TWI830468B - 含乙烯基芳香脂環族共聚合物、樹脂組成物及其製品 - Google Patents
含乙烯基芳香脂環族共聚合物、樹脂組成物及其製品 Download PDFInfo
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 41
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
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- 239000002516 radical scavenger Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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Abstract
本發明提供一種含乙烯基芳香脂環族共聚合物、樹脂組成物及其製品,樹脂組成物包括含乙烯基芳香脂環族共聚合物,由樹脂組成物製成的製品,其Tg大於200℃、介電常數Dk(10GHz)為3.0以下且介電損耗Df(10GHz)為0.0014以下。
Description
本發明是有關於一種共聚合物、樹脂組成物及其製品,且特別是有關於一種含乙烯基芳香脂環族共聚合物、樹脂組成物及其製品。
一般低介電樹脂例如液態橡膠因具有優異介電特性,如介電常數Dk以及介電損耗Df,因此,成為了高頻印刷電路板的基板材料首選樹脂之一。
然而,液態橡膠為熱塑性樹脂,即使改質反應基也偏少,將其直接應用於銅箔基板容易存在以下缺點:1.Tg過低、2.反應性不佳、3.難以加工成型、4.融熔黏度高,因此,需要設計新型改質結構才能符合印刷電路板的使用需求。
基於上述,如何開發出具有優異電性並符合印刷電路板其他特性需求,例如高Tg、低膨脹係數、低吸水率的特性材料,
並將其應於高頻基板製造,為本領域技術人員亟欲發展的目標。
本發明提供一種含乙烯基芳香脂環族共聚合物、樹脂組成物及其製品,使其具備高玻璃轉移溫度、低介電常數Dk及介電耗損Df。
在本發明的一實施例中,含乙烯基芳香脂環族共聚合物的分子量Mn為2000至6000。
在本發明的一實施例中,在含乙烯基芳香脂環族共聚合物中,脂環族的莫耳比為10%至40%,乙烯基的莫耳比為10%至40%,苯乙烯的莫耳比為20%至90%。
本發明的樹脂組成物包括上述含乙烯基芳香脂環族共聚合物、聚苯醚樹脂、三烯丙基異三聚氰酸酯、雙馬來醯亞胺樹脂、耐燃劑以及無機填料。
在本發明的一實施例中,耐燃劑包括磷系阻燃劑。
在本發明的一實施例中,無機填料包括二氧化矽。
在本發明的一實施例中,以樹脂組成物的總重量計,含乙烯基芳香脂環族共聚合物的含量為5wt%至20wt%,聚苯醚樹脂的含量為5wt%至30wt%,三烯丙基異三聚氰酸酯的含量為5wt%至20wt%,雙馬來醯亞胺樹脂的含量為5wt%至20wt%,耐燃劑的含量為5wt%至20wt%,無機填料的含量為30wt%至60wt%。
本發明的製品,由上述樹脂組成物進行加工方法而製成,加工方法包括含浸及熱壓成型。
在本發明的一實施例中,製品的Tg大於200℃、介電常數Dk(10GHz)為3.0以下且介電損耗Df(10GHz)為0.0014以下。
基於上述,本發明提供一種含乙烯基芳香脂環族共聚合物,含有可反應雙鍵,藉由分子間交聯,不僅改善其反應性、耐熱性、耐化學性、耐寒性、低溫柔韌性和電性並提高溶劑溶解度,更由於本發明的乙烯基芳香脂環族共聚合物含有非極性骨幹結構,在電場中不易受到極化,可大幅降低介電常數Dk(10GHz)及介電損耗Df(10GHz),且丙酮中的溶劑溶解性為40%。
以下,將詳細描述本發明的實施例。然而,這些實施例為例示性,且本發明揭露不限於此。
在本文中,由「一數值至另一數值」表示的範圍,是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此,某一特定數值範圍的記載,涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍,如同在說明書中說明文寫出該任意數值和該較小數值範圍一樣。
在本實施例中,含乙烯基芳香脂環族共聚合物的分子量Mn例如是2000至6000。在含乙烯基芳香脂環族共聚合物中,脂環族的莫耳比例如是10%至40%,乙烯基的莫耳比例如是10%至40%,苯乙烯的莫耳比例如是20%至90%。
在本實施例中,含乙烯基芳香脂環族共聚合物的製造方
法可包括合成反應製程及析出純化製程,方法可包括以下步驟。首先,準備反應容器,內部設有攪拌混合器。選取自由基控制劑、自由基起始劑以及可反應乙烯基結構原料,自由基控制劑可包括2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)或4-羥基-2,2,6,6-四甲基-1-氧化哌啶,自由基起始劑可包括過氧苯甲醯(Benzoyl peroxide,BPO)或偶氮二異丁腈(AIBN),可反應乙烯基結構原料可包括2-乙烯基萘、苯乙烯、二乙烯基苯(DVB)、丁二烯、4-乙烯基聯苯、雙環戊二烯DCPD)、降冰片烯等等,其中I、X、Y、Z的莫耳比例如是1:2至5:2至10:2至10,I為自由基捕捉劑,X、Y、Z為不同種類可反應乙烯基結構。在溫度0℃至150℃下,於非質子溶劑中反應1小時至5小時,非質子溶劑可包括甲苯、二甲基甲醯胺(Dimethylformamide,DMF)。反應液加甲醇析出固體、過濾,經真空乾燥,即可得到本發明的含乙烯基芳香脂環族共聚合物。
本發明也提供一種樹脂組成物,包括上述含乙烯基芳香脂環族共聚合物、聚苯醚樹脂、三烯丙基異三聚氰酸酯、雙馬來醯亞胺樹脂、耐燃劑以及無機填料。在本實施例中,耐燃劑可包括磷系耐燃劑,無機填料可包括二氧化矽。以樹脂組成物的總重量計,含乙烯基芳香脂環族共聚合物的含量例如是5至20wt%,聚苯醚樹脂的含量例如是5wt%至30wt%,三烯丙基異三聚氰酸酯的含量例如是5wt%至20wt%,雙馬來醯亞胺樹脂的含量例如是5wt%至20wt%,耐燃劑的含量例如是5wt%至20wt%,無
機填料的含量例如是30wt%至60wt%。
本發明也提供一種製品,由上述樹脂組成物進行加工方法而製成,所述加工方法可包括含浸及熱壓成型。在本實施例中,製品的Tg可大於200℃、介電常數Dk(10GHz)可為3.0以下且介電損耗Df(10GHz)可為0.0014以下。
以下,藉由實驗例來詳細說明上述本發明的含乙烯基芳香脂環族共聚合物、樹脂組成物及其製品。然而,下述實驗例並非用以限制本發明。
為了本發明的含乙烯基芳香脂環族共聚合物可改善製品的反應性、耐熱性、耐化學性、耐寒性、低溫柔韌性和電性並提高溶劑溶解度,以下特別作此實驗例。
(1)玻璃轉移溫度:使用熱重量分析儀(Thermogravimetric Analyzer,TGA),測試橡膠樹脂材料的玻璃轉移溫度。
(2)介電常數(10GHz):使用介電分析儀(Dielectric Analyzer)(型號HP Agilent E5071C),測試橡膠樹脂材料在頻率10G Hz時的介電常數。
(3)介電損耗(10GHz):使用介電分析儀(Dielectric
Analyzer)(型號HP Agilent E5071C),測試橡膠樹脂材料在頻率10G Hz時的介電損耗。
(4)剝離強度測試:根據IPC-TM-650-2.4.8測試方法,測試金屬基板的剝離強度。
(5)耐熱性:將金屬基板於溫度為120℃、壓力為2atm的壓力鍋中加熱120分鐘,再浸入288℃焊錫爐中,並記錄爆板的所需時間,爆板時間超過10min以“OK”表示,爆板時間短於10min以“NG”表示。
以下表1中列出本發明含乙烯基芳香脂環族共聚合物的合成條件,以此製造製備例1至製備例6的乙烯基芳香脂環族共聚合物。
依照莫耳比1:40:2:1:1,取3.9g(等同0.025mol)自由基控制劑TEMPO、104g(等同1mol)苯乙烯、6.6g(等同0.05mol)DCPD、3.3g(等同0.025mol)DVB以及6g(等同0.025mol)BPO起始劑。將上述原料溶於500ml甲苯中,投入設有攪拌混合器的1L四頸圓底反應燒瓶,對反應燒瓶通入氮氣以去除空氣及水氣,在常壓下,啟動攪拌混合器,在300rpm下對反應溶液均勻混合。當反應溫度達到120℃時,反應溶液的所有固含量溶解成清澈紅褐色溶液,反映條件設定在反應溫度120℃下反應3小時,使得清澈紅褐色溶液改變為黏稠紅褐色溶液,將溶液滴至甲醇中沉澱聚合物,將所得到的聚合物過濾及真空乾燥,即可得到本發明的含乙烯基芳香脂環族共聚合物。
將表1所製成的製備例1至製備例6的含乙烯基芳香脂環族共聚合物以及市售取得的B1000、B2000及RI257樹脂,以樹脂組成物形式製成銅箔基板,加工方法可包括含浸及熱壓成型。將一玻璃纖維布,分別浸入實施例1至實施例4以及比較例1至比較例10的橡膠樹脂材料中,經含浸、乾燥與成型的步驟之後,
可獲得一預浸片(prepreg)。樹脂組成物的成分比例以及銅箔基板的測試結果列於以下表2中。由表2可得知,使用本發明含乙烯基芳香脂環族共聚合物的合成方法,可使樹脂PDI介於1至1.4,且適合製成高Tg大於200℃、介電常數Dk(10GHz)為3.0以下且介電損耗Df(10GHz)為0.0014以下的銅箔基板。
綜上所述,基於上述,本發明提供一種含乙烯基芳香脂環族共聚合物,含有可反應雙鍵,藉由分子間交聯,不僅改善其反應性、耐熱性、耐化學性、耐寒性、低溫柔韌性和電性並提高溶劑溶解度,更由於本發明的乙烯基芳香脂環族共聚合物含有非
極性骨幹結構,在電場中不易受到極化,可大幅降低介電常數Dk(10GHz)及介電損耗Df(10GHz),介電常數Dk(10GHz)為3.0以下,介電損耗Df(10GHz)為0.0014以下,且丙酮中的溶劑溶解性為40%,因此,具有優異電性並符合印刷電路板其他特性需求。相較於一般低介電芳香族樹脂,本發明的含乙烯基芳香脂環族共聚合物可改善脆性、提高韌性、提高耐熱性及對溶劑提高溶解量,適合製成高Tg大於200℃、介電常數Dk(10GHz)為3.0以下且介電損耗Df(10GHz)為0.0014以下的銅箔基板,更具備多樣使用用途,與其他樹脂混合硬化後,其特性仍具備高的玻璃轉化溫度(Tg)、更低的介電常數Dk及介電損耗Df。
Claims (7)
- 如請求項1所述的含乙烯基芳香脂環族共聚合物,其中所述含乙烯基芳香脂環族共聚合物的分子量Mn為2000至6000。
- 一種樹脂組成物,包括:如請求項1或請求項2所述的含乙烯基芳香脂環族共聚合物;聚苯醚樹脂;三烯丙基異三聚氰酸酯;雙馬來醯亞胺樹脂;耐燃劑;以及 無機填料,其中以所述樹脂組成物的總重量計,所述含乙烯基芳香脂環族共聚合物的含量為5至20wt%,所述聚苯醚樹脂的含量為5wt%至30wt%,所述三烯丙基異三聚氰酸酯的含量為5wt%至20wt%,所述雙馬來醯亞胺樹脂的含量為5wt%至20wt%,所述耐燃劑的含量為5wt%至20wt%,所述無機填料的含量為30wt%至60wt%。
- 如請求項3所述的樹脂組成物,其中所述耐燃劑包括磷系耐燃劑。
- 如請求項3所述的樹脂組成物,其中所述無機填料包括二氧化矽。
- 一種樹脂組成物製成的製品,由請求項3至請求項5中任一項所述的樹脂組成物進行加工方法而製成,所述加工方法包括含浸及熱壓成型。
- 如請求項6所述的樹脂組成物製成的製品,所述製品的Tg大於200℃、介電常數Dk(10GHz)為3.0以下且介電損耗Df(10GHz)為0.0014以下。
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