD P(来自Chemtura的亚磷酸三(对壬基苯基)酯)。
也可加入通常用于重叠模塑组合物中以实现不同的性质并满足特定的应用要求的其它添加剂。此类添加剂包括例如蜡、增塑剂、填料、颜料、流动改性剂、染料、脱模剂或抗静电剂,其可根据目的以少量或较大量掺入粘合剂配制物中。
向精密电子组件施加大的压力会损坏组件。本发明的重叠模塑组合物在210℃通过ASTM D3236测量的粘度低于75,000cP。在另一个实施方案中,所述重叠模塑组合物在210℃的粘度低于50,000cP。由于在210℃的低粘度,本发明的重叠模塑组合物可用于低压模塑方法。
用以制造本发明的包含精密电子组件的制品的模塑方法的实例包括熔融挤出、熔融注塑和溶液流延。
将重叠模塑材料熔融,并注射到具有电子组件的封闭模具或中空部件中。冷却重叠模塑组合物后,将电子组件与重叠模塑组合物从模具中取出。电子组件包括连接器、传感器、电容器、微型开关、LED、印刷电路板、电缆束和转发器。较高的压力和高温不适合于电子组件。低压重叠模塑在0.5-200巴和70℃-240℃进行。本发明的重叠模塑组合物可优选在低于200巴并且在240℃,更优选在低于150巴、120巴、60巴并且在210℃经历低压重叠模塑。此外,所述重叠模塑组合物尽管用于低压重叠模塑但具有高的热稳定性。事实上,所述重叠模塑组合物具有高于约135℃,优选高于约140℃的软化点。
在一个实施方案中,所述重叠模塑组合物非常适合于包含光学组件的电子组件。根据ASTM D1003,所述重叠模塑组合物具有优选大于85%,更优选大于90%的高透光率。根据BYK Spectro-guide和如Hunter Lab所述的HunterL、A、b色标测量的初始色度(b值)小于6,优选小于4。所述重叠模塑组合物甚至在老化至少3000小时后仍然保持其光学透明度和色度。
尽管在本发明的重叠模塑组合物中使用一定量的增粘剂,但所述重叠模塑组合物在室温下不发粘。即使用大于10重量%和大于20重量%的量的增粘树脂,所述重叠模塑组合物的模量也大于1×107达因/厘米2,并且没有观察到手指发粘。
所属领域的技术人员应了解,可在不背离本发明的精神和范围的情况下对其进行多种修改和改变。本文所述的特定实施方案仅作为实例提供,并且本发明仅受限于各项所附权利要求以及所述权利要求的等同物的全部范围。
实施例
重叠模塑混合物可以由本领域技术人员通过双螺杆挤出机或者能够加工嵌段共聚物的其它混合或挤出设备制备。对于此处所列的重叠模塑实施例,使用Brabender(西格马型桨式混合机)。将所有组分装载在Brabender中,并在180℃混合,直到均匀。根据在混合机中的停留时间,样品的初始色度可以变化。最佳色度通过最小化停留时间,例如通过在210℃范围内的温度下使用挤出机来实现。
粘度用Brookfield粘度计和Thermosel加热室用27号转子在210℃测量。
软化点用Mettler Toledo FP83HT滴点仪测量。将样品以1.7℃/min(约3°F/min)的速率加热。
粘性在环境温度,即23-25℃通过手指触摸测量。如果重叠模塑材料对于手指发粘,则认为它的粘度为“是”。
流变测量用Rheometric Scientific RDA-III受控应变流变仪以10弧度/秒的频率用间隔2mm的平行板(8mm)进行。记录在25℃的储能模量(G’)。
为测量透射率、b值和UV老化测试,将重叠模塑组合物用黄铜模板和Carver实验室压机制成2mm厚的片。将样品在200℃在膜之间压制,以最大限度地减少表面上由水分或气泡造成的缺陷或者聚硅氧烷污染。
对于2mm厚的模塑样品,在550nm下测量透射率。透射率通过PerkinElmer Lambda 35UV/Vis分光光度计用2nm狭缝和240nm/min的扫描速度测量。使用Labsphere RSA-PE-20反射球附件。透射率值与重叠模塑组合物的透明度/透明度直接相关。
用BYK Spectro-guide测量色度。记录CIE L*a*b色标上的b值。负b值表示存在蓝色,而正b值表示存在黄色。越接近零的值表示较低的色度。
UV老化在QUV加速老化测试仪中使用UVA-340灯泡(0.68W/m2的典型辐照度,Q-Lab)进行。在UV老化20周(约3360小时)后测量透射率和色度结果。
具有大于40%MMA和增粘剂的嵌段共聚物的实施例在表1中示出。
表1.
*甲基丙烯酸甲酯-丙烯酸正丁酯-甲基丙烯酸甲酯嵌段共聚物
预期实施例1和2的初始透射率和初始b值与实施例3和4基本上类似。
尽管在组合物中具有大于30重量%的增粘剂,但重叠模塑实施例1-4不发粘,在210℃粘度小于75,000cP,模量值大于107,软化点高于135℃,具有高透射率/透明度以及低色度(b值)。
向重叠模塑组合物中加入紫外线吸收剂羟基苯基苯并三唑和受阻胺光稳定剂使得甚至在加速UV老化20周后仍然具有高透射率/透明度和低色度(b值)。
表2列出对比例。如上所述制备样品,并如表1中所述以相同方式进行测试。
对比例1使用MMA含量低于35重量%的嵌段共聚物。所得重叠模塑组合物在室温下发粘,并且在25℃具有高粘度和低模量。在对比例1B中加入增粘剂降低粘度;然而,它在室温下仍然发粘。
对比例2的高粘度不适合低压注塑。
对比例3的软化温度低于135℃。软化温度低于135℃具有低的尺寸稳定性。优选的是,本发明的重叠模塑组合物具有等于或高于135℃的软化温度,同时在210℃具有低粘度。
对比例4对应于EP 2 345 698的实施例3,并且对比例5对应于WO2009/054553的实施例5。两种样品都不发粘,具有高的模量和高的软化温度,然而,粘度对于低压注塑而言太高。
并非所有的紫外线吸收剂都适用于本发明。在对比例6中加入Tinuvin1577导致重叠模塑组合物的初始透射率降低。UV老化该样品20周导致2mm厚的样品起雾以及色度增加。此类样品将不适合光学装置。
Claims (24)
1.重叠模塑组合物,其包含:
1)[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的所述[A]单体;
2)增粘树脂;并且
其中所述组合物在210℃的粘度小于75,000cP,所述粘度是根据ASTMD3236测量;
其中所述组合物的模量在25℃大于1×107达因/厘米2;并且
其中所述重量%是基于所述组合物的总重量的。
2.根据权利要求1所述的重叠模塑组合物,其中所述[A]单体选自甲基丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、甲基丙烯酸环己酯、(甲基)丙烯酸甲酯和它们的混合物。
3.根据权利要求1所述的重叠模塑组合物,其中所述[B]单体选自丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸异辛酯和它们的混合物。
4.根据权利要求1所述的重叠模塑组合物,其中所述[A]单体是(甲基)丙烯酸甲酯,并且所述[B]单体是丙烯酸正丁酯。
5.根据权利要求1所述的重叠模塑组合物,其中所述增粘树脂选自α-甲基苯乙烯、松香酯、氢化和/或歧化松香酯、苯乙烯化萜烯、萜烯酚、脂族改性的芳族树脂和它们的混合物。
6.根据权利要求1所述的重叠模塑组合物,其还包含平均分子量小于约20,000Da的末端嵌段增粘树脂。
7.根据权利要求6所述的重叠模塑组合物,其中所述末端嵌段增粘树脂是聚甲基丙烯酸甲酯。
8.根据权利要求1所述的重叠模塑组合物,其还包含约0.05-约5重量%的选自苯并三唑、三嗪和二苯甲酮的紫外线吸收剂。
9.根据权利要求1所述的重叠模塑组合物,其中所述紫外线稳定剂是苯并三唑。
10.根据权利要求9所述的重叠模塑组合物,其中所述苯并三唑是羟基苯基苯并三唑。
11.根据权利要求1所述的重叠模塑组合物,其还包含约0.05-约5重量%的受阻胺光稳定剂。
12.根据权利要求1所述的重叠模塑组合物,其还包含抗氧化剂、粘度调节剂、着色剂、填料、消泡剂、增塑剂、脱模剂或抗静电剂。
13.制品,其包含电子组件和重叠模塑组合物,其中所述重叠模塑组合物包含:
1)[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的所述[A]单体;
2)增粘树脂;
3)约0.05-约5重量%的选自苯并三唑、三嗪和二苯甲酮的紫外线吸收剂;并且
其中所述重量%是基于所述组合物的总重量的;并且
其中所述组合物的根据ASTM D6090测量的软化点大于135℃。
14.根据权利要求13所述的制品,其中所述[A]单体是(甲基)丙烯酸甲酯,并且所述[B]单体是丙烯酸正丁酯。
15.根据权利要求13所述的制品,其中所述紫外线稳定剂是苯并三唑。
16.根据权利要求15所述的制品,其中所述苯并三唑是羟基苯基苯并三唑。
17.根据权利要求13所述的制品,其还包含约0.05-约5重量%的受阻胺光稳定剂。
18.根据权利要求13所述的制品,其为光学装置、含LED的装置或光导管。
19.根据权利要求13所述的制品,其中所述重叠模塑组合物包覆所述电子组件。
20.根据权利要求13所述的制品,其中所述组合物在550nm的透射率大于85%,所述透射率是根据ASTM D1003并且采用2nm狭缝和240nm/min的扫描速度测量的。
21.根据权利要求13所述的制品,其中对于2mm厚度,根据ASTMG154在QUV室中使用UVA-340灯泡暴露于紫外光3000小时后,所述重叠模塑组合物具有小于8的色度(b值)。
22.在电子组件上形成重叠模塑件的方法,其包括以下步骤:
(a)制备重叠模塑组合物,其包含:
1)[A]-[B]-[A]共聚物,其中[A]是Tg大于约30℃的硬嵌段单体,并且[B]是Tg小于约20℃的软嵌段单体,并且所述共聚物包含大于35重量%的所述[A]单体;
2)增粘树脂;
3)约0.05-约5重量%的选自苯并三唑、三嗪和二苯甲酮的紫外线吸收剂;并且
其中所述重量%是基于所述组合物的总重量的;
(b)将所述重叠模塑组合物在小于150巴的压力下施加在所述电子组件上;以及
(c)冷却所述重叠模塑组合物。
23.根据权利要求22所述的方法,其中采用小于120巴的压力来施加所述重叠模塑组合物。
24.根据权利要求23所述的方法,其中采用小于60巴的压力来施加所述重叠模塑组合物。
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US13/804,811 US9127153B2 (en) | 2012-11-02 | 2013-03-14 | Molding and overmolding compositions for electronic devices |
PCT/US2013/066296 WO2014070541A1 (en) | 2012-11-02 | 2013-10-23 | Molding and overmolding compositions for electronic devices |
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JP6226996B2 (ja) | 2017-11-08 |
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