TW202106735A - 嵌段共聚物組合物、預浸料及由其製備之層壓體 - Google Patents

嵌段共聚物組合物、預浸料及由其製備之層壓體 Download PDF

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TW202106735A
TW202106735A TW109114720A TW109114720A TW202106735A TW 202106735 A TW202106735 A TW 202106735A TW 109114720 A TW109114720 A TW 109114720A TW 109114720 A TW109114720 A TW 109114720A TW 202106735 A TW202106735 A TW 202106735A
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Taiwan
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block
resin composition
weight
copolymer
mol
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TW109114720A
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English (en)
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瑞棟 丁
牛亞明
斌 楊
夏微兒 慕德曼
偉特 法蘭克 德
楊慧嫻
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荷蘭商克雷頓聚合物研究公司
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Publication of TW202106735A publication Critical patent/TW202106735A/zh

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Abstract

揭示了一種允許生產耐熱性及加工性優異之層壓之片材之樹脂組合物，其包含：a)嵌段共聚物，其中上述嵌段共聚物包括至少一個包含聚合之無環共軛二烯單元例如丁二烯單元之聚合物嵌段及至少一個含共軛環狀二烯例如1,3-環己二烯或特徵在於Tg大於100℃之單體單元之聚合物嵌段；b)固化引發劑；及 c)視情況選用的選自聚丁二烯聚合物及丁二烯與苯乙烯或其他苯乙烯類單體之共聚物之二烯基聚合物，d)視情況選用的添加劑，包括但不限於多官能之可共固化之添加劑、二烯基橡膠、鹵化或非鹵化之阻燃劑、無機或有機填料或纖維、抗氧化劑、黏合劑促進劑及成膜聚合物。

Description

嵌段共聚物組合物、預浸料及由其製備之層壓體
本發明係關於低耗散、低介電之可固化之嵌段共聚物組合物及由其製成之產品，包括覆銅層壓體及印刷電路板。
隨著電子技術之飛速發展，大容量之電腦系統及網路要求高頻信號傳輸，且電路基板適合於高頻及高速傳輸。期望電路基板在高頻及低傳輸損耗(例如介電損耗、導體損耗及輻射損耗)下操作信號。傳輸損耗會減弱電信號並破壞信號可靠性。
傳統上，印刷電路板使用環氧樹脂，上述樹脂具有較高之介電常數及介電損耗角正切值。環氧樹脂可與酚類化合物、胺或酸酐固化劑結合使用以提高性能。這種樹脂組合物仍然難以獲得低損耗因數。聚苯醚樹脂(PPO，或稱為聚氧化伸苯基樹脂)由於其低耗散性能而被用於層壓體中，但是其阻燃性仍然不足。其高黏度限制了其分子量或其在製劑中之含量，且缺乏交聯性。遙爪乙烯基官能化之低分子量PPO樹脂由於其改善之溶解性及交聯性而用於層壓體中，但所得損耗因數被不利影響。
已經揭示了苯乙烯-丁二烯-苯乙烯嵌段共聚物用於印刷電路板組合物中，例如，包含1,2-聚丁二烯、聚異戊二烯及其改性之(羥基、甲基丙烯酸酯及羧酸酯封端之)或反應後之樹脂(環氧、馬來酸酐或胺基甲酸酯改性之)丁二烯或異戊二烯樹脂用於印刷電路板。所描述之苯乙烯類嵌段共聚物受到其剛性聚苯乙烯嵌段之有限溫度性能之限制。
仍然需要改良之組合物以用於覆銅層壓體及由其製備之印刷電路板之介電化合物，上述改良之組合物具有良好的可加工性、低的溶液黏度、有效的固化能力、高的軟化點溫度和低的損耗因數、高頻率下的低介電常數特性。
在一態樣中，揭示了一種用於製造固化製品或印刷電路板之低黏度樹脂組合物。上述樹脂組合物包含5-99重量%之嵌段共聚物，其中上述嵌段共聚物包含至少A嵌段以及B、B'及C嵌段中之至少一個。每個A嵌段係包含至少一種無環共軛二烯之聚合單元之非氫化的聚(無環共軛二烯)聚合物。每個B嵌段係GPC嵌段Mp低於25 kg/mol之聚(1,3-環二烯)均聚物。每個B'嵌段係GPC嵌段Mp低於30 kg/mol之聚(1,3-環二烯-共-單烯基芳烴)共聚物。每個C嵌段係包含至少一個Tg高於100℃之高Tg烯基芳烴單元之聚(烯基芳烴)聚合物或共聚物。上述嵌段共聚物具有：偶聯前之GPC峰值分子量Mp小於50,000 g/mol，乘以A嵌段含量之重量分率之GPC峰值分子量Mp大於500 g/mol。上述樹脂組合物進一步包含0.1-10重量%之固化引發劑；及最多95重量%之一或多種選自以下之添加劑：多官能之可共固化之添加劑、二烯基橡膠、鹵化或非鹵化之阻燃劑、無機或有機填料或纖維、抗氧化劑、黏合促進劑及成膜聚合物。
在另一態樣中，揭示了由上述樹脂組合物製備之預浸料及層壓之片材。
以下術語將在整個說明書中使用，並具有以下含義。
在用於表示幾個元素或元素類別(例如X、Y及Z)時，「一或多種」或「至少一種」係指選自X或Y或Z之單個元素或元素之組合，例如X及Y、Y及Z、或X及Z。
「預浸料」係指藉由用樹脂浸漬或支撐或增強織物而獲得的浸漬之織物。
「覆銅層壓體」或「CCL」係指印刷電路板(「PCB」)之基本材料，或電路基板。藉由與在浸入樹脂後之增強材料(例如玻璃纖維織物)之一側或兩側上之銅覆層一起層壓來獲得CCL。在某些實施方案中，藉由將一層或多層預浸料與一層或多層銅箔層進行層壓來獲得CCL。層壓係藉由在強力的熱、壓力及真空條件下將一層或多層銅及預浸料壓製在一起而獲得。
「印刷電路板」可以藉由蝕刻CCL之銅表面以產生電子電路來獲得。將蝕刻之CCL組裝成帶有鑽孔及電鍍孔之多層構型，以在各層之間建立電連接。
術語「單烯基芳烴」及「烯基芳烴」同義使用。
「高Tg單元」係指若均聚或共聚成高分子量（例如100,000 g/mol）則表現出高於100℃之DSC玻璃化轉變溫度(Tg)之聚合單體單元。
「分子量」(MW)係指聚合物嵌段或嵌段共聚物之苯乙烯當量分子量(kg/mol)。MW可以根據ASTM 5296-19，使用聚苯乙烯校準標準物，藉由凝膠滲透層析法(GPC)進行量測。可以使用市售之聚苯乙烯分子量標準物來校準層析儀。當已知聚合物之苯乙烯含量及二烯鏈段之乙烯基含量時，可以將苯乙烯當量MW轉換為真實分子量。偵測儀可以是紫外線及折射率偵測儀之組合。
除非另有說明，「峰值分子量」、Mp、「GPC峰值分子量」或「GPC Mp」係指在GPC跡線之峰處測得之MW。如上所述，分子量係苯乙烯當量。
本發明係關於一種包含嵌段共聚物之樹脂組合物，其用於製造預浸料及層壓體，特別係用於PCB。
嵌段共聚物組分：第一組分係嵌段共聚物。上述嵌段共聚物廣泛地包括至少一個包含至少一種無環共軛二烯之聚合單元之非氫化之聚(無環共軛二烯)嵌段A，及至少一個由高Tg單元組成之聚合物嵌段。
在某些實施方案中，高Tg嵌段選自B、B'及C。B嵌段係聚(1,3-環二烯)均聚物。1,3-環二烯單體之非限制性實例係1,3-環己二烯(CHD)。在某些實施方案中，B嵌段之GPC嵌段Mp＜25 kg/mol，或＜20 kg/mol，或＜15 kg/mol，或＜9 kg/mol，或＞2 kg/mol。
B'嵌段係聚(1,3-環二烯)無規共聚物嵌段。上述無規共聚物嵌段可包括一或多種共聚單體，例如單烯基芳烴，例如苯乙烯或對嵌段C所述之任何單烯基芳烴。在某些實施方案中，B'嵌段之GPC嵌段Mp＜30 kg/mol，或＜25 kg/mol，或＜20 kg/mol，或＜9 kg/mol，且＞2 kg/mol。
C嵌段係至少包含Tg＞100℃或＞125℃或＞150℃或＜250℃之高Tg單烯基芳烴單元之聚(烯基芳烴)聚合物或共聚物。在某些實施方案中，C嵌段之GPC嵌段Mp＜20 kg/mol，或＜15 kg/mol，或＜10 kg/mol。實例包括鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、α-甲基苯乙烯、對-α-二甲基苯乙烯、乙烯基-苯并環丁烯、乙烯基聯苯、金剛烷基苯乙烯、1,1-二苯基-乙烯及苯并富勒烯。
在某些實施方案中，上述嵌段共聚物具有一般構型A-B，(A-B-)n X，A-B'，(A-B'-)n X，A-B-A，A-B'-A，A-B-C，A-B'-C， A-C-B，A-C-B'，(B-A-)n X，(B'-A-)n X，B-A-B，B'-A-B'，(A-C-B-)nX，(A-C-B'-)n X，A-C-B-A，A-C-B'-A，A-C，A-C-A，(A-C-)nX，其中n為2-50之整數，X為偶聯劑殘基。
在某些實施方案中，每個A嵌段係包含至少一種無環共軛二烯之聚合單元之非氫化之聚(無環共軛二烯)聚合物。在某些實施方案中，每個A嵌段係具有小於50重量%之1,4-聚合單元之聚丁二烯(PBd)嵌段。在某些實施方案中，每個B嵌段係聚(1,3-環二烯)均聚物，每個B'嵌段係聚(1,3-環二烯-共-單烯基芳烴)共聚物。在某些實施方案中，每個C嵌段係包含至少一個高Tg烯基芳烴單元之聚(烯基芳烴)聚合物或共聚物。1,3-環二烯單元CD單體之聚合可以藉由1,2-及1,4-加成機理進行。因此，對於CD單體如CHD(環己二烯)，1,4-加成產生1,4-二取代(類似於對二取代苯環)之環己烷重複單元(在本文中亦稱為「p-CHD」或「PCHD」)。
上述嵌段共聚物可以藉由本領域已知之方法製備。在某些實施方案中，具有聚合之CD及無環共軛二烯單元嵌段之聚合物嵌段之微結構或乙烯基含量(其又取決於二烯單元之1,2-加成相對1,4-加成之程度)可以藉由改變用於較低之1,4加成單元及因此較高之「乙烯基」含量之微結構改性劑（例如四甲基乙二胺(TMEDA)、二乙氧基丙烷(DEP)、1,4-二氮雜雙環[2.2.2]辛烷(DABCO)）之相對量來控制。1,2-加成CD(例如1,3-環己二烯)導致在聚合物主鏈上形成1,2-環己-3-烯-二基，而1,4-加成導致在聚合物主鏈上形成1,4-環己-2-烯-二基。
在某些實施方案中，藉由在合適之溶劑混合物中使單體同時或順序地與陰離子聚合引發劑體系(例如正丁基鋰)接觸，在對於第一嵌段25-70℃之溫度，及對於第二嵌段25-50℃之溫度下，製備上述嵌段共聚物。在基本上形成嵌段共聚物之主鏈之後，可以將活性嵌段共聚物偶聯並封端以提供(偶聯之)二嵌段共聚物，或者可以用第三嵌段進行延伸(及偶聯)。可以藉由沈澱及蒸發來分離及回收聚合物。
在某些實施方案中，在偶聯之前，上述嵌段共聚物之GPC峰值分子量Mp＜50 kg/mol，或＜45 kg/mol，或＜35 kg/mol，或＞5 kg/mol。
在某些實施方案中，在偶聯後，上述嵌段共聚物之乘以A嵌段含量重量分率之GPC Mp＞500 g/mol，或＞1 kg/mol，或＞10 kg/mol，或＜100 kg/mol。
在某些實施方案中，上述嵌段共聚物包含小於5重量%或＜4重量%或＞0.1重量%之不同於碳及氫之原子。
在某些實施方案中，上述嵌段共聚物之DSC Tg＞100℃，或＞110℃，或＞125℃，或＞175℃，或＜250℃。在某些實施方案中，上述嵌段共聚物之在1 GHz之介電常數Dk＜2.6，或＜2.3，或＜2.1，或＞1.5；在1 GHz之介電損耗因數Df＜0.003，或＜0.002，或＜0.001，或＞0.00001。
在某些實施方案中，上述嵌段共聚物在25℃於甲苯中25重量%之溶液黏度＜2000 mPa.s，或＜1800 mPa.s，或＜1500 mPa.s，或＞10 mPa.s；或者，在25℃於二甲苯中50重量%之溶液黏度＜10,000 mPa.s，或＜8,000 mPa.s，或＜5,000 mPa.s，或＞10 mPa.s。
上述樹脂組合物中嵌段共聚物之量為5-99重量%，或5-80重量%，或＞8重量%，或10-30重量%，或＜70重量%，基於上述樹脂組合物之總重量。
固化劑/引發劑：上述樹脂組合物還包含產生自由基之化合物，亦稱為固化劑或固化引發劑。實例包括但不限於疊氮化物、過氧化物、硫及硫衍生物。自由基引發劑特別較佳作為固化引發劑。產生自由基之化合物亦稱為固化催化劑，其在升高之溫度下或在紫外線或其他能量添加之觸發作用下產生自由基。產生自由基之化合物確保樹脂組合物可在不存在紫外線或觸發能量之情況下在低溫下可加工，但在活化溫度下或在紫外線或引入觸發能量下產生高濃度之自由基。產生自由基之化合物可以包括能夠在升高之溫度下或在添加觸發能量例如UV輻射之後產生自由基之任何化合物。
產生自由基之化合物之實例係有機過氧化物，例如2,5-二甲基-2,5-二(第三丁基過氧)-己-3-炔、過氧化二第三丁基、過氧化第三丁基枯基、二（第三丁基過氧異丙基)苯、2,5-二甲基-2,5-二(第三丁基過氧)己烷、過氧化二枯基等。典型之非過氧引發劑包括諸如2,3-二甲基-2,3-二苯基丁烷、2,3-三甲基甲矽烷氧基-2,3-二苯基丁烷等之化合物。典型之UV自由基引發劑係2,2-二甲氧基-1,2-二苯基乙-1-酮。在某些實施方案中，固化引發劑係具有＞120℃之1小時半衰期溫度之過氧化物。
當使用時，固化引發劑之存在量為0.1-10重量%，或0.3-7重量%，或1-5重量%，基於上述樹脂組合物之總重量。
添加劑：上述樹脂組合物可以進一步包含一或多種添加劑，包括但不限於多官能之可共固化之添加劑、二烯基橡膠、鹵化或非鹵化之阻燃劑、無機或有機填料或纖維、單乙烯基化合物或本領域已知之其他添加劑，例如抗氧化劑、著色劑、穩定劑，黏合促進劑、增韌劑及成膜添加劑，其量為0.1-50重量%，基於上述樹脂組合物之重量。
由多乙烯基化合物構成之多官能之可共固化之添加劑之實例包括低分子量二乙烯基苯或雙(乙烯基苯基)乙烷或二乙烯基萘，三羥甲基丙烷三甲基丙烯酸酯或三羥甲基丙烷三丙烯酸酯或三烯丙基異氰脲酸酯或三烯丙基氰脲酸酯，或多乙烯基化合物，如乙烯基官能化之PPE(亦稱為烯丙基改性之聚苯醚)，例如Sabic之SA-9000，或Mitsubishi Gas Chemical之OPE 2st，或二烯基聚合物，例如二烯之均聚物，或不同烯烴及/或二烯之共聚物(包括三嵌段共聚物)，其在聚合物主鏈中具有雙鍵。二烯基聚合物在室溫下可以為液態或固態，包括用於介電基板之不飽和樹脂，例如聚丁二烯聚合物，或丁二烯與苯乙烯或類似苯乙烯類單體之共聚物。
其他添加劑之實例包括具有(甲基)丙烯醯基之聚丁二烯橡膠，具有(甲基)丙烯醯基之聚異戊二烯橡膠，具有(甲基)丙烯醯基之丁二烯及異戊二烯之共聚物橡膠，具有(甲基)丙烯醯基之丁二烯及正丁烯之共聚物橡膠等。在某些實施方案中，二烯基聚合物選自聚丁二烯、聚異戊二烯、丁二烯-苯乙烯共聚物、異戊二烯-苯乙烯共聚物、丁二烯-苯乙烯-甲基丙烯酸酯之三嵌段共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物、丁二烯-苯乙烯-丙烯腈共聚物、丁二烯-苯乙烯-馬來酸酐共聚物、及其任何組合。
液態丁二烯共聚物之實例係丁二烯-共-苯乙烯及丁二烯-共-丙烯腈。除了聚丁二烯或聚異戊二烯嵌段被氫化外，含不飽和丁二烯或異戊二烯之聚合物亦可含有與第一類似之第二嵌段共聚物，從而形成聚乙烯嵌段(在聚丁二烯之情況下)或乙烯-丙烯共聚物(在聚異戊二烯之情況下)。
第二類多官能之可共固化之添加劑由非乙烯基烯烴化合物如雙馬來醯亞胺樹脂如4,4'-雙(馬來醯亞胺基)-二苯甲烷構成。
在一些實施方案中，可共固化之添加劑係未氫化之嵌段共聚物，其峰值分子量為20,000-200,000原子質量單位。峰值分子量可以藉由凝膠滲透層析法(GPC)並基於聚苯乙烯標準物來確定，對應於將產生與被測聚合物相同之峰最大值之聚苯乙烯分子量。
阻燃劑：在某些實施方案中，上述樹脂組合物還包含選自含磷阻燃劑及溴化阻燃劑之阻燃劑。溴化阻燃劑之實例包括乙烯-雙(四溴鄰苯二甲醯亞胺)、1,2-雙(五溴苯基)乙烷及2,4,6-三(2,4,6-三溴苯氧基)-1,3,5-三嗪。含磷阻燃劑之實例包括雙酚磷酸二苯酯，多磷酸銨，對苯二酚雙(磷酸二苯酯)，雙酚A雙(磷酸二苯酯)，三(2-羧乙基)膦(TCEP)，磷酸三(氯異丙基)酯，磷酸三甲酯(TMP)，二甲基甲基膦酸酯(DMMP)，間苯二酚雙(二甲苯基磷酸酯)，磷腈，三聚氰胺多磷酸酯，9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)及其衍生物或樹脂，三聚氰胺氰脲酸酯及三羥乙基異氰脲酸酯。在某些實施方案中，阻燃劑化合物可以係DOPO化合物，DOPO樹脂(例如DOPO-HQ，DOPO-NQ，DOPO-PN及DOPO-BPN)及含DOPO之環氧樹脂，其中DOPO-BPN可以係雙酚酚醛清漆化合物，例如DOPO-BPAN，DOPO-BPFN及DOPO-BPSN。
在某些實施方案中，阻燃劑係非反應性阻燃劑，其在其化學結構中不包含反應性官能基。
阻燃劑通常以5-25重量%或8-20重量%或至少10重量%之量存在，基於上述樹脂組合物之總重量。
填料：上述樹脂組合物還包含至少一種無機及/或有機填料。無機填料可用於抑制熱膨脹係數並提高層壓之片材之韌性。可以使用有機填料來降低層壓之片材之介電常數。
示例性之填料包括二氧化鈦(金紅石及銳鈦礦)，鈦酸鋇，鈦酸鍶，二氧化矽（包括熔融無定形二氧化矽），剛玉，矽灰石，芳族聚醯胺纖維，玻璃纖維，Ba2 Ti9 O20 ，玻璃球，石英，氮化硼，氮化鋁，碳化矽，氧化鈹，氧化鋁，氧化鎂，氫氧化鎂，三聚氰胺多磷酸酯，三聚氰胺氰脲酸酯，蜜白胺，蜜胺（Melon），蜜勒胺，胍，磷氮烷，矽氮烷，DOPO(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)，DOPO(10-5-二羥基苯基，10-H-9-側氧基磷醯苯二酚(oxaphosphaphenanthrenelo)-氧化物)，雲母，滑石粉，奈米黏土，鋁矽酸鹽(天然及合成)及熱解法二氧化矽，可單獨使用或組合使用。可以對填料進行表面處理以使其表面不吸水並且與組合物中之其他成分更相容或對自由基具有反應性。這種表面處理包括用有機矽烷偶聯劑例如乙烯基矽烷或烷基矽烷或芳基矽烷之處理。
有機填料之實例包括氟基、聚苯乙烯基、二乙烯基苯基及聚醯亞胺基填料。氟基填料包括聚四氟乙烯(PTFE)、聚全氟烷氧基樹脂、聚氟乙烯-丙烯樹脂、聚四氟乙烯-聚乙烯共聚物、聚偏二氟乙烯、聚氯三氟乙烯樹脂等。
在某些實施方案中，可以用一或多種偶聯劑例如矽烷、鋯酸酯或鈦酸酯處理填料。可以對填料進行預處理，或者可以將偶聯劑添加至上述樹脂組合物中。
填料之量可高達60重量%或可高達75重量%，或5-50重量%，或至少20重量%，基於上述樹脂組合物之重量。
視情況選用的黏合促進聚合物：上述樹脂組合物可視情況包含添加以增加對銅箔之黏附力之聚合物，例如聚(亞芳基醚)、官能化之氫化苯乙烯嵌段共聚物。
在某些實施方案中，黏合促進聚合物選自羧基官能化之聚(亞芳基醚)、馬來酸酐官能化之苯乙烯-乙烯/丁烯-苯乙烯(SEBS)或具有由氫化形式之共軛二烯與苯乙烯之共聚物構成之嵌段之氫化之嵌段共聚物，例如來自Kraton Polymers之Kraton A。
亦可以使用視情況選用的單乙烯基化合物，例如苯乙烯，α-甲基苯乙烯，對甲基苯乙烯，溴苯乙烯，二溴苯乙烯。
若存在，則可以最多25重量%或最多20重量%或3-15重量%或5-10重量%之量加入黏合促進聚合物，基於上述樹脂組合物之重量。
溶劑：在製備中，可以添加溶劑以改變上述樹脂組合物之固體含量並調節上述樹脂組合物之黏度。合適之溶劑包括例如酮，例如甲基乙基酮等，醚，例如二丁基醚等，酯，例如乙酸乙酯等，醯胺，例如二甲基甲醯胺等，芳族烴，例如苯、甲苯、二甲苯等，及氯代烴，例如三氯乙烯等；可以單獨使用每種溶劑或組合使用渠等。
較佳之溶劑選自甲醇，乙醇，乙二醇甲基醚，丙酮，甲基乙基酮，甲基異丁基酮，環己酮，甲苯，二甲苯，乙酸甲氧基乙酯，乙酸乙氧基乙酯，乙酸丙氧基乙酯，乙酸乙酯，二甲基甲醯胺，丙二醇甲基醚，γ-丁內酯(GBL)及二異丁基酮(DIBK)。
所用溶劑之量取決於各組分之溶解性、填料量、施用方法及其他因素。在某些實施方案中，溶劑占10-50重量%固體，或15-40重量%固體，基於溶劑及固體之總重量。
其他視情況選用的組分：在某些實施方案中，低損耗因數樹脂組合物可進一步添加以下添加劑中之至少一種：偶聯劑、界面活性劑、增韌劑、黏度調節劑、潤濕劑、抗氧化劑、著色劑等。
添加劑之選擇取決於應用、期望之性能，選擇以增強或基本上不負面影響電路子組件之電性能，例如介電常數、損耗因數、介電損耗及/或其他期望之性能。添加固化促進劑以提高樹脂組合物之反應速率。界面活性劑有助於確保無機填料在樹脂組合物中之均勻分佈，並避免無機填料之聚集。增韌劑有助於改善樹脂組合物之韌性。
增韌劑可以係橡膠樹脂、羧基封端之聚丁二烯丙烯腈及/或核-殼聚合物。示例性之抗氧化劑包括自由基清除劑及金屬減活劑。可以存在偶聯劑以促進或參與將金屬表面或填料表面與聚合物連接之共價鍵之形成。示例性偶聯劑包括3-巰基丙基甲基二甲氧基矽烷及3-巰基丙基三甲氧基矽烷及六亞甲基二矽氮烷。
偶聯劑可以係矽烷及/或矽氧烷化合物。例如，胺基矽烷化合物、胺基矽氧烷化合物、苯乙烯基矽烷化合物、苯乙烯基矽氧烷化合物、丙烯酸矽烷化合物、丙烯酸矽氧烷化合物、甲基丙烯酸矽烷化合物、甲基丙烯酸矽氧烷化合物、乙烯基矽烷、烷基矽烷化合物及烷基矽氧烷化合物。
在某些實施方案中，上述樹脂組合物還包含本領域已知之黏合促進劑，例如金屬黏合促進劑，例如含N之雜環，其可以與金屬箔形成錯合物，從而增強金屬箔與樹脂層之間的黏合，其量為0.1-2重量%，基於上述樹脂組合物之總重量。在某些實施方案中，代替添加至樹脂組合物中，黏合促進劑以在水或有機溶劑中之溶液或分散體之形式被施加至電阻金屬層。
在某些實施方案中，上述樹脂組合物進一步包含最多15重量%之選自下述之黏合促進聚合物：聚(亞芳基醚)、羧基官能化之聚(亞芳基醚)及馬來酸酐官能化之苯乙烯-乙烯/丁烯-苯乙烯(SEBS)。在某些實施方案中，用上述共聚物、選自硫固化劑及過氧化物固化劑之固化引發劑、以及作為共固化添加劑之二烯基橡膠形成可固化之組合物。
上述樹脂組合物可包含另外之可溶性聚合物，例如聚苯醚樹脂，聚烯烴，苯乙烯聚合物，苯乙烯嵌段共聚物或氫化之苯乙烯嵌段共聚物，高Tg烴聚環烯烴。這些聚合物以少量使用以改性樹脂組合物並改善其成膜能力、抗衝擊性、Tg及加工特性。
在某些實施方案中，若用於除CCL以外之用途，則上述樹脂組合物可包含二烯橡膠以形成輪胎膠料。在這種情況下，一旦在橡膠狀組合物中固化，本發明之嵌段共聚物表現為可固化之增強樹脂。
取決於各添加劑，視情況選用的組分之量可為0.1-25重量%，或＞0.2重量%，或＞0.5重量%，或＜10重量%，或＜15重量%，基於上述樹脂組合物之總重量。
應用：上述樹脂組合物適用於層壓體，例如覆銅層壓體，用於印刷電路板，其係藉由用樹脂浸漬基底或增強材料(例如玻璃基纖維、機織織物、交叉層壓體等)，然後將樹脂部分或全部固化形成預浸料而生產。為了製造層壓體，將一層或多層預浸料與一層或多層銅層壓在一起。印刷電路板可用於許多高頻及高數據速度之電氣及電子應用，尤其係損耗因數小於0.006之應用。
用於上述樹脂組合物中之嵌段共聚物還可以用於需要高溫性能之其他固化應用中，例如黏合劑、塗料、LED封裝樹脂、天線罩樹脂、固化橡膠應用(例如輪胎胎面中之橡膠膠料)以及其他樹脂之添加劑。
製備方法：在一個製備高頻CCL或電路基板之方法中，將上述各組分結合在一起，其中包括上述嵌段共聚物、固化引發劑及視情況選用的組分，例如多官能之可共固化之試劑（例如二烯基聚合物）、阻燃劑及其他視情況選用的組分。用溶劑，例如甲苯、二甲苯、MEK及其混合物，將樹脂混合物稀釋至合適之黏度，形成膠溶液或清漆。用上述膠溶液將增強材料或基底例如纖維、玻璃氈、木漿紙、玻璃纖維布(視情況已經用偶聯劑處理)浸漬至期望之厚度。然後藉由溶劑蒸發自經浸漬之玻璃纖維中除去溶劑，形成預浸料。
在某些實施方案中，藉由在低於固化引發劑之活化溫度之溫度下蒸發溶劑，或者蒸發足夠長之時間以蒸發溶劑但沒有達到膠凝時間，來形成預浸料。膠凝時間係指自材料開始軟化至發生膠凝之時間，其中膠凝係自黏性液體至彈性凝膠之不可逆轉之轉變。在某些實施方案中，藉由將上述樹脂浸漬至基底例如纖維製品中，並使所得經浸漬之基底半固化或者在有或沒有額外之樹脂組合物之情況下將塗覆之纖維熱壓在一起，來形成預浸料。
接下來，將預浸料與在其間之銅箔層壓在一起，並在150-250℃之溫度及20-70 kg/cm2 之壓力下固化，從而形成電路基板。
樹脂組合物之性能：上述樹脂組合物之特徵在於具有低介電損耗，特別係損耗因數Df小於或等於0.02，小於或等於0.006，或小於或等於0.003，均在1或10GHz下量測。上述樹脂組合物之特徵在於具有低介電常數Dk，特別係介電常數小於或等於4.4，小於或等於3.8，或小於或等於3.4，所有這些都係在1或10 GHz下量測。上述介電材料還具有小於或等於80 ppm/℃、小於或等於60 ppm/℃或小於或等於50 ppm/℃之低CTE(熱膨脹係數)，所有均在0-150℃之範圍量測。
上述樹脂組合物還具有0.2-0.7 W/mK或0.3-0.5 W/mK之良好導熱係數。
上述樹脂組合物可進一步具有低吸濕性，這導致在使用中及儲存期間對環境條件不那麼敏感之包裝基板。在某些實施方案中，在23℃下浸入水中24小時後，吸濕率為0.05-0.3%。
上述樹脂組合物可以達到V-0或至少V-1或至少V-2之UL 94等級。在一個實施方案中，V-0等級係在不存在溴化或氯化阻燃劑之情況下獲得的。
上述樹脂組合物亦係可固化的，這意味著在固化上述組合物之後導致＞15%或＞30%或＞50%之凝膠形成。固化之後，上述樹脂組合物之特徵在於具有＜20、＜10或＜5或＜2或＜1.5之溶脹比。溶脹比定義為在過量溶劑中溶脹之凝膠重量與乾燥之凝膠重量之間的比率。固化之樹脂組合物之特徵還在於其Tg＞100℃，或＞110℃，或＞120℃，或＞150℃，或＜250℃。
實例 以下說明性實例係非限制性的。實例中使用了以下成分： DCP：過氧化二枯基 B3000：Mn為3200 g/mol且具有＜10%之1,4-單元含量之液態聚丁二烯 TAIC：三烯丙基異氰脲酸酯 嵌段共聚物1係偶聯之嵌段共聚物PBd-PCHD-PBd，其如下製備：在不鏽鋼乾燥之鋼反應器中，加入1公升純化及乾燥之環己烷溶劑，加入14.2毫升正丁基鋰（1.6莫耳），然後加入3.3公克TMEDA。將溶液加熱至40℃，並加入4.6公克純化之1,3-丁二烯單體。使反應進行45分鐘，並自溶液中收集第一個小樣品用於GPC分析及NMR。NMR證實了該第一單體完全聚合。然後將90公克純化之1,3-環己二烯加入溶液中，並使其聚合45分鐘。自溶液中收集第二個小樣品用於GPC及NMR分析。NMR證實第二單體接近完全聚合。然後，加入另外之4.5公克純化之1,3-丁二烯單體。使反應進行60分鐘。收集第三份樣品用於GPC分析及NMR分析。NMR證實第三單體幾乎完全聚合。然後藉由添加甲醇殺滅活性溶液。用抗氧化劑穩定聚合物溶液，並藉由在過量醇中沈澱來分離樣品，並在升高之溫度下真空乾燥。對於三個分別收集之樣品，用聚苯乙烯校準之GPC得到主峰分子量Mp＝730 g/mol, Mp＝8150 g/mol及Mp＝8760 g/mol。最終產物之NMR分析得到在聚丁二烯嵌段中之35重量%之1,4-單元之含量及65重量%之1,2-單元之含量。
嵌段共聚物2係如下製備之嵌段共聚物PCHD-PBd：在不鏽鋼乾燥之鋼反應器中，加入6公升純化及乾燥之環己烷溶劑，並加入40毫升第二丁基鋰(1.3莫耳)。將溶液加熱至35℃，然後將800公克純化之1,3-環己二烯與DEP一起添加至該溶液中並使其聚合120分鐘。自溶液中收集第一個小樣品用於GPC及NMR分析。NMR證實了第一單體幾乎完全聚合。再添加200公克純化之1,3-丁二烯單體。使反應進行90分鐘。收集第二個樣品用於GPC分析及NMR分析。NMR證實第二單體幾乎完全聚合。然後藉由添加甲醇殺滅活性溶液。用抗氧化劑穩定聚合物溶液，在過量醇中沈澱，並在升高之溫度下真空乾燥。對於兩個收集之樣品，用聚苯乙烯校準之GPC得到一個主峰分子量為Mp＝21700 g/mol，另一個為Mp＝34300 g/mol。最終產物之NMR分析得到在聚丁二烯嵌段中之24重量%之1,4-單元含量及76重量%之1,2-單元含量。
將GPC嵌段分子量Mp或嵌段ΔMp計算為在所考慮之嵌段完成時測得之線性共聚物之GPC峰值分子量與就在聚合所考慮之嵌段之前測得之同一線性聚合物之GPC峰值分子量之間的差。GPC用聚苯乙烯標準物校準，因此Mp值以聚苯乙烯當量分子量表示。
表1及表2總結了實例中使用之嵌段共聚物之描述及性能。
表1
   嵌段結構 嵌段重量比 GPC嵌段1 ΔMp GPC嵌段2 ΔMp GPC嵌段3 ΔMp Mp*A 重量分率 聚丁二烯 1,4-單元含量
      重量% kg/mol kg/mol kg/mol g/mol 重量%
嵌段共聚物1 A-B-A 4.8-91.2-4 0.73 7.42 0.61* 771 35
嵌段共聚物2 B-A 80-20 21.7 12.6 - 6860 24
表2
   DSC Tg℃ 25℃下於二甲苯中50重量%之溶解度 25℃下於甲苯中25重量%之S.V.–mPa.s 25℃下於甲苯中35重量%之S.V. –mPa.s
嵌段共聚物1 103 - - 4246
嵌段共聚物2 134 - 104 448
實例1-6：上述材料之用量見表3。還顯示了乾燥及固化(180℃，1小時)後之組合物之性能。 表3
   單位 實例1 實例2 實例3 實例4 實例5 實例6
嵌段共聚物1 份 100 90 - - - -
嵌段共聚物2 份 - - 100 70 100 -
DCP 份 6 6 1 3 - 3
B3000 份 - 10 - 30 - 100
TAIC 份 - - - 0.45 - -
   份 - - - - - -
固化溫度/時間 ℃/min 180/60 180/60 180/60 180/60 180/60 180/60
固化之Tg ℃ 137 136 124 157 135 ＜100
凝膠含量 重量% 57 67 15 72 無 -
溶脹比    6.8 5.5 - 5.7 - -
實例5表明，沒有固化引發劑不能使嵌段共聚物在180℃下以60分鐘之固化週期有效地固化。有效之固化導致顯著的凝膠含量，且凝膠之溶脹比不太高。實例5不能合適地固化(凝膠含量為約0%)。實例6在固化前及後沒有足夠之Tg。

Claims (15)

  1. 一種可固化之樹脂組合物，其包含： a)5-99重量%之嵌段共聚物，其中上述嵌段共聚物包含至少A嵌段以及B、B'及C嵌段中之至少一個； 其中每個A嵌段係包含至少一種無環共軛二烯之聚合單元之非氫化之聚(無環共軛二烯)聚合物；每個B嵌段係GPC嵌段Mp＜25 kg/mol之聚(1,3-環二烯)均聚物；每個B'嵌段係GPC嵌段Mp＜30 kg/mol之聚(1,3-環二烯-共-單烯基芳烴)共聚物；每個C嵌段係包含至少一種Tg＞100℃之高Tg烯基芳烴單元之聚(烯基芳烴)聚合物或共聚物；及上述嵌段共聚物在偶聯前之GPC峰值分子量Mp＜50 kg/mol，上述嵌段共聚物之乘以A嵌段含量重量分率之GPC峰分子量Mp＞500 g/mol； b)0.1-10重量%之固化引發劑；及 c)最多95重量%之一或多種選自下述之添加劑：多官能之可共固化之添加劑、二烯基橡膠、鹵化或非鹵化之阻燃劑、無機或有機填料或纖維、抗氧化劑、黏合劑促進劑及成膜聚合物。
  2. 如請求項1之可固化之樹脂組合物，其中上述嵌段共聚物具有選自以下之任何結構：A-B，(A-B-)n X，A-B'，(A-B'-)n X，A-B-A，A-B'-A，A-B-C，A-B'-C ，A-C-B，A-C-B'，(B-A-)n X，(B'-A-)n X，B-A-B，B'-A-B'，(A-C-B-)n X，(A-C-B'-)n X，A-C-B-A，A-C-B'-A，A-C，A-C-A及(A-C-)n X，其中n為2-50之整數，X為偶聯劑殘基。
  3. 如請求項1或2之可固化之樹脂組合物，其中固化後上述樹脂組合物具有＞15%之凝膠含量。
  4. 如請求項1或2之可固化之樹脂組合物，其中在偶聯前上述嵌段共聚物之GPC峰值分子量Mp ＜35 kg/mol。
  5. 如請求項1或2之可固化之樹脂組合物，其中上述嵌段共聚物a)包含少於5重量%之不同於碳及氫之原子。
  6. 如請求項1或2之可固化之樹脂組合物，其中上述嵌段共聚物a)之DSC Tg＞100℃，25℃下於甲苯中25重量%之溶液黏度＜2000 mPa.s。
  7. 如請求項1或2之可固化之樹脂組合物，其中每個A嵌段係具有＜50重量%之1,4-聚合單元之聚丁二烯嵌段；B及B'嵌段各自獨立地具有＜9 kg/mol之GPC嵌段Mp分子量；及C嵌段具有＜20 kg/mol之GPC嵌段Mp分子量。
  8. 如請求項1或2之可固化之樹脂組合物，其中： 上述固化引發劑b)係1小時半衰期溫度＞120℃之過氧化物；及 上述一或多種添加劑係選自下述之多官能之可共固化之添加劑：DVB、BVPE、TAC、TAIC、乙烯基官能化之PPE樹脂、雙馬來醯亞胺樹脂、在室溫下呈液態或固態之二烯基聚合物，其中上述二烯基聚合物選自聚丁二烯、聚異戊二烯、丁二烯-苯乙烯共聚物、異戊二烯-苯乙烯共聚物、丁二烯-苯乙烯-甲基丙烯酸酯之三嵌段共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物、丁二烯-苯乙烯-丙烯腈共聚物、丁二烯-苯乙烯-馬來酸酐共聚物、及其組合。
  9. 如請求項1或2之可固化之樹脂組合物，其中上述嵌段共聚物a)具有小於10,000 mPa.s之25℃下於二甲苯中50重量%之溶液黏度、＜2.6之在1 GHz之介電常數Dk及＜0.003之在1 GHz之介電損耗因數Df。
  10. 如請求項1或2之可固化之樹脂組合物，其進一步包含最多15重量%之選自下述之黏合促進聚合物：聚(亞芳基醚)、羧基官能化之聚(亞芳基醚)及馬來酸酐官能化之苯乙烯-乙烯/丁烯-苯乙烯(SEBS)。
  11. 一種預浸料，其藉由下述步驟形成： 使用藉由將5-90重量%之如請求項1至10中任一項之可固化之樹脂組合物溶解在溶劑中獲得的溶液來塗覆基底； 蒸發上述溶劑，形成塗覆之基底；及 在上述塗覆之基底之至少一側上，用銅箔包覆上述塗覆之基底；及 熱壓上述銅箔及上述塗覆之基底，形成預浸料。
  12. 一種覆銅層壓體，其包括如請求項11之預浸料。
  13. 一種印刷電路板，其包括如請求項12之覆銅層壓體。
  14. 一種電路子組件，其包括： 導電金屬層，及 塗覆有樹脂組合物之基底， 其中上述樹脂組合物包含： a)5-99重量%之嵌段共聚物，其中上述嵌段共聚物包含至少A嵌段以及B、B'及C嵌段中之至少一個；其中每個A嵌段係包含至少一種無環共軛二烯之聚合單元之非氫化之聚(無環共軛二烯)聚合物；每個B嵌段係GPC嵌段Mp＜25 kg/mol之聚(1,3-環二烯)均聚物；每個B'嵌段係GPC嵌段Mp＜30 kg/mol之聚(1,3-環二烯-共-單烯基芳烴)共聚物；每個C嵌段係包含至少一個Tg＞100℃之高Tg烯基芳烴單元之聚(烯基芳烴)聚合物或共聚物；及上述嵌段共聚物在偶聯前之GPC峰值分子量Mp＜50 kg/mol，上述嵌段共聚物之乘以A嵌段含量重量分率之GPC峰分子量Mp＞500 g/mol; b)0.1-10重量%之固化引發劑；及 c)最多95重量%之一或多種選自下述之添加劑：多官能之可共固化之添加劑、二烯基橡膠、鹵化或非鹵化之阻燃劑、無機或有機填料或纖維、抗氧化劑、黏合促進劑及成膜聚合物； 其中，上述電路子組件在10 GHz之損耗因數Df小於0.006，以及在10 GHz之介電常數Dk小於3.8。
  15. 如請求項14之電路子組件，其中上述可固化之樹脂組合物中之嵌段共聚物a)具有選自以下之任何結構：A-B，(A-B-)n X，A-B'，(A-B'-)n X，A-B-A，A-B'-A，A-B-C，A-B'-C，A-C-B，A-C-B'，(B-A-)n X，(B'-A-)n X ，B-A-B，B'-A-B'，(A-C-B-)n X，(A-C-B'-)n X，A-C-B-A，A-C-B'-A，A-C，A-C-A及(A-C-)n X，其中n係2-50之整數，X係偶聯劑殘基；及在上述可固化之樹脂組合物中之嵌段共聚物a)具有＞100℃之DSC Tg及＜2000 cP 之25℃下於甲苯中25重量%之溶液黏度。
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