CN102504333A - 一种无机填充物、树脂组合物及其应用 - Google Patents
一种无机填充物、树脂组合物及其应用 Download PDFInfo
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Abstract
本发明公开了一种无机填充物,其特征在于,以氧化物换算的质量百分比计,该无机填充物包含:(1)62~80wt%的SiO2;(2)0~10wt%的Al2O3;(3)20~30wt%的B2O3;(4)0~1wt%的Na2O或K2O或二者的组合;其中该无机填充物最大粒径在100μm以下。本发明还公开了含有该无机填充物的树脂组合物及该树脂组合物在制备印制电路板中的应用。使用本发明的无机填充物制备而成的层压板,在具备良好钻孔性的同时,具有更优的介电性能,将采用该无机填充物制成的层压板用于制备高频传输印制电路板,表现出良好的高频传输性能。
Description
技术领域
本发明涉及一种电学材料,尤其涉及一种适用于印制电路板的无机填充物、含有该无机填充物的树脂组合物及它们在制备印制电路板中的应用。
背景技术
层压板是印制电路板的制造原料。目前,现有技术中通常采用的层压板制造方法为将树脂组合物含浸于玻璃纤维布上,经由烘烤后形成半固化胶片,再将半固化胶片与上下两层铜箔叠合后经真空、热压方式压合成铜箔层压板,其中半固化胶片固化形成铜箔层压板的绝缘层。
为了改善铜箔层压板绝缘层的导热、镭射钻孔性及热膨胀性,业界通常都会在树脂组合物中添加一定量的无机填充物。
对于物质介电性能,本领域中通常会用介电常数(Dielectric constant,Dk)和耗散因子(Dissipation factor,Df)进行描述,通常情况下Dk, Df值越低则介电性能越佳,而Dk, Df值越高则意味着较差的介电性能。现有技术使用的无机填充物包含二氧化硅(熔融态、非熔融态或多孔结构)、氢氧化铝、氧化铝、氧化镁、滑石、云母粉及二氧化硅与氧化铝等氧化物的共熔物等种类。其中,由于二氧化硅与氧化铝等氧化物共熔的复合无机填充物具有良好的钻孔性,如电子级玻璃纤维(E-glass)填料及G2-C粉体(SIBELCO公司产品名)等,因而被广泛用于层压板的制备,然而现有技术中所公开的该类复合无机填充物普遍存在介电性能不佳的缺陷,在1MHz频率下,介电常数(Dielectric constant,Dk)通常在5.0~6.0之间,耗散因子(Dissipation factor,Df)通常在0.001~0.002之间,甚至更高,因而无法或者难于满足电子工业中高频传输的发展要求。
发明内容
为了解决上述技术问题,本发明提供了一种无机填充物,用于制备印制电路板中的层压板。该无机填充物相较于现有技术中公开的E-glass填料及G2-C粉体等无机填充物,在具备良好钻孔性的同时,具有更优的介电性能,将采用该无机填充物制成的层压板用于制备高频传输印制电路板,表现出良好的高频传输性能。
本发明公开了一种无机填充物,以氧化物换算的质量百分比计,该无机填充物包含:(1)62~80wt%的SiO2;(2)0~10wt%的Al2O3;(3)20~30wt%的B2O3;(4)0~5wt%的的Na2O或K2O或二者的组合;其中该无机填充物最大粒径在100μm以下。
优选地,以氧化物换算的质量百分比计,本发明的无机填充物包含:(1)66~72wt%的SiO2;(2)3~5wt%的Al2O3;(3)22~30wt%的B2O3;(4)0~0.1wt%的Na2O或K2O或二者的组合;所述无机填充物的粒径优选控制在1~10μm范围内。
本发明所公开的无机填充物,相比于现有技术中E-glass填料及G2-C粉体等无机填充物,其区别在于不含CaO,或者即便添加CaO也会将CaO的含量控制在小于0.1wt%,而通过介电性能的测试实验表明,本发明的无机填充物由于不含CaO或者低含量的CaO而具有较低的Dk/Df值,亦即具有良好的介电性能。
另外,相比于现有技术中E-glass填料及G2-C粉体等无机填充物,本发明所公开的无机填充物,具有更高的B2O3含量,而通过介电性能的测试实验表明,B2O3的含量较高使得本发明的无机填充物能达到较低的Dk/Df值,亦即具有良好的介电性能。
如表1所示的几种无机填充物的组成份及介电性能比较,由数据显示,相比于现有技术中E-glass填料及G2-C粉体等无机填充物,本发明公开的无机填充物Dk/Df值较低,具有更好的介电性能。
表一、现有技术与本发明无机填充物的介电性能比较
本发明所述的无机填充物,其制造方法一般是按照配比中氧化物的比例将矿物或添加物加入高温炉内,经由煅烧、挑选、粉碎、分级等工序制成,该无机填充物的粒径分布视需求控为纳米级或微米级, 一般粒径分布为100μm以下,优选为1~10μm。较小的粒径分布有助于提升无机填充物在树脂组合物中的分散性及后续电路板制程中的填孔流胶性。
优选地,本发明所述的无机填充物,其介电常数在1MHz下小于4.1,其耗散因子在1MHz下小于0.001。较佳地,该无机填充物的介电常数通常在1MHz下约为4.0,其耗散因子在1MHz下约为0.0008。按照上述方案中无机填充物的配比,并将介电性能控制在此优选范围内,使采用该无机填充物制成的层压板,在用于制备高频传输印制电路板时,表现出良好的高频传输性能。
优选地,本发明所述之无机填充物,进一步包括对该无机填充物进行表面预处理的偶联剂,所述偶联剂为硅烷偶联剂、硅氧烷偶联剂、钛酸酯偶联剂、硼酸酯偶联剂、稀土偶联剂、锆酸酯偶联剂、铝酸酯偶联剂、含氟偶联剂中的一种或两种以上的组合。通过采用偶联剂对该无机填充物进行表面预处理,能够增加无机填充物与环氧树脂体系的结合强度。
另一方面,本发明所解决的技术问题还在于树脂组合物,用其制成的层压板具有良好的钻孔加工性能,并具有出色的介电性能,适合用于制作高频电路板。
为此,本发明的提供一种树脂组合物包含上述方案中揭示的无机填充物和至少一种树脂。
其中,该无机填充物包含:(1)62~80wt%的SiO2;(2)0~10wt%的Al2O3;(3)20~30wt%的B2O3;(4)0~5wt%的Na2O或K2O或二者的组合;其中该无机填充物最大粒径在100μm以下。
所述树脂为环氧树脂、苯酚树脂、酚醛树脂、酸酐树脂、苯乙烯树脂、丁二烯树脂、聚酰胺树脂、聚酰亚胺树脂、聚酯树脂、聚醚树脂、聚苯醚树脂、氰酸酯树脂、异氰酸酯树脂、马来酰亚胺树脂、苯并恶嗪树脂、溴化树脂、含磷树脂、含氮树脂中的一种或两种以上的组合。
优选地,该树脂组合物进一步包含固化促进剂,所述固化促进剂为2-甲基咪唑、1-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-苯基-甲基咪唑、三氟化硼胺复合物、氯化乙基三苯基鏻、4-二甲基胺基吡啶中的至少一者的刘易斯碱,或锰、铁、钴、镍、铜及锌中至少一者之金属盐化合物的刘易斯酸,或有机过氧化物,所述有机过氧化物为过氧化二异丙苯。
优选地,该树脂组合物还包括下列阻燃性化合物中的至少一种:多溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺、双酚联苯磷酸盐、聚磷酸铵、对苯二酚-双-(二苯基磷酸盐)、双酚A-双-(二苯基磷酸盐)、三(2-羟乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、聚磷酸三聚氰胺、磷氮基化合物、偶磷氮化合物、9,10-二氢-9-氧杂-10-磷菲-10-氧化物及其衍生物或树脂、三聚氰胺尿酸酯及三-羟乙基异氰尿酸酯。
优选地,该树脂组合物进一步包含偶联剂,所述偶联剂为硅烷偶联剂、硅氧烷偶联剂、钛酸酯偶联剂、硼酸酯偶联剂、稀土偶联剂、锆酸酯偶联剂、铝酸酯偶联剂、含氟偶联剂中的一种或两种以上的组合。
另外,本发明所解决的技术问题还在于提供了含有本发明所揭示的树脂组合物制备而成的半固化胶片、层压板和电路板。
其中,该半固化胶片包含增强材料及本发明提供的树脂组合物,所述增强材料包覆于经由加热成半固化态的树脂组合物,所述增强材料为无机纤维、有机合成纤维中的一种或二者的混合物。该层压板包括至少一金属箔及至少一绝缘层,该绝缘层系上述半固化胶片经固化而成。而该电路板中包括至少一种上述层压板。
具体实现时,半固化胶片、层压板及印制电路板路板的制作方法,包括如下步骤:
1、将树脂胶液中加入所述无机填充物,及阻燃剂、固化剂、固化促进剂、偶联剂、溶剂,在25~45℃区间范围内搅拌均匀后制成成胶;
2、将增强材料,通常是玻璃纤维布,在上述成胶中浸渍后,再进入烤箱中烘烤一定时间即制得半固化胶片,烘烤温度为120~260℃区间范围内;
3、将上述半固化胶片与金属箔叠合好后放入真空热压机中,在压力50~600psi区间范围内、热盘温度50~260℃区间范围内压制得到层压板;
4、将上述层压板经曝光、前处理、AOI检查、棕黑化、钻孔、电镀、蚀刻、压合等工序即制得印制电路板。
相比于现有技术中的无机填充料,本发明公开的无机填充物在用于制备印制电路板时,表现出良好的钻孔性及更为优异的介电性能,更适合用于制作高频传输印制电路板。
下面结合具体实施例进一步详细描述本发明,但本发明不局限于这些实施方式,任何在本发明基本精神上的改进或替代,仍属于本发明权利要求书中所要求保护的范围。
具体实施方式
为使本发明更加容易理解,下面将进一步阐述本发明的具体实施例。
实施例1:无机填充物的制备一
按照如下配比中氧化物的比例准备原料:
(1)72wt%的SiO2;(2)5wt%的Al2O3;(3)22wt%的B2O3;(4)0.001wt%的Na2O及0.001wt%的K2O。
将称取的上述氧化物配比的矿物或添加物加入高温炉内,经由1500℃煅烧48小时后,再经由挑选、粉碎、分级工序制备而成,制备过程中,无机组合物成品的粒径控制在100μm以下,在本发明实施例中,将无机组合物成品的粒径控制在1~10μm范围内,以便于后续采用本发明的无机组合物的电子材料能够表现出良好的性能。
实施例2:无机填充物的制备二
按如下比例称取制备无机填充物的原料:
(1)66wt%的SiO2;(2)3wt%的Al2O3;(3)30wt%的B2O3;(4)0.001wt%的Na2O及0.001wt%的K2O。
其制备方法同实施例1,对无机组合物成品粒径的控制也参照实施例1。
实施例3:树脂组合物的制备一
按如下比例称取制备树脂组合物的原料:
(1)50重量份的双酚A酚醛环氧树脂;(2)50重量份的甲酚酚醛环氧树脂;(3)5重量份的N,N-二乙基氰乙酰胺;(4)0.5重量份的2-甲基咪唑;(5)50重量份的丁酮;(6)40重量份的如实施例1所述的无机填充物;(7)0.2重量份的硅烷偶联剂。
将上述成分在25~45℃区间范围内搅拌均匀后制成成胶。
实施例4:树脂组合物的制备二
按如下比例称取制备树脂组合物的原料:
(1)50重量份的双酚A酚醛环氧树脂;(2)50重量份的甲酚酚醛环氧树脂;(3)5重量份的N,N-二乙基氰乙酰胺;(4)0.5重量份的2-甲基咪唑;(5)50重量份的丁酮;(6)40重量份的如实施例2所述的无机填充物;(7)0.2重量份的硅烷偶联剂。
将上述成分在25~45℃区间范围内搅拌均匀后制成成胶。
实施例5:半固化胶片的制备一
将实施例3中制得的树脂组合物均匀含浸于玻璃纤维布上,放入烤箱经由170℃烘烤3分钟后制成半固化胶片。
实施例6:半固化胶片的制备二
将实施例4中制得的树脂组合物均匀含浸于玻璃纤维布上,放入烤箱经由170℃烘烤3分钟后制成半固化胶片。
实施例7:
将两片铜箔叠合于一片实施例5所制得的半固化胶片两侧,再放入真空热压机中,在压力50~600psi区间范围内、热盘温度50~260℃区间范围内压制得到铜箔层压板,其中半固化胶片固化形成两铜箔间的绝缘层。当然在本发明的其他实施例中,也会更加具体需要设置一片以上的半固化胶片,对应地,叠合在一起到铜箔会是三层或多层,保证半固化胶片能够在相邻的两层铜箔之间固化形成有效的绝缘层即可。
实施例8:
将两片铜箔叠合于一片实施例6所制得的半固化胶片两侧,再放入真空热压机中,在压力50~600psi区间范围内、热盘温度50~260℃区间范围内压制得到铜箔层压板,其中半固化胶片固化形成两铜箔间的绝缘层。当然在本发明的其他实施例中,也会更加具体需要设置一片以上的半固化胶片,对应地,叠合在一起到铜箔会是三层或多层,保证半固化胶片能够在相邻的两层铜箔之间固化形成有效的绝缘层即可。
比较例1:
按如下比例称取制备无机填充物的原料:
(1)56wt%的SiO2;(2)12wt%的Al2O3;(3)20wt%的CaO;(4)5wt%的B2O3;(5)0.01wt%的MgO;(6)0.001wt%的Na2O及0.001wt%的K2O。
参照实施例1中的方法制备无机填充物。
比较例2:
按如下比例称取制备树脂组合物的原料:
(1)50重量份的双酚A酚醛环氧树脂;(2)50重量份的甲酚酚醛环氧树脂;(3)5重量份的N,N-二乙基氰乙酰胺;(4)0.5重量份的2-甲基咪唑;(5)50重量份的丁酮;(6)40重量份的如比较例1所述的无机填充物;(7)0.2重量份的硅烷偶联剂。
将上述成分在25~45℃区间范围内搅拌均匀后制成成胶。
比较例3:
将比较例2中制得的树脂组合物均匀含浸于玻璃纤维布上,放入烤箱经由170℃烘烤3分钟后制成半固化胶片。
比较例4:
将两片铜箔叠合于一片比较例3所制得的半固化胶片两侧,参照实施例7中的方法制备层压板。
将实施例7、8及比较例4所得的层压板按照IPC-TM650的测试方法进行测试,结果如表2所示。
表2 层压板性能测试比较结果
由表2数据显示,实施例7与8所述层压板的Dk及Df值相较于比较例4层压板的Dk及Df值更低,因此实施例7与8的电性较佳,显示本发明揭露之无机填充物能提供较佳的介电性能。此外,比较实施例7与8所述层压板的电性结果显示,实施例8拥有较低的Dk及Df值,显示实施例8使用的无机填充物因含有较少量的CaO与较多量的B2O3,使得相较于实施例7使用的无机填充物具有较低的Dk及Df值,即较佳的介电性能。
另外,根据钻针磨耗量的测量原理可知,当钻针钻2500孔后,由于钻针的切削边缘会不断与上述各层压板产生接触磨耗,在切削边缘的切削转角处会产生磨耗,磨耗量主要就是对切削转角处进行测量。比较表2中钻针磨耗量数据可见,本发明实施例7和8所述层压板在钻针钻2500孔后的磨耗量与比较例4稍小,因此相较于比较例4中使用的无机填充物而言,实施例7和8使用的无机填充物具有稍小的钻针磨耗量,即良好的钻孔加工性。
综上所述,本发明所述的新型无机填充物的加入有效降低了层压板的介电常数和耗散因子,同时具有良好的钻孔加工性,适合用于制作高频传输印制电路板。
实施例9:本发明电路板的制备
将复数个实施例8所制得之铜箔层压板经由微影蚀刻制程形成表面电路,并与复数个实施例6所制得的半固化胶片交错叠置于两片铜箔间,之后经高温高压制程形成电路基板,并以电路板加工制程进行处理,以制成本发明的电路板。根据表2中的数据完全可以预知,通过上述方法制备的电路板,由于其采用了本发明的无机填充物,适合用作制作高频传输印制电路板。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
Claims (10)
1.一种无机填充物,其特征在于,以氧化物换算的质量百分比计,该无机填充物包含:(1)62~80wt%的SiO2;(2)0~10wt%的Al2O3;(3)20~30wt%的B2O3;(4)0~5wt%的的Na2O或K2O或二者的组合;其中该无机填充物最大粒径在100μm以下。
2.如申请权利要求1所述的无机填充物,其特征在于:介电常数于1MHz下小于4.1,其耗散因子于1MHz下小于0.001。
3.一种树脂组合物,其特征在于:该树脂组合物中包含权利要求1或2中所述的无机填充物和至少一种树脂。
4.如申请权利要求3所述的树脂组合物,其特征在于:所述树脂为环氧树脂、苯酚树脂、酚醛树脂、酸酐树脂、苯乙烯树脂、丁二烯树脂、聚酰胺树脂、聚酰亚胺树脂、聚酯树脂、聚醚树脂、聚苯醚树脂、氰酸酯树脂、异氰酸酯树脂、马来酰亚胺树脂、苯并恶嗪树脂、溴化树脂、含磷树脂、含氮树脂中的一种或两种以上的组合。
5.如申请权利要求3所述的树脂组合物,其特征在于:该树脂组合物进一步包含固化促进剂,所述固化促进剂为2-甲基咪唑、1-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-苯基-甲基咪唑、三氟化硼胺复合物、氯化乙基三苯基鏻、4-二甲基胺基吡啶中的至少一者的刘易斯碱,或锰、铁、钴、镍、铜及锌中至少一者之金属盐化合物的刘易斯酸,或有机过氧化物,所述有机过氧化物为过氧化二异丙苯。
6.如申请权利要求3所述的树脂组合物,其特征在于,该树脂组合物还包括下列阻燃性化合物中的至少一种:多溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺、双酚联苯磷酸盐、聚磷酸铵、对苯二酚-双-(二苯基磷酸盐)、双酚A-双-(二苯基磷酸盐)、三(2-羟乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、聚磷酸三聚氰胺、磷氮基化合物、偶磷氮化合物、9,10-二氢-9-氧杂-10-磷菲-10-氧化物及其衍生物或树脂、三聚氰胺尿酸酯及三-羟乙基异氰尿酸酯。
7.如申请权利要求3所述的树脂组合物,其特征在于:该树脂组合物进一步包含偶联剂,所述偶联剂为硅烷偶联剂、硅氧烷偶联剂、钛酸酯偶联剂、硼酸酯偶联剂、稀土偶联剂、锆酸酯偶联剂、铝酸酯偶联剂、含氟偶联剂中的一种或两种以上的组合。
8.一种半固化胶片,其特征在于:该半固化胶片包含增强材料及权利要求3所述的树脂组合物,所述增强材料包覆有经由加热成半固化态的树脂组合物,所述增强材料为无机纤维、有机合成纤维中的一种或二者的混合物。
9.一种层压板,包括至少一金属箔及至少一绝缘层,其特征在于:该绝缘层系权利要求8所述的半固化胶片经固化而成。
10.一种电路板,其特征在于:该电路板包括至少一种如申请权利要求9所述的层压板。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1272424A (zh) * | 1999-04-29 | 2000-11-08 | 北京化工大学 | 一种复合基覆铜箔层压板及其制造方法 |
CN101547558A (zh) * | 2009-04-21 | 2009-09-30 | 无锡宏仁电子材料科技有限公司 | 一种覆铜箔基板及其制备方法 |
CN101594987A (zh) * | 2006-10-26 | 2009-12-02 | Agy控股公司 | 低介电玻璃纤维 |
JP2010260781A (ja) * | 2009-04-07 | 2010-11-18 | Nippon Electric Glass Co Ltd | 無機充填材及びその製造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0639338B2 (ja) * | 1986-06-20 | 1994-05-25 | 日本電気硝子株式会社 | 繊維用ガラス組成物 |
US6245841B1 (en) * | 1998-03-23 | 2001-06-12 | General Electric Company | Cyanate ester based thermoset compositions |
TWI388623B (zh) * | 2009-10-02 | 2013-03-11 | Nanya Plastics Corp | A thermosetting epoxy resin composition for improving the drilling processability of printed circuit boards |
-
2011
- 2011-11-02 CN CN201110340880.3A patent/CN102504333B/zh active Active
-
2012
- 2012-10-30 TW TW101140090A patent/TWI488897B/zh active
- 2012-11-01 US US13/666,399 patent/US20130108875A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1272424A (zh) * | 1999-04-29 | 2000-11-08 | 北京化工大学 | 一种复合基覆铜箔层压板及其制造方法 |
CN101594987A (zh) * | 2006-10-26 | 2009-12-02 | Agy控股公司 | 低介电玻璃纤维 |
JP2010260781A (ja) * | 2009-04-07 | 2010-11-18 | Nippon Electric Glass Co Ltd | 無機充填材及びその製造方法 |
CN101547558A (zh) * | 2009-04-21 | 2009-09-30 | 无锡宏仁电子材料科技有限公司 | 一种覆铜箔基板及其制备方法 |
Also Published As
Publication number | Publication date |
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TWI488897B (zh) | 2015-06-21 |
CN102504333B (zh) | 2014-05-14 |
US20130108875A1 (en) | 2013-05-02 |
TW201319136A (zh) | 2013-05-16 |
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