CN116265445A - 苯并恶嗪树脂、树脂组合物及由其制成的铜箔基板 - Google Patents

苯并恶嗪树脂、树脂组合物及由其制成的铜箔基板 Download PDF

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CN116265445A
CN116265445A CN202211230743.9A CN202211230743A CN116265445A CN 116265445 A CN116265445 A CN 116265445A CN 202211230743 A CN202211230743 A CN 202211230743A CN 116265445 A CN116265445 A CN 116265445A
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resin
benzoxazine
resin composition
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copper foil
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廖世灏
杨敏原
周雅燕
邱政鸿
陈正中
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Yuanhong Applied Materials Co ltd
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Abstract

本申请涉及苯并恶嗪树脂、树脂组合物及由其制成的铜箔基板。该苯丙恶嗪树脂包括如下式1‑1的化合物，其中，n介于1至5之间，R1、R2、R3、R4如本文所定义。

Description

苯并恶嗪树脂、树脂组合物及由其制成的铜箔基板
技术领域
本发明关于一种树脂，尤指一种适用于电子组件的苯并恶嗪树脂。
背景技术
苯并恶嗪是一种含氮且具有类似酚醛树脂结构的热固性树脂，由O原子和N原子构成的六元杂环化合物体系，苯并恶嗪一般是由酚类化合物、一级胺和甲醛类化合物通过曼尼希反应(Mannich reaction)制得的化合物，在加热或催化剂的作用下，开环聚合生成一种类似酚醛树脂的网状结构。
由于苯并恶嗪树脂具有低体积收缩率(在聚合过程中无小分子副产物)；低吸湿率；优良的耐热性、机械性、电气性以及阻燃性等优点，因此，苯并恶嗪树脂被广泛应用于复合材料的基体树脂、无溶剂浸渍漆、电子封装材料、阻燃材料和电绝缘材料等领域，其中，苯并恶嗪树脂乃为制造铜箔基板(Copper Clad Laminate，CCL)的重要材料。
习知的苯并恶嗪树脂可参阅Jiangbing Chen等人在Applied Polymer Materials期刊于2019年所发表的「Design and Preparation of Benzoxazine Resin with High-Frequency Low Dielectric Constants and Ultralow Dielectric Losses」(Appl.Polym.Mater.2019,1,4,625-630)，该文献揭示的苯并恶嗪树脂中的R1是含甲基的DAM，因而使得苯并恶嗪树脂的加工性差，脆性高，不利于后续制成为铜箔基板及电路板，且不易加工，故实用性不高。
随现今对于电路板的要求日益升高，利用现有苯并恶嗪树脂制成的铜箔基板的耐热性、机械性及尺寸稳定性等性质仍有改善的空间。
发明内容
本发明的主要目的在于解决现有苯并恶嗪树脂制成的铜箔基板的耐热性、机械性及尺寸稳定性等性质有待改善的问题。
为达上述目的，本发明提供一种树脂，包括如下式1-1的化合物：
Figure BDA0003881143980000021
其中，n介于1至5之间，R1选自以下所组成的群组：
Figure BDA0003881143980000022
Figure BDA0003881143980000031
Figure BDA0003881143980000041
其中，n2介于2至6之间；
Figure BDA0003881143980000042
其中，n3介于1至5之间；
Figure BDA0003881143980000051
其中，n4介于2至10之间；
Figure BDA0003881143980000052
其中，R2为选自C1-C10碳链或以下所组成的群组：
Figure BDA0003881143980000053
Figure BDA0003881143980000061
其中，R3为单键或选自以下所组成的群组：
Figure BDA0003881143980000062
Figure BDA0003881143980000071
Figure BDA0003881143980000081
Figure BDA0003881143980000091
其中，R4为H、C1至C12烷基或烯丙基；
其中，R5为苯环、H或C1至C12烷基。
为达上述目的，本发明还提供一种如下式的树脂：
Figure BDA0003881143980000092
其中，n介于1至5之间。
为达上述目的，本发明更提供一种如下式的树脂：
Figure BDA0003881143980000093
其中，n介于1至5之间。
本发明基于分子设计特性，提供一种长链型且含有可交联官能基团的苯并恶嗪树脂，具有高韧性与优异的机械性质(如抗拉强度与伸长率)，能大幅改善现有聚苯并恶嗪制成的铜箔基板之脆性、加工性不佳以及尺寸稳定性不佳的问题。根据选择不同的R1，长链(long chain)可改善机械性质(如抗拉强度与伸长率)，应用于铜箔基板之中可降低孔裂及白纹的产生；脂肪族(aliphatic)可改善苯并恶嗪树脂的电气性质，增加阻抗与降低Dk/Df，应用于铜箔基板之中可以增加绝缘阻抗且降低高频损耗，且脂肪族(aliphatic)还可增加苯并恶嗪树脂中对溶剂的溶解度，应用于铜箔基板之中可降低溶剂使用量，具有环保与低成本的优点；环链(cyclic chain)、长链(long chain)、环状脂肪族(cyclic aliphatic)及Si皆可降低苯并恶嗪树脂的吸湿性及降低Dk/Df；芳香族(aromatic)可增加苯并恶嗪树脂的耐热性以及机械性质。进一步地，利用本发明揭示的苯并恶嗪树脂制备的印刷电路板，除阻燃性能达到UL94 V0级，也具有优异的耐热性、高尺寸稳定性、高机械强度、高韧性、耐离子迁移性以及优异的加工性能。
具体实施方式
本发明揭露一种具有如下式1-1的结构的苯并恶嗪树脂：
Figure BDA0003881143980000101
其中，n介于1至5之间，可为整数或非整数，R1选自以下所组成的群组：
Figure BDA0003881143980000111
/>
Figure BDA0003881143980000121
Figure BDA0003881143980000131
/>
其中，n2介于2至6之间；
Figure BDA0003881143980000132
其中，n3介于1至5之间；
Figure BDA0003881143980000133
其中，n4介于2至10之间。
Figure BDA0003881143980000141
其中，R2为选自C1-C10碳链或以下所组成的群组：
Figure BDA0003881143980000142
Figure BDA0003881143980000151
其中，R3为单键或选自以下所组成的群组：
Figure BDA0003881143980000152
/>
Figure BDA0003881143980000161
/>
Figure BDA0003881143980000171
其中，R4为H、C1至C12烷基或烯丙基。
其中，R5为苯环、H或C1至C12烷基。
根据选择不同的R1，长链(long chain)可改善机械性质(如抗拉强度与伸长率)，应用于铜箔基板之中可降低孔裂及白纹的产生；脂肪族(aliphatic)可改善苯并恶嗪树脂的电气性质，增加阻抗与降低Dk/Df，应用于铜箔基板之中可以增加绝缘阻抗且降低高频损耗，且脂肪族(aliphatic)还可增加苯并恶嗪树脂中对溶剂的溶解度，应用于铜箔基板之中可降低溶剂使用量，具有环保与低成本的优点；环链(cyclic chain)、长链(long chain)、环状脂肪族(cyclic aliphatic)及Si皆可降低苯并恶嗪树脂的吸湿性及降低Dk/Df；芳香族(aromatic)可增加苯并恶嗪树脂的耐热性以及机械性质。
以本发明的苯并恶嗪树脂的R1的式1-3来说，由于采用了醚基化合物，与现有技术采用的DAM((4,4’-二氨基二苯基)甲烷，(4,4’-diaminodiphenyl)methane)相比，式1-3的加工性优异，大幅改善了苯并恶嗪树脂的加工性(式1-3、式1-4、式1-10、式1-11、式1-12、式1-15亦同)。另一方面，以本发明的苯并恶嗪树脂的R1为式1-2、式1-4、式1-5、式1-6、式1-7、式1-11、式1-12、式1-15来说，与上列的现有技术相比，侧炼的结构可以提高溶解度，亦提升可加工性，对于成品的外观和物性，皆有正面的功效。
以本发明的苯并恶嗪树脂的R1为式1-8、式1-9、式1-16来说，环状芳香族(cyclicaromatic chain)亦提供了低吸湿性及低Dk/Df，且改善耐热性及机械性质。以本发明的苯并恶嗪树脂的R1为式1-13、式1-14来说，脂肪族长链(aliphatic long chain)提供优异的机械性质。
Figure BDA0003881143980000191
为H。
Figure BDA0003881143980000192
根据本发明一实施例，提供一种如下式结构的树脂(后称BZ-7)。即，在式1-1之中，R1为
Figure BDA0003881143980000193
R2为H，R3为/>
Figure BDA0003881143980000194
R4为H。
Figure BDA0003881143980000195
BZ-1以及BZ-7在玻璃转化温度(glass transition temperature，Tg)、Z轴热膨胀系数(Z-CTE)以及抗撕强度具备平衡的优异表现，因此特别适合用于实务上的量产。
在一实施例中，用于合成式1-1的苯并恶嗪树脂的材料主要包括二元胺、二元酚、一元酚以及甲醛，制备上，先将二元胺、二元酚以及一元酚加入一四口可分离式反应瓶中而得到一溶液，该反应瓶配置有加热装置、温度计、搅拌机、冷却管、滴入装置及减压回收装置，以甲苯作为溶剂，再滴入甲醛。反应的通式如下：
Figure BDA0003881143980000201
其中，n介于1至5之间，可为整数或非整数。举例来说，Z1选自单价烃基、单价烃氧基及卤基。Z2及/或Z3可为以下化合物：
Figure BDA0003881143980000202
/>
Figure BDA0003881143980000211
以下为说明上述揭示的树脂的合成方法。
【合成例1-1】
将846g的二(3-甲基-4-氨基-6-乙基)苯甲烷(4,4'-Methylenebis(2-ethyl-6-methylaniline)，MMEA)、228g的双酚A(Bisphenol A，BPA)、376g的酚(Phenol)以及600g的甲苯加入一3公升的四口可分离式反应瓶中而得到一溶液，对该溶液升温至约40℃并搅拌均匀，搅拌时在20分钟内逐滴加入819g的甲苯溶液(含有44wt.％的甲醛)至该溶液中，并继续加热该溶液直到约90℃，维持该溶液于约90℃的温度并反应3小时。
待反应3小时，停止加热及搅拌并静置20分钟，待该溶液分成二层后，移除上层的水相及微量的乳化物，再加热至约90℃并利用减压(低于约90毫米汞柱)的方式回收溶剂，待温度至约130℃且回收全部溶剂后，即获得重量约1730g之氮氧杂环化合物(即苯并恶嗪树脂)。
【合成例1-2】
将600g的4,4'二胺基二苯醚(4,4'-Oxydianiline，ODA)、456g的双酚A(BisphenolA，BPA)、188g的酚(Phenol)以及600g的甲苯加入一四口可分离式反应瓶中而得到一溶液，对该溶液升温至约40℃并搅拌均匀，搅拌时在20分钟内逐滴加入819g的甲苯溶液(含有44wt.％的甲醛)至该溶液中，并继续加热该溶液直到约90℃，维持该溶液于约90℃的温度并反应3小时，反应式如下。
待反应3小时，停止加热及搅拌并静置20分钟，待该溶液分成二层后，移除上层的水相及微量的乳化物，再加热至约90℃并利用减压(低于约90毫米汞柱)的方式回收溶剂，待温度至约130℃且回收全部溶剂后，即获得重量约1385g之氮氧杂环化合物(即苯并恶嗪树脂)。
【合成例1-3至合成例1-8】
合成方法如以上所述，而所选用的材料及配比则和以上合成例1-1、1-2列如下表1。合成例1-1至合成例1-8分别对应表1中的BZ-1至BZ-8，而表1的数字为各合成例的单体摩尔比。
在应用上，式1-1的树脂可以和其他材料混合来做使用，在一例子中，式1-1的树脂可以和填料、热固性树脂、补强材料以及增韧剂在一溶剂中混合、溶解或分散而制成漆状的形式，该溶剂可为任何可溶解或分散上述各成分、但不与该等成分反应的惰性溶剂，包含但不限于甲苯、γ-丁内酯、甲乙酮、环己酮、丁酮、丙酮、二甲苯、甲基异丁基酮、N,N-二甲基甲酰胺(N,N-dimethyl formamide，DMF)、N,N-二甲基乙酰胺(N,N-dimethyl acetamide，DMAc)、N-甲基吡咯烷酮(N-methyl-pyrolidone，NMP)或以上的组合。
另一方面，本发明还揭示一种树脂组合物以及由该树脂组合物制成的铜箔基板。该树脂组合物包括重量百分比介于30至50之间的苯并恶嗪树脂(如式1-1)、一重量百分比介于35至55之间的填料、一重量百分比介于6至15之间的热固性树脂以及一重量百分比介于8至20之间的增韧剂。
为具体说明本发明技术，以下以根据本发明式1-1的苯并恶嗪制作印刷电路板用的金属箔积层板(Metal clad laminate plate)来说明，并与其他的比较例进行比较，比较例所采用的苯并恶嗪树脂的化学式如下式2-1所列。表2显示了不同实施例的配方，单位为重量比例。
Figure BDA0003881143980000231
Figure BDA0003881143980000241
当式2-1的苯并恶嗪树脂为ODA-BZ时，R如下式2-2所列：
Figure BDA0003881143980000242
当式2-1的苯并恶嗪树脂为MDA-BZ时，R如下式2-3所列：
Figure BDA0003881143980000243
先将式1-1的苯并恶嗪和一填料、一热固性树脂以及一增韧剂在一溶剂中混合，该填料为粒径为10μm的二氧化硅(SiO2)，该热固性树脂采用购自于大和化学型号为KI-70的双马来酰亚胺树脂(BMI)，该增韧剂采用型号为
Figure BDA0003881143980000244
100的丁二烯-苯乙烯共聚物，该溶剂为使用甲苯、甲乙酮、及γ-丁内酯之混合物作为溶剂，得到一漆，接着利用辊式涂布机将一基材(或称补强材料)浸渍于该漆，，之后在175°下干燥，从而获得半固化态的预浸渍片。本实施例中，该基材采用型号2116的玻璃纤维布，厚度为0.08毫米，而该预浸渍片之漆含量为54wt.％。
将四片该预浸渍片堆栈后，在最上方及最下方各设置一张0.5盎司的铜箔。随后置于一热压机中进行高温热压固化，以3.0℃/分钟的升温速度升温至200℃至220℃之间，并在该温度下，以15公斤/平方公分的压力热压180分钟，接着冷却至室温，即制成一双面覆铜积层板。
对上述制程得到的双面覆铜积层板，进行玻璃转化温度(glass transitiontemperature，Tg)、Z轴的热膨胀系数(Z-CTE)、抗撕强度以及耐热测试的量测，结果显示在表3。
Tg是利用动态热机械分析仪(dynamic thermomechanical analyzer,DMA)依IPC-TM-650 2.4.24.4规范的方法进行测量。Z-CTE是利用热机械分析仪(thermal mechanicalanalyzer，TMA)依IPC-TM-6502.4.24.5规范的方法进行测量，在低于Tg的温度(50℃至260℃之间)量测在Z轴方向上的热膨胀系数改变率。抗撕强度是测量需要多少力才能将1/8英寸宽度的铜箔自板面上垂直撕起。耐热测试是将经干燥的双面覆铜积层板在300℃的锡焊浴中浸泡100秒，重复3次后观察外观，若外观有鼓泡凸起则为不佳，若外观无鼓泡凸起则表示耐热性优良，纪录为○。
Figure BDA0003881143980000261
/>
Figure BDA0003881143980000271
/>
Figure BDA0003881143980000281
/>

Claims (9)

1.一种苯并恶嗪树脂，其特征在于，包括如下式1-1的化合物：
Figure FDA0003881143970000011
其中，n介于1至5之间，R1选自以下所组成的群组：
Figure FDA0003881143970000012
Figure FDA0003881143970000021
其中，n2介于2至6之间；
Figure FDA0003881143970000031
其中，n3介于1至5之间；
Figure FDA0003881143970000032
其中，n4介于2至10之间；
Figure FDA0003881143970000033
其中，R2为选自C1-C10碳链或以下所组成的群组：
-H
(式1-17)
Figure FDA0003881143970000034
Figure FDA0003881143970000041
-CH3
(式1-21)
-CH2-CH3
(式1-22)
Figure FDA0003881143970000042
其中，R3为单键或选自以下所组成的群组：
-CH2-
(式1-24)
Figure FDA0003881143970000043
Figure FDA0003881143970000051
-O-
(式1-28)
Figure FDA0003881143970000052
Figure FDA0003881143970000061
其中，R4为H、C1至C12烷基或烯丙基，
其中，R5为苯环、H或C1至C12烷基。
2.一种树脂组合物，其特征在于，包括重量百分比介于30至50之间的如权利要求1所述的苯并恶嗪树脂、重量百分比介于35至55之间的填料、重量百分比介于6至15之间的热固性树脂以及重量百分比介于8至20之间的增韧剂。
3.一种铜箔基板，由权利要求2所述的树脂组合物制成。
4.一种如下式的苯并恶嗪树脂：
Figure FDA0003881143970000071
其中，n介于1至5之间。
5.一种树脂组合物，其特征在于，包括重量百分比介于30至50之间的如权利要求4所述的苯并恶嗪树脂、重量百分比介于35至55之间的填料、重量百分比介于6至15之间的热固性树脂以及重量百分比介于8至20之间的增韧剂。
6.一种铜箔基板，由权利要求5所述的树脂组合物制成。
7.一种如下式的苯并恶嗪树脂：
Figure FDA0003881143970000072
其中，n介于1至5之间。
8.一种树脂组合物，其特征在于，包括重量百分比介于30至50之间的如权利要求7所述的苯并恶嗪树脂、重量百分比介于35至55之间的填料、重量百分比介于6至15之间的热固性树脂以及重量百分比介于8至20之间的增韧剂。
9.一种铜箔基板，由权利要求8所述的树脂组合物制成。
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