CN114561073B - 一种无纤维增强的含氟树脂基高频覆铜板及其制备方法 - Google Patents

一种无纤维增强的含氟树脂基高频覆铜板及其制备方法 Download PDF

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CN114561073B
CN114561073B CN202210170383.1A CN202210170383A CN114561073B CN 114561073 B CN114561073 B CN 114561073B CN 202210170383 A CN202210170383 A CN 202210170383A CN 114561073 B CN114561073 B CN 114561073B
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向中荣
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Abstract

本发明提供了一种无纤维增强的含氟树脂基高频覆铜板，包括位于中间的含氟树脂基板和位于所述含氟树脂基板两侧的铜箔；所述含氟树脂基板通过以下步骤制备：S1、向1～80wt/v％无机填料溶液中加入偶联剂，于20～100℃下搅拌反应0.5～72h，过滤、烘干得到改性无机填料；S2、将步骤S1得到的改性无机填料加入羟基化含氟树脂中，加热到220～350℃，搅拌5～18h，制备得到含氟树脂混合物；S3、将步骤S2制备得到的含氟树脂混合物加入注塑机中，设置料筒温度为250～380℃，模具温度为180～260℃，注塑压力为50～80Mpa，常温冷却即得到含氟树脂基板；本发明的无纤维增强的含氟树脂基高频覆铜板，具有低吸湿性、低介电常数、低介电损耗，且铜箔剥离强度高、粘合性较好，不易发生脱落的优点。

Description

一种无纤维增强的含氟树脂基高频覆铜板及其制备方法
技术领域
本发明属于通信材料领域，具体涉及一种无纤维增强的含氟树脂基高频覆铜板及其制备方法。
背景技术
当下，信息电子产业处于高速发展阶段，正逐步成为各国的支柱产业之一。覆铜板是信息电子产业的关键材料之一，已广泛应用在通信基站、卫星、自动售货机、电脑、手机乃至逐步兴起的可穿戴设备、无人驾驶汽车、无人机和智能机器人等多个领域。
含氟树脂因其自身特有的化学结构而拥有极低的介电常数和介电损耗、高热稳定性和化学稳定性，是一种制作高频覆铜板的理想材料。但是一般情况下，含氟树脂的高分子链柔性极大，常需要引入玻纤布等增强材料以提高含氟树脂基板的机械强度。然而，玻纤布等增强材料的使用将不可避免地提高含氟树脂基板的介电常数，由此降低了含氟树脂基板介电性能的可调节性。后来，人们开始着手研发无纤维增强的含氟树脂基覆铜板。例如，美国专利US4849284和US5024871在无机填料的表面分别修饰上了硅烷偶联剂和钛酸酯/锆酸酯偶联剂，以提高无机填料与含氟树脂基体之间的相互作用力，但是含氟树脂因其化学稳定性，不能与偶联剂发生化学反应，难以在树脂基体与无机填料之间生成化学键。
专利CN201710579838.4提供了一种无纤维增强的含氟树脂基覆铜板及其制备方法，通过偶联剂和部分含氟聚合物共同修饰无机填料，提高无机填料与含氟树脂基体之间的相互作用力。尽管本专利得到的含氟基板机械强度相对偶联剂单一修饰无机填料得到的含氟基板有所提高，但是机械强度提高有限。
发明内容
针对现有技术中的问题，本发明提供了一种无纤维增强的含氟树脂基高频覆铜板的制备方法，通过该方法制备得到的含氟树脂基高频覆铜板，具有低吸湿性、低介电常数、低介电损耗，且铜箔剥离强度高、粘合性较好，不易发生脱落的优点。
为实现以上技术目的，本发明的技术方案是：
一种无纤维增强的含氟树脂基高频覆铜板，包括位于中间的含氟树脂基板和位于所述含氟树脂基板两侧的铜箔；
所述含氟树脂基板通过以下步骤制备：
S1、向1～80wt/v％无机填料溶液中加入偶联剂，于20～100℃下搅拌反应0.5～72h，过滤、烘干得到改性无机填料；
S2、将步骤S1得到的改性无机填料加入羟基化含氟树脂中，加热到220～350℃，搅拌5～18h，制备得到含氟树脂混合物；
S3、将步骤S2制备得到的含氟树脂混合物加入注塑机中，设置料筒温度为250～380℃，模具温度为180～260℃，注塑压力为50～80Mpa，常温冷却即得到含氟树脂基板。
本发明步骤S1中所述无机填料为碳化硅、二氧化硅、氧化铝、石墨烯、硅微粉、氮化硼、氮化铝中的一种或是几种的混合物；所述无机填料是空心球或者实体。
本发明步骤S1所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、硼酸酯偶联剂、锆酸酯偶联剂、稀土偶联剂、磷酸酯偶联剂和磺酰叠氮偶联剂及其衍生物中的一种或多种的混合物。
本发明步骤S1中所述无机填料与所述偶联剂的质量比为50～500：1。
本发明步骤S2中所述改性无机填料与所述羟基化含氟树脂的质量比为1：10～50。
本发明步骤S2中所述羟基化含氟树脂的制备方法，包括如下步骤：
A、将含氟树脂进行挤出流延成膜，得到厚度为1～10um的含氟树脂薄膜；
B、将步骤A的含氟树脂薄膜放入等离子体反应器中，抽真空通氧气，进行等离子活化处理；
C、将步骤B等离子活化后的含氟树脂薄膜加入四氢呋喃溶剂中，搅拌直至溶解，随后加入还原剂，加热到80～150℃，氧化还原处理0.5～3h，得到羟基化含氟树脂。
本发明步骤A中所述含氟树脂为聚四氟乙烯、四氟乙烯-全氟烷基乙烯基醚共聚物和四氟乙烯-六氟丙烯共聚物中的一种或多种。
本发明步骤B中所述等离子活化的条件为：等离子体放电压力为25～30Pa，照射时间为1000～1200s，照射功率为150～300W。
本发明步骤C中所述还原剂为水合肼、碳酸氢钠、甲醛、氢化铝锂、糖类化合物、抗坏血酸、谷胱甘肽或氨基酸中的一种或多种。
本发明还提供了一种无纤维增强的含氟树脂基高频覆铜板的制备方法，包括以下步骤：将所述含氟树脂基板上下两侧与铜箔配成叠层，在叠层的上下两侧再层叠上钢板，然后放入热压机中，设置层压温度为150～430℃，层压压力为50～200kg/cm2，层压6～28h，得到无纤维增强的含氟树脂基高频覆铜板。
从以上描述可以看出，本发明具备以下优点：
1、通过本发明制备方法得到的含氟树脂基高频覆铜板，具有低吸湿性、低介电常数、低介电损耗，且铜箔剥离强度高、粘合性较好，不易发生脱落的优点。
2、本发明的无机填料经偶联剂表面处理，促进了无机填料在含氟树脂基体内的分散性，同时含氟树脂先后经等离子活性处理和氧化还原处理，将羟基引入含氟树脂上，羟基化含氟树脂能与改性后的无机填料形成良好的浸润性界面，提高了含氟树脂、无机填料和铜箔三者之间的粘结性和相容性，增强了三者之间的相互作用力，从而使制备得到的高频覆铜板具有吸湿性低、高剥离强度的优点，保证高频覆铜板在使用过程中不会出现铜箔分层、脱落的问题。
附图说明
图1为本发明的无纤维增强的含氟树脂基高频覆铜板剖面图。
附图标记：1、铜箔，2、含氟树脂基板。
具体实施方式
下面通过实施例，进一步阐述本发明的特点，但不对本发明的权利要求做任何限定。
实施例1
本实施例提供了一种无纤维增强的含氟树脂基高频覆铜板，包括位于中间的含氟树脂基板2和位于所述含氟树脂基板两侧的铜箔1，如图1所示；
所述含氟树脂基板2通过以下步骤制备：
S1、向1wt/v％空心球碳化硅溶液中加入硅烷偶联剂(无机填料与偶联剂的质量比为50：1)，于20℃下搅拌反应72h，过滤、烘干得到改性无机填料；
S2、将步骤S1得到的改性无机填料加入羟基化含氟树脂中(所述改性无机填料与所述羟基化含氟树脂的质量比为1：10)，加热到220℃，搅拌18h，制备得到含氟树脂混合物；
S3、将步骤S2制备得到的含氟树脂混合物加入注塑机中，设置料筒温度为250℃，模具温度为180℃，注塑压力为50Mpa，常温冷却即得到含氟树脂基板。
其中，步骤S2中所述羟基化含氟树脂的制备方法，包括如下步骤：
A、将聚四氟乙烯进行挤出流延成膜，得到厚度为1um的含氟树脂薄膜；
B、将步骤A的含氟树脂薄膜放入等离子体反应器中，抽真空通氧气，进行等离子活化处理，其中，等离子体放电压力为25Pa，照射时间为1000s，照射功率为150W；
C、将步骤B等离子活化后的含氟树脂薄膜加入四氢呋喃溶剂中，搅拌直至溶解，随后加入水合肼，加热到80℃，氧化还原处理3h，得到羟基化含氟树脂。
本实施例还提供了所述无纤维增强的含氟树脂基高频覆铜板的制备方法，包括以下步骤：将所述含氟树脂基板2上下两侧与铜箔1配成叠层，在叠层的上下两侧再层叠上钢板，然后放入热压机中，设置层压温度为150℃，层压压力为50kg/cm2，层压28h，得到无纤维增强的含氟树脂基高频覆铜板。
实施例2
本实施例提供了一种无纤维增强的含氟树脂基高频覆铜板，包括位于中间的含氟树脂基板2和位于所述含氟树脂基板两侧的铜箔1，如图1所示；
所述含氟树脂基板2通过以下步骤制备：
S1、向80wt/v％空心球石墨烯溶液中加入磷酸酯偶联剂(无机填料与偶联剂的质量比为500：1)，于100℃下搅拌反应0.5h，过滤、烘干得到改性无机填料；
S2、将步骤S1得到的改性无机填料加入羟基化含氟树脂中(所述改性无机填料与所述羟基化含氟树脂的质量比为1：50)，加热到350℃，搅拌5h，制备得到含氟树脂混合物；
S3、将步骤S2制备得到的含氟树脂混合物加入注塑机中，设置料筒温度为380℃，模具温度为260℃，注塑压力为50Mpa，常温冷却即得到含氟树脂基板。
其中，步骤S2中所述羟基化含氟树脂的制备方法，包括如下步骤：
A、将四氟乙烯-六氟丙烯共聚物进行挤出流延成膜，得到厚度为10um的含氟树脂薄膜；
B、将步骤A的含氟树脂薄膜放入等离子体反应器中，抽真空通氧气，进行等离子活化处理，其中，等离子体放电压力为30Pa，照射时间为1200s，照射功率为300W；
C、将步骤B等离子活化后的含氟树脂薄膜加入四氢呋喃溶剂中，搅拌直至溶解，随后加入甲醛，加热到150℃，氧化还原处理3h，得到羟基化含氟树脂。
本实施例还提供了所述无纤维增强的含氟树脂基高频覆铜板的制备方法，包括以下步骤：将所述含氟树脂基板2上下两侧与铜箔1配成叠层，在叠层的上下两侧再层叠上钢板，然后放入热压机中，设置层压温度为430℃，层压压力为200kg/cm2，层压6h，得到无纤维增强的含氟树脂基高频覆铜板。
实施例3
本实施例提供了一种无纤维增强的含氟树脂基高频覆铜板，包括位于中间的含氟树脂基板2和位于所述含氟树脂基板两侧的铜箔1，如图1所示；
所述含氟树脂基板2通过以下步骤制备：
S1、向30wt/v％实体氮化硼溶液中加入钛酸酯偶联剂(无机填料与偶联剂的质量比为200：1)，于60℃下搅拌反应24h，过滤、烘干得到改性无机填料；
S2、将步骤S1得到的改性无机填料加入羟基化含氟树脂中(所述改性无机填料与所述羟基化含氟树脂的质量比为1：30)，加热到280℃，搅拌12h，制备得到含氟树脂混合物；
S3、将步骤S2制备得到的含氟树脂混合物加入注塑机中，设置料筒温度为320℃，模具温度为210℃，注塑压力为60Mpa，常温冷却即得到含氟树脂基板。
其中，步骤S2中所述羟基化含氟树脂的制备方法，包括如下步骤：
A、将四氟乙烯-全氟烷基乙烯基醚共聚物进行挤出流延成膜，得到厚度为8um的含氟树脂薄膜；
B、将步骤A的含氟树脂薄膜放入等离子体反应器中，抽真空通氧气，进行等离子活化处理，其中，等离子体放电压力为28Pa，照射时间为1100s，照射功率为220W；
C、将步骤B等离子活化后的含氟树脂薄膜加入四氢呋喃溶剂中，搅拌直至溶解，随后加入抗坏血酸，加热到120℃，氧化还原处理2h，得到羟基化含氟树脂。
本实施例还提供了所述无纤维增强的含氟树脂基高频覆铜板的制备方法，包括以下步骤：将所述含氟树脂基板2上下两侧与铜箔1配成叠层，在叠层的上下两侧再层叠上钢板，然后放入热压机中，设置层压温度为240℃，层压压力为180kg/cm2，层压18h，得到无纤维增强的含氟树脂基高频覆铜板。
对比例1
本对比例为市售的高频覆铜板。
对比例2
本对比例按照专利CN201710579838.4的制备方法制备得到高频覆铜板。
性能测试
实施例1～3和对比例1～2制备的高频覆铜板进行吸水率、剥离强度测试，并检测其介电常数，其中剥离强度按照IPC-TM-6502.4.8方法中“热应力后”实验条件进行测试，吸水率按照ASTM D570规范测试，结果如下表所示。
Figure BDA0003517868150000091
综上可得：经过本发明制备方法制备得到的高频覆铜板具有超低吸水率，而且介电常数在2.13～2.25之间，具有较高的传输速率；而且实施例3的剥离强度是对比例2的1.52倍，说明本发明的含氟树脂经羟基化处理后，使得含氟树脂与无机填料以及铜箔的粘结性更强，所以铜箔剥离强度更高。
可以理解的是，以上关于本发明的具体描述，仅用于说明本发明而并非受限于本发明实施例所描述的技术方案。本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换，以达到相同的技术效果；只要满足使用需要，都在本发明的保护范围之内。

Claims (10)

1.一种无纤维增强的含氟树脂基高频覆铜板，其特征在于，包括位于中间的含氟树脂基板和位于所述含氟树脂基板两侧的铜箔；
所述含氟树脂基板通过以下步骤制备：
S1、向1～80wt/v％无机填料溶液中加入偶联剂，于20～100℃下搅拌反应0.5～72h，过滤、烘干得到改性无机填料；
S2、将步骤S1得到的改性无机填料加入羟基化含氟树脂中，加热到220～350℃，搅拌5～18h，制备得到含氟树脂混合物；
S3、将步骤S2制备得到的含氟树脂混合物加入注塑机中，设置料筒温度为250～380℃，模具温度为180～260℃，注塑压力为50～80MPa ，常温冷却即得到含氟树脂基板。
2.根据权利要求1所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤S1中所述无机填料为碳化硅、二氧化硅、氧化铝、石墨烯、硅微粉、氮化硼、氮化铝中的一种或是几种的混合物；所述无机填料是空心球或者实体。
3.根据权利要求1所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤S1所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、硼酸酯偶联剂、锆酸酯偶联剂、稀土偶联剂、磷酸酯偶联剂和磺酰叠氮偶联剂及其衍生物中的一种或多种的混合物。
4.根据权利要求1所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤S1中所述无机填料与所述偶联剂的质量比为50～500：1。
5.根据权利要求1所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤S2中所述改性无机填料与所述羟基化含氟树脂的质量比为1：10～50。
6.根据权利要求1所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤S2中所述羟基化含氟树脂的制备方法，包括如下步骤：
A、将含氟树脂进行挤出流延成膜，得到厚度为1～10um的含氟树脂薄膜；
B、将步骤A的含氟树脂薄膜放入等离子体反应器中，抽真空通氧气，进行等离子活化处理；
C、将步骤B等离子活化后的含氟树脂薄膜加入四氢呋喃溶剂中，搅拌直至溶解，随后加入还原剂，加热到80～150℃，氧化还原处理0.5～3h，得到羟基化含氟树脂。
7.根据权利要求6所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤A中所述含氟树脂为聚四氟乙烯、四氟乙烯-全氟烷基乙烯基醚共聚物和四氟乙烯-六氟丙烯共聚物中的一种或多种。
8.根据权利要求6所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤B中所述等离子活化的条件为：等离子体放电压力为25～30Pa，照射时间为1000～1200s，照射功率为150～300W。
9.根据权利要求6所述无纤维增强的含氟树脂基高频覆铜板，其特征在于，步骤C中所述还原剂为水合肼、碳酸氢钠、甲醛、氢化铝锂、糖类化合物、抗坏血酸、谷胱甘肽或氨基酸中的一种或多种。
10.根据权利要求1～9任一所述的一种无纤维增强的含氟树脂基高频覆铜板的制备方法，其特征在于，包括以下步骤：将所述含氟树脂基板上下两侧与铜箔配成叠层，在叠层的上下两侧再层叠上钢板，然后放入热压机中，设置层压温度为150～430℃，层压压力为50～200kg/cm2，层压6～28h，得到无纤维增强的含氟树脂基高频覆铜板。
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