CN103338932A - 电子器件包装用层叠片材及其成型体 - Google Patents
电子器件包装用层叠片材及其成型体 Download PDFInfo
- Publication number
- CN103338932A CN103338932A CN2012800066281A CN201280006628A CN103338932A CN 103338932 A CN103338932 A CN 103338932A CN 2012800066281 A CN2012800066281 A CN 2012800066281A CN 201280006628 A CN201280006628 A CN 201280006628A CN 103338932 A CN103338932 A CN 103338932A
- Authority
- CN
- China
- Prior art keywords
- quality
- composition
- laminated sheet
- graft rubber
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Classifications
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Abstract
本发明公开了一种电子器件包装用层叠片材，该层叠片材包含表面层、中芯层和背面层，上述表面层以及上述背面层含有橡胶改性苯乙烯类共聚物（A）和聚醚酯酰胺（B），所述橡胶改性苯乙烯类共聚物（A）的接枝橡胶的接枝率为30～50%、接枝橡胶粒径为0.1～0.5μm且含有5～25质量%的丁二烯，上述中芯层包含含有橡胶改性苯乙烯类共聚物（C）和5～50质量%的该层叠片材的再生材料的树脂组合物，所述橡胶改性苯乙烯类共聚物（C）的接枝橡胶的接枝率为70～90%，接枝橡胶粒径为0.4～1.0μm，且含有5～15质量%的丁二烯。该层叠片材的防静电性、透明性以及耐折强度等的物性平衡优异，并且即使将再生材料添加到中芯层中，隔着载带检查时的视觉辨认性也良好，所以可适用于压纹载带等电子器件包装用片材的制作。
Description
技术领域
本发明涉及用于电子器件的包装的透明树脂层叠片材以及使用它进行成型而得到的压纹载带等。
背景技术
一般来说，用于将IC、LSI等电子器件安装到电子设备的压纹载带采用将由氯乙烯树脂、苯乙烯类树脂、聚碳酸酯类树脂等热塑性树脂构成的片材热成型为压纹形状而成的载带。上述压纹载带需要采取对策防止静电对所述电子器件造成损害，例如采用了由通过使热塑性树脂含有碳黑等导电性填充物而使表面固有电阻率在108Ω/sq.以下的树脂组合物构成的片材等不透明片材。另一方面，电子器件中，对于收纳例如电容器那样因静电危害而损坏的可能性小的电子器件的压纹载带，由于在从外部看到作为内容物的电子器件、检测记载于该器件的文字方面有利，使用以前述的透明性比较良好的热塑性树脂为基材的透明型压纹载带。
但是，从这些电子器件的小型化、安装速度的高速化的需要出发，不仅因静电危害导致器件破坏，而且因静电使得器件向载带附着、移动，导致安装不良这一问题暴露出来，作为防静电对策，要求对透明型载带也赋予防静电性。
作为透明型压纹载带用片材，有将通用聚苯乙烯树脂和苯乙烯-丁二烯嵌段共聚物混合而成的片材（专利文献1等）、由含有苯乙烯类单体单元和（甲基）丙烯酸酯类单体单元的橡胶改性苯乙烯类聚合物构成的片材（专利文献2等）等苯乙烯类树脂片材。载带根据其使用形态要求保持透明性、耐冲击性、耐弯折性以及成型性等的物性平衡，迄今，为了获得上述特性的提高和良好的物性平衡，一直在进行各种研究。进而，作为赋予防静电性的技术，例如进行在表面涂布防静电剂或将防静电剂混入到树脂中。
但是，现有的透明型防静电片材存在如下问题：若重视防静电性，则片材的耐折强度低，片材容易在挤出方向断开或裂开，或者透明性降低。特别是对于透明性，一般使用雾度、全光线透过率这样的指标，但随着器件的小型化，即使雾度、全光线透过率为良好的值，在隔着载带检查器件时，有时视觉辨认性、即记载于器件的文字等的判别性差。
另外，通常，在通过共挤出成型制造层叠片材时，从模中挤出的片材的两端部因修边而产生被称为“耳朵”的部分。一般将该“耳朵”、卷缠片材时的开始部分等如果保持原状则不能构成产品的部分粉碎或再粒料化，作为再生材料，添加到例如中芯层原料中进行再利用。即使像这样添加再生材料，从层叠片材的生产率方面考虑，该片材的特性良好并且能够进行如上所述的隔着载带的检查也是极其重要的。但是，现有的层叠片材存在添加了再生材料时透明性以及上述视觉辨认性显著下降的问题。
现有技术文献
专利文献
专利文献1：日本特开2003-055526号公报
专利文献2：日本特开2003-253069号公报
发明内容
本发明的目的在于得到层叠片材以及压纹载带，该层叠片材是压纹载带等电子器件的包装中使用的透明型树脂片材，防静电性、透明性、视觉辨认性以及耐折强度、耐冲击性等的物性平衡优异，并且即使将再生材料添加到中芯层中，物性平衡、透明性以及隔着载带检查时的视觉辨认性也良好。
本发明人等对于上述课题进行了深入研究，结果发现上述隔着载带的视觉辨认性与JIS K7105规定的图像鲜明度具有强相关性，在表面层中含有聚醚酯酰胺作为防静电成分的苯乙烯-（甲基）丙烯酸酯共聚物的层叠片材中，通过由特定的树脂组合物构成各层，能够得到解决了上述全部课题的片材，从而完成了本发明。
即，本发明的第一实施方式提供一种层叠片材，是在中芯层的单侧表面形成表面导电层而得到的层叠片材，或在单侧表面形成表面导电层并且在另一表面形成背面导电层而得到的层叠片材，其中，
上述表面层和/或背面层包含含有75～95质量%的下述（A）成分以及25～5质量%的（B）成分的树脂组合物，上述中芯层包含含有95～50质量%的（C）成分以及5～50质量%的该层叠片材的再生材料的树脂组合物，
（A）成分、（B）成分以及（C）成分的折射率差分别为0.05以下。
（A）成分：包含基体树脂（A-1）和接枝橡胶（A-2），接枝橡胶（A-2）的接枝率为30～50%、接枝橡胶粒径为0.1～0.5μm，是含有5～25质量%丁二烯的、包含苯乙烯类单体和（甲基）丙烯酸酯类单体的橡胶改性苯乙烯类共聚物。
（B）成分：聚醚酯酰胺。
（C）成分：包含基体树脂（C-1）和接枝橡胶（C-2），接枝橡胶（C-2）的接枝率为70～90%、接枝橡胶粒径为0.4～1.0μm，是含有5～15质量%丁二烯的、包含苯乙烯类单体和（甲基）丙烯酸酯类单体的橡胶改性苯乙烯类共聚物。
在进一步的实施方式中，优选上述（A）成分包含60～90质量%的下述基体树脂（A-1）和40～10质量%的接枝橡胶（A-2）。
（A-1）：包含20～70质量%的苯乙烯类单体单元和80～30质量%的（甲基）丙烯酸酯单体单元，是质均分子量为5×104～1×105的共聚物。
（A-2）：包含聚丁二烯和与（A-1）相同组成的接枝链的接枝橡胶。
在更进一步的实施方式中，上述（C）成分优选包含50～85质量%的下述基体树脂（C-1）和50～15质量%的接枝橡胶（C-2）。
（C-1）：包含30～80质量%的苯乙烯类单体单元、70～20质量%的（甲基）丙烯酸酯单体单元和0～10质量%的丙烯酸正丁酯，是质均分子量为1×105～1.5×105的共聚物。
（C-2）：包含苯乙烯-丁二烯嵌段共聚物和与（C-1）相同组成的接枝链的接枝橡胶。
另外，本发明的其他方案提供使用上述层叠片材的电子器件包装容器、载带以及电子器件输送用托盘。
根据本发明，能够得到具有防静电性、透明性、视觉辨认性以及耐折强度均优异的层叠片材，即使将片材的一部分用作再生材料，对视觉辨认性、物性平衡的影响也小，通过对该层叠片材实施气压成型等热成型，能够制造具有持续的防静电效果的电子器件包装用成型体。作为该成型体的例子，可以举出压纹载带。
具体实施方式
下面，对用于实施本发明的方式进行详细说明。
本发明的一个实施方式的层叠片材是由含有上述（A）成分和（B）成分的表面层和/或背面层以及含有（C）成分的中芯层构成的层叠片材，该层叠片材在如后所述进行制膜时，将该层叠片材两端的被称为所谓“耳朵”的部分、卷缠片材时的开始部分等如果保持原样则不能构成产品的部分粉碎、进行再粒料化而得到的物质作为中芯层的原料加入（C）成分中进行添加。（A）成分或（C）成分分别包含基体树脂和含有接枝橡胶的树脂。接枝橡胶是制备上述共聚物组合物时，在作为橡胶成分分散或乳化有聚丁二烯或苯乙烯-丁二烯嵌段共聚物的水中，使上述苯乙烯类单体和（甲基）丙烯酸酯单体通过一般的方法进行聚合时产生的凝胶状物，该接枝橡胶的接枝率为接枝链相对于接枝橡胶中的橡胶成分的质量比。该接枝率可以通过聚合时的单体的添加量、聚合温度、聚合时间等条件进行调整。
本发明中接枝率以及基体树脂的各单体的构成的测定是通过一般方法对含有接枝橡胶的橡胶改性苯乙烯类共聚物进行测定而得到的值。且该接枝率是如下所述地测定而得到的值。将（A）成分或（C）成分的橡胶改性苯乙烯类共聚物溶解于甲苯后，将离心分离而得的沉淀物用真空干燥机干燥，将该沉淀物的质量设为接枝橡胶的质量X。进而，求出使用该沉淀物通过热解气相色谱法定量的苯乙烯类单体的质量Y和（甲基）丙烯酸酯类单体的质量Z，由式：接枝率（%）=100×（Y+Z）/｛X-（Y+Z）｝算出。另一方面，基体树脂的各单体的组成如下算出：将（A）成分或（C）成分的橡胶改性苯乙烯类共聚物溶解于甲苯后，分别取出离心分离而得的沉淀物和上清液，加入甲醇，使苯乙烯类单体沉淀。将该沉淀物干燥，对溶于氘代氯仿的测定试样，使用FT-NMR（日本电子株式会社制造，FX-90Q型）进行13C测定，由苯乙烯类单体以及（甲基）丙烯酸酯类单体的峰面积算出各单体的构成比。
应予说明，中芯层的树脂组成是如下求出的组成：将中芯层分离，溶于氘代氯仿，使用FT-NMR（日本电子株式会社制造，FX-90Q型）进行13C测定，由苯乙烯类单体以及（甲基）丙烯酸酯类单体的峰面积算出各单体的构成比而求出。另外，防静电剂的含量是将中芯层保持固体状态通过热解气相色谱法进行定量而求出的含量。
本发明的一个实施方式的层叠片材是由上述含有（A）成分和（B）成分的表面层和/或背面层以及含有（C）成分的中芯层构成的层叠片材。（A）成分或（C）成分如下制备：在作为橡胶成分分散或乳化有聚丁二烯或苯乙烯-丁二烯嵌段共聚物的水中，使用特定比率的苯乙烯类单体和（甲基）丙烯酸酯单体，通过常规的自由基聚合进行制备。此时，其中的一部分作为接枝链连接到上述橡胶成分上构成接枝橡胶。本发明中，（A）成分以及（C）成分中的接枝橡胶分别作为（A-2）以及（C-2）。另一方面，也生成不构成接枝链的共聚物，这些基体树脂分别作为（A-1）或（C-1）。另外，本发明的树脂组合物的（A）成分以及（C）成分中，（A-1）以及（C-1）也可以分别另行加入仅由苯乙烯类单体和（甲基）丙烯酸酯单体构成的共聚物进行配合。
本发明所称苯乙烯类单体是指苯乙烯或者其衍生物。作为衍生物，例如可以举出α-甲基苯乙烯、对甲基苯乙烯、邻甲基苯乙烯、对叔丁基苯乙烯等。优选为苯乙烯。苯乙烯类单体可以单独使用或并用2种以上。另外，（甲基）丙烯酸酯类单体是指丙烯酸酯、甲基丙烯酸酯的衍生物，例如可以举出甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-甲基己酯、丙烯酸2-乙基己酯等。（甲基）丙烯酸酯类单体可以单独使用或并用2种以上。
作为配合到表面层以及背面层中的（B）成分，从与上述（A）成分混合几乎不破坏透明性并且能够取得持续的防静电效果方面考虑，可以使用聚醚酯酰胺。其添加量，从得到良好的透明性和防静电效果方面考虑，（A）成分为75～95质量%，而（B）成分在25～5质量%的范围内。从透明性的观点考虑，优选（B）成分为折射率与（A）成分接近的物质。进而，用作再生材料时，优选接近（C）成分，更优选（A）、（B）以及（C）成分间的折射率差在0.05%以下。
本发明的一个实施方式的层叠片材的总厚度一般为100～700μm，表面层以及背面层的厚度，从片材的透明性以及各种机械特性的平衡方面考虑，优选分别在总厚度的3～20%的范围内。并且表面层以及背面层如上所述包含含有75～95质量%的（A）成分和25～5质量%的（B）成分的树脂组合物。（B）成分超过25质量%时，透明性降低。（B）成分低于5质量%时，防静电性能降低。
（A）成分是实施了橡胶改性的苯乙烯类单体和（甲基）丙烯酸酯类单体的共聚物，该（A）成分的共聚物含有基体树脂（A-1）和接枝橡胶（A-2），接枝橡胶（A-2）的接枝率为30～50%、接枝橡胶粒径为0.1～0.5μm，并且是相对于100质量%的（A）成分含有5～25质量%丁二烯的、包含苯乙烯类单体和（甲基）丙烯酸酯类单体的橡胶改性苯乙烯类共聚物。
接枝橡胶（A-2）的接枝率低于30%时，透明性降低。接枝率超过50%时，沿片材的挤出方向（MD）的耐折强度显著降低（在垂直方向（TD）取样得到的样品的耐折强度）。另外，接枝橡胶粒径超过0.5μm时，橡胶的收缩量增加导致表面变得粗糙，隔着载带辨认记载于所收纳的器件的文字等的视觉辨认性大幅降低。接枝橡胶粒径为0.1μm以下时，耐折强度显著降低。而如果使（A）成分中的丁二烯如上所述在5～25质量%的范围内，则能够得到透明性、上述视觉辨认性以及耐折强度等的平衡良好的层叠片材。本发明人等发现如上所述该“视觉辨认性”与JIS K7105中规定的“图像鲜明度”具有强相关性，就表面层、背面层以及中芯层的树脂组成进行了评价。以下本发明对于“视觉辨认性”的评价基于该“图像鲜明度”的评价进行。
进而，为了表现出优异的透明性以及上述视觉辨认性，优选（A）成分的共聚物包含60～90质量%的基体树脂（A-1）和40～10质量%的接枝橡胶（A-2），上述基体树脂（A-1）是包含20～70质量%的苯乙烯类单体单元和80～30质量%的（甲基）丙烯酸酯单体单元的共聚物，上述接枝橡胶（A-2）包含聚丁二烯和与（A-1）相同组成的接枝链。另外，（A-1）成分的质均分子量（Mw）优选为5×104～1×105。Mw低于5×104时，耐折强度可能变差，如果超过1×105，则用作再生材料时，向（C）成分中的分散性差，有时透明性降低。
另外，从层叠片材的耐折强度等物性和透明性的观点考虑，本发明的一个实施方式中构成中芯层的（C）成分的树脂组合物为包含含有5～25质量%丁二烯的苯乙烯类单体和（甲基）丙烯酸酯类单体的橡胶改性共聚物。接枝橡胶（C-2）的粒径为0.4～1.0μm、接枝率为70～90质量%是极为重要的。接枝橡胶的粒径低于0.4μm时，耐折强度低，超过1.0μm时，透明性变差。使表面层以及背面层所含有的接枝橡胶（A-2）如上所述为比较低的接枝率、使中芯层的接枝橡胶（C-2）的接枝率如此为高范围是本发明的重要特征，由此能够得到上述耐折强度和透明性均优异的层叠片材。
从耐折强度和透明性的平衡方面考虑，优选该（C）成分包含50～85质量%的基体树脂（C-1）和50～15质量%的接枝橡胶（C-2）。另外，（C-1）成分的质均分子量（Mw）优选为1×105～1.5×105。Mw低于1×105时，有时成型性、耐折强度降低，可能难以得到良好的冲击强度的片材。另外，Mw超过1.5×105时，接枝橡胶的分散性降低，可能导致透明性降低。另外，接枝橡胶（C-2）通常具有与基体树脂（C-1）相同组成的接枝链。
本发明的一个实施方式中构成层叠片材的树脂可以根据需要添加抗氧化剂、耐气候剂、润滑剂、增塑剂、着色剂、防静电剂、矿物油、阻燃剂等添加剂。进而，为了使片材的表面特性良好，可以在表面涂布防静电剂、有机硅、防雾剂等。
制造本发明的层叠片材的方法没有特别限定，可以由一般的方法制造。例如通过使用具有多歧管的多层T模的挤出成型或使用进料块的T模法挤出成型而适当制造。另外，此种层叠片材的制造方法中，一般将在片材挤出工序中产生的所谓“耳朵”的部分等粉碎，作为再生材料添加到中芯层中。
将再生材料添加到中芯层中的量，在以中芯层总量为100质量%时，优选表面层以及背面层的一种成分即（B）成分聚醚酯酰胺在不超过3质量%的范围内，一般向中芯层中的再生材料的添加量在以中芯层总量为100质量%时优选在5～50质量%的范围内。
通过使用本发明的层叠片材，利用真空成型、气压成型、压制成型等公知的片材成型方法（热成型），能够提供载带（压纹载带）、托盘等自由形状的电子器件包装容器。一般在此种层叠片材中，添加上述再生材料将片材制膜时，片材或其热成型品的雾度显著提高，或者即使雾度保持在低水平，该片材的图像鲜明度也不足够。本发明的层叠片材是采用上述树脂作为表面层和背面层以及中芯层中使用的树脂的层叠片材，从而即使将再生材料添加到中芯层中，作为该层叠片材的热成型品，也能够制造防静电性、透明性、视觉辨认性、耐折强度以及耐冲击强度均良好的透明型压纹载带。
在通过上述成型方法形成的收纳部收纳电子器件后，载带（压纹载带）由盖带进行覆盖并卷绕成卷盘状制成载带体，用于电子器件的保管和运输。
电子器件包装体是指收纳有电子器件的载带、托盘等包装形态的电子器件包装容器。作为所包装的电子器件，没有特别限定，例如有IC、LED（发光二极管）、电阻、液晶、电容器、晶体管、压电元件寄存器、滤波器、石英振子、晶体振荡器、二极管、连接器、开关、电位器、继电器、电感器等。另外，也可用于使用了上述电子器件的中间产品、最终产品的包装。
实施例
（评价方法）
通过以下方法评价本发明的各实施例以及比较例中得到的层叠片材。
（1）层叠片材的透明性
基于JIS K7105，测定雾度以及全光线透过率。
雾度的值在15%以下。
（2）层叠片材的视觉辨认性
基于JIS K7374，测定图像鲜明度。光学梳齿宽度根据与视觉的相关性而采用1mm。图像鲜明度是指透过塑料观察到的物体图像以何种鲜明度被观察到的值，作为具体数值，是表示本发明的课题之一的“视觉辨认性”的值。图像鲜明度的值为88%以上。
（3）耐折强度
基于ASTM D2176，制作长度120mm、宽度15mm、厚度0.3mm的试验片材，使用东洋精机制作所制造的MIT耐折疲劳试验机，从片材上以MD（片材的挤出方向）以及TD（与片材的挤出方向垂直的方向）为长度方向进行取样，进行MIT耐折强度测定。此时，以弯折角度135度、弯折速度每分钟175次、测定载荷9.8N进行试验。MD为100次以上，TD为50次以上。
（4）表面电阻率
基于JIS K6911，在23℃×50%RH环境下进行测定。
应予说明，对于防静电性能，测得的表面电阻率为1012～1013Ω/sq.时，对静态下的故障防止（防灰尘附着）有效，为1010～1012Ω/sq.时，对动态下的故障防止（因摩擦等而产生静电时的防静电）有效。
（实施例1～10）
将表1所示的（A）成分橡胶改性苯乙烯类共聚物（树脂1、树脂2以及树脂11）和（B）成分作为防静电剂的聚醚酯酰胺（PELESTAT NC6321/三洋化成）按表2所示的比例进行混合，作为表面层以及背面层的树脂组合物，将（C）成分的橡胶改性苯乙烯类共聚物（树脂3、树脂4以及树脂12）和再生材料混合作为中芯层，使用φ65mm挤出机（L/D=32）1台、φ40mm挤出机（L/D=26）2台以及600mm宽度的T模，采用多歧管法得到平均厚度300μm、表面层/中芯层/背面层=5/90/5的2种3层层叠片材。评价结果示于表3。
[表3]
（比较例1～14）
将上述（A）成分、（C）成分以及（B）按表4所示的比例混合得到各树脂组合物的混合物，除此之外，与实施例1～10同样地得到2种3层的层叠片材。评价结果示于表5。
[表5]
以上，通过实施方式说明了本发明，但并不是说本发明的保护范围限定于上述实施方式所记载的范围。可对上述实施方式实施各种变更或改良，这对本领域技术人员来说是显而易见的。另外，由权利要求书的记载可知这样的实施了变更或改良的方案也包括在本发明的保护范围内。
产业上的可利用性
由本发明的层叠片材，利用真空成型、气压成型、压制成型等公知的片材成型方法（热成型），能够得到载带（压纹载带）、托盘等自由形状的电子器件包装容器。根据本发明的层叠片材，即使将再生材料添加到中芯层中，作为该层叠片材的热成型品，也能够制造防静电性、透明性、视觉辨认性、耐折强度以及耐冲击强度均良好的透明型压纹载带。
Claims (6)
1.一种层叠片材，其包含表面层、中芯层和背面层，
所述表面层以及所述背面层包含含有75～95质量%的下述（A）成分以及25～5质量%的（B）成分的树脂组合物，所述中芯层包含含有95～50质量%的（C）成分以及5～50质量%的该层叠片材的再生材料的树脂组合物，
（A）成分、（B）成分以及（C）成分的折射率差分别为0.05以下；
（A）成分：包含基体树脂（A-1）和接枝橡胶（A-2），接枝橡胶（A-2）的接枝率为30～50%、接枝橡胶粒径为0.1～0.5μm，是含有5～25质量%丁二烯的、包含苯乙烯类单体和（甲基）丙烯酸酯类单体的橡胶改性苯乙烯类共聚物，
（B）成分：聚醚酯酰胺，
（C）成分：包含基体树脂（C-1）和接枝橡胶（C-2），接枝橡胶（C-2）的接枝率为70～90%、接枝橡胶粒径为0.4～1.0μm，是含有5～15质量%丁二烯的、包含苯乙烯类单体和（甲基）丙烯酸酯类单体的橡胶改性苯乙烯类聚合物。
2.如权利要求1所述的层叠片材，其中，所述（A）成分包含60～90质量%的下述基体树脂（A-1）和40～10质量%的接枝橡胶（A-2），
（A-1）：包含20～70质量%的苯乙烯类单体单元和80～30质量%的（甲基）丙烯酸酯单体单元，是质均分子量为5×104～1×105的共聚物，
（A-2）：包含聚丁二烯和与（A-1）相同组成的接枝链的接枝橡胶。
3.如权利要求1或2所述的层叠片材，其中，
所述（C）成分包含50～85质量%的下述基体树脂（C-1）和50～15质量%的接枝橡胶（C-2），
（C-1）：包含30～80质量%的苯乙烯类单体单元、70～20质量%的（甲基）丙烯酸酯单体单元以及0～10质量%的丙烯酸正丁酯，是质均分子量为1×105～1.5×105的共聚物，
（C-2）：包含苯乙烯-丁二烯嵌段共聚物和与（C-1）相同组成的接枝链的接枝橡胶。
4.一种电子器件包装容器，使用了权利要求1～4中的任一项所述的片材。
5.一种载带，使用了权利要求1～4中的任一项所述的片材。
6.一种电子器件输送用托盘，使用了权利要求1～4中的任一项所述的片材。
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