CN110358252B - 一种无铅高可靠性fr-4覆铜板生产用胶液 - Google Patents

一种无铅高可靠性fr-4覆铜板生产用胶液 Download PDF

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CN110358252B
CN110358252B CN201910558359.3A CN201910558359A CN110358252B CN 110358252 B CN110358252 B CN 110358252B CN 201910558359 A CN201910558359 A CN 201910558359A CN 110358252 B CN110358252 B CN 110358252B
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周培峰
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Abstract

本发明涉及一种无铅高可靠性FR‑4覆铜板生产用胶液，属于覆铜板技术领域。主要原料包括高溴环氧树脂22‑26份，E‑51基础树脂14‑18份，四官能环氧树脂2‑4份，聚己二酸/对苯二甲酸丁二酯4‑16份，线性双酚A甲醛树脂28‑32份，促进剂0.0200‑0.0210份，无机填料15‑18份，溶剂12‑15份。本发明所制备的FR‑4覆铜板既保证了产品的耐热性，又保证了基材与铜箔之间具有良好的粘合性，提高了电路板制作时焊盘的拉脱强度，能够满足PCB加工制程对于板材耐热性能及加工性能方面的要求。

Description

一种无铅高可靠性FR-4覆铜板生产用胶液
技术领域
本发明涉及一种无铅高可靠性FR-4覆铜板生产用胶液，属于覆铜板技术领域。
背景技术
作为电子工业的基础材料，覆铜板主要用于加工制造印刷线路板，广泛应用于电子通信及仪器仪表。FR-4覆铜板是以环氧树脂作粘合剂，以电子级玻璃纤维布作增强材料的一类阻燃基板，常温至150℃左右仍有较高的机械强度，具有良好的尺寸稳定性、抗冲击性和耐湿性能，干态、湿态下的电气性能优良。FR-4环氧覆铜板是覆铜板系列产品中用量最大、用途最为广泛的一类覆铜板产品，是制作多层印制电路板的重要基材。
而随着电子电器产品的薄型化、多功能化、集成化的发展，要求电路板线路更细、更密，厚度更薄，同时使用的信号频率更高，信号传输的速度更快，失真更小。普通电路板已经无法全面满足这些新的要求，尤其是在焊盘拉脱强度方面。由于轻薄、短小的设计方式与无铅焊锡的要求，焊盘尺寸、线宽和线路间距变小，无铅焊料焊接温度较高，导致在焊接操作的高温环境下，焊盘与基材的附着力变差，导致拉脱强度降低，最终影响电路板工作的可靠性。
发明内容
本发明所要解决的技术问题是针对上述现有技术提供一种无铅高可靠性FR-4覆铜板生产用胶液，在高温工作环境下，保证基材与铜箔之间具有良好的粘合性。
本发明解决上述问题所采用的技术方案为：一种无铅高可靠性FR-4覆铜板生产用胶液，由下列按重量份配比的原料制成：
Figure BDA0002107514270000011
所述的高溴环氧树脂，环氧当量385-476g/mol，溴含量48-50％；所述的四官能环氧树脂是指在分子结构中含有四个环氧基的环氧树脂。
所述的线性双酚A甲醛树脂的分子结构式如下：
Figure BDA0002107514270000021
所述无机填料为SiO2、CaO、Al2O3、MgO中的一种或任意比例的混合物。
所述溶剂为丙酮、丁酮、丙二醇单甲醚中的一种或任意混合物。
所述促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的一种或任意两种以上的混合物。
所述半结晶型聚己二酸/对苯二甲酸丁二酯的相对密度1.3～1.45。
以上所述原料均为市售。
本发明的无铅高可靠性FR-4覆铜板的制备方法，将线性双酚A甲醛树脂与E-51基础树脂、高溴环氧树脂、四官能环氧树脂、半结晶型聚己二酸/对苯二甲酸丁二酯、促进剂、无机填料和溶剂高速搅拌均匀制成胶液，浸渍玻璃布烘烤制成半固化片，再将半固化片按要求叠配，双面覆以电解铜箔，于真空压机中热压成覆铜板。其工艺制程及参数参照行业普通制程及参数要求，无特定特殊要求。
与现有技术相比，本发明的优点在于：一种无铅高可靠性FR-4覆铜板生产用胶液，用一种富含-OH基的环氧树脂为主体，在树脂体系中添加聚己二酸/对苯二甲酸丁二酯属于半结晶型聚合物，其熔点温度低，与环氧树脂、线性双酚A甲醛树脂的相融性好对，其加入不影响胶液对玻纤布的浸渍效果，另外，在固化后提高了整个树脂体系的结晶度，有利于提高半固化材料的刚度和拉伸强度。以韧性较好的双酚A甲醛树脂作为固化剂，咪唑类为促进剂，添加一种或多种高耐热的无机填料为填充料，混合一定比例的溶剂配制而成的胶液，本发明既保证了产品的耐热性，又保证了基材与铜箔之间具有良好的粘合性，提高了电路板制作时焊盘的拉脱强度，能够满足PCB加工制程对于板材耐热性能及加工性能方面的要求。
附图说明
图1为本发明实施例一种无铅高可靠性FR-4覆铜板的PAD测试数值表。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1：
一种无铅高可靠性FR-4覆铜板的制备方法，其步骤包括：
按以下胶液配制比例配制FR-4胶液：
Figure BDA0002107514270000031
将上述物料按配比投入剪切釜中，并加入溶剂丙酮，高速搅拌均匀制得胶液。
用电子级E型玻璃布浸渍以上胶液，烘烤后制成半固化片，再将半固化片按要求叠配，双面覆以电解铜箔在温度228℃、面压30kgf/cm2条件下固化2～3h，得到高可靠性无铅FR-4覆铜板，板材主要性能见表1。
实施例2：
一种无铅高可靠性FR-4覆铜板的制备方法，其步骤包括：
按以下胶液配制比例配制FR-4胶液：
Figure BDA0002107514270000032
将上述物料按配比投入剪切釜中，并加入溶剂丁酮、丙二醇单甲醚，高速搅拌均匀制得胶液。
用电子级E型玻璃布浸渍以上胶液，烘烤后制成半固化片，再将半固化片按要求叠配，双面覆以电解铜箔在温度224℃、面压30kgf/cm2条件下固化2～3h，得到高可靠性无铅FR-4覆铜板，板材主要性能见表1。
表1板材主要性能
Figure BDA0002107514270000041
从表1可以看出，该发明制作的FR-4板材，具有优异的综合性能，胶液的粘结力变大，可满足高端PCB的使用要求。
另外，如图1所示，实施例1的FR-4覆铜板的PAD测试数值，在经历3次IR炉后，实测PAD强度不明显降低，电路板制作时的焊盘的拉脱强度高、保持性好。
除上述实施例外，本发明还包括有其他实施方式，凡采用等同变换或者等效替换方式形成的技术方案，均应落入本发明权利要求的保护范围之内。

Claims (8)

1.一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：由下列按重量份配比的原料制成：
高溴环氧树脂 22-26份
E-51基础树脂 14-18份
四官能环氧树脂 2-4份
线性双酚A甲醛树脂 28-32份
半结晶型聚己二酸/对苯二甲酸丁二酯 4-16份
促进剂 0.0200-0.0210份
无机填料 15-18份
溶剂 12-15份。
2.根据权利要求1所述的一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：所述高溴环氧树脂，环氧当量385-476g/mol，溴含量48-50%；所述的四官能环氧树脂是指在分子结构中含有四个环氧基的环氧树脂。
3.根据权利要求1所述的一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：所述线性双酚A甲醛树脂的分子结构式如下：
Figure DEST_PATH_IMAGE002
。
4. 根据权利要求1所述的一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：所述无机填料为SiO2、CaO、Al2O3、MgO 中的一种或任意比例的混合物。
5.根据权利要求1所述的一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：所述溶剂为丙酮、丁酮、丙二醇单甲醚中的一种或任意混合物。
6.根据权利要求1所述的一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：所述促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的一种或任意两种以上的混合物。
7.根据权利要求1所述的一种无铅高可靠性FR-4覆铜板生产用胶液，其特征在于：半结晶型聚己二酸/对苯二甲酸丁二酯相对水的密度为1.3～1.45。
8.一种无铅高可靠性FR-4覆铜板的制备方法，其特征在于：将线性双酚A甲醛树脂与E-51基础树脂、聚己二酸/对苯二甲酸丁二酯、高溴环氧树脂、四官能环氧树脂、促进剂、无机填料和溶剂高速搅拌均匀制成胶液，浸渍玻璃布烘烤制成半固化片，再将半固化片按要求叠配，双面覆以电解铜箔，于真空压机中热压成覆铜板。
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CN103642446A (zh) * 2013-12-10 2014-03-19 上海南亚覆铜箔板有限公司 无铅高耐热覆铜板及其制备方法
CN107245221A (zh) * 2017-05-23 2017-10-13 建滔电子材料（江阴）有限公司 一种无铅高耐热覆铜板生产用胶液
CN109677058A (zh) * 2018-12-24 2019-04-26 龙宇电子(梅州)有限公司 一种无铅tg140覆铜板的制作方法

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CN103642446A (zh) * 2013-12-10 2014-03-19 上海南亚覆铜箔板有限公司 无铅高耐热覆铜板及其制备方法
CN107245221A (zh) * 2017-05-23 2017-10-13 建滔电子材料（江阴）有限公司 一种无铅高耐热覆铜板生产用胶液
CN109677058A (zh) * 2018-12-24 2019-04-26 龙宇电子(梅州)有限公司 一种无铅tg140覆铜板的制作方法

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