CN106519569A - 一种高cti值无卤素阻燃胶液及其制备的半固化片和覆铜板 - Google Patents

一种高cti值无卤素阻燃胶液及其制备的半固化片和覆铜板 Download PDF

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CN106519569A
CN106519569A CN201610947533.XA CN201610947533A CN106519569A CN 106519569 A CN106519569 A CN 106519569A CN 201610947533 A CN201610947533 A CN 201610947533A CN 106519569 A CN106519569 A CN 106519569A
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周培峰
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KINGBOARD (FOGANG) LAMINATE PLATE CO Ltd
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Abstract

本发明公开了一种高CTI值无卤素阻燃胶液及其制备的半固化片和覆铜板，胶液由阻燃环氧树脂、球形晶体填料、固化剂、促进剂和溶剂制备而成，利用该胶液制备半固化片及覆铜板。本发明制备的胶液含有独特的完整球形或近似球形的低硬度、高耐热性、高白度的晶体填料，该填料经特殊的表面处理，不含任何卤素及锑等物质，阻燃性达到UL94V‑0标准。通过本发明制备的半固化片和覆铜板具有优异的电气性能，耐漏电起痕指数可达0级(CTI>600V)，可应用于HDI及高多层线路板中，符合ROSH等相关环保规定。

Description

一种高CTI值无卤素阻燃胶液及其制备的半固化片和覆铜板
技术领域
本发明涉及阻燃材料领域，具体是一种高CTI值无卤素阻燃胶液及其制备的半固化片和覆铜板。
背景技术
20世纪80年代末至90年代中期，很多厂家在开发无卤素阻燃覆铜板，多采用在环氧树脂中添加磷化合物的方法，但这些专利发明都遇到了一个共同的问题：所制出的覆铜板的耐热性、耐湿性低以及层间结合力差，耐漏电起痕指数低。有些采用大量添加氢氧化铝为主阻燃剂的工艺路线去解决无卤素覆铜板阻燃性差的问题，但在板的耐热性及物理性能方面都有较大的负面影响。
之后，出现了通过环氧树脂与磷化合物直接反应的树脂合成工艺技术，同时环氧树脂选用了酚醛型环氧树脂全部或部分替代二官能环氧树脂，由此制作的覆铜板耐热性及耐湿性得到了提高。但单独使用该树脂制作覆铜板阻燃性仍未能达到UL94－V0级。为了提高阻燃，同时不降低板材耐热性，目前很多厂家添加二氧化硅或半脱水氢氧化铝协同阻燃，前者缺陷是硬度太高，对PCB下游钻孔及锣边时对工具磨损较大，后者价格昂贵，而且两者都是角型结构，较难浸透到玻璃布中。
因此本发明为改善以上问题，使用了双酚A酚醛型含磷环氧树脂配以一种特殊表面处理的完整球形或近似球形、低硬度、高耐热性、高白度的晶体填料，制作出性能优异的半固化片及覆铜板。
发明内容
本发明的目的在于提供一种符合环保要求的高CTI值无卤素阻燃胶液及其制备的半固化片和覆铜板，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种高CTI值无卤素阻燃胶液，由以下重量份的原料制备而成：阻燃环氧树脂60～90份，球形晶体填料10～40份，固化剂0.5～5份，促进剂0.05～1份，溶剂30～60份。
作为本发明进一步的方案：所述的阻燃环氧树脂为含磷环氧树脂、含磷环氧树脂与无卤素环氧树脂的复合物。
作为本发明进一步的方案：所述的球形晶体填料为强基化合物包覆的硫酸钡。
作为本发明进一步的方案：所述的固化剂为双氰胺或芳香族二苯胺，所述芳香族二苯胺包括但不限于4,4-二氨基二苯甲烷、4,4-二氨基二苯醚、4,4-二氨基二苯砜中的一种。
作为本发明进一步的方案：所述的促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、N-甲基咪唑、2－苯基咪唑、三氟化硼胺单乙胺、硼酸中的一种或多种复合物。
作为本发明进一步的方案：所述的溶剂为二甲基甲酰胺、丙酮、丁酮、环己酮、丙二醇甲醚、丙二醇甲醚醋酸脂、乙二醇甲醚中一种或多种复合物。
作为本发明进一步的方案：所述的含磷环氧树脂为
中的一种或多种复合物。
作为本发明再进一步的方案：所述的无卤素环氧树脂为
中的一种。
一种半固化片及覆铜板，其涂覆有权利要求1～8中任一项的高CTI值无卤素阻燃胶液。
一种所述的半固化片及覆铜板的制备方法，具体步骤如下：(1)在带有高剪切搅拌装置的搅拌釜中依次加入无卤素环氧树脂、双氰胺、2-甲基咪唑，低速搅拌2.5～3.5h，待搅拌均匀后加入球形晶体填料，高剪切搅拌55～65min，即得到粘稠的无卤素阻燃胶液；(2)以电子级玻璃布进行浸润后经立式烘箱在130～200℃下烘烤5～52min，得到无卤素的半固化片；(3)将该半固化片按要求的尺寸裁切，与铜箔一起放入5～55Pa的真空热压机中压制5～60min，制得所需的覆铜板。
与现有技术相比，本发明的有益效果是：
本发明制备的胶液含有独特的完整球形或近似球形的低硬度、高耐热性、高白度的晶体填料，该填料经特殊的表面处理，不含任何卤素及锑等物质，阻燃性达到UL94V-0标准。通过本发明制备的半固化片和覆铜板具有优异的电气性能，耐漏电起痕指数可达0级(CTI>600V)，可应用于HDI及高多层线路板中，符合ROSH等相关环保规定。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1～3
球形晶体填料：D50：0.5～0.7μm，D97：小于3μm；
密度：3.2～3.8g/cm3；松装密度：0.3～0.5g/cm3；
熔点：1580℃；硬度：2.5～3.5；白度：大于98％
不溶于水和酸、乙醇，无毒，符合ROHS要求。
阻燃环氧树脂：环氧当量为268g/Eq。
固化剂为双氰胺(DICY，纯度>99.5％)。
促进剂为2-甲基咪唑(2-MI，纯度>99.0％)。
有机溶剂为丙酮、二甲基甲酰胺(DMF)中的一种或者二种。
上述物质的配比见表1所列。
无卤阻燃环氧树脂胶液的制备：
第一阶段中按配方把环氧树脂、固化剂、固化促进剂和有机溶剂搅拌混合，生产可在高温下固化的环氧树脂胶液；随后在第二阶段中在高剪切分散混合状态下加入球型晶体填料。
表1球形晶体填料填充的无卤素胶液的配方
组分 实施例1 实施例2 实施例3
无卤阻燃环氧树脂 79 73 66
DICY 2 1.9 1.7
2-MI 0.009 0.008 0.007
DMF 12 12 12
丙酮 3 3 3
球形晶体填料 5 10.1 17.3
以该种胶液经过玻璃布上胶，层压等工艺，制备出双面覆铜板。覆铜板测试结果见表3。
对比例1～3
按照实施例3的方法，采用表2所示的配方制备滑石粉、氢氧化铝、硅微粉填充环氧树脂胶液复合材料。其中，滑石粉径约为0.8μm，容积密度为0.10g/cm3。氢氧化铝径约为1.8μm，容积密度为0.80g/cm3；硅微粉平均粒径为6.5μm。比表面积>0.65m2/g，松散密度为0.75g/cm3，纯度>99.5％
表2滑石粉、氢氧化铝、硅微粉填充的无卤素胶液的配方
组分 对比例1 对比例2 对比例3
无卤阻燃环氧树脂 66 66 66
DICY 1.7 1.7 1.7
2-MI 0.007 0.007 0.007
DMF 12 12 12
丙酮 3 3 3
滑石粉 17 — —
氢氧化铝 — 17 —
硅微粉 — — 17
以该种胶液经过玻璃布上胶，层压等工艺，制备出双面覆铜板。覆铜板测试结果见表3、表4。
表3实施例覆铜板测试结果
性能 实施例1 实施例2 实施例3
Tg(℃) 161.33 160.43 159.45
T-288℃(min) >60 >60 >60
288(℃)耐焊性(min) >3 >3 >3
CTE(50-260℃)％ 3.58 3.25 2.92
剥离强度(N/mm) 1.58 1.51 1.46
燃烧性 V-1 V-1 V-0
CTI 175V 300V 600V
表4对比例覆铜板测试结果
使用实施例3的配方制作的覆铜板，各项性能达到了较高的水平，耐热性好，剥离强度高，阻燃可以满足V0级，CTI值可达600V以上。
在测试的过程中，得到以上参数所使用的测试方法有：
(1)玻璃化转变温度(Tg)，测试方法采用差示扫描量热法(DSC)。
(2)热分层时间(T-288)，测试方法采用热机械分析法(TMA)。
(3)热膨胀系数(CTE)，测试方法采用热机械分析法(TMA)。
(4)燃烧性，按美国UL94垂直燃烧法。
(5)CTI，采用IEC60112-2009标准方法
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。

Claims (10)

1.一种高CTI值无卤素阻燃胶液，其特征在于，由以下重量份的原料制备而成：阻燃环氧树脂60～90份，球形晶体填料10～40份，固化剂0.5～5份，促进剂0.05～1份，溶剂30～60份。
2.根据权利要求1所述的高CTI值无卤素阻燃胶液，其特征在于，所述的阻燃环氧树脂为含磷环氧树脂、含磷环氧树脂与无卤素环氧树脂的复合物。
3.根据权利要求1所述的高CTI值无卤素阻燃胶液，其特征在于，所述的球形晶体填料为强基化合物包覆的硫酸钡。
4.根据权利要求1所述的高CTI值无卤素阻燃胶液，其特征在于，所述的固化剂为双氰胺或芳香族二苯胺，所述芳香族二苯胺包括但不限于4,4-二氨基二苯甲烷、4,4-二氨基二苯醚、4,4-二氨基二苯砜中的一种。
5.根据权利要求1所述的高CTI值无卤素阻燃胶液，其特征在于，所述的促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、N-甲基咪唑、2－苯基咪唑、三氟化硼胺单乙胺、硼酸中的一种或多种复合物。
6.根据权利要求1所述的高CTI值无卤素阻燃胶液，其特征在于，所述的溶剂为二甲基甲酰胺、丙酮、丁酮、环己酮、丙二醇甲醚、丙二醇甲醚醋酸脂、乙二醇甲醚中一种或多种复合物。
7.根据权利要求2所述的高CTI值无卤素阻燃胶液，其特征在于，所述的含磷环氧树脂为
中的一种或多种复合物。
8.根据权利要求2所述的高CTI值无卤素阻燃胶液，其特征在于，所述的无卤素环氧树脂为
中的一种。
9.一种半固化片及覆铜板，其特征在于，其涂覆有权利要求1～8中任一项的高CTI值无卤素阻燃胶液。
10.一种如权利要求9所述的半固化片及覆铜板的制备方法，其特征在于，具体步骤如下：(1)在带有高剪切搅拌装置的搅拌釜中依次加入无卤素环氧树脂、双氰胺、2-甲基咪唑，低速搅拌2.5～3.5h，待搅拌均匀后加入球形晶体填料，高剪切搅拌55～65min，即得到粘稠的无卤素阻燃胶液；(2)以电子级玻璃布进行浸润后经立式烘箱在130～200℃下烘烤5～52min，得到无卤素的半固化片；(3)将该半固化片按要求的尺寸裁切，与铜箔一起放入5～55Pa的真空热压机中压制5～60min，制得所需的覆铜板。
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