CN109796728A - 一种聚多酚改性的碳氢组合物基半固化片及其制备的覆铜板 - Google Patents
一种聚多酚改性的碳氢组合物基半固化片及其制备的覆铜板 Download PDFInfo
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- CN109796728A CN109796728A CN201910090260.5A CN201910090260A CN109796728A CN 109796728 A CN109796728 A CN 109796728A CN 201910090260 A CN201910090260 A CN 201910090260A CN 109796728 A CN109796728 A CN 109796728A
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- Prior art keywords
- polyphenol
- poly
- hydrocarbon composition
- epoxy resin
- modified
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- 235000013824 polyphenols Nutrition 0.000 title claims abstract description 70
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract description 67
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
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- 239000011889 copper foil Substances 0.000 claims abstract description 11
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/04—Fibres or whiskers inorganic
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Abstract
本发明涉及一种聚多酚改性的碳氢组合物基半固化片及其制备的覆铜板。本发明选用端羟基、端氨基或端巯基修饰的聚芳醚或聚烯烃树脂为基体树脂，环氧树脂为主要固化剂，构建了介电性能优异的碳氢组合物。同时，本发明还将聚多酚修饰到增强材料和填料的表面，因聚多酚含有丰富的羟基官能团，可参与到端基修饰的聚芳醚或聚烯烃与环氧树脂的交联固化反应中来，由此将基体树脂直接键连到增强材料和填料的表面，增强了他们的相容性和粘结力。进一步地，用该半固化片和铜箔制作的高频覆铜板，其热‑机械性能佳、介电性能优异、综合性能稳定性好、均匀性佳、铜箔剥离强度高，能满足高频、高速通信领域对基板材料的各项综合性能要求。
Description
技术领域
本发明属于通信材料领域，具体涉及一种聚多酚改性的碳氢组合物基半固化片及其制备的覆铜板。
背景技术
覆铜板是信息电子产业的关键材料之一，已广泛应用在通信基站、卫星、无人驾驶汽车、无人机和智能机器人等多个领域。聚苯醚和聚烯烃树脂因具有优异的介电性能，可用来制作覆铜板。现如今，人们已开发出了聚苯醚基和聚二烯烃基热固型的覆铜板。其中，热固型聚苯醚树脂主要有侧乙烯基修饰和端乙烯基修饰两大类。侧乙烯基修饰聚苯醚的制备过程需要用到丁基锂等反应性极强、危险度高、毒性大的物质，生产工艺极为复杂。端乙烯基修饰的聚苯醚已经实现了商品化，然而其固化过程需要添加额外的交联剂。比如，CN1745142A和WO2006/023371A1采用TAIC和不饱和烯烃单体等为热固型聚苯醚的小分子交联固化剂，然而，在上胶、半固化片烘烤等生产过程中，此类小分子交联固化剂极易挥发，导致聚苯醚的固化程度和半固化片的品质难控、且污染严重。为解决此问题，CN102807658B和CN103467967A改用聚二烯烃等高分子交联固化剂。但是，除了聚苯乙烯，聚苯醚一般与其他树脂的相容性都不好，致使半固化片复合基体内的树脂分相严重。
此外，覆铜板制作过程中常用的玻纤布和无机填料（例如氧化硅、氧化铝等），表面含有丰富的亲水性官能团——羟基，而乙烯基修饰的聚苯醚基和聚二烯烃不含有含氧、含氮等亲水性官能团，与玻纤布和无机填料的相容性不佳，由此制备得到的覆铜板不同部位的介电性能及其均匀性不完美，不适合于制作多层覆铜板，也就难以满足当下高频、高速通信领域对覆铜板材料的功能多元化和复杂化、线路布置高密度化等各项要求。
在无机填料、玻纤布或是铜箔表面修饰上偶联剂，是一种常用的增强它们与基体树脂之间相互作用力的方法。《先进功能材料》杂志（Advanced Functional Materials,2007, 318, 426.）报道了一些植物多酚在紫外光照射下可通过氧化聚合在几乎所有物质的表面迅速、强有力地吸附。同时，聚多酚含有丰富的羟基官能团，可参与到环氧树脂的固化过程中来。因此，聚多酚是一种潜在的有效改善覆铜板基体中各物料之间相互作用力和粘结力的物质。
发明内容
本发明的目的在于提供一种聚多酚改性的碳氢组合物基半固化片。
本发明的另一个目的在于提供一种由该半固化片制备得到的热-机械性能优异、介电性能及其均匀性好、铜箔剥离强度高的高频高速覆铜板。
本发明解决上述问题采用的技术方案是一种聚多酚改性的碳氢组合物基半固化片，依次通过以下步骤制得：
S1、用0.1~80mg/mL多酚水溶液浸渍增强材料，在非惰性气氛且紫外光照射下晾置5~360min后，经干燥得到产物，即表面修饰了聚多酚的增强材料，记为聚多酚@增强材料；
S2、向0.1~80mg/mL多酚水溶液中加入0.1~25wt/v%填料，在非惰性气氛且紫外光照射下搅拌分散均匀，浸泡5~720min后，经过滤、洗涤、干燥得到产物，即表面修饰了聚多酚的填料，记为聚多酚@填料；
S3、配置固含量为35~75wt/v%碳氢组合物的均匀分散液，将该均匀分散液浸渍所述聚多酚@增强材料，经烘烤干燥得到半固化片，
所述多酚为分子式中含有邻苯二酚或邻苯三酚结构的植物多酚中的一种或几种的混合物，所述多酚水溶液的pH值在4.5和9.0之间，所述非惰性气氛为含有氧气的气氛，其中氧气占非惰性气体的含量≥3v/v%，所述紫外光的波长≤340nm，紫外光的光强≥1mW/cm2，紫外光照射时的环境温度≤50℃，紫外光光源与照射物之间的距离≤100cm，所述碳氢组合物包括了端基修饰的碳氢聚合物、主固化次、次固化剂、固化促进剂、所述聚多酚@填料和阻燃剂六类组分。
进一步优选的技术方案在于：步骤S1中，所述增强材料为106、1080、2116和7628电子级无碱玻纤布、或氟树脂纤维编织布中的一种，所述聚多酚@增强材料中的聚多酚占增强材料质量的0.03~1.0wt%。
进一步优选的技术方案在于：步骤S2中，所述的填料由无机填料和有机填料组成，其中所述无机填料为SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、BN、SiC、Si3N4、Al(OH)3、Mg(OH)2、SrTiO3、BaTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3、氧化石墨、氟化石墨、滑石粉、云母粉、高岭土、粘土、实心玻璃微珠、空心玻璃微珠、玻璃纤维、玄武岩纤维和碳纤维中的一种、或是几种的混合物，所述无机填料的粒径≤100um，其用量占碳氢组合物的12~60wt%；
所述有机填料为超高分子量聚乙烯纤维、凯夫拉纤维、氟树脂和聚酰亚胺及其衍生物中的一种、或是几种的混合物，所述有机填料的含量为碳氢组合物的1~20wt%，所述聚多酚@填料中的聚多酚占填料质量的0.03~1.0wt%。
进一步优选的技术方案在于：步骤S3中，所述碳氢聚合物为聚芳醚和聚烯烃及其衍生物中的一种或几种的混合物，所述的端基为胺基、羟基和巯基中的一种或几种，所述端基修饰的碳氢聚合物占总的碳氢组合物的4~25wt%。
进一步优选的技术方案在于：步骤S3中，所述主固化剂为环氧树脂，具体为双酚A型环氧树脂、氢化双酚A型环氧树脂、双酚S型环氧树脂、双酚F型环氧树脂、双环戊二烯型环氧树脂、萘环结构环氧树脂、联苯型环氧树脂、杂环型环氧树脂、酚醛型环氧树脂、有机硅环氧树脂、多官能团环氧树脂、脂肪族环氧树脂和氰酸酯改性环氧树脂及其衍生物中的一种或几种的混合物，所述的主固化剂占碳氢组合物的15~68wt%；
所述次固化剂为活性聚酯、二元醇、多元醇、二元胺、多元胺、二硫醇、多元硫醇、二元酚、多元酚、酚醛树脂、氰酸酯树脂、酸酐、双氰胺和苯并噁嗪及其衍生物中的一种或几种的混合物，所述次固化剂占碳氢组合物的0.1~12wt%；
所述固化促进剂为叔胺类化合物、咪唑类化合物、膦类化合物、取代脲类化合物、酚类化合物和三氟化硼胺类络合物中的一种或几种的混合物，所述的固化促进剂占主固化剂的0.02~5.0wt%；
所述阻燃剂为铝镁系阻燃剂、硼锌系阻燃剂、钼锡系阻燃剂、溴系阻燃剂、三氧化二锑、磷系阻燃剂和氮系阻燃剂及其衍生物中的一种或多种的混合物，所述的阻燃剂占碳氢组合物的1~50wt%。
进一步优选的技术方案在于：步骤S3中，所述均匀分散液的溶剂为可使得碳氢组合物均匀分散的有机溶剂中的一种或几种的混合物。
进一步优选的技术方案在于：步骤S3中，所述烘烤干燥分为两个阶段，第一阶段烘烤干燥温度为30~110℃，第二阶段烘烤干燥温度为110~180℃。
一种采用聚多酚改性的碳氢组合物基半固化片制备的覆铜板，依次通过以下步骤制得：将所述半固化片和覆于表层的铜箔叠合在一起，经层压得到覆铜板，其中半固化片的张数≥1，铜箔的张数为1或2，层压温度为130~280℃，层压压力为80~130kg/cm2，层压时间为5min~480min。
本发明选用端羟基、端氨基或端巯基修饰的聚芳醚或聚烯烃树脂为基体树脂，环氧树脂为主要固化剂，构建了介电性能优异的碳氢组合物。同时，本发明还将聚多酚修饰到增强材料和填料的表面，因聚多酚含有丰富的羟基官能团，可参与到端基修饰的聚芳醚或聚烯烃与环氧树脂的交联固化反应中来，由此将基体树脂直接键连到增强材料和填料的表面，增强了他们的相容性和粘结力。在本发明中，用增强材料浸渍碳氢组合物的分散液、再经烘烤干燥制得的半固化片含胶量均匀、浸胶质量佳、树脂附着力强、表面平整、强韧性和粘性适宜。进一步地，用该半固化片和铜箔制作的高频覆铜板，其热-机械性能佳、介电性能优异、综合性能稳定性好、均匀性佳、铜箔剥离强度高。
发明人还发现，聚多酚在增强材料和填料表面的修饰量不可过少，否则增强材料、填料和基体树脂之间的相互作用力提升不明显；但聚多酚的修饰量也不可过多，否则覆铜板的介电损耗会增大。
本发明制备条件温和、生产成本低、易于批量化和规模化生产、普适性强，具有良好的工业化生产基础和广阔的应用前景。
具体实施方式
以下通过实施例进一步详细说明本发明提供的一种采用聚多酚改性的碳氢组合物基半固化片、以及用该半固化片制备得到的高频覆铜板。然而，该实施例仅仅是作为提供说明，而不是限定本发明。
实施例 1~5
将1080玻纤布于40mg/mL多酚水溶液中浸泡30min并同时进行紫外光照射，紫外光的波长为260nm，紫外光的光强为10mW/cm2，环境温度为30℃，紫外光光源与照射物之间的距离为30cm，随后取出得到表面修饰了聚多酚的1080玻纤布，记为“聚多酚@1080玻纤布”。将填料在40mg/mL多酚的水溶液中搅拌、浸泡30min并同时进行紫外光照射，紫外光的波长为260nm，紫外光的光强为10mW/cm2，环境温度为30℃，紫外光光源与照射物之间的距离为10cm，后经过滤、洗涤、干燥，得到表面修饰了聚多酚的填料，记为“聚多酚@填料”。将端羟基修饰的碳氢聚合物、主固化剂、次固化剂、固化促进剂、“聚多酚@填料”和阻燃剂均匀分散在甲苯中，控制该分散液的固含量在60wt%，再将“聚多酚@1080玻纤布”在该均匀分散液中浸胶，经烘烤得到半固化片。第一阶段烘烤干燥温度为60~100℃；第二阶段烘烤干燥温度为100~170℃。取8张半固化片叠合在一起，两面分别附上loz铜箔，在真空、加压、高温下层压数小时后制得覆铜板。具体配方详见下表。
对比例 1
对比例1采用未经聚多酚修饰的1080玻纤布和填料，其他工艺与实施例1相同。
对比例 2
对比例2采用聚多酚修饰的填料，而未采用聚多酚修饰的1080玻纤布，其他工艺与实施例1相同。
其中，半固化片和覆铜板的各项测试性能如下所示。
如对比例1所示，若玻纤布和填料的表面未经聚多酚修饰，基体树脂无法直接键连到玻纤布和填料表面，三者之间的粘结力不强，所制备得到的覆铜板耐浸焊性和钻孔性不佳。若只单独在填料的表面修饰上聚多酚，如对比例2所示，覆铜板基体内各组分的粘结力有所提高，其耐浸焊性和钻孔性得以提升，但程度不明显。只有在玻纤布和填料表面均修饰上聚多酚，如实施例1~5所示，因聚多酚可参与到端基修饰的聚芳醚或聚烯烃与环氧树脂的交联固化反应中来，基体树脂将直接键连到玻纤布和填料的表面，最大程度地提升了覆铜板基体内各组分之间的粘结力，在进一步提高板材的耐浸焊性和钻孔性的同时，因板子均匀性的提升、基体树脂内自由体积和缺陷的减少，而使得覆铜板的吸水率和介质损耗也有一定程度的下降。
本发明制备条件温和，生产成本较低，易于批量化、规模化生产，具有良好的工业化生产基础和广阔的应用前景。
Claims (8)
1.一种聚多酚改性的碳氢组合物基半固化片，其特征在于依次通过以下步骤制得：
S1、用0.1~80mg/mL多酚水溶液浸渍增强材料，在非惰性气氛且紫外光照射下晾置5~360min后，经干燥得到产物，即表面修饰了聚多酚的增强材料，记为聚多酚@增强材料；
S2、向0.1~80mg/mL多酚水溶液中加入0.1~25wt/v%填料，在非惰性气氛且紫外光照射下搅拌分散均匀，浸泡5~720min后，经过滤、洗涤、干燥得到产物，即表面修饰了聚多酚的填料，记为聚多酚@填料；
S3、配置固含量为35~75wt/v%碳氢组合物的均匀分散液，将该均匀分散液浸渍所述聚多酚@增强材料，经烘烤干燥得到半固化片，
所述多酚为分子式中含有邻苯二酚或邻苯三酚结构的植物多酚中的一种或几种的混合物，所述多酚水溶液的pH值在4.5和9.0之间，所述非惰性气氛为含有氧气的气氛，其中氧气占非惰性气体的含量≥3v/v%，所述紫外光的波长≤340nm，紫外光的光强≥1mW/cm2，紫外光照射时的环境温度≤50℃，紫外光光源与照射物之间的距离≤100cm，所述碳氢组合物包括了端基修饰的碳氢聚合物、主固化次、次固化剂、固化促进剂、所述聚多酚@填料和阻燃剂六类组分。
2.根据权利要求1所述的一种聚多酚改性的碳氢组合物基半固化片，其特征在于：步骤S1中，所述增强材料为106、1080、2116和7628电子级无碱玻纤布、或氟树脂纤维编织布中的一种，所述聚多酚@增强材料中的聚多酚占增强材料质量的0.03~1.0wt%。
3.根据权利要求1所述的一种聚多酚改性的碳氢组合物基半固化片，其特征在于：步骤S2中，所述填料包括有机填料，所述有机填料为超高分子量聚乙烯纤维、凯夫拉纤维、氟树脂和聚酰亚胺及其衍生物中的一种、或是几种的混合物，所述有机填料的含量为碳氢组合物的1~20wt%，所述聚多酚@填料中的聚多酚占填料质量的0.03~1.0wt%。
4.根据权利要求1所述的一种聚多酚改性的碳氢组合物基半固化片，其特征在于：步骤S3中，所述碳氢聚合物为聚芳醚和聚烯烃及其衍生物中的一种或几种的混合物，所述的端基为胺基、羟基和巯基中的一种或几种，所述端基修饰的碳氢聚合物占总的碳氢组合物的4~25wt%。
5.根据权利要求1所述的一种聚多酚改性的碳氢组合物基半固化片，其特征在于：步骤S3中，所述主固化剂为环氧树脂，具体为双酚A型环氧树脂、氢化双酚A型环氧树脂、双酚S型环氧树脂、双酚F型环氧树脂、双环戊二烯型环氧树脂、萘环结构环氧树脂、联苯型环氧树脂、杂环型环氧树脂、酚醛型环氧树脂、有机硅环氧树脂、多官能团环氧树脂、脂肪族环氧树脂和氰酸酯改性环氧树脂及其衍生物中的一种或几种的混合物，所述的主固化剂占碳氢组合物的15~68wt%；
所述次固化剂为活性聚酯、二元醇、多元醇、二元胺、多元胺、二硫醇、多元硫醇、二元酚、多元酚、酚醛树脂、氰酸酯树脂、酸酐、双氰胺和苯并噁嗪及其衍生物中的一种或几种的混合物，所述次固化剂占碳氢组合物的0.1~12wt%；
所述固化促进剂为叔胺类化合物、咪唑类化合物、膦类化合物、取代脲类化合物、酚类化合物和三氟化硼胺类络合物中的一种或几种的混合物，所述的固化促进剂占主固化剂的0.02~5.0wt%；
所述阻燃剂为铝镁系阻燃剂、硼锌系阻燃剂、钼锡系阻燃剂、溴系阻燃剂、三氧化二锑、磷系阻燃剂和氮系阻燃剂及其衍生物中的一种或多种的混合物，所述的阻燃剂占碳氢组合物的1~50wt%。
6.根据权利要求1所述的一种聚多酚改性的碳氢组合物基半固化片，其特征在于：步骤S3中，所述均匀分散液的溶剂为可使得碳氢组合物均匀分散的有机溶剂中的一种或几种的混合物。
7.根据权利要求1所述的一种聚多酚改性的碳氢组合物基半固化片，其特征在于：步骤S3中，所述烘烤干燥分为两个阶段，第一阶段烘烤干燥温度为30~110℃，第二阶段烘烤干燥温度为110~180℃。
8.一种采用如权利要求1所述的聚多酚改性的碳氢组合物基半固化片制备的覆铜板，其特征在于依次通过以下步骤制得：将所述半固化片和覆于表层的铜箔叠合在一起，经层压得到覆铜板，其中半固化片的张数≥1，铜箔的张数为1或2，层压温度为130~280℃，层压压力为80~130kg/cm2，层压时间为5min~480min。
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