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CN106939117B - 树脂组合物及其应用 - Google Patents

树脂组合物及其应用 Download PDF

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CN106939117B
CN106939117B CN201710249615.1A CN201710249615A CN106939117B CN 106939117 B CN106939117 B CN 106939117B CN 201710249615 A CN201710249615 A CN 201710249615A CN 106939117 B CN106939117 B CN 106939117B
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tertiary butyl
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CN106939117A (zh
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李宏途
肖浩
罗文�
王建军
王铁
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WUXI GRACE ELECTRONIC MATERIAL TECHNOLOGY Co.,Ltd.
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Abstract

本发明涉及一种树脂组合物，包括如下重量份的组分：聚环氧树脂10‑40份；固化剂20‑50份；促进剂0.01‑1份；功能性填料5‑40份；阻燃剂10‑30份；所述聚环氧树脂包括：双酚Z型环氧树脂或叔丁基改性苯酚酚醛型环氧树脂中的至少一种，和/或，环戊二烯环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂或双酚M型环氧树脂中的一种或几种。采用上述树脂组合物制备的覆铜板，在1GHz频率RC70条件下，具有较低的介电常数(Dk≦3.4)和低介质损耗(Df≦0.01)，同时具有高玻璃化温度。可较好的应用在类载板系统，解决了此系统对板材低介电常数的需求。

Description

树脂组合物及其应用
技术领域
本发明涉及高分子材料技术领域，特别是涉及一种树脂组合物及其应用。
背景技术
电子设计在不断提高整机性能的同时，也在努力缩小其尺寸。从手机到智能武器的小型便携式产品中，"小"是永远不变的追求。高密度集成(High DensityInterconnection，简称HDI)技术可以使终端产品设计更加小型化，同时满足电子性能和效率的更高标准。HDI目前广泛应用于手机、数码(摄)像机、笔记本电脑、汽车电子和其它数码产品等，其中以手机的应用最为广泛。但目前手机板主流的HDI，能够承载的主被动组件已经到了极限，而在越来越多功能都想要塞在一部手机里，同时寸土寸金的空间又要尽量容纳更大的电池(电池绝对是目前科技最大的短板)，因此，最近工程师就把脑筋动到PCB身上，着手将手机用的PCB极细线路化，因此这种“类载板PCB(Substrate-Like PCB，简称SLP)”也就因运而生了。智能型手机HDI的线宽间距约为50μm/50μm，SLP的规格需求则是30μm/30μm。这种“类载板PCB”基于现有HDI技术、类似于IC载板，但等级还不到IC载板。这种“类载板PCB”精细度会比传统HDI来得高，但它毕竟还是用来承载各类主动被组件的PCB，而不是用在半导体封装的IC载板。说穿了，“类载板PCB”就是用来取代传统的“HDI PCB”，以顺应手机或是其它智能型产品大量导入SiP封装的潮流。
此类类载板设计，由于用于移动设备，所以要求材料环保，一般都要求为无卤素材料。并且这种材料由于使用温度较高，并对材料的尺安要求较高，所需材料的特性为高玻璃化温度(High Tg)和低的膨胀系数(Low CTE)。手机后续的发展趋势也是越来越小，越来越薄，并且线宽要越来越小，因此要求材料一定要具有低的介电常数(Low Dk)。因此此类需求是最新的设计，满足此类要求并且性价比较高的材料鲜有报道。
发明内容
基于此，本发明的目的是提供一种应用于半固化片的树脂组合物。
具体的技术方案如下：
一种树脂组合物，包括如下重量份的组分：
所述聚环氧树脂包括：双酚Z型环氧树脂或叔丁基改性苯酚酚醛型环氧树脂中的至少一种，和/或，环戊二烯环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂或双酚M型环氧树脂中的一种或几种。
在其中一些实施例中，所述双酚Z型环氧树脂的结构式如下：
所述叔丁基改性苯酚酚醛型环氧树脂的结构式如下：
其中n1为0-5；
所述环戊二烯环氧树脂的结构式如下：
其中n2为0-10；
或，其中n3为0-10。
在其中一些实施例中，所述固化剂选自：叔丁基改性苯酚酚醛树脂、苯乙烯马来酸酐共聚物或活性酯中的一种或几种。
所述叔丁基改性苯酚酚醛树脂的结构式为：
其中n4为0-5；
所述苯乙烯马来酸酐共聚物的结构式为：
其中X:Y＝1-8:1，n5为8-12；
所述活性酯的结构式为：
其中n6为0-5。
在其中一些实施例中，所述促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-乙基咪唑，2-苯基咪唑或苄基二甲胺；所述功能性填料选自熔融二氧化硅、复合二氧化硅、结晶二氧化硅、球形二氧化硅、中空二氧化硅、氢氧化铝、勃姆石、氧化铝、高岭土、滑石粉或氢氧化镁中的一种或几种，所述功能性填料的粒径中度值为1-30μm；所述阻燃剂为磷系阻燃剂。
在其中一些实施例中，所述功能性填料为熔融二氧化硅、球形二氧化硅或中空二氧化硅中的一种或几种，其中熔融二氧化硅的粒径中度值为2-3μm，球形二氧化硅的粒径中度值为2-3μm，中空二氧化硅的粒径中度值为9-10μm。
本发明的另一目的是提供上述树脂组合物在制备半固化片或覆铜板中的应用。
本发明的另一目的是提供一种半固化片。
一种半固化片，包括玻璃纤维布和上述树脂组合物，所述树脂组合物占所述半固化片总重量的40-80％。
本发明的另一目的是提供上述半固化片的制备方法，包括如下步骤：将所述玻璃纤维布浸渍于权利要求1-5任一项所述的树脂组合物，于150-180℃烘干，即得所述半固化片。
本发明的另一目的是提供一种覆铜板，包括上述半固化片和铜箔。
本发明的另一目的是提供一种覆铜板的制备方法，包括如下步骤：将铜箔、上述半固化片和铜箔依次层叠，再于170-220℃下压合，即得所述覆铜板。
上述树脂组合物选用了特定的聚环氧树脂(包括：双酚Z型环氧树脂或叔丁基改性苯酚酚醛型环氧树脂中的至少一种，和/或环戊二烯环氧树脂)，并配以特定的固化剂(叔丁基改性苯酚酚醛树脂、苯乙烯马来酸酐共聚物或活性酯中的一种或几种)以及特定的功能性填料(熔融二氧化硅、球形二氧化硅或中空二氧化硅中的一种或几种)。双酚Z型环氧树脂，叔丁基改性苯酚酚醛型环氧树脂，叔丁基改性环戊二烯环氧树脂，叔丁基改性苯酚酚醛树脂这几类树脂中含有脂肪环或叔丁基，导致树脂的极性较低；苯乙烯马来酸酐共聚物和活性酯固化剂由于固化环氧树脂后，整体结构没有羟基，所以整个体系的极性较低，制备的材料会具有较低的介电常数。中空二氧化硅由于结构中含有空气，二空气的介电常数最低，为1，所以体系中使用中空二氧化硅可有效的降低体系的介电常数。熔融二氧化硅和球形二氧化硅本身纯度较高，具有优异的介电性能，介电常数为3.8左右，而比较例中的复合二氧化硅介电常数约为6.6。
采用上述树脂组合物制备的覆铜板，在1GHz频率RC70条件下，具有较低的介电常数(Dk≦3.4)和低介质损耗(Df≦0.01)，同时具有高玻璃化温度。可较好的应用在类载板系统，解决了此系统对板材低介电常数的需求。
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。
本实施例中所采用的原料如下：
(A)聚环氧树脂化合物
A1：XEV-1131M80(双酚Z环氧树脂与叔丁基改性苯酚酚醛型环氧树脂共混物，SHIN-A)；
A2：GEBR580K70(DOPO-PNE，含磷环氧树脂，宏昌)；
A3:203EK80(双酚A酚醛环氧树脂，圣泉)；
A4：KES-7790(DCPD-POP，叔丁基改性环戊二烯环氧树脂，kolon)；
(B)固化剂
B1：XHV-3100APM65(叔丁基改性酚醛树脂，SHIN-A)
B2:EF-30(苯乙烯马来酸酐共聚物，SMA)
B3：EF-60(苯乙烯马来酸酐共聚物，SMA)
B4：SHC-5800TM65(活性酯固化剂，SHIN-A)
B5:PF8120(酚醛树脂，圣泉)
(C)促进剂
C1：十一烷基咪唑(日本四国化成)
C2：DMAP(二甲氨基吡啶，天宇化工)
(D)功能性填料
D1：FS1002(熔融二氧化硅，中位粒径为2-3μm，联瑞)
D2:DQ1028L(球形二氧化硅，中位粒径为2-3μm，联瑞)
D3：iM30K(中空二氧化硅，中位粒径为9-10μm，3M)
D4：DB1003(复合二氧化硅，中位粒径为2-3μm，联瑞)
(E)无卤阻燃剂，为SPB100(聚磷睛，大冢)
实施例1-6及对比例1-4配料表如下：
采用上述树脂组合物(实施例1-6及对比例1-4)制备半固化片，包括如下步骤：
将玻璃纤维布浸渍于权利要求1-5任一项所述的树脂组合物，于150-180℃烘干，即得半固化片，其中树脂组合物占所述半固化片总重量的40-80％。
采用上述半固化片(由实施例1-6及对比例1-4的树脂组合物制备得到的)制备覆铜板，包括如下步骤：
将铜箔、上述半固化片和铜箔依次层叠，再于170-220℃下压合，即得覆铜板。
上述覆铜板的性能测试结果如下：
比较例1和比较例2与实施例1和2对比，主要更换环氧树脂后，介电性能和介电损耗上升，达不到目标；比较例3与实施例1、2、5对比，主要更换固化剂后，介电性能和介电损耗上升，达不到目标；比较例4与实施例1、3、6对比，主要为更换填料后，介电性能和介电损耗上升，达不到目标。整个比较的趋势主要是考察介电常数和介电损耗。
以上特性的测试方法如下：
(1)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按IPC-TM-6502.4.25所规定的DSC方法进行测定；
(2)热分层时间T-288：按照IPC-TM-650 2.4.24.1方法进行测定；
(3)剥离强度：按照IPC-TM-650 2.4.9规定测试；
(4)吸水性：为PCT蒸煮2h前后重量差值相对于PCT前样品重量的比率；
(5)PCT为在121℃105KPa压力锅中蒸煮2h，浸入288℃锡炉中，记录爆板分层时间；
(6)热膨胀系数Z轴CTE(TMA)：按照IPC-TM-650 2.4.24.方法进行测定；
(7)燃烧性：依据UL94垂直燃烧法测定。
(8)介电常数及介质损耗值：按照IPC-TM-650 2.5.5.9使用平行板法测定1GHz下的介电常数及介质损耗值；
(9)热分解温度(Td)：按照IPC-TM-650 2.4.26所规定的方法进行测定。
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 (7)

1.一种树脂组合物，其特征在于，包括如下重量份的组分：
所述聚环氧树脂选自：双酚Z环氧树脂与叔丁基改性苯酚酚醛型环氧树脂共混物、含磷环氧树脂、双酚A酚醛环氧树脂和叔丁基改性环戊二烯环氧树脂中的一种或几种；
所述双酚Z型环氧树脂的结构式如下：
所述叔丁基改性苯酚酚醛型环氧树脂的结构式如下：
其中n1为0-5；
所述环戊二烯环氧树脂的结构式如下：
其中n2为0-10；
或，其中n3为0-10；
所述固化剂选自：叔丁基改性苯酚酚醛树脂、苯乙烯马来酸酐共聚物或活性酯中的一种或几种；
所述叔丁基改性苯酚酚醛树脂的结构式为：
其中n4为0-5；
所述苯乙烯马来酸酐共聚物的结构式为：
其中X:Y＝1-8:1，n5为8-12；
所述活性酯的结构式为：
其中n6为0-5；
所述功能性填料为熔融二氧化硅、球形二氧化硅或中空二氧化硅中的一种或几种，其中熔融二氧化硅的粒径中度值为2-3μm，球形二氧化硅的粒径中度值为2-3μm，中空二氧化硅的粒径中度值为9-10μm；
所述阻燃剂为磷系阻燃剂。
2.根据权利要求1所述的树脂组合物，其特征在于，所述促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-乙基咪唑，2-苯基咪唑或苄基二甲胺。
3.权利要求1或2所述的树脂组合物在制备半固化片或覆铜板中的应用。
4.一种半固化片，其特征在于，包括玻璃纤维布和权利要求1或2所述的树脂组合物，所述树脂组合物占所述半固化片总重量的40-80％。
5.权利要求4所述的半固化片的制备方法，其特征在于，包括如下步骤：将所述玻璃纤维布浸渍于权利要求1或2所述的树脂组合物，于150-180℃烘干，即得所述半固化片。
6.一种覆铜板，其特征在于，包括权利要求4所述的半固化片和铜箔。
7.一种覆铜板的制备方法，其特征在于，包括如下步骤：将铜箔、权利要求4所述的半固化片和铜箔依次层叠，再于170-220℃下压合，即得所述覆铜板。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585440A (zh) * 2012-01-16 2012-07-18 广州宏仁电子工业有限公司 用于覆铜箔基板的高cti值无卤阻燃型树脂组合物
CN102633990A (zh) * 2012-04-05 2012-08-15 广东生益科技股份有限公司 环氧树脂组合物及使用其制作的半固化片与覆铜箔层压板
CN102850722A (zh) * 2012-09-07 2013-01-02 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
CN103073846A (zh) * 2013-01-18 2013-05-01 腾辉电子（苏州）有限公司 无卤低介电环氧树脂组合物
CN103965588A (zh) * 2014-05-28 2014-08-06 苏州生益科技有限公司 无卤热固性树脂组合物、半固化片及层压板
CN105086365A (zh) * 2015-08-03 2015-11-25 广东生益科技股份有限公司 一种覆铜板用环氧树脂组合物及其应用
CN105778430A (zh) * 2014-12-26 2016-07-20 广东生益科技股份有限公司 一种环氧树脂组合物以及使用它的预浸料和层压板

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585440A (zh) * 2012-01-16 2012-07-18 广州宏仁电子工业有限公司 用于覆铜箔基板的高cti值无卤阻燃型树脂组合物
CN102633990A (zh) * 2012-04-05 2012-08-15 广东生益科技股份有限公司 环氧树脂组合物及使用其制作的半固化片与覆铜箔层压板
CN102850722A (zh) * 2012-09-07 2013-01-02 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
CN103073846A (zh) * 2013-01-18 2013-05-01 腾辉电子（苏州）有限公司 无卤低介电环氧树脂组合物
CN103965588A (zh) * 2014-05-28 2014-08-06 苏州生益科技有限公司 无卤热固性树脂组合物、半固化片及层压板
CN105778430A (zh) * 2014-12-26 2016-07-20 广东生益科技股份有限公司 一种环氧树脂组合物以及使用它的预浸料和层压板
CN105086365A (zh) * 2015-08-03 2015-11-25 广东生益科技股份有限公司 一种覆铜板用环氧树脂组合物及其应用

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