CN113969041A - 一种树脂组合物及使用其制备的半固化片、金属箔层压板 - Google Patents
一种树脂组合物及使用其制备的半固化片、金属箔层压板 Download PDFInfo
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- CN113969041A CN113969041A CN202111481953.0A CN202111481953A CN113969041A CN 113969041 A CN113969041 A CN 113969041A CN 202111481953 A CN202111481953 A CN 202111481953A CN 113969041 A CN113969041 A CN 113969041A
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Abstract
本发明公开了一种树脂组合物,以固体重量计,包括:(a)环氧树脂100份;(b)固化剂4~40份;(c)触变剂0.01~3份;(d)酚氧树脂1~10份;(e)促进剂0~10份。本发明通过酚氧树脂和触变剂搭配使用,改善半固化片的表观缺陷,主要是采用触变剂来改善胶液流动性,将少量的高分子量酚氧树脂很好地浸润于玻纤布纤维之间,从而改善表观平滑性、表观鱼眼和缺胶等现象。
Description
技术领域
本发明涉及电子材料技术领域,具体涉及一种树脂组合物及使用其制备的半固化片、金属箔层压板。
背景技术
随着技术的升级,汽车市场、智能手机等消费类电子市场对PCB提出了新的需求,印制电路板的布线密度高密化、高集成化要求越来越高,同时迫于各国的环境法规出台,无铅制程的导入,环氧树脂很难满足层压板对耐热性、加工性的性能要求。
覆铜板用半固化片(亦称粘结片)表观鱼眼和缺胶等问题,是半固化片的常见缺陷。原因在于,半固化片产品生产过程中,因环氧树脂混合后的相容性差异,造成树脂间的界面张力不同,致使共聚物表面张力不均而产生表观缺陷。若鱼眼数量较多和缺胶较多,则在后续的压板成型过程中,容易出现树脂填胶不足而形成基材次表观微气泡等缺陷,严重影响产品性能。而随着电子产品不断轻薄化的发展,板材及粘结片越来越薄,带来填胶困难逐步增大。因此,不少PCB客户对半固化片的表观进行了严格监管,尤其对主要用于消费电子如手机、笔电等的无卤产品,要求更高。对CCL厂商来说,只有彻底了解并解决表观问题并提供给客户,才能确保高质量产品符合客户的一致性验收要求,减少或避免因验收不合格或使用问题而发生投诉等不良影响。
中国发明专利CN106575625A公开了膜状粘接剂、使用膜状粘接剂的半导体封装及其制造方法,该专利通过采用环氧树脂、环氧树脂固化剂、苯氧树脂、二氧化硅填充剂来降低半导体芯片多层叠化中在高温短时间固化是的孔洞的发生,也即,缩短固化时间,降低封装龟裂。
中国发明专利CN 105602195 A公开了一种树脂组合物、半固化片和覆铜板,其中采用环氧树脂60~100份、酚氧树脂20~60份和固化剂1~10份,其中环氧树脂包括联苯环氧树脂90~100%和四官能UV阻挡箱环氧树脂0~10%,酚氧树脂的分子量为30000~80000。该专利将环氧树脂和酚氧树脂结合使用,耐贮藏性较高,该半固化片和采用该半固化片制备的覆铜板均可长期保存,且其具有高刚性和剪切时不掉粉的特性。其中,该专利实现上述目的主要是利用酚氧树脂的高刚性、硬度韧性及良好的尺寸稳定性。
因此,开发一种具有高的耐湿热性能、高玻璃化转变温度、较好的板材厚度均一性、平滑的半固化片表观的树脂组合物,具有积极的现实意义。
发明内容
本发明的目的是提供一种树脂组合物及使用其制备的半固化片、金属箔层压板,该组合物具有高的耐湿热性能、高玻璃化转变温度、较好的板材厚度均一性、平滑的半固化片表观,使用其制备的半固化片和金属箔层压板具有良好的稳定性,高耐热性能以及表观平整无缺陷。
为实现上述目的,本发明提供了以下技术方案:
一种树脂组合物,以固体重量计,包括:(a)环氧树脂100份;(b)固化剂4~40份;(c)触变剂0.01~3份;(d)酚氧树脂1~10份;(e)促进剂0~10份。
上述技术方案中,所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、MDI改性环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、三官能酚型环氧树脂、四苯基乙烷环氧树脂、联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、异氰酸酯型环氧树脂、芳烷基线型酚醛环氧树脂、脂环族类环氧树脂、缩水甘油胺型环氧树脂、缩水甘油酯型环氧树脂、含磷环氧树脂中的一种。
优选地,所述环氧树脂选自萘环型环氧树脂、联苯型环氧树脂或双环戊二烯型环氧树脂;其中,所述萘环型环氧树脂的结构式如下结构式(Ⅲ)所示,所述联苯型环氧树脂的结构式如下结构式(Ⅳ)所示,所述双环戊二烯型环氧树脂的结构式如下结构式(Ⅴ)所示:
上述技术方案中,所述固化剂选自胺系化合物、酰胺系化合物、酸酐系化合物、酚系化合物、苯并噁嗪类化合物、活性酯类化合物中的一种或几种。
优选地,所述胺系化合物选自二氨基二苯基甲烷、二氨基二苯砜、二亚乙基三胺、双羧基邻苯二甲酰亚胺、咪唑、双氰胺、二氨基二苯醚中的一种或几种;优选为二氨基二苯基甲烷和/或二氨基二苯砜;所述酰胺系化合物可以是低分子聚酰胺。
优选地,所述酸酐系化合物选自邻苯二甲酸酐、顺丁烯二酸酐、四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐、马来酰亚胺桐油酸酐和苯乙烯-马来酸酐、偏苯三甲酸酐、均苯四甲酸二酐、马来酸酐、氢化邻苯二甲酸酐、纳迪克酸酐中的一种或几种;优选为苯乙烯-马来酸酐。
优选地,所述酚系化合物选自酚醛树脂、苯并恶嗪树脂、双酚、单酚、多羟基酚、苯二酚、联苯苯酚型酚醛树脂、联苯苯酚型萘酚树脂、双环戊二烯苯酚加成型树脂、苯酚芳烷基树脂、萘酚芳烷基树脂、三羟甲基甲烷树脂中的一种或几种;更优选地,酚醛树脂为双酚A酚醛树脂、苯酚酚醛树脂、萘酚酚醛树脂。
所述活性酯类化合物优选为如下结构式(Ⅺ)所示的化合物:
(Ⅺ),其中,X为苯基或者萘基;j为0或1;k为0或1;n表示重复单元,为0.25~1.25。
更进一步优选,所述固化剂选自双氰胺、二氨基二苯砜、二氨基二苯甲烷、苯乙烯-马来酸酐共聚物、酚醛树脂、活性酯或苯并噁嗪中的至少一种。
上述技术方案中,所述酚氧树脂的分子量在1万-20万之间的一种或多种树脂。优选的,所述酚氧树脂的分子量为3万-10万。
酚氧树脂是一类由二元酚与环氧氯丙烷缩聚而成的无定形聚羟基醚高聚物。常用的二元酚是二酚基丙烷,密度1.18~1.32g/cm3。耐酸、碱、脂肪烃,能溶于丙酮、氯代烃、芳烃等,对紫外线敏感,耐候性不佳。耐热性差,最高使用温度75℃。综合机械性能好,有高的刚性、硬度韧性及良好的尺寸稳定性。抗拉强度65MPa,挠曲强度96MPa,抗应力开裂性良好。以二酚基丙烷与环氧氯丙烷在甲苯、丁醇、丙酮溶液中缩聚而成。因此,现有技术中,一般采用添加酚氧树脂来改善产品的韧性。例如,中国发明专利CN 105602195 A树脂组合物、半固化片和覆铜板,采用环氧树脂和酚氧树脂来改善半固化片和覆铜板的脆性高导致裁切、钻孔和冲孔等操作过程掉粉尘的问题,并延长产品的储存时间,其中酚氧树脂的含量为环氧树脂的20-100重量%。但是,本发明选用特定的环氧树脂和酚氧树脂组合来改善高的半固化片的耐湿热性能、玻璃化转变温度及板材厚度均一性和平滑的半固化片表观等性能。本实施例发现,通过与触变剂搭配使用,当添加量在1~10%范围内即可取得非常好的效果。
本发明通过酚氧树脂和触变剂配合使用,改善半固化片的表观缺陷,主要是采用触变剂来改善胶液流动性,将少量的高分子量酚氧树脂很好地浸润于玻纤布纤维之间,从而降低聚合物间的界面张力,可以改善胶水内各种树脂的相容性,影响各个树脂的分子间作用力,促使树脂组合物整体的表面张力均衡,达到改善表观的作用。从而改善表观平滑性、表观鱼眼和缺胶等现象。当酚氧树脂含量超过10重量份时,影响固化物的耐热性和CTE值,当酚氧树脂含量低于1重量份时,难以改善表面缺陷。触变剂含量超过3重量份时,胶液粘度过低,板材流胶大,影响板材厚度均匀性,触变剂含量少于0.01重量份时,胶液粘度高,大分子量酚氧树脂难以分散,影响表观。
进一步地,上述技术方案中,所述的触变剂是疏水型气相二氧化硅或/和膨润土。优选地,为经表面处理的疏水型气相二氧化硅。所述表面处理剂为硅烷偶联剂,如含环氧基、氨基、乙烯基、丙烯酸酯基或烯丙基的硅烷偶联剂。表面改性的疏水型气相二氧化硅,可以改善环氧树脂体系的流变特性。
上述技术方案中,以树脂组合物100重量份计,所述树脂组合物中还含有30-90重量份填料。所述填料为有机填料和/或无机填料,其中,无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的一种或者任意几种的混合物;所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚砜粉末中的至少一种。更优选地,所述无机填料选自熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母、玻璃纤维粉中的至少一种。优选地,所述填料为二氧化硅,更优选地,为经表面处理的球形二氧化硅。所述表面处理剂为硅烷偶联剂,如含环氧基、氨基、乙烯基、丙烯酸酯基或烯丙基的硅烷偶联剂。优选地,所述填料的粒径中度值为1~15微米,例如1微米、2微米、5微米、8微米、10微米、11微米、12微米、13微米、14微米。更优选地,所述填料的粒径中度值为1~10微米。
上述技术方案中,根据最终产品的不同要求,在所述树脂组合物还包括0~5份其他助剂。所述其他助剂包括偶联剂、分散剂、染料。所述偶联剂为硅烷偶联剂,如环氧硅烷偶联剂或氨基硅烷偶联剂;所述分散剂为γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷等具有氨基且具有水解性基团或羟基的氨基系硅烷化合物、3-丙烯酰氧基丙基三甲氧基硅烷等具有环氧基且具有水解性基团或羟基的环氧系硅烷化合物、γ-甲基丙烯酰氧基丙基三甲氧基硅烷等具有乙烯基且具有水解性基团或羟基的乙烯基系硅烷化合物、阳离子系硅烷偶联剂;分散剂可用BYK制的Disperbyk-110、111、118、180、161、2009、BYK-W996、W9010、W903(均为产品名);所述染料为荧光染料和黑色染料,其中荧光染料为吡唑啉等,所述黑色染料为炭黑(液态或粉末状)、吡啶络合物、偶氮络合物、苯胺黑、黑滑石粉、钴铬铬金属氧化物、吖嗪、酞菁等。
本发明同时请求保护一种采用上述树脂组合物制作的半固化片,将所述树脂组合物用溶剂溶解制成胶液,然后将增强材料浸渍在上述胶液中,将浸渍后的增强材料加热干燥后,即可得到所述半固化片。其中,所述增强材料为天然纤维、有机合成纤维、有机织物或者无机织物;优选地,所述增强材料采用玻璃纤维布,玻璃纤维布中优选使用开纤布或扁平布。此外,在所述增强材料采用玻璃纤维布时,所述玻璃纤维布一般都需要进行化学处理,以改善树脂组合物与玻璃纤维布的界面之间结合。所述化学处理主要方法是偶联剂处理。所用偶联剂优选用环氧硅烷或者氨基硅烷等,以提供良好的耐水性和耐热性。
所述半固化片的制备方法为:将增强材料浸渍在上述的树脂组合物胶液中,然后将浸渍后的增强材料在50~170℃环境下烘烤1~10min,干燥后即可得到所述半固化片。
本发明同时请求保护一种层压板,在一张上述的半固化片的单面或双面覆上金属箔,或者将至少2张上述的半固化片叠加后,在其单面或双面覆上金属箔,热压成形,即可得到所述层压板。所述层压板的制备步骤如下:在一张上述半固化片的单面或双面覆上金属箔,或者将至少2张上述半固化片叠加后,在其单面或双面覆上金属箔,热压成形,即可得到金属箔层压板。上述层压板的压制条件为:在0.2~2MPa压力和180~250℃温度下压制2~4小时。具体地,所述半固化片的数量可根据需要的层压板的厚度来确定,可用一张或多张。所述金属箔,可以是铜箔,也可以是铝箔,其材质不限;所述金属箔的厚度也没有特别限制,如5微米、8微米、12微米、18微米、35微米或70微米均可。
通过采用上述技术方案,本发明与现有技术相比具有以下优点:
(1)本发明通过酚氧树脂和触变剂搭配使用,改善半固化片的表观缺陷,主要是采用触变剂来改善胶液流动性,将少量的高分子量酚氧树脂很好地浸润于玻纤布纤维之间,从而改善表观平滑性、表观鱼眼和缺胶等现象。
(2)由本发明的热固性树脂组合物制得的层压板具有良好得耐热性、HCT性能、抗剥离强度、耐CAF性能,综合性能良好,并树脂体系流胶不受控以及基材质量和板材厚度均一性较差等问题。
具体实施方式
下面结合本发明的具体内容,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,都属于本发明的保护范围。
下面结合实施例对本发明进一步描述。
下文中无特别说明的,“份”代表“重量份”。
一种热固性树脂组合物,以固体重量计,包括组分如下,参见下表所示:采用如下表1的组分和配比制得:
表1实施例和对照例的组分配比表
胶液的混制:
根据表1中的配方,将配方中所有组分配制成固含量为60%的热固性树脂组合物胶液。配置方法包括首先取适量的二甲基甲酰胺和丁酮(按质量比DMF:MEK为1:1)的混合有机溶剂,将配方量的固化剂、触变剂和促进剂溶解于该混合溶剂中,将其混合均匀(搅拌60min以上),得到混合溶液,再将环氧树脂、和酚氧树脂依次加入上述混合溶液中,搅拌均匀后形成树脂胶液,固含量为60%。
按照下述条件制备成层压板:
增强材料:电子级7628玻纤布;
金属箔:18微米,电解铜箔;
层数:5;
成型后板材厚度:1.0mm;
预浸渍半固化条件:170℃/5min;
固化条件:150℃/60min+220℃/150min;
各性能的测试结果显示于表2中:
表2实施例和对照例的性能测试对照表
表中各性能的测试方法如下:
(1)玻璃化转变温度(Tg):根据差示扫描量热法,按照IPC-TM-650 2.4.25所规定的DSC方法进行测定。
(2)剥离强度(PS):按照IPC-TM-650 2.4.8方法中的“热应力后”实验条件,测试金属盖层的剥离强度。
(3)浸锡耐热性:使用50×50mm的两面带铜样品,浸入288℃的焊锡中,记录样品分层气泡的时间。
(4)潮湿处理后浸锡耐热性:将25块100×100mm的基材试样在121℃、105Kpa的加压蒸煮处理装置内保持3hr后,浸入288℃的焊锡槽中2min,观察试样是否发生分层鼓泡等现象。
(5)吸水率:按照IPC-TM-6502.6.2.1的方法进行测定。
(6)热分解温度Td:按照IPC-TM-6502.4.26方法进行测定。
(7)热膨胀系数Z轴CTE(TMA):按照IPC-TM-650 2.4.24方法进行测定。
(8)半固化片表观:目视半固化片表观,无明显鱼眼、火山口等的表面半固化片表观良好,存在鱼眼等表明半固化表观一般。
(9)基材表观:目视CCL基材表观,无明显缺胶、针孔等的基材表观良好,存在缺胶、针孔等的基材表观一般。
从上表可知,对比例1采用的是酚氧树脂添加量为20重量份,与实施例相比,压制板材耐热和CTE性能较差,且基材表观一般。
对比例2采用的是不添加酚氧,与实施例相比,半固化片和压制板材的表观一般。
对比例3采用的是不添加触变剂,与实施例相比,半固化片和压制板材的表观一般。
实施例1-7中,酚氧树脂的添加量为1~10重量份,环氧树脂以酚类环氧树脂(双酚A环氧树脂)及MDI改性环氧树脂为例,得到的组合物进行性能测试可见,当两种环氧树脂同时添加时具有更佳的耐热性能和良好表观,且当酚氧树脂的添加量1重量份时即可表现出良好的性能。
实施例8和实施例9为触变剂的添加量对比例,半固化片和压制板材表观良好。也即触变剂添加量在0.01~3重量份时均具有良好的表观性能。其中,与对比例2和3相比,对比例2在不添加酚氧树脂条件下,对比例3不添加触变剂,对比例4的触变剂添加量大于3重量份,半固化片均不能获得良好的性能,特别是厚度均匀性明显下降。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (9)
1.一种热固性树脂组合物,以固体重量计,其特征在于,包括:
(a)环氧树脂:100份;
(b)固化剂:4~40份;
(c)触变剂:0.01~3份;
(d)酚氧树脂:1~10份;
(e)促进剂:0~10份。
2.根据权利要求1所述的热固性树脂组合物,其特征在于,所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、MDI改性环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、三官能酚型环氧树脂、四苯基乙烷环氧树脂、联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、异氰酸酯型环氧树脂、芳烷基线型酚醛环氧树脂、脂环族类环氧树脂、缩水甘油胺型环氧树脂、缩水甘油酯型环氧树脂、含磷环氧树脂中的一种。
3.根据权利要求1所述的热固性树脂组合物,其特征在于,所述固化剂选自胺系化合物、酰胺系化合物、酸酐系化合物、酚系化合物、苯并噁嗪类化合物、活性酯类化合物中的一种或几种。
4.根据权利要求1所述的热固性树脂组合物,其特征在于,所述酚氧树脂的分子量在1万-20万之间的一种或多种树脂。
5.根据权利要求1所述的热固性树脂组合物,其特征在于,所述的触变剂是疏水型气相二氧化硅或/和膨润土。
6.根据权利要求1所述的热固性树脂组合物,其特征在于,所述树脂组合物中还包括填料。
7.根据权利要求1所述的热固性树脂组合物,其特征在于,所述促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑、以及异辛酸锌中的至少一种。
8.一种采用如权利要求1~7任意所述的树脂组合物制备的半固化片,其特征在于:将权利要求1~7任意所述的树脂组合物用溶剂溶解制成胶液,然后将增强材料浸渍在上述胶液中,将浸渍后增强材料加热干燥后,即可得到所述半固化片。
9.一种采用如权利要求1~7任意所述的树脂组合物制备的层压板,其特征在于:在一张由权利要求8所述的半固化片的单面或双面覆上金属箔,或者将至少2张由权利要求8所述的半固化片叠加后,在其单面或双面覆上金属箔,热压成形,即可得到所述层压板。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117186588A (zh) * | 2023-09-18 | 2023-12-08 | 同宇新材料(广东)股份有限公司 | 一种电子电路基材用的高耐热树脂组合物及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104245874A (zh) * | 2012-04-26 | 2014-12-24 | 古河电气工业株式会社 | 膜状接合剂用组合物及其制造方法、膜状接合剂和使用了膜状接合剂的半导体封装及其制造方法 |
CN109135652A (zh) * | 2018-08-09 | 2019-01-04 | 陕西生益科技有限公司 | 一种高导热增韧树脂组合物及其应用 |
CN109181234A (zh) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | 一种高导热高韧性树脂组合物及其应用 |
CN109265920A (zh) * | 2018-08-09 | 2019-01-25 | 陕西生益科技有限公司 | 一种高导热树脂组合物及其应用 |
-
2021
- 2021-12-07 CN CN202111481953.0A patent/CN113969041A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104245874A (zh) * | 2012-04-26 | 2014-12-24 | 古河电气工业株式会社 | 膜状接合剂用组合物及其制造方法、膜状接合剂和使用了膜状接合剂的半导体封装及其制造方法 |
CN109135652A (zh) * | 2018-08-09 | 2019-01-04 | 陕西生益科技有限公司 | 一种高导热增韧树脂组合物及其应用 |
CN109181234A (zh) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | 一种高导热高韧性树脂组合物及其应用 |
CN109265920A (zh) * | 2018-08-09 | 2019-01-25 | 陕西生益科技有限公司 | 一种高导热树脂组合物及其应用 |
Non-Patent Citations (1)
Title |
---|
李东光: "《新编实用化工产品配方与制备 胶黏剂分册》", 中国纺织出版社, pages: 413 - 416 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117186588A (zh) * | 2023-09-18 | 2023-12-08 | 同宇新材料(广东)股份有限公司 | 一种电子电路基材用的高耐热树脂组合物及其制备方法 |
CN117186588B (zh) * | 2023-09-18 | 2024-04-12 | 同宇新材料(广东)股份有限公司 | 一种电子电路基材用的高耐热树脂组合物及其制备方法 |
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