CN116514412A - 改性玻璃微珠及其制备方法和应用 - Google Patents

改性玻璃微珠及其制备方法和应用 Download PDF

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CN116514412A
CN116514412A CN202310463314.4A CN202310463314A CN116514412A CN 116514412 A CN116514412 A CN 116514412A CN 202310463314 A CN202310463314 A CN 202310463314A CN 116514412 A CN116514412 A CN 116514412A
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hollow glass
glass beads
maleic acid
glass bead
copper
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马玉民
张勇
陆瑜翀
李瑶
王建斌
王珂
司浩然
蔡建武
陶新良
范若彬
洪聪哲
刘亚杰
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Zhengzhou Hollowlite Materials Co ltd
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Zhengzhou Hollowlite Materials Co ltd
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Abstract

本发明提供了一种改性玻璃微珠，包括空心玻璃微珠和在空心玻璃微珠表面接枝上马来酸，且马来酸与所述空心玻璃微珠表面形成共价键。本发明还提供了一种改性玻璃微珠的制备方法，包括马来酸酐在水溶液中水解成马来酸，马来酸的羧基与空心玻璃微珠表面羟基形成氢键，经过干燥脱水使马来酸和空心玻璃微珠表面形成共价键。本发明还提供了一种应用上述改性玻璃微珠的树脂组合物、半固化片、覆铜板。上述改性玻璃微珠上的马来酸含双键，双键可以参与到基体树脂的固化中，与基体树脂形成三维网络结构，将空心玻璃微珠固定在基体树脂体系中，所以在覆铜板剥离时，空心玻璃微珠很难从基体树脂中拔出，防止剥离时树脂基体层发生破坏，从而提高其剥离强度。

Description

改性玻璃微珠及其制备方法和应用
技术领域
本发明涉及覆铜板技术领域，尤其涉及一种改性玻璃微珠及其制备方法和应用。
背景技术
随着5G通讯技术的发展，印制电路板(PCB)的布线逐渐高密度化，信号传输高速化，要求PCB的基板材料具有低介电损耗(Df)和低介电常数(Dk)，既保证通信信号能在线路中高速稳定传输，同时又保证信号在传输过程中损耗极低。如此就需要在树脂基体中加入大量的空心玻璃微珠等填充物，来降低介电性能。例如，专利申请CN 112500686A中公开了一种树脂组合物及其应用，所述树脂组合物包括树脂和空心玻璃微珠的组合，所述空心玻璃微珠具有如下粒径分布：D10为大于8μm，D50为15～25μm，D90小于40μm，D100小于60μm。该专利申请公开的树脂组合物中添加特定粒径分布的空心玻璃微珠，不同粒径的空心玻璃微珠之间相互配合，使树脂组合物具有优异的介电性能，且在制造覆金属箔板的过程中不容易发生破球现象，制备好的覆铜板具有较好的抗压性能。
但是，若要保证极低的Dk和Df，需要向树脂基体中加入大量的空心玻璃微珠等填充物，空心玻璃微珠的质量分数可高达40％，由于空心玻璃微珠属于无机材料，与覆铜板基体树脂的界面相容性差，所以空心玻璃微珠和基体树脂粘接强度不够，在测试剥离强度时直接从树脂基体层破坏，从而导致覆铜板的剥离强度降低。
发明内容
有鉴于此，本发明的一个目的是提供一种改性玻璃微珠及其制备方法，使得改性玻璃微珠可以有效提高极低损耗高频高速覆铜板的剥离强度，在测试剥离时不从基体树脂层发生破坏。
本发明的第二个目的是提供一种应用上述改性玻璃微珠的覆铜板用树脂组合物、半固化片和覆铜板，该覆铜板的介电损耗均能达到极低损耗级别甚至超低损耗级别的同时，还能具有低介电常数甚至是超低介电常数，以及较高的剥离强度，确保剥离测试过程中不从基体树脂层发生破坏。
为达到上述目的，本发明采用以下技术方案：
一种改性玻璃微珠，包括空心玻璃微珠和在空心玻璃微珠表面接枝上马来酸，且马来酸与所述空心玻璃微珠表面形成共价键。
优选地，空心玻璃微珠(缩写：HGMs)粒径为5～20μm，真密度为0.6～0.7g/cm3。更优选地，HGMs选自本公司生产的HM10、HM15、HS70、HS65、HS60等型号的玻璃微珠。
一种上述改性玻璃微珠的制备方法，包括：马来酸酐在水溶液中水解成马来酸，马来酸的羧基与HGMs表面羟基形成氢键，然后经过干燥脱水使马来酸和HGMs表面形成共价键，即获得改性玻璃微珠。根据改性玻璃微珠的改性历程，马来酸(MAH)和HGMs表面形成的共价键，主要可能是由羧酸和羟基脱除一个水分子形成的。优选地，马来酸酐的加入量为HGMs质量的3.5％～4.5％。
其中，上述改性玻璃微珠的主要改性历程如下所示：
基上所述制备方法，包括：在搅拌作用下，将HGMs、马来酸酐和水混合并加热至50℃～60℃，反应4～6h使马来酸与HGMs充分反应；然后进行过滤和洗涤处理；之后在80～100℃下干燥2～3h，得到上述改性玻璃微珠。
一种覆铜板用树脂组合物，包括以下质量份的原料：碳氢树脂30～60份、固化剂2～6份、阻燃剂5～10份、上述改性玻璃微珠30～50份、混合溶剂15～30份。
其中，所述碳氢树脂为苯乙烯-丁二烯共聚物、丁二烯均聚物、苯乙烯均聚物、苯乙烯-二乙烯基苯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物等热固性碳氢树脂中的一种或多种。
所述固化剂为过氧化二叔丁基、过氧化二异丙苯、二乙烯基苯和1,3-双丁基过氧异丙基苯中的一种或多种。
所述阻燃剂为氢氧化铝、氢氧化镁、有机磷系阻燃剂、磷-氮系阻燃剂、二氧化硅等阻燃剂中的一种或多种。
所述溶剂为甲苯、二甲苯、丙酮、丁酮、环己酮、二甲基甲酰胺、乙二醇和甲醚中的至少两种的混合物。
本发明提供的上述覆铜板用树脂组合物的制备方法为现有技术，先向所述混合溶剂中加入所述固化剂，并搅拌至所述固化剂溶解；再加入所述碳氢树脂搅拌均匀；然后再加入所述促进剂充分搅拌均匀；最后加入阻燃剂和上述改性玻璃微珠，搅拌均匀，熟化8～10h即可制得上述树脂组合物。
本发明的目的之三在于提供一种半固化片(Prepreg，PP片)，该半固化片包括增强材料以及通过浸渍干燥后附着其上的上述覆铜板用树脂组合物。
优选地，所述增强材料选自天然纤维、有机合成纤维、有机织物、无机纤维中的任意一种或至少两种组合，更优选为无纺布或有纺玻璃纤维布。
上述半固化片的制备工艺为现有工艺，主要包括：先通过浸胶槽在所述增强材料中浸上所述树脂组合物，再在烘箱中烘烤，剪裁到合适的尺寸，得到半固化片。
本发明的目的之四在于提供一种覆铜板，该覆铜板包括半固化片层叠体以及覆于所述半固化片层叠体一侧或两侧的铜箔，其中，所述半固化片层叠体由若干张上述半固化片层叠设置而成。优选地，所述铜箔厚度为18～35μm。
覆铜板的制备方法为现有技术，根据需求的覆铜板厚度，先将若干张PP片层叠在一起，并在层叠后的半固化片的一侧或两侧覆上涂布有胶粘剂的铜箔；再利用热压机进行压合即可。优选地，压合温度170～250℃，压力10～40kg/cm3，压合时间110～180min。其中，涂布在铜箔上的胶粘剂为现有的覆铜板用胶粘剂。
本发明提供的上述改性玻璃微珠，通过利用马来酸酐水解产物在空心玻璃微珠表面化学接枝进行改性，在空心玻璃微珠表面接枝上含马来酸，马来酸上的双键可以参与到基体树脂的固化中，与基体树脂形成三维网络结构，牢牢将空心玻璃微珠固定在基体树脂体系中，所以在覆铜板剥离时，空心玻璃微珠很难从基体树脂中拔出，防止剥离时树脂基体层发生破坏，从而提高其剥离强度。
具体实施方式
下面通过具体实施方式，对本发明的技术方案做进一步的详细描述。
实施例1～3
本发明实施例提供一种改性玻璃微珠，包括空心玻璃微珠和在空心玻璃微珠表面接枝上含双键的马来酸，且马来酸与所述空心玻璃微珠表面形成共价键。实施例1～3采用的空心玻璃微珠为本公司生产的型号为HS70的空心玻璃微珠。实施例1～3提供的改性玻璃微珠下面分别用A1、A2、A3表示。
本发明实施例还提供一种改性玻璃微珠的制备方法包括：将空心玻璃微珠加入带有搅拌器的容器中，加入去离子水，充分搅拌10min，然后加入马来酸酐，搅拌加热到60℃，使马来酸酐水解成马来酸，充分反应4h，使马来酸的羧基与空心玻璃微珠表面的羟基形成氢键，然后过滤，用去离子水充分洗涤5次，90℃左右干燥24h，使马来酸和微珠表面形成共价键即可。其中，改性玻璃微珠A1、A2、A3中的马来酸酐的加入量分别为空心玻璃微珠加入质量的3.5％、4％、4.5％。
实施例4～7
(1)覆铜板用树脂组合物
实施例4～7各提供一种覆铜板用树脂组合物，原料组成如表1所示。
表1覆铜板用树脂组合物的原料质量份配比表
上述覆铜板用树脂组合物的制备工艺包括：先将混合溶剂搅拌均匀加入调胶槽中，然后加入固化剂搅拌至溶解，加入热固性碳氢树脂搅拌均匀，最后加入阻燃剂和改性玻璃微珠，搅拌均匀，熟化9h后即可。
(2)半固化片
各实施例还提供一种半固化片，该半固化片包括扁平玻璃布(NE-glass)以及通过浸渍干燥后附着其上的对应的上述(1)提供的覆铜板用树脂组合物。
上述半固化片的制备工艺包括：先通过浸胶槽在NE-glass中充分浸上对应的上述覆铜板用树脂组合物，获得浸胶料；将浸胶料在烘箱中170℃烘烤10min，剪裁到合适的尺寸即可。
(3)覆铜板
各实施例提供一种覆铜板，该覆铜板包括2张层叠设置的上述半固化片以及覆于该层叠设置的上述(2)提供的半固化片两侧的25μm厚的铜箔。
上述覆铜板的制备方法包括：先将2张半固化片层叠在一起，在2张铜箔的表面分别涂布丙烯酸硅烷；再在层叠设置的半固化片的两面分别覆上涂布有胶粘剂的铜箔，然后利用热压机进行压合，压合温度约200℃，压力约30kg/cm3，压合时间约150min即可得到覆铜板。
对比例
对比例1～7各提供一种覆铜板，其与实施例5提供的覆铜板的结构基本相同，主要不同之处在于：
对比例1～4采用的改性玻璃微珠中的马来酸酐的加入量分别为空心玻璃微珠质量的1％、2％、3％、5％，其它不变；
对比例5采用硅烷偶联剂KH570改性玻璃微珠替代其中的改性玻璃微珠A2，且KH570的加入量为空心玻璃微珠质量的3％(3％为KH570改性最佳用量)，本对比例采用的KH570改性玻璃微珠的制备方法与实施例1～3提供的改性玻璃微珠的制备方法相同，其它不变；
对比例6采用未改性的空心玻璃微珠替代改性玻璃微珠A2，其它不变；
对比例7未添加空心玻璃微珠，其它不变。
对比例8和9各提供一种覆铜板，其与实施例7提供的覆铜板的结构基本相同，主要不同之处在于：对比例7采用KH570改性玻璃微珠(与对比例5采用的改性玻璃微珠相同)，对比例8采用未改性的空心玻璃微珠替代改性玻璃微珠A2，其它均不变。
性能验证试验
下面针对实施例4～7及对比例1～9提供的覆铜板进行以下性能测试，测试结果如表2所示
1)剥离强度：按照标准IPC-TM-6502.4.9方法中的"热应力后"实验条件，其中，铜箔和胶粘剂(丙烯酸硅烷)界面剥离，标记为A；胶粘剂层内聚剥离破坏，标记为B；胶粘剂和基体树脂层(半固化片)界面剥离破坏，标记为C；基体树脂层剥离破坏，标记为D；
2)介电常数：按照标准IPC-TM-650 -2.5.5.9，10GHz；
3)介电损耗：按照标准IPC-TM-650 -2.5.5.9，10GHz；
4、分层时间(TMA法)：按照标准IPC-TM-650 -2.4.24.1；
表2覆铜板性能测试结果表
结合表2，从实施例4～6及对比例1～4提供的试验数据来看，当马来酸酐的加入量为空心玻璃微珠质量的3.5％～4.5％时，剥离强度大于1.0N/mm。其中，马来酸酐的加入量为空心玻璃微珠质量的4％时，为最佳添加量，使用对应的改性玻璃微珠A2使覆铜板具有最高的剥离强度。本发明提供的改性玻璃微珠之所以能具有较大的玻璃强度主要是由于马来酸酐水解后形成马来酸，马来酸分子两端都可以和空心玻璃微珠表面羟基发生接枝反应，相当于有两只手同时抓住了空心玻璃微球，同时马来酸的双键参与到基体树脂的固化网络中，使空心玻璃微球与基体树脂形成紧密连接的结构，从而使覆铜板在剥离时不会从基体树脂层发生破坏，主要从胶粘剂和基体树脂层界面剥离。
结合实施例5和对比例5～7、实施例7和对比例8～9，覆铜板采用本发明实施例提供的改性玻璃微珠的剥离强度，高于对比例采用的硅烷偶联剂KH570改性玻璃微珠、未改性玻璃微珠以及不添加玻璃微珠的情况。
最后应当说明的是：以上实施例仅用以说明本发明的技术方案而非对其限制；尽管参照较佳实施例对本发明进行了详细的说明，所属领域的普通技术人员应当理解：依然可以对本发明的具体实施方式进行修改或者对部分技术特征进行等同替换；而不脱离本发明技术方案的精神，其均应涵盖在本发明请求保护的技术方案范围当中。

Claims (10)

1.一种改性玻璃微珠，其特征在于，包括空心玻璃微珠和在空心玻璃微珠表面接枝上马来酸，且马来酸与所述空心玻璃微珠表面形成共价键。
2. 根据权利要求1所述的改性玻璃微珠，其特征在于，所述空心玻璃微珠粒径为5～20μm，真密度为0.6～0.7 g/cm3。
3.一种改性玻璃微珠的制备方法，包括：马来酸酐在水溶液中水解成马来酸，马来酸的羧基与空心玻璃微珠表面羟基形成氢键，然后经过干燥脱水使马来酸和所述空心玻璃微珠表面形成共价键，即获得改性玻璃微珠。
4.根据权利要求3所述的制备方法，其特征在于，马来酸酐的加入量为所述空心玻璃微珠质量的3.5%～4.5%。
5. 根据权利要求3或4所述的制备方法，其特征在于，在搅拌作用下，将所述空心玻璃微珠、马来酸酐和水混合并加热至50℃～60℃，反应4～6 h使马来酸与所述空心玻璃微珠充分反应；依次进行过滤和洗涤处理；在80～100℃下干燥2～3 h，得到所述改性玻璃微珠。
6.一种覆铜板用树脂组合物，其特征在于，包括以下质量份的原料：碳氢树脂30～60份、固化剂2～6份、阻燃剂5～10份、权利要求1或2所述的改性玻璃微珠30～50份、混合溶剂15～30份。
7.根据权利要求6所述的树脂组合物，其特征在于，所述碳氢树脂为苯乙烯-丁二烯共聚物、丁二烯均聚物、苯乙烯均聚物、苯乙烯-二乙烯基苯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物中的一种或多种。
8.根据权利要求6或7所述的树脂组合物，其特征在于，所述混合溶剂为甲苯、二甲苯、丙酮、丁酮、环己酮、二甲基甲酰胺、乙二醇和甲醚中的至少两种的混合物。
9.一种半固化片，其特征在于，包括增强材料以及通过浸渍干燥后附着其上的权利要求6～8任一项所述的树脂组合物。
10.一种覆铜板，其特征在于，包括半固化片层叠体以及覆于所述半固化片层叠体一侧或两侧的铜箔，其中，所述半固化片层叠体由若干张权利要求9所述的半固化片层叠设置而成。
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