CN111875916B - 嵌段共聚物组合物、预浸料和由其制备的层压体 - Google Patents

嵌段共聚物组合物、预浸料和由其制备的层压体 Download PDF

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CN111875916B
CN111875916B CN202010373321.1A CN202010373321A CN111875916B CN 111875916 B CN111875916 B CN 111875916B CN 202010373321 A CN202010373321 A CN 202010373321A CN 111875916 B CN111875916 B CN 111875916B
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block
resin composition
block copolymer
curable resin
mol
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CN111875916A (zh
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丁瑞栋
牛亚明
B·杨
X·穆德曼斯
F·德维特
杨慧娴
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Kraton Polymers Research BV
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Abstract

公开了一种允许生产耐热性和加工性优异的层压的片材的树脂组合物，其包含：a)嵌段共聚物，其中所述嵌段共聚物包括至少一个包含聚合的无环共轭二烯单元例如丁二烯单元的聚合物嵌段和至少一个含共轭环状二烯例如1,3‑环己二烯或特征在于Tg大于100℃的单体单元的聚合物嵌段；b)固化引发剂；和c)任选的选自聚丁二烯聚合物和丁二烯与苯乙烯或其它苯乙烯类单体的共聚物的二烯基聚合物，d)任选的添加剂，包括但不限于多官能的可共固化的添加剂、二烯基橡胶、卤化或非卤化的阻燃剂、无机或有机填料或纤维、抗氧化剂、粘合剂促进剂和成膜聚合物。

Description

嵌段共聚物组合物、预浸料和由其制备的层压体
技术领域
本公开内容涉及低耗散、低介电的可固化的嵌段共聚物组合物和由其制成的产品，包括覆铜层压体和印刷电路板。
背景技术
随着电子技术的飞速发展，大容量的计算机系统和网络要求高频信号传输，且电路基板适合于高频和高速传输。期望电路基板在高频和低传输损耗(例如介电损耗、导体损耗和辐射损耗)下操作信号。传输损耗会减弱电信号并破坏信号可靠性。
传统上，印刷电路板使用环氧树脂，该树脂具有较高的介电常数和介电损耗角正切值。环氧树脂可与酚类化合物、胺或酸酐固化剂结合使用以提高性能。这种树脂组合物仍然难以获得低损耗因数。聚苯醚树脂(PPO，或称为聚氧化亚苯基树脂)由于其低耗散性能而被用于层压体中，但是其阻燃性仍然不足。其高粘度限制了其分子量或其在制剂中的含量，且缺乏交联性。遥爪乙烯基官能化的低分子量PPO树脂由于其改善的溶解性和交联性而用于层压体中，但所得损耗因数被不利影响。
已经公开了苯乙烯-丁二烯-苯乙烯嵌段共聚物用于印刷电路板组合物中，例如，包含1,2-聚丁二烯、聚异戊二烯及其改性的(羟基、甲基丙烯酸酯和羧酸酯封端的)或反应后的树脂(环氧、马来酸酐或氨基甲酸酯改性的)丁二烯或异戊二烯树脂用于印刷电路板。所描述的苯乙烯类嵌段共聚物受到其刚性聚苯乙烯嵌段的有限温度性能的限制。
仍然需要改进的组合物以用于覆铜层压体和由其制备的印刷电路板的介电化合物，所述改进的组合物具有良好的可加工性、低的溶液粘度、有效的固化能力、高的软化点温度和低的损耗因数、高频率下的低介电常数特性。
发明内容
一方面，公开了一种用于制造固化制品或印刷电路板的低粘度树脂组合物。所述树脂组合物包含5-99重量％的嵌段共聚物，其中所述嵌段共聚物包含至少A嵌段以及B、B’和C嵌段中的至少一个。每个A嵌段是包含至少一种无环共轭二烯的聚合单元的非氢化的聚(无环共轭二烯)聚合物。每个B嵌段是GPC嵌段Mp低于25kg/mol的聚(1,3-环二烯)均聚物。每个B′嵌段是GPC嵌段Mp低于30kg/mol的聚(1,3-环二烯-共-单烯基芳烃)共聚物。每个C嵌段是包含至少一个Tg高于100℃的高Tg烯基芳烃单元的聚(烯基芳烃)聚合物或共聚物。所述嵌段共聚物具有：偶联前的GPC峰值分子量Mp小于50,000g/mol，乘以A嵌段含量的重量分数的GPC峰值分子量Mp大于500g/mol。所述树脂组合物进一步包含0.1-10重量％的固化引发剂；和最多95重量％的一种或多种选自以下的添加剂：多官能的可共固化的添加剂、二烯基橡胶、卤化或非卤化的阻燃剂、无机或有机填料或纤维、抗氧化剂、粘合促进剂和成膜聚合物。
另一方面，公开了由所述树脂组合物制备的预浸料和层压的片材。
以下术语将在整个说明书中使用，并具有以下含义。
在用于表示几个元素或元素类别(例如X、Y和Z)时，“一种或多种”或“至少一种”是指选自X或Y或Z的单个元素或元素的组合，例如X和Y、Y和Z、或X和Z。
“预浸料”是指通过用树脂浸渍或支撑或增强织物而获得的浸渍的织物。
“覆铜层压体”或“CCL”是指印刷电路板(“PCB”)的基本材料，或电路基板。通过与在浸入树脂后的增强材料(例如玻璃纤维织物)的一侧或两侧上的铜覆层一起层压来获得CCL。在某些实施方案中，通过将一层或多层预浸料与一层或多层铜箔层进行层压来获得CCL。层压是通过在强力的热、压力和真空条件下将一层或多层铜和预浸料压制在一起而获得。
“印刷电路板”可以通过蚀刻CCL的铜表面以产生电子电路来获得。将蚀刻的CCL组装成带有钻孔和电镀孔的多层构型，以在各层之间建立电连接。
术语“单烯基芳烃”和“烯基芳烃”同义使用。
“高Tg单元”是指如果均聚或共聚成高分子量(例如100,000g/mol)则表现出高于100℃的DSC玻璃化转变温度(Tg)的聚合单体单元。
“分子量”(MW)是指聚合物嵌段或嵌段共聚物的苯乙烯当量分子量(kg/mol)。MW可以根据ASTM 5296-19，使用聚苯乙烯校准标准物，通过凝胶渗透色谱法(GPC)进行测量。可以使用市售的聚苯乙烯分子量标准物来校准色谱仪。当已知聚合物的苯乙烯含量和二烯链段的乙烯基含量时，可以将苯乙烯当量MW转换为真实分子量。检测仪可以是紫外线和折射率检测仪的组合。
除非另有说明，“峰值分子量”、Mp、“GPC峰值分子量”或“GPC Mp”是指在GPC迹线的峰处测得的MW。如上所述，分子量是苯乙烯当量。
本公开内容涉及一种包含嵌段共聚物的树脂组合物，其用于制造预浸料和层压体，特别是用于PCB。
嵌段共聚物组分：第一组分是嵌段共聚物。所述嵌段共聚物广泛地包括至少一个包含至少一种无环共轭二烯的聚合单元的非氢化的聚(无环共轭二烯)嵌段A，和至少一个由高Tg单元组成的聚合物嵌段。
在某些实施方案中，高Tg嵌段选自B、B′和C。B嵌段是聚(1,3-环二烯)均聚物。1,3-环二烯单体的非限制性实例是1,3-环己二烯(CHD)。在某些实施方案中，B嵌段的GPC嵌段Mp<25kg/mol，或<20kg/mol，或<15kg/mol，或<9kg/mol，或>2kg/mol。
B’嵌段是聚(1,3-环二烯)无规共聚物嵌段。所述无规共聚物嵌段可包括一种或多种共聚单体，例如单烯基芳烃，例如苯乙烯或对嵌段C所述的任何单烯基芳烃。在某些实施方案中，B’嵌段的GPC嵌段Mp＜30kg/mol，或<25kg/mol，或<20kg/mol，或<9kg/mol，且>2kg/mol。
C嵌段是至少包含Tg>100℃或>125℃或>150℃或<250℃的高Tg单烯基芳烃单元的聚(烯基芳烃)聚合物或共聚物。在某些实施方案中，C嵌段的GPC嵌段Mp<20kg/mol，或<15kg/mol，或<10kg/mol。实例包括邻甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯、α-甲基苯乙烯、对-α-二甲基苯乙烯、乙烯基-苯并环丁烯、乙烯基联苯、金刚烷基苯乙烯、1,1-二苯基-乙烯和苯并富勒烯。
在某些实施方案中，所述嵌段共聚物具有一般构型A-B，(A-B-)nX，A-B'，(A-B'-)nX，A-B-A，A-B'-A，A-B-C，A-B'-C，A-C-B，A-C-B'，(B-A-)nX，(B'-A-)nX，B-A-B，B'-A-B'，(A-C-B-)nX，(A-C-B'-)nX，A-C-B-A，A-C-B'-A，A-C，A-C-A，(A-C-)nX，其中n为2-50的整数，X为偶联剂残基。
在某些实施方案中，每个A嵌段是包含至少一种无环共轭二烯的聚合单元的非氢化的聚(无环共轭二烯)聚合物。在某些实施方案中，每个A嵌段是具有小于50重量％的1,4-聚合单元的聚丁二烯(PBd)嵌段。在某些实施方案中，每个B嵌段是聚(1,3-环二烯)均聚物，每个B'嵌段是聚(1,3-环二烯-共-单烯基芳烃)共聚物。在某些实施方案中，每个C嵌段是包含至少一个高Tg烯基芳烃单元的聚(烯基芳烃)聚合物或共聚物。1,3-环二烯单元CD单体的聚合可以通过1,2-和1,4-加成机理进行。因此，对于CD单体如CHD(环己二烯)，1,4-加成产生1,4-二取代(类似于对二取代苯环)的环己烷重复单元(在本文中也称为“p-CHD”或“PCHD”)。
所述嵌段共聚物可以通过本领域已知的方法制备。在某些实施方案中，具有聚合的CD和无环共轭二烯单元嵌段的聚合物嵌段的微结构或乙烯基含量(其又取决于二烯单元的1,2-加成相对1,4-加成的程度)可以通过改变用于较低的1,4加成单元和因此较高的“乙烯基”含量的微结构改性剂(例如四甲基乙二胺(TMEDA)、二乙氧基丙烷(DEP)、1,4-二氮杂双环[2.2.2]辛烷(DABCO))的相对量来控制。1,2-加成CD(例如1,3-环己二烯)导致在聚合物主链上形成1,2-环己-3-烯-二基，而1,4-加成导致在聚合物主链上形成1,4-环己-2-烯-二基。
在某些实施方案中，通过在合适的溶剂混合物中使单体同时或顺序地与阴离子聚合引发剂体系(例如正丁基锂)接触，在对于第一嵌段25-70℃的温度，和对于第二嵌段25-50℃的温度下，制备所述嵌段共聚物。在基本上形成嵌段共聚物的主链之后，可以将活性嵌段共聚物偶联并封端以提供(偶联的)二嵌段共聚物，或者可以用第三嵌段进行延伸(和偶联)。可以通过沉淀和蒸发来分离和回收聚合物。
在某些实施方案中，在偶联之前，所述嵌段共聚物的GPC峰值分子量Mp<50kg/mol，或<45kg/mol，或<35kg/mol，或>5kg/mol。
在某些实施方案中，在偶联后，所述嵌段共聚物的乘以A嵌段含量重量分数的GPCMp>500g/mol，或>1kg/mol，或>10kg/mol，或<100kg/mol。
在某些实施方案中，所述嵌段共聚物包含小于5重量％或＜4重量％或＞0.1重量％的不同于碳和氢的原子。
在某些实施方案中，所述嵌段共聚物的DSCTg>100℃，或>110℃，或>125℃，或>175℃，或<250℃。在某些实施方案中，所述嵌段共聚物的在1GHz的介电常数Dk<2.6，或<2.3，或<2.1，或>1.5；在1GHz的介电损耗因数Df<0.003，或<0.002，或<0.001，或>0.00001。
在某些实施方案中，所述嵌段共聚物在25℃于甲苯中25重量％的溶液粘度＜2000mPa.s，或＜1800mPa.s，或＜1500mPa.s，或＞10mPa.s；或者，在25℃于二甲苯中50重量％的溶液粘度<10,000mPa.s，或<8,000mPa.s，或<5,000mPa.s，或>10mPa.s。
所述树脂组合物中嵌段共聚物的量为5-99重量％，或5-80重量％，或>8重量％，或10-30重量％，或<70重量％，基于所述树脂组合物的总重量。
固化剂/引发剂：所述树脂组合物还包含产生自由基的化合物，也称为固化剂或固化引发剂。实例包括但不限于叠氮化物、过氧化物、硫和硫衍生物。自由基引发剂特别优选作为固化引发剂。产生自由基的化合物也称为固化催化剂，其在升高的温度下或在紫外线或其他能量添加的触发作用下产生自由基。产生自由基的化合物确保树脂组合物可在不存在紫外线或触发能量的情况下在低温下可加工，但在活化温度下或在紫外线或引入触发能量下产生高浓度的自由基。产生自由基的化合物可以包括能够在升高的温度下或在添加触发能量例如UV辐射之后产生自由基的任何化合物。
产生自由基的化合物的实例是有机过氧化物，例如2,5-二甲基-2,5-二(叔丁基过氧)-己-3-炔、过氧化二叔丁基、过氧化叔丁基枯基、二(叔丁基过氧异丙基)苯、2,5-二甲基-2,5-二(叔丁基过氧)己烷、过氧化二枯基等。典型的非过氧引发剂包括诸如2,3-二甲基-2,3-二苯基丁烷、2,3-三甲基甲硅烷氧基-2,3-二苯基丁烷等的化合物。典型的UV自由基引发剂是2,2-二甲氧基-1,2-二苯基乙-1-酮。在某些实施方案中，固化引发剂是具有＞120℃的1小时半衰期温度的过氧化物。
当使用时，固化引发剂的存在量为0.1-10重量％，或0.3-7重量％，或1-5重量％，基于所述树脂组合物的总重量。
添加剂：所述树脂组合物可以进一步包含一种或多种添加剂，包括但不限于多官能的可共固化的添加剂、二烯基橡胶、卤化或非卤化的阻燃剂、无机或有机填料或纤维、单乙烯基化合物或本领域已知的其他添加剂，例如抗氧化剂、着色剂、稳定剂，粘合促进剂、增韧剂和成膜添加剂，其量为0.1-50重量％，基于所述树脂组合物的重量。
由多乙烯基化合物构成的多官能的可共固化的添加剂的实例包括低分子量二乙烯基苯或双(乙烯基苯基)乙烷或二乙烯基萘，三羟甲基丙烷三甲基丙烯酸酯或三羟甲基丙烷三丙烯酸酯或三烯丙基异氰脲酸酯或三烯丙基氰脲酸酯，或多乙烯基化合物，如乙烯基官能化的PPE(也称为烯丙基改性的聚苯醚)，例如Sabic的SA-9000，或Mitsubishi GasChemical的OPE 2st，或二烯基聚合物，例如二烯的均聚物，或不同烯烃和/或二烯的共聚物(包括三嵌段共聚物)，其在聚合物主链中具有双键。二烯基聚合物在室温下可以为液态或固态，包括用于介电基板的不饱和树脂，例如聚丁二烯聚合物，或丁二烯与苯乙烯或类似苯乙烯类单体的共聚物。
其他添加剂的实例包括具有(甲基)丙烯酰基的聚丁二烯橡胶，具有(甲基)丙烯酰基的聚异戊二烯橡胶，具有(甲基)丙烯酰基的丁二烯和异戊二烯的共聚物橡胶，具有(甲基)丙烯酰基的丁二烯和正丁烯的共聚物橡胶等。在某些实施方案中，二烯基聚合物选自聚丁二烯、聚异戊二烯、丁二烯-苯乙烯共聚物、异戊二烯-苯乙烯共聚物、丁二烯-苯乙烯-甲基丙烯酸酯的三嵌段共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物、丁二烯-苯乙烯-丙烯腈共聚物、丁二烯-苯乙烯-马来酸酐共聚物、及其任何组合。
液态丁二烯共聚物的实例是丁二烯-共-苯乙烯和丁二烯-共-丙烯腈。除了聚丁二烯或聚异戊二烯嵌段被氢化外，含不饱和丁二烯或异戊二烯的聚合物也可含有与第一类似的第二嵌段共聚物，从而形成聚乙烯嵌段(在聚丁二烯的情况下)或乙烯-丙烯共聚物(在聚异戊二烯的情况下)。
第二类多官能的可共固化的添加剂由非乙烯基烯烃化合物如双马来酰亚胺树脂如4,4'-双(马来酰亚氨基)-二苯甲烷构成。
在一些实施方案中，可共固化的添加剂是未氢化的嵌段共聚物，其峰值分子量为20,000-200,000原子质量单位。峰值分子量可以通过凝胶渗透色谱法(GPC)并基于聚苯乙烯标准物来确定，对应于将产生与被测聚合物相同的峰最大值的聚苯乙烯分子量。
阻燃剂：在某些实施方案中，所述树脂组合物还包含选自含磷阻燃剂和溴化阻燃剂的阻燃剂。溴化阻燃剂的实例包括乙烯-双(四溴邻苯二甲酰亚胺)、1,2-双(五溴苯基)乙烷和2,4,6-三(2,4,6-三溴苯氧基)-1,3,5-三嗪。含磷阻燃剂的实例包括双酚磷酸二苯酯，多磷酸铵，对苯二酚双(磷酸二苯酯)，双酚A双(磷酸二苯酯)，三(2-羧乙基)膦(TCEP)，磷酸三(氯异丙基)酯，磷酸三甲酯(TMP)，二甲基甲基膦酸酯(DMMP)，间苯二酚双(二甲苯基磷酸酯)，磷腈，三聚氰胺多磷酸酯，9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)及其衍生物或树脂，三聚氰胺氰脲酸酯和三羟乙基异氰脲酸酯。在某些实施方案中，阻燃剂化合物可以是DOPO化合物，DOPO树脂(例如DOPO-HQ，DOPO-NQ，DOPO-PN和DOPO-BPN)和含DOPO的环氧树脂，其中DOPO-BPN可以是双酚酚醛清漆化合物，例如DOPO-BPAN，DOPO-BPFN和DOPO-BPSN。
在某些实施方案中，阻燃剂是非反应性阻燃剂，其在其化学结构中不包含反应性官能团。
阻燃剂通常以5-25重量％或8-20重量％或至少10重量％的量存在，基于所述树脂组合物的总重量。
填料：所述树脂组合物还包含至少一种无机和/或有机填料。无机填料可用于抑制热膨胀系数并提高层压的片材的韧性。可以使用有机填料来降低层压的片材的介电常数。
示例性的填料包括二氧化钛(金红石和锐钛矿)，钛酸钡，钛酸锶，二氧化硅(包括熔融无定形二氧化硅)，刚玉，硅灰石，芳族聚酰胺纤维，玻璃纤维，Ba2Ti9O20，玻璃球，石英，氮化硼，氮化铝，碳化硅，氧化铍，氧化铝，氧化镁，氢氧化镁，三聚氰胺多磷酸酯，三聚氰胺氰脲酸酯，蜜白胺，蜜胺(Melon)，蜜勒胺，胍，磷氮烷，硅氮烷，DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)，DOPO(10-5-二羟基苯基，10-H-9-氧代磷酰苯二酚(oxaphosphaphenanthrenelo)-氧化物)，云母，滑石粉，纳米粘土，铝硅酸盐(天然和合成)和热解法二氧化硅，可单独使用或组合使用。可以对填料进行表面处理以使其表面不吸水并且与组合物中的其他成分更相容或对自由基具有反应性。这种表面处理包括用有机硅烷偶联剂例如乙烯基硅烷或烷基硅烷或芳基硅烷的处理。
有机填料的实例包括氟基、聚苯乙烯基、二乙烯基苯基和聚酰亚胺基填料。氟基填料包括聚四氟乙烯(PTFE)、聚全氟烷氧基树脂、聚氟乙烯-丙烯树脂、聚四氟乙烯-聚乙烯共聚物、聚偏二氟乙烯、聚氯三氟乙烯树脂等。
在某些实施方案中，可以用一种或多种偶联剂例如硅烷、锆酸酯或钛酸酯处理填料。可以对填料进行预处理，或者可以将偶联剂添加至所述树脂组合物中。
填料的量可高达60重量％或可高达75重量％，或5-50重量％，或至少20重量％，基于所述树脂组合物的重量。
任选的粘合促进聚合物：所述树脂组合物可任选地包含添加以增加对铜箔的粘附力的聚合物，例如聚(亚芳基醚)、官能化的氢化苯乙烯嵌段共聚物。
在某些实施方案中，粘合促进聚合物选自羧基官能化的聚(亚芳基醚)、马来酸酐官能化的苯乙烯-乙烯/丁烯-苯乙烯(SEBS)或具有由氢化形式的共轭二烯与苯乙烯的共聚物构成的嵌段的氢化的嵌段共聚物，例如来自Kraton Polymers的KratonA。
也可以使用任选的单乙烯基化合物，例如苯乙烯，α-甲基苯乙烯，对甲基苯乙烯，溴苯乙烯，二溴苯乙烯。
如果存在，则可以最多25重量％或最多20重量％或3-15重量％或5-10重量％的量加入粘合促进聚合物，基于所述树脂组合物的重量。
溶剂：在制备中，可以添加溶剂以改变所述树脂组合物的固体含量并调节所述树脂组合物的粘度。合适的溶剂包括例如酮，例如甲基乙基酮等，醚，例如二丁基醚等，酯，例如乙酸乙酯等，酰胺，例如二甲基甲酰胺等，芳族烃，例如苯、甲苯、二甲苯等，和氯代烃，例如三氯乙烯等；可以单独使用每种溶剂或组合使用它们。
优选的溶剂选自甲醇，乙醇，乙二醇甲基醚，丙酮，甲基乙基酮，甲基异丁基酮，环己酮，甲苯，二甲苯，乙酸甲氧基乙酯，乙酸乙氧基乙酯，乙酸丙氧基乙酯，乙酸乙酯，二甲基甲酰胺，丙二醇甲基醚，γ-丁内酯(GBL)和二异丁基酮(DIBK)。
所用溶剂的量取决于各组分的溶解性、填料量、施用方法和其他因素。在某些实施方案中，溶剂占10-50重量％固体，或15-40重量％固体，基于溶剂和固体的总重量。
其他任选的组分：在某些实施方案中，低损耗因数树脂组合物可进一步添加以下添加剂中的至少一种：偶联剂、表面活性剂、增韧剂、粘度调节剂、润湿剂、抗氧化剂、着色剂等。
添加剂的选择取决于应用、期望的性能，选择以增强或基本上不负面影响电路子组件的电性能，例如介电常数、损耗因数、介电损耗和/或其他期望的性能。添加固化促进剂以提高树脂组合物的反应速率。表面活性剂有助于确保无机填料在树脂组合物中的均匀分布，并避免无机填料的聚集。增韧剂有助于改善树脂组合物的韧性。
增韧剂可以是橡胶树脂、羧基封端的聚丁二烯丙烯腈和/或核-壳聚合物。示例性的抗氧化剂包括自由基清除剂和金属减活剂。可以存在偶联剂以促进或参与将金属表面或填料表面与聚合物连接的共价键的形成。示例性偶联剂包括3-巯基丙基甲基二甲氧基硅烷和3-巯基丙基三甲氧基硅烷和六亚甲基二硅氮烷。
偶联剂可以是硅烷和/或硅氧烷化合物。例如，氨基硅烷化合物、氨基硅氧烷化合物、苯乙烯基硅烷化合物、苯乙烯基硅氧烷化合物、丙烯酸硅烷化合物、丙烯酸硅氧烷化合物、甲基丙烯酸硅烷化合物、甲基丙烯酸硅氧烷化合物、乙烯基硅烷、烷基硅烷化合物和烷基硅氧烷化合物。
在某些实施方案中，所述树脂组合物还包含本领域已知的粘合促进剂，例如金属粘合促进剂，例如含N的杂环，其可以与金属箔形成络合物，从而增强金属箔与树脂层之间的粘合，其量为0.1-2重量％，基于所述树脂组合物的总重量。在某些实施方案中，代替添加到树脂组合物中，粘合促进剂以在水或有机溶剂中的溶液或分散体的形式被施加到电阻金属层。
在某些实施方案中，所述树脂组合物进一步包含最多15重量％的选自下述的粘合促进聚合物：聚(亚芳基醚)、羧基官能化的聚(亚芳基醚)和马来酸酐官能化的苯乙烯-乙烯/丁烯-苯乙烯(SEBS)。在某些实施方案中，用所述共聚物、选自硫固化剂和过氧化物固化剂的固化引发剂、以及作为共固化添加剂的二烯基橡胶形成可固化的组合物。
所述树脂组合物可包含另外的可溶性聚合物，例如聚苯醚树脂，聚烯烃，苯乙烯聚合物，苯乙烯嵌段共聚物或氢化的苯乙烯嵌段共聚物，高Tg烃聚环烯烃。这些聚合物以少量使用以改性树脂组合物并改善其成膜能力、抗冲击性、Tg和加工特性。
在某些实施方案中，如果用于除CCL以外的用途，则所述树脂组合物可包含二烯橡胶以形成轮胎胶料。在这种情况下，一旦在橡胶状组合物中固化，本发明的嵌段共聚物表现为可固化的增强树脂。
取决于各添加剂，任选的组分的量可为0.1-25重量％，或>0.2重量％，或>0.5重量％，或<10重量％，或<15重量％，基于所述树脂组合物的总重量。
应用：所述树脂组合物适用于层压体，例如覆铜层压体，用于印刷电路板，其是通过用树脂浸渍基底或增强材料(例如玻璃基纤维、机织织物、交叉层压体等)，然后将树脂部分或全部固化形成预浸料而生产。为了制造层压体，将一层或多层预浸料与一层或多层铜层压在一起。印刷电路板可用于许多高频和高数据速度的电气和电子应用，尤其是损耗因数小于0.006的应用。
用于所述树脂组合物中的嵌段共聚物还可以用于需要高温性能的其他固化应用中，例如粘合剂、涂料、LED封装树脂、天线罩树脂、固化橡胶应用(例如轮胎胎面中的橡胶胶料)以及其他树脂的添加剂。
制备方法：在一个制备高频CCL或电路基板的方法中，将上述各组分结合在一起，其中包括所述嵌段共聚物、固化引发剂和任选的组分，例如多官能的可共固化的试剂(例如二烯基聚合物)、阻燃剂和其他任选的组分。用溶剂，例如甲苯、二甲苯、MEK及其混合物，将树脂混合物稀释至合适的粘度，形成胶溶液或清漆。用所述胶溶液将增强材料或基底例如纤维、玻璃毡、木浆纸、玻璃纤维布(任选地已经用偶联剂处理)浸渍到期望的厚度。然后通过溶剂蒸发从经浸渍的玻璃纤维中除去溶剂，形成预浸料。
在某些实施方案中，通过在低于固化引发剂的活化温度的温度下蒸发溶剂，或者蒸发足够长的时间以蒸发溶剂但没有达到胶凝时间，来形成预浸料。胶凝时间是指从材料开始软化到发生胶凝的时间，其中胶凝是从粘性液体到弹性凝胶的不可逆转的转变。在某些实施方案中，通过将所述树脂浸渍到基底例如纤维制品中，并使所得经浸渍的基底半固化或者在有或没有额外的树脂组合物的情况下将涂覆的纤维热压在一起，来形成预浸料。
接下来，将预浸料与在其间的铜箔层压在一起，并在150-250℃的温度和20-70kg/cm2的压力下固化，从而形成电路基板。
树脂组合物的性能：所述树脂组合物的特征在于具有低介电损耗，特别是损耗因数Df小于或等于0.02，小于或等于0.006，或小于或等于0.003，均在1或10GHz下测量。所述树脂组合物的特征在于具有低介电常数Dk，特别是介电常数小于或等于4.4，小于或等于3.8，或小于或等于3.4，所有这些都是在1或10GHz下测量。上述介电材料还具有小于或等于80ppm/℃、小于或等于60ppm/℃或小于或等于50ppm/℃的低CTE(热膨胀系数)，所有均在0-150℃的范围测量。
所述树脂组合物还具有0.2-0.7W/mK或0.3-0.5W/mK的良好导热系数。
所述树脂组合物可进一步具有低吸湿性，这导致在使用中和储存期间对环境条件不那么敏感的包装基板。在某些实施方案中，在23℃下浸入水中24小时后，吸湿率为0.05-0.3％。
所述树脂组合物可以达到V-0或至少V-1或至少V-2的UL 94等级。在一个实施方案中，V-0等级是在不存在溴化或氯化阻燃剂的情况下获得的。
所述树脂组合物也是可固化的，这意味着在固化所述组合物之后导致＞15％或＞30％或＞50％的凝胶形成。固化之后，所述树脂组合物的特征在于具有＜20、＜10或＜5或＜2或＜1.5的溶胀比。溶胀比定义为在过量溶剂中溶胀的凝胶重量与干燥的凝胶重量之间的比率。固化的树脂组合物的特征还在于其Tg>100℃，或>110℃，或>120℃，或>150℃，或<250℃。
实施例
以下说明性实施例是非限制性的。实施例中使用了以下成分：
DCP：过氧化二枯基
B3000：Mn为3200g/mol且具有＜10％的1,4-单元含量的液态聚丁二烯
TAIC：三烯丙基异氰脲酸酯
嵌段共聚物1是偶联的嵌段共聚物PBd-PCHD-PBd，其如下制备：在不锈钢干燥的钢反应器中，加入1升纯化和干燥的环己烷溶剂，加入14.2毫升正丁基锂(1.6摩尔)，然后加入3.3克TMEDA。将溶液加热至40℃，并加入4.6克纯化的1,3-丁二烯单体。使反应进行45分钟，并从溶液中收集第一个小样品用于GPC分析和NMR。NMR证实了该第一单体完全聚合。然后将90克纯化的1,3-环己二烯加入溶液中，并使其聚合45分钟。从溶液中收集第二个小样品用于GPC和NMR分析。NMR证实第二单体接近完全聚合。然后，加入另外的4.5克纯化的1,3-丁二烯单体。使反应进行60分钟。收集第三份样品用于GPC分析和NMR分析。NMR证实第三单体几乎完全聚合。然后通过添加甲醇杀灭活性溶液。用抗氧化剂稳定聚合物溶液，并通过在过量醇中沉淀来分离样品，并在升高的温度下真空干燥。对于三个分别收集的样品，用聚苯乙烯校准的GPC得到主峰分子量Mp＝730g/mol,Mp＝8150g/mol和Mp＝8760g/mol。最终产物的NMR分析得到在聚丁二烯嵌段中的35重量％的1,4-单元的含量和65重量％的1,2-单元的含量。
嵌段共聚物2是如下制备的嵌段共聚物PCHD-PBd：在不锈钢干燥的钢反应器中，加入6升纯化和干燥的环己烷溶剂，并加入40毫升仲丁基锂(1.3摩尔)。将溶液加热至35℃，然后将800克纯化的1,3-环己二烯与DEP一起添加到该溶液中并使其聚合120分钟。从溶液中收集第一个小样品用于GPC和NMR分析。NMR证实了第一单体几乎完全聚合。再添加200克纯化的1,3-丁二烯单体。使反应进行90分钟。收集第二个样品用于GPC分析和NMR分析。NMR证实第二单体几乎完全聚合。然后通过添加甲醇杀灭活性溶液。用抗氧化剂稳定聚合物溶液，在过量醇中沉淀，并在升高的温度下真空干燥。对于两个收集的样品，用聚苯乙烯校准的GPC得到一个主峰分子量为Mp＝21700g/mol，另一个为Mp＝34300g/mol。最终产物的NMR分析得到在聚丁二烯嵌段中的24重量％的1,4-单元含量和76重量％的1,2-单元含量。
将GPC嵌段分子量Mp或嵌段ΔMp计算为在所考虑的嵌段完成时测得的线性共聚物的GPC峰值分子量与就在聚合所考虑的嵌段之前测得的同一线性聚合物的GPC峰值分子量之间的差。GPC用聚苯乙烯标准物校准，因此Mp值以聚苯乙烯当量分子量表示。
表1和表2总结了实施例中使用的嵌段共聚物的描述和性能。
表1
表2
实施例1-6：上述材料的用量见表3。还显示了干燥和固化(180℃，1小时)后的组合物的性能。
表3
单位 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
嵌段共聚物1 份 100 90 - - - -
嵌段共聚物2 份 - - 100 70 100 -
DCP 份 6 6 1 3 - 3
B3000 份 - 10 - 30 - 100
TAIC 份 - - - 0.45 - -
份 - - - - - -
固化温度/时间 ℃/min 180/60 180/60 180/60 180/60 180/60 180/60
固化的Tg ℃ 137 136 124 157 135 <100
凝胶含量 重量％ 57 67 15 72 无 -
溶胀比 6.8 5.5 - 5.7 - -
实施例5表明，没有固化引发剂不能使嵌段共聚物在180℃下以60分钟的固化周期有效地固化。有效的固化导致显著的凝胶含量，且凝胶的溶胀比不太高。实施例5不能合适地固化(凝胶含量为约0％)。实施例6在固化前和后没有足够的Tg。

Claims (14)

1.一种可固化的树脂组合物，其包含：
a)5-99重量％的嵌段共聚物，其中所述嵌段共聚物包含至少A嵌段以及B、B′和C嵌段中的至少一个；
其中每个A嵌段是包含至少一种无环共轭二烯的聚合单元的非氢化的聚(无环共轭二烯)聚合物；每个B嵌段是GPC嵌段Mp<25kg/mol的聚(1,3-环二烯)均聚物；每个B'嵌段是GPC嵌段Mp<30kg/mol的聚(1,3-环二烯-共-单烯基芳烃)共聚物；每个C嵌段是包含至少一种Tg＞100℃的高Tg烯基芳烃单元的聚(烯基芳烃)聚合物；和所述嵌段共聚物在偶联前的GPC峰值分子量Mp＜50kg/mol，所述嵌段共聚物在偶联后的GPC峰值分子量Mp乘以A嵌段含量重量分数＞500g/mol；
b)0.1-10重量％的固化引发剂；和
c)最多95重量％的一种或多种选自下述的添加剂：多官能的可共固化的添加剂、二烯基橡胶、卤化或非卤化的阻燃剂、无机或有机填料或纤维、抗氧化剂、粘合剂促进剂和成膜聚合物；
其中所述可固化的树脂组合物具有≤3.4的在1GHz或10GHz的介电常数Dk和≤0.003的在1GHz或10GHz的介电损耗因数Df；和
其中通过固化所述可固化的树脂组合物形成的固化的树脂具有>15％的凝胶含量和>100℃的Tg；
其中所述可固化的树脂组合物中的各组分之和为100％。
2.权利要求1所述的可固化的树脂组合物，其中所述嵌段共聚物具有选自以下的任何结构：A-B，(A-B-)nX，A-B'，(A-B'-)nX，A-B-A，A-B'-A，A-B-C，A-B'-C，A-C-B，A-C-B'，(B-A-)nX，(B'-A-)nX，B-A-B，B'-A-B'，(A-C-B-)nX，(A-C-B'-)nX，A-C-B-A，A-C-B'-A，A-C，A-C-A和(A-C-)nX，其中n为2-50的整数，X为偶联剂残基。
3.权利要求1-2任一项所述的可固化的树脂组合物，其中在偶联前所述嵌段共聚物的GPC峰值分子量Mp＜35kg/mol。
4.权利要求1-2任一项所述的可固化的树脂组合物，其中所述嵌段共聚物a)包含少于5重量％的不同于碳和氢的原子。
5.权利要求1-2任一项所述的可固化的树脂组合物，其中所述嵌段共聚物a)的DSC Tg>100℃，25℃下于甲苯中25重量％的溶液粘度<2000mPa.s。
6.权利要求1-2任一项所述的可固化的树脂组合物，其中每个A嵌段是具有＜50重量％的1,4-聚合单元的聚丁二烯嵌段；B和B’嵌段各自独立地具有＜9kg/mol的GPC嵌段Mp分子量；和C嵌段具有＜20kg/mol的GPC嵌段Mp分子量。
7.权利要求1-2任一项所述的可固化的树脂组合物，其中：
所述固化引发剂b)是1小时半衰期温度>120℃的过氧化物；和
所述一种或多种添加剂是选自下述的多官能的可共固化的添加剂：二乙烯基苯、双(乙烯基苯基)乙烷、三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、乙烯基官能化的PPE树脂、双马来酰亚胺树脂、在室温下呈液态或固态的二烯基聚合物，其中所述二烯基聚合物选自聚丁二烯、聚异戊二烯、丁二烯-苯乙烯共聚物、异戊二烯-苯乙烯共聚物、丁二烯-苯乙烯-甲基丙烯酸酯的三嵌段共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物、丁二烯-苯乙烯-丙烯腈共聚物、丁二烯-苯乙烯-马来酸酐共聚物、及其组合。
8.权利要求1-2任一项所述的可固化的树脂组合物，其中所述嵌段共聚物a)具有小于10,000mPa.s的25℃下于二甲苯中50重量％的溶液粘度。
9.权利要求1-2任一项所述的可固化的树脂组合物，其进一步包含最多15重量％的选自下述的粘合促进聚合物：聚(亚芳基醚)、羧基官能化的聚(亚芳基醚)和马来酸酐官能化的苯乙烯-乙烯/丁烯-苯乙烯。
10.一种预浸料，其通过下述步骤形成：
使用通过将5-90重量％的权利要求1-9任一项所述的可固化的树脂组合物溶解在溶剂中获得的溶液来涂覆基底；
蒸发所述溶剂，形成涂覆的基底；和
在所述涂覆的基底的至少一侧上，用铜箔包覆所述涂覆的基底；和
热压所述铜箔和所述涂覆的基底，形成预浸料。
11.一种覆铜层压体，其包括权利要求10所述的预浸料。
12.一种印刷电路板，其包括权利要求11所述的覆铜层压体。
13.一种电路子组件，其包括：
导电金属层，和
涂覆有可固化的树脂组合物的基底，
其中所述可固化的树脂组合物包含：
a)5-99重量％的嵌段共聚物，其中所述嵌段共聚物包含至少A嵌段以及B、B′和C嵌段中的至少一个；其中每个A嵌段是包含至少一种无环共轭二烯的聚合单元的非氢化的聚(无环共轭二烯)聚合物；每个B嵌段是GPC嵌段Mp<25kg/mol的聚(1,3-环二烯)均聚物；每个B'嵌段是GPC嵌段Mp<30kg/mol的聚(1,3-环二烯-共-单烯基芳烃)共聚物；每个C嵌段是包含至少一个Tg＞100℃的高Tg烯基芳烃单元的聚(烯基芳烃)聚合物；和所述嵌段共聚物在偶联前的GPC峰值分子量Mp＜50kg/mol，所述嵌段共聚物在偶联后的GPC峰值分子量Mp乘以A嵌段含量重量分数＞500g/mol；
b)0.1-10重量％的固化引发剂；和
c)最多95重量％的一种或多种选自下述的添加剂：多官能的可共固化的添加剂、二烯基橡胶、卤化或非卤化的阻燃剂、无机或有机填料或纤维、抗氧化剂、粘合促进剂和成膜聚合物；
其中所述可固化的树脂组合物中的各组分之和为100％；
其中，所述电路子组件在10GHz的损耗因数Df小于0.006，以及在10GHz的介电常数Dk小于3.8。
14.权利要求13所述的电路子组件，其中所述可固化的树脂组合物中的嵌段共聚物a)具有选自以下的任何结构：A-B，(A-B-)nX，A-B'，(A-B'-)nX，A-B-A，A-B'-A，A-B-C，A-B'-C，A-C-B，A-C-B'，(B-A-)nX，(B'-A-)nX，B-A-B，B'-A-B'，(A-C-B-)nX，(A-C-B'-)nX，A-C-B-A，A-C-B'-A，A-C，A-C-A和(A-C-)nX，其中n是2-50的整数，X是偶联剂残基；和在所述可固化的树脂组合物中的嵌段共聚物a)具有＞100℃的DSC Tg和<2000cP的25℃下于甲苯中25重量％的溶液粘度。
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