CN111793327A - 一种高速高频覆铜板用环氧树脂组合物及其制备方法 - Google Patents

一种高速高频覆铜板用环氧树脂组合物及其制备方法 Download PDF

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CN111793327A
CN111793327A CN202010652630.2A CN202010652630A CN111793327A CN 111793327 A CN111793327 A CN 111793327A CN 202010652630 A CN202010652630 A CN 202010652630A CN 111793327 A CN111793327 A CN 111793327A
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epoxy resin
clad plate
resin composition
copper
flame retardant
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刘政
杨永亮
郑宝林
李凌云
栾好帅
王丽亚
姜晓亮
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Abstract

本发明属于覆铜板生产技术领域，尤其涉及一种高速高频覆铜板用环氧树脂组合物及其制备方法。本发明中，苯并恶嗪型改性环氧树脂中的氮元素本身具有很好的阻燃效应，辅以无卤阻燃填料，可以达到非常好的阻燃效果，阻燃性可达UL94 V‑0级，而且产物中没有卤元素，符合RoHS指令的要求，对环境污染程度相对较低；活性酯作为固化剂固化环氧树脂，可以改善产品的耐热性、尺寸稳定性、低吸水率和低Dk/Df等。本发明制得的覆铜板具有良好的介电性能、玻璃化转变温度(Tg)、低膨胀系数、热分层时间(T288)>60min，可以达到UL94V‑0级，基本可以满足5G通信所用电子产品的使用要求。

Description

一种高速高频覆铜板用环氧树脂组合物及其制备方法
技术领域
本发明属于覆铜板生产技术领域，尤其涉及一种高速高频覆铜板用环氧树脂组合物及其制备方法。
背景技术
本世纪以来，以人工智能AI等为代表的世界电子信息产业的发展日新月异，高科技电子产品已成为当今世界上最有潜力的产业之一。然而随着电子产品向无人化、智能化、高性能化发展，对于各种电子产品所用印刷电路板覆铜板的要求也就随之提高，包括：高阻燃性、高耐热性、高玻璃化温度(Tg)、低膨胀系数、优异的介电性能等。
目前所用的覆铜板，都是以玻璃纤维布增强的环氧树脂基体覆铜板(简称FR-4)。传统的环氧覆铜板是在环氧树脂体系中引入卤素，比如四溴双酚A环氧树脂，然而含溴、氯等卤素的电子废弃物在分解及燃烧过程中会产生大量的有害物质，会危害人的身体健康，也会造成不可逆转的环境污染问题。另外现有的无卤环氧体系制作的高速高频覆铜板，其玻璃化温度基本在190-210℃之间，热分层时间在30-45min左右，根本满足不了当今5G通讯的技术要求。
21世纪是信息技术飞速发展的时代,各种高智能化的电子产品已经成为日常生活中不可或缺的一部分，所以今后电子信息通讯的主要核心还是往高频、高速方向发展；在高速高频技术持续发展的今天,5G通信即将成为未来电子通信的大方向，覆铜板作为其电子产品的重要组成部分之一，其介电常数(Dk)和介损耗因子(Df)自然而然成为了应用在高频领域所关注的重中之重的两项性能指标之一。
发明内容
本发明针对上述现有技术存在的不足，提供一种高速高频覆铜板用环氧树脂组合物及其制备方法。
本发明解决上述技术问题的技术方案如下：一种高速高频覆铜板用环氧树脂组合物，其组分按照重量份数计包括：苯并恶嗪改性环氧树脂10-60份、双酚A型环氧树脂8-20份、活性酯固化剂10-40份、咪唑类催化剂0.1-0.9份、无机填料10-40份和无卤阻燃填料10-50份，余量为溶剂；
其中，所述苯并恶嗪改性环氧树脂的结构式如下：
Figure BDA0002575550960000021
式中，R为含1-3个碳原子的的烷基；R1为含1-15个碳原子的烷基或含1-10个碳原子的苯基；n为1-5的整数。
进一步，所述苯并恶嗪改性环氧树脂的环氧当量为240-300g/eq。
进一步，所述双酚A型环氧树脂是双酚A和环氧氯丙烷在氢氧化钠存在下反应生成的，其结构式为：
Figure BDA0002575550960000031
式中，n＝0-25。
采用上述进一步方案的有益效果是，n值小于2的为低相对分子质量环氧树脂，软化点低于50℃，也称为软环氧树脂；n值在2-5之间的为中等相对分子质量环氧树脂，软化点在50-95℃之间；而n值大于5的称为高相对分子质量环氧树脂，软化点在100℃以上。
进一步，所述活性酯固化剂为由DIC Co.,Ltd.提供的HPC-8000-65T。
采用上述进一步方案的有益效果是，极性基团的存在是导致材料Dk和Df居高不下的重要因素。一般来说，极性基团越多，Dk和Df就越高，反之，极性基团越低，则Dk和Df越小。本发明使用的活性酯满足低吸水率和低Dk/Df的指标要求，其可以作为环氧树脂的固化剂，可以极大降低极性基团在树脂中的比重，从而降低树脂的Dk和Df，从而达到改善介电性能的目的。
进一步，所述咪唑类催化剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或4-二甲氨基吡啶中的一种或两种以上。
所述无机填料为滑石粉、硅微粉或云母粉中的一种或两种以上。
所述无卤阻燃填料为氢氧化铝、氢氧化镁、氮系阻燃剂、磷系阻燃剂或三氧化二锑中的一种或两种以上。
所述溶剂为丙酮、丁酮、二甲苯、丙二醇单甲醚或环已酮中的一种或两种以上。
本发明的第二个目的在于提供一种高速高频覆铜板的制备方法，步骤如下：
(1)环氧树脂组合物的制备
将苯并恶嗪改性环氧树脂、双酚A型环氧树脂、活性酯固化剂、咪唑类催化剂溶解在溶剂中，然后加入无机填料和无卤阻燃填料,搅拌乳化分散1-3h,凝胶260-390s(171℃)；控制固体含量为55-70％；
(2)将玻璃纤维布浸渍步骤(1)的环氧树脂组合物后，经过150-170℃烘箱烘烤4-7min,得粘结片；将若干张粘结片叠合在一起，在其一面或者两面上覆盖铜箔，放置在不锈钢板之间,然后置于真空压机中，在10-40kg/cm2、170-220℃条件下热压90-180min制成。
进一步，步骤(2)中，所述玻璃纤维布的规格为7628或2116。
进一步，所述粘结片的树脂流动度为15-35％，树脂含量为40-70％,凝胶时间为150-190s(171℃)。
进一步，所述铜箔的厚度为12-35μm。
本发明的有益效果是：
本发明中，苯并恶嗪型改性环氧树脂中的氮元素本身具有很好的阻燃效应，辅以无卤阻燃填料，可以达到非常好的阻燃效果，阻燃性可达UL94 V-0级，而且产物中没有卤元素，符合RoHS指令的要求，对环境污染程度相对较低；活性酯作为固化剂固化环氧树脂，可以改善产品的耐热性、尺寸稳定性、低吸水率和低Dk/Df等。本发明制得的覆铜板具有良好的介电性能、玻璃化转变温度(Tg)、低膨胀系数、热分层时间(T288)>60min，可以达到UL94V-0级，基本可以满足5G通信所用电子产品的使用要求。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
一种高速高频覆铜板的制备方法，步骤如下：
(1)环氧树脂组合物的制备
将35份苯并恶嗪改性环氧树脂(R为甲基；R1为甲基；n＝4)、20份双酚A型环氧树脂(环氧当量180-260g/eq)、40份活性酯固化剂、0.21份4-二甲氨基吡啶溶解在混合溶剂(丙酮、二甲苯、环已酮)中，然后加入15份硅微粉、10份氢氧化铝、10份氮系阻燃剂,搅拌乳化分散2h；控制固体含量为65％；
(2)将玻璃纤维布7628和2116浸渍步骤(1)的环氧树脂组合物后，经过170℃烘箱烘烤7min,得粘结片，粘结片的树脂流动度为25±4％，树脂含量为55±5％；将8张粘结片叠合在一起，在其两面上各覆盖18μm铜箔，放置在不锈钢板之间,然后置于真空压机中，在35kg/cm2、175±3℃条件下热压180min，制成双面覆铜板。
实施例2
一种高速高频覆铜板的制备方法，步骤如下：
(1)环氧树脂组合物的制备
将45份苯并恶嗪改性环氧树脂(R为含乙基；R1为丙基；n＝2)、8份双酚A型环氧树脂(环氧当量180-260g/eq)、39份活性酯固化剂、0.24份2-甲基咪唑、0.13份4-二甲氨基吡啶溶解在混合溶剂(丙酮、丙二醇单甲醚)中，然后加入15份硅微粉、12份氢氧化铝、10份磷系阻燃剂,搅拌乳化分散2h；控制固体含量为65％；
(2)将玻璃纤维布7628和2116浸渍步骤(1)的环氧树脂组合物后，经过170℃烘箱烘烤6min,得粘结片，粘结片的树脂流动度为24±3％，树脂含量为52±4％；将8张粘结片叠合在一起，在其两面上各覆盖18μm铜箔，放置在不锈钢板之间,然后置于真空压机中，在40kg/cm2、190±6℃条件下热压120min，制成双面覆铜板。
实施例3
一种高速高频覆铜板的制备方法，步骤如下：
(1)环氧树脂组合物的制备
将40份苯并恶嗪改性环氧树脂(R为甲基；R1为苯环；n＝3)、18份双酚A型环氧树脂(环氧当量180-260g/eq)、35份活性酯固化剂、0.3份2-乙基-4-甲基咪唑、0.11份4-二甲氨基吡啶溶解在混合溶剂(丙酮、丁酮、二甲苯)中，然后加入10份滑石粉、20份氢氧化镁、10份磷系阻燃剂,搅拌乳化分散2h；控制固体含量为65％；
(2)将玻璃纤维布7628和2116浸渍步骤(1)的环氧树脂组合物后，经过170℃烘箱烘烤6min,得粘结片，粘结片的树脂流动度为25±3％，树脂含量为53±3％；将8张粘结片叠合在一起，在其两面上各覆盖18μm铜箔，放置在不锈钢板之间,然后置于真空压机中，在40kg/cm2、185±3℃条件下热压90min，制成双面覆铜板。
对比例1
一种普通覆铜板的制备方法，步骤如下：
(1)环氧树脂组合物的制备
将35份联苯型环氧树脂(型号NC3000)、18份苯酚-芳烷基环氧树脂、47份含磷酚醛树脂、0.3份2-乙基咪唑、20份三氧化二锑、10份重晶石溶解在混合溶剂(丙酮、丁酮)中，搅拌乳化分散2h,固体含量为65％；
(3)将玻璃纤维布7628和2116浸渍步骤(1)的环氧树脂组合物后，经过170℃烘箱烘烤6min,得粘结片，粘结片的树脂流动度为21±3％，树脂含量为55±3％；将8张粘结片叠合在一起，在其两面上各覆盖18μm铜箔，放置在不锈钢板之间,然后置于真空压机中，在40kg/cm2、220±3℃条件下热压180min，制成双面覆铜板。
对比例2
一种普通覆铜板的制备方法，步骤如下：
(1)环氧树脂组合物的制备
将51份联苯型环氧树脂(型号NC3000)、15份苯酚-芳烷基环氧树脂、40份邻甲酚型酚醛环氧树脂、0.21份咪唑、15份硅微粉、10份重晶石溶解在混合溶剂(丙酮、丙二醇单甲醚)中，搅拌乳化分散2h,固体含量为65％；
(2)将玻璃纤维布7628和2116浸渍步骤(1)的环氧树脂组合物后，经过170℃烘箱烘烤7min,得粘结片，粘结片的树脂流动度为25±4％，树脂含量为55±4％；将8张粘结片叠合在一起，在其两面上各覆盖18μm铜箔，放置在不锈钢板之间,然后置于真空压机中，在40kg/cm2、220±3℃条件下热压120min，制成双面覆铜板。
将实施例1-3和对比例1-2所得覆铜板进行指标测试，各指标测试方法如下：
a、玻璃化转变温度(Tg),测试方法采用热机械分析法(TMA)
b、热膨胀系数(CTE),测试方法采用热机械分析法(TMA)
c、热分解温度(Td),测试方法采用热重分析法(TGA)
d、燃烧性，依据美国UL94垂直燃烧法测定
e、热分层时间(T288),测试方法采用热机械分析法(TMA)
f、剥离强度,测试方法按照IPC-TM-6502.4.9测量
g、介电常数(Dk)和介质损耗(Df)，测试方法按照ASTM-D150和
IPC-TM-6502.5.5.9测量
h、加工性，测试方法按照IPC-TM-6502.4.7测量
i、耐浸焊性，测试方法IPC-TM-6502.6.8测量。
表1为实施例1-3和对比例1-2所得样品的各项性能对照表。
表1
Figure BDA0002575550960000081
由表1可以看出，相比于对比例1和对比例2，实施例1-3利用本发明的环氧树脂组合物制备的覆铜板，其具有高Tg、高耐热性、低吸水性、热分层时间(T288)>60min、良好的介电性能等优良的综合性能，且达到无卤阻燃要求，具有良好的加工性能。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

1.一种高速高频覆铜板用环氧树脂组合物，其特征在于，其组分按照重量份数计包括：苯并恶嗪改性环氧树脂10-60份、双酚A型环氧树脂8-20份、活性酯固化剂10-40份、咪唑类催化剂0.1-0.9份、无机填料10-40份和无卤阻燃填料10-50份，余量为溶剂；
其中，所述苯并恶嗪改性环氧树脂的结构式如下：
Figure FDA0002575550950000011
式中，R为含1-3个碳原子的烷基；R1为含1-15个碳原子的烷基或含1-10个碳原子的苯基；n为1-5的整数。
2.根据权利要求1所述的高速高频覆铜板用环氧树脂组合物，其特征在于，所述苯并恶嗪改性环氧树脂的环氧当量为240-300g/eq。
3.根据权利要求1所述的高速高频覆铜板用环氧树脂组合物，其特征在于，所述双酚A型环氧树脂是双酚A和环氧氯丙烷在氢氧化钠存在下反应生成的，其结构式为：
Figure FDA0002575550950000012
式中，n＝0-25。
4.根据权利要求1所述的高速高频覆铜板用环氧树脂组合物，其特征在于，所述活性酯固化剂为HPC-8000-65T；
所述咪唑类催化剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或4-二甲氨基吡啶中的一种或两种以上；
所述无机填料为滑石粉、硅微粉或云母粉中的一种或两种以上；
所述无卤阻燃填料为氢氧化铝、氢氧化镁、氮系阻燃剂、磷系阻燃剂或三氧化二锑中的一种或两种以上；
所述溶剂为丙酮、丁酮、二甲苯、丙二醇单甲醚或环已酮中的一种或两种以上。
5.一种利用权利要求1-4任一项所述高速高频覆铜板用环氧树脂组合物制备高速高频覆铜板的方法，其特征在于，步骤如下：
(1)环氧树脂组合物的制备
将苯并恶嗪改性环氧树脂、双酚A型环氧树脂、活性酯固化剂、咪唑类催化剂溶解在溶剂中，然后加入无机填料和无卤阻燃填料,搅拌乳化分散1-3h，凝胶260-390s；控制固体含量为55-70％；
(2)将玻璃纤维布浸渍步骤(1)的环氧树脂组合物后，经过150-170℃烘箱烘烤4-7min,得粘结片；将若干张粘结片叠合在一起，在其一面或者两面上覆盖铜箔，放置在不锈钢板之间,然后置于真空压机中，在10-40kg/cm2、170-220℃条件下热压90-180min制成。
6.根据权利要求5所述的方法，其特征在于，步骤(2)中，所述玻璃纤维布的规格为7628或2116；
所述粘结片的树脂流动度为15-35％，树脂含量为40-70％,凝胶时间为150-190s；
所述铜箔的厚度为12-35μm。
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Application publication date: 20201020

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