CN107227001B - 一种无卤热固性树脂组合物以及含有它的预浸料、层压板和印制电路板 - Google Patents

一种无卤热固性树脂组合物以及含有它的预浸料、层压板和印制电路板 Download PDF

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CN107227001B
CN107227001B CN201610176723.6A CN201610176723A CN107227001B CN 107227001 B CN107227001 B CN 107227001B CN 201610176723 A CN201610176723 A CN 201610176723A CN 107227001 B CN107227001 B CN 107227001B
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halogen
thermosetting resin
weight
resin composite
parts
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CN107227001A (zh
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游江
黄天辉
许永静
杨中强
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201610176723.6A priority Critical patent/CN107227001B/zh
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Priority to EP16849924.2A priority patent/EP3412722B1/en
Priority to US15/515,230 priority patent/US10494502B2/en
Priority to ES16849924T priority patent/ES2856079T3/es
Priority to KR1020177008221A priority patent/KR101894682B1/ko
Priority to PCT/CN2016/099093 priority patent/WO2017161843A1/zh
Priority to JP2018526132A priority patent/JP6752886B2/ja
Priority to TW105131953A priority patent/TWI598403B/zh
Publication of CN107227001A publication Critical patent/CN107227001A/zh
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Abstract

本发明提供了一种无卤热固性树脂组合物及含有它的预浸料、层压板和印制电路板。所述无卤热固性树脂组合物，以有机固形物按100重量份计，包括如下组分：(A)无卤环氧树脂：30‑60重量份；(B)酚醛固化剂：10‑35重量份；(C)含磷阻燃剂。本发明所提供的无卤热固性树脂组合物制成的预浸料和层压板，具有优异的尺寸稳定性和介电性能、高粘合力、高耐热性、低吸水率以及良好工艺加工性，并能实现无卤阻燃，达到UL94V‑0。

Description

一种无卤热固性树脂组合物以及含有它的预浸料、层压板和 印制电路板
技术领域
本发明属于覆铜板技术领域，具体涉及一种无卤热固性树脂组合物以及含有它的预浸料、层压板和印制电路板。
背景技术
传统的印制电路用层压板通常采用溴系阻燃剂来实现阻燃，特别是采用四溴双酚A型环氧树脂，这种溴化环氧树脂具有良好的阻燃性，但它在燃烧时会产生溴化氢气体。此外，近年来在含溴、氯等卤素的电子电气设备废弃物的燃烧产物中已检测出二噁英、二苯并呋喃等致癌物质，因此溴化环氧树脂的应用受到限制。2006年7月1日，欧盟的两份环保指令《关于报废电气电子设备指令》和《关于在电气电子设备中限制使用某些有害物质指令》正式实施，无卤阻燃覆铜箔层压板的开发成为业界的热点，各层压板基材厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。
随着消费电子产品的精细化、薄型化以及功能需求的增加，层压板基材介质层厚度以及线宽越来越小，所使用的玻纤布越来越薄。在线宽越来越小的条件下若需要保证阻抗不变，介质层必须有足够低的介电常数(Dk)。而增强材料变薄会导致基材的刚性不足，在PCB加工过程中易发生翘曲、胀缩等问题，影响PCB加工的良率，因此基材的尺寸稳定性至关重要。同时，PCB在承载更多元器件的情况下，对焊盘结合力方面的要求更加突出，这就要求基材同时具备较高的粘合力。目前消费电子用无卤中Tg基材有很大一部分仍然采用DICY、DDS等胺类固化剂，这种基材拥有优异的粘合力，但刚性、介电性能和耐热性较差，难以满足超薄HDI制程的要求。
发明内容
基于此，本发明的目的之一在于提供一种无卤热固性树脂组合物。使用该无卤热固性树脂组合物制造的预浸料、层压板和印制电路板具有优异的尺寸稳定性和介电性能、高粘合力、高的刚性、高耐热性、低吸水率以及良好的工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
为了实现上述目的，本发明采用了如下技术方案：
一种无卤热固性树脂组合物，以有机固形物按100重量份计，包括如下组分：
(A)无卤环氧树脂：30-60重量份；
(B)酚醛固化剂：10-35重量份；
(C)含磷阻燃剂；
所述无卤环氧树脂包括具有式(a)结构的环氧树脂：
其中，T1和T2分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱn)所示的结构，n1和n3表示重复单元，均独立地为1以上，优选1～20的整数，例如2、3、4、5、6、8、10、15或20，n2表示重复单元，为0以上的整数，优选0～20的整数，例如0、1、2、3、4、5、6、8、10、12、15或20；
n4表示重复单元，为1以上的整数，例如2、3、4、5、6、8、10、15或20；
式(Ⅱn)中，Tn和Tn’分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱn)所示的结构，且以氢原子或式(I)的结构封端，n为≥3的正整数；n5和n6表示重复单元，均独立地为0以上的整数，优选0～20的整数，例如2、3、4、5、6、8、10、15或20，n7表示重复单元，为1以上的整数，优选1～20的整数，例如1、2、3、4、5、6、8、10、12、15或20。
所述具有式(a)结构的环氧树脂分子量为1000～20000，例如1500、1800、2000、2500、3000、3500、4000、4500、5000、7200、8400、9600、12000、15000、18000、19500等。
所述具有式(a)结构的环氧树脂占组分(A)无卤环氧树脂的重量百分比为50％以上。
本发明所述具有式(a)结构的环氧树脂中，式(Ⅱn)并不是一个特定的通式，当n为3时，式(Ⅱ3)中具有支链T3和T3’，且T3和T3’分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱ4)；此时的式(Ⅱ4)中具有支链T4和T4’，且T4和T4’分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱ4)；此时的式(Ⅱ4)中具有支链T4和T4’，且T4和T4’分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱ5)；……(以此若干循环)，式(Ⅱn)中具有支链Tn和Tn’，且Tn和Tn’分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱn)；但是，对于具有式(a)结构的环氧树脂式(IIn)的结构不能无限循环，当通过循环达到分子量为1000～20000时，可以采用氢原子或式(I)的结构进行封端。
发明人为实现上述目的，进行了反复深入的研究，结果发现：通过将包含具有特定结构的无卤环氧树脂、酚醛固化剂、含磷阻燃剂及其他任选地物质适当混合而得到的无卤热固性树脂组合物，可达到上述目的。
本发明采用特定结构的无卤环氧树脂为主体树脂，其分子结构对称，且含有含N五元杂环结构，拥有较高的玻璃化转变温度(Tg)、高尺寸稳定性、刚性、高粘合力、高耐热性和阻燃好等优点，此外，其还有着优异的介电性能，可以降低固化物介电常数和介电损耗值。用酚醛作为固化剂，不仅能保证固化物拥有较高的尺寸稳定性和耐热性，可以充分发挥含规整结构从而介电性能优异的优势。
本发明除充分利用上述三种组分各自的优势之外，并通过其之间的协同作用，最大程度地发挥了各组分的优势，使得到的固化物具有优异的尺寸稳定性和介电性能、高粘合力、高耐热性、低吸水率以及良好工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
本发明中的组分(A)，即无卤环氧树脂，可以提供固化后树脂及其制成 的层压板所需的介电性能、尺寸稳定性、粘合力、耐热性、阻燃性能以及力学性能。
以有机固形物按100重量份计，所述组分(A)无卤环氧树脂的添加量为30～60重量份，例如32重量份、34重量份、36重量份、38重量份、40重量份、42重量份、44重量份、46重量份、48重量份、50重量份、52重量份、54重量份、56重量份、58重量份或60重量份。
优选地，除具有式(a)结构的环氧树脂外，所述组分(A)无卤环氧树脂还包括其他无卤环氧树脂，所述其他无卤环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、苯酚型酚醛环氧树脂、双酚A型酚醛环氧树脂、邻甲酚酚醛环氧树脂、双环戊二烯型环氧树脂、异氰酸酯型环氧树脂、含磷环氧树脂、Xylok型环氧树脂或联苯型环氧树脂中的至少任意一种或者至少两种的混合物。在本发明中，其他无卤环氧树脂占组分(A)无卤环氧树脂的重量百分比为0～50％。
优选地，所述其他无卤环氧树脂选自含磷环氧树脂。
在本发明中，具有式(a)结构的新型无卤环氧树脂的制备方法为：
在装有聚四氟乙烯搅拌器、温度计、冷凝回流器和氮气导入管的四口瓶(500mL)中，投入环氧当量为177g/eq左右的线性酚醛环氧树脂100份，加热到180-195℃，于190℃左右加入异氰酸酯当量为125g/eq的二苯基甲烷二异氰酸酯(MDI)15-20份，投入2-乙基4-甲基咪唑(促进剂)2份，于180-195℃反应12小时，不断取样用FT-IR直至确认异氰酸酯峰完全消失，停止搅拌加热，然后脱溶剂得到环氧当量为230-260g/eq，软化点为70-80℃的新型无卤环氧树脂。
以有机固形物按100重量份计，所述组分(B)酚醛固化剂在保证固化物拥 有优异的尺寸稳定性和耐热性的同时赋予了固化物优异的介电性能，添加量为10～35重量份，例如12重量份、14重量份、16重量份、18重量份、20重量份、22重量份、24重量份、26重量份、28重量份、30重量份、32重量份或34重量份。
优选地，所述组分(B)酚醛固化剂选自具有如下结构的酚醛树脂中的任意一种或者至少两种的混合物：
其中，X1、X2和X3各自独立地选自R1选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
Y1和Y2各自独立地选自单键、-CH2-、 中的任意一种，m为1～10的任意整数，例如2、3、4、5、6、7、8、9或10，R2选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种。
本发明中所述的组分(C)，即含磷阻燃剂，使无卤热固性树脂组合物具有阻燃特性，符合UL 94V-0要求。阻燃剂的添加量根据固化物阻燃性达到UL 94V-0级别要求而定，并没有特别的限制，优选地，以有机固形物按100重量份计，所述组分(C)含磷阻燃剂的添加量为5～30重量份，例如7重量份、9重量份、11重量份、13重量份、15重量份、17重量份、19重量份、21重量 份、23重量份、25重量份、27重量份、29重量份。
优选地，所述组分(C)含磷阻燃剂为三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、膦酸酯或聚膦酸酯中的任意一种或者至少两种的混合物。所述混合物例如三(2,6-二甲基苯基)膦和10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物的混合物，2,6-二(2,6-二甲基苯基)膦基苯和10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物的混合物，苯氧基磷腈化合物、磷酸酯和聚磷酸酯的混合物，三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯和聚磷酸酯的混合物。
以有机固形物按100重量份计，本发明所述的无卤热固性树脂组合物还可以包含0～5重量份的胺类固化剂，作为酚醛树脂的共固化剂不仅能提高固化物玻璃化转变温度(Tg)，还能改善加工性，同时加入胺类固化剂能促进酚醛固化剂与环氧树脂的反应，降低固化条件从而降低能耗提高生产效率。此外，胺类固化剂因含N元素拥有优异的粘合力，进一步提高固化物的粘合力，同时，胺类固化剂当量小，交联密度高，能提高固化物玻璃化转变温度(Tg)，从而进一步提高固化物的刚性以及尺寸稳定性。胺类固化剂的添加量为0～5重量份，例如0重量份、0.4重量份、0.8重量份、1.2重量份、1.6重量份、2.0重量份、2.4重量份、2.8重量份、3.2重量份、3.6重量份、4重量份、4.4重量份或4.8重量份。
优选地，所述的胺类固化剂为双氰胺(DICY)、二氨基二苯砜(DDS)、二氨基二苯醚(DDE)或二氨基二苯甲烷(DDM)中的任意一种或至少两种的 混合物。所述的混合物例如双氰胺和二氨基二苯砜的混合物、双氰胺和二氨基二苯醚的混合物、双氰胺和二氨基二苯甲烷的混合物、二氨基二苯砜和二氨基二苯醚的混合物。
本发明所述“有机固形物按100重量份计”是指的本发明所述无卤热固性树脂组合物中有机组分的固含量相加为100重量份。所述有机固形物的重量份数为树脂、固化剂和阻燃剂的固形物重量份数之和，所述填料和固化促进剂不计入有机固形物，本发明中，所述的无卤环氧树脂、酚醛固化剂、含磷阻燃剂、胺类固化剂、阻燃剂的固形物均计入本发明所述的有机固形物中。
优选地，本发明中所述的树脂组合物还包括填料，主要用来调整组合物的一些物性效果，如降低热膨胀系数(CTE)、降低吸水率和提高热导率等，以有机固形物按100重量份计，填料为0～200重量份，且不包括0；
优选地，所述填料选自有机填料或无机填料，优选无机填料，进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅。
优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物。
优选地，以无机填料质量为100％计，所述表面处理剂的用量为0.1～5.0％，优选0.5～3.0％，进一步优选0.75～2.0％。
优选地，所述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任意一种或者至少两种的混合物，优选熔融二氧化硅、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、云母或玻璃纤维粉中的任意一种或者至少两种的混合 物。所述混合物例如熔融二氧化硅和结晶型二氧化硅的混合物，球型二氧化硅和空心二氧化硅的混合物，氢氧化铝和氧化铝的混合物，滑石粉和氮化铝的混合物，氮化硼和碳化硅的混合物，硫酸钡和钛酸钡的混合物，钛酸锶、碳酸钙和硅酸钙的混合物，云母、玻璃纤维粉、熔融二氧化硅和结晶型二氧化硅的混合物，球型二氧化硅、空心二氧化硅、氢氧化铝和氧化铝的混合物，滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡和钛酸钡的混合物，钛酸锶、碳酸钙、硅酸钙、云母和玻璃纤维粉的混合物。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。所述混合物例如聚四氟乙烯粉末和聚苯硫醚的混合物，聚四氟乙烯粉末和聚醚砜粉末的混合物，聚苯硫醚和聚醚砜粉末的混合物，聚四氟乙烯粉末、聚苯硫醚和聚醚砜粉末的混合物。
优选地，最佳填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的中度值为1～10μm，位于此粒径段的填料具有良好的分散性。
优选地，以有机固形物按100重量份计，本发明所述填料的添加量为0～100重量份，且不包括0重量份，优选1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份、100重量份。
优选地，本发明中所述的树脂组合物还包括固化促进剂，使树脂固化并加快树脂固化速度。以有机固形物按100重量份计，所述固化促进剂的添加量为0.01～0.5重量份，例如0.02重量份、0.05重量份、0.08重量份、0.11重量份、0.14重量份、0.17重量份、0.2重量份、0.23重量份、0.26重量份、0.29重量份、0.32重量份、0.35重量份、0.38重量份、0.41重量份、0.44重量份或0.47 重量份。
优选地，所述固化促进剂选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物，优选2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或三苯基膦中的任意一种或至少两种的混合物。
优选地，所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
优选地，所述哌啶类化合物为2,3-二氨基哌啶、2,5-二氨基哌啶、2,6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4,4-二甲基哌啶中的任意一种或至少两种的混合物。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述无卤热固性树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述无卤热固性树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明无卤热固性树脂组合物的胶液的常规制备方法为：先将固形物放入，然后加入液态溶剂，搅拌至固形物完全溶解后，再加入液态树脂和固化促进剂，继续搅拌均匀即可，最后用溶剂调整溶液固体含量至65％-75％而制成胶液。
一种预浸料，包括增强材料及通过含浸干燥后附着其上的如上所述的无卤热固性树脂组合物。
本发明的预浸料是使用上述的无卤热固性树脂组合物加热干燥制得的，所 使用的基料为无纺织物或其它织物，例如天然纤维、有机合成纤维以及无机纤维。
使用上述胶液含浸玻璃布等增强材料，将含浸好的增强材料在155℃的烘箱中加热干燥4-8分钟制成预浸料。
一种层压板，其包括至少1张如上所述的预浸料。
一种覆金属箔层压板，其包括至少1张叠合的如上所述的预浸料、及压覆在叠合的预浸料一侧或两侧的金属箔，可经过加热加压成形而制得。即，本发明的覆金属箔层压板包括通过加热和加压使一张或一张以上的预浸料粘合在一起而制成的层压板，以及粘合在层压板一面或两面以上的金属箔。
示例性的覆金属箔层压板是使用上述的预浸料1片和2片0.5盎司(18μm厚度)的金属箔叠合在一起，通过热压机层压，从而压制成双面覆金属箔的层压板。所述的层压须满足以下要求：①层压的升温速率通常在料温80～120℃时应控制在1.5～2.5℃/min；②层压的压力设置，外层料温在120～150℃施加满压，满压压力为350psi左右；③固化时，控制料温在180℃，并保温90min。所述的金属箔为铜箔、镍箔、铝箔及SUS箔等，其材质不限。
一种印制电路板，其包括至少1张如上所述的预浸料。
与已有技术相比，本发明具有如下有益效果：
本发明采用特定结构的无卤环氧树脂为主体树脂，该无卤环氧树脂结构对称性高且含有五元杂环结构，除了拥有玻璃化转变温度较高、介电性能优异、高耐热性、阻燃好等优点外，还有着优异的尺寸稳定性和粘合力，用作主体树脂可以提高固化物的模量、尺寸稳定性以及粘合力。此外，该无卤环氧树脂含有N元素，与含磷阻燃剂有协同阻燃效果，能减少固化物阻燃性达到UL94V-0所需磷含量。
此外，本发明采用酚醛树脂作为固化剂，使得固化物拥有较高的刚性和耐热性，同时可以充分发挥因结构规整从而介电性能优异优势。
而且，本发明的无卤热固性树脂组合物还可以加入胺类固化剂，胺类固化剂因含N元素拥有优异的粘合力，进一步提高固化物的粘合力，同时，胺类固化剂当量小，交联密度高，能提高固化物玻璃化转变温度(Tg)，从而进一步提高固化物的刚性以及尺寸稳定性。
综上，使用该无卤热固性树脂组合物制成的预浸料和层压板具有优异的尺寸稳定性和介电性能、高粘合力、高耐热性、低吸水率以及良好的工艺加工性，并能实现无卤阻燃，达到UL94 V-0。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
针对上述制成的印制电路用层压板(1片预浸料)测试其玻璃化转变温度、尺寸稳定性、介电常数、介电损耗因素、剥离强度、耐热性、吸水性、阻燃性等性能，如下实施例进一步详细说明与描述。
请参阅制备例1、实施例1-7和比较例1-6。
制备例1具有式(a)结构的新型无卤环氧树脂的制备
在装有聚四氟乙烯搅拌器、温度计、冷凝回流器和氮气导入管的四口瓶(500mL)中，投入环氧当量为177g/eq左右的线性酚醛环氧树脂100份，加热到180-195℃，于190℃左右加入异氰酸酯当量为125g/eq的二苯基甲烷二异氰酸酯(MDI)15-20份，投入2-乙基4-甲基咪唑(促进剂)2份，于180-195℃反应12小时，不断取样用FT-IR直至确认异氰酸酯峰完全消失，停止搅拌加热，然后脱溶剂得到环氧当量为230-260g/eq，软化点为70-80℃的新型无卤环氧树脂。
兹将本发明实施例详细说明如下，但本发明并非局限在实施例范围。下文中无特别说明，其份代表重量份，其％代表“重量％”。
(A)无卤环氧树脂
(A-1)新型无卤环氧树脂(制备方法见上，结构见权利要求1，环氧当量：246g/eq)
(A-2)线性酚醛环氧树脂KEP-1138(韩国KOLON商品名)
(A-3)双环戊二烯型环氧树脂HP-7200H(大日本油墨商品名)
(A-4)异氰酸酯改性环氧树脂XZ-97103(美国DOW商品名)
(B)酚醛树脂
(B-1)双环戊二烯型酚醛树脂PD9110(中国台湾长春商品名)
(B-2)联苯型酚醛树脂MEH-7851H(日本明和商品名)
(B-3)线性酚醛树脂
(C)胺类固化剂
(C-1)双氰胺DICY(宁夏大荣商品名)
(C-2)二氨基二苯砜(中国台湾寅生商品名)
(D)含磷阻燃剂
XZ92741(美国DOW商品名)
(E)2-苯基咪唑(日本四国化成)
(F)填料
球型硅微粉(平均粒径为1至10μm，纯度99％以上)
表1、各实施例和比较例的配方组成及其物性数据
表2、各实施例比较例的配方组成及其物性数据
以上特性的测试方法如下：
(a)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(b)尺寸稳定性
按照IPC-TM-650 2.4.39方法进行测定，分别测量样品A态尺寸和处理后的尺寸，计算经纬向尺寸变化率。样品处理条件：2h/150℃。
(c)介电常数、介电损耗因素
根据使用条状线的共振法，按照IPC-TM-650 2.5.5.5测定1GHz下的介电损耗、介电损耗因素。
(d)剥离强度
按照IPC-TM-650 2.4.8方法中的“热应力后”的实验条件，测试金属盖层 的剥离强度。
(e)吸水性
按照IPC-TM-650 2.6.2.1方法进行测定。
(f)耐浸焊性
按照IPC-TM-650 2.4.13.1观察分层起泡时间。
(g)难燃烧性
依据UL 94垂直燃烧法测定。
从表1和表2的物性数据可知，比较例1中使用特种酚醛固化剂与胺类固化剂复合固化线性酚醛环氧时介电常数和介电损耗较高，且剥离强度偏低；比较例2采用特种酚醛固化剂与胺类固化剂复合固化双环戊二烯型酚醛环氧，所制成的覆铜板尺寸稳定性较差，剥离强度较低，且阻燃只能达到ULV-1级；比较例3采用特种酚醛固化剂和胺类固化剂复合固化异氰酸酯改性环氧，所制得的覆铜板介电性能和尺寸稳定性均较差；比较例4中采用普通线性酚醛固化剂与胺类固化剂复合固化无卤环氧树脂，所制得的覆铜板介电性能较差，难以满足消费电子轻薄短小的要求；比较例5采用双环戊二烯型酚醛固化剂与胺类固化剂复合固化环氧树脂，其中新型无卤环氧树脂占环氧树脂比例低于50％，所制得的覆铜板尺寸稳定性和介电性能稍差；比较例6采用双环戊二烯型酚醛树脂和胺类固化剂复合固化大量新型无卤环氧树脂，新型无卤环氧比例超过70重量份，所制成的覆铜板尺寸稳定性和介电性能均一般，吸水率稍高，且阻燃有所不足，难以达到V-0级。
实施例1-7，采用特种酚醛固化剂或与胺类固化剂复合固化环氧树脂，所制得的覆铜板拥有较高的玻璃化转变温度、优异的尺寸稳定性和介电性能、高剥离强度和高耐热性，并能实现无卤阻燃，达到UL94 V-0。
如上所述，与一般的无卤层压板相比，本发明的印制电路用层压板具有更优异的尺寸稳定性和介电性能、高粘合力、高耐热性、低吸水率以及良好工艺加工性，适用于高密度互联领域。另外本发明卤素含量在JPCA无卤标准要求范围内能达到难燃性试验UL94中的V-0标准，有环保的功效。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (31)

1.一种无卤热固性树脂组合物，以有机固形物按100重量份计，包括如下组分：
(A)无卤环氧树脂：30-60重量份；
(B)酚醛固化剂：10-35重量份；
(C)含磷阻燃剂；
所述无卤环氧树脂包括具有式(a)结构的环氧树脂：
其中，T1和T2分别各自独立地为氢原子、式(Ⅰ)或式(Ⅱn)所示的结构，n1和n3表示重复单元，均独立地为1以上的整数，n2表示重复单元，为0以上的整数；
n4表示重复单元，为1以上的整数；
式(Ⅱn)中，Tn和Tn’分别各自独立地为氢原子或式(Ⅰ)所示的结构，且以氢原子或式(I)的结构封端；n5和n6表示重复单元，均独立地为0以上的整数，n7表示重复单元，为1以上的整数；
所述具有式(a)结构的环氧树脂分子量为1000～20000；
所述具有式(a)结构的环氧树脂占组分(A)无卤环氧树脂的重量百分比为50％以上；
所述组分(B)酚醛固化剂选自具有如下结构的酚醛树脂中的任意一种或者至少两种的混合物：
其中，X1、X2和X3各自独立地选自R1选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
Y1和Y2各自独立地选自 中的任意一种，m为1～10的任意整数，R2选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种。
2.如权利要求1所述的无卤热固性树脂组合物，除具有式(a)结构的环氧树脂外，所述组分(A)无卤环氧树脂还包括其他无卤环氧树脂，所述其他无卤环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、苯酚型酚醛环氧树脂、双酚A型酚醛环氧树脂、邻甲酚酚醛环氧树脂、双环戊二烯型环氧树脂、异氰酸酯型环氧树脂、含磷环氧树脂、Xylok型环氧树脂或联苯型环氧树脂中的至少任意一种或者至少两种的混合物。
3.如权利要求2所述的无卤热固性树脂组合物，其特征在于，所述其他无卤环氧树脂选自含磷环氧树脂。
4.如权利要求1-3之一所述的无卤热固性树脂组合物，其特征在于，以有机固形物按100重量份计，所述组分(C)含磷阻燃剂的添加量为5～30重量份。
5.如权利要求1-3之一所述的无卤热固性树脂组合物，其特征在于，所述组分(C)含磷阻燃剂为三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、膦酸酯或聚膦酸酯中的任意一种或者至少两种的混合物。
6.如权利要求1-3之一所述的无卤热固性树脂组合物，其特征在于，以有机固形物按100重量份计，所述无卤热固性树脂组合物还包含0～5重量份的胺类固化剂。
7.如权利要求6所述的无卤热固性树脂组合物，其特征在于，所述的胺类固化剂为双氰胺、二氨基二苯砜、二氨基二苯醚或二氨基二苯甲烷中的任意一种或至少两种的混合物。
8.如权利要求1-3之一所述的热固性树脂组合物，其特征在于，所述无卤热固性树脂组合物还包括填料，以有机固形物按100重量份计，填料为0～200重量份，且不包括0。
9.如权利要求8所述的无卤热固性树脂组合物，其特征在于，所述填料选自有机填料或无机填料。
10.如权利要求8所述的无卤热固性树脂组合物，其特征在于，所述填料选自无机填料。
11.如权利要求8所述的无卤热固性树脂组合物，其特征在于，所述填料选自经过表面处理的无机填料。
12.如权利要求8所述的无卤热固性树脂组合物，其特征在于，所述填料为经过表面处理的二氧化硅。
13.如权利要求11或12所述的无卤热固性树脂组合物，其特征在于，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物。
14.如权利要求13所述的无卤热固性树脂组合物，其特征在于，以无机填料质量为100％计，所述表面处理剂的用量为0.1～5.0％。
15.如权利要求13所述的无卤热固性树脂组合物，其特征在于，以无机填料质量为100％计，所述表面处理剂的用量为0.5～3.0％。
16.如权利要求13所述的无卤热固性树脂组合物，其特征在于，以无机填料质量为100％计，所述表面处理剂的用量为0.75～2.0％。
17.如权利要求9-11之一所述的无卤热固性树脂组合物，其特征在于，所述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任意一种或者至少两种的混合物。
18.如权利要求9-11之一所述的无卤热固性树脂组合物，其特征在于，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、云母或玻璃纤维粉中的任意一种或者至少两种的混合物。
19.如权利要求9所述的无卤热固性树脂组合物，其特征在于，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。
20.如权利要求8所述的无卤热固性树脂组合物，其特征在于，所述填料为二氧化硅，填料的粒径中度值为1～15μm。
21.如权利要求20所述的无卤热固性树脂组合物，其特征在于，所述填料的粒径中度值为1～10μm。
22.如权利要求8所述的无卤热固性树脂组合物，其特征在于，以有机固形物按100重量份计，所述无卤热固性树脂组合物中，所述填料的添加量为0～100重量份，且不包括0重量份。
23.如权利要求1-3之一所述的无卤热固性树脂组合物，其特征在于，所述无卤热固性树脂组合物还包括固化促进剂。
24.如权利要求23所述的无卤热固性树脂组合物，其特征在于，以组分(A)、组分(B)和组分(C)的添加量之和为100重量份计，所述固化促进剂的添加量为0.01～0.5重量份。
25.如权利要求23所述的无卤热固性树脂组合物，其特征在于，所述固化促进剂选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物。
26.如权利要求25所述的无卤热固性树脂组合物，其特征在于，所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
27.如权利要求25所述的无卤热固性树脂组合物，其特征在于，所述哌啶类化合物为2,3-二氨基哌啶、2,5-二氨基哌啶、2,6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4,4-二甲基哌啶中的任意一种或至少两种的混合物。
28.如权利要求23所述的无卤热固性树脂组合物，其特征在于，所述固化促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或三苯基膦中的任意一种或至少两种的混合物。
29.一种预浸料，包括增强材料及通过含浸干燥后附着其上的如权利要求1-28之一所述的无卤热固性树脂组合物。
30.一种层压板，其包括至少1张如权利要求29所述的预浸料。
31.一种印制电路板，其包括至少1张如权利要求29所述的预浸料。
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JP6752886B2 (ja) 2020-09-09
TW201734125A (zh) 2017-10-01
KR101894682B1 (ko) 2018-09-04
CN107227001A (zh) 2017-10-03
WO2017161843A1 (zh) 2017-09-28
EP3412722A1 (en) 2018-12-12
US20180086895A1 (en) 2018-03-29
ES2856079T3 (es) 2021-09-27
EP3412722B1 (en) 2021-01-20
JP2018538391A (ja) 2018-12-27
TWI598403B (zh) 2017-09-11
KR20170121145A (ko) 2017-11-01

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