TWI600699B - Resin composition, prepreg using the same, and laminated board - Google Patents
Resin composition, prepreg using the same, and laminated board Download PDFInfo
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Description
本發明關於一種樹脂組成物,更詳細而言,關於一種印刷電路板用預浸體所使用的樹脂組成物、一種使該樹脂組成物含浸或塗佈於基材之預浸體,以及一種硬化該預浸體而得的層合板。
近年來,電子機器或通訊機器、個人電腦等所廣泛採用的半導體,其高積體化、高機能化、高密度實裝化越發加速進行,伴隨於此,對於印刷電路板所使用的貼金屬箔層合板而言,必須是耐熱性或低吸水性等特性優異的層合板。以往,印刷電路板用的層合板廣泛採用藉由二氰二醯胺使環氧樹脂硬化的FR-4型層合板。然而,此型的層合板在因應高耐熱性化的要求方面有其極限。
耐熱性優異的印刷電路板用樹脂已知有氰酸酯樹脂。近年來,半導體塑膠封裝用等高機能性印刷電路板用的樹脂組成物,廣泛採用例如將雙酚A型氰酸酯樹脂與其他熱硬化性樹脂或熱塑性樹脂加以混合的樹脂組成物。此雙酚A型氰酸酯樹脂具有優異的電氣特性、機械特性、耐藥品性、接著性等特性,然而在嚴酷的條件下,會有吸水性或吸濕耐熱性不足的情況。
因此,以使特性更進一步提升為目標,而進行具有其他構造的氰酸酯樹脂的開發。
另外,隨著半導體的高積體化、高機能化、高密度實裝化,印刷電路板的高放熱性逐漸受到重視。因此需要一種具有高耐熱、低吸水性,而且為高導熱性的層合板。作為這樣的層合板用的樹脂組成物,有文獻提出一種具有高耐熱,且低吸水性的樹脂組成物(專利文獻1)。然而,此樹脂組成物的導熱性不足。
另外也有文獻提出一種添加無機填充材以提高導熱性的樹脂組成物(專利文獻2)。然而,若添加無機填充材,則樹脂組成物的吸水率變高,而難以兼顧高熱傳導率與低吸水性。
專利文獻1:日本特開2007-45984號公報
專利文獻2:日本特開平7-202364號公報
本發明人等這次所得到的見解,是藉由在特定的氰酸酯樹脂及環氧樹脂中摻合特定量的無機填充材,可得到具有優異耐熱性、導熱性及吸水性的樹脂組成物。本發明依照這些見解而完成。
因此,本發明之目的為提供一種樹脂組成物,其係具有優異的耐熱性、導熱性及吸水性。
此外,本發明另一個目的為提供一種預浸體,其係使上述樹脂組成物含浸或塗佈於基材而成,以及硬化該預浸體而得之層合板。
依照本發明所得到的樹脂組成物,係含有下述式(1)所表示之氰酸酯樹脂(A)、環氧樹脂(B)、無機填充材(C)而成,並且前述無機填充材(C)係相對於前述氰酸酯樹脂(A)及前述環氧樹脂(B)的合計摻合量100質量份而言含有301~700質量份而成。
(式中,R各自獨立,表示氫原子或甲基,n表示1~50之整數)。
依照本發明所得到的樹脂組成物,由於含有上述式(I)所表示之氰酸酯樹脂,因為該分子構造的緣故,而使得反應阻礙的因素減少,故硬化性優異,另外,使用由本發明所得到的樹脂組成物的層合板或貼金屬箔之層合板,由於具有優異的耐熱性、導熱性及吸水性,因此適合用於對應高密度化的印刷電路板材料,在工業方面實用性極高。
依照本發明所得到的樹脂組成物,其必須成分含有上述式(I)所表示之氰酸酯樹脂(A)、環氧樹脂(B)、無機填充材(C)。以下針對構成依照本發明所得到的樹脂組成物之各成分作說明。
在本發明之中所使用的氰酸酯樹脂(A)係上述式(I)所表示之聚合物或預聚合物。這種氰酸酯樹脂(A),係使萘酚芳烷基樹脂(其係由α-萘酚或β-萘酚等萘酚類與對二甲苯二醇、α,α'-二甲氧基-對二甲苯、1,4-二(2-羥基-2-丙基)苯等縮合劑發生反應而得)與氰酸進行縮聚合所得,其製法並未受到特別限定,可藉由周知的方法製造。例如可藉由使下述式(II)所表示之萘酚芳烷基樹脂與鹵化氰在不活性有機溶劑中,鹼性化合物的存在下進行反應,而製造出上述氰酸酯樹脂(A)。另外還可藉由在含水的溶液中,由上述萘酚芳烷基樹脂與鹼性化合物形成鹽,接下來進行此鹽與鹵化氰的2相系界面反應,而製造出氰酸酯樹脂(A)。
(式中,R各自獨立,表示氫原子或甲基,n表示1~50之整數)
在上述式(I)之中,取代基R各自獨立,表示氫原子或甲基,而特別適合使用取代基R為氫的α-萘酚芳烷基型氰酸酯樹脂。另外,在上述式(I)之中,n表示1~50之整數,而亦可將1種或2種以上n為相異的複數個氰酸酯樹脂(A)適當地混合使用。
從耐熱性、溶劑溶解性及硬化性的觀點看來,上述氰酸酯樹脂(A)係以相對於氰酸酯樹脂(A)及環氧樹脂(B)的合計摻合量100質量份而言含有10~90質量份為佳,較佳為30~70質量份。
在本發明中所使用的環氧樹脂(B)只要是一分子中具有2個以上環氧基的化合物,則並無特別限制,可使用周知的物質。可列舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、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、溴化雙酚A型環氧樹脂、溴苯酚酚醛型環氧樹脂、3官能酚型環氧樹脂、4官能酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、酚芳烷基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、脂環式環氧樹脂、多元醇型環氧樹脂、含磷環氧樹脂、縮水甘油基胺、縮水甘油基酯、丁二烯等將雙鍵環氧化所產生的化合物、由含羥基的矽樹脂類與表氯醇的反應所得到的化合物等。在該等之中尤其適合使用雙酚A型環氧樹脂、雙酚F型環氧樹脂、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、溴化雙酚A型環氧樹脂、溴苯酚酚醛型環氧樹脂、聯苯型環氧樹脂、酚芳烷基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂。該等環氧樹脂(B)可單獨使用,或可將兩種以上適當地組合使用。另外,上述環氧樹脂(B)為單體、寡聚物及樹脂的任一形態皆可。
從耐熱性、導熱性及吸水性的觀點看來,環氧樹脂(B)係以相對於氰酸酯樹脂(A)及環氧樹脂(B)的合計摻合量100質量份而言含有10~90質量份為佳,較佳為30~70質量份。
在本發明中所使用的無機填充材(C)只要是電路配線板用的樹脂組成物通常所使用的無機填充材,即可無特別限制地使用。可列舉例如天然二氧化矽、熔融二氧化矽、無定形二氧化矽、中空二氧化矽等二氧化矽類、氫氧化鋁、氫氧化鋁加熱處理品(將氫氧化鋁加熱處理,而使結晶水減少一部分)、水鋁礦、氫氧化鎂等金屬水合物、氧化鉬、鉬酸鋅等鉬化合物、硼酸鋅、錫酸鋅、氧化鋁、黏土、高嶺土、氮化硼、氧化鎂、氮化鋁、氮化矽、碳酸鎂、滑石、燒成黏土、燒成高嶺土、燒成滑石、雲母、玻璃短纖維(E玻璃或D玻璃等玻璃微粉末類)、中空玻璃等。從熱傳導率的觀點看來,在該等之中尤其適合使用氫氧化鋁、氫氧化鋁加熱處理品(將氫氧化鋁加熱處理,而使結晶水減少一部分)、水鋁礦、氫氧化鎂等金屬水合物、硼酸鋅、氧化鋁、氮化硼、氧化鎂、氮化鋁、氮化矽、碳酸鎂等。該等無機填充材可單獨使用,或可將兩種以上適當地組合使用。
從分散性的觀點看來,無機填充材(C)的平均粒徑(D50)係以0.1~20μm為佳。此外,D50意指中位數粒徑,並且為在將所測得的粉粒體粒度分布分成2部分時,使顆粒大的一側與顆粒小的一側成為等量的粒徑。無機填充材的D50值一般而言藉由濕式雷射繞射、散射法進行測定。另外,在本發明中,亦可將兩種以上粒度分布或平均粒徑相異的無機填充材適當地組合使用。
在依照本發明所得到的樹脂組成物中,無機填充材(C)係相對於前述氰酸酯樹脂(A)及前述環氧樹脂(B)的合計摻合量100質量份而言含有301~700質量份而成。由於在上述氰酸酯(A)及環氧樹脂(B)中,以這樣的摻合量添加無機填充材(C),會使得熱傳導率大幅地提升,而且使樹脂組成物的流動性提升,因此可減低預浸體成形時的孔隙等成形不良。較佳的範圍為351~700質量份。
無機填充材(C)可單獨添加至樹脂組成物,而亦可與矽烷偶合劑或濕潤分散劑併用而添加。矽烷偶合劑只要是一般無機物的表面處理所使用的矽烷偶合劑,即可無特別限制地使用。可列舉例如γ-胺丙基三乙氧基矽烷、N-β-(胺乙基)-γ-胺丙基三甲氧基矽烷等胺基矽烷系、γ-縮水甘油醚基丙基三甲氧基矽烷等環氧矽烷系、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等乙烯基矽烷系、N-β-(N-乙烯基苄基胺基乙基)-γ-胺丙基三甲氧基矽烷鹽酸鹽等陽離子型矽烷系、苯基矽烷系等,然而並不受該等所限定。另外,上述矽烷偶合劑可單獨使用,或可將兩種以上適當地組合使用。
濕潤分散劑只要是在塗料用方面一般所使用的分散安定劑,即可無特別限制地使用。該等分散安定劑亦可使用市售的物品,可適合使用例如Byk-Chemie Japan股份有限公司製的Disperbyk-110、111、180、161、BYK-W996、W9010、W903等。
依照本發明所得到的樹脂組成物亦可進一步含有馬來醯亞胺化合物(D)。馬來醯亞胺化合物(D)只要是一分子中具有1個以上馬來醯亞胺基的化合物,即可無特別限制地使用。可列舉例如雙(4-馬來醯亞胺苯基)甲烷、2,2-雙{4-(4-馬來醯亞胺苯氧基)-苯基}丙烷、雙(3,5-二甲基-4-馬來醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、雙(3,5-二乙基-4-馬來醯亞胺苯基)甲烷、參(4-馬來醯亞胺苯基)甲烷等。該等馬來醯亞胺化合物可單獨使用,或可將兩種以上適當地組合使用。另外,不僅可為單體的形態,亦可為預聚合物的形態,而且還可為雙馬來醯亞胺化合物與胺化合物之預聚合物的形態。從耐熱性的觀點看來,在該等之中尤其適合使用雙(4-馬來醯亞胺苯基)甲烷、2,2-雙{4-(4-馬來醯亞胺苯氧基)-苯基}丙烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷。
從耐熱性及吸水性的觀點看來,馬來醯亞胺化合物(D)係以相對於氰酸酯樹脂(A)及馬來醯亞胺化合物(D)的合計摻合量100質量份而言含有5~75質量份為佳,較佳為10~70質量份。
依照本發明所得到的樹脂組成物,除了上述成分以外,還可因應必要而含有其他成分。例如為了適當地調節硬化速度,亦可含有硬化促進劑。硬化促進劑只要是一般作為氰酸酯樹脂(A)或環氧樹脂(B)的硬化促進劑所使用的物質,即可無特別限制地使用。可列舉例如銅、鋅、鈷、鎳等有機金屬鹽類、咪唑類及其衍生物、3級胺等。另外,上述硬化促進劑可單獨使用,或可將兩種以上適當地組合使用。硬化促進劑的添加量可從樹脂的硬化程度或樹脂組成物的黏度等的觀點考量而適當地調整,通常為相對於樹脂總量100質量份而言的0.01~15質量份左右。
另外,依照本發明所得到的樹脂組成物亦可在不損及所希望特性的範圍,添加其他熱硬化性樹脂、熱塑性樹脂及其寡聚物或彈性體類等各種高分子化合物、其他難燃性的化合物、添加劑等。該等只要是一般所使用的物品,即可無特別限制地使用。例如難燃性的化合物可列舉磷酸酯、磷酸三聚氰胺等磷化合物、三聚氰胺或苯并胍胺等含氮化合物、含噁肼環的化合物、矽系化合物等。添加劑可列舉紫外線吸收劑、抗氧化劑、光聚合起始劑、螢光增白劑、光增感劑、染料、顏料、增黏劑、潤滑劑、消泡劑、分散劑、均勻劑、光澤劑、聚合禁止劑等,可因應必要而單獨使用或將兩種以上適當地組合使用。
依照本發明所得到的樹脂組成物亦可因應必要含有有機溶劑。有機溶劑是為了使樹脂組成物的黏度下降,並且為了提升操作性同時提高與玻璃布的含浸性的目的而使用。有機溶劑只要是使氰酸酯樹脂(A)及環氧樹脂(B)之混合物相溶的物質,即可無特別限制地使用。可列舉例如丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類、苯、甲苯、二甲苯等芳香族烴類、二甲基甲醯胺或二甲基乙醯胺等醯胺類等,然而並不受該等所限定。另外,該等有機溶劑可單獨使用,或可將兩種以上適當地組合使用。
依照本發明所得到的樹脂組成物可藉由將上述氰酸酯樹脂(A)、環氧樹脂(B)及無機填充材(C)混合而得到。混合方法並不受特別限定,例如使氰酸酯樹脂(A)與環氧樹脂(B)以既定濃度溶於上述有機溶劑,並在該溶液中添加無機填充材(C),然後以溶解器或均質攪拌機攪拌30~120分鐘,藉此可製造出樹脂組成物。
由本發明所得到的預浸體,係使上述樹脂組成物含浸或塗佈於基材所得到之物。基材可採用各種印刷電路板材料所使用的周知物質。可列舉例如E玻璃、D玻璃、S玻璃、NE玻璃、石英等無機纖維、聚醯亞胺、聚醯胺、聚酯、聚對伸苯基苯并雙噁唑等有機纖維,可依照所使用的用途或性能而適當地選擇。另外,該等基材可因應必要而單獨使用或將兩種以上適當地組合使用。
基材的形態只要能夠含浸或塗佈樹脂組成物,即可無特別限制地使用。可列舉例如織布、不織布、粗紗、切股氈、表面氈等。另外,基材的厚度通常為0.01~0.30mm左右,然而並不受此範圍所限定。
從與樹脂的密著性或吸濕耐熱性的觀點看來,上述基材亦可實施表面處理,例如能夠以矽烷偶合劑等對基材表面作表面處理。另外,在使用織布作為基材的情況下,亦可對織布進行物理性開纖。
另外,在本發明中,在薄形物品用途方面所使用的基材可採用聚醯亞胺、聚醯胺、聚酯等薄膜。該等薄膜的厚度並不受特別限制,而以0.002~0.05mm左右為佳。另外,在使用薄膜作為基材的情況下,從與樹脂的密著性的觀點看來,係以藉電漿處理等對基材作表面處理為佳。
由本發明所得到的預浸體可藉由使上述樹脂組成物含浸或塗佈於基材而製造。例如藉由使由上述樹脂組成物與有機溶劑所構成之樹脂清漆含浸或塗佈於基材之後,在100~200℃的乾燥機中加熱1~60分鐘,使樹脂半硬化而製造。樹脂組成物(含有無機填充材)相對於基材而言的含量,係以相對於預浸體全體而言在40~95質量%的範圍為佳。
將上述預浸體層合,並使其成形(硬化),可形成層合板。層合板係藉由將1枚或2枚以上的上述預浸體重疊,依照需要在其單面或雙面配置銅或鋁等金屬箔而層合,使其成形(硬化)而製造。所使用的金屬箔只要是在印刷電路板材料方面所使用的物品,即可無特別限制地使用。另外,層合成形可採用通常的印刷電路板用層合板及多層板的方法。例如,層合成形的條件一般而言為使用多段壓延、多段真空壓延、連續成形、壓力釜成形機或真空層壓機等,溫度為100~300℃、壓力為2~100kgf/cm2、加熱時間在0.05~5小時的範圍。另外在本發明中,亦可藉由將上述預浸體與另外準備的內層用配線板組合並且層合成形,而製成多層板。
以下揭示實施例及比較例,對於本發明作詳細說明,而本發明並不受該等限定。
使上述式(III)所表示之α-萘酚芳烷基樹脂(SN495V,OH基當量:236g/eq.,新日鐵化學製;含有n為1~5之物)0.47莫耳(以OH基換算)溶於氯仿500ml,在此溶液中添加三乙胺0.7莫耳,並在-10℃花費1.5小時於其中滴入0.93莫耳氯化氰的氯仿溶液300g,在攪拌30分鐘之後,進一步滴入0.1莫耳三乙胺與氯仿30g的混合溶液,攪拌30分鐘而使反應結束。將所產生的三乙胺鹽酸鹽濾除之後,將所得到的濾液以0.1N鹽酸500ml洗淨然後以水500ml洗淨,重覆進行該洗淨4次。以硫酸鈉使其乾燥之後,在75℃進行蒸發,進一步在90℃減壓脫氣,藉此得到褐色固體而且以上述式(I)所表示之α-萘酚芳烷基型氰酸酯樹脂。對於所得到的氰酸酯樹脂藉由紅外吸收光譜進行分析的結果,確認了在2264cm-1附近有氰酸酯基的吸收。
將上述方式所得到的α-萘酚芳烷基型氰酸酯樹脂50質量份、聯苯芳烷基型環氧樹脂(NC-3000FH,日本化藥製)50質量份、矽烷偶合劑(Z6040,東麗道康寧製)3質量份、濕潤分散劑(BYK-W903,Byk-Chemie Japan製)5質量份加以混合,並使其溶於甲基乙基酮,然後混合氧化鋁(DAW-03、電化學工業製)490質量份及辛酸錳0.1質量份而調製出清漆。將所得到的清漆以甲基乙基酮稀釋,使其含浸塗佈於厚度0.05mm的E玻璃布,並且在160℃加熱乾燥7分鐘,藉此得到樹脂含量82質量%的預浸體。
將8枚如上述方式所得到的預浸體重疊,在其上下方配置12μm厚的電解銅箔(3EC-III,三井金屬礦業股份有限公司製),以壓力30kgf/cm2、溫度220℃進行層合成形120分鐘,藉此得到厚度0.8mm的貼銅層合板。
將實施例1所使用的α-萘酚芳烷基型氰酸酯樹脂40質量份、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷(BMI-70,KI化成製)20質量份、聯苯芳烷基型環氧樹脂(NC-3000FH)40質量份、矽烷偶合劑(Z6040)5質量份、濕潤分散劑(BYK-W903)3質量份加以混合,並使其溶於甲基乙基酮,然後混合氧化鋁(DAW-03,電化學工業製)400質量份、氮化硼(HP-4W,水島合金鐵製)50質量份、2,4,5-三苯基咪唑(東京化成製)1份及辛酸錳0.05質量份而調製出清漆。將所得到的清漆以甲基乙基酮稀釋,使其含浸塗佈於厚度0.05mm的E玻璃布,並且在160℃加熱乾燥8分鐘,藉此得到樹脂含量81質量%的預浸體。接下來使用所得到的預浸體,與實施例1同樣的方式得到厚度0.8mm的貼銅層合板。
將實施例1所使用的α-萘酚芳烷基型氰酸酯樹脂35質量份、雙馬來醯亞胺三嗪樹脂BT2670(三菱瓦斯化學製)5質量份、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷20質量份、聯苯芳烷基型環氧樹脂(NC-3000FH)40質量份、矽烷偶合劑(Z6040)2質量份、濕潤分散劑(BYK-W903)5質量份加以混合,並使其溶於甲基乙基酮,然後混合水鋁礦(BN100,河合石灰製)310質量份、2,4,5-三苯基咪唑(東京化成製)1質量份及辛酸錳0.05質量份而調製出清漆。將所得到的清漆以甲基乙基酮稀釋,使其含浸塗佈於厚度0.05mm的E玻璃布,並在160℃加熱乾燥7分鐘,藉此得到樹脂含量79質量%的預浸體。接下來使用所得到的預浸體,以與實施例1同樣的方式得到厚度0.8mm的貼銅層合板。
將實施例1所使用的α-萘酚芳烷基型氰酸酯樹脂60質量份、苯酚酚醛型環氧樹脂(N770,DIC製)20質量份、萘酚芳烷基型環氧樹脂(ESN-475V,新日鐵化學製)20質量份、濕潤分散劑(BYK-W903)3質量份加以混合,並以甲基乙基酮使其溶解,然後混合氧化鎂(PSF-WZ,神島化學工業製)330質量份及辛酸錳0.1質量份而調製出清漆。將所得到的清漆以甲基乙基酮稀釋,使其含浸塗佈於厚度0.05mm的E玻璃布,並在160℃8分鐘加熱乾燥,藉此得到樹脂含量80質量%的預浸體。接下來使用所得到的預浸體,以與實施例1同樣的方式得到厚度0.8mm的貼銅層合板。
將實施例1所使用的α-萘酚芳烷基型氰酸酯樹脂25質量份、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷25質量份、萘酚芳烷基型環氧樹脂(ESN-475V)50質量份加以混合,並使其溶於甲基乙基酮,然後混合氧化鋁(AA-3,住友化學製)460質量份、2,4,5-三苯基咪唑(東京化成製)1質量份及辛酸錳0.05質量份而調製出清漆。將所得到的清漆以甲基乙基酮稀釋,使其含浸塗佈於厚度0.05mm的E玻璃布,並在160℃加熱乾燥7分鐘,藉此得到樹脂含量82質量%的預浸體。接下來使用所得到的預浸體,以與實施例1同樣的方式得到厚度0.8mm的貼銅層合板。
除了在實施例3之中,使用2,2-雙(4-氰酸苯酯)丙烷之預聚合物(BT2070,三菱瓦斯化學製)代替萘酚芳烷基型氰酸酯樹脂以外,係以與實施例3同樣的方式調製出清漆,並以與實施例3同樣的方式得到厚度0.8mm的貼銅層合板。
除了在實施例1之中,將氧化鋁(DAWO3)的添加量由490質量份變更為200質量份以外,係以與實施例1同樣的方式調製出清漆。使用此清漆,以與實施例1同樣的方式得到樹脂含量79質量%的預浸體。接下來,使用所得到的預浸體,以與實施例1同樣的方式得到厚度0.8mm的貼銅層合板。
除了在實施例4之中,使用二氧化矽(FB-3SDC、電化學工業製)代替氧化鎂(PSF-WZ)以外,係以與實施例4同樣的方式調製出清漆,並以與實施例4同樣的方式得到厚度0.8mm的貼銅層合板。
除了在實施例4之中,使用燒成滑石(BST-200L,日本滑石製)代替氧化鎂(PSF-WZ)以外,係以與實施例4同樣的方式調製出清漆,並以與實施例4同樣的方式得到厚度0.8mm的貼銅層合板。
除了在實施例2之中,將氧化鋁(DAW-03)400質量份及氮化硼(HP-4W)50質量份的使用變更為氧化鋁(DAW-03)750質量份以外,係以與實施例2同樣的方式調製出清漆,並以與實施例2同樣的方式得到厚度0.8mm的貼銅層合板。
對於如上述方式所得到的各層合板,藉下述方式評估熱傳導率、玻璃轉移溫度及吸水率。此外,關於比較例5的層合板,由於產生孔隙,因此熱傳導率、玻璃轉移溫度及吸水率的任一項評估皆無法進行。
1)熱傳導率:使用氙閃光燈分析儀,計算出面方向的熱傳導率。
2)玻璃轉移溫度:依據JIS C6481,以DMA法進行測定。
3)吸水率:依據JIS C6481,以壓力鍋測試機(平山製作所製,PIC-3型)在121℃、2氣壓進行處理5小時後,測定其吸水率。
評估結果如下述表1所示。
由表1看來明顯可知,實施例1~5的貼銅層合板,其熱傳導率、耐熱性及吸水率任一者皆優異。相對於此,比較例1的貼銅層合板採用了2,2-雙(4-氰酸苯酯)丙烷之預聚合物作為氰酸酯樹脂,而其吸水率差。另外,比較例3及4的貼銅層合板含有二氧化矽或燒成滑石等矽酸化合物系無機填充材作為無機填充材,而其熱傳導率差,吸水率也不足。此外,無機填充材摻合量少的比較例2的貼銅層合板,其熱傳導率不足,另一方面,無機填充材摻合量多的比較例5貼銅層合板產生孔隙,而為不堪使用之物。
Claims (8)
- 一種樹脂組成物,其係含有:以下述式(I)所表示之氰酸酯樹脂(A)、環氧樹脂(B)、及無機填充材(C)而成,並且前述無機填充材(C),係相對於前述氰酸酯樹脂(A)及前述環氧樹脂(B)的合計摻合量100質量份而言含有301~700質量份而成,其中前述無機填充材(C)係由氧化鎂、氮化鋁及氮化矽所構成之群中所選出1種以上,
- 如申請專利範圍第1項之樹脂組成物,其中前述氰酸酯樹脂(A),係相對於氰酸酯樹脂(A)及環氧樹脂(B)的合計摻合量100質量份而言含有10~90質量份而成。
- 如申請專利範圍第1項之樹脂組成物,其中前述環氧樹脂(B),係相對於氰酸酯樹脂(A)及環氧樹脂(B)的合計摻合量100質量份而言含有10~90質量份而成。
- 如申請專利範圍第1項之樹脂組成物,其中進一步含有馬來醯亞胺化合物(D)而成。
- 如申請專利範圍第4項之樹脂組成物,其中前述馬來醯亞胺化合物(D),係相對於氰酸酯樹脂(A)及馬來醯亞胺化合物(D)的合計摻合量100質量份而言含有5~75質量份而成。
- 一種預浸體,其係將如申請專利範圍第1~5項中任一項之樹脂組成物含浸或塗佈於基材而成。
- 一種層合板,其係硬化如申請專利範圍第6項之預浸體而得。
- 一種貼金屬箔之層合板,其係將如申請專利範圍第6項之預浸體與金屬箔層合並且硬化而成。
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CN101580626B (zh) | 2009-01-24 | 2012-02-08 | 南亚塑胶工业股份有限公司 | 一种高导热无卤难燃树脂组合物及其预浸渍体及涂层物 |
EP2402388B1 (en) | 2009-02-25 | 2017-01-04 | Mitsubishi Gas Chemical Company, Inc. | Prepreg and laminated sheet |
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US8852734B2 (en) * | 2009-10-14 | 2014-10-07 | Sumitomo Bakelite Company, Ltd. | Epoxy resin composition, prepreg, metal-clad laminate, printed wiring board and semiconductor device |
KR101945076B1 (ko) * | 2011-11-07 | 2019-02-01 | 미츠비시 가스 가가쿠 가부시키가이샤 | 수지 조성물, 이것을 사용한 프리프레그 및 적층판 |
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2011
- 2011-05-31 JP JP2012518400A patent/JP5849948B2/ja active Active
- 2011-05-31 CN CN201710542439.0A patent/CN107254144B/zh active Active
- 2011-05-31 EP EP11789805.6A patent/EP2578631B1/en active Active
- 2011-05-31 SG SG10201504246UA patent/SG10201504246UA/en unknown
- 2011-05-31 US US13/701,034 patent/US10017660B2/en active Active
- 2011-05-31 KR KR1020127031828A patent/KR101781666B1/ko active IP Right Grant
- 2011-05-31 SG SG2012087524A patent/SG186089A1/en unknown
- 2011-05-31 WO PCT/JP2011/062496 patent/WO2011152402A1/ja active Application Filing
- 2011-05-31 CN CN2011800273709A patent/CN103038284A/zh active Pending
- 2011-06-02 TW TW100119384A patent/TWI600699B/zh active
Patent Citations (2)
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US20060089070A1 (en) * | 1999-07-29 | 2006-04-27 | Morio Gaku | Glass fabric base material/thermosetting resin copper-clad laminate having a high-elasticity |
CN1803916A (zh) * | 2005-01-13 | 2006-07-19 | 三菱瓦斯化学株式会社 | 树脂组合物和使用该组合物的预浸渍体和层压材料 |
Also Published As
Publication number | Publication date |
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SG186089A1 (en) | 2013-01-30 |
CN107254144A (zh) | 2017-10-17 |
JPWO2011152402A1 (ja) | 2013-08-01 |
KR20130098883A (ko) | 2013-09-05 |
TW201211144A (en) | 2012-03-16 |
KR101781666B1 (ko) | 2017-09-25 |
WO2011152402A1 (ja) | 2011-12-08 |
US10017660B2 (en) | 2018-07-10 |
CN107254144B (zh) | 2020-02-18 |
US20130157061A1 (en) | 2013-06-20 |
EP2578631A1 (en) | 2013-04-10 |
CN103038284A (zh) | 2013-04-10 |
EP2578631A4 (en) | 2015-05-06 |
EP2578631B1 (en) | 2017-09-20 |
SG10201504246UA (en) | 2015-06-29 |
JP5849948B2 (ja) | 2016-02-03 |
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