TWI671355B - 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板 - Google Patents

樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板 Download PDF

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TWI671355B
TWI671355B TW107100199A TW107100199A TWI671355B TW I671355 B TWI671355 B TW I671355B TW 107100199 A TW107100199 A TW 107100199A TW 107100199 A TW107100199 A TW 107100199A TW I671355 B TWI671355 B TW I671355B
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Taiwan
Prior art keywords
resin
resin composition
weight
parts
dopo
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TW107100199A
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English (en)
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TW201930448A (zh
Inventor
Chih Wei Liao
廖志偉
Guan Syun Tseng
曾冠勛
Tsung Hsien Lin
林宗賢
Ju Ming Huang
黃竹鳴
Chen Hua Yu
游鎭華
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Taiwan Union Technology Corporation
台燿科技股份有限公司
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Application filed by Taiwan Union Technology Corporation, 台燿科技股份有限公司 filed Critical Taiwan Union Technology Corporation
Priority to TW107100199A priority Critical patent/TWI671355B/zh
Priority to CN201810014021.7A priority patent/CN109988288B/zh
Priority to US16/009,266 priority patent/US11339258B2/en
Publication of TW201930448A publication Critical patent/TW201930448A/zh
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Publication of TWI671355B publication Critical patent/TWI671355B/zh

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Abstract

本發明提供一種樹脂組合物，其包含以下成分：(A)無鹵環氧樹脂；(B)硬化劑；以及(C)具有下式(I)結構之含磷酚醛樹脂： 其中，m、n、l、R1、及R2係如本文中所定義。

Description

樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔 積層板、與印刷電路板
本發明係關於一種樹脂組合物，特別是關於一種包含經9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)或其衍生物改質之含磷酚醛樹脂的樹脂組合物。本發明之樹脂組合物可與玻璃纖維構成複合材料或預浸漬片，或進一步作為金屬箔的接著劑，製成金屬箔積層板或印刷電路板。
隨著電子通訊技術中對於資料傳輸量的需求不斷增加之趨勢，電子產品的訊號傳輸不斷往更高頻的區域去應用，使得電子材料必須具備更低的介電常數(Dk)與介電損耗因子(Df)。另外，為了落實無鉛、無鹵素之環保製程，印刷電路板中的介電層材料必須使用無鉛、無鹵素之材料來製作，例如必須使用非鹵素系統的阻燃劑、無鹵素的環氧樹脂等。然而，符合上述要求的樹脂組合物配方所製得的電子材料在電性、耐熱性、無鹵阻燃等各方面特性並無法達到全面且均衡的狀態。
已知可透過將酚醛樹脂以DOPO改質後添加於環氧樹脂組合物中，作為環氧樹脂之硬化劑並提供提高難燃性之效果。例如US 20070221890 A1揭露了一種DOPO改質酚化合物及DOPO改質酚醛化合 物，其為一種非鹵素系統的阻燃劑，亦即業界熟知之含磷阻燃劑DOPO-BN(已存在許多商品化之產品，例如可購自Dow Chemical；型號：92741)。然而，使用此阻燃劑所製得之電子材料存在吸水性高、Df高等缺點，在高頻材料方面的應用始終有所限制。
US 20120095170 A1亦揭露了一種經DOPO改質之含磷酚醛樹脂，然而，其結構中具有非對稱的-OH基，對電子材料的電學性質會產生不良影響，並且如該文獻中所記載，使用此阻燃劑所製得之電子材料還存在耐熱性不足的問題(玻璃轉移溫度(Tg)太低)，在應用上必須與一般線性酚醛樹脂併用，來彌補此缺陷。
WO 2016101540 A1亦揭露了一種DOPO改質含磷酚醛樹脂，其化學結構中包含了二環戊二烯型酚(DCPD phenol)，然而，該含磷酚醛樹脂中之二環戊二烯型酚結構所產生的立體障礙大，使得該含磷酚醛樹脂溶解度不佳，產生了加工性方面的問題。
WO2016074288揭露了一種包含聚苯醚樹脂以及分子中具有DCPD結構及(1,1,3,3-四甲基)丁基結構基團的環氧樹脂的樹脂組合物，然而，除了前述DCPD的結構對溶解度所造成之不利影響外，該樹脂組合物還存在所製得之電子材料難燃性不佳的問題，必須額外添加阻燃劑。
因此，雖然先前技術中已知以DOPO對酚醛樹脂進行改質的作法，但在實際應用上仍有許多待改進的空間。尤其，目前仍亟需一種各項物化性質優異且同時具有低Dk值、低Df值、高Tg值等特性的無鹵樹脂組合物。
有鑑於前述之現況，本發明提供一種樹脂組合物配方，其中將無鹵環氧樹脂搭配硬化劑及具特定結構的含磷酚醛樹脂使用，該含磷酚 醛樹脂除因含有磷成分而能賦予本發明樹脂組合物及其製品良好難燃特性外，還能夠為樹脂組合物帶來良好電性、耐熱性、尺寸安定性及耐濕性，從而能製得兼具良好電性及物化特性的電子材料。
因此，本發明之一目的在於提供一種樹脂組合物，包含：(A)無鹵環氧樹脂；(B)硬化劑；以及(C)具有下式(I)結構之含磷酚醛樹脂： 於式(I)中，m、n、及l各自獨立為0至10之整數，但m、n、及l不同時為0，以及R1及R2各自獨立為9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)、DOPO衍生物或胺基三氮雜苯酚醛(amino triazine novolac，ATN)樹脂之殘基，或-O(CH2)3CH3，且條件為R1及R2中至少一者為DOPO或DOPO衍生物之殘基。
於本發明之部分實施態樣中，式(I)中之R1及R2各自獨 立為DOPO之殘基、之殘基、或-O(CH2)3CH3，且條件為R1及R2中至少一者為DOPO之殘基。
於本發明之部分實施態樣中，該硬化劑係選自以下群組：二胺基二苯碸(diaminodiphenyl sulfone，DDS)、胺基三氮雜苯酚醛(ATN)樹脂、雙馬來醯亞胺(bismaleimide，BMI)樹脂、多官能性馬來醯亞胺 樹脂、苯乙烯馬來酸酐(styrene maleic anhydride，SMA)樹脂、苯并噁嗪樹脂(benzoxazine)、及其組合。
於本發明之部分實施態樣中，該硬化劑(B)對該含磷酚醛樹脂(C)的重量比係約0.2：1至約3：1，較佳約0.3：1至約1.5：1。
於本發明之部分實施態樣中，以100重量份之無鹵環氧樹脂(A)計，該硬化劑(B)之含量為約5重量份至約60重量份，且該含磷酚醛樹脂(C)之含量為約10重量份至約50重量份。
於本發明之部分實施態樣中，樹脂組合物更包含選自以下群組之共硬化劑：二氰二胺(Dicy)、氰酸酯(cyanate ester)樹脂、酚醛樹脂(phenol novolac，PN)、二胺基二苯甲烷(diaminodiphenylmethane)、苯乙烯-乙烯基酚共聚物、及其組合。
於本發明之部分實施態樣中，樹脂組合物更包含一核殼橡膠(core/shell rubber)。
於本發明之部分實施態樣中，樹脂組合物更包含選自以下群組之成分：填料、阻燃劑、催化劑、分散劑、增韌劑、及其組合。所述填料例如可選自以下群組：二氧化矽(如中空二氧化矽)、氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、滑石、黏土、氮化鋁、氮化硼、氫氧化鋁、碳化鋁矽、碳化矽、碳酸鈉、二氧化鈦、氧化鋅、氧化鋯、石英、鑽石、類鑽石、石墨、煅燒高嶺土、白嶺土、雲母、水滑石、聚四氟乙烯(PTFE)粉末、玻璃珠、陶瓷晶鬚、奈米碳管、奈米級無機粉體、及其組合。
本發明之另一目的在於提供一種預浸漬片，其係藉由將一基材含浸或塗佈如上所述之樹脂組合物，並乾燥該經含浸或塗佈之基材而製得。
本發明之再一目的在於提供一種金屬箔積層板。其係藉由將如上所述之預浸漬片與金屬箔加以層合而製得，或係藉由將如上所述之樹脂組合物塗佈於金屬箔並乾燥該經塗佈之金屬箔而製得。
本發明之又一目的在於提供一種印刷電路板，其係由如上所述之金屬箔積層板所製得。
為使本發明之上述目的、技術特徵及優點能更明顯易懂，下文係以部分具體實施態樣進行詳細說明。
以下將具體地描述根據本發明之部分具體實施態樣；惟，在不背離本發明之精神下，本發明尚可以多種不同形式之態樣來實踐，不應將本發明保護範圍解釋為限於說明書所陳述者。
除非文中有另外說明，於本說明書中(尤其是在後述專利申請範圍中)所使用之「一」、「該」及類似用語應理解為包含單數及複數形式。
除非文中有另外說明，於本說明書中描述溶液、混合物或組合物中所含之成分時，係以固含量(dry weight)計算，即，未納入溶劑之重量。
本文中，用詞「約」係指所指定之量可增加或減少一本領域技藝人士可認知為一般且合理的大小的量。
本發明對照現有技術之功效在於，本發明樹脂組合物使用了特定結構的含磷酚醛樹脂，其分子結構中具有非極性或低極性的烷基碳鏈段，可增益樹脂組合物所製電子材料之電學性質，其分子結構末端之衍生自DOPO或DOPO衍生物之殘基可賦予所製電子材料良好難燃性質，而其 分子結構末端之低碳數烷基或衍生自胺基三氮雜苯酚醛(ATN)樹脂之殘基則可進一步增益所製電子材料之電學性質及提升樹脂組合物之交聯密度，使得所製電子材料之電性及耐熱性(如Tg)更為優異。茲就本發明樹脂組合物之各成分及製備方式提供詳細說明如下。
1. 樹脂組合物
本發明樹脂組合物係包含無鹵環氧樹脂(A)、硬化劑(B)、以及具有特定結構之含磷酚醛樹脂(C)等必要成分，以及可視需要之選用成分。
1.1. 無鹵環氧樹脂(A)
本文中，無鹵環氧樹脂係指在一分子中具有至少二個環氧官能基且不含鹵素的熱硬化型樹脂，例如多官能基環氧樹脂、線性酚醛環氧樹脂、或其組合。所述多官能基環氧樹脂包括雙官能基環氧樹脂、四官能基環氧樹脂、八官能基環氧樹脂等。無鹵環氧樹脂之實例包括但不限於：酚醛型環氧樹脂、雙酚型環氧樹脂、二環戊二烯(DCPD)型環氧樹脂、二苯乙烯型環氧樹脂、含三嗪(triazine)骨架之環氧樹脂、含茀骨架之環氧樹脂、三酚基甲烷型環氧樹脂、聯苯型環氧樹脂、伸茬基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、脂環式環氧樹脂、及其組合。酚醛型環氧樹脂之實例包括但不限於苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、及雙酚F酚醛型環氧樹脂。雙酚型環氧樹脂之實例包括但不限於雙酚A型環氧樹脂、雙酚F型環氧樹脂、及雙酚S型環氧樹脂。環氧樹脂的實例尚可包括多官能酚類及蒽等多環芳香族類之二縮水甘油醚化合物。此外，可導入磷至環氧樹脂中而形成含磷環氧樹脂，例如經DOPO改質之環氧樹脂。
1.2. 硬化劑(B)
硬化劑含有反應性官能基之成分，其可參與固化反應，並形成網狀結構，從而增益所製電子材料之特性，例如改良其玻璃轉移溫度(Tg)、吸水性、Df等特性。
一般而言，於本發明之樹脂組合物中，以100重量份之無鹵環氧樹脂(A)計，硬化劑(B)之含量為約5重量份至約60重量份，例如6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、17重量份、19重量份、20重量份、22重量份、24重量份、25重量份、27重量份、30重量份、32重量份、35重量份、37重量份、40重量份、42重量份、45重量份、48重量份、50重量份、52重量份、55重量份、或58重量份，但本發明不以此為限，本發明所屬技術領域具通常知識者仍可依據實際需要調整硬化劑(B)之用量。
於本發明之部分實施態樣中，硬化劑(B)係選自以下群組：二胺基二苯碸(DDS)、胺基三氮雜苯酚醛(ATN)樹脂、雙馬來醯亞胺(BMI)樹脂、多官能性馬來醯亞胺樹脂、苯乙烯馬來酸酐(SMA)樹脂、苯并噁嗪樹脂、及其組合。於使用上述硬化劑之情況下，所製電子材料可具有更好的耐熱性(玻璃轉移溫度(Tg)更高)。以下茲就上述硬化劑提供進一步說明。
1.2.1. 二胺基二苯碸(DDS)樹脂
二胺基二苯碸(DDS)樹脂是一種芳香族胺類硬化劑，其實 例包括但不限於3,3,-二胺基二苯碸()及4,4,-二胺基二 苯碸()。
1.2.2. 胺基三氮雜苯酚醛(ATN)樹脂
胺基三氮雜苯酚醛(ATN)樹脂可改善所製電子材料的耐熱性，同時又可提高金屬箔積層板之介電層與金屬箔的附著力。一般而言，胺基三氮雜苯酚醛樹脂可藉由將苯酚化合物、醛類化合物、及胍胺化合物，在酸性觸媒(如草酸、對甲苯磺酸等)存在下，進行反應而製得。苯酚化合物之實例包括苯酚、甲酚、或二甲苯酚；醛類化合物之實例包括甲醛、以及胍胺化合物可為如下結構式所代表之一或多種化合物： 其中R可為胺基(蜜胺)、苯基(苄胍胺)、或如甲基(甲基胍胺)等烷基。
胺基三氮雜苯酚醛樹脂之實例包括但不限於以下結構式所表示之化合物：
1.2.3. 雙馬來醯亞胺(BMI)樹脂
雙馬來醯亞胺樹脂係一種具有二個馬來醯亞胺官能基的化合物。馬來醯亞胺官能基具有反應性碳-碳雙鍵，可與樹脂組合物中的其他不飽和官能基進行反應而發生交聯固化作用，並且可改善樹脂組合物固化後所得之材料的耐熱性。具體而言，雙馬來醯亞胺樹脂可由以下結構式表示： 其中，R3為一有機基團，且較佳係選自以下群組之基團：伸甲基(-CH2-)、 4,4'-二苯甲烷基()、間伸苯基()、雙酚A二苯醚基 ()、3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷基 ()、4-甲基-1,3-伸苯基()、及(2,2,4-三甲基)伸 己基()。
雙馬來醯亞胺樹脂的具體實例包括但不限於：1,2-雙馬來醯亞胺基乙烷、1,6-雙馬來醯亞胺基己烷、1,3-雙馬來醯亞胺基苯、1,4-雙馬來醯亞胺基苯、2,4-雙馬來醯亞胺基甲苯、4,4'-雙馬來醯亞胺基二苯基甲烷、4,4'-雙馬來醯亞胺基二苯基醚、3,3'-雙馬來醯亞胺基二苯基碸、4,4'-雙馬來醯亞胺基二苯基碸、4,4'-雙馬來醯亞胺基二環己基甲烷、3,5-雙(4-馬來醯亞胺基苯基)吡啶、2,6-雙馬來醯亞胺基吡啶、1,3-雙(馬來醯亞胺基甲基)環己烷、1,3-雙(馬來醯亞胺基甲基)苯、1,1-雙(4-馬來醯亞胺基苯基)環己烷、1,3-雙(二氯馬來醯亞胺基)苯、4,4'-雙檸康醯亞胺基二苯基甲烷(4,4'-biscitraconimidodiphenylmethane)、2,2-雙(4-馬來醯亞胺基苯基)丙烷、1-苯基-1,1-雙(4-馬來醯亞胺基苯基)乙烷、α,α-雙(4-馬來醯亞胺基苯基)甲苯、3,5-雙馬來醯亞胺基-1,2,4-三唑、N,N'-伸乙基雙馬來醯亞胺、N,N'-六亞甲基雙馬來醯亞胺、N,N'-間-伸苯基雙馬來醯亞胺、N,N'-對-伸苯基雙馬來醯亞胺、N,N'-4,4'-二苯基甲烷雙馬來醯亞胺、N,N'-4,4'-二苯基醚雙馬來醯亞胺、N,N'-4,4'-二苯基碸雙馬來醯亞胺、 N,N'-4,4'-二環己基甲烷雙馬來醯亞胺、N,N'-α,α'-4,4'-二亞甲基環己烷雙馬來醯亞胺、N,N'-間二甲苯雙馬來醯亞胺、N,N'-4,4'-二苯基環己烷雙馬來醯亞胺、及N,N'-亞甲基雙(3-氯-對-伸苯基)雙馬來醯亞胺。商業上可購得之雙馬來醯亞胺樹脂包括KI Chemical公司之型號為BMI-70及BMI-80的產品，以及大和化成工業之型號為BMI-1000、BMI-4000、BMI-5000、BMI-5100、及BMI-7000的產品。前述雙馬來醯亞胺可單獨使用或混合使用，本領域具通常知識者可依據實際需要而自行調配。於後附實施例中，係使用BMI-70(R3為3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷基)。
1.2.4. 多官能性馬來醯亞胺樹脂
於本文中，多官能性馬來醯亞胺樹脂係指具有多個馬來醯亞胺官能基的寡聚物，通常為苯胺(aniline)或甲醛(formaldehyde)與馬來酸酐(maleic anhydride)的縮合反應產物。具體而言，多官能性馬來醯亞胺樹脂可由以下結構式表示： 其中，p為1至10之整數。
有關多官能性馬來醯亞胺樹脂的說明可參考US 4,435,560，該專利文獻全文在此引入作為參考。商業上可購得之多官能性馬來醯亞胺樹脂包括大和化成工業之型號為BMI-2000及BMI-2300(CAS號：67784-74-1)的產品。
1.2.5. 苯乙烯馬來酸酐(SMA)樹脂
苯乙烯-馬來酸酐(SMA)樹脂為苯乙烯單體與馬來酸酐單體之共聚物，具有降低Dk及Df的效果，此外，其分子中的衍生自馬來酸酐的基團為優良的官能基，能與環氧樹脂充分進行反應，因此另有提升Tg的效果。具體而言，苯乙烯-馬來酸酐樹脂係具有以下重複單元之聚合物： 其中，q1一般為1至10之整數，q2一般為10至40之整數。
於苯乙烯-馬來酸酐樹脂中，苯乙烯的莫耳比佔比越高(即q1值越大者)，所製得之電子材料的Df值越低，故電學性質較佳，但玻璃轉移溫度(Tg)較差(q1=1時，Tg為約155℃，q1=8時，Tg則僅為約104℃)；此外，若苯乙烯的莫耳比佔比過高(如q1≧8)，將使得所製得之預浸漬片的表面沾黏性提高，而容易產生自身黏合，如此將不利加工操作。反之，苯乙烯的莫耳比佔比越低(例如q1≦3)，所製得之電子材料的Tg越高，故耐熱性越好，但所製材料的質地較脆，加工時易產生粉屑污染。因此，在上述重複單元中q1值較佳為3至8，滿足此條件之苯乙烯-馬來酸酐樹脂包括可購自Cray Valley公司之型號為SMA EF-40(q1=4)與EF-30(q1=3)的產品。
1.2.6. 苯并噁嗪樹脂
苯并噁嗪樹脂係指由酚類羥基化合物、一級胺及甲醛依下列反應所製得之化學物質：
於上述反應式中，該酚類羥基化合物之實例包括但不限於多官能基酚(如鄰苯二酚、間苯二酚、或對苯二酚)、聯酚化合物、雙酚化合物(如雙酚A、雙酚F、或雙酚S)、三酚化合物、及酚醛樹脂(如酚醛清漆樹脂或蜜胺酚醛樹脂)。一級胺(R4-NH2)之R4可為烷基、環烷基、苯基、或經烷基或烷氧基取代之苯基，其實例包括但不限於甲胺及經或未經取代之苯胺。甲醛(HCHO)可以福馬林或多聚甲醛的方式提供。
苯并噁嗪樹脂可於添加至本發明之樹脂組合物前，預先經過開環聚合反應，而以預聚物的形式添加至樹脂組合物中。關於此類預聚物之製備與使用，可見US 2012097437 A(申請人：Taiwan Union Technology公司)，該專利申請案之全文併於此作為參照。
1.3. 具有式(I)結構之含磷酚醛樹脂(C)
本發明樹脂組合物中包含具有以下式(I)結構之含磷酚醛樹脂(C)，其經由DOPO或DOPO衍生物於分子末端改質，且在酚醛主鏈的苯酚結構中引入了三級丁基及/或(1,1,3,3)四甲基丁基。
於式(I)中，m、n、及l各自獨立為0至10之整數，但m、n、及l不同時為0，以及R1及R2各自獨立為DOPO、DOPO衍生物或胺基三氮雜苯酚醛(ATN)樹脂之殘基，或-O(CH2)3CH3，且條件為R1及R2中至少一者為DOPO或DOPO衍生物之殘基，以賦予所製電子材料難燃性質。
於式(I)中，m、n、l之值越大，主鏈上的-OH基越多，越能提升樹脂組合物固化後的交聯密度。當R1及R2分別為DOPO或DOPO 衍生物之殘基時，該含磷酚醛樹脂具有較佳的難燃性質。當R1及R2僅其中之一者為DOPO或DOPO衍生物之殘基，另一者為-O(CH2)3CH3時，該含磷酚醛樹脂具有較佳的電學性質。當R1及R2僅其中之一者為DOPO或DOPO衍生物之殘基，另一者為ATN之殘基時，該含磷酚醛樹脂具有較佳的反應性。
上述具式(I)結構之含磷酚醛樹脂(C)的製備方法並無特殊限制且並非本發明之技術重點所在，本領域技藝人士於觀得本案說明書揭露後當可依所具備之通常知識視需要選擇合宜之方式自行製備或以商購方式取得。例如，可依一般方法製得具式(I)主鏈結構之酚醛樹脂後，再以DOPO、DOPO衍生物、ATN等進行酚醛樹脂之末端改質，以製得具式(I)結構之含磷酚醛樹脂(C)。相關改質方法可參照例如US20070221890、US 8124716、US 20140249253等，上述文獻及其引用文獻，在此引入全文作為參考。於後附實施例中，係使用購自Kolon Industries公司之型號為KEG3320B65的產品，其中R1及R2係各自獨立為DOPO 之殘基、之殘基或-O(CH2)3CH3。具式(I)結構之含磷酚醛樹脂(C)另可購自Dow Chemical公司。
於本發明之樹脂組合物中，以100重量份之無鹵環氧樹脂(A)計，該含磷酚醛樹脂(C)之含量為約10重量份至約50重量份，例如11重量份、12重量份、13重量份、14重量份、15重量份、17重量份、19重量份、20重量份、22重量份、24重量份、25重量份、27重量份、30重量份、32重量份、35重量份、37重量份、40重量份、或45重量份。
於本發明之樹脂組合物中，硬化劑(B)對該含磷酚醛樹脂(C)的重量比係約0.2：1至約3：1，較佳為約0.3：1至約1.5：1，例如0.36：1、0.37：1、0.4：1、0.5：1、0.55：1、0.6：1、0.65：1、0.7：1、0.75：1、0.8：1、0.85：1、0.9：1、1：1、1.05：1、1.1：1、1.15：1、1.2：1、1.25：1、1.3：1、1.35：1、1.4：1或1.45：1。
1.4. 視需要之其他成分
於本發明樹脂組合物中，可視需要包含其他成分，例如下文所述之共硬化劑、核殼橡膠、及本領域所習知之添加劑，以改良樹脂組合物所製電子材料之物化性質或樹脂組合物在製造過程中的可加工性。
1.4.1. 共硬化劑
於本發明之樹脂組合物中，除硬化劑(B)外，可進一步包含其他習知可適用於環氧樹脂之硬化劑，例如含-OH基的化合物、含胺基的化合物、酸酐化合物、及活性酯化合物；且共硬化劑之用量並無特殊限制，可由本發明所屬技術領域具通常知識者依據實際需要進行調整。共硬化劑之實例包括但不限於二氰二胺(Dicy)、氰酸酯(cyanate ester)樹脂、酚醛樹脂(phenol novolac，PN)、二胺基二苯甲烷(diaminodiphenylmethane)、及苯乙烯-乙烯基酚共聚物，且前述共硬化劑可單獨使用或任意組合使用。於後附實施例中係使用二氰二胺(Dicy)。
1.4.2. 核殼橡膠
本發明之樹脂組合物中可進一步包含核殼橡膠作為增韌劑，以改善所製電子材料的脆性，使電子材料變得強韌。本文中，核殼橡膠係指一種具有雙層結構之橡膠。該雙層結構包括核層(內層)及一包覆該核層之殼層(外層)。核層通常由二烯類彈性體(diene elastomer)或矽氧烷(siloxane)所構成，主要功能為吸收應力。殼層通常由與樹脂組 合物中其他成分相容性高的高分子材料所構成，例如由丙烯酸類單體、甲基丙烯酸類單體、苯乙烯單體、及丙烯腈單體之一或多者所形成之聚合物或共聚物，其主要功能為包覆在核層的外部，以利核殼橡膠與樹脂組合物相容，而於樹脂組合物中具有良好的分散性。
核殼橡膠可藉由本領域習知之任意製備方法來製備，例如可藉由US 2009/0298970中所揭露的方法來製備，該專利文獻全文在此引入作為參考。商業上可購得之核殼橡膠的實例包括KANEKA公司之型號為MX-120、MX-125、MX-130、MX-156、MX-551、及KANE ACE系列的產品，以及Mitsubishi Rayon公司之型號為METABLEN SX-006的產品。
一般而言，為了在不影響樹脂組合物本身特性之前提下提供所欲之增韌功效，核殼橡膠的含量以樹脂組合物固含量計，通常為約1重量%至約20重量%，例如2重量%、4重量%、4.5重量%、6重量%、7重量%、8重量%、8.5重量%、9重量%、10重量%、12重量%、13重量%、14重量%、16重量%、17重量%、18重量%、或19重量%，較佳約1重量%至約15重量%，更佳約1重量%至約5重量%，但本發明不以此為限。
1.4.3. 其他添加劑
可應用於本發明之樹脂組合物中之添加劑的實例包括但不限於填料、阻燃劑、催化劑、分散劑、及增韌劑，且各該添加劑可單獨使用或組合使用。
於本發明之部分實施態樣中，樹脂組合物中進一步添加填料，以增益所製得之電子材料的物化性質。所述填料之實例包括但不限於二氧化矽(如中空二氧化矽)、氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、滑石、黏土、氮化鋁、氮化硼、氫氧化鋁、碳化鋁矽、碳化矽、碳酸鈉、二 氧化鈦、氧化鋅、氧化鋯、石英、鑽石、類鑽石、石墨、煅燒高嶺土、白嶺土、雲母、水滑石、聚四氟乙烯(polytetrafluoroethylene，PTFE)粉末、玻璃珠、陶瓷晶鬚、奈米碳管、及奈米級無機粉體，且各該填料可單獨使用或任意組合使用。一般而言，以樹脂組合物固含量計，填料的含量通常為0重量%至約40重量%，例如1重量%、3重量%、5重量%、7重量%、10重量%、15重量%、20重量%、22重量%、25重量%、30重量%、或35重量%，但不以此為限，本發明所屬技術領域具通常知識者仍可依據實際需要進行調整。
於本發明之部分實施態樣中，樹脂組合物中進一步添加催化劑，以促進環氧官能基開環進行交聯反應，並降低樹脂組合物之固化反應溫度。催化劑的種類並無特殊限制，只要其能促進環氧官能基開環並降低固化反應溫度即可。舉例言之，催化劑可為三級胺、四級胺、咪唑化合物、或吡啶化合物，且各該催化劑可單獨使用或混合使用。催化劑之實例包括但不限於2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、二甲苄胺、2-(二甲胺甲基)苯酚、2,4,6-三(二甲胺甲基)苯酚、2,3-二胺基吡啶、2,5-二胺基吡啶、2,6-二胺基吡啶、4-二甲基胺基吡啶、2-胺基-3-甲基吡啶、2-胺基-4-甲基吡啶、及2-胺基-3-硝基吡啶。一般而言，以樹脂組合物固含量計，催化劑的含量通常為約0.5重量%至約5重量%，例如1重量%、1.5重量%、2重量%、2.5重量%、3重量%、3.5重量%、4重量%、或4.5重量%，但不以此為限，本發明所屬技術領域具通常知識者仍可依據實際需要進行調整。
1.5 樹脂組合物之製備
關於本發明樹脂組合物之製備，可藉由將樹脂組合物各成分，包括無鹵環氧樹脂、硬化劑、具式(I)之含磷酚醛樹脂、及視需要之 其他成分，以攪拌器均勻混合並溶解或分散於溶劑中而製成清漆狀的形式，供後續加工利用。所述溶劑可為任何可溶解或分散樹脂組合物各成分、但不與該等成分反應的惰性溶劑。舉例言之，可用以溶解或分散樹脂組合物各成分之溶劑包含但不限於甲苯、γ-丁內酯、甲乙酮、環己酮、丁酮、丙酮、二甲苯、甲基異丁基酮、N,N-二甲基甲醯胺(N,N-dimethyl formamide，DMF)、N,N-二甲基乙醯胺(N,N-dimethyl acetamide，DMAc)、及N-甲基吡咯烷酮(N-methyl-pyrolidone，NMP)，且各該溶劑可單獨使用或混合使用。溶劑之用量並無特殊限制，原則上只要能使樹脂組合物各組分均勻溶解或分散於其中即可。於本發明之部分實施態樣中，係使用甲苯、甲乙酮、及γ-丁內酯之混合物作為溶劑。
2. 預浸漬片
本發明亦提供一種由上述樹脂組合物所製得之預浸漬片，其中係藉由將一基材含浸如上述之樹脂組合物或將上述之樹脂組合物塗佈於一基材，並進行乾燥而製得。常用之基材包括玻璃纖維補強材料(如玻璃纖維織物或不織物、玻璃紙、或玻璃氈)、牛皮紙、短絨棉紙、天然纖維布、有機纖維布(如液晶高分子)等。於本發明之部分實施態樣中，係使用2116強化玻璃纖維布作為補強材，並在175℃下加熱乾燥2至15分鐘(B-階段)，從而製得半固化狀態的預浸漬片。
3. 金屬箔積層板及印刷電路板
本發明亦提供一種由上述預浸漬片製得之金屬箔積層板，其包含一介電層及一金屬層，其中該介電層係由如上述之預浸漬片所提供。其中，可層疊複數層之上述預浸漬片，且於層疊該預浸漬片所構成的介電層之至少一外側表面層疊一金屬箔(如銅箔)以提供一層疊物，並對該層疊物進行一熱壓操作而得到金屬箔積層板。或者，可將上述之樹脂組合物 直接塗佈於一金屬箔並進行乾燥，而製得金屬箔積層板。此外，可經由進一步圖案化金屬箔積層板之外側金屬箔，而製得印刷電路板。
4. 實施例
4.1. 量測方式說明
茲以下列具體實施態樣進一步例示說明本發明，其中，所採用之量測儀器及方法分別如下：
[吸水性測試]
進行壓力鍋蒸煮試驗(pressure cooker test，PCT)試驗，將金屬箔積層板置於壓力容器中，在121℃、飽和相對濕度(100% R.H.)及1.2大氣壓的環境下2小時，測試金屬箔積層板的耐濕能力。
[耐浸焊性測試]
將乾燥過的金屬箔積層板在288℃的錫焊浴中浸泡一定時間後，觀察是否出現爆板情形，例如觀察金屬箔積層板是否產生分層或脹泡現象。
[抗撕強度測試]
抗撕強度係指金屬箔對經熱壓層合之預浸漬片的附著力而言，於本文中係以1/8英寸寬度的銅箔自板面上垂直撕起，以其所需力量的大小來表達附著力的強弱。
[玻璃轉移溫度(Tg)測試]
利用動態機械分析儀(Differential Scanning Calorimeter，DSC)量測玻璃轉移溫度(Tg)。玻璃轉移溫度的測試規範為電子電路互聯與封裝學會(The Institute for Interconnecting and Packaging Electronic Circuits，IPC)之IPC-TM-650.2.4.25C及24C號檢測方法。
[熱膨脹率測試]
以TA儀器(TA instrument)公司之熱膨脹分析儀(機型TA 2940)量測，量測條件為在50℃至260℃之溫度區間以每分鐘10℃之升溫速率升溫，量測樣品(3平方毫米大小之金屬箔積層板)在厚度方向(Z軸方向)的熱膨脹率。
[難燃性測試]
利用UL94V：垂直燃燒測試方法，將金屬箔積層板以垂直位置固定，以本生燈燃燒，比較其自燃熄滅與助燃特性。難燃等級之排序為：V0>V1>V2。
[介電常數(Dk)與介電損耗因子(Df)量測]
根據ASTM D150規範，在工作頻率10GHz下，計算介電常數(Dk)與介電損耗因子(Df)。用於測試之預浸漬片的樹脂含量(Resin Content，RC)為約53%。
[耐鹼性測試]
將不含銅箔之積層板(即，僅使用本發明預浸漬片層合並經熱壓而成之積層板)浸泡於濃度20重量%之NaOH溶液中，於90℃下持續10分鐘，之後觀察積層板外觀是否有被咬蝕現象，若無咬蝕現象則記錄為「通過」，若有咬蝕現象則記錄為「失敗」。
[鑽針磨耗測試]
以直徑0.3毫米之鑽針對金屬箔積層板鑽孔，並於鑽孔次數達2000次之後觀察鑽針頭部的磨耗。由於鑽針之切削邊緣(cutting edge，CE)在鑽孔過程中會不斷與積層板接觸磨耗，在切削邊緣CE之切削轉角(cutting corner，CC)處會產生磨耗，因此本測試中係針對切削轉角CC處進行量測以得到磨耗率。
4.2. 原物料資訊列表：
4.3. 樹脂組合物之製備
以表1所示之比例配製實施例1至7及比較例1至3之樹脂組合物，其中係將各成分於室溫下使用攪拌器混合，並加入甲苯、甲乙酮、及γ-丁內酯(皆購自Fluka公司)，接著將所得混合物於室溫下攪拌60至120分鐘後，製得各該樹脂組合物。
4.4. 金屬箔積層板之製備及性質量測
分別使用所製得之樹脂組合物製備實施例1至7及比較例1至3之金屬箔積層板。首先，經由輥式塗佈機，將玻璃纖維布(型號：2116，厚度：0.08毫米)分別浸漬於實施例1至7及比較例1至3之樹脂組合物中，並控制玻璃纖維布之厚度至一合適程度。接著，將浸漬後的玻璃纖維布置於175℃之乾燥機中加熱乾燥2至15分鐘，藉此製得半固化狀態 (B-stage)的預浸漬片(預浸漬片之樹脂含量為約53%)。之後，將四片預浸漬片層合，並在其二側的最外層各層合一張0.5盎司之銅箔，隨後置於熱壓機中進行高溫熱壓固化。熱壓條件為：以3.0℃/分鐘之升溫速度升溫至200℃至220℃，並在該溫度下，以全壓15公斤/平方公分(初壓8公斤/平方公分)之壓力熱壓180分鐘。
依照前文所載量測方法測量實施例1至7及比較例1至3之預浸漬片與金屬箔積層板之各項性質，包括吸水性、耐浸焊性、抗撕強度、玻璃轉移溫度(Tg)、熱膨脹率、難燃等級、介電常數(Dk)、散逸因子(Df)、耐鹼性、及鑽針磨耗%，並將結果紀錄於表2中。
如表2所示，使用本發明樹脂組合物所製得之電子材料在各項物化性質表現均可達令人滿意之程度，尤其具有優異的吸水性、耐熱性及電學性質，且具有優異的加工性(鑽針磨耗率)。具體言之，實施例1與比較例1、實施例2與比較例2、及實施例7與比較例3之比較均顯示，相較於其他DOPO改質之含磷酚醛樹脂，本發明使用具式(I)結構之含磷酚醛樹脂可提供更低的吸水率、熱膨脹率、Df、及鑽針磨耗率、以及更好的耐熱性(Tg高)。
上述實施例僅為例示性說明本發明之原理及其功效，並闡述本發明之技術特徵，而非用於限制本發明之保護範疇。任何熟悉本技術者在不違背本發明之技術原理及精神下，可輕易完成之改變或安排，均屬本發明所主張之範圍。因此，本發明之權利保護範圍係如後附申請專利範圍所列。

Claims (13)

  1. 一種樹脂組合物，包含：(A)無鹵環氧樹脂；(B)硬化劑；以及(C)具有下式(I)結構之含磷酚醛樹脂：於式(I)中，m、n、及l各自獨立為0至10之整數，但m、n、及l不同時為0，以及R1及R2各自獨立為9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)、DOPO衍生物或胺基三氮雜苯酚醛(amino triazine novolac，ATN)樹脂之殘基，且條件為R1及R2中至少一者為DOPO或DOPO衍生物之殘基。
  2. 如請求項1之樹脂組合物，其中於式(I)中，R1及R2各自獨立為DOPO之殘基或之殘基，且條件為R1及R2中至少一者為DOPO之殘基。
  3. 如請求項1之樹脂組合物，其中該硬化劑係選自以下群組：二胺基二苯碸(diaminodiphenyl sulfone，DDS)、胺基三氮雜苯酚醛(ATN)樹脂、雙馬來醯亞胺(bismaleimide，BMI)樹脂、多官能性馬來醯亞胺樹脂、苯乙烯馬來酸酐(styrene maleic anhydride，SMA)樹脂、苯并噁嗪(benzoxazine)樹脂、及其組合。
  4. 如請求項1至3中任一項之樹脂組合物，其中該硬化劑(B)對該含磷酚醛樹脂(C)的重量比係約0.2：1至約3：1。
  5. 如請求項4之樹脂組合物，其中該硬化劑(B)對該含磷酚醛樹脂(C)的重量比係約0.3：1至約1.5：1。
  6. 如請求項1至3中任一項之樹脂組合物，其中以100重量份之無鹵環氧樹脂(A)計，該硬化劑(B)之含量為約5重量份至約60重量份，且該含磷酚醛樹脂(C)之含量為約10重量份至約50重量份。
  7. 如請求項1至3中任一項之樹脂組合物，更包含選自以下群組之共硬化劑：二氰二胺(Dicy)、氰酸酯(cyanate ester)樹脂、酚醛樹脂(phenol novolac，PN)、二胺基二苯甲烷(diaminodiphenylmethane)、苯乙烯-乙烯基酚共聚物、及其組合。
  8. 如請求項1至3中任一項之樹脂組合物，更包含一核殼橡膠(core/shell rubber)。
  9. 如請求項1至3中任一項之樹脂組合物，更包含選自以下群組之成分：填料、阻燃劑、催化劑、分散劑、增韌劑、及其組合。
  10. 如請求項9之樹脂組合物，其中該填料係選自以下群組：二氧化矽、氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、滑石、黏土、氮化鋁、氮化硼、氫氧化鋁、碳化鋁矽、碳化矽、碳酸鈉、二氧化鈦、氧化鋅、氧化鋯、石英、鑽石、類鑽石、石墨、煅燒高嶺土、白嶺土、雲母、水滑石、聚四氟乙烯(polytetrafluoroethylene，PTFE)粉末、玻璃珠、陶瓷晶鬚、奈米碳管、奈米級無機粉體、及其組合。
  11. 一種預浸漬片，其係藉由將一基材含浸或塗佈如請求項1至10中任一項之樹脂組合物，並乾燥該經含浸或塗佈之基材而製得。
  12. 一種金屬箔積層板，其係藉由將如請求項11所述之預浸漬片與金屬箔加以層合而製得，或係藉由將請求項1至10中任一項之樹脂組合物塗佈於金屬箔並乾燥該經塗佈之金屬箔而製得。
  13. 一種印刷電路板，其係由如請求項12之金屬箔積層板所製得。
TW107100199A 2018-01-03 2018-01-03 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板 TWI671355B (zh)

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