CN103131007B - 热固性树脂组合物及应用其的积层板及电路板 - Google Patents
热固性树脂组合物及应用其的积层板及电路板 Download PDFInfo
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- CN103131007B CN103131007B CN201110376733.1A CN201110376733A CN103131007B CN 103131007 B CN103131007 B CN 103131007B CN 201110376733 A CN201110376733 A CN 201110376733A CN 103131007 B CN103131007 B CN 103131007B
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- Prior art keywords
- resin
- epoxy resin
- bisphenol
- benzoxazine
- resin composition
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- 239000011347 resin Substances 0.000 claims abstract description 86
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003822 epoxy resin Substances 0.000 claims description 51
- 229920000647 polyepoxide Polymers 0.000 claims description 51
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 41
- 239000003063 flame retardant Substances 0.000 claims description 29
- 239000011256 inorganic filler Substances 0.000 claims description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 19
- 239000005011 phenolic resin Substances 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
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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 description 20
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- 239000004744 fabric Substances 0.000 description 5
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- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 4
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Abstract
本发明提供一种包含萘环、联苯或蒽环结构的苯并恶嗪树脂,以及包含该苯并恶嗪树脂的树脂组合物、积层板及电路板。本发明借着于树脂组合物中包含特定结构的苯并恶嗪树脂,以使可达到低介电常数、低介电损耗、高刚性及高耐热性;可制作成半固化胶片或树脂膜,进而达到可应用于积层板及电路板的目的。
Description
技术领域
本发明关于一种苯并恶嗪树脂,尤指一种应用于积层板及电路板的苯并恶嗪树脂。
背景技术
为因应世界环保潮流及绿色法规,无卤素(Halogen-free)为当前全球电子产业的环保趋势,世界各国及相关电子大厂陆续对其电子产品,制定无卤素电子产品的量产日程表。欧盟的有害物质限用指令(Restriction of HazardousSubstances,RoHS)实施后,包含铅、镉、汞、六价铬、聚溴联苯与聚溴二苯醚等物质,已不得用于制造电子产品或其零组件。印刷电路板(Printed CircuitBoard,PCB)为电子电机产品的基础,无卤素以对印刷电路板为首先重点管制对象,国际组织对于印刷电路板的卤素含量已有严格要求,其中国际电工委员会(IEC)61249-2-21规范要求溴、氯化物的含量必须低于900ppm,且总卤素含量必须低于1500ppm;日本电子回路工业会(JPCA)则规范溴化物与氯化物的含量限制均为900ppm;而绿色和平组织现阶段大力推动的绿化政策,要求所有的制造商完全排除其电子产品中的聚氯乙烯及溴系阻燃剂,以符合兼具无铅及无卤素的绿色电子。因此,材料的无卤化成为目前业者的重点开发项目。
新世代的电子产品趋向轻薄短小,并适合高频传输,因此电路板的配线走向高密度化,电路板的材料选用走向更严谨的需求。高频电子组件与电路板接合,为了维持传输速率及保持传输讯号完整性,电路板的基板材料必须兼具较低的介电常数(dielectric constant,Dk)及介电损耗(又称损失因子,dissipation factor,Df)。同时,为了于高温、高湿度环境下依然维持电子组件正常运作功能,电路板也必须兼具耐热、难燃及低吸水性的特性。环氧树脂由于接着性、耐热性、成形性优异,故广泛使用于电子零组件及电机机械的覆铜箔积层板或密封材。从防止火灾的安全性观点而言,要求材料具有阻燃性,一般以无阻燃性的环氧树脂,配合外加阻燃剂的方式达到阻燃的效果,例如,在环氧树脂中通过导入卤素,尤其是溴,而赋予阻燃性,提高环氧基的反应性。
然而,近来的电子产品,倾向于轻量化、小型化、电路微细化,在如此的要求下,比重大的卤化物在轻量化的观点上并不理想。另外,在高温下经长时间使用后,可能会引起卤化物的解离,而有微细配线腐蚀之虞。再者使用过后的废弃电子零组件,在燃烧后会产生卤化物等有害化合物,对环境亦不友善。为取代上述的卤化物阻燃剂,有研究使用磷化合物作为阻燃剂,例如添加磷酸酯(台湾I238846号专利)或红磷(台湾322507号专利)于环氧树脂组合物中。然而,磷酸酯会因产生水解反应而使酸离析,导致影响其耐迁移性;而红磷的阻燃性虽高,但在消防法中被指为危险物品,在高温、潮湿环境下因为会发生微量的膦气体。
已知的铜箔基板(或称铜箔积层板)制作的电路板技术中,利用一环氧树脂与硬化剂作为热固性树脂组合物原料,将补强材(如玻璃纤维布)与该热固性树脂组成加热结合形成一半固化胶片(prepreg),再将该半固化胶片与上、下两片铜箔于高温高压下压合而成。现有技术一般使用环氧树脂与具有羟基(-OH)的酚醛(phenol novolac)树脂硬化剂作为热固性树脂组成原料,酚醛树脂与环氧树脂结合会使环氧基开环后形成另一羟基,羟基本身会提高介电常数及介电损耗值,且易与水分结合,增加吸湿性。
台湾第308566号专利及第460537号专利,揭示一种包含二氢氧氮萘环树脂的热固性树脂组合物,该二氢氧氮萘环树脂如双酚A苯并恶嗪树脂(Bisphenol-A Benzoxazine,BPA-BZ)或双酚F苯并恶嗪树脂(Bisphenol-FBenzoxazine,BPF-BZ),其可改善组合物的硬化性,且不牺牲机械性质。台湾第201114853号专利,公开了一种二环戊二烯-二氢苯并恶嗪树脂(Dicyclopenta-diene-Dihydrobenzoxazine,DCPD-BZ),由于该苯并恶嗪树脂的饱和环状结构,运用在热固性树脂组合物中,可有效降低热膨胀系数、降低基板的介电常数与介电损耗。
就电气性质而言,主要需考虑的包括材料的介电常数以及介电损耗。一般而言,由于基板的讯号传送速度与基板材料的介电常数的平方根成反比,故基板材料的介电常数通常越小越好;另一方面,由于介电损耗越小代表讯号传递的损失越少,故介电损耗较小的材料所能提供的传输质量也较为良好。
因此,如何开发出具有低介电常数以及低介电损耗的材料,并将其应用于高频印刷电路板的制造,乃是现阶段印刷电路板材料供货商亟欲解决的问题。
发明内容
有鉴于上述已知技术的缺憾,发明人有感其未臻于完善,遂竭其心智悉心研究克服,凭其从事该项产业多年的累积经验,进而研发出一种苯并恶嗪树脂,以期达到低介电常数、低介电损耗、高刚性及高耐热性的目的。
本发明的主要目的在提供一种苯并恶嗪树脂,其借着包含萘环、联苯或蒽环结构,应用于热固性树脂组中可达到低介电常数、低介电损耗、高刚性及高耐热性,可制作成半固化胶片或树脂膜,进而达到可应用于积层板及电路板的目的。
为达上述目的,本发明提供一种苯并恶嗪树脂,其选自下列化合物的其中一者:
(式一);
(式二);
(式三);
(式四);
(式五);
其中,n及m为任意正整数,Y代表氢基、脂肪族官能团或芳香族官能团。
本发明所述的含萘环、联苯或蒽环结构的苯并恶嗪树脂,具有苯并恶嗪的官能团,其可与酚类或胺类等其它交联剂(cross-linking agent)反应键结,且其分别具有萘环、联苯或蒽环结构,可提供该树脂高刚性及高耐热性。本发明所述的含萘环、联苯、蒽环结构的苯并恶嗪树脂,可应用于树脂产业,如一般常见的环氧树脂应用产业,作为接着剂、金属箔基板的绝缘层材料或半固化胶片等。
本发明所述的含萘环结构的苯并恶嗪树脂,由含萘环的酚醛树脂(naphthalene type phenol novolac),与苯胺及甲醛等三种原料所合成,其合成方法使用现有技术中普遍使用的方法。同理,含联苯结构的苯并恶嗪树脂及含蒽环结构的苯并恶嗪树脂,分别为含联苯的酚醛树脂(biphenyl type phenolnovolac)及含蒽环的酚醛树脂(anthracene type phenol novolac),与苯胺及甲醛等三种原料所合成。
本发明的另一目的为提供一种热固性树脂组合物,其包含:(1)上述的苯并恶嗪树脂;以及(2)交联剂。该树脂组合物具有高耐热性及高刚性。
所述的交联剂选自下列群组的至少一者:苯酚树脂、胺树脂、酚醛树脂、酸酐树脂、苯乙烯树脂、丁二烯树脂、聚酰胺树脂、聚酰亚胺树脂、聚酯树脂、聚醚树脂、聚苯醚树脂、氰酸酯树脂、异氰酸酯树脂、马来酰亚胺树脂、双酚A苯并恶嗪树脂、双酚F苯并恶嗪树脂、溴化树脂、含磷树脂及含氮树脂。该交联剂的作用在于与本发明所述的含萘环、联苯或蒽环结构的苯并恶嗪树脂键结,完成交联反应。
上述的组合物,其进一步包含环氧树脂及硬化促进剂。
所述的环氧树脂选自下列群组的至少一种:双酚A(bisphenol A)环氧树脂、双酚F(bisphenol F)环氧树脂、双酚S(bisphenol S)环氧树脂、双酚AD(bisphenol AD)环氧树脂、酚醛(phenol novolac)环氧树脂、双酚A酚醛(bisphenol A novolac)环氧树脂、双酚F酚醛(bisphenol F novolac)环氧树脂、邻甲酚(o-cresol novolac)环氧树脂、三官能团(trifunctional)环氧树脂、四官能团(tetrafunctional)环氧树脂、多官能团(multifunctional)环氧树脂、二环戊二烯环氧树脂(dicyclopentadiene epoxy resin)、含磷环氧树脂、对二甲苯环氧树脂(p-xylene epoxy resin)、萘型(naphthalene)环氧树脂、苯并哌喃型(benzopyran)环氧树脂、联苯酚醛(biphenyl novolac)环氧树脂及酚基苯烷基酚醛(phenolaralkyl novolac)环氧树脂。
所述的硬化促进剂选自下列群组的至少一者:路易斯碱及路易斯酸。其中路易斯碱可包括咪唑、三氟化硼胺复合物、氯化乙基三苯基鏻(ethyltriphenylphosphonium chloride)、2-甲基咪唑(2-methylimidazole,2MI)、2-苯基咪唑(2-phenyl-1H-imidazole,2PI)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole,2E4MI)、三苯基膦(triphenylphosphine,TPP)、4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)等。路易斯酸则可包括锰、铁、钴、镍、铜及锌的金属盐化合物。添加硬化促进剂的主要目的,在于增加所述树脂组合物的反应速率。
上述的组合物,其进一步包含选自下列群组中的至少一者:无机填充物、界面活性剂、增韧剂、阻燃剂、有机硅弹性体及溶剂。
所述无机填充物并无特别限制,已知用于积层板的无机填充物均可,例如:二氧化硅(熔融态或非熔融态与多孔质)、氧化铝、氧化镁、氢氧化镁、碳酸钙、氮化铝、氮化硼、氢氧化铝、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、碳酸镁、钛酸钾、陶瓷纤维、云母、勃姆石(Boehmite,ALOOH)、氢氧化铝(Aluminium Trihydrate,ATH,Al(OH)3)、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧滑石、滑石、氮化硅、莫莱石、段烧高岭土、黏土、碱式硫酸镁晶须、莫莱石晶须、硫酸钡、氢氧化镁晶须、氧化镁晶须、氧化钙晶须、纳米碳管、纳米级二氧化硅与其相关无机粉体、或具有有机核外层壳为绝缘体修饰的粉体粒子。且无机填充物可为球型、纤维状、板状、粒状、片状或针须状,并可选择性经由界面活性剂预处理。
无机填充物可为粒径100μm以下的颗粒粉末,且较佳为粒径1至20μm的颗粒粉末,最佳为粒径1μm以下的纳米尺寸颗粒粉末;针须状无机填充物可为直径50μm以下且长度1至200μm的粉末。添加无机填充物的主要目的,在于增加所述树脂组合物的热传导性,改良热膨胀性及机械强度,且提高刚性,优选使无机填充物均匀分布于该树脂组合物中。
所述界面活性剂,或称硅氧烷偶合剂(Siloxane)可使用公知者,并无特别限定,具体而言,选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基参(β-甲氧基-乙氧基硅烷)、γ-环氧丙氧基丙基三甲氧基硅烷、γ-胺丙基三乙氧基硅烷,其中分散剂可为BYK-103、BYK-901、BYK-161或BYK-164等。
添加界面活性剂的主要目的,在于改善无机填充物于所述树脂组合物中的均匀分散性。
所述增韧剂选自:橡胶树脂、聚丁二烯、核壳聚合物等添加物。添加增韧剂的主要目的,在于改善树脂组合物的韧性。
所述阻燃剂选自:含磷阻燃剂、含氮阻燃剂(如Melamine Cyanurate——氰尿酸三聚氰胺)、含溴阻燃剂(TBBPA,Tetra-Bromo-Bisphenol A,四溴双酚A)的其一者或其组合,其中,含磷耐燃剂可为磷酸盐类含磷耐燃剂或DOPO类含磷耐燃剂,前者与树脂并无交联性,且可为例如Exolit OP 935(可购自Clariant公司)、SPB-100(聚双苯氧基磷腈,可购自大冢化学)、PX-200(可购自大八化学);后者与树脂具有交联性,且可为例如由DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)或其衍生物所取代的双酚酚醛树脂(Bisphenol novolac,BPN)或酚醛树脂(Phenol novolac,PN),如DOPO-双酚A酚醛树脂(DOPO-bisphenol-A novolac,DOPO-BPAN)或DOPO-酚醛树脂(DOPO-phenolnovolac,DOPO-PN),但不以此为限。
所述有机硅弹性体(Hybrid type silicone powder)一般为橡胶及树脂型复合粉体,较佳为球状粉体,添加有机硅弹性体可增加本发明的热固性树脂组成的耐热性且冲击吸收性。该有机硅弹性体并无特别限制,已知用于积层板的有机硅弹性体均可,例如:信越生产的X-52-7030、KMP-605、KMP-602、KMP-601、KMP-600、KMP-590及KMP-594等产品。
所述溶剂包含甲醇、乙醇、乙二醇单甲醚、丙酮、甲基乙基酮、甲基异丁基酮、环己酮、甲苯、二甲苯、甲氧基乙基乙酸酯、乙氧基乙基乙酸酯、丙氧基乙基乙酸酯、乙酸乙酯、二甲基甲酰胺、丙二醇甲基醚等溶剂或其混合溶剂。添加溶剂的主要目的,在于改变所述树脂组合物的固含量,并调变该树脂组合物的黏度。
本发明的再一目的为提供一种无卤无磷树脂组合物,其包含:(1)萘型环氧树脂;(2)上述的苯并恶嗪树脂;(3)硬化促进剂;以及选择性添加(4)氢氧化铝及勃姆石中的一者或其组合。
本发明所述的无卤无磷树脂组合物,使用氢氧化铝或勃姆石作为阻燃剂,有效改善现有技术使用卤素阻燃剂(如溴化阻燃剂)于燃烧时会释放戴奥辛(Dioxin)等有害物,及使用含磷阻燃剂会造成较差的化学阻抗性。本发明使用氢氧化铝及勃姆石作为阻燃剂的原理,为利用高温时氢氧化铝及勃姆石会释放出结晶水以阻止火焰继续燃烧。此外,使用萘型环氧树脂(特别是四官能萘型环氧树脂),及本发明所述的含萘环、联苯或蒽环结构的苯并恶嗪树脂,因具有萘环、联苯或蒽环等高耐热耐燃结构,搭配氢氧化铝及勃姆石使用,可有效达到UL-94规范的V-0耐燃功效。
上述的组合物,其进一步包含选自下列群组中的至少一者:无机填充物、界面活性剂、增韧剂、阻燃剂、有机硅弹性体及溶剂。
本发明的再一目的提供一种半固化胶片,其具有低介电常数、低介电损耗、高刚性、高耐热性及不含卤素等特性。据此,本发明所提供的半固化胶片可包含一补强材及前述的无卤树脂组合物,其中该无卤树脂组合物以含浸等方式附着于该补强材上,并经由高温加热形成半固化态。其中,补强材可为纤维材料、织布及不织布,如玻璃纤维布等,其可增加该半固化胶片的机械强度。此外,该补强材可选择性经由硅烷偶合剂或硅氧烷偶合剂进行预处理,如经硅烷偶合剂预处理的玻璃纤维布。前述的半固化胶片经由高温加热或高温且高压下加热可固化形成固化胶片或是固态绝缘层,其中无卤树脂组合物若含有溶剂,则该溶剂会于高温加热程序中挥发移除。
本发明的再一目的为提供一种积层板,其具有低介电常数、低介电损耗、高刚性、高耐热性及不含卤素等特性,且特别适用于高速度高频率讯号传输的电路板。据此,本发明提供一种积层板,其包含两个或两个以上的金属箔及至少一绝缘层。其中,金属箔可进一步包含铜与铝、镍、铂、银、金等至少一种金属的合金;绝缘层由前述的半固化胶片于高温高压下固化而成,如将前述半固化胶片叠合于两个铜箔之间且于高温与高压下进行压合而成。该积层板进一步经由制作线路等制程加工后,可形成一电路板,且该电路板与电子组件接合后于高温、高湿度等严苛环境下操作而并不影响其质量。
本发明的再一目的为提供一种电路板,其包含上述的积层板,具有低介电常数、低介电损耗、高刚性、高耐热性及不含卤素等特性,适用于高速度高频率的讯号传输。其中,该电路板包含至少一个前述的积层板,且该电路板可由已知的制程制作而成。
为进一步描述本发明,以使本领域技术人员具有通常知识者可据以买施,以下谨以数个实施例进一步说明本发明。然应注意者,以下实施例仅用以对本发明做进一步的说明,并非用以限制本发明的实施范围,且任何本领域技术人员在不违背本发明的精神下所得以达成的修饰及变化,均属于本发明的范围。
具体实施方式
为充分了解本发明的目的、特征及功效,现通过下述具体的实施例,对本发明作一详细说明,说明如后。
分别将实施例2至5的树脂组合物列表于表一,比较例1至4的树脂组合物列表于表三。
实施例1(E1)
一种树脂组合物,包括以下成份:
(A)100重量份的式一所示苯并恶嗪树脂;
(B)20重量份的酚醛树脂(Phenol novolac)。
实施例2(E2)
一种树脂组合物,包括以下成份:
(A)100重量份的二环戊二烯环氧树脂(HP-7200);
(B)75重量份的式三所示苯并恶嗪树脂;
(C)10重量份的胺基三嗪酚醛树脂(Amino triazine novolac,ATN);
(D)30重量份的DOPO-BPAN树脂阻燃剂;
(E)80重量份的二氧化硅(Silica)无机填充物;
(F)0.3重量份的2E4MI催化剂;
(G)20重量份的甲基乙基酮(MEK)。
实施例3(E3)
一种树脂组合物,包括以下成份:
(A)50重量份的二环戊二烯环氧树脂(HP-7200);
(B)50重量份的双酚A环氧树脂(BE-188E);
(C)40重量份的双酚A苯并恶嗪树脂(BPA-BZ);
(D)35重量份的式三所示苯并恶嗪树脂;
(E)25重量份的苯乙烯马来酸酐树脂(Styrene-maleic anhydride,SMA);
(F)30重量份的磷腈化合物(SPB-100)阻燃剂;
(G)70重量份的熔融态二氧化硅(Fused silica)无机填充物;
(H)0.35重量份的2E4MI催化剂;
(I)20重量份的甲基乙基酮(MEK)。
实施例4(E4)
一种树脂组合物,包括以下成份:
(A)100重量份的双酚A氰酸酯树脂(BA-230S);
(B)40重量份的式五所示苯并恶嗪树脂;
(C)30重量份的聚苯醚树脂(PPO);
(D)10重量份的萘型酚树脂(EXB-9500);
(E)50重量份的熔融态二氧化硅(Fused silica)无机填充物;
(F)25重量份的含磷阻燃剂(PX-200);
(G)0.01重量份的辛酸锌催化剂(Zn);
(H)20重量份的甲基乙基酮(MEK)。
实施例5(E5)
一种无卤无磷树脂组合物,包括以下成份:
(A)100重量份的四官能萘型环氧树脂(HP-4700);
(B)40重量份的式一所示苯并恶嗪树脂;
(C)20重量份的萘型酚树脂(EXB-9500);
(D)0.3重量份的2E4MI催化剂;
(E)50重量份的勃姆石(Boehmite)无机填充物;
(F)20重量份的甲基乙基酮(MEK)。
比较例1(C1)
一种树脂组合物,包括以下成份:
(A)100重量份的二环戊二烯环氧树脂(HP-7200);
(B)75重量份的双酚A苯并恶嗪树脂(BPA-BZ);
(C)10重量份的胺基三嗪酚醛树脂(Amino triazine novolac,ATN);
(D)30重量份的DOPO-BPAN树脂阻燃剂;
(E)80重量份的二氧化硅(Silica)无机填充物;
(F)0.3重量份的2E4MI催化剂;
(G)20重量份的甲基乙基酮。
比较例2(C2)
一种树脂组合物,包括以下成份:
(A)50重量份的二环戊二烯环氧树脂(HP-7200);
(B)50重量份的双酚A环氧树脂(BE-188E);
(C)75重量份的双酚A苯并恶嗪树脂(BPA-BZ);
(D)25重量份的苯乙烯马来酸酐树脂(Styrene-maleic anhydride,SMA);
(E)30重量份的磷腈化合物(SPB-100)阻燃剂;
(F)70重量份的熔融态二氧化硅(Fused silica)无机填充物;
(G)0.35重量份的2E4MI催化剂;
(H)20重量份的甲基乙基酮。
比较例3(C3)
一种树脂组合物,包括以下成份:
(A)100重量份的双酚A氰酸酯树脂(BA-230S);
(B)40重量份的双酚A苯并恶嗪树脂(BPA-BZ);
(C)30重量份的聚苯醚树脂(PPO);
(D)10重量份的萘型酚树脂(EXB-9500);
(E)50重量份的熔融态二氧化硅(Fused silica)无机填充物;
(F)25重量份的含磷阻燃剂(PX-200);
(G)0.01重量份的辛酸锌催化剂(Zn);
(H)20重量份的甲基乙基酮(MEK)。
比较例4(C4)
一种树脂组合物,包括以下成份:
(A)100重量份的四官能萘型环氧树脂(HP-4700);
(B)40重量份的双酚A苯并恶嗪树脂(BPA-BZ);
(C)20重量份的萘型酚树脂(EXB-9500);
(D)0.3重量份的2E4MI催化剂;
(E)50重量份的二氧化硅(Silica)无机填充物;
(F)20重量份的甲基乙基酮(MEK)。
将上述实施例2至5及比较例1至4的树脂组合物,分批于搅拌槽中混合均匀后置入一含浸槽中,再将玻璃纤维布通过上述含浸槽,使树脂组合物附着于玻璃纤维布,再进行加热烘烤成半固化态而得半固化胶片。
将上述分批制得的半固化胶片,取同一批的半固化胶片四张及两张18μm铜箔,依铜箔、四片半固化胶片、铜箔的顺序进行叠合,再于真空条件下经由190℃压合2小时形成铜箔基板,其中四片半固化胶片固化形成两铜箔间的绝缘层。
分别将上述含铜箔基板及铜箔蚀刻后的不含铜基板做物性量测,物性量测项目包含玻璃转化温度(Tg)、含铜基板耐热性(T288)、含铜基板浸锡测试(浸焊温度(solder dip)288℃,10秒,测耐热回数,S/D)、介电常数(Dk越低越佳)、介电损耗(Df越低越佳)、耐燃性(燃烧测试(flaming test),UL94,其中等级优劣排列为V-0>V-1>V-2)。
其中实施例2至5的树脂组合物制作的基板物性量测结果列表于表二中,比较例1至4的树脂组合物制作的基板物性量测结果列表于表四中。由表二及表四,综合比较实施例2至5及比较例1至4可发现,依本发明所描述的苯并恶嗪树脂,相较于已知技术所使用的双酚A苯并恶嗪树脂,能提升基板耐热性(Tg、T288、S/D)。此外,实施例5的树脂组合物不含阻燃剂,亦可达到UL94V-0耐燃标准,对照比较例4只有较差的V-2耐燃性。
表一
表二
表三
表四
如上所述,本发明完全符合专利三要件:新颖性、创造性和实用性。以新颖性和创造性而言,本发明借着于树脂组合物中包含特定的苯并恶嗪树脂,以使可达到低介电常数、低介电损耗、高刚性及高耐热性;可制作成半固化胶片或树脂膜,进而达到可应用于积层板及电路板的目的;就实用性而言,利用本发明所衍生的产品,当可充分满足目前市场的需求。
本发明在上文中已以较佳实施例描述,然本领域技术人员应理解的是,该实施例仅用于描绘本发明,而不应解读为限制本发明的范围。应注意的是,举凡与该实施例等效的变化与置换,均应设为涵盖于本发明的范畴内。因此,本发明的保护范围当以权利要求书所界定的为准。
Claims (10)
1.一种苯并恶嗪树脂,其特征在于,其选自下列化合物的其中一者:
其中,n及m为任意正整数,Y代表氢基、脂肪族官能团或芳香族官能团。
2.一种热固性树脂组合物,其特征在于,其包含:(1)如权利要求1所述的苯并恶嗪树脂;以及(2)交联剂。
3.如权利要求2所述的组合物,其特征在于,其中该交联剂选自下列群组的至少一种:苯酚树脂、胺树脂、酚醛树脂、酸酐树脂、苯乙烯树脂、丁二烯树脂、聚酰胺树脂、聚酰亚胺树脂、聚酯树脂、聚醚树脂、聚苯醚树脂、氰酸酯树脂、异氰酸酯树脂、马来酰亚胺树脂、双酚A苯并恶嗪树脂、双酚F苯并恶嗪树脂、溴化树脂、含磷树脂及含氮树脂。
4.如权利要求2所述的组合物,其特征在于,其进一步包含环氧树脂及硬化促进剂。
5.如权利要求4所述的组合物,其特征在于,其中该环氧树脂选自下列群组的至少一种:双酚A环氧树脂、双酚F环氧树脂、双酚S环氧树脂、双酚AD环氧树脂、酚醛环氧树脂、双酚A酚醛环氧树脂、双酚F酚醛环氧树脂、邻甲酚环氧树脂、三官能团环氧树脂、四官能团环氧树脂、多官能团环氧树脂、二环戊二烯环氧树脂、含磷环氧树脂、对二甲苯环氧树脂、萘型环氧树脂、苯并哌喃型环氧树脂、联苯酚醛环氧树脂及酚基苯烷基酚醛环氧树脂。
6.一种无卤无磷树脂组合物,其特征在于,其包含:(1)萘型环氧树脂;(2)如权利要求1所述的苯并恶嗪树脂;(3)硬化促进剂;以及选择性添加(4)氢氧化铝及勃姆石中的一种或其组合。
7.如权利要求2或6所述的组合物,其特征在于,其进一步包含选自下列群组中的至少一种:无机填充物、界面活性剂、增韧剂、阻燃剂、有机硅弹性体及溶剂。
8.一种半固化胶片,其特征在于,其包含如权利要求2~7中任一项所述的组合物。
9.一种积层板,其特征在于,其包含如权利要求8所述的半固化胶片。
10.一种电路板,其特征在于,其包含如权利要求9所述的积层板。
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CN103555002B (zh) * | 2013-11-05 | 2015-06-10 | 重庆市锦艺硅材料开发有限公司 | 覆铜板用无机填料的制备方法 |
CN105199384B (zh) * | 2015-09-21 | 2017-10-27 | 四川天策聚材科技有限公司 | 透明型阻燃苯并噁嗪纳米复合材料及其制备方法 |
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CN111164127A (zh) * | 2017-10-20 | 2020-05-15 | 日本化药株式会社 | 硬化性树脂组合物、清漆、预浸体、硬化物、及积层板或覆铜积层板 |
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