CN112759891A - 环氧树脂组合物及含有其的透明复合材料、层压板 - Google Patents

环氧树脂组合物及含有其的透明复合材料、层压板 Download PDF

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Publication number
CN112759891A
CN112759891A CN202011577184.XA CN202011577184A CN112759891A CN 112759891 A CN112759891 A CN 112759891A CN 202011577184 A CN202011577184 A CN 202011577184A CN 112759891 A CN112759891 A CN 112759891A
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CN
China
Prior art keywords
epoxy resin
laminate
prepreg
resin composition
parts
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Pending
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CN202011577184.XA
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English (en)
Inventor
漆小龙
余家斌
朱扬杰
陈健雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Ying Hua New Mstar Technology Ltd
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Guangdong Ying Hua New Mstar Technology Ltd
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Application filed by Guangdong Ying Hua New Mstar Technology Ltd filed Critical Guangdong Ying Hua New Mstar Technology Ltd
Priority to CN202011577184.XA priority Critical patent/CN112759891A/zh
Publication of CN112759891A publication Critical patent/CN112759891A/zh
Priority to PCT/CN2021/109669 priority patent/WO2022142325A1/zh
Priority to US18/270,154 priority patent/US20240066849A1/en
Priority to EP21913073.9A priority patent/EP4253478A1/en
Pending legal-status Critical Current

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Abstract

本发明涉及一种环氧树脂组合物及含有其的透明复合材料、层压板。所述环氧树脂组合物包括环氧树脂A以及环氧树脂B；所述环氧树脂A的折射率为1.54～1.8、透光率大于90％；所述环氧树脂B的折射率为1.54～1.8、透光率大于90％；所述环氧树脂A为有机硅改性环氧树脂，所述环氧树脂B为其他种类环氧树脂。与现有技术相比，本发明具备如下有益效果：本发明将满足特定条件的有机硅改性环氧树脂与其他种类的同样满足该特定条件的环氧树脂组合，形成特定的环氧树脂组合物，该环氧树脂组合物与固化剂以及固化促进剂制备的复合材料，兼具高透光率和高弯曲强度的优势，并且该复合材料还具有高粘结强度。

Description

环氧树脂组合物及含有其的透明复合材料、层压板
技术领域
本发明涉及复合材料技术领域，特别是涉及一种环氧树脂组合物及含有其的透明复合材料、层压板。
背景技术
随着电子行业的迅速发展，对高透明复合材料的需求越来越迫切，传统的透明复合材料例如：一种透明树脂组合物，其具有不低于45的阿贝数，所述透明树脂组合物包含透明树脂(a)和玻璃填料(b)。进一步地：该透明树脂组合物中的所述透明树脂(a)和所述玻璃填料(b)之间的折射率差不大于0.01；该透明树脂组合物中的所述透明树脂(a)由至少一种折射率高于所述玻璃填料(b)的物质和至少一种折射率低于所述玻璃填料(b)的物质构成；该透明树脂组合物中的所述玻璃填料(b)具有1.45至1.55的折射率；该透明树脂组合物中的所述透明树脂(a)为以至少双官能(甲基)丙烯酸酯为主要成分的交联丙烯酸酯树脂，所述交联丙烯酸酯树脂含有含脂环式结构的(甲基)丙烯酸酯作为其构成。
如上所述的传统透明复合材料，虽然在透光率上有所提升，然而弯曲强度欠佳。
发明内容
基于此，本发明的主要目的是提供一种环氧树脂组合物及含有其的透明复合材料、层压板。将本发明提供的环氧树脂组合物与固化剂以及固化促进剂为原料形成的复合材料，不仅具有较高的透光率，而且还具有较高的弯曲强度。
具体技术方案包括：
一种环氧树脂组合物，所述环氧树脂组合物包括环氧树脂A以及环氧树脂B；
所述环氧树脂A的折射率为1.54～1.8、透光率大于90％；
所述环氧树脂B的折射率为1.54～1.8、透光率大于90％；
所述环氧树脂A为有机硅改性环氧树脂，所述环氧树脂B为其他种类环氧树脂。
在其中一个实施例中，所述有机硅改性环氧树脂选自端羟基聚二甲基硅烷改性环氧树脂环氧树脂、聚甲基苯基硅氧烷改性环氧树脂、氨基封端的聚二甲基硅氧烷改性环氧树脂以及氨丙基封端的二甲基二苯基硅氧烷改性环氧树脂中的至少一种。
在其中一个实施例中，所述其他种类环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、缩水甘油酯型环氧树脂以及多酚型缩水甘油醚环氧树脂中的一种。
在其中一个实施例中，所述环氧树脂A与所述环氧树脂B的质量之比为(1～3)：1。
在其中一个实施例中，所述环氧树脂A与所述环氧树脂B的质量之比为(1.25～2)：1。
一种环氧树脂复合材料，所述环氧树脂复合材料包括如上所述的环氧树脂组合物、固化剂以及固化促进剂。
在其中一个实施例中，所述固化剂选自乙二胺、己二胺改性物、己二胺加成物、双氰胺、二氨基二苯基甲烷以及二氨基二苯基砜中的至少一种。
在其中一个实施例中，所述固化促进剂选自N,N-二甲基苄胺、三乙胺、N,N-二甲基苯胺、咪唑类促进剂以及过氧化物类促进剂中的至少一种。
在其中一个实施例中，所述环氧树脂复合材料还包括其他功能助剂，所述其他功能助剂选自抗氧化剂、抗紫外助剂、分散剂以及稀释剂中的至少一种。
如上所述的环氧树脂复合材料的制备方法，所述制备方法包括如下步骤：
取所述的环氧树脂组合物、固化剂、固化促进剂以及溶剂，混合。
在其中一个实施例中，所述溶剂为二甲基甲酰胺或/和丙二醇甲醚。
一种预浸料，所述预浸料的制备原料包括玻璃填料以及树脂材料，所述树脂材料的制备原料包含如上所述的环氧树脂组合物，或者选用如上所述的环氧树脂复合材料。
如上所述的预浸料的制备方法，所述制备方法包括如下步骤：
将所述玻璃填料浸渍于所述树脂材料，加热。
在其中一个实施例中，所述加热的温度为150℃～180℃，所述加热的时长为2min～5min。
一种层压板，所述层压板包括由预浸料叠制的层叠体，所述预浸料的制备原料包含如上所述的环氧树脂组合物，或者包含如上所述的环氧树脂复合材料，或者所述预浸料选用如上所述的预浸料。
在其中一个实施例中，所述层叠体的单侧或者双侧还覆有离型膜。
如上所述的层压板的制备方法，所述制备方法包括如下步骤：取所述预浸料，叠合，真空热压。
在其中一个实施例中，所述真空热压的条件包括：温度为150℃～180℃，压力为10kgf/cm2～20kgf/cm2，热压成形时长为60min～90min。
在其中一个实施例中，所述制备方法还包括在叠合所得层叠体的单侧或者双侧覆上离型膜。
与现有技术相比，本发明具备如下有益效果：
本发明将满足特定条件(1.54～1.8、透光率大于90％)的有机硅改性环氧树脂与其他种类的同样满足该特定条件的环氧树脂组合，形成特定的环氧树脂组合物，该环氧树脂组合物与固化剂以及固化促进剂制备的复合材料，兼具高透光率和高弯曲强度的优势，并且该复合材料还具有高粘结强度。
具体实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本发明实施例提供一种环氧树脂组合物，所述环氧树脂组合物包括环氧树脂A以及环氧树脂B；
所述环氧树脂A的折射率为1.54～1.8、透光率大于等于90％；
所述环氧树脂B的折射率为1.54～1.8、透光率大于等于90％；
所述环氧树脂A为有机硅改性环氧树脂，所述环氧树脂B为其他种类环氧树脂。
在其中一个示例中，所述环氧树脂A的折射率为1.65、透光率为90％；所述环氧树脂B的折射率为1.54、透光率为90％。
在其中一个示例中，所述有机硅改性环氧树脂选自端羟基聚二甲基硅烷改性环氧树脂环氧树脂(折射率为1.65、透光率90％)、聚甲基苯基硅氧烷改性环氧树脂(折射率为1.65、透光率90％)、氨基封端的聚二甲基硅氧烷改性环氧树脂(折射率为1.65、透光率90％)以及氨丙基封端的二甲基二苯基硅氧烷改性环氧树脂(折射率为1.65、透光率90％)中的至少一种。
在其中一个示例中，所述其他种类环氧树脂选自双酚A型环氧树脂(折射率为1.54、透光率90％)、双酚F型环氧树脂(折射率为1.54、透光率90％)、缩水甘油酯型环氧树脂(折射率为1.54、透光率90％)以及多酚型缩水甘油醚环氧树脂(折射率为1.54、透光率90％)中的一种。
在其中一个示例中，所述环氧树脂A与所述环氧树脂B的质量之比为(1～3)：1。
在其中一个示例中，所述环氧树脂A与所述环氧树脂B的质量之比为(1.25～2)：1。
本发明实施例提供一种环氧树脂复合材料，所述环氧树脂复合材料包括如上所述的环氧树脂组合物、固化剂以及固化促进剂。
可以理解的是，为实现理想的固化效果，可以选择适量的固化剂以及促进剂。在其中一个示例中，本发明实施例提供的环氧树脂复合材料，以质量份计，包括：
环氧树脂A 40份～60份、
环氧树脂B 20份～40份、
固化剂 5份～10份，以及
固化促进剂：0.5份～3份。
可以理解的是，为实现理想的固化效果，可以选择合适种类的固化剂以及促进剂。
在其中一个示例中，所述固化剂选自乙二胺、己二胺改性物、己二胺加成物、双氰胺、二氨基二苯基甲烷以及二氨基二苯基砜中的至少一种。
在其中一个示例中，所述固化促进剂选自N,N-二甲基苄胺、三乙胺、N,N-二甲基苯胺、咪唑类促进剂以及过氧化物类促进剂中的至少一种。
在其中一个示例中，所述环氧树脂复合材料还包括其他功能助剂，本发明实施例所述的其他功能助剂包括但不限于抗氧化剂、抗紫外助剂、分散剂以及稀释剂等。本发明实施例所述的抗氧化剂例如抗氧化剂1010等，抗紫外助剂例如紫外线吸收剂UV-O，分散剂例如分散剂5040，稀释剂例如烯丙基缩水甘油醚。
本发明实施例提供如上所述的环氧树脂复合材料的制备方法，所述制备方法包括如下步骤：
取所述的环氧树脂组合物、固化剂、固化促进剂以及溶剂，混合。
在其中一个示例中，所述溶剂为二甲基甲酰胺或/和丙二醇甲醚。优选地，所述溶剂为二甲基甲酰胺。
可以理解的是，本发明实施例对溶剂中的用量不做特别限定，例如在制备如下配方的环氧树脂复合材料时采用50份～100份的溶剂，该处所述的环氧树脂复合材料配方为：环氧树脂A 40份～60份、环氧树脂B20份～40份、固化剂5份～10份以及固化促进剂0.5份～3份。
本发明实施例提供一种预浸料，所述预浸料的制备原料包括玻璃填料以及树脂材料，所述树脂材料的制备原料包含如上所述的环氧树脂组合物，或者选用如上所述的环氧树脂复合材料。
本发明实施例所述的玻璃填料包括但不限于玻璃纤维布，例如可以为1080玻璃纤维布(基重48g/m2)。
本发明实施例提供如上所述的预浸料的制备方法，所述制备方法包括如下步骤：
将所述玻璃填料浸渍于所述树脂材料，加热。
在其中一个示例中，所述加热的温度为150℃～180℃，所述加热的时长为2min～5min。
本发明实施例提供一种层压板，所述层压板包括由预浸料叠制的层叠体，所述预浸料的制备原料包含如上所述的环氧树脂组合物，或者包含如上所述的环氧树脂复合材料，或者所述预浸料选用如上所述的预浸料。
在其中一个示例中，所述层叠体的单侧或者双侧还覆有离型膜。
本发明实施例提供如上所述的层压板的制备方法，所述制备方法包括如下步骤：取所述预浸料，叠合，真空热压。
在其中一个示例中，所述真空热压的条件包括：温度为150℃～180℃，压力为10kgf/cm2～20kgf/cm2，热压成形时长为60min～90min。
在其中一个示例中，所述制备方法还包括在叠合所得层叠体的单侧或者双侧覆上离型膜。
实施例1：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将40份有机硅改性环氧树脂、20份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例2：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将50份端羟基聚二甲基硅烷改性环氧树脂、20份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例3：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将60份端羟基聚二甲基硅烷改性环氧树脂、20份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例4：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将40份端羟基聚二甲基硅烷改性环氧树脂、30份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例5：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将50份端羟基聚二甲基硅烷改性环氧树脂、30份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例6：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将60份端羟基聚二甲基硅烷改性环氧树脂、30份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例7：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将40份端羟基聚二甲基硅烷改性环氧树脂、40份双酚A型环氧树脂以及1份抗氧化剂1010、0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例8：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将50份端羟基聚二甲基硅烷改性环氧树脂、40份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例9：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将60份端羟基聚二甲基硅烷改性环氧树脂、40份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例10：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将40份端羟基聚二甲基硅烷改性环氧树脂、25份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例11：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将50份端羟基聚二甲基硅烷改性环氧树脂、25份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例12：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将60份端羟基聚二甲基硅烷改性环氧树脂、25份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例13：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将80份端羟基聚二甲基硅烷改性环氧树脂、10份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
实施例14：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将30份端羟基聚二甲基硅烷改性环氧树脂、60份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
对比例1：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将85份端羟基聚二甲基硅烷改性环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
对比例2：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将85份双酚A型环氧树脂、1份抗氧化剂1010以及0.5份2-甲基咪唑加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤3min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在15kgf/cm2的压力条件，制品温度在180℃条件下固化60分钟，制成0.6mm厚度的层压板。
对比例3
本对比例是实施例12的对比例，相对于实施例12的差别之处在于，采用二苯基硅二醇改性环氧树脂(折射率1.5，透光率90％)代替了实施例12的端羟基聚二甲基硅烷改性环氧树脂。
对比例4
本对比例是实施例12的对比例，相对于实施例12的差别之处在于，采用酚醛环氧树脂(折射率1.5，透光率90％)代替了实施例12的有双酚A型环氧树脂。
对比例5
本对比例是实施例12的对比例，相对于实施例12的差别之处在于，采用折射率为1.54～1.8、透光率大于90％的非有机硅改性环氧树脂(聚碳酸酯)代替了实施例12的有机硅改性环氧树脂。
性能测试
取上述各实施例和对比例的层压板，进行如下测试：
1、透光率：分光光度仪。
2、粘结强度：参考IPC-TM-650 2.4.8，将基板裁成宽3.18mm,长50.8mm的样条粘到硬背板，顺着基板某一层玻璃布将其剥开12.7mm的距离，然后用夹子夹住剥开的那一层用测试剥离强度的方法测试层间结合力。
3、弯曲强度：IPC-TM-650 2.4.4。
表1
Figure BDA0002863690600000151
Figure BDA0002863690600000161
表2
Figure BDA0002863690600000162
表4
Figure BDA0002863690600000163
表5
Figure BDA0002863690600000164
Figure BDA0002863690600000171
实施例15：
(1)将5份乙二胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将40份有氨基封端的聚二甲基硅氧烷改性环氧树脂、20份双酚F型环氧树脂、1份抗紫外助剂(具体为紫外吸收剂UV-O)以及0.5份三乙胺加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱150℃烘烤5min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在10kgf/cm2的压力条件，制品温度在150℃条件下固化80分钟，制成0.6mm厚度的层压板。
实施例16：
(1)将5份双氰胺以及50份二甲基甲酰胺加入到配料瓶充分搅拌溶解后，依次将40份氨丙基封端的二甲基二苯基硅氧烷改性环氧树脂、20份缩水甘油酯型环氧树脂、1份分散剂(具体为分散剂5040)以及0.5份N,N-二甲基苯胺加入到配料瓶充分搅拌后制备成胶液。
(2)用此胶液浸渍1080玻璃纤维布(基重48g/m2)，于热风循环烤箱180℃烘烤2min后得到树脂含量为68％的预浸料。
(3)将6片预浸料重叠，在该层叠体上下两面各覆盖一张离型膜，置于可程式控温控压的真空压机中，在真空状态，在20kgf/cm2的压力条件，制品温度在180℃条件下固化50分钟，制成0.6mm厚度的层压板。
参照上述性能测试方法对实施例15和实施例16所得层压板进行测试，结果见下表：
表6
Figure BDA0002863690600000181
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (19)

1.一种环氧树脂组合物，其特征在于，所述环氧树脂组合物包括环氧树脂A以及环氧树脂B；
所述环氧树脂A的折射率为1.54～1.8、透光率大于90％；
所述环氧树脂B的折射率为1.54～1.8、透光率大于90％；
所述环氧树脂A为有机硅改性环氧树脂，所述环氧树脂B为其他种类环氧树脂。
2.根据权利要求1所述的环氧树脂组合物，其特征在于，所述有机硅改性环氧树脂选自端羟基聚二甲基硅烷改性环氧树脂环氧树脂、聚甲基苯基硅氧烷改性环氧树脂、氨基封端的聚二甲基硅氧烷改性环氧树脂以及氨丙基封端的二甲基二苯基硅氧烷改性环氧树脂中的至少一种。
3.根据权利要求1所述的环氧树脂组合物，其特征在于，所述其他种类环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、缩水甘油酯型环氧树脂以及多酚型缩水甘油醚环氧树脂中的一种。
4.根据权利要求1至3任一项所述的环氧树脂组合物，其特征在于，所述环氧树脂A与所述环氧树脂B的质量之比为(1～3)：1。
5.根据权利要求4所述的环氧树脂组合物，其特征在于，所述环氧树脂A与所述环氧树脂B的质量之比为(1.25～2)：1。
6.一种环氧树脂复合材料，其特征在于，所述环氧树脂复合材料包括权利要求1至5任一项所述的环氧树脂组合物、固化剂以及固化促进剂。
7.根据权利要求6所述的环氧树脂复合材料，其特征在于，所述固化剂选自乙二胺、己二胺改性物、己二胺加成物、双氰胺、二氨基二苯基甲烷以及二氨基二苯基砜中的至少一种。
8.根据权利要求6所述的环氧树脂复合材料，其特征在于，所述固化促进剂选自N,N-二甲基苄胺、三乙胺、N,N-二甲基苯胺、咪唑类促进剂以及过氧化物类促进剂中的至少一种。
9.根据权利要求6至8任一项所述的环氧树脂复合材料，其特征在于，所述环氧树脂复合材料还包括其他功能助剂，所述其他功能助剂选自抗氧化剂、抗紫外助剂、分散剂以及稀释剂中的至少一种。
10.权利要求6至9任一项所述的环氧树脂复合材料的制备方法，其特征在于，所述制备方法包括如下步骤：
取所述的环氧树脂组合物、固化剂、固化促进剂以及溶剂，混合。
11.根据权利要求10所述的环氧树脂复合材料的制备方法，其特征在于，所述溶剂为二甲基甲酰胺或/和丙二醇甲醚。
12.一种预浸料，其特征在于，所述预浸料的制备原料包括玻璃填料以及树脂材料，所述树脂材料的制备原料包含权利要求1至5任一项所述的环氧树脂组合物，或者选用权利要求6至9任一项所述的环氧树脂复合材料。
13.权利要求12所述的预浸料的制备方法，其特征在于，所述制备方法包括如下步骤：
将所述玻璃填料浸渍于所述树脂材料，加热。
14.根据权利要求13所述的预浸料的制备方法，其特征在于，所述加热的温度为150℃～180℃，所述加热的时长为2min～5min。
15.一种层压板，其特征在于，所述层压板包括由预浸料叠制的层叠体，所述预浸料的制备原料包含权利要求1至5任一项所述的环氧树脂组合物，或者包含权利要求6至9任一项所述的环氧树脂复合材料，或者所述预浸料选用权利要求12所述的预浸料。
16.根据权利要求15所述的层压板，其特征在于，所述层叠体的单侧或者双侧还覆有离型膜。
17.权利要求15或者16所述的层压板的制备方法，其特征在于，所述制备方法包括如下步骤：取所述预浸料，叠合，真空热压。
18.根据权利要求17所述的层压板的制备方法，其特征在于，所述真空热压的条件包括：温度为150℃～180℃，压力为10kgf/cm2～20kgf/cm2，热压成形时长为60min～90min。
19.根据权利要求17或者18所述的层压板的制备方法，其特征在于，所述制备方法还包括在叠合所得层叠体的单侧或者双侧覆上离型膜。
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