CN107953630B - 一种受热可弯曲成型的覆铜板及其制备方法 - Google Patents
一种受热可弯曲成型的覆铜板及其制备方法 Download PDFInfo
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Abstract
本发明的目的是提供一种受热可弯曲成型的覆铜板，不仅改善了覆铜板的韧性、保持良好的热性能和尺寸性能，而且还降低了后期电路板成型的成本，在电路板的生产中，取得了良好的经济效益。该铜板由铜箔和半固化片叠合热压成型，所述半固化片是由若干层电子级玻璃纤维布浸渍混合液后经烘箱烘烤制得，所述混合液按重量份计算包括环氧树脂50～80份，酚醛树脂20～50份，韧性树脂5～20份，溶剂20～50份，固化剂1.0～5.0份，促进剂0.005～1.0份。
Description
技术领域
本发明涉及电路基板领域，具体是一种受热可弯曲成型的覆铜板及其制备方法。
背景技术
电子信息产品的多功能化发展，对印制电路板提出了高密度化和多维组装的要求，进一步也对覆铜板提出了更优的加工性能的要求。为了满足印制电路板的多维组装要求，目前市场上多采用刚挠结合板的技术来实现，但刚挠结合板的制作需要将刚性覆铜板和挠性覆铜板进行拼接，会出现层压时分界处线路压断、厚度匹配控制困难等问题，工艺复杂，合格率低，制造成本高。
现有技术中，也有对刚性覆铜板或热固性复合材料增柔增韧的配方设计，但这些方案会出现增韧后出现热性能下降现象，或成型后受热形变现象，并不能满足多维组装的需求。例如发明专利CN106183233A中所述一种软性耐弯折铝基覆铜板，Tg和热膨胀系数将下降，无法满足消费类电子产品电路板多维组装的需求；CN105255115A中所述受热可再次成型的热固性树脂体系复合材料，成型后再次受热将有一定程度回弹，无法在高温环境下长期使用。此外，也有一些专利使用了苯氧树脂作为原材料进行粘接力方面的改进，但并不能做到增柔增韧，例如CN101977984中所述多层印刷布线板配方，使用了含有特定结构的苯氧树脂，该结构表现刚性，缺少韧性，无法实现多维组装成型。
另外，刚性覆铜板中加入增韧材料，往往会导致覆铜板Tg等热性能下降、Z轴CTE性能下降等不良后果。
发明内容
本发明的目的是提供一种受热可弯曲成型的覆铜板，不仅改善了覆铜板的韧性、保持良好的热性能和尺寸性能，而且还降低了后期电路板成型的成本，在电路板的生产中，取得了良好的经济效益。该覆铜板由铜箔和半固化片叠合热压成型，所述半固化片是由若干层电子级玻璃纤维布浸渍混合液后经烘箱烘烤制得，所述混合液按重量份计算包括环氧树脂50～80份，酚醛树脂20～50份，韧性树脂5～20份，溶剂20～50份，固化剂1.0～5.0份，促进剂0.005～1.0份；
其中，所述环氧树脂选自双酚A环氧树脂、溴化环氧树脂、含磷环氧树脂、双官能团环氧树脂、多官能团环氧树脂中的一种或两种以上；
所述酚醛树脂选自线性酚醛树脂、线性双酚A甲醛树脂、含磷酚醛树脂中的一种或两种以上；
所述韧性树脂选自一种或两种以上双酚A型苯氧树脂，其中，双酚A型苯氧树脂的分子量为1～2万，且在苯氧树脂主链中大量存在醚基、异丙撑基、异丙醇基。
作为优选，所述固化剂选自电子级双氰胺、4，4-二氨基二苯砜。
作为优选，所述促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑中的一种或者两者的混合物。
作为优选，所述填料选自二氧化硅、氢氧化铝、滑石粉、碳酸钙中的一种或者两种以上。
作为优选，所述溶剂选自丙酮、丁酮、环己酮、丙二醇甲醚、丙二醇甲醚醋酸酯、甲苯中的一种或多种。
作为优选，所述环氧树脂为含磷环氧树脂，异氰酸酯改性环氧树脂以及多官能团环氧树脂的混合物。
作为优选，所述双酚A型苯氧树脂的分子量为2万。
作为优选，所述电子级玻璃纤维布选自1027、1037、1080或2116标准布或仿布。
本发明的另一个目的是提供所述的受热可弯曲成型的覆铜板的制备方法，该制备方法包括以下步骤：步骤1)将环氧树脂、酚醛树脂、韧性树脂、固化剂、促进剂、填料和溶剂按权利要求1所述重量份均匀混合得到混合液；
步骤2)将电子级玻璃纤维布浸渍步骤1)所得混合液，经烘箱150℃～180℃烘烤，冷却后得到流动度15％-20％的半固化片；
步骤3)将步骤2)所得半固化片与铜箔交替叠合，双面覆铜箔，在温度100℃～200℃，压力0.5～5Mpa的条件下真空热压成型，得到受热可弯曲成型的覆铜板。将覆铜板进行1-4次弯曲成型，成型后每个内角范围在90～180度。
作为优选，所述覆铜板优选为2～10层受热可弯曲成型的覆铜板；在本发明一个具体的实施方式中，得到的覆铜板的厚度为0.75mm左右。
本发明的另一个目的是提供一种用于覆铜板的预浸料组合物，该组合物按重量份计算包括环氧树脂50～80份，酚醛树脂20～50份，韧性树脂5～20份，固化剂1.0～5.0份，促进剂0.005～1.0份；其中，所述环氧树脂选自双酚A环氧树脂、溴化环氧树脂、含磷环氧树脂、双官能团环氧树脂、多官能团环氧树脂中的一种或两种以上；所述酚醛树脂选自线性酚醛树脂、线性双酚A甲醛树脂、含磷酚醛树脂中的一种或两种以上；所述韧性树脂选自一种或两种以上双酚A型苯氧树脂，其中，双酚A型苯氧树脂的分子量为1～2万，且在苯氧树脂主链中大量存在醚基、异丙撑基、异丙醇基。
与现有技术相比，本发明具有以下有益效果：
本发明专利开发的受热可弯曲成型的覆铜板，具有优异的耐热性和阻燃性，稳定的机械性能和电学性能，既具有刚性覆铜板工艺简单、制造成本低的优点，解决了刚性覆铜板弯曲成型后折断、分层的问题，又具有挠性覆铜板可静态弯曲的优点，可以满足印制电路板多维组装的要求。将在实现多维组装成型效果的同时，仍保证Tg、Td-5％及其他热性能、Z轴CTE性能依然满足2～10层无卤或无铅印制线路板的组装需求。
本发明提供的受热可弯曲成型的覆铜板的制备方法简单易操作，弯曲成型的方法简单，适合连续化生产，生产效率高。
附图说明
图1为本发明提供的弯曲成型的覆铜板的结构示意图；
图2为弯曲成型温度曲线。
具体实施方式
下面对本发明作进一步详细的说明。
实施例1-5：一种受热可弯曲成型的覆铜板
本发明涉及的一种受热可弯曲成型的覆铜板可以通过以下步骤实现：
步骤一，将所需物料按照表1所示比例均匀混合成混合胶液；
步骤二，将电子级玻璃纤维布1080浸渍上述混合液，经烘箱150℃～180℃烘烤，冷却后得到流动度15％-20％的半固化片；
步骤三，将上述半固化片与Hoz铜箔交替叠合，在温度100℃～200℃，压力0.5～5Mpa的条件下真空热压成型，得到厚度为0.75mm的受热可弯曲成型的覆铜板；然后进行1-4次弯曲成型，如图1所示，成型后每个内角范围在90～180度。
对比例1：一种不含韧性树脂的常规无卤覆铜板
本对比例涉及的一种不含韧性树脂的常规无卤覆铜板对比例通过以下步骤实现：
步骤一，将所需物料按照表1所示比例均匀混合成混合胶液；
步骤二，将电子级玻璃纤维布1080浸渍上述混合液，经烘箱150℃～180℃烘烤，冷却后得到流动度15％-20％的半固化片；
步骤三，将上述半固化片与Hoz铜箔交替叠合，在温度100℃～200℃，压力0.5～5Mpa的条件下真空热压成型，得到厚度为0.75mm的普通无卤覆铜板。
对比例2：一种受热可弯曲成型的覆铜板
本对比例涉及的一种受热可弯曲成型的覆铜板通过以下步骤实现：
步骤一，所需物料按照表1所示比例均匀混合成混合胶液；
步骤二，将电子级玻璃纤维布1080浸渍上述混合液，经烘箱150℃～180℃烘烤，冷却后得到流动度15％-20％的半固化片；
步骤三，将上述半固化片与Hoz铜箔交替叠合，在温度100℃～200℃，压力0.5～5Mpa的条件下真空热压成型，得到厚度为0.75mm的受热可弯曲成型的覆铜板。
对比例3：一种含韧性树脂的受热不可弯曲成型的覆铜板
本对比例涉及的一种含韧性树脂的受热不可弯曲成型的覆铜板通过以下步骤实现：
步骤一，所需物料按照表1所示比例均匀混合成混合胶液；
步骤二，将电子级玻璃纤维布1080浸渍上述混合液，经烘箱150℃～180℃烘烤，冷却后得到流动度15％-20％的半固化片；
步骤三，将上述半固化片与Hoz铜箔交替叠合，在温度100℃～200℃，压力0.5～5Mpa的条件下真空热压成型，得到厚度为0.75mm的受热可弯曲成型的覆铜板。
表1
| 物料 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 对比例1 | 对比例2 | 对比例3 |
| 环氧树脂A | 17 | 17 | 17 | 17 | 17 | 17 | 17 | |
| 环氧树脂B | 35 | 35 | 35 | 35 | 35 | 35 | 35 | |
| 环氧树脂C | 17 | 17 | 17 | 17 | 17 | 17 | 17 | 19 |
| 环氧树脂D | 30 | |||||||
| 环氧树脂E | 20 | |||||||
| 酚醛树脂A | 21 | 21 | 21 | 21 | 21 | 21 | 21 | 21 |
| 酚醛树脂B | 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| 酚醛树脂C | 10 | |||||||
| 苯氧树脂A | 5 | 10 | ||||||
| 苯氧树脂B | 5 | 10 | 15 | 25 | 5 | |||
| 固化剂 | 3 | 3 | 3.5 | 3.5 | 3.5 | 3 | 3.5 | 3.3 |
| 促进剂 | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 | 0.70 |
| 无机填料 | 45 | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| 溶剂 | 28 | 28 | 28 | 28 | 28 | 28 | 28 | 28 |
其中，环氧树脂A和D为含磷环氧树脂，环氧树脂B和E为异氰酸酯改性环氧树脂，环氧树脂C为多官能团环氧树脂；酚醛树脂A和C为含磷酚醛树脂，酚醛树脂B为多官能团酚醛树脂。苯氧树脂A为分子量1万的苯氧树脂，苯氧树脂B为分子量2万的苯氧树脂,且苯氧树脂A和苯氧树脂B中存在大量的醚基、异丙撑基、异丙醇基。
试验例
将实施例1，2，3，4，5制备得到的受热可弯曲成型的覆铜板和不加韧性树脂的普通覆铜板性能进行对比，其结果如表2所示，其中，弯曲成型通过模压工艺实现。
供参考的弯曲成型条件如下：第一步，图2为弯曲成型温度曲线，加热待成型材料，待料温达到180摄氏度后保持120s；第二步，使用模压设备弯曲成型，模压过程保持20s，且温度大于180摄氏度；
表2
如上表所示，与对比例1相比，实施例1，2，3，4，5的弯曲成型效果较不含韧性树脂的常规无卤覆铜板有明显改善，同时Tg、Td-5％性能无明显差异，Z轴CTE稍有波动，但仍能符合无卤覆铜板α1≤60ppm/℃，热膨胀系数≤4.0％的要求。其中实施例1，2有一定的弯曲成型改善效果，实施例3，4，5的弯曲成型效果显著。这5组实施例可以根据终端PCB设计要求，综合考虑成型角度、Z轴CTE等性能后，进行选用。
对比例2中，将苯氧树脂组分提高到25份后，出现了Tg、Td-5％热性能显著下降，热膨胀系数显著增大的现象，虽然可以实现受热后弯曲成型，但无法满足无卤印制线路板在装配、使用过程中对热性能和尺寸性能的需求。对比例3中，更换2种环氧树脂和1种酚醛树脂后，热性能提升，但韧性下降，尽管添加了与实施例3等量的韧性树脂，也无法达到弯曲成型的效果。
高分子量的苯氧树脂，因其结构中含有大量的醚基、异丙撑基、异丙醇基，使聚合物具有良好的韧性。同时，由于其支链上具有众多可反应基团，其与环氧树脂的结合紧密，提高体系的韧性的同时不降低交联密度，几乎不影响热性能。随着苯氧树脂份数的增加并且超过20份时，其与环氧树脂体系逐渐无法完全结合，游离的苯氧树脂导致体系热性能和尺寸性能的下降。
但实施例3和对比例3的对比说明，本发明描述的一种受热可弯曲成型覆铜板，增韧机理并不仅仅是在普通FR-4配方中添加一定量的韧性树脂。因为体系的热性能、Z轴CTE性能和韧性还受到体系交联密度的影响，交联密度越大，热性能越好，但韧性越差；也受到体系中其他基团的影响。此外，本发明描述的一种受热可弯曲成型覆铜板，还需满足阻燃、吸水性、铜箔剥离强度等多种性能需求，因此在原材料的选择上，还需考虑体系的综合性能平衡和稳定。
此外，通过本发明的方法制备一种受热可弯曲成型覆铜板，还具有如下优点：
1.本发明制备的覆铜板具有良好的机械性能、电学性能、阻燃性能，可以满足无卤或无铅覆铜板加工制程和使用环境的要求；
2.本发明工艺方法简单易操作，适合连续化生产，生产效率高；
3.本发明制备的覆铜板受热弯曲成型的方法简单，效率高；
4.本发明使用的原材料均可通过商业途径获得。
Claims (3)
1.一种受热可弯曲成型的覆铜板，其特征在于：该覆铜板由铜箔和半固化片叠合热压成型，所述半固化片是由若干层电子级玻璃纤维布浸渍混合液后经烘箱烘烤制得，所述混合液按重量份计包括环氧树脂50～80份，酚醛树脂20～50份，韧性树脂5～20份，溶剂20～50份，固化剂1.0～5.0份，促进剂0.005～1.0份，无机填料45份；
其中，所述环氧树脂选自双酚A环氧树脂、溴化环氧树脂、含磷环氧树脂、双官能团环氧树脂、多官能团环氧树脂中的一种或两种以上；
所述酚醛树脂选自线性酚醛树脂、线性双酚A甲醛树脂、含磷酚醛树脂中的一种或两种以上；
所述韧性树脂选自一种或两种以上双酚A型苯氧树脂，其中，所述双酚A型苯氧树脂的分子量为2万，且在苯氧树脂主链中存在醚基、异丙撑基、异丙醇基；
所述环氧树脂为含磷环氧树脂、异氰酸酯改性环氧树脂以及多官能团环氧树脂的混合物；
所述酚醛树脂为含磷酚醛树脂和多官能团酚醛树脂的混合物；
其中，所述固化剂选自电子级双氰胺、4，4-二氨基二苯砜；所述促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑中的一种或者两者的混合物；所述无机填料选自二氧化硅、氢氧化铝、滑石粉、碳酸钙中的一种或者两种以上；所述溶剂选自丙酮、丁酮、环己酮、丙二醇甲醚、丙二醇甲醚醋酸酯、甲苯中的一种或多种；所述电子级玻璃纤维布选自1027、1037、1080或2116标准布或仿布。
2.一种根据权利要求1所述的受热可弯曲成型的覆铜板的制备方法，其特征在于：该制备方法包括以下步骤：
步骤1)将环氧树脂、酚醛树脂、韧性树脂、固化剂、促进剂、填料和溶剂按权利要求1所述重量份均匀混合得到混合液；
步骤2)将电子级玻璃纤维布浸渍步骤1)所得混合液，经烘箱150℃～180℃烘烤，冷却后得到流动度15％-20％的半固化片；
步骤3)将步骤2)所得半固化片与铜箔交替叠合，双面覆铜箔，在温度100℃～200℃，压力0.5～5Mpa的条件下真空热压成型，得到受热可弯曲成型的覆铜板。
3.一种用于覆铜板的预浸料组合物，其特征在于：该组合物按重量份计算包括环氧树脂50～80份，酚醛树脂20～50份，韧性树脂5～20份，固化剂1.0～5.0份，促进剂0.005～1.0份，填料45份；
其中，所述环氧树脂选自双酚A环氧树脂、溴化环氧树脂、含磷环氧树脂、双官能团环氧树脂、多官能团环氧树脂中的一种或两种以上；
所述酚醛树脂选自线性酚醛树脂、线性双酚A甲醛树脂、含磷酚醛树脂中的一种或两种以上；
所述韧性树脂选自一种或两种以上双酚A型苯氧树脂，其中，双酚A型苯氧树脂的分子量为2万，且在苯氧树脂主链中大量存在醚基、异丙撑基、异丙醇基；
所述环氧树脂为含磷环氧树脂、异氰酸酯改性环氧树脂以及多官能团环氧树脂的混合物；
所述酚醛树脂为含磷酚醛树脂和多官能团酚醛树脂的混合物；
其中，所述固化剂选自电子级双氰胺、4，4-二氨基二苯砜；所述促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑中的一种或者两者的混合物；所述填料选自二氧化硅、氢氧化铝、滑石粉、碳酸钙中的一种或者两种以上；所述溶剂选自丙酮、丁酮、环己酮、丙二醇甲醚、丙二醇甲醚醋酸酯、甲苯中的一种或多种。
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Denomination of invention: A thermally bendable copper clad plate and its preparation method Effective date of registration: 20231128 Granted publication date: 20220405 Pledgee: Agricultural Bank of China Limited Hangzhou Yuhang Branch Pledgor: ZHEJIANG HUAZHENG NEW MATERIAL GROUP Co.,Ltd. Registration number: Y2023980067733 |