CN105778414B - 一种环氧树脂组合物以及使用它的预浸料和层压板 - Google Patents
一种环氧树脂组合物以及使用它的预浸料和层压板 Download PDFInfo
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- CN105778414B CN105778414B CN201410831488.2A CN201410831488A CN105778414B CN 105778414 B CN105778414 B CN 105778414B CN 201410831488 A CN201410831488 A CN 201410831488A CN 105778414 B CN105778414 B CN 105778414B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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Abstract
本发明提供了一种环氧树脂组合物以及使用它的预浸料和层压板。所述环氧树脂组合物包括如下组分:(A)酰亚胺改性环氧树脂;(B)交联剂;其中,所述酰亚胺改性环氧树脂为具有式(1)或/和式(2)结构的环氧树脂。由该环氧树脂组合物制成的预浸料与层压板具有高玻璃化转变温度、低介电常数、低介质损耗因子、高耐湿热性、高韧性和良好的工艺加工性。
Description
技术领域
本发明属于覆铜板技术领域,具体涉及一种环氧树脂组合物以及使用它的预浸料、层压板和印制电路板。
背景技术
近年来,随着信息通讯设备高性能化、高功能化以及网络化的发展,为了高速传输及处理大容量信息,操作信号趋向于高频化,同时,为了满足各类电子产品的发展趋势要求,电路板向着高多层、高布线密度的方向发展,这就要求基板材料不仅具有良好的介电性能来满足信号高频传输的需要,而且要求具有良好的耐热性和机械加工性来满足多层印制电路板可靠性和加工性的需求。
聚酰亚胺是综合性能最佳的有机高分子材料之一,耐高温达400℃以上,但其存在溶解度低,加工工艺难。
双马来酰亚胺(简称BMI)是由聚酰亚胺树脂体系派生的另一类树脂体系,是以马来酰亚胺为活性端基的双官能团化合物,克服了环氧树脂耐热性相对较低的缺点,但依然存在溶解度低,容易分相和固化成型温度高等问题。
CN101831051公开了含萘环、双环戊二烯环和酰亚胺结构的环氧树脂,但由于萘环含量较高,且含有溶解性差的均苯四甲酸二酐,导致脆性大、溶解性差且容易出现相分离,另外其成本高。
发明内容
针对已有技术的问题,本发明的目的在于提供一种环氧树脂组合物以及使用它的预浸料和层压板。使用该树脂组合物制造的层压板具有高玻璃化转变温度、低介电常数、低介质损耗因子、高耐湿热性、高韧性和良好的工艺加工性。
本发明人为实现上述目的进行了反复深入的研究,结果发现:酰亚胺改性环氧树脂和交联剂,及其他可选地组分适当混合得到的组合物,可实现上述目的。
一种环氧树脂组合物,其包括如下组分:
(A)酰亚胺改性环氧树脂;
(B)交联剂;
其中,所述酰亚胺改性环氧树脂为具有式(1)或/和式(2)结构的环氧树脂:
式(1)和式(2)中的A均独立地为未取代的苯基或被C1~C4的烷基取代的苯基;式(1)和式(2)中的A可以相同,也可以不同;n1、n2和n3均独立地为大于等于1的整数。
式(1)和式(2)中的R均独立地为:或
式(1)中,R'为其中R''为单键、或
优选地,所述酰亚胺改性环氧树脂为具有式(2)结构的环氧树脂。
进一步优选地,所述酰亚胺改性环氧树脂为具有如下结构的环氧树脂,其兼具有耐热性和韧性:
A为苯基,R为
本发明所采用的酰亚胺改性环氧树脂,具有良好的溶解性和工艺加工性,且主链中含有酰亚胺结构,使其具有更好的玻璃化转变温度。因此,酰亚胺改性环氧树脂的加入可以明显提升固化物的玻璃化转变温度,并改善固化物的韧性。
本发明利用上述两种必要组分之间的相互配合以及相互协同促进作用,得到了如上的环氧树脂组合物。采用该环氧树脂组合物制成的预浸料及层压板,具有高玻璃化转变温度、低介电常数、低介质损耗因子、高耐湿热性、高韧性和良好的工艺加工性。
在本发明中,交联剂种类的选择和合理的搭配能使组合物实现不同的性能。优选地,所述交联剂为活性酯、酸酐化合物或酚醛树脂中的任意一种或者至少两种的混合物。
优选地,所述活性酯为具有官能团酯基的活性酯交联剂,酸酐化合物可以为苯乙烯马来酸酐等酸酐化合物。酚醛树脂可为线性酚醛树脂、联苯酚酚醛树脂、烷基酚酚醛树脂、DCPD酚醛树脂或TCPD酚醛树脂等含羟基的酚醛树脂。
进一步优选地,所述交联剂为活性酯或/和酸酐化合物,其与环氧树脂反应具有更好的介电性能。
更优选地,所述交联剂为具有如下结构的活性酯,由于该活性酯的特殊结构,其中的苯基、萘基、环戊二烯等刚性结构赋予该活性酯高的耐热性,同时由于其结构的规整性及与环氧树脂反应过程中无二次羟基产生,赋予其良好的电性能和低吸水性:
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。
优选地,所述酰亚胺改性环氧树脂环氧当量与交联剂中活性基团的当量的比值为1:0.9~1.1。
即,所述交联剂为活性酯时,所述酰亚胺改性环氧树脂环氧当量与交联剂中活性酯的酯基当量比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。所述交联剂为酸酐化合物时,所述酰亚胺改性环氧树脂环氧当量与交联剂中酸酐化合物的酸酐当量比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。所述交联剂为酚醛树脂时,所述酰亚胺改性环氧树脂环氧当量与交联剂中酚醛树脂的羟基当量比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。
所述交联剂为活性酯和酸酐化合物时,所述酰亚胺改性环氧树脂环氧当量与活性酯的酯基当量和酸酐化合物的酸酐当量的之和比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。所述交联剂为活性酯和酚醛树脂时,所述酰亚胺改性环氧树脂环氧当量与活性酯的酯基当量和酚醛树脂的羟基当量之和的比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。所述交联剂为酸酐化合物和酚醛树脂时,所述酰亚胺改性环氧树脂环氧当量与酸酐化合物的酸酐当量和酚醛树脂的羟基当量之和比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。所述交联剂为活性酯、酸酐化合物和酚醛树脂时,所述酰亚胺改性环氧树脂环氧当量与活性酯的酯基当量、酸酐化合物的酸酐当量和酚醛树脂的羟基当量之和比值为1:0.9~1.1,例如1:10.92、1:0.94、1:0.96、1:0.98、1:1、1:1.02、1:1.04、1:1.06或1:1.08。
优选地,所述环氧树脂组合物还包括固化促进剂,其使树脂固化并加快树脂固化速度。以组分(A)和组分(B)添加量之和为100重量份计,所述固化促进剂的添加量为0.05~1重量份,例如0.08重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份或0.95重量份。
优选地,所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑中的任意一种或者至少两种的混合物。
优选地,所述环氧树脂组合物还包括阻燃剂,该阻燃剂为含溴阻燃剂或/和无卤阻燃剂。
优选地,以组分(A)和组分(B)添加量之和为100重量份计,所述阻燃剂的添加量为5~50重量份,例如5重量份、10重量份、15重量份、25重量份、30重量份、35重量份、40重量份或45重量份。
优选地,所述含溴阻燃剂选自十溴二苯乙烷、溴化聚苯乙烯、乙撑双四溴邻苯二甲酰亚胺或含溴环氧树脂中的任意一种或者至少两种的混合物。
优选地,所述无卤阻燃剂为三(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、苯氧基膦腈化合物、硼酸锌、氮磷系膨胀型、有机聚合物阻燃剂、含磷酚醛树脂或含磷双马来酰亚胺中的任意一种或者至少两种的混合物。
优选地,所述环氧树脂组合物还包含填料,所述填料为有机填料或/和无机填料,其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。
优选地,以组分(A)和组分(B)的添加量之和为100重量份计,所述填料的添加量为0~100重量份且不包括0,优选0~50重量份且不包括0。所述填料的添加量例如为0.5重量份、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重量份或95重量份。
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,钛酸锶和碳酸钙的混合物,硅酸钙、云母和玻璃纤维粉的混合物,熔融二氧化硅、结晶型二氧化硅和球型二氧化硅的混合物,空心二氧化硅、氢氧化铝和氧化铝的混合物,滑石粉、氮化铝和氮化硼的混合物,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,聚醚砜粉末和聚四氟乙烯粉末的混合物,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,所述填料为二氧化硅,填料的粒径中度值为1~15μm,优选填料的粒径中度值为1~10μm。
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环氧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,所述环氧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。
本发明的树脂组合物的常规制作方法:取一容器,先将固体组分放入,然后加入液体溶剂,搅拌直至完全溶解后,加入液体树脂、填料、阻燃剂、固化促进剂,继续搅拌均匀即可,最后用溶剂调整液体固含量至60%~80%而制成胶液。
本发明的目的之二在于提供一种预浸料,其包括增强材料及通过含浸干燥后附着其上的如上所述的环氧树脂组合物。
示例性的增强材料如无纺织物或/和其他织物,例如天然纤维、有机合成纤维以及无机纤维。
使用该胶液含浸增强材料如玻璃布等织物或有机织物,将含浸好的增强材料在155℃的烘箱中加热干燥5~10分钟即可得到预浸料。
本发明的目的之三在于提供一种层压板,其包括至少一张如上所述的预浸料。
本发明的目的之四在于提供一种印制电路板,其包括至少一张如上所述的预浸料。
与现有技术相比,本发明具有如下有益效果:
(1)本发明在环氧树脂主链中引入刚性较强的酰亚胺基团,改善了现有酰亚胺树脂的溶解性、工艺加工性及韧性差的问题,与此同时,其相对于现有的典型环氧树脂具有更好的耐热性;
(2)使用该环氧树脂组合物制作的预浸料、层压板和覆金属箔层压板,具有高玻璃化转变温度、低介电常数、低介质损耗因子、高耐湿热性、高韧性和良好的工艺加工性。
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。
根据上述所制成的一种环氧树脂组合物覆金属箔层压板,测试其玻璃化转变温度、介电常数、介电损耗因子和PCT及PCT吸水率和韧性,如下述实施例加于详细说明与描述,其中有机树脂的质量份按有机固形物质量份计。
制备例1:式(1)结构的环氧树脂合成
将对氨基苯酚11g和200g丁酮加入带有搅拌器、温度计、氮气导入管和回流冷凝器的圆底烧瓶中,水浴加热,加快其溶解,将浓度为20%(重量百分比)的双酚A型二醚二酐用丁酮溶液130g滴加至反应器中,控制好滴加速度,以便其在1h内滴加完,30℃下继续反应2h,蒸除丁酮,加入DMF 160g和甲苯40g的混合溶剂,加入催化剂对甲基苯磺酸(P-TSA)0.25g,在110℃下反应8h,反应结束,减压蒸除部分溶剂,水洗,过滤,重结晶,真空干燥,得到含苯环和酰亚胺结构的羟基化合物如下所示:
向四口烧瓶中投入80.2g上一步反应得到含苯环和酰亚胺结构的羟基化合物、18.6g 4,4-二羟基联苯、6g甲醛、0.25g对甲基苯磺酸和250g溶剂甲基异丁基酮,150℃下反应6-8h,反应结束后水洗、脱溶剂得到中间体。
将上一步得到25g中间体放入四口烧瓶中,再称取100g环氧氯丙烷缓慢加入,待其溶解后,开始升温,并在滴液漏斗中加入1mol的质量分数为33%的NaOH溶液,控制速度,使其在1h内滴加完,控制反应温度在100℃,滴加完后保温5h,冷却后水洗,再升温至120℃蒸馏,蒸出过量环氧氯丙烷,反应结束,减压蒸除部分溶剂,水洗,过滤,重结晶,真空干燥,得如下的环氧树脂:
A为苯环,R为R'为
制备例2:式(2)结构的环氧树脂合成
将对氨基苯酚11g和200g丁酮加入带有搅拌器、温度计、氮气导入管和回流冷凝器的圆底烧瓶中,水浴加热,加快其溶解,将浓度为20%(重量百分比)的双酚A型二醚二酐用丁酮溶液130g滴加至反应器中,控制好滴加速度,以便其在1h内滴加完,30℃下继续反应2h,蒸除丁酮,加入DMF 160g和甲苯40g的混合溶剂,加入催化剂对甲基苯磺酸(P-TSA)0.25g,在110℃下反应8h,反应结束,减压蒸除部分溶剂,过滤,重结晶,真空干燥,得到含苯环和酰亚胺结构的羟基化合物如下所示:
在四口烧瓶中投入80.2g上一步反应得到含苯环和酰亚胺结构的羟基化合物、6g甲醛、0.25g对甲基苯磺酸和200g溶剂甲基异丁基酮,150℃下反应6~8h,反应结束后水洗、脱溶剂得到中间体。
将上一步得到25g中间体放入四口烧瓶中,再称取150g环氧氯丙烷缓慢加入,待其溶解后,开始升温,并在滴液漏斗中加入1mol的质量分数为33%的NaOH溶液,控制速度,使其在1h内滴加完,控制反应温度在100℃,滴加完后保温5h,冷却后水洗,再升温至120℃蒸馏,蒸出过量环氧氯丙烷,得如下的环氧树脂:
A为苯环,R为
实施例1
取一容器,加入60重量份的A1,加入适量的MEK,活性酯交联剂HPC-8000-65T,加入适量的固化促进剂4-二甲氨基吡啶,继续搅拌均匀,最后用溶剂调整液体固含量至60%~80%而制成胶液。用玻璃纤维布浸渍上述胶液,即成胶液。用玻璃纤维布浸渍上述胶液,并控制至适当厚度,然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合,在其两侧分别压覆一张铜箔,放进热压机中固化制成所述的环氧树脂覆铜板层压板。物性数据如表1所示。
实施列2~6
制作工艺和实施列1相同,配方组成及其物性指标如表1所示。
比较例1~3
制作工艺与实施例1相同,配方组成及其物性指标如表2所示。
表1.各实施例的配方组成及其物性数据
表2各比较例的配方组成及其物性数据。
注:表中皆以固体组分重量份计。
表1和表2列举的材料具体如下:
A1:制备例1合成的环氧树脂。
A2:制备例2合成的环氧树脂。
A3:含萘环、双环戊二烯环和酰亚胺结构的环氧树脂。
NC-3000H:联苯型酚醛环氧树脂(日本化药商品名,环氧当量288g/eq)。
7200-3H:双环戊二烯型酚醛环氧树脂(日本DIC商品名,环氧当量285g/eq)。
HPC-8000-65T:活性酯交联剂(日本DIC商品名,酯基当量223g/eq)。
EF40:苯乙烯马来酸酐(沙多玛商品名,酸酐当量为260g/eq)。
2812:线性酚醛树脂(韩国momentive商品名,羟基当量为105g/eq)。
4-二甲氨基吡啶:促进剂(广荣化学商品名)。
以上特性的测试方法如下:
(1)玻璃化转变温度(Tg):根据差示扫描量热法(DSC),按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(2)介电常数和介电损耗因子:按照IPC-TM-6502.5.5.9所规定的方法进行测试,测试频率为10GHZ。
(3)PCT后耐浸焊性评价:将覆铜板表面的铜箔蚀刻后,评价基板;将基板放置压力锅中,在120℃、105KPa条件下处理2h;后浸渍在288℃的锡炉中,当基板分层爆板时记录相应时间;当基板在锡炉中超过5min还没出现气泡或分层时即可结束评价。3块中如有0,1,2,3块出现气泡或分层现象记为0/3,1/3,2/3,3/3。。
(4)落锤冲击韧性:使用落锤冲击仪,冲击仪落锤高度40cm,下落重锤重量为1Kg,韧性好坏评价:十字架清晰,说明产品韧性越好,以字符◎表示;十字架模糊,说明产品的韧性差、脆性大,以字符△表示;十字架清晰程度介于清晰和模糊之间,说明产品的韧性一般,以字符○表示。
物性分析。
从表1和表2的物性数据可知,比较例中,采用活性酯固化联苯环氧树脂和双环戊二烯环氧树脂,介电性能优,且具有低吸水率,但其玻璃化转变温度较低,而比较例1中,含萘环、双环戊二烯环和酰亚胺结构的环氧树脂,虽然具有高玻璃化转变温度,但其溶解性差,容易出现相分离且脆性大。而实施例中,加入本发明所述的酰亚胺环氧树脂后,固化物不仅具有高的玻璃化转变温度、好的韧性和PCT耐湿热性且介电性能优。
如上所述,与一般的层压板相比,本发明的环氧电路基板具有高玻璃化转变温度、低介电常数、低介质损耗因子、高耐湿热性、高韧性和良好的工艺加工性。
以上所述,仅为本发明的较佳实施例,对于本领域的普通技术人员来说,可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形,而所有这些改变和变形都应属于本发明权利要求的范围。
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 (25)
1.一种环氧树脂组合物,其特征在于,其包括如下组分:
(A)酰亚胺改性环氧树脂;
(B)交联剂;
其中,所述酰亚胺改性环氧树脂为具有式(1)或/和式(2)结构的环氧树脂:
式(1)和式(2)中的A均独立地为未取代的苯基或被C1~C4的烷基取代的苯基;n1、n2和n3均独立地为大于等于1的整数;
式(1)和式(2)中的R均独立地为
式(1)中,R'为其中R″为单键、
2.如权利要求1所述的环氧树脂组合物,其特征在于,所述酰亚胺改性环氧树脂为具有式(2)结构的环氧树脂。
3.如权利要求2所述的环氧树脂组合物,其特征在于,所述酰亚胺改性环氧树脂为具有如下结构的环氧树脂:
A为苯基,R为
4.如权利要求1~2之一所述的环氧树脂组合物,其特征在于,所述交联剂为活性酯、酸酐化合物或酚醛树脂的任意一种或者至少两种的混合物。
5.如权利要求4所述的环氧树脂组合物,其特征在于,所述交联剂为活性酯或/和酸酐化合物。
6.如权利要求5所述的环氧树脂组合物,其特征在于,所述交联剂为具有如下结构的活性酯:
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。
7.如权利要求1~2之一所述的环氧树脂组合物,其特征在于,所述酰亚胺改性环氧树脂环氧当量与交联剂中活性基团的当量的比值为1:0.9~1.1。
8.如权利要求1-2之一所述的环氧树脂组合物,其特征在于,所述环氧树脂组合物还包括固化促进剂。
9.如权利要求8所述的环氧树脂组合物,其特征在于,以组分(A)和组分(B)添加量之和为100重量份计,所述固化促进剂的添加量为0.05~1重量份。
10.如权利要求8所述的环氧树脂组合物,其特征在于,所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑中的任意一种或者至少两种的混合物。
11.如权利要求1-2之一所述的环氧树脂组合物,其特征在于,所述环氧树脂组合物还包括阻燃剂。
12.如权利要求11所述的环氧树脂组合物,其特征在于,所述阻燃剂为含溴阻燃剂或/和无卤阻燃剂。
13.如权利要求11所述的环氧树脂组合物,其特征在于,以组分(A)和组分(B)添加量之和为100重量份计,所述阻燃剂的添加量为5~50重量份。
14.如权利要求12所述的环氧树脂组合物,其特征在于,所述含溴阻燃剂选自十溴二苯乙烷、溴化聚苯乙烯、乙撑双四溴邻苯二甲酰亚胺或含溴环氧树脂中的任意一种或者至少两种的混合物。
15.如权利要求12所述的环氧树脂组合物,其特征在于,所述无卤阻燃剂为三(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、苯氧基膦腈化合物、硼酸锌、氮磷系膨胀型、有机聚合物阻燃剂、含磷酚醛树脂或含磷双马来酰亚胺中的任意一种或者至少两种的混合物。
16.如权利要求1-2之一所述的环氧树脂组合物,其特征在于,所述环氧树脂组合物还包含填料,所述填料为有机填料或/和无机填料。
17.如权利要求16所述的环氧树脂组合物,其特征在于,以组分(A)和组分(B)的添加量之和为100重量份计,所述填料的添加量为0~100重量份且不包括0。
18.如权利要求17所述的环氧树脂组合物,其特征在于,以组分(A)和组分(B)的添加量之和为100重量份计,所述填料的添加量为0~50重量份且不包括0。
19.如权利要求16所述的环氧树脂组合物,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。
20.如权利要求16所述的环氧树脂组合物,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。
21.如权利要求16所述的环氧树脂组合物,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。
22.如权利要求21所述的环氧树脂组合物,其特征在于,所述填料的粒径中度值为1~10μm。
23.一种预浸料,其包括增强材料及通过含浸干燥后附着其上的如权利要求1-22之一所述的环氧树脂组合物。
24.一种层压板,其包括至少一张如权利要求23所述的预浸料。
25.一种印制电路板,其包括至少一张如权利要求23所述的预浸料。
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