CN107663367B - 低介电常数材料与其前驱物 - Google Patents
低介电常数材料与其前驱物 Download PDFInfo
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- CN107663367B CN107663367B CN201610657416.XA CN201610657416A CN107663367B CN 107663367 B CN107663367 B CN 107663367B CN 201610657416 A CN201610657416 A CN 201610657416A CN 107663367 B CN107663367 B CN 107663367B
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Abstract
本揭露提供的低介电常数材料的前驱物,包括:(a)清漆组合物;5‑30重量份的(b)聚四氟乙烯与聚硅氧烷的复合微粉;以及0.05‑3重量份的(c)界面活性剂,其中(a)清漆组合物包括:(a1)100重量份的聚苯醚树脂、20至30重量份的三烯丙基异氰脲酸酯、与0.01至0.03重量份的引发剂;(a2)100重量份的聚苯醚树脂、20至30重量份的橡胶、20至30重量份的三烯丙基异氰脲酸酯、与0.01至0.03重量份的引发剂;或者(a3)100重量份的聚酰胺酰亚胺与双马来酰亚胺的共聚物。
Description
技术领域
本揭露关于低介电常数材料,更特别关于其前驱物的组成。
背景技术
随着电子信息产品逐渐向着高频化、高速化方向发展,具有低介电常数(Dk)和低介电损耗(Df)的绝缘材料在印制电路板用基板的应用逐渐受到重视。
聚四氟乙烯(PTFE)具有许多独特的特性,如耐高温、耐化学性、离型性、低吸水性及绝缘性,尤其是具有极低的介电常数(Dk)和介电损耗(Df),在高频覆铜板的应用已经有多年的历史。一般含PTFE覆铜板的应用可以分为两种,一种是将玻纤布含浸于PTFE乳液中,另一种则是混合PTFE乳液与无机陶瓷粉。
除了PTFE外,聚苯醚、BT树脂、氰酸酯树脂亦常作为低介电常数(Dk)和低介电损耗(Df)覆铜板的黏着材料。然而上述材料制成的覆铜板其介电常数,高于PTFE制成的覆铜板的介电常数。此外,可在清漆组合物如聚苯醚树脂、双马来酰亚胺(BMI)与三嗪(BT,Bismaleimide Triazine)的聚合物树脂、氰酸酯树脂、聚酰胺酰亚胺及其衍生物、或环氧树脂系统中,加入PTFE以降低介电常数和介电损耗。然而上述树脂是属于油性系统,通常不可能与PTFE乳液兼容,因此只能加入PTFE微粉来达到目的。然而一般小粒径的PTFE微粉(平均粒径约在4-10μm)虽容易均匀分散在一般有机高分子中,但其低分子量(约在10万以下)会提高介电常数与介电损耗。至于高分子量的PTFE微粉(分子量高于200万),其平均粒径范围过大(介于30-500μm之间)而不易均匀分散在一般油性树脂系统中,容易团聚,在树脂中分布不均,造成电性能不一致。
综上所述,目前亟需新的低介电常数材料与其前驱物,以改善高分子量的PTFE微粉与清漆组合物的兼容性。
发明内容
本揭露一实施例提供的低介电常数材料的前驱物,包括:(a)清漆组合物;5-30重量份的(b)聚四氟乙烯与聚硅氧烷的复合微粉;以及0.05-3重量份的(c)界面活性剂,其中(a)清漆组合物包括:(a1)100重量份的聚苯醚树脂、20至30重量份的三烯丙基异氰脲酸酯、与0.01至0.03重量份的引发剂;(a2)100重量份的聚苯醚树脂、20至30重量份的橡胶、20至30重量份的三烯丙基异氰脲酸酯、与0.01至0.03重量份的引发剂;或者(a3)100重量份的聚酰胺酰亚胺与双马来酰亚胺的共聚物。
具体实施方式
本揭露一实施例提供的低介电常数材料的前驱物,包括:(a)清漆组合物;5-30重量份的(b)四氟乙烯与聚硅氧烷的复合微粉;以及0.05-3重量份的(c)界面活性剂。若(b)聚四氟乙烯与聚硅氧烷的复合微粉的比例过低,则介电常数无法降低。若(b)聚四氟乙烯与聚硅氧烷的复合微粉的比例过高,则半固化片在压合后的粘接力过低。若(c)界面活性剂的比例过低,则聚四氟乙烯和聚硅氧烷复合粉末无法很好地分散。若(c)界面活性剂的比例过高,则影响压合形成的层压板的介电损耗性能。本揭露所使用的界面活性剂,主要的功能是能降低本发明树脂组成物的表面张力,帮助聚四氟乙烯与聚硅氧烷的复合微粉可以均匀分散在树脂组成物。界面活性剂通常是非离子型氟系界面活性剂,如杜邦Capstone FS3100,日本AGC清美化学的氟系界面活剂S-386,S-611、及非离子型硅系界面活性剂,如Momentive的CoatOSil*1211,优先选择非离子型氟系界面活性剂。
在一实施中,(a)清漆组合物包括(a1)100重量份的聚苯醚树脂、20至30重量份的三烯丙基异氰脲酸酯(TAIC)、与0.01至0.03重量份的引发剂;(a2)100重量份的聚苯醚树脂、20至30重量份的橡胶、20至30重量份的TAIC、与0.01至0.03重量份的引发剂;或者100重量份的(a3)聚酰胺酰亚胺与双马来酰亚胺的共聚物。若TAIC的比例过低,则压合形成的层压板的玻璃转换温度(Tg)不够高且耐热性差。若TAIC的比例过高,则降低压合形成的层压板的介电性能。在一实施例中,聚苯醚树脂为末端为甲基丙烯酰氧基的聚苯醚树脂(如Sabic公司所售的SA-9000)、末端乙烯苄基醚的聚苯醚树脂(如三菱瓦斯化学所售OPE-2st)、或上述的组合。在一实施例中,橡胶包括聚丁二烯、苯乙烯-丁二烯-苯乙烯嵌段聚合物(SBS)、短链聚甲基苯乙烯、或上述的组合。若橡胶的比例过低,则影响压合形成的层压板的介电性能。若橡胶的比例过高,则会降低压合形成的层压板的Tg。在一实施例中,引发剂可为偶氮类如2,2’-偶氮二双(2,4-二甲基正戊腈)(2,2’-azobis(2,4-dimethylvaleronitrile))、二甲基-2,2’-偶氮双(2-丙酸甲酯)(dimethyl2,2’-azobis(2-methylpropionate)、2,2-偶氮双异丁腈(2,2-azobisisobutyronitrile)、2,2-偶氮双(2-甲基异丁腈)(2,2-azobis(2-methylisobutyronitrile))、1,1’-偶氮双(环己烷-1-腈)(1,1’-azobis(cyclohexane-1-carbonitrile))、2,2’-偶氮双[N-2-丙基-2-甲基丙酰胺](2,2’-azobis[N-(2-propenyl)-2-methylpropionamide])、1-[(氰基-1-甲基乙基)-偶氮基]甲酰胺(1-[(cyano-1-methylethyl)azo]formamide)、2,2’-偶氮双(N-丁基-2-甲基丙酰胺)(2,2’-azobis(N-butyl-2-methylpropionamide))、2,2’-偶氮双(N-环己基-2-甲基丙酰胺)(2,2’-azobis(N-cyclohexyl-2-methylpropionamide)、或其他合适的偶氮类引发剂;过氧化物类包括苯甲酰基过氧化物(benzoyl peroxide)、1,1-双(第三丁基过氧基)环己烷(1,1-bis(tert-butylperoxy)cyclohexane)、2,5-双(第三丁基过氧基)-2,5-二甲基环己烷(2,5-bis(tert-butylperoxy)-2,5-dimethylcyclohexane)、2,5-双(第三丁基过氧基)-2,5-二甲基-3-环己炔(2,5-bis(tert-
butylperoxy)-2,5-dimethyl-3-cyclo-hexyne)、过氧化二叔丁基(Di-t-butylperoxide)、双(1-(第三丁基过氧基)-1-甲基乙基)苯(bis(1-(tert-butylpeorxy)-1-methy-ethyl)benzene)、第三丁基过氧化氢(tert-butylhydroperoxide)、第三丁基过氧化物(tert-
butyl peroxide)、第三丁基过氧基苯甲酸(tert-butyl peroxybenzoate)、茴香基过氧化氢(Cumene hydroperoxide)、环己酮基过氧化物(cyclohexanone peroxide)、二茴香基过氧化物(dicumyl peroxide)、月桂基过氧化物(lauroyl peroxide)、或其他合适的过氧化物。上述的引发剂除可单一使用外,亦可混合使用,端视需要而定。若引发剂的比例过低,则会降低反应物的交联密度,进而降低压合形成的层压板的Tg,若引发剂的比例过高,则反应速率过快,不易操作。
在一实施例中,(a3)聚酰胺酰亚胺与双马来酰亚胺的共聚物中,聚酰胺酰亚胺是由二苯基甲烷二异氰酸酯(MDI)和偏苯三酸酐(TMA)聚合而成。双马来酰亚胺可为4,4’-双马来酰亚胺二苯甲烷、双(3-乙基-5-甲基-4-马来酰亚胺基苯基)甲烷、或上述的组合。聚酰胺酰亚胺与双马来酰亚胺的重量比介于70:100到70:50之间。若双马来酰亚胺的比例过低,则所形成的层压板其层与层之间容易分层,层压板机械强度低,且层压板子容易变形。若双马来酰亚胺的比例过高,组合物放久之后则,会有部分的双马来酰亚胺沉淀出来,影响组合物储存安定性,此外因交联密度太高,也会造成所形成的层压板太脆。
本揭露一实施例提供的聚四氟乙烯(PTFE)与聚硅氧烷的复合微粉中,PTFE与聚硅氧烷的重量比介于95:5至90:10之间。若PTFE的比例过低,聚硅氧烷相对量过大,造成聚四氟乙烯(PTFE)与聚硅氧烷的复合微粉本身的介电常数及介电损耗偏高,降低介电常数及介电损耗的效果。若PTFE的比例过高,则PTFE与聚硅氧烷所形成的复合材料不够硬,无法顺利使用气流粉碎的方法,将其粒径有效的降低到平均粒径为2-10微米,粒径会过大,同时也会造成分散性不好,会影响层压板的成形性和粘接性,半固化片的外观也会不好。PTFE的重均分子量可介于200万至500万之间。上述PTFE与聚硅氧烷的复合微粉其平均粒径(D50)可介于2μm至10μm之间。若复合微粉的平均粒径过大,则会造成半固化片的外观不佳,不平坦且有颗粒状PTFE存在再办固化片的表面。
在本揭露一实施例中,PTFE与聚硅氧烷的复合微粉其制备方法包括:将100重量份的PTFE与10~40重量份的硅烷混合均匀。视混合情况可加入适当的溶剂来润湿PTFE,且溶剂没有特别限定,只要能润湿PTFE的溶剂皆可,比如醇类如甲醇、乙醇、异丙醇,或苯类如甲苯或二甲苯。
在其他实施例中,可进一步将60~80%的硅烷替换为硅溶胶,以进一步提高复合材料的耐热性。若硅溶胶的添加量过高,则会影响硅烷在PTFE中的反应速率,硅烷在水解缩合的反应过程中容易凝胶。硅烷可渗透至PTFE的孔隙之间,经水解缩合反应(原位聚合)形成网状结构的聚硅氧烷,可防止PTFE进一步聚集,以达分散PTFE的效果。另一方面,聚硅氧烷可包覆PTFE的表面以硬化PTFE,使其易于粉碎。若硅烷的用量过高,则所形成的复合微粉中聚硅氧烷量过多,而失去PTFE的特性。若硅烷的用量过低,则硅烷无法包覆PTFE,造成PTFE分散效果不佳,亦造成包覆聚硅氧烷的PTFE不够脆,而无法以一般的气流粉碎法制备微粉。
接着将占PTFE和硅烷总重的0.1~0.0001%重量份的催化剂加入上述混合物后混合均匀,再加水使硅烷于PTFE中进行原位聚合反应,以形成聚硅氧烷。催化剂并无特别限定,只要能催化硅烷水解的触媒皆可,比如硫酸、盐酸、甲酸、醋酸、柠檬酸、胺类、氢氧化钾、或氢氧化钠。若催化剂用量过高,则水解缩合反应速率过快,反应不易控制,容易造成硅烷凝胶产生粒子。若催化剂用量过低,则水解缩合反应速率过慢,反应时间过长。水与硅烷的莫耳比介于0.5:1至3:1之间。若水的用量过高,则会造成反应相分离;若水的用量过少,则使硅烷水解不充分,残留过多的硅烷,影响产物效果。
在本揭露一实施例中,上述原位聚合反应的温度介于室温(约25℃)至45℃之间,且反应时间介于4小时至16小时之间。若原位聚合反应的温度过高及/或反应时间过长,则水解缩合反应不易控制。若原位聚合反应的温度过低及/或反应时间过短,则硅烷无法充分进行水解缩合反应。
在本发明一实施例中,PTFE优选为由四氟乙烯(TFE)单体经悬浮聚合或分散聚合所制备的PTFE,其重均分子量介于200万至500万之间,具有较好的不粘黏性。上述PTFE可为悬浮聚合,由于悬浮聚合不使用含氟界面活性剂,因此不含PFOA。上述PTFE可进一步包含少量能改善烘烤(熔结)期间的成膜能力的共聚单体改性剂如全氟烯烃,特别是六氟丙烯(HFP)或全氟(烷基乙烯基)醚,其中烷基含有1~5个碳原子,优选为全氟(丙基乙烯基)醚(PPVE)、全氟(甲基乙烯基)醚(PMVE)。上述改性剂的用量不足以让PTFE具有熔融加工性,而上述共聚物称为改性PTFE。一般改性剂的用量低于3wt%,优选低于1wt%。聚四氟乙烯的型态为粉状或凝聚状,粒径在20~260μm左右。值得注意的是,上述PTFE完全不含全氟辛酸(PFOA)。
在一实施例中,硅烷为R1 mR2 nSi(OR3)4-m-n、R4 jR5 kSiCl4-j-k、或上述的组合,其中m、n、j、k各自为0或正整数,m+n=0至2的整数,且j+k=0至3的整数。R1、R2、R4、与R5各自选自H、C1-6的烷基(如甲基、乙基、丙基、或丁基)、C3-6的环烷基(如环戊基或环己基)、C2-6的烯基(如乙烯基或丙烯基)、芳香基(如苯基)、卤化C1-6的烃基(如氯甲基或γ-氯丙基)、胺基(如γ-胺丙基)、甲基丙烯酰氧基(如γ-甲基丙烯酰氧基丙基或γ-缩水甘油醚氧基丙基)、环氧基(如3,4-环氧环己烷乙基)、巯基(如γ-巯丙基)、硫基、脲基(如γ-脲丙基)、或异氰酸基(如γ-异氰酸基丙基)。R3为C1-3的烷基如甲基、乙基、或丙基。在本发明一实施例中,硅烷可以为甲基三甲氧基硅烷、甲基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、乙烯基三甲氧基硅烷、正硅酸乙酯、聚硅酸乙酯(TEOS-40)、正硅酸甲酯、γ-胺丙基三乙氧基硅烷、N-(γ-胺乙基)-γ-胺丙基三甲氧基硅烷、3-(2,3-环氧丙氧基)丙基三甲氧基硅烷、2-(3,4-环氧环己烷)乙基三甲氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、γ-脲丙基三乙氧基硅烷、γ-异氰酸基丙基三乙氧基硅烷、四氯硅烷、甲基三氯硅烷、苯基三氯硅烷、甲基苯基二氯硅烷、乙烯基三氯硅烷、或上述的组合。在本发明一实施例中,硅烷优选为苯基三甲氧基硅烷,乙烯基三甲氧基硅烷、正硅酸乙酯、3-(2,3-环氧丙氧基)丙基三甲氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、或上述的组合。
接下来,干燥聚硅氧烷与聚四氟乙烯的混合物。举例来说,可先升温除水混合物至无水分脱出为止,再将以100目滤布过滤混合物得湿粉。接着将湿粉于200℃至300℃下烘干2小时至4小时即得干粉。烘干主要的目的除了要除去水及溶剂外,另外一个目的是要使聚硅氧烷的硅醇基(Si-OH)减少,避免残留过多的硅醇基,影响到介电常数和介电损耗。秤重干粉可得硅含量,公式如下:聚硅氧烷%=[(干粉重-聚四氟乙烯重)/干粉重]×100%。
最后物理粉碎干粉如气流粉碎,即可得PTFE与聚硅氧烷的复合微粉,其平均粒径(D50)介于2.0μm至10μm之间,且PTFE与聚硅氧烷的重量比介于95:5至90:10之间。复合微粉中的PTFE其重均分子量,与一开始采用的PTFE的重均分子量实质上相同。上述物理粉碎法如气流粉碎分级法只会粉碎复合材料,而不会裂解其中的PTFE。
在一实施例中,还可添加30重量份的阻燃剂至介电材料的前驱物中,其中阻燃剂并不特别限定,满足阻燃要求即可,例如溴系阻燃剂如十溴二苯乙烷等,或是磷氮系阻燃剂如环状苯氧基磷腈化合物等。
在本发明一实施例中,还可进一步添加0.5-1重量份的硅烷偶联剂和20-40重量份的二氧化硅至介电材料的前驱物中。上述硅烷偶联剂可为(3-环氧丙氧丙基)三甲氧基硅烷、(3-环氧丙氧丙基)三乙氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、或上述的组合。硅烷偶联剂可在无机物质和有机物质的接口之间架起「分子桥」,把两种性质悬殊的材料连接在一起,以提高复合材料的性能和增加粘接强度的作用。不同树脂系统需选择不同的硅烷偶联剂。以聚苯醚系统为例,可优先采用3-(甲基丙烯酰氧)丙基三甲氧基硅烷作为硅烷偶联剂。在介电材料的前驱物中添加二氧化硅如熔融型二氧化硅,有助于降低树脂固化物的热膨胀系数并降低成本。
上述低介电常数材料的介电常数介于3.4至3.8之间,且介电损耗介于0.002至0.015之间。与直接采用PTFE微粉与清漆组合物的前驱物相较,采用PTFE与聚硅氧烷的复合微粉与清漆组合物的前驱物所形成的低介电常数材料具有较低的介电常数与介电损耗。
为让本揭露的上述和其他目的、特征、和优点能更明显易懂,以实施例说明如下。
实施例
本发明所用的药品名称及来源列举如下,但不仅限于所列药品:
PTFE粉:
CGM 031B,购自中昊晨光化工研究院有限公司,平均粒径介于70μm至90μm之间。
CGM 031C,购自中昊晨光化工研究院有限公司,平均粒径介于130μm至260μm之间。
CGM 16(F),购自中昊晨光化工研究院有限公司,平均粒径介于25μm。
含硅化合物:
苯基三甲氧基硅烷:购自Wacker的XL70。
(3-环氧丙氧丙基)三甲氧基硅烷:购自Dow Corning的Z 6040。
3-(甲基丙烯酰氧)丙基三甲氧基硅烷:购自Evonic的Dynasylan MEMO。
正硅酸乙酯:购自Wacker的TES 28。
氧化硅溶胶:购自阿克苏的Levasil CT20DH。
二苯基甲烷二异氰酸酯:购自日本Nippon polyurethane Industry Co.LtdMillionate MT.
偏苯三酸酐(TMA):购自台湾恒洲贸易公司。
N-甲基吡咯烷酮(NMP):购自BASF。
二甲基乙酰胺(DMAC):购自杜邦公司。
4,4’-双马来酰亚胺二苯甲烷:购自日本Daiwakasei Industry Co.,LTD.的BMI-1000。
末端为甲基丙烯酰氧基的聚苯醚树脂:购自Sabic的SA-9000。
三烯丙基异氰脲酸酯(Triallylisocyanurate,TAIC):购自中国湖南以翔化工有限公司。
聚丁二烯橡胶:购自Cray Valley的Ricon 153。
苯乙烯-丁二烯-苯乙烯嵌段聚合物(SBS):购自Kraton的D1155。
短链聚甲基苯乙烯:购自Eastman的F115。
溴系阻燃剂:购自Albemarle的Saytex 8010。
熔融型二氧化硅:购自台湾硅比科的Megasil 525。
引发剂:购自中国广州沁丰化工有限公司的过氧化二叔丁基(Di-t-butylperoxide)。
界面活性剂:购自日本AGC清美化学的氟界面活性剂S386。
玻璃布:购自台玻集团的玻璃纤维布2116。
下述实施例1至4为聚四氟乙烯与含硅化合物的复合微粉的制备方式。
实施例1
在反应容器中加入1000g的PTFE粉(CGM 031B),加入适量的甲醇,搅拌使PTFE粉全部润湿,然后加入100g的苯基三甲氧基硅烷搅拌均匀,再加入0.01g的浓硫酸作催化剂混合均匀,最后加入10g的水,控制反应温度不超过45℃反应4小时。
将上述混合液升温至沸腾以除去水分,然后用100目滤布过滤得湿粉,于300℃烘干湿粉4小时后得干粉(秤重1053g)。经气流粉碎分级干粉,即得平均粒径(D50)为10μm的聚四氟乙烯与聚硅氧烷的复合微粉。
实施例2
在反应容器中加入1000g的PTFE粉(CGM 031C),加入适量的甲醇,搅拌使PTFE粉全部润湿,然后加入120g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷搅拌均匀,再加入1g的盐酸作催化剂混合均匀,最后加入20g的水,控制反应温度不超过45℃反应6小时。
将上述混合液升温至沸腾以除去水分,然后用100目滤布过滤得湿粉,于200℃烘干湿粉4小时后得干粉(秤重1064g)。经气流粉碎分级干粉,即得平均粒径(D50)为6.0μm的聚四氟乙烯与聚硅氧烷的复合微粉。
实施例3
在反应容器中加入1000g的PTFE粉(CGM 16(F)),加入适量的甲醇,搅拌使PTFE粉全部润湿,然后加入200g的3-(2,3-环氧丙氧基)丙基三甲氧基硅烷搅拌均匀,再加入0.1g的盐酸作催化剂混合均匀,最后加入40g的水,控制反应温度不超过45℃反应16小时。
将上述混合液升温至沸腾以除去水分,然后用100目滤布过滤得湿粉,于200℃下烘干湿粉2小时后得干粉(秤重1098g)。经气流粉碎分级干粉,即得平均粒径(D50)为4.0μm的聚四氟乙烯与聚硅氧烷的复合微粉。
实施例4
在反应容器中加入1000g的PTFE粉(CGM 031B),加入适量的异丙醇,搅拌使PTFE粉全部润湿,然后加入160g的正硅酸乙酯和240g的氧化硅溶胶搅拌均匀,再加入1.2g的浓硫酸作催化剂混合均匀,控制反应温度不超过45℃反应12小时。
将上述混合液升温至沸腾除去水分,然后用100目滤布过滤得湿粉,于300℃下烘干湿粉4小时后得干粉(秤重1110g)。经气流粉碎分级干粉,即得平均粒径(D50)为2.0μm的聚四氟乙烯与聚硅氧烷的复合微粉。
第1表
实施例5
100g的聚苯醚(SA-9000)、100g的甲苯、20g的三烯丙基异氰脲酸酯(TAIC)、20g的实施例1制备的PTFE与聚硅氧烷的复合微粉、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、40g的二氧化硅、0.01g的引发剂、与0.2g的界面活性剂混合均匀。
实施例6
100g的聚苯醚(SA-9000)、100g的甲苯、30g的TAIC、20g的实施例2制备的PTFE与聚硅氧烷的复合微粉、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、40g的二氧化硅、0.03g的引发剂、与0.2g的界面活性剂混合均匀。
实施例7
100g的聚苯醚(SA-9000)、100g的甲苯、25g的TAIC、5g的实施例3制备的PTFE与聚硅氧烷的复合微粉、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、40g的二氧化硅、0.02g的引发剂、与0.05g的界面活性剂混合均匀。
实施例8
100g的聚苯醚(SA-9000)、100g的甲苯、25g的TAIC、30g的实施例4制备的PTFE与聚硅氧烷的复合微粉、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、40g的二氧化硅、0.02g的引发剂、与3g的界面活性剂混合均匀。
实施例9
100g的聚苯醚、120g的甲苯、30g的TAIC、4g的聚丁二烯、8g的SBS、8g的短链聚甲基苯乙烯、30g的实施例1制备的PTFE与聚硅氧烷的复合微粉、30g的阻燃剂、0.01g的引发剂、与0.3g的界面活性剂混合均匀。
实施例10
100g的聚苯醚、120g的甲苯、20g的TAIC、6g的聚丁二烯、12g的SBS、12g的短链聚甲基苯乙烯、30g的实施例2制备的PTFE与聚硅氧烷的复合微粉、30g的阻燃剂、0.03g的引发剂、与1.5g的界面活性剂混合均匀。
比较例1
100g的聚苯醚(SA-9000)、100g的甲苯、25g的TAIC、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、40g的二氧化硅、与0.02g的引发剂混合均匀。
比较例2
100g的聚苯醚(SA-9000)、100g的甲苯、25g的TAIC、30g的PTFE粉(CGM 031B)、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、40g的二氧化硅、0.02g引发剂、与0.3g的界面活性剂混合均匀。
比较例3
100g的聚苯醚、120g的甲苯、20g的TAIC、4g的聚丁二烯、8g的SBS、8g的短链聚甲基苯乙烯、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、与0.01g的引发剂混合均匀。
比较例4
100g的聚苯醚、120g的甲苯、20g的TAIC、4g的聚丁二烯、8g的SBS、8g的短链聚甲基苯乙烯、30g的PTFE粉(CGM 031B)、30g的阻燃剂、1g的3-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂、0.01g的引发剂、与1.5g的界面活性剂混合均匀。
实施例11
将203g的二苯基甲烷二异氰酸酯(MDI)和149.8g偏苯三酸酐(TMA)加入390g的N-甲基吡咯烷酮(NMP)中,在120℃反应3小时,然后再加入1.52g的TMA继续反应1小时制得聚酰胺酰亚胺,再加入260g的NMP调节固含量至35%。
将100g的双马来酰亚胺加入到200g的上述聚酰胺酰亚胺溶液(固含量35%)中,在120℃下反应2小时形成PAI-BMI树脂溶液,再加入40g的二甲基乙酰胺(DMAC)调节固含量至50%。
实施例12
取200g的实施例11制备的PAI-BMI树脂溶液(固含量50%),加入20g的实施例1制备的PTFE与聚硅氧烷的复合微粉、与2g的界面活性剂混合均匀。
实施例13
将203g的MDI与149.8g的TMA加入390g的NMP中,在120℃反应3小时,然后再加入1.52g TMA继续反应1小时,制得聚酰胺酰亚胺后,再加入260g的NMP调节固含量至35%。
将50g的双马来酰亚胺加入200g的上述的聚酰胺酰亚胺溶液(固含量35%)中,在120℃下反应2小时形成PAI-BMI树脂溶液。
实施例14
取208g的实施例13的PAI-BMI树脂溶液,加入30g的实施例4制备的PTFE与聚氧硅烷的复合微粉、与3g的界面活性剂混合均匀。
比较例5
取200g的实施例11的PAI-BMI树脂溶液,加入20g的PTFE粉(CGM031B)、与2g的界面活性剂混合均匀。
比较例6
取200g上述实施例11的PAI-BMI树脂溶液。
第2表
第3表
半固化片与铜箔基板的制作方法
取第2与3表中的树脂组合物,和其他配料混合后以筛网(100~200mesh)过滤,形成胶液状的预浸料。接着以含浸机将玻璃纤维布含浸于预浸料中(含浸规格:2116),并将胶含量控制在50±2%。接着在170℃条件下烘烤上述含浸后的玻璃纤维布2-3min,制成半固化片。将6片上述半固化片堆栈后,测其介电常数及介电损耗,如第4与5表所示。接着在半固化片堆栈的双侧放上铜箔后再进行压合(压合温度为210℃,压合时间为150分钟,压合压力为200psi),以制成铜箔基板。
第4表
第5表
由第4与5表可知,本揭露的PTFE与聚硅氧烷的复合微粉,其PTFE虽具有高分子量的特性,但因表面经过聚硅氧烷的处理,经气流粉碎后所得到的复合微粉,可以容易及均匀地分散在聚苯醚树脂(或聚酰胺酰亚胺和双马来酰亚胺的共聚物)中,并可以降低聚苯醚树脂(或聚酰胺酰亚胺和双马来酰亚胺的共聚物)的介电常数(Dk)和介电损耗(Df)。一般高分子量的PTFE粉,不易分散在聚苯醚树脂(或聚酰胺酰亚胺和双马来酰亚胺的共聚物)中,在分散的过程中,PTFE粉容易团聚,分散不均匀,造成半固化片的外观不佳,不平坦且有颗粒状PTFE。
在第4与5表中的测定方法如下:
玻璃化温度(Tg)测试方法采用美国电子电路成型标准(IPC standard),IPC-TM-650-2.4.25(DSC法)。
剥离强度(PS)测试:采用美国电子电路成型标准(IPC standard),IPC-TM-650-2.4.8中的「热应力后」实验条件,测试金属盖层的剥离强度。
浸锡耐热性测试:使用50×50mm的铜箔基板,浸入288℃的焊锡中,记录样品分层起泡的时间。
耐湿热性能(PCT)测试:采用高压锅蒸煮实验(PCT),板材经高压锅(0.105Mpa)121℃,连续蒸煮120分钟后,浸入288℃的焊锡中,记录样品分层起泡的时间。
介电常数及介电损耗测试方法:测试样板的大小(长×宽×厚)为70mm×3.5mm×0.75mm,使用日本AET的仪器,测量2GHZ的介电常数和低介电损耗,使用的方法是依照JIS-Compliant C 2565的共振腔法(Resonant Cavity)。
虽然本揭露已以数个实施例揭露如上,然其并非用以限定本揭露,任何所属技术领域中具有通常知识者,在不脱离本揭露的精神和范围内,当可作任意的更动与润饰,因此本揭露的保护范围当视后附的申请专利范围所界定者为准。
Claims (9)
1.一种低介电常数材料的前驱物,包括:
清漆组合物;
5-30重量份的聚四氟乙烯与聚硅氧烷的复合微粉,其中,所述复合微粉通过硅烷在聚四氟乙烯中原位水解缩合形成聚硅氧烷,聚硅氧烷包覆聚四氟乙烯而形成;以及
0.05-3重量份的界面活性剂,
其中所述清漆组合物包括:
100重量份的聚苯醚树脂、20至30重量份的三烯丙基异氰脲酸酯、与0.01至0.03重量份的引发剂;
100重量份的聚苯醚树脂、20至30重量份的橡胶、20至30重量份的三烯丙基异氰脲酸酯、与0.01至0.03重量份的引发剂;或者
100重量份的聚酰胺酰亚胺与双马来酰亚胺的共聚物。
2.根据权利要求1所述的低介电常数材料的前驱物,其中该聚苯醚为末端基为甲基丙烯酰氧的聚苯醚树脂、末端乙烯苄基醚的聚苯醚树脂、或上述的组合。
3.根据权利要求1所述的低介电常数材料的前驱物,其中该聚苯醚的分子量为2000-5000。
4.根据权利要求1所述的低介电常数材料的前驱物,其中聚酰胺酰亚胺与双马来酰亚胺的共聚物中,聚酰胺酰亚胺与双马来酰亚胺的重量比介于70:100至70:50之间。
5.根据权利要求1所述的低介电常数材料的前驱物,其中该双马来酰亚胺包括4,4’-双马来酰亚胺二苯甲烷、双(3-乙基-5-甲基-4-马来酰亚胺基苯基)甲烷、或上述的组合。
6.根据权利要求1所述的低介电常数材料的前驱物,其中该橡胶包括聚丁二烯、苯乙烯-丁二烯-苯乙烯嵌段聚合物、短链聚甲基苯乙烯、或上述的组合。
7.根据权利要求1所述的低介电常数材料的前驱物,其中聚四氟乙烯与聚硅氧烷的重量比介于95:5至90:10之间。
8.根据权利要求1所述的低介电常数材料的前驱物,其中聚四氟乙烯的重均分子量介于200万至500万之间。
9.根据权利要求1所述的低介电常数材料的前驱物,其中聚四氟乙烯与聚硅氧烷的复合微粉的平均粒径介于2μm至10μm之间。
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