CN114103372A - 一种高耐热无卤cem-1覆铜板的制备方法 - Google Patents

一种高耐热无卤cem-1覆铜板的制备方法 Download PDF

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CN114103372A
CN114103372A CN202111439464.9A CN202111439464A CN114103372A CN 114103372 A CN114103372 A CN 114103372A CN 202111439464 A CN202111439464 A CN 202111439464A CN 114103372 A CN114103372 A CN 114103372A
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resin
phosphorus
lining
glue solution
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杨永亮
郑宝林
陈长浩
栾好帅
王彦
谢峰
姜大鹏
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Abstract

本发明涉及一种高耐热无卤CEM‑1覆铜板的制备方法，包括如下步骤：1)表料半固化片胶液的制备；2)里料一浸树脂胶液制备；3)里料二浸树脂胶液制备；4)表料半固化片的制备；5)里料半固化片的制备；6)CEM‑1覆铜板的制备。本发明提供的表料胶液固化体系中少量添加酚醛树脂，可改善表料与里料的匹配性，从而提高界面的结合强度改善耐热性；里料一浸树脂胶液使用高耐热含磷树脂，可大幅降低木浆纸的可燃性，从而避免使用三聚氰胺甲醛树脂或其他热固性低分子树脂，改善了产品的柔韧性及稳定性。

Description

一种高耐热无卤CEM-1覆铜板的制备方法
技术领域
本发明属于覆铜板技术领域，具体涉及一种高耐热无卤CEM-1覆铜板的制备方法。
背景技术
覆铜板广泛用于制造各类家用电器、电子信息产品及工业电子产品所用的印制电路板，作为印制电路板的基板材料，起着承载装联电子元器件、形成导电线路图形及在层间和线路间绝缘的三大功能，是一种重要的电子基础材料。
覆铜板的阻燃性是电子产品重要的安全性能之一。卤素类阻燃材料(含Cl、Br)以其经济性与可靠性，在印制电路基材产业中已应用多年，然而，随着全球性环境保护呼声的日益高涨，卤素类阻燃材料的环境负荷及对人体健康的影响正密切受到关注，已有许多国家的组织和机构相继在含卤产品的燃烧产物中检测出二噁英、二苯并呋喃等致癌物质。含卤产品在燃烧过程中发烟量很大，会释放出剧毒物质卤化氢，严重威胁人体健康。因此研发和应用无卤型阻燃材料，生产环保型印制电路基材，已成为近年来覆铜板技术发展的新趋势。
目前无卤化覆铜板是利用氮磷协同阻燃，并添加无机填料，达到阻燃FV0级。但是在CEM-1板材中，里料增强材料为木浆纸，其本身易燃，要想达到FV0级需要大量的氮磷阻燃剂，这样势必会影响板材的其他性能，导致其耐热性、柔韧性普遍较差。
发明内容
本发明针对上述现有技术存在的不足，提供一种高耐热无卤CEM-1覆铜板的制备方法，改善表料与里料的匹配性，从而提高界面的结合强度改善耐热性；降低木浆纸的可燃性，从而避免使用三聚氰胺甲醛树脂或其他热固性低分子树脂，改善产品的柔韧性及稳定性。
一种高耐热无卤CEM-1覆铜板的制备方法，其特征在于，包括如下步骤：
1)表料半固化片胶液的制备：按重量份数计，将25-35份含磷环氧树脂、1-5份增韧环氧、1-5份低分子环氧、1-2份潜伏性固化剂、2-4份酚醛树脂、25-35份表料填料和20-30份溶剂混合，搅拌均匀；
2)里料一浸树脂胶液制备：按重量份数计，将5-15份高耐热含磷阻燃剂、85-95份溶剂混合，搅拌均匀；
3)里料二浸树脂胶液制备：按重量份数计，将20-35份低分子含磷环氧、5-15份E-51树脂、10-20份含氮酚醛、1-5份改性酚醛、10-20份阻燃填料、1-10份里料填料、20-30份溶剂混合，搅拌均匀；
4)将电子级玻纤布浸渍在步骤1)制得的胶液中，在130-190℃条件下烘干，控制含胶量为40-50％，流动度为6-14％，得表料半固化片；
5)将湿强木浆纸浸渍在步骤2)制得的胶液中，在130-150℃条件下烘干，控制含胶量为8-10％的一浸料片，再将一浸料片浸渍在步骤3)制得的胶液中，在160-180℃条件下烘干，控制含胶量为58-62％，得里料半固化片；
6)取2-6张步骤5)制得的里料半固化片叠加在一起，在两侧均铺覆一张步骤4)所得的表料半固化片，再在每张表料半固化片的外侧铺覆有一张铜箔，在160-180℃、60-90Kgf/cm2条件下热压90-150min，即得CEM-1覆铜板。
进一步，步骤1)中，所述含磷环氧树脂为DOPO型环氧树脂、NQ改性DOPO性环氧树脂、HQ改性DOPO型环氧树脂的一种或两种以上的混合；所述潜伏性固化剂为DICY和/或DDS；所述表料填料为氢氧化铝、氢氧化镁、磷酸三苯酯、氮磷阻燃剂中的一种或两种以上的混合。
进一步，步骤2)中，所述高耐热含磷阻燃剂的磷含量为20-26％，热分解温度＞300℃。
进一步，步骤3)中，所述低分子含磷环氧为DOPO型环氧树脂，环氧当量为200-300g/eq；所述含氮酚醛的氮含量为12-16％，羟基当量为120-130；所述改性酚醛为腰果酚改性酚醛和/或桐油改性酚醛；所述阻燃填料为含磷、氮的热固性反应物，没有反应活性，磷含量10-15％，氮含量20-30％，粒径2-5μm；所述里料填料为氢氧化铝、氢氧化镁、硅微粉、滑石粉中的一种或两种以上的混合。
本发明每一步骤所用溶剂独立地选自甲醇、丙酮、丁酮、丙二醇甲醚、DMF、甲苯中的一种或两种以上的混合。
在本发明中，含胶量是指浸胶用树脂乳液纯固体占浸胶料片重量的百分比；流动度是指浸胶用树脂乳液在70±5kg/cm2的压力、160±2℃下流出的重量占浸胶用树脂乳液总重量的百分比。
与现有技术相比，本发明的有益效果如下：
(1)本发明提供的表料胶液固化体系中少量添加酚醛树脂，改善表料与里料的匹配性，从而提高界面的结合强度改善耐热性；
(2)本发明提供的里料一浸树脂胶液使用高耐热含磷树脂，可大幅降低木浆纸的可燃性，从而避免使用三聚氰胺甲醛树脂或其他热固性低分子树脂，改善了产品的柔韧性及稳定性；
(3)本发明制得的覆铜板板材的耐热性能够达到288℃、27s以上漂焊不分层、不起泡，耐热性有明显提高；阻燃达到FV0级；柔韧性明显改善，具有优良的冲孔加工性，适用于无铅回流焊制程及一般条件的喷锡制程，可提高加工效率和焊接可靠性。
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，所用的计量单位为重量份。
实施例1
一种高耐热无卤CEM-1覆铜板的制备方法，包括如下步骤：
(1)表料半固化片胶液的制备：将30份DOPO型环氧树脂、3.5份烷基长链改性增韧环氧树脂、5份低分子环氧E-51、1.5份潜伏性固化剂DICY、2份苯酚酚醛树脂、28份氢氧化铝:氢氧化镁＝1:1的混合表料填料、30份DMF:丁酮＝4:1的混合溶剂，混合，搅拌均匀；
(2)里料一浸树脂胶液制备：将10份高耐热含磷阻燃剂磷含量为23％、90份甲醇:丙酮＝4:1的混合溶剂，混合、搅拌均匀；
(3)里料二浸树脂胶液制备：将22份低分子含磷环氧DOPO型环氧树脂、10份低分子E-51环氧、13份含氮酚醛树脂、5份腰果酚改性酚醛、15份含磷氮阻燃填料、5份里料填料氢氧化铝、30份甲醇:丙酮＝2:1的混合溶剂，混合，搅拌均匀；
(4)将电子级玻纤布浸渍在步骤(1)制得的胶液中，在170℃条件下烘干，控制含胶量为45±5％，流动度为10±4％，制得表料半固化片；
(5)将湿强木浆纸浸渍在步骤(2)制得的胶液中，在140℃条件下烘干，控制含胶量为9％的一浸料片，然后再将其浸渍在步骤(3)制得的胶液中，在170℃条件下烘干，控制含胶量为60±2％的里料半固化片；
(6)取4张步骤(5)制得的里料半固化片叠加在一起，在双面覆有一张步骤(4)所得的表料半固化片，最后在表料半固化片上覆有一张铜箔，在170℃、单位面积压力60Kgf/cm2条件下热压120min，制得高耐热无卤CEM-1覆铜板。
实施例2
一种高耐热无卤CEM-1覆铜板的制备方法，包括如下步骤：
(1)表料半固化片胶液的制备：将25份DOPO型环氧树脂、10份HQ改性DOPO性环氧树脂、3.5份烷基长链改性增韧环氧、3份低分子环氧E-51、1.0份DICY：DDS＝2:1的混合潜伏性固化剂、3份苯酚酚醛树脂、20份氢氧化镁、5份氮磷阻燃剂、27.5份DMF:丙二醇甲醚＝1:1的混合溶剂，混合，搅拌均匀；
(2)里料一浸树脂胶液制备：将12份高耐热含磷阻燃剂磷含量为23％、88份溶剂甲醇混合、搅拌均匀；
(3)里料二浸树脂胶液制备：将24份低分子含磷环氧DOPO型环氧树脂、8份低分子E-51环氧、13份含氮酚醛树脂、5份桐油改性酚醛、14份含磷氮阻燃填料、6份里料填料氢氧化镁、30份甲醇：丙酮：丁酮＝7:2:1的混合溶剂，混合，搅拌均匀；
(4)将电子级玻纤布浸渍在步骤(1)制得的胶液中，在170℃条件下烘干，控制含胶量为45±5％，流动度为10±4％，制得表料半固化片；
(5)将湿强木浆纸浸渍在步骤(2)制得的胶液中，在140℃条件下烘干，控制含胶量为9％的一浸料片，然后再将其浸渍在步骤(3)制得的胶液中，在170℃条件下烘干，控制含胶量为60±2％的里料半固化片；
(6)取4张步骤(5)制得的里料半固化片叠加在一起，在双面覆有一张步骤(4)所得的表料半固化片，最后在表料半固化片上覆有一张铜箔，在170℃、单位面积压力60Kgf/cm2条件下热压120min，制得高耐热无卤CEM-1覆铜板。
对比例
一种覆铜板的制备方法，包括如下步骤：
(1)表料半固化片胶液的制备：将40份DOPO型环氧树脂、3份潜伏性固化剂DICY、29份填料氢氧化铝、28份溶剂DMF混合，搅拌均匀；
(2)里料一浸树脂胶液制备：将35份水溶性三聚氰胺酚醛树脂、65份甲醇:软水:丙酮＝6:3:1的混合溶剂，混合、搅拌均匀；
(3)里料二浸树脂胶液制备：将18份低分子含磷环氧DOPO型环氧树脂、18份低分子E-51环氧、16份含氮酚醛树脂、15份阻燃填料磷酸三苯酯、33份甲醇：丙酮＝1:1的混合溶剂，混合，搅拌均匀；
(4)将电子级玻纤布浸渍在步骤(1)制得的胶液中，在170℃条件下烘干，控制含胶量为45±5％，流动度为10±4％，制得表料半固化片；
(5)将湿强木浆纸浸渍在步骤(2)制得的胶液中，在140℃条件下烘干，控制含胶量为14％的一浸料片，然后再将其浸渍在步骤(3)制得的胶液中，在170℃条件下烘干，控制含胶量为60±2％的里料半固化片；
(6)取4张步骤(5)制得的里料半固化片叠加在一起，在双面覆有一张步骤(4)所得的表料半固化片，最后在表料半固化片上覆有一张铜箔，在170℃、单位面积压力60Kgf/cm2条件下热压120min，制得CEM-1覆铜板。
测试方法说明：
1)剥离强度：IPC-TM-650 2.4.8.1
2)耐浸焊/288℃：IPC-TM-650 2.4.13.1
3)阻燃性：UL94阻燃实验标准
4)弯曲强度：IPC-TM-650 2.4.4
将实施例1和2所得CEM-1覆铜板以及现有CEM-1覆铜板进行相关指标检测，如表1所示。
表1各实施例与对比例的指标检测实验数据
指标名称 单位 实施例1 实施例2 对比例
剥离强度 N/mm 1.47 1.43 1.37
耐浸焊/288℃ s 28 30 10
阻燃性 s 17 20 26
弯曲强度(纵向) MPa 340 350 420
弯曲强度(横向) MPa 315 320 350
通过对比表1中的测试实验数据可以看出，本申请实施例制得的覆铜板板材的耐热性能够达到288℃、27s以上漂焊不分层、不起泡，耐热性有明显提高；板材的弯曲强度降低明显，能更好的适应冲孔加工工艺，且产品其他性能保持稳定。
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 (5)

1.一种高耐热无卤CEM-1覆铜板的制备方法，其特征在于，包括如下步骤：
1)表料半固化片胶液的制备：按重量份数计，将25-35份含磷环氧树脂、1-5份增韧环氧、1-5份低分子环氧、1-2份潜伏性固化剂、2-4份酚醛树脂、25-35份表料填料和20-30份溶剂混合，搅拌均匀；
2)里料一浸树脂胶液制备：按重量份数计，将5-15份高耐热含磷阻燃剂、85-95份溶剂混合，搅拌均匀；
3)里料二浸树脂胶液制备：按重量份数计，将20-35份低分子含磷环氧、5-15份E-51树脂、10-20份含氮酚醛、1-5份改性酚醛、10-20份阻燃填料、1-10份里料填料、20-30份溶剂混合，搅拌均匀；
4)将电子级玻纤布浸渍在步骤1)制得的胶液中，在130-190℃条件下烘干，控制含胶量为40-50％，流动度为6-14％，得表料半固化片；
5)将湿强木浆纸浸渍在步骤2)制得的胶液中，在130-150℃条件下烘干，控制含胶量为8-10％的一浸料片，再将一浸料片浸渍在步骤3)制得的胶液中，在160-180℃条件下烘干，控制含胶量为58-62％，得里料半固化片；
6)取2-6张步骤5)制得的里料半固化片叠加在一起，在两侧均铺覆一张步骤4)所得的表料半固化片，再在每张表料半固化片的外侧铺覆有一张铜箔，在160-180℃、60-90Kgf/cm2条件下热压90-150min，即得CEM-1覆铜板。
2.根据权利要求1所述的制备方法，其特征在于，步骤1)中，所述含磷环氧树脂为DOPO型环氧树脂、NQ改性DOPO性环氧树脂、HQ改性DOPO型环氧树脂的一种或两种以上的混合；所述潜伏性固化剂为DICY和/或DDS；所述表料填料为氢氧化铝、氢氧化镁、磷酸三苯酯、氮磷阻燃剂中的一种或两种以上的混合。
3.根据权利要求1所述的制备方法，其特征在于，步骤2)中，所述高耐热含磷阻燃剂的磷含量为20-26％，热分解温度＞300℃。
4.根据权利要求1所述的制备方法，其特征在于，步骤3)中，所述低分子含磷环氧为DOPO型环氧树脂，环氧当量为200-300g/eq；所述含氮酚醛的氮含量为12-16％，羟基当量为120-130；所述改性酚醛为腰果酚改性酚醛和/或桐油改性酚醛；所述阻燃填料为含磷、氮的热固性反应物，没有反应活性，磷含量10-15％，氮含量20-30％，粒径2-5μm；所述里料填料为氢氧化铝、氢氧化镁、硅微粉、滑石粉中的一种或两种以上的混合。
5.根据权利要求1-4任一项所述的制备方法，其特征在于，步骤1)、2)和3)中，溶剂独立地选自甲醇、丙酮、丁酮、丙二醇甲醚、DMF、甲苯中的一种或两种以上的混合。
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