CN110551257A - 树脂组合物及其预浸渍片、金属箔积层板和印刷电路板 - Google Patents

树脂组合物及其预浸渍片、金属箔积层板和印刷电路板 Download PDF

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Publication number
CN110551257A
CN110551257A CN201910389847.6A CN201910389847A CN110551257A CN 110551257 A CN110551257 A CN 110551257A CN 201910389847 A CN201910389847 A CN 201910389847A CN 110551257 A CN110551257 A CN 110551257A
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Prior art keywords
resin composition
metal foil
composition according
group
polyphenylene ether
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CN201910389847.6A
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CN110551257B (zh
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刘淑芬
洪金贤
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Taiwan Union Technology Corp
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Taiwan Union Technology Corp
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Abstract

一种树脂组合物及其预浸渍片、金属箔积层板和印刷电路板，其中树脂组合物，包含：(A)具有不饱和官能基的聚苯醚树脂；以及(B)具下式(I)的第一交联剂：

Description

树脂组合物及其预浸渍片、金属箔积层板和印刷电路板
技术领域
本发明是关于一种树脂组合物，特别是关于一种含有经二苯基膦氧改质的二烯丙基异氰酸酯作为交联剂的无卤素难燃性树脂组合物。本发明树脂组合物可与补强材构成复合材料或预浸渍片(prepreg)，或可进一步作为金属箔的接着剂，制备背胶铜箔(resin-coated copper，RCC)、金属箔积层板(metal-clad laminate)、印刷电路板(printedcircuit board，PCB)等。
背景技术
近来，在电子通讯技术领域中对于资料传输量的需求不断增加，使得电子产品的应用进入高频及高速传输领域，目前多使用聚苯醚树脂系积层板来满足高频高速传输的需求。另外，随着环保意识抬头，在电子材料中使用的含卤素的阻燃剂逐渐被淘汰，取而代之的是无卤素阻燃剂，例如金属氢氧化物、含氮化合物、含磷化合物等。
关于聚苯醚树脂系积层板的制备，通常会将聚苯醚树脂搭配使用三烯丙基异氰酸酯(triallyl isocyanurate，TAIC)或三烯丙基氰酸酯(triallyl cyanurate，TAC)的单体化合物作为交联剂。然而，TAIC与TAC的沸点低(约145℃，低于预浸渍片的半固化工艺温度)，容易在积层板的制造过程中自树脂组合物配方中挥发，造成配方失真，进而导致最终所得到的电子材料特性异常。
针对上述问题，专利文献US 9,809,690提供一种解决方案，其中将TAIC或TAC聚合成高分子颗粒，再以填料的型式将这些高分子颗粒添加至树脂组合物中，以此解决TAIC或TAC单体易于积层板的制造过程中挥发的问题。然而，为了达到充分的交联效果，必须添加相当量的TAIC或TAC高分子颗粒填料，此连同其他常用填料(如SiO2)一同构成树脂组合物中的填料成分，造成树脂组合物所含填料比例过高，而衍生其他负面影响，其中包括树脂组合物的动黏度(DV)过高，导致在压合操作时的流动性不佳，导致所制得的积层板的外观不良，另外也会导致介电层与铜箔的接着力变差。
因此，目前仍亟需一种能够解决TAIC或TAC单体挥发性过高且不会衍生上述不利影响的技术方案。
发明内容
有鉴于上述技术问题，本发明提供一种树脂组合物，包含具有不饱和官能基的聚苯醚树脂以及经二苯基膦氧(diphenyl phosphine oxide，DPPO)改质的二烯丙基异氰酸酯(本文也称“DPPO-DAIC”)作为交联剂。本发明树脂组合物能够解决“三烯丙基异氰酸酯(TAIC)”交联剂容易挥发的问题，且所制得的树脂组合物具有良好流动性而特别适用于树脂组合物须使用高含量填料的情形，所制得的金属箔积层板具有良好外观平整性以及铜箔接着强度。
因此，本发明的一个目的在于提供一种树脂组合物，包含：
(A)具有不饱和官能基的聚苯醚树脂；以及
(B)具下式(I)的第一交联剂：
于本发明的部分实施方案中，聚苯醚树脂(A)如下式(II)所示：
其中，
R31、R32、R33、R34各自独立为氢、经取代或未经取代的C1至C5烷基；
m与n各自独立为0至100的整数，但m与n不同时为0；
Z为不存在、芳基、－O－、其中R35、R36各自独立为氢或C1至C12烷基；
X与Y各自独立为不存在、羰基(carbonyl group)或具有烯基的基团；以及
A1与A2各自独立为
于本发明的部分实施方案中，聚苯醚树脂(A)对第一交联剂(B)的重量比为13：1至1：1。
于本发明的部分实施方案中，树脂组合物还包含一含乙烯基的弹性体。该含乙烯基的弹性体可例如选自以下群组：聚丁二烯(polybutadiene)、苯乙烯丁二烯共聚物(styrene-butadiene(SB)copolymer)、苯乙烯丁二烯苯乙烯嵌段共聚物(styrene-butadiene-styrene(SBS)block copolymer)、聚异戊二烯(polyisoprene)、苯乙烯异戊二烯共聚物、苯乙烯异戊二烯苯乙烯嵌段共聚物(styrene-isoprene-styrene(SIS)blockcopolymer)、丙烯腈丁二烯共聚物、丙烯腈丁二烯苯乙烯嵌段共聚物及前述的组合。
于本发明的部分实施方案中，树脂组合物还包含选自以下群组的添加型含磷阻燃剂：次磷酸金属盐(phosphinate)、聚磷酸盐(polyphosphate)、鏻盐(phosphonium salt)、磷酸酯(phosphate ester)、磷腈(phosphazene)、亚磷酸酯(phosphite ester)、膦氧化物(phosphine oxide)及前述的组合。
于本发明的部分实施方案中，树脂组合物还包含选自以下群组的填料：二氧化硅、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氮化硅、碳化铝硅、碳化硅、碳酸钠、碳酸镁、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、石墨烯、钛酸钾、钛酸锶、钛酸钡、陶瓷纤维、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧高岭土、白岭土、云母、勃姆石、水滑石、奈米碳管、聚四氟乙烯(PTFE)粉体、中空玻璃珠、奈米级无机粉体及前述的组合。
于本发明的部分实施方案中，树脂组合物还包含选自以下群组的(C)第二交联剂：多官能型烯丙基化合物(polyfunctional allylic compound)、多官能型丙烯酸酯(polyfunctional acrylate)、多官能型丙烯酰胺(polyfunctional acrylamide)、多官能型苯乙烯化合物(polyfunctional styrenic compound)、双马来酰亚胺化合物(bismaleimide compound)及前述的组合。更特定言之，第二交联剂(C)是双马来酰亚胺化合物。
本发明的另一目的在于提供一种预浸渍片，其是将一基材含浸或涂布如上所述的树脂组合物，并干燥该经含浸或涂布的基材而制得。
本发明的又一目的在于提供一种金属箔积层板，其是通过将如上所述的预浸渍片与金属箔加以层合而制得，或是通过将如上所述的树脂组合物涂布于金属箔并干燥该经涂布的金属箔而制得。
本发明的再一目的在于提供一种印刷电路板，其是由如上所述的金属箔积层板所制得。
为使本发明的上述目的、技术特征及优点能还明显易懂，下文以部分具体实施方案进行详细说明。
具体实施方式
以下将具体地描述根据本发明的部分具体实施方案；但是，在不背离本发明的精神下，本发明还可以多种不同形式的方案来实践，不应将本发明保护范围限于所述具体实施方案。
除非文中有另外说明，于本说明书中(尤其是在权利要求书中)所使用的“一”、“该”及类似用语应理解为包含单数及复数形式。
除非文中有另外说明，于本说明书中描述溶液、混合物或组合物中所含的成分时，以固含量(dry weight)计算，即，未纳入溶剂的重量。
除非另有说明，于本说明书中(尤其是在权利要求书中)，所使用的“第一”、“第二”及类似用语仅是用于区隔所描述的元件或成分，本身并无特殊涵义，且非意欲指代先后顺序。
本发明对照现有技术的功效在于，本发明树脂组合物是以经二苯基膦氧改质的二烯丙基异氰酸酯(DPPO-DAIC)作为交联剂，不仅能够解决三烯丙基异氰酸酯(TAIC)交联剂容易挥发的问题，同时能保持树脂组合物在高填料含量情况下仍保有良好流动性，所制得的金属箔积层板具有优异平整性。现以部分实施方案说明本发明相关技术特征及功效如下。
1.树脂组合物
本发明树脂组合物是包含具有不饱和官能基的聚苯醚树脂(A)以及具式(I)的第一交联剂(B)等必要成分，以及其他视需要的选用成分。各成分的详细说明如下。
1.1.聚苯醚树脂(A)
本文中，聚苯醚树脂是指在分子主链中至少具有重复单元且在末端具有不饱和官能基的树脂，其中R各自独立为氢或C1至C5的烷基，且v为1至100的整数。所述不饱和官能基是指能够与其他具有不饱和官能基的成分发生加成聚合反应的基团，而所述加成聚合反应可于存在有聚合引发剂的情况下通过光或热而引发。不饱和官能基的实例包括但不限于乙烯基(vinyl)、乙烯苄基(vinyl benzyl)、烯丙基(allyl)、丙烯酰基(acryloyl)、丙烯酸酯基(acrylic)及甲基丙烯酸酯基(methacrylic)。具有不饱和官能基的聚苯醚树脂的实例包括但不限于含乙烯基的聚苯醚树脂、含烯丙基的聚苯醚树脂、含乙烯苄基的聚苯醚树脂、含丙烯酰基的聚苯醚树脂、含丙烯酸酯基的聚苯醚树脂及含甲基丙烯酸酯基的聚苯醚树脂。各具有不饱和官能基的聚苯醚树脂可单独使用或任意组合使用。
具有不饱和官能基的聚苯醚树脂的制备方式并非本发明的技术重点，且本发明所属技术领域普通技术人员基于本说明书的记载与所具备的现有知识能够得知，于此不加赘述。具有不饱和官能基的聚苯醚树脂的相关制备方式文献可列举美国专利第US 6,995,195B2号(含乙烯基的聚苯醚树脂)、美国专利第US 5,218,030 A号(含烯丙基的聚苯醚树脂)、美国专利第US 5,352,745 A号(含甲基丙烯酸酯基的聚苯醚树脂)、美国专利第US 6,352,782 B2号及美国专利申请案早期公开第US 2016/0280913 A1号，这些文献全文并于此以供参考。
于本发明的部分实施方案中，聚苯醚树脂(A)如下式(II)所示：
于式(II)中，R31、R32、R33、R34各自独立为氢、经取代或未经取代的C1至C5烷基；m与n各自独立为0至100的整数，但m与n不同时为0；Z为不存在、芳基、－O－、其中R35、R36各自独立为氢或C1至C12烷基；X与Y各自独立为不存在、羰基(carbonyl group)或具有烯基的基团；以及A1与A2各自独立为
于本发明树脂组合物中，具有不饱和官能基的聚苯醚树脂(A)的重量平均分子量(weight average molecular weight，Mw)可为1000至50,000，较佳为1000至10,000，更佳为1000至5000。若聚苯醚树脂的Mw大于上述范围，则树脂组合物的流动性、溶解度等性质可能变差，造成后续加工困难。反之，若聚苯醚树脂的Mw低于上述范围，则树脂组合物的电学性质及尺寸稳定性可能变差。
1.2.第一交联剂(B)
本文中，交联剂是指具有不饱和官能基而能够与聚苯醚树脂发生交联反应以形成立体网状结构的成分，不饱和官能基的定义同前文所述。于本发明树脂组合物中，是使用下式(I)的第一交联剂作为必要成分：
式(I)的第一交联剂是一种经二苯基膦氧(DPPO)改质的二烯丙基异氰酸酯(DAIC)，其合成方式将于后附实施例进一步说明。DPPO-DAIC不存在现有TAIC或TAC单体的挥发性过高的问题，因此在积层板的制造过程中不会因成分挥发而产生树脂组合物的成分配比失真的情形。
另外，DPPO-DAIC本身也可提供阻燃剂的功能，在适当添加量下可赋予树脂组合物所制电子材料良好阻燃性。由于DPPO-DAIC属反应型阻燃剂，可避免一般添加型阻燃剂在所制电子材料中常发生的相分离或迁移至材料表面等问题。
于本发明树脂组合物中第一交联剂(B)的用量并无特殊限制，可由本发明所属技术领域中视需要调整。惟，为充分发挥聚苯醚树脂本身的性质并提供充分交联效果，第一交联剂(B)的用量较佳使得聚苯醚树脂(A)对第一交联剂(B)的重量比为13：1至1：1，例如12：1、11：1、10：1、9：1、8：1、7：1、6：1、5：1、4：1、3：1、或2：1。
1.3.其他视需要的选用成分
于本发明树脂组合物中，可视需要进一步包含其他选用成分，例如下文将例举说明的含乙烯基的弹性体、添加型含磷阻燃剂、填料、第二交联剂及本领域所现有的添加剂，以适应性改良树脂组合物在制造过程中的可加工性，或改良树脂组合物所制电子材料的物化性质。本领域所现有的添加剂包括但不限于聚合引发剂及固化促进剂。
1.3.1.含乙烯基的弹性体
于本文中，弹性体指具有黏弹性而可赋予电子材料韧性(toughness)的聚合物。于本发明的部分实施方案中，树脂组合物进一步包括含乙烯基的弹性体，含乙烯基的弹性体可与其他具有不饱和官能基的成分发生交联反应，使所制电子材料具有较佳韧性及较低的Dk值与Df值。
一般而言，含乙烯基的弹性体是通过使具有碳-碳不饱和键的单体的重复单元聚合而形成，且聚合物的分子主链上、支链上或末端基团存在有悬挂乙烯基(pendentvinyl)，其中悬挂乙烯基的含量(pendent vinyl content)通常以百分比表示，较佳为大于10％，更佳为大于50％。
含乙烯基的弹性体可例举由共轭二烯类单体化合物(conjugated-diene monomercompound)所聚合而成的同元聚合物以及由共轭二烯类单体化合物与其他单体共聚而成的共聚合物，其Mw可为200至100,000，较佳为1000至5000，更佳为1000至3000。共轭二烯类单体化合物的实例包括丁二烯及异戊二烯，且其他单体的实例包括苯乙烯及马来酸酐。
含乙烯基的弹性体的实例包括但不限于聚丁二烯(polybutadiene)、苯乙烯丁二烯共聚物(styrene-butadiene(SB)copolymer)、苯乙烯丁二烯苯乙烯嵌段共聚物(styrene-butadiene-styrene(SBS)block copolymer)、聚异戊二烯(polyisoprene)、苯乙烯异戊二烯共聚物、苯乙烯异戊二烯苯乙烯嵌段共聚物(styrene-isoprene-styrene(SIS)block copolymer)、丙烯腈丁二烯共聚物及丙烯腈丁二烯苯乙烯嵌段共聚物。各含乙烯基的弹性体可单独使用或任意组合使用。
商业上可购得的含乙烯基的弹性体包括可购自克雷威利(Cray Valley)的型号为Ricon 100、Ricon 181、Ricon 184、Ricon 104H、Ricon 250、Ricon257、Ricon 157、Ricon130、Ricon 130MA、Ricon 184MA的产品，可购自日本曹达(Nippon Soda)的型号为B3000产品，以及可购自壳牌石油(Shell Oil)的型号为Kraton DX1300产品。
于本发明树脂组合物中，具有不饱和官能基的聚苯醚树脂(A)对含乙烯基的弹性体的重量比例较佳为9：1至1：1，例如8：1、7：1、6：1、5：1、4：1、3：1或2：1。若含乙烯基的弹性体的重量比例过高(例如高于所述较佳比例范围)，可能导致所制电子材料的耐热性及尺寸稳定性变差；反之，若含乙烯基的弹性体的重量比例过低(例如低于所述较佳比例范围)，则含乙烯基的弹性体可能无法提供所需要的增韧功效，导致所制电子材料的物理性质变差。
1.3.2.添加型含磷阻燃剂
本发明树脂组合物可视需要进一步包含添加型含磷阻燃剂，也即不具有反应性不饱和官能基的含磷化合物，其中为符合本发明树脂组合物的无卤素需求，该添加型含磷阻燃剂应为无卤素阻燃剂。添加型含磷阻燃剂的实例包括但不限于次磷酸金属盐(phosphinate)、聚磷酸盐(polyphosphate)、鏻盐(phosphonium salt)、磷酸酯(phosphateester)、磷腈(phosphazene)、亚磷酸酯(phosphite ester)、膦氧化物(phosphine oxide)及前述的组合。
次磷酸盐的实例包括但不限于二烷基次磷酸铝、三(二乙基次磷酸)铝、三(甲基乙基次磷酸)铝、三(二苯基次磷酸)铝、双(二乙基次磷酸)锌、双(甲基乙基次磷酸)锌、双(二苯基次磷酸)锌、双(二乙基次磷酸)氧钛、双(甲基乙基次磷酸)氧钛及双(二苯基次磷酸)氧钛。商业上可购得的次磷酸盐包括可购自科莱恩(CLARIANT)的型号为OP-935的产品。
聚磷酸盐的实例包括但不限于聚磷酸蜜胺(melamine polyphosphate)、聚磷酸蜜白胺(melam polyphosphate)及聚磷酸蜜勒胺(melem polyphosphate)。商业上可购得的聚磷酸盐包括可购自巴斯夫(BASF)的型号为Melapur 200的产品。
鏻盐的实例包括但不限于四苯基鏻四苯基硼酸盐(tetraphenylphosphoniumtetraphenylborate)。磷酸酯的实例包括但不限于缩合磷酸酯化合物以及环状磷酸酯化合物。缩合磷酸酯化合物的实例包括但不限于磷酸三苯酯(triphenyl phosphate)、磷酸三甲苯酯(tricresyl phosphate)、磷酸二甲苯二苯酯(xylenyl-diphenyl phosphate)、磷酸甲苯二苯酯(cresyl-diphenyl phosphate)、间苯二酚双-二甲苯基磷酸酯(resorcinol bis-xylenylphosphate，RXP)、间苯二酚双-二苯基磷酸酯(resorcinol bis-diphenylphosphate，RDP)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide，DOPO)。商业上可购得的磷酸酯包括可购自大八化学的型号为PX-200及PX-202的产品，以及可购自恒桥产业的型号为CG-686及CG-RDP的产品。
磷腈包括环状磷腈化合物及直链状磷腈化合物。商业上可购得的磷腈包括可购自大冢化学的型号为BP-PZ、SPB-100及SPH-100的产品。亚磷酸酯的实例包括但不限于亚磷酸三甲酯(trimethylphosphite)及亚磷酸三乙酯(triethylphosphite)。膦氧化物的实例包括但不限于三-(4-甲氧基苯基)膦氧(tris-(4-methoxyphenyl)phosphine oxide)、三苯基膦氧(triphenyl phosphine oxide)、二苯基膦氧(diphenyl phosphine oxide)及其衍生物。商业上可购得的膦氧化物包括可购自晋一化工的型号为PQ-60的产品，以及可购自片山化学的型号为BPO-13与BPE-3的产品。
1.3.3.填料
本发明树脂组合物可视需要进一步包含填料以改善所制得电子材料的机械强度、导热性及尺寸稳定性。合适的填料的实例包括但不限于选自以下群组的填料：二氧化硅(例如球型二氧化硅、熔融态二氧化硅、非熔融态二氧化硅、多孔质二氧化硅或中空二氧化硅)、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氮化硅、碳化铝硅、碳化硅、碳酸钠、碳酸镁、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、石墨烯、钛酸钾、钛酸锶、钛酸钡、陶瓷纤维、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧高岭土、白岭土、云母、勃姆石、水滑石、奈米碳管、聚四氟乙烯(PTFE)粉体、中空玻璃珠及奈米级无机粉体。前述填料可单独使用或任意组合使用，且可于添加至树脂组合物之前先以偶合剂(例如硅烷偶合剂)进行表面改质，以增加填料与树脂组合物其他成分的相容性及树脂组合物的可加工性。于后附实施例中，是使用钛酸锶、二氧化钛或二氧化硅。
1.3.4.第二交联剂
本发明树脂组合物可视需要进一步包含其他不饱和官能基交联剂，本文也称“第二交联剂”。第二交联剂可为任何现有的具有不饱和官能基而能够与聚苯醚树脂(A)发生交联反应的成分，但是考量材料挥发性，第二交联剂较佳不包含三烯丙基异氰尿酸酯(TAIC)或三烯丙基氰尿酸酯(TAC)。
第二交联剂的实例包括但不限于多官能型烯丙基系化合物、多官能型丙烯酸酯、多官能型苯乙烯系化合物、双马来酰亚胺化合物、及多官能型丙烯酰胺。前述各多官能型交联剂可单独使用或任意组合使用。
多官能型烯丙基系化合物是指含有至少二个烯丙基的化合物。多官能型烯丙基系化合物的实例包括但不限于二烯丙基邻苯二甲酸酯(diallyl phthalate)、二烯丙基间苯二甲酸酯(diallyl isophthalate)、三烯丙基偏苯三甲酸酯(triallyl trimellitate)、三烯丙基均苯三甲酸酯(triallyl mesate)及前述化合物的预聚物。
多官能型丙烯酸酯是指含有至少两个丙烯酸酯基的化合物。多官能型丙烯酸酯的实例包括但不限于三羟甲基丙烷三(甲基)丙烯酸酯(trimethylolpropane tri(meth)acrylate)、1,6-己二醇二(甲基)丙烯酸酯(1,6-hexanediol di(meth)acrylate)、乙二醇二(甲基)丙烯酸酯(ethyleneglycol di(meth)acrylate)、丙二醇二(甲基)丙烯酸酯(propyleneglycol di(meth)acrylate)、1,3-丁二醇二(甲基)丙烯酸酯(1,3-butanedioldi(meth)acrylate)、1,4-丁二醇二(甲基)丙烯酸酯(1,4-butanediol di(meth)acrylate)、环己烷二甲醇二(甲基)丙烯酸酯(cyclohexane dimethanol di(methyl)acrylate)、二乙二醇二(甲基)丙烯酸酯(diethylene glycol di(meth)acrylate)、三乙二醇二(甲基)丙烯酸酯(triethylene glycol di(meth)acrylate)及含有前述化合物的预聚物。
多官能型苯乙烯系化合物是指在芳香环上连接有至少两个烯基(alkenyl)的化合物。多官能型苯乙烯系化合物的实例包括但不限于1,3-二乙烯基苯(1,3-divinylbenzene)、1,4-二乙烯基苯(1,4-divinylbenzene)、三乙烯基苯(trivinylbenzene)、1,3-二异丙烯基苯(1,3-diisopropenylbenzene)、1,4-二异丙烯基苯(1,4-diisopropenylbenzene)、1,2-双(对乙烯基苯基)乙烷(1,2-bis(p-vinylphenyl)ethane)、1,2-双(间乙烯基苯基)乙烷(1,2-bis(m-vinylphenyl)ethane)、1-(对乙烯基苯基)-2-(间乙烯基苯基)乙烷(1-(p-vinylphenyl)-2-(m-vinylphenyl)-ethane)、1,4-双(对乙烯基苯基乙基)苯(1,4-bis(p-vinylphenylethyl)benzene)、1,4-双(间乙烯基苯基乙基)苯(1,4-bis(m-vinylphenylethyl)benzene)、1,3-双(对乙烯基苯基乙基)苯(1,3-bis(p-vinylphenylethyl)benzene)、1,3-双(间乙烯基苯基乙基)苯(1,3-bis(m-vinylphenylethyl)benzene)、1-(对乙烯基苯基乙基)-4-(间乙烯基苯基乙基)苯(1-(p-vinylphenylethyl)-4-(m-vinylphenylethyl)benzene)、1-(对乙烯基苯基乙基)-3-(间乙烯基苯基乙基)苯(1-(p-vinylphenylethyl)-3-(m-vinylphenylethyl)benzene)及含有前述化合物的预聚物。
双马来酰亚胺化合物是指具有至少两个马来酰亚胺官能基(maleimidefunctional group)的化合物。双马来酰亚胺化合物的具体实例包括但不限于1,2-双马来酰亚胺基乙烷、1,6-双马来酰亚胺基己烷、1,3-双马来酰亚胺基苯、1,4-双马来酰亚胺基苯、2,4-双马来酰亚胺基甲苯、4,4'-双马来酰亚胺基二苯基甲烷、4,4'-双马来酰亚胺基二苯基醚、3,3'-双马来酰亚胺基二苯基砜、4,4'-双马来酰亚胺基二苯基砜、4,4'-双马来酰亚胺基二环己基甲烷、3,5-双(4-马来酰亚胺基苯基)吡啶、2,6-双马来酰亚胺基吡啶、1,3-双(马来酰亚胺基甲基)环己烷、1,3-双(马来酰亚胺基甲基)苯、1,1-双(4-马来酰亚胺基苯基)环己烷、1,3-双(二氯马来酰亚胺基)苯、4,4'-双柠康酰亚胺基二苯基甲烷(4,4'-biscitraconimidodiphenylmethane)、2,2-双(4-马来酰亚胺基苯基)丙烷、1-苯基-1,1-双(4-马来酰亚胺基苯基)乙烷、α,α-双(4-马来酰亚胺基苯基)甲苯、3,5-双马来酰亚胺基-1,2,4-三唑、N,N'-伸乙基双马来酰亚胺、N,N'-六亚甲基双马来酰亚胺、N,N'-间-伸苯基双马来酰亚胺、N,N'-对-伸苯基双马来酰亚胺、N,N'-4,4'-二苯基甲烷双马来酰亚胺、N,N'-4,4'-二苯基醚双马来酰亚胺、N,N'-4,4'-二苯基砜双马来酰亚胺、N,N'-4,4'-二环己基甲烷双马来酰亚胺、N,N'-α,α'-4,4'-二亚甲基环己烷双马来酰亚胺、N,N'-间二甲苯双马来酰亚胺、N,N'-4,4'-二苯基环己烷双马来酰亚胺及N,N'-亚甲基双(3-氯-对-伸苯基)双马来酰亚胺。
1.3.5.聚合引发剂
本发明树脂组合物可视需要进一步包含聚合引发剂以帮助聚合反应的进行。聚合引发剂的实例包括但不限于偶氮二异丁腈、偶氮二(2-异丙基)丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化乙酰异丁酰、过氧化二乙酰、过氧化(2,4-二氯苯甲酰)、过氧化(2-二甲基苯甲酰)、过氧化十二酰、过氧化二碳酸二异丙酯(diisopropyl peroxydicarbonate)、过氧化双(3,5,5-三甲基己酰)、过氧化环己酮、过氧化甲乙酮、过氧化二碳酸二环己丙酯(dicyclohexylpropyl peroxydicarbonate)、过氧化二碳酸二环己酯、过氧化二碳酸二(4-三级丁基环己酯)、过氧化二碳酸二(2-乙基己基)酯、过氧化二碳酸双(2-苯基乙氧基)酯、过氧化二碳酸双十六烷基酯、过氧化苯甲酸三级丁酯、过氧化苯乙酸三级丁酯、过氧乙酸、过氧化三甲基乙酸三级丁酯(tert-butyl peroxypivalate)、过氧化三甲基乙酸三级己酯、过氧化新癸酸异丙苯酯、三级丁基过氧化氢、异丙苯过氧化氢、对薄荷烷过氧化氢(p-menthane hydroperoxide)、过氧化二三级丁基、过氧化氢、过硫酸铵、过硫酸钾、过氧化物-烷基金属及氧-烷基金属。各聚合引发剂可单独使用或任意组合使用。
1.4.树脂组合物的配比
本发明树脂组合物各必要成分及选用成分的比例可视需要调整，但是，聚苯醚树脂(A)对第一交联剂(B)的重量比较佳为13：1至1：1，例如12：1、11：1、10：1、9：1、8：1、7：1、6：1、5：1、4：1、3：1、或2：1。于本发明的部分实施方案中，本发明树脂组合物是包含如下比例的成分：5重量份至70重量份的聚苯醚树脂(A)、5重量份至80重量份的第一交联剂(B)、3重量份至65重量份的第二交联剂、0重量份至50重量份的含乙烯基的弹性体、5重量份至80重量份的填料以及0重量份至70重量份的添加型含磷阻燃剂，但本发明不以此为限。
1.5.树脂组合物的制备
关于本发明树脂组合物的制备，可通过将树脂组合物各成分，包括聚苯醚树脂(A)、式(I)的第一交联剂(B)及其他选用组分，以搅拌器均匀混合并溶解或分散于溶剂中，供后续加工利用。所述溶剂可为任何可溶解或分散树脂组合物各成分、但不与这些成分反应的惰性溶剂。举例言之，可用以溶解或分散树脂组合物各成分的溶剂包含但不限于：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)及N-甲基吡咯烷酮(N-methyl-pyrolidone，NMP)。各溶剂可单独使用或混合使用。溶剂的用量并无特殊限制，原则上只要能使树脂组合物各组分均匀溶解或分散于其中即可。
2.预浸渍片
本发明也提供一种由上述树脂组合物所制得的预浸渍片，其中是通过将一基材含浸或涂布如上所述的树脂组合物，并干燥该经含浸或涂布的基材而制得。预浸渍片的制备方法并无特殊限制，且乃本发明所属技术领域普通技术人员基于本说明书的记载与所具备的现有知识可轻易完成。具体言之，含浸或涂布树脂组合物的方法包括但不限于浸渍、辊式涂布、模具涂布、棒式涂布及喷雾。经含浸或涂布的基材可在80℃至180℃的温度下干燥1至20分钟，从而获得半固化态(B-阶段)的预浸渍片。
常用的基材包含玻璃纤维补强材料(玻璃纤维织物、玻璃纸、玻璃毡等)、牛皮纸、短绒棉纸、天然纤维布、有机纤维布等。基材的实例包括但不限于织布、不织布、玻璃粗纱布(glass roving cloth)、玻璃布(glass cloth)、切股玻璃纤维(chopped glass fiber)、中空玻璃纤维(hollow glass fiber)、玻璃毡(glass mat)、玻璃表面毡(glass surfacingmat)、非织造玻璃织物(non-woven glass fabric)及陶瓷纤维织物(ceramic fiberfabrics)。可用于形成基材的原料的实例包括但不限于E-型的玻璃纤维、NE-型的玻璃纤维、S-型的玻璃纤维、L-型的玻璃纤维、T-型的玻璃纤维、D-型的玻璃纤维、石英(quartz)、芳香族聚酰胺(aramid)及液晶高分子(liquid crystal polymer)。考量到所制电子材料的介电性质，较佳是使用具有低Df值的基材，例如由E-型的玻璃纤维、NE-型的玻璃纤维、S-型的玻璃纤维与L-型的玻璃纤维所构成的基材。
于本发明的部分实施方案中，是使用2116强化玻璃纤维布作为补强材(基材)，并在175℃下加热干燥2至15分钟(B-阶段)，从而制得半固化状态的预浸渍片。
3.金属箔积层板及印刷电路板
本发明也提供一种由上述预浸渍片制得的金属箔积层板，其包含一介电层及一金属层，且可通过将前文所述的预浸渍片与金属箔加以层合而制得，或通过将前文所述的树脂组合物涂布于金属箔，接着干燥该经涂布的金属箔而制得，其中介电层是由上述预浸渍片所提供。于使用预浸渍片制备金属箔积层板的情况中，可层叠多层的上述预浸渍片，接着于经层叠的预浸渍片所构成的介电层的至少一外侧表面层叠一金属箔(如铜箔)以提供一层叠物，并对该层叠物进行热压操作而得到金属箔积层板。
上述金属箔积层板可通过进一步图案化其外侧的金属箔，而形成印刷电路板。
4.实施例
4.1.测量方式说明
现以下列具体实施方案进一步例示说明本发明，其中，所采用的测量仪器及方法分别如下：
[介电常数(Dk)与介电耗损因子(Df)测量]
根据IPC-TM-650 2.5.5.13规范，在工作频率10GHz下，计算金属箔积层板的介电常数(Dk)与介电耗损因子(Df)。用于测试的金属箔积层板中的预浸渍片的树脂含量(ResinContent，RC)为54％。
[玻璃转移温度(Tg)测试]
利用动态机械分析仪(dynamic mechanical analysis，DMA)来测量介电层的玻璃转移温度(Tg)，介电层的定义如前所述。所使用的仪器为精工仪器(Seiko Instruments)制造的型号为“DMS100”的黏弹性分光计(viscoelasticity spectrometer)。测试条件如下：使用弯曲模组，频率设定为10Hz，升温速率设定为5℃/分钟，在自室温升温至280℃的过程中进行动态黏弹性的测量，所测得的tanδ为极大值时的温度即为Tg。
[难燃性测试]
利用UL94V：垂直燃烧测试方法，将金属箔积层板以垂直位置固定，以本生灯燃烧，比较其自燃熄灭与助燃特性。难燃等级的排序为：V0>V1>V2。
[尺寸稳定性测试]
将四片预浸渍片层合以制备待测样品。根据IPC-TM-650 2.4.24.5规范，使用热机械分析仪测量待测样品在低于Tg的温度下的热膨胀系数(coefficient of thermalexapansion，CTE)α1及在Z轴方向上的热膨胀系数改变率(总z-CTE)。α1是在50℃至120℃的温度范围内测得，单位为ppm/℃。总z-CTE是在50℃至260℃的温度范围内测得，单位为％。
[铜箔接着强度测试]
测试金属箔对经层合的预浸渍片的接着强度，以1/8英寸宽度的铜箔自板面上垂直撕起，以其所需力量的大小来表达接着强度。接着强度的单位为磅力/英寸(lbf/in)。
[铜箔积层板(copper clad laminate，CCL)外观评价]
将金属积层板通过蚀刻去除金属铜箔，以目视观察去除铜箔后的积层板表面。如未发现孔隙、污点或树脂分离，代表因树脂组合物具有良好流动性，即所制得的积层板具有良好外观，纪录为“○”；若发现孔隙、污点或树脂分离，代表因树脂组合物的流动性不佳，导致所制得的积层板外观不良，纪录为“×”。
4.2.实施例及比较例用的原物料资讯列表
表1：原物料资讯列表
原物料 说明及来源
SA9000 具有不饱和官能基的聚苯醚树脂，购自沙特基础工业
OPE-2st 具有不饱和官能基的聚苯醚树脂，购自三菱瓦斯化学
DPPO-DAIC 式(I)的第一交联剂，可自行合成
DCP 交联剂，过氧化二异丙基苯(dicumyl peroxide)
DVB 交联剂，二乙烯苯(divinylbenzene)
Ricon 181 含乙烯基的弹性体，丁二烯-苯乙烯共聚物，购自克雷威利
Ricon 100 含乙烯基的弹性体，丁二烯-苯乙烯共聚物，购自克雷威利
BP-PZ 含磷阻燃剂，购自大冢化学
PQ-60 含磷阻燃剂，购自晋一化工
OP-935 含磷阻燃剂，购自科莱恩
PX-200 含磷阻燃剂，购自大八化学
SrTiO<sub>3</sub> 无机填料，购自福禄的型号为218的产品
TiO<sub>2</sub> 无机填料，购自新秀波的型号为HTO2的产品
SiO<sub>2</sub> 无机填料，购自硅比科的型号为525的产品
Perbutyl P 聚合引发剂，购自日本油脂
4.3.树脂组合物的制备
4.3.1.式(I)的第一交联剂的合成
首先将67克的二苯基磷氧(diphenyl phosphine oxide，DPPO)在氮气下加热至90℃并维持1小时至完全熔化。之后，缓慢加入83克三烯丙基异氰酸脲酯(triallylisocyanurate，TAIC)，再进一步加热至135℃反应2小时，接着冷却至室温即得到结构式(I)化合物，测得其熔点为30℃，其磷含量为6.9％，氮含量为9.3％。
4.3.2.树脂组合物
以表2-1、表2-2及表3所示的比例配制实施例1至12及比较例1至3的树脂组合物。
表2-1：实施例1至6的树脂组合物的组成
表2-2：实施例7至12的树脂组合物的组成
表3：比较例1至3的树脂组合物的组成
4.4.金属箔积层板的制备及性质测量
分别使用所制得的树脂组合物来制备实施例1至12及比较例1至3的金属箔积层板。首先，通过辊式涂布机，将玻璃纤维布(型号：2116，厚度：0.08毫米)分别浸渍于实施例1至12及比较例1至3的树脂组合物中，并控制玻璃纤维布的厚度至合适程度。接着，将浸渍后的玻璃纤维布置于175℃的干燥机中加热干燥2至15分钟，借此制得半固化状态(B-阶段)的预浸渍片(预浸渍片的树脂含量为54％)。之后，将四片预浸渍片层合，并在其两侧的最外层各层合一张0.5盎司的铜箔，随后置于热压机中进行高温热压固化。热压条件为：以3.0℃/分钟的升温速度升温至200℃至220℃，并在该温度下，以全压15公斤/平方厘米(初压8公斤/平方厘米)的压力热压180分钟。
依照前文所记载的测量方法测量实施例1至12及比较例1至3的预浸渍片与金属箔积层板的各项性质，包括介电常数(Dk)、介电耗损因子(Df)、玻璃转移温度(Tg)、难燃性、热膨胀数α1、在Z轴方向上的热膨胀数改变率(总z-CTE)、铜箔接着强度及铜箔积层板(CCL)外观评价，并将结果纪录于表4中。
表4：实施例及比较例的预浸渍片与金属箔积层板的性质
如表4所示，采用本发明树脂组合物所制的电子材料在所有物化性质及介电性质表现上均可达到令人满意的程度；尤其，即使是在高填料含量的情况下，本发明树脂组合物仍具有良好的流动性，因此所制得的铜箔积层板可具有良好的外观。相较于此，采用非本发明树脂组合物所制的电子材料并无法在所有物化性质及介电性质上均达到令人满意的程度，尤其所制得的铜箔积层板的外观不良。
上述实施例仅为例示性说明本发明的原理及其功效，并阐述本发明的技术特征，而非用于限制本发明的保护范畴。任何本领域技术人员在不违背本发明的技术原理及精神下，可轻易完成的改变或安排，均属本发明所主张的范围。因此，本发明的权利保护范围如权利要求书所列。

Claims (12)

1.一种树脂组合物，其特征在于，包含：
(A)具有不饱和官能基的聚苯醚树脂；以及
(B)具下式(I)的第一交联剂：
2.如权利要求1所述的树脂组合物，其特征在于，其中该聚苯醚树脂(A)如下式(II)所示：
其中，
R31、R32、R33、R34各自独立为氢、经取代或未经取代的C1至C5烷基；
m与n各自独立为0至100的整数，但m与n不同时为0；
Z为不存在、芳基、－O－、其中R35、R36各自独立为氢或C1至C12烷基；
X与Y各自独立为不存在、羰基或具有烯基的基团；以及
A1与A2各自独立为
3.如权利要求1所述的树脂组合物，其特征在于，其中该聚苯醚树脂(A)对该第一交联剂(B)的重量比为13：1至1：1。
4.如权利要求1至3中任一项所述的树脂组合物，其特征在于，还包含一含乙烯基的弹性体。
5.如权利要求4所述的树脂组合物，其特征在于，其中该含乙烯基的弹性体是选自以下群组：聚丁二烯、苯乙烯丁二烯共聚物、苯乙烯丁二烯苯乙烯嵌段共聚物、聚异戊二烯、苯乙烯异戊二烯共聚物、苯乙烯异戊二烯苯乙烯嵌段共聚物、丙烯腈丁二烯共聚物、丙烯腈丁二烯苯乙烯嵌段共聚物及前述的组合。
6.如权利要求1至3中任一项所述的树脂组合物，其特征在于，还包含选自以下群组的添加型含磷阻燃剂：次磷酸金属盐、聚磷酸盐、鏻盐、磷酸酯、磷腈、亚磷酸酯、膦氧化物及前述的组合。
7.如权利要求1至3中任一项所述的树脂组合物，其特征在于，还包含选自以下群组的填料：二氧化硅、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氮化硼、氮化硅、碳化铝硅、碳化硅、碳酸钠、碳酸镁、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、石墨烯、钛酸钾、钛酸锶、钛酸钡、陶瓷纤维、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧高岭土、白岭土、云母、勃姆石、水滑石、奈米碳管、聚四氟乙烯粉体、中空玻璃珠、奈米级无机粉体及前述的组合。
8.如权利要求1至3中任一项所述的树脂组合物，其特征在于，还包含选自以下群组的(C)第二交联剂：多官能型烯丙基化合物、多官能型丙烯酸酯、多官能型丙烯酰胺、多官能型苯乙烯化合物、双马来酰亚胺化合物及前述的组合。
9.如权利要求8所述的树脂组合物，其特征在于，其中该第二交联剂(C)是双马来酰亚胺化合物。
10.一种预浸渍片，其特征在于，其是将一基材含浸或涂布如权利要求1至9中任一项所述的树脂组合物，并干燥该经含浸或涂布的基材而制得。
11.一种金属箔积层板，其特征在于，其是通过将如权利要求10所述的预浸渍片与金属箔加以层合而制得，或是通过将如权利要求1至9中任一项所述的树脂组合物涂布于金属箔并干燥该经涂布的金属箔而制得。
12.一种印刷电路板，其特征在于，其是由权利要求11所述的金属箔积层板所制得。
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