TWI803657B - 印刷配線板用樹脂組成物、預浸體、疊層板、覆金屬箔疊層板、印刷配線板及多層印刷配線板 - Google Patents
印刷配線板用樹脂組成物、預浸體、疊層板、覆金屬箔疊層板、印刷配線板及多層印刷配線板 Download PDFInfo
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- TWI803657B TWI803657B TW108122740A TW108122740A TWI803657B TW I803657 B TWI803657 B TW I803657B TW 108122740 A TW108122740 A TW 108122740A TW 108122740 A TW108122740 A TW 108122740A TW I803657 B TWI803657 B TW I803657B
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 29
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Images
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Abstract
一種印刷配線板用樹脂組成物,含有苯酚化合物(A)、馬來醯亞胺化合物(B)、環氧化合物(C)、環狀碳二亞胺化合物(D)、無機填充材(E)、及硬化促進劑(F),前述無機填充材(E)之含量,相對於樹脂固體成分100質量份為100~250質量份。
Description
本發明關於印刷配線板用樹脂組成物、預浸體、疊層板、覆金屬箔疊層板、印刷配線板及多層印刷配線板。
近年,伴隨廣泛使用於電子設備、通訊器材、個人電腦等之半導體封裝體的高功能化、小型化進展,半導體封裝體用之各零件的高整合化、高密度安裝化近年來越發加速。
例如,專利文獻1中揭示一種使用於電子零件的樹脂組成物,其包含熱硬化性樹脂、與環狀碳二亞胺化合物。據該文獻揭示:樹脂組成物藉由包含環狀碳二亞胺化合物,可在凝膠時間、熔融黏度等流動特性不降低的情況下使玻璃轉移溫度(Tg)變高。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2017-125150號公報
[發明所欲解決之課題]
近年,使用印刷配線板(特別是多層無芯基板)製造電子零件(封裝體)時,高耐熱性、耐藥品性、低吸水性、介電特性(低介電率及低介電損耗正切)、及阻燃性的改善成為重要課題。專利文獻1假定將樹脂組成物用於密封材料、芯層、堆疊(build-up)層、阻焊層等之基板材料、白色發光二極體等受光元件。但是,專利文獻1中並未探討改善耐藥品性、電特性及阻燃性。
又,印刷配線板所使用之材料(組成物)含有多官能之熱硬化性樹脂的話,可改善耐熱性,故係有效。但是,對於上述含有多官能之熱硬化性樹脂的材料(組成物),要求進一步改善耐藥品性及電特性(低介電率及低介電損耗正切)。
本發明係鑒於上述問題而成,旨在提供以良好的平衡同時滿足優異的流動特性、耐熱性、耐藥品性、及電特性的印刷配線板用樹脂組成物、預浸體、疊層板、覆金屬箔疊層板、印刷配線板及多層印刷配線板。
[解決課題之手段]
本案發明人等為了解決上述課題而進行努力研究的結果,發現藉由將苯酚化合物(A)、馬來醯亞胺化合物(B)、環氧化合物(C)、環狀碳二亞胺化合物(D)、無機填充材(E)、及硬化促進劑(F)予以組合,並使無機填充材(E)之含量成為特定範圍內,可解決上述課題,而完成了本發明。
亦即,本發明如下。
[1]一種印刷配線板用樹脂組成物,含有苯酚化合物(A)、馬來醯亞胺化合物(B)、環氧化合物(C)、環狀碳二亞胺化合物(D)、無機填充材(E)、及硬化促進劑(F),
前述無機填充材(E)之含量,相對於樹脂固體成分100質量份為100~250質量份。
[2]如[1]之印刷配線板用樹脂組成物,其中,前述環狀碳二亞胺化合物(D)之含量,相對於樹脂固體成分100質量份為2.0~15質量份。
[3]如[1]或[2]之印刷配線板用樹脂組成物,其中,前述環狀碳二亞胺化合物(D)之含量,相對於樹脂固體成分100質量份為2.5~12.0質量份。
[4]如[1]~[3]中任一項之印刷配線板用樹脂組成物,其中,前述馬來醯亞胺化合物(B)之含量,相對於樹脂固體成分100質量份為10~30質量份。
[5]如[1]~[4]中任一項之印刷配線板用樹脂組成物,其中,
前述環狀碳二亞胺化合物(D)具有下式(1)表示之環狀結構,
且形成前述環狀結構之原子數為8~50,
[化1]
式(1)中,L為作為脂肪族基、脂環族基、芳香族基或將該等予以組合而得之基的2~4價鍵結基,前述鍵結基亦可含有雜原子及/或取代基。
[6]如[1]~[5]中任一項之印刷配線板用樹脂組成物,其中,前述環狀碳二亞胺化合物(D)包含1分子內含有2個以上之碳二亞胺基的多價環狀碳二亞胺化合物。
[7]如[6]之印刷配線板用樹脂組成物,其中,前述多價環狀碳二亞胺化合物係下式(2)表示之化合物,
[化2]
式(2)中,X係下式(3)表示之4價基,Ar1
~Ar4
各自獨立地為作為伸苯基或萘二基的2價連接基,前述連接基亦可具有取代基。
[化3]
[8]如[7]之印刷配線板用樹脂組成物,其中,前述式(2)表示之化合物係下式(4)表示之化合物。
[化4]
[9]如[1]~[8]中任一項之印刷配線板用樹脂組成物,其中,前述硬化促進劑(F)包含咪唑化合物及/或有機磷化合物。
[10]如[1]~[9]中任一項之印刷配線板用樹脂組成物,其中,前述硬化促進劑(F)包含下式(5)表示之化合物,
[化5]
式(5)中,Ar5
各自獨立地表示苯基、萘基、聯苯基、或蒽基,該等基亦可具有取代基,R1
表示氫原子、烷基、芳基,R1
表示烷基或芳基時,亦可具有取代基。
[11]如[1]~[10]中任一項之印刷配線板用樹脂組成物,其中,前述無機填充材(E)含有選自於由二氧化矽、軟水鋁石、及氧化鋁構成之群組中之1種以上。
[12]一種預浸體,包含:
基材,及
含浸或塗布於該基材的如[1]~[11]中任一項之印刷配線板用樹脂組成物。
[13]一種疊層板,具有如[12]之預浸體。
[14]一種覆金屬箔疊層板,具有:
如[12]之預浸體,及
配置於前述預浸體之單面或兩面的金屬箔。
[15]一種印刷配線板,包含:
由如[12]之預浸體形成的絕緣層,及
形成於該絕緣層之表面的導體層。
[16]一種多層印刷配線板,具有:
多個絕緣層,係由第1絕緣層、與疊層在前述第1絕緣層之單面側的1個或多個第2絕緣層構成;及
多個導體層,係由配置在前述多個絕緣層中的各絕緣層之間的第1導體層、與配置在前述多個絕緣層之最外層之表面的第2導體層構成;
前述第1絕緣層及前述第2絕緣層分別具有如[12]之預浸體。
[發明之效果]
根據本發明,可提供以良好的平衡同時滿足優異的流動特性、耐熱性、耐藥品性、及電特性的印刷配線板用樹脂組成物、預浸體、疊層板、覆金屬箔疊層板、印刷配線板及多層印刷配線板。
以下,針對用以實施本發明的形態(以下稱為「本實施形態」。)進行詳細地說明,但本發明並不限定於此,在不脫離其要旨的範圍內可進行各種變形。
本說明書中所稱「樹脂固體成分」,除非有特別說明,否則係指本實施形態之印刷配線板用樹脂組成物中之除了溶劑及填充材以外的成分,樹脂固體成分100質量份係指印刷配線板用樹脂組成物中之除了溶劑及填充材以外的成分之合計為100質量份。
[印刷配線板用樹脂組成物]
本實施形態之印刷配線板用樹脂組成物(亦簡稱為「樹脂組成物」。),含有苯酚化合物(A)、馬來醯亞胺化合物(B)、環氧化合物(C)、環狀碳二亞胺化合物(D)、無機填充材(E)、及硬化促進劑(F)。無機填充材(E)之含量,相對於樹脂固體成分100質量份為100~250質量份。本實施形態之樹脂組成物藉由具備上述構成,例如能以良好的平衡同時滿足優異的流動特性、耐熱性、耐藥品性、低吸水性、及電特性。因此,本實施形態之樹脂組成物可用作印刷配線板用材料,藉由本實施形態之樹脂組成物獲得之印刷配線板,其耐熱性、耐藥品性、低吸水性及電特性優異。在不使流動特性惡化的情況下改善如此之各特性的原因據認為如下,但原因不限定於此。環狀碳二亞胺化合物(D)由於具有高熔點,故例如於預浸體製作時之溫度(約140℃)與各樹脂之反應性低,從而不會使樹脂組成物之流動特性惡化。另外,於溫度更高的壓製成形時,環狀碳二亞胺化合物(D)會熔融,並與熱硬化性樹脂(例如酚醛樹脂、環氧樹脂)反應,從而形成高交聯密度之結構體,因此使玻璃轉移溫度、耐藥品性得到改善。又,環狀碳二亞胺化合物(D)藉由與苯酚性或醇性羥基反應而形成交聯結構,可減少會使介電損耗正切惡化的羥基,故硬化物的介電損耗正切降低。
(苯酚化合物(A))
本實施形態之樹脂組成物含有苯酚化合物(A)。本說明書中所稱「化合物」,係指包含樹脂的概念。苯酚化合物(A)可列舉1分子中具有2個以上之苯酚性羥基的苯酚化合物。如此之苯酚化合物並無特別限制,例如可列舉:雙酚類(例如,雙酚A、雙酚E、雙酚F、雙酚S等)、二烯丙基雙酚類(例如,二烯丙基雙酚A、二烯丙基雙酚E、二烯丙基雙酚F、二烯丙基雙酚S等)、雙酚型酚醛樹脂(例如,雙酚A型樹脂、雙酚E型樹脂、雙酚F型樹脂、雙酚S型樹脂等)、苯酚類酚醛清漆樹脂(例如,苯酚酚醛清漆樹脂、萘酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等)、環氧丙酯型酚醛樹脂、萘型酚醛樹脂、蒽型酚醛樹脂、二環戊二烯型酚醛樹脂、聯苯型酚醛樹脂、脂環族酚醛樹脂、多元醇型酚醛樹脂、芳烷基型酚醛樹脂、苯酚改性芳香族烴甲醛樹脂等。該等苯酚化合物可單獨使用1種,或將2種以上組合使用。
該等之中,考量線熱膨脹率(CTE)、玻璃轉移溫度(Tg)、耐熱性及低吸水性更加優異的觀點,苯酚化合物(A)宜為芳烷基型酚醛樹脂。
(芳烷基型酚醛樹脂)
芳烷基型酚醛樹脂並無特別限制,例如可列舉下式(A1)表示之化合物。
[化6]
式(A1)中,Ara1
各自獨立地表示苯環或萘環,Ara2
表示苯環、萘環、或聯苯環,R2a
各自獨立地表示氫原子或甲基,m表示1~50之整數,各環亦可具有羥基以外之取代基(例如,碳數1~5之烷基或苯基等)。
考量線熱膨脹率(CTE)、玻璃轉移溫度(Tg)、銅箔剝離強度、耐熱性及低吸水性更加優異的觀點,式(A1)表示之化合物宜為式(A1)中Ara1
為萘環且Ara2
為苯環的化合物(亦稱為「萘酚芳烷基型酚醛樹脂」。)、及式(A1)中Ara1
為苯環且Ara2
為聯苯環的化合物(亦稱為「聯苯芳烷基型酚醛樹脂」。)。
芳烷基型酚醛樹脂可使用市售品,亦可使用利用公知方法合成的製品。芳烷基型酚醛樹脂的市售品可列舉:日本化藥(股)公司製品的「KAYAHARD GPH-65」、「KAYAHARD GPH-78」、「KAYAHARD GPH-103」(均為式(A3)表示之聯苯芳烷基型酚醛樹脂)、新日鐵化學(股)公司製品的「SN-495-V」(式(A2)表示之萘酚芳烷基型酚醛樹脂)。
苯酚化合物(A)之含量並無特別限定,考量玻璃轉移溫度(Tg)、耐熱性及低吸水性更加優異的觀點,相對於樹脂固體成分100質量份宜為15~45質量份,為20~40質量份更佳,為25~35質量份又更佳。
(馬來醯亞胺化合物(B))
本實施形態之樹脂組成物含有馬來醯亞胺化合物(B)。馬來醯亞胺化合物(B)可列舉1分子中具有1個以上之馬來醯亞胺基的馬來醯亞胺化合物。如此之馬來醯亞胺化合物並無特別限制,例如可列舉:1分子中具有1個馬來醯亞胺基的單馬來醯亞胺化合物(例如,N-苯基馬來醯亞胺、N-羥基苯基馬來醯亞胺等)、1分子中具有2個以上之馬來醯亞胺基的聚馬來醯亞胺化合物(例如,雙(4-馬來醯亞胺苯基)甲烷、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)、該等馬來醯亞胺化合物與胺化合物的預聚物等。該等馬來醯亞胺化合物可單獨使用1種,或將2種以上組合使用。該等之中,考量線熱膨脹係數(CTE)、玻璃轉移溫度(Tg)、耐熱性更加優異的觀點,馬來醯亞胺化合物(B)宜為聚馬來醯亞胺化合物。
聚馬來醯亞胺化合物並無特別限制,例如可列舉於苯環鍵結有多個馬來醯亞胺基的化合物(例如,間伸苯基雙馬來醯亞胺等伸苯基雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺等)、於直鏈狀或分支狀烷基鏈之兩末端鍵結有馬來醯亞胺基的化合物(例如,1,6-雙馬來醯亞胺-(2,2,4-三甲基)己烷等)、雙酚A二苯醚雙馬來醯亞胺、下式(B1)表示之化合物。
該等之中,考量線熱膨脹係數(CTE)、玻璃轉移溫度(Tg)、耐熱性更加優異的觀點,馬來醯亞胺化合物(B)宜為下式(B1)表示之化合物。
[化9]
式(B1)中,R4a
及R5a
各自獨立地表示氫原子或碳數1~5之烷基,宜表示氫原子。R4b
各自獨立地表示氫原子或甲基,考量更有效且確實地發揮本發明之作用效果的觀點,宜表示氫原子。s表示1以上之整數,宜為1~100,更佳為1~10。
式(B1)表示之化合物之具體例可列舉: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)甲烷等。
馬來醯亞胺化合物(B)可使用市售品,亦可使用利用公知方法製得的製備品。馬來醯亞胺化合物(B)的市售品可列舉:K・I Chemical(股)公司製品的「BMI-70」、「BMI-80」、大和化成工業(股)公司製品的「BMI-1000P」、「BMI-3000」、「BMI-4000」、「BMI-5100」、「BMI-7000」、「BMI-2300」等。
就馬來醯亞胺化合物(B)之含量而言,考量玻璃轉移溫度(Tg)、耐熱性優異的觀點,相對於樹脂固體成分100質量份宜為5~50質量份,為8~40質量份更佳,為10~30質量份又更佳。
(環氧化合物(C))
本實施形態之樹脂組成物含有環氧化合物(C)。環氧化合物(C)可列舉1分子中具有2個以上之環氧基的環氧化合物。如此之環氧化合物並無特別限制,例如可列舉:雙酚型環氧樹脂(例如,雙酚A型環氧樹脂、雙酚E型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂)、二烯丙基雙酚型環氧樹脂(例如,二烯丙基雙酚A型環氧樹脂、二烯丙基雙酚E型環氧樹脂、二烯丙基雙酚F型環氧樹脂、二烯丙基雙酚S型環氧樹脂等)、苯酚類酚醛清漆型環氧樹脂(例如,苯酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂)、芳烷基型環氧樹脂、含有聯苯骨架之聯苯型環氧樹脂、含有萘骨架之萘型環氧樹脂、含有蒽骨架之蒽型環氧樹脂、環氧丙酯型環氧樹脂、多元醇型環氧樹脂、含有異氰尿酸酯環之環氧樹脂、二環戊二烯型環氧樹脂、由雙酚A型結構單元與烴系結構單元構成之環氧樹脂、它們的鹵化物。該等環氧化合物可單獨使用1種,或將2種以上組合使用。
該等之中,考量線熱膨脹係數(CTE)、玻璃轉移溫度(Tg)、銅箔剝離強度、耐熱性更加優異的觀點,環氧化合物(C)宜為選自於由芳烷基型環氧樹脂、萘型環氧樹脂構成之群組中之1種以上,為萘型環氧樹脂更佳。
(芳烷基型環氧樹脂)
就芳烷基型環氧樹脂而言,例如可列舉下式(C1)表示之化合物。
[化10]
式(C1)中,Arc1
各自獨立地表示苯環或萘環,Arc2
表示苯環、萘環、或聯苯環,R3a
各自獨立地表示氫原子或甲基,k表示1~50之整數,各環亦可具有環氧丙氧基以外之取代基(例如,碳數1~5之烷基或苯基)。
式(C1)中,k表示1~50之整數,考量更有效且確實地發揮本發明之作用效果的觀點,宜表示1~10之整數,表示1~6之整數更佳,為1~3特佳。
此外,芳烷基型環氧樹脂含有式(C1)表示之化合物時,可含有k相同的多種化合物,亦可含有k不同的多種化合物。芳烷基型環氧樹脂含有k不同的多種化合物時,宜含有式(C1)中k為1~3的化合物。
就式(C1)表示之化合物而言,考量線熱膨脹率(CTE)、耐熱性及低吸水性更加優異的觀點,宜為式(C1)中Arc1
為萘環且Arc2
為苯環的化合物(亦稱為「萘芳烷基型環氧樹脂」。)、及Arc1
為苯環且Arc2
為聯苯環的化合物(亦稱為「聯苯芳烷基型環氧樹脂」。)。
芳烷基型環氧樹脂可使用市售品,亦可使用利用公知方法製得的製備品。作為萘芳烷基型環氧樹脂的市售品,例如可列舉:新日鐵住金化學(股)公司製品的「Epotohto(註冊商標)ESN-155」、「Epotohto(註冊商標)ESN-355」、「Epotohto(註冊商標)ESN-375」、「Epotohto(註冊商標)ESN-475V」、「Epotohto(註冊商標)ESN-485」、「Epotohto(註冊商標)ESN-175」、日本化藥(股)公司製品的「NC-7000」、「NC-7300」、「NC-7300L」、DIC(股)公司製品的「HP-5000」、「HP-9900」等。作為聯苯芳烷基型環氧樹脂的市售品,例如可列舉:日本化藥(股)公司製品的「NC-3000」、「NC-3000L」、「NC-3000FH」、「NC-3000H」等。
(萘型環氧樹脂)
萘型環氧樹脂並無特別限定,例如可列舉係上述萘芳烷基型環氧樹脂以外之環氧樹脂且具有萘骨架的環氧樹脂。作為萘型環氧樹脂之具體例,例如可列舉下式(C5)表示之環氧樹脂、伸萘基醚型環氧樹脂等。考量線熱膨脹係數(CTE)、玻璃轉移溫度(Tg)、耐熱性及低吸水性更加優異的觀點,萘型環氧樹脂宜為伸萘基醚型環氧樹脂。
[化14]
上述式(C5)表示之環氧樹脂可使用市售品,亦可使用利用公知方法製得的製備品。作為市售品,可列舉DIC(股)公司製品的「HP-4710」等。
伸萘基醚型環氧樹脂並無特別限制,例如可列舉下式(C6)表示之化合物。
[化15]
式(C6)中,R3b
各自獨立地表示氫原子、碳數1~5之烷基、芳烷基、苄基、萘基或含有環氧丙氧基之萘基,k1表示0~10之整數。
式(C6)中,k1表示0~10之整數,考量更有效且確實地發揮本發明之作用效果的觀點,宜表示0~6之整數,表示0~4之整數更佳,為2~3特佳。
考量更有效且確實地發揮本發明之作用效果的觀點,式(C6)中,R3b
宜各自獨立地表示氫原子、碳數1~5之烷基、芳烷基、及萘基。
式(C6)表示之化合物中,分子中之含有環氧基之環氧丙氧基數宜為2~6,為2~4更佳。
此外,伸萘基醚型環氧樹脂含有式(C6)表示之化合物時,可含有k1相同的多種化合物,亦可含有k1不同的多種化合物。伸萘基醚型環氧樹脂含有k1不同的多種化合物時,宜含有式(C6)中k1為0~4的化合物,含有k1為2~3的化合物更佳。
伸萘基醚型環氧樹脂可使用市售品,亦可使用利用公知方法製得的製備品。作為伸萘基醚型環氧樹脂的市售品,例如可列舉:DIC(股)公司製品的「HP-4032」、「HP-6000」、「EXA-7300」、「EXA-7310」、「EXA-7311」、「EXA-7311L」、「EXA7311-G3」等。
環氧化合物(C)之含量並無特別限定,考量玻璃轉移溫度(Tg)、耐熱性及線熱膨脹率更加優異的觀點,相對於樹脂固體成分100質量份宜為5~50質量份,為20~45質量份更佳,為25~40質量份又更佳,為25~35質量份特佳。
(其他熱硬化性化合物)
本實施形態之樹脂組成物亦可含有除了苯酚化合物(A)、馬來醯亞胺化合物(B)、及環氧化合物(C)以外的其他熱硬化性化合物。此處所稱「熱硬化性化合物」,係指可藉由加熱而硬化的化合物。就熱硬化性化合物而言,可列舉分子中具有至少1個以上之可藉由加熱而在相同官能基彼此之間或不同官能基之間進行聚合反應或交聯反應的官能基(亦稱為「熱硬化性官能基」。)的化合物。熱硬化性官能基並無特別限定,例如可列舉:氰氧基(-O-C≡N)、烯丙基、經烯基取代之納迪克醯亞胺基、羥基、胺基、異氰酸酯基、其他可聚合之不飽和基等。
(氰酸酯化合物)
其他熱硬化性化合物亦可包含氰酸酯化合物。氰酸酯化合物可列舉1分子中具有1個以上之氰氧基(氰酸酯基)的化合物。就氰酸酯化合物而言,例如可列舉:1分子中含有2個以上之氰氧基的芳香族烴化合物、含有2個以上之氰氧基的2個芳香環藉由連接基鍵結而得的化合物、酚醛清漆型氰酸酯、雙酚型氰酸酯、二烯丙基雙酚型氰酸酯(例如,二烯丙基雙酚A型氰酸酯、二烯丙基雙酚F型氰酸酯、二烯丙基雙酚E型氰酸酯、二烯丙基雙酚S型氰酸酯等)、芳烷基型氰酸酯、該等氰酸酯的預聚物。氰酸酯化合物可單獨使用1種,或將2種以上組合使用。
就1分子中具有2個以上之氰氧基的芳香族烴化合物而言,例如可列舉式(I)表示之化合物。
式(I):Ar-(OCN)p
式(I)中,Ar表示苯環、萘環及聯苯環中之任一者,p表示2以上之整數。
就式(I)中p為2以上的化合物而言,並無特別限定,例如可列舉:1,3-二氰氧基苯、1,4-二氰氧基苯、1,3,5-三氰氧基苯、1,3-二氰氧基萘、1,4-二氰氧基萘、1,6-二氰氧基萘、1,8-二氰氧基萘、2,6-二氰氧基萘、2,7-二氰氧基萘、1,3,6-三氰氧基萘、4,4’-二氰氧基聯苯等。
含有2個以上之氰氧基的2個芳香環藉由連接基鍵結而得的化合物並無特別限定,例如可列舉雙(4-氰氧基苯基)醚、雙(4-氰氧基苯基)硫醚、雙(4-氰氧基苯基)碸等。
就酚醛清漆型氰酸酯而言,例如可列舉下式(1x)表示之化合物。
[化17]
式(1x)中,R1a
可有多個取代在各芳香環上,各自獨立地表示氫原子、碳數1~5之烷基,R1b
各自獨立地表示氫原子或甲基(宜為氫原子),n表示1~10之整數。
式(1x)中,n為1~10之整數,考量更有效且確實地發揮本發明之作用效果的觀點,宜為1~6之整數。
此外,酚醛清漆型氰酸酯含有式(1x)表示之化合物時,可含有n相同的多種化合物,亦可含有n不同的多種化合物。
式(1x)表示之化合物並無特別限定,例如可列舉雙(3,5-二甲基-4-氰氧基苯基)甲烷、雙(4-氰氧基苯基)甲烷、2,2’-雙(4-氰氧基苯基)丙烷等。
雙酚型氰酸酯並無特別限定,例如可列舉苯酚化合物之項目所例示之雙酚的苯酚性羥基之氫原子取代為氰基(-C≡N)而得的化合物。具體而言,可列舉:雙酚A型氰酸酯、雙酚E型氰酸酯、雙酚F型氰酸酯、雙酚AD型氰酸酯、雙酚B型氰酸酯、雙酚AP型氰酸酯、雙酚S型氰酸酯、雙酚Z型氰酸酯、雙酚TMC型氰酸酯等。
雙酚型氰酸酯可使用市售品,亦可使用利用公知方法製得的製備品。作為雙酚型氰酸酯的市售品,例如可列舉三菱瓦斯化學(股)公司製品的「CA210」等。
芳烷基型氰酸酯並無特別限定,例如可列舉萘酚芳烷基型氰酸酯、聯苯芳烷基型氰酸酯等。
式(1a)中,n1為1~10之整數,考量更有效且確實地發揮本發明之作用效果的觀點,宜為1~6之整數。
此外,萘酚芳烷基型氰酸酯含有式(1a)表示之化合物時,可含有n1相同的多種化合物,亦可含有n1不同的多種化合物。
就聯苯芳烷基型氰酸酯而言,例如可列舉下式(1b)表示之化合物。
[化19]
式(1b)中,R1e
各自獨立地表示氫原子或碳數1~5之烷基,R1f
各自獨立地表示氫原子或甲基(宜為氫原子),n2表示1~10之整數。
式(1b)中,n2表示1~10之整數,考量更有效且確實地發揮本發明之作用效果的觀點,宜表示1~6之整數。
此外,聯苯芳烷基型氰酸酯含有式(1b)表示之化合物時,可含有n2相同的多種化合物,亦可含有n2不同的多種化合物。
芳烷基型氰酸酯可使用市售品,亦可使用利用公知方法合成的製品。就芳烷基型氰酸酯的合成方法而言,例如可列舉:使與目的之芳烷基型氰酸酯對應的酚醛樹脂(以下,亦稱為「對應的酚醛樹脂」。)、鹵化氰、及鹼性化合物在鈍性有機溶劑中反應的方法;使藉由使對應的酚醛樹脂與鹼性化合物在水溶液中反應而形成的鹽、及鹵化氰進行2相系界面反應的方法等。無論何種方法,均可藉由使對應的酚醛樹脂之苯酚性羥基之氫原子氰酸酯化而獲得芳烷基型氰酸酯。更詳細而言,例如可使用實施例記載之方法等。
就氰酸酯化合物之含量而言,相對於樹脂固體成分100質量份可為30質量份以下(例如,0質量份以上且30質量份以下),考量更有效且確實地發揮本發明之作用效果的觀點,宜為15質量份以下,為10質量份以下更佳,為5質量份以下又更佳。
(經烯基取代之納迪克醯亞胺化合物)
其他熱硬化性化合物亦可包含經烯基取代之納迪克醯亞胺化合物。就經烯基取代之納迪克醯亞胺化合物而言,例如可列舉分子中具有1個以上之經烯基取代之納迪克醯亞胺基的化合物。作為經烯基取代之納迪克醯亞胺化合物,例如可列舉下式(5a)表示之化合物。
[化20]
式(5a)中,R6a
各自獨立地表示氫原子、或碳數1~6之烷基,R6b
表示碳數1~6之伸烷基、伸苯基、伸聯苯基、伸萘基、或下式(5b)或(5c)表示之基。
[化21]
式(5b)中,R6c
表示亞甲基、異亞丙基、或CO、O、S、或SO2
表示之取代基。
[化22]
式(5c)中,R6d
各自獨立地表示碳數1~4之伸烷基、或碳數5~8之伸環烷基。
經烯基取代之納迪克醯亞胺化合物可使用市售品,亦可使用利用公知方法製得的製備品。經烯基取代之納迪克醯亞胺化合物的市售品並無特別限定,例如可列舉丸善石油化學(股)公司製品的「BANI-M」、「BANI-X」等。
經烯基取代之納迪克醯亞胺化合物宜包含2官能性經烯基取代之納迪克醯亞胺化合物。本說明書中所稱「2官能性經烯基取代之納迪克醯亞胺化合物」,係指1分子中具有2個經烯基取代之納迪克醯亞胺基(1分子中之經烯基取代之納迪克醯亞胺基的數目為2)的化合物。
經烯基取代之納迪克醯亞胺化合物之含量,相對於樹脂固體成分100質量份可為30質量份以下(例如,0質量份以上且30質量份以下),考量更有效且確實地發揮本發明之作用效果的觀點,宜為15質量份以下,為10質量份以下更佳,為5質量份以下又更佳。
具有可聚合之不飽和基的化合物並無特別限制,例如可列舉:乙烯、丙烯、苯乙烯、二乙烯基苯、二乙烯基聯苯等乙烯基化合物;(甲基)丙烯酸甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、聚丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等1多或多元醇的(甲基)丙烯酸酯類;雙酚A型環氧(甲基)丙烯酸酯、雙酚F型環氧(甲基)丙烯酸酯等環氧(甲基)丙烯酸酯類;苯并環丁烯樹脂等。
氧雜環丁烷樹脂並無特別限制,例如可列舉:氧雜環丁烷、2-甲基氧雜環丁烷、2,2-二甲基氧雜環丁烷、3-甲基氧雜環丁烷、3,3-二甲基氧雜環丁烷等烷基氧雜環丁烷、3-甲基-3-甲氧基甲基氧雜環丁烷、3,3’-二(三氟甲基)全氟氧雜環丁烷、2-氯甲基氧雜環丁烷、3,3-雙(氯甲基)氧雜環丁烷、聯苯型氧雜環丁烷、東亞合成(股)公司製品的「OXT-101」、「OXT-121」等。
(無機填充材(E))
本實施形態之樹脂組成物含有無機填充材(E)。無機填充材(E)並無特別限定,可列舉:二氧化矽類、矽化合物(例如,白碳黑等)、金屬氧化物(例如,氧化鋁、鈦白、氧化鋅、氧化鎂、氧化鋯等)、金屬氮化物(例如,氮化硼、凝聚氮化硼、氮化矽、氮化鋁等)、金屬硫酸化物(例如,硫酸鋇等)、金屬氫氧化物(例如,氫氧化鋁、氫氧化鋁加熱處理品(例如,將氫氧化鋁進行加熱處理,以減少一部分結晶水而得者)、軟水鋁石、氫氧化鎂等)、鉬化合物(例如,氧化鉬、鉬酸鋅等)、鋅化合物(例如,硼酸鋅、錫酸鋅等)、黏土、高嶺土、滑石、煅燒黏土、煅燒高嶺土、煅燒滑石、雲母、E-玻璃、A-玻璃、NE-玻璃、C-玻璃、L-玻璃、D-玻璃、S-玻璃、M-玻璃G20、玻璃短纖維(包含E玻璃、T玻璃、D玻璃、S玻璃、Q玻璃等之玻璃微粉末類。)、中空玻璃、球狀玻璃等。該等無機填充材可單獨使用1種,或將2種以上組合使用。該等之中,考量線熱膨脹係數(CTE)、彎曲模量、阻燃性更加優異的觀點,無機填充材(E)宜為選自於由二氧化矽、金屬氫氧化物、及金屬氧化物構成之群組中之至少1種,為選自於由二氧化矽、軟水鋁石、及氧化鋁構成之群組中之至少1種更佳,為二氧化矽又更佳。
就二氧化矽類而言,例如可列舉:天然二氧化矽、熔融二氧化矽、合成二氧化矽、非晶二氧化矽、二氧化矽氣溶膠(AEROSIL)、中空二氧化矽等。該等之中,宜為熔融二氧化矽。
無機填充材(E)之含量相對於樹脂固體成分100質量份為100~250質量份。藉由無機填充材(E)之含量為100質量份以上,線熱膨脹係數(CTE)、彎曲模量、阻燃性優異。無機填充材(E)之含量超過250質量份的話,無法獲得充分的流動特性,成形困難,不適合於印刷配線板之用途。考量同樣的觀點,無機填充材(E)之含量宜為120~230質量份,為140~210質量份更佳,為150~200質量份又更佳。
(有機填充材(I))
本實施形態之樹脂組成物亦可含有有機填充材(I)。就有機填充材而言,例如可列舉:苯乙烯型粉末、丁二烯型粉末、丙烯酸型粉末等橡膠粉末;核殼型橡膠粉末;聚矽氧型粉末等。該等有機填充材可單獨使用1種,或將2種以上組合使用。該等之中,宜為聚矽氧型粉末。
就聚矽氧型粉末而言,例如可列舉聚矽氧樹脂粉末、聚矽氧橡膠粉末、聚矽氧複合粉末等。該等之中,宜為聚矽氧複合粉末。
有機填充材(I)之含量相對於樹脂固體成分100質量份宜為10~35質量份,為15~30質量份更佳,為20~25質量份又更佳。
(矽烷偶聯劑(G))
本實施形態之樹脂組成物亦可更含有矽烷偶聯劑(G)。本實施形態之樹脂組成物藉由含有矽烷偶聯劑(G),會有無機填充材(E)之分散性更加優異,或本實施形態之樹脂組成物之各成分與後述基材之黏接強度更加優異的傾向。
就矽烷偶聯劑(G)而言,可列舉一般使用於無機物之表面處理的矽烷偶聯劑,可列舉:胺基矽烷系化合物(例如,γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷等)、環氧矽烷系化合物(例如,γ-環氧丙氧基丙基三甲氧基矽烷等)、丙烯酸矽烷系化合物(例如,γ-丙烯醯氧基丙基三甲氧基矽烷等)、陽離子矽烷系化合物(例如,N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷鹽酸鹽等)、苯基矽烷系化合物等。該等矽烷偶聯劑可單獨使用1種,或將2種以上組合使用。該等之中,矽烷偶聯劑(G)宜為環氧矽烷系化合物。就環氧矽烷系化合物而言,例如可列舉:信越化學工業(股)公司製品的「KBM-403」、「KBM-303」、「KBM-402」、「KBE-403」等。
矽烷偶聯劑(G)之含量相對於樹脂固體成分100質量份可為約0.1~10.0質量份,宜為0.5~8.0質量份,為1.0~6.0質量份更佳。
(濕潤分散劑(H))
本實施形態之樹脂組成物亦可更含有濕潤分散劑(H)。本實施形態之樹脂組成物藉由含有濕潤分散劑(H),會有無機填充材(E)之分散性更加優異的傾向。
就濕潤分散劑(H)而言,只要是用以使無機填充材(E)分散的公知分散劑(分散穩定劑)即可,例如可列舉:BYK Japan(股)製的DISPER BYK-110、111、118、180、161、BYK-W996、W9010、W903等。
就濕潤分散劑(H)之含量而言,考量無機填充材(E)之分散性更加優異的觀點,相對於樹脂固體成分100質量份宜為0.1~5.0質量份,為0.2~3.0質量份更佳,為0.5~1.5質量份又更佳。
(環狀碳二亞胺化合物(D))
本實施形態之樹脂組成物含有環狀碳二亞胺化合物(D)。就環狀碳二亞胺化合物(D)而言,例如可列舉分子內具有1個以上之環狀結構,且1個環狀結構中具有1個碳二亞胺基的化合物。環狀碳二亞胺化合物係分子內具有1個以上之環狀結構,且1個環狀結構中具有1個碳二亞胺基者。樹脂組成物藉由含有環狀碳二亞胺化合物(D),可在不會使流動性惡化的情況下維持充分的成形性,且玻璃轉移溫度變高,耐熱性優異,或電特性優異。
環狀結構具有碳二亞胺基(-N=C=N-),其第1氮原子與第2氮原子藉由鍵結基鍵結。形成環狀結構之原子數宜為8~50,為10~30更佳,為10~20又更佳。此處,形成環狀結構之原子數意指直接構成環狀結構之原子的數目。例如,若為8員環則形成環狀結構之原子數為8,若為50員環則形成環狀結構之原子數為50。藉由形成環狀結構之原子數為8以上,具備環狀碳二亞胺化合物的穩定性良好,容易保存,容易使用的優點。又,形成環狀結構之原子數超過50之環狀碳二亞胺化合物的合成困難。
雜原子係指O、N、S及P。鍵結基之中,2個價鍵係用來形成環狀結構。L為3價或4價鍵結基時,L藉由單鍵、雙鍵、原子、原子團而與聚合物或其他環狀結構鍵結。
式(1-1)中,Ar101
及Ar102
各自獨立地為亦可含有雜原子及取代基的2~4價之碳數5~15之芳香族烴基。
Ar101
及Ar102
表示之芳香族烴基並無特別限制,例如可列舉亦可具有含雜原子之雜環結構的碳數5~15之伸芳基、碳數5~15之芳烴三基、碳數5~15之芳烴四基。此處,伸芳基(2價)可列舉伸苯基、萘二基等。芳烴三基(3價)可列舉苯三基、萘三基等。芳烴四基(4價)可列舉苯四基、萘四基等。該等芳香族烴基亦可具有取代基。就取代基而言,可列舉:碳數1~20之烷基、碳數6~15之芳基、鹵素原子、硝基、醯胺基、羥基、酯基、醚基、醛基等。
Ar101
及Ar102
宜為伸苯基、萘二基、苯三基、萘三基、或苯四基,為伸苯基、或苯三基更佳。
式(1-2)中,R101
及R102
可各自獨立地列舉:亦可含有雜原子及/或取代基的2~4價之碳數1~20之脂肪族基(脂肪族烴基)、2~4價之碳數3~20之脂環族基(脂環族烴基)及它們的組合、或該等脂肪族基及/或脂環族基與2~4價之碳數5~15之芳香族基(芳香族烴基)的組合。
R101
及R102
表示之脂肪族基並無特別限制,例如可列舉碳數1~20之伸烷基、碳數1~20之烷三基、碳數1~20之烷四基等。伸烷基可列舉:亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十二基、伸十六基等。烷三基可列舉:甲烷三基、乙烷三基、丙烷三基、丁烷三基、戊烷三基、己烷三基、庚烷三基、辛烷三基、壬烷三基、癸烷三基、十二烷三基、十六烷三基等。烷四基可列舉:甲烷四基、乙烷四基、丙烷四基、丁烷四基、戊烷四基、己烷四基、庚烷四基、辛烷四基、壬烷四基、癸烷四基、十二烷四基、十六烷四基等。該等脂肪族基亦可具有取代基。就取代基而言,可列舉:碳數1~20之烷基、碳數6~15之芳基、鹵素原子、硝基、醯胺基、羥基、酯基、醚基、醛基等。
脂環族基可列舉碳數3~20之伸環烷基、碳數3~20之環烷三基、碳數3~20之環烷四基。伸環烷基可列舉:伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環庚基、伸環辛基、伸環壬基、伸環癸基、伸環十二基、伸環十六基等。環烷三基可列舉:環丙烷三基、環丁烷三基、環戊烷三基、環己烷三基、環庚烷三基、環辛烷三基、環壬烷三基、環癸烷三基、環十二烷三基、環十六烷三基等。環烷四基可列舉:環丙烷四基、環丁烷四基、環戊烷四基、環己烷四基、環庚烷四基、環辛烷四基、環壬烷四基、環癸烷四基、環十二烷四基、環十六烷四基等。該等脂環族基亦可具有取代基。就取代基而言,可列舉:碳數1~20之烷基、碳數6~15之芳基、鹵素原子、硝基、醯胺基、羥基、酯基、醚基、醛基等。
芳香族基可列舉:亦可具有含雜原子之雜環結構的碳數5~15之伸芳基、碳數5~15之芳烴三基、碳數5~15之芳烴四基。伸芳基可列舉伸苯基、萘二基等。芳烴三基(3價)可列舉苯三基、萘三基等。芳烴四基(4價)可列舉苯四基、萘四基等。該等芳香族基亦可具有取代基。就取代基而言,可列舉:碳數1~20之烷基、碳數6~15之芳基、鹵素原子、硝基、醯胺基、羥基、酯基、醚基、醛基等。
R101
及R102
宜各自獨立地為亞甲基、伸乙基、亞乙烯基、伸苯基或醚基,為亞甲基、伸苯基或醚基更佳。
式(1-1)及(1-2)中,X1
及X2
各自獨立地為亦可含有雜原子及/或取代基的2~4價之碳數1~20之脂肪族基、2~4價之碳數3~20之脂環族基、2~4價之碳數5~15之芳香族基或它們的組合。
X1
及X2
中之脂肪族基、脂環族基及芳香族基的示例,可列舉與上述R101
及R102
中所例示者相同之基。X1
及X2
宜為亞甲基、伸乙基、亞乙烯基、或醚基,為亞甲基或醚基更佳。
式(1-1)及(1-2)中,s及k宜各自獨立地為0~10,為0~3更佳,為0~1又更佳。s及k各自超過10之環狀碳二亞胺化合物的合成困難,成本會增加。此外,s或k為2以上時,作為重複單元之X1
或X2
也可和其他X1
或X2
不同。
式(1-3)中,X3
為亦可含有雜原子及/或取代基的2~4價之碳數1~20之脂肪族基、2~4價之碳數3~20之脂環族基、2~4價之碳數5~15之芳香族基或它們的組合。
X3
中之脂肪族基、脂環族基及芳香族基的示例,可列舉與上述R101
、R102
、X1
及X2
中所例示者相同之基。X3
宜為亞甲基、伸乙基、亞乙烯基、或醚基,為亞甲基或醚基更佳。
又,Ar101
、Ar102
、R101
、R102
、X1
、X2
及X3
亦可具有選自於O原子、N原子、S原子及P原子之雜原子。惟,雜原子為N原子時,該N原子係以硝基及/或醯胺基的形態存在。
又,L為2價鍵結基時,Ar101
、Ar102
、R101
、R102
、X1
、X2
及X3
均為2價基。L為3價鍵結基時,Ar101
、Ar102
、R101
、R102
、X1
、X2
及X3
中之1個為3價基。L為4價鍵結基時,Ar101
、Ar102
、R101
、R102
、X1
、X2
及X3
中之1個為4價基,或Ar101
、Ar102
、R101
、R102
、X1
、X2
及X3
中之2個為3價基。
L為3價或4價鍵結基,且L與具有碳二亞胺基之其他環狀結構鍵結的態樣,可列舉式(1)表示之2個以上之環狀結構藉由選自於螺環結構、單鍵、碳數1~10之伸烷基、碳數6~10之芳香族環結構、碳數4~12之環烷環結構等的碳數1~15(宜為1~12)之共有部分而鍵結的態樣。如此之態樣之具體例示於下式(2)、(4)、(5)。
[化27]
環狀碳二亞胺化合物(D)亦可為下式(i)表示之環狀碳二亞胺化合物。此外,下式(i)表示之環狀碳二亞胺化合物可於分子中具有2個以上之碳二亞胺基,亦可具有1個碳二亞胺基。
[化28]
式(i)中,Xa為下式(i-1)~(i-3)表示之2價基或下式(i-4)表示之4價基。Xa為2價時q為0,Xa為4價時q為1。Ar201
~Ar204
各自獨立地為芳香族烴基。該等芳香族烴基亦可具有碳數1~6之烷基或苯基作為取代基。
[化29]
式(i-1)中,n為1~6之整數。
[化30]
式(i-2)中,m及n各自獨立地為0~3之整數。
[化31]
式(i-3)中,R301
及R302
各自獨立地表示碳數1~6之烷基、苯基。
[化32]
考量玻璃轉移溫度(Tg)、耐藥品性、耐熱性更加優異的觀點,環狀碳二亞胺化合物(D)宜包含1分子內含有2個以上之碳二亞胺基的多價環狀碳二亞胺化合物。考量硬化性能更加優異的觀點,環狀碳二亞胺化合物(D)包含1分子內含有2個或3個碳二亞胺基的多價環狀碳二亞胺化合物更佳。該等多價環狀碳二亞胺化合物可單獨使用1種,或將2種以上組合使用。
就多價環狀碳二亞胺化合物而言,例如可列舉上述碳二亞胺化合物中於1分子內含有2個以上之碳二亞胺基者。該等之中,考量玻璃轉移溫度(Tg)、耐藥品性、耐熱性更加優異的觀點,宜為下式(2)表示之化合物。
[化34]
式(2)中,X係下式(3)表示之4價基,Ar1
~Ar4
各自獨立地為作為伸苯基(例如,鄰伸苯基)或萘二基(例如,1,2-萘二基)的2價連接基,該連接基亦可具有取代基。就取代基而言,可列舉:碳數1~20之烷基、碳數6~15之芳基、鹵素原子、硝基、醯胺基、羥基、酯基、醚基、醛基等。又,該等連接基亦可具有含雜原子之雜環結構。
[化35]
該等環狀碳二亞胺化合物(D)可利用公知的方法(例如,國際公開第2010/071213號小冊記載之方法)製造。
環狀碳二亞胺化合物(D)之含量,相對於樹脂固體成分100質量份宜為1.0~30質量份,為2.0~15質量份更佳,為2.5~12.0質量份又更佳。藉由環狀碳二亞胺化合物(D)之含量為1.0質量份以上,會有耐藥品性、耐熱性及電特性更加優異的傾向,藉由環狀碳二亞胺化合物(D)之含量為30質量份以下,會有阻燃性更加優異的傾向。
(硬化促進劑(F))
樹脂組成物更含有硬化促進劑(F)。硬化促進劑(F)並無特別限制,例如可列舉咪唑化合物、有機磷化合物等。
考量硬化性優異的觀點,咪唑化合物宜包含下式(5)表示之咪唑化合物。
[化37]
式(5)中,Ar5
各自獨立地表示苯基、萘基、聯苯基、或蒽基,該等基亦可具有取代基,R1
表示氫原子、烷基、芳基,R1
表示烷基或芳基時,亦可具有取代基。
Ar5
宜為苯基。R1
宜為芳基,為苯基更佳。
就式(5)表示之咪唑化合物而言,例如可列舉:2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,4,5-三苯基咪唑、2-苯基-4-甲基咪唑等。
該等之中,咪唑化合物宜為2,4,5-三苯基咪唑、及/或2-苯基-4-甲基咪唑,為2,4,5-三苯基咪唑更佳。藉由使用如此之咪唑化合物,會有硬化性更為改善的傾向。
又,有機磷化合物並無特別限制,例如可列舉:[4-(N,N-二甲基胺基)苯基]二第三丁基膦、1,1’-雙(二異丙基膦基)二茂鐵、1,1’-雙(二第三丁基膦基)二茂鐵、1,1’-雙(二苯基膦基)二茂鐵、1,2-雙(二苯基膦基)乙烷、1,2-雙(二苯基膦基)乙炔、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,5-雙(二苯基膦基)戊烷、2,2’-雙(二苯基膦基)二苯醚、2-羧基乙基三苯基溴化鏻、9,9-二甲基-4,5-雙(二第三丁基膦基)-9H- 、9,9-二甲基-4,5-雙(二苯基膦基)-9H- 、異丙基三苯基碘化鏻、四氟硼化正丁基二(第三丁基)鏻、正丁基三苯基溴化鏻、正丙基三苯基溴化鏻、四-對甲苯基硼化對甲苯基三苯基鏻、2-(三苯基正膦基)丁酸乙酯、2-(三苯基正膦基)丙酸乙酯、乙基三苯基溴化鏻、二第三丁基(2-丁烯基)膦、四氟硼化二第三丁基(2-丁烯基)鏻、二第三丁基(3-甲基-2-丁烯基)膦、四氟硼化二第三丁基(3-甲基-2-丁烯基)鏻、二第三丁基苯基膦、四苯基硼化二第三丁基甲基鏻、四氟硼化二第三丁基甲基鏻、二苯基-2-吡啶基膦、二苯基環己基膦、二苯基氧膦對苯二酚、二苯基膦基苯乙烯、四正丁基氯化鏻、四正丁基氫氧化鏻、四正丁基溴化鏻、四正丁基鏻月桂酸鹽、四正丁基鏻乙酸鹽、四氟硼化四苯基鏻、四苯基溴化鏻、四-對甲苯基硼化四苯基鏻、四苯基硼化四苯基鏻、三-2,4-二甲苯基膦、三-2,5-二甲苯基膦、三-3,5-二甲苯基膦、三間甲苯基膦、三正辛基膦、三正辛基氧化膦、三正丁基膦、三鄰甲苯基膦、三對甲苯基膦、三第三丁基膦、四苯基硼化三第三丁基鏻、四氟硼化三第三丁基鏻、三環己基膦、參(鄰甲氧基苯基)膦、參(對第三丁基苯基)膦、參(對第三丁氧基苯基)膦、參(對甲氧基苯基)膦、參(二乙基胺基)膦、三苯基膦、三苯基膦三苯基硼烷、三苯基氧化膦、雙(四-正丁基鏻)均苯四甲酸鹽、苄基三苯基氯化鏻、甲基三苯基氯化鏻、甲基三苯基溴化鏻、甲氧基甲基三苯基氯化鏻等。
其中,宜為三苯基膦、三鄰甲苯基膦、三間甲苯基膦、三對甲苯基膦、三-2,4-二甲苯基膦、三-2,5-二甲苯基膦、三-3,5-二甲苯基膦、參(對第三丁基苯基)膦、參(對甲氧基苯基)膦、參(鄰甲氧基苯基)膦、參(對第三丁氧基苯基)膦、二苯基環己基膦、二苯基-2-吡啶基膦等苯基膦、三環己基膦、三正丁基膦等烷基膦。藉由使用如此之有機磷化合物,會有硬化性更為改善,且耐熱性更為改善的傾向。
咪唑化合物或有機磷化合物之含量,相對於樹脂固體成分100質量份可為約0.1~10質量份,考量更有效且確實地發揮本發明之作用效果的觀點,宜為0.2~5.0質量份,為0.3~1.0質量份更佳。
咪唑化合物及有機磷化合物以外之其他硬化促進劑(F)並無特別限制,例如可列舉:有機過氧化物(例如,過氧化苯甲醯、過氧化月桂醯、過氧化乙醯、過氧化對氯苯甲醯、二過氧鄰苯二甲酸二第三丁酯等)、偶氮化合物(例如,偶氮雙腈等)、3級胺類(例如,N,N-二甲基苄胺、N,N-二甲基苯胺、N,N-二甲基甲苯胺、N,N-二甲基吡啶、2-N-乙基苯胺基乙醇、三正丁胺、吡啶、喹啉、N-甲基啉、三乙醇胺、三乙二胺、四甲基丁烷二胺、N-甲基哌啶等)、有機金屬鹽(例如,環烷酸鉛、硬脂酸鉛、環烷酸鋅、辛酸鋅、油酸錫、馬來酸二丁基錫、環烷酸錳、環烷酸鈷、乙醯丙酮鐵等)、將該等有機金屬鹽溶解於苯酚、雙酚等含有羥基之化合物而得者、無機金屬鹽(例如,氯化錫、氯化鋅、氯化鋁等)、有機錫化合物(例如,二辛基氧化錫、其他烷基錫、烷基氧化錫等)。該等硬化促進劑可單獨使用1種,或將2種以上組合使用。
就硬化促進劑(F)之總含量而言,考量更有效且確實地發揮本發明之作用效果的觀點,相對於樹脂固體成分100質量份宜為5.0質量以下,為3.0質量份以下更佳,為0.3~1.0質量份又更佳。
[溶劑]
本實施形態之樹脂組成物亦可含有溶劑。本實施形態之樹脂組成物藉由含有溶劑,會有因樹脂組成物之製備時之黏度降低,而使得操作性(處理性)更加優異,或於基材之含浸性更加優異的傾向。
就溶劑而言,只要可使樹脂組成物中之各成分之一部分或全部溶解,則無特別限定,例如可列舉:酮類(丙酮、甲乙酮、甲基賽珞蘇等)、芳香族烴類(例如,甲苯、二甲苯等)、醯胺類(例如,二甲基甲醛等)、丙二醇單甲醚及其乙酸酯等。該等溶劑可單獨使用1種,或將2種以上組合使用。
本實施形態之樹脂組成物之製造方法並無特別限定,例如可列舉將各成分一次性地或逐次地摻合至溶劑並進行攪拌的方法。此時,為了使各成分均勻地溶解或分散,可使用攪拌、混合、混練處理等公知的處理。
[預浸體]
本實施形態之預浸體包含:基材、及含浸或塗布於基材的本實施形態之樹脂組成物。如前述,預浸體亦可為藉由公知的方法獲得的預浸體,具體而言,可藉由將本實施形態之樹脂組成物含浸或塗布於基材後,以100~200℃之條件進行加熱乾燥,而使其半硬化(B階段化)來獲得。
本實施形態之預浸體亦包含將半硬化狀態之預浸體以200~230℃之加熱溫度及60~180分鐘之加熱時間之條件使其熱硬化而獲得之硬化物的形態。
預浸體中之樹脂組成物之含量,以預浸體之固體成分換算,相對於預浸體之總量宜為30~90體積%,更佳為35~85體積%,又更佳為40~80體積%。藉由樹脂組成物之含量落在上述範圍內,有成形性更為改善的傾向。此外,預浸體之固體成分,係指預浸體中除了溶劑以外的成分,例如填充材包含在預浸體之固體成分中。
(基材)
基材並無特別限定,例如可列舉各種印刷配線板之材料所使用的公知基材。基材之具體例可列舉:玻璃基材、玻璃以外的無機基材(例如,石英等由玻璃以外之無機纖維構成的無機基材)、有機基材(例如,由全芳香族聚醯胺、聚酯、聚對伸苯基苯并雙㗁唑、聚醯亞胺等有機纖維構成的有機基材)等。該等基材可單獨使用1種,或將2種以上組合使用。該等之中,考量進一步改善剛性,或加熱尺寸穩定性更加優異的觀點,宜為玻璃基材。
(玻璃基材)
就構成玻璃基材之纖維而言,例如可列舉:E玻璃、D玻璃、S玻璃、T玻璃、Q玻璃、L玻璃、NE玻璃、HME玻璃等。該等之中,考量強度與低吸水性更加優異的觀點,構成玻璃基材之纖維宜為選自於由E玻璃、D玻璃、S玻璃、T玻璃、Q玻璃、L玻璃、NE玻璃、及HME玻璃構成之群組中之1種以上之纖維。
基材的形態並無特別限定,例如可列舉:織布、不織布、粗紗、切股氈、表面氈等形態。織布的織法並無特別限定,例如已知有平織、斜子織、斜紋織等,可從該等公知者中根據目的之用途、性能適當選擇來使用。又,可理想地使用將該等予以開纖處理而得者、以矽烷偶聯劑等進行表面處理而得之玻璃織布。基材的厚度、質量並無特別限定,通常可理想地使用約0.01~0.3mm者。
[疊層板]
本實施形態之疊層板具有本實施形態之預浸體。本實施形態之疊層板包含1個或多個預浸體,包含多個時,具有預浸體疊層而成之形態。本實施形態之疊層板藉由具有本實施形態之預浸體,耐熱性、耐藥品性、低吸水性及電特性優異。
[覆金屬箔疊層板]
本實施形態之覆金屬箔疊層板具有:本實施形態之預浸體、及配置在預浸體之單面或兩面的金屬箔。本實施形態之覆金屬箔疊層板包含1個或多個預浸體。預浸體的數目為1個時,覆金屬箔疊層板具有金屬箔配置在預浸體之單面或兩面的形態。預浸體的數目為多個時,覆金屬箔疊層板具有金屬箔配置在經疊層之預浸體(預浸體之疊層體)之單面或兩面的形態。本實施形態之覆金屬箔疊層板藉由具有本實施形態之預浸體,耐熱性、耐藥品性、低吸水性及電特性優異。
就金屬箔(導體層)而言,只要是使用於各種印刷配線板材料的金屬箔即可,例如可列舉銅、鋁等的金屬箔,銅的金屬箔可列舉壓延銅箔、電解銅箔等銅箔。導體層的厚度例如為1~70μm,宜為1.5~35μm。
疊層板及覆金屬箔疊層板的成形方法及其成形條件並無特別限定,可使用一般的印刷配線板用疊層板及多層板的方法及條件。例如,於疊層板或覆金屬箔疊層板之成形時可使用多層壓製機、多層真空壓製機、連續成形機、高壓釜成形機等。又,於疊層板或覆金屬箔疊層板之成形(疊層成形)時,通常溫度為100~300℃,壓力為面壓2~100kgf/cm2
,加熱時間為0.05~5小時之範圍。進一步,視需要亦可於150~300℃之溫度實施後硬化。尤其使用多層壓製機時,考量充分促進預浸體之硬化的觀點,宜為溫度200℃~250℃、壓力10~40kgf/cm2
、加熱時間80分鐘~130分鐘,為溫度215℃~235℃、壓力25~35kgf/cm2
、加熱時間90分鐘~120分鐘更佳。又,藉由將上述預浸體、與另外製作的內層用配線板予以組合並疊層成形,亦可製成多層板。
[印刷配線板]
本實施形態之印刷配線板具有:由本實施形態之預浸體形成的絕緣層、及形成於絕緣層之表面的導體層。本實施形態之印刷配線板,例如可藉由將本實施形態之覆金屬箔疊層板的金屬箔蝕刻成預定的配線圖案以製成導體層而形成。本實施形態之印刷配線板藉由具有本實施形態之預浸體,耐熱性、耐藥品性、低吸水性及電特性優異。
本實施形態之印刷配線板,具體而言例如可利用以下之方法製造。首先,準備本實施形態之覆金屬箔疊層板。將覆金屬箔疊層板之金屬箔蝕刻成預定的配線圖案,製作具有導體層(內層電路)之內層基板。然後,在內層基板之導體層(內層電路)表面,按照順序疊層預定數目之預浸體、與外層電路用金屬箔,進行加熱加壓而成形為一體(疊層成形),藉此得到疊層體。此外,疊層成形之方法及其成形條件,係與上述疊層板及覆金屬箔疊層板中之疊層成形之方法及其成形條件同樣。然後,於疊層體施以通孔(through hole)、介層孔(via hole)用之開孔加工,在藉此形成之孔的壁面形成用以使導體層(內層電路)與外層電路用金屬箔導通的鍍敷金屬皮膜。然後,將外層電路用金屬箔蝕刻成預定的配線圖案,製作具有導體層(外層電路)之外層基板。如此可製造印刷配線板。
又,不使用覆金屬箔疊層板時,亦可於上述預浸體形成成為電路之導體層,並製作印刷配線板。此時,導體層的形成也可使用無電解鍍敷的方法。
[多層印刷配線板(多層無芯基板)]
本實施形態之多層印刷配線板具有:多個絕緣層,係由第1絕緣層、與疊層在第1絕緣層之單面側的1個或多個第2絕緣層構成;及多個導體層,係由配置在多個絕緣層中的各絕緣層之間的第1導體層、與配置在多個絕緣層之最外層之表面的第2導體層構成;第1絕緣層及第2絕緣層分別具有本實施形態之預浸體。本實施形態之多層印刷配線板之具體例示於圖1。圖1所示之多層印刷配線板包含第1絕緣層(1)、與疊層在第1絕緣層(1)之單面方向(圖示下面方向)的2個第2絕緣層(2),第1絕緣層(1)及2個第2絕緣層(2)分別由1個本實施形態之預浸體形成。又,圖1所示之多層印刷配線板具有係由配置在多個絕緣層(1、2)中的各絕緣層之間的第1導體層(3)、及配置在該等多個絕緣層(1、2)之最外層的第2導體層(3)構成的多個導體層。
本實施形態之多層印刷配線板,例如為僅在第1絕緣層之單面方向疊層第2絕緣層而成的所謂無芯類型之多層印刷配線板(多層無芯基板)。本實施形態之多層印刷配線板之製造方法例如可參照公知的方法。
[實施例]
以下利用實施例及比較例針對本發明進行進一步說明,但本發明並不限定於該等實施例。
[實施例1]
將作為苯酚化合物(A)之萘酚芳烷基型苯酚(新日鐵住金化學(股)「SN-495-V」)36.8質量份、作為馬來醯亞胺化合物(B)之酚醛清漆型馬來醯亞胺(大和化成(股)「BMI-2300」)24.6質量份、作為環氧化合物(C)之伸萘基醚型環氧化合物(DIC(股)「HP-6000」)38.6質量份、矽烷偶聯劑(G)(信越化學工業(股)「KBM-403」)5.0質量份、濕潤分散劑(H)(BYK-Japan(股)「DISPERBYK-161」)1.0質量份、作為無機填充材(E)之球狀二氧化矽e1(Admatechs(股)製品「SC2050-MB」)100質量份、作為無機填充材(E)之球狀二氧化矽e2(Admatechs(股)「SC5050-MOB」)100質量份、作為有機填充材(I)之聚矽氧複合粉末(信越化學工業(股)「KMP605M」)25質量份、環狀碳二亞胺化合物(D)(帝人(股)「TCC」)5.0質量份、作為硬化促進劑(F)之咪唑化合物(TCI(股)「TPIZ」:2,4,5-三苯基咪唑)0.5質量份予以混合,之後利用甲乙酮稀釋,獲得清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[實施例2]
將環狀碳二亞胺化合物(D)的摻合量由5.0質量份變更為10質量份,除此以外,與實施例1同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[實施例3]
將環狀碳二亞胺化合物(D)的摻合量由5.0質量份變更為15質量份,除此以外,與實施例1同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[實施例4]
將與實施例2同樣製得之清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#2116),並在140℃加熱乾燥3分鐘,得到具有約100μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為58體積%。
[實施例5]
使用有機磷化合物(北興化學工業(股)「TPTP」:三-對甲苯基膦)0.5質量份替代咪唑化合物(TCI(股)「TPIZ」:2,4,5-三苯基咪唑),除此以外,與實施例2同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#2116),並在140℃加熱乾燥3分鐘,得到具有約100μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為58體積%。
[比較例1]
將球狀二氧化矽e1的摻合量由100質量份變更為150質量份,球狀二氧化矽e2的摻合量由100質量份變更為150質量份,環狀碳二亞胺化合物(D)的摻合量由5.0質量份變更為0質量份,除此以外,與實施例1同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[比較例2]
將環狀碳二亞胺化合物(D)的摻合量由5.0質量份變更為0質量份,除此以外,與實施例1同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[比較例3]
加入非環狀碳二亞胺化合物(日清紡製「V-05」)10質量份,除此以外,與比較例1同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[比較例4]
將與比較例2同樣製得之清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#2116),並在140℃加熱乾燥3分鐘,得到具有約100μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為58體積%。
[比較例5]
使用有機磷化合物(北興化學工業(股)「TPTP」:三-對甲苯基膦)0.5質量份替代咪唑化合物(TCI(股)「TPIZ」:2,4,5-三苯基咪唑),除此以外,與比較例2同樣進行,得到清漆(樹脂組成物)。該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#2116),並在140℃加熱乾燥3分鐘,得到具有約100μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為58體積%。
[比較例6]
將環狀碳二亞胺化合物(D)的摻合量由0質量份變更為5.0質量份,除此以外,與比較例1同樣進行,得到清漆(樹脂組成物)。將該清漆(樹脂組成物)含浸塗覆於E玻璃織布(IPC#1280),並在140℃加熱乾燥3分鐘,得到具有約80μm之厚度的預浸體。獲得之預浸體中之樹脂組成物(固體成分量(包含填料))之含量為73體積%。
[物性測定評價]
使用實施例1~5及比較例1~6中獲得之清漆或預浸體,依以下各項目所示之程序製作物性測定評價用樣品,並測定評價流動特性、焊料耐熱性、玻璃轉移溫度(Tg)、耐除膠渣性、吸水率、電特性及阻燃性。實施例及比較例的結果示於表1。
[流動特性]
將獲得之預浸體捏鬆並採取預浸體中之樹脂組成物的粉末,將該粉放入預定的模具中進行直接加壓成形,製成樹脂棒。然後,將樹脂棒投入Koka型流動性測定儀(島津製作所製,「CFT-500D」)之加熱部,測定於120±0.2℃時之熔融黏度(單位:Pa・s)。
○:100Pa・s以上且未達1500Pa・s
△:1500Pa・s以上且未達3000Pa・s
×:3000Pa・s以上
[焊料耐熱性]
使將依下列[電特性]之項目記載之方法獲得的覆金屬箔疊層板裁切成50mm×50mm之大小而製作的樣品在300℃焊料中漂浮30分鐘,藉由目視判定有無外觀異常。評價基準如下(n=3)。此外,比較例1及6在成形時產生了空隙,故無法製造疊層板。因此,比較例1及6未進行焊料耐熱性的評價。
〇:3點均無分層(delamination)
×:3點均有分層
[玻璃轉移溫度]
在獲得之1片預浸體的上下兩面配置銅箔(三井金屬礦業(股)公司製「3EC-VLP」,厚度12μm),以壓力30kgf/cm2
、溫度220℃之條件實施100分鐘的疊層成形(熱硬化),獲得具有由預浸體形成之絕緣層、與銅箔的覆銅箔疊層板。該覆銅箔疊層板之絕緣層的厚度為約80~100μm。將獲得之覆銅箔疊層板之表面銅箔利用蝕刻除去。之後,利用切割鋸裁切成大小5.0mm×20mm,得到測定用樣品。使用該測定用樣品,依據JIS C6481使用動態黏彈性分析裝置(TA Instrument製)並藉由DMA法測定玻璃轉移溫度(Tg)(n=3之平均值)。此外,比較例1及6在成形時產生了空隙,故無法製造疊層板。因此,比較例1及6未進行玻璃轉移溫度的評價。
[耐藥品性(耐除膠渣性)]
將依[玻璃轉移溫度]之項目記載之方法獲得之覆金屬箔疊層板的銅箔利用蝕刻除去,然後進行下列浸漬處理。首先,將除去了銅箔的疊層板在膨潤液(Atotech Japan(股)製品,Swelling Dip Securiganth P)中於80℃浸漬10分鐘。然後,將經浸漬之疊層板在粗糙化液(Atotech Japan(股)製品,Concentrate Compact CP)中於80℃浸漬5分鐘。然後,將經浸漬之疊層板在中和液(Atotech Japan(股)製品,Reduction Conditioner Securiganth P500)中於45℃浸漬10分鐘。測定實施該浸漬處理3次後的質量減少量(質量%)。此外,比較例1及6在成形時產生了空隙,故無法製造疊層板。因此,比較例1及6未進行耐除膠渣性的評價。
[低吸水性]
將依[玻璃轉移溫度]之項目記載之方法獲得之覆金屬箔疊層板之兩面的銅箔利用蝕刻除去。之後,將裁切成30mm×30mm的樣品依據JIS C648,利用加壓蒸煮器試驗機(平山製作所(股)製品,PC-3型)測定經於121℃、2大氣壓且24小時之條件處理後的吸水率。吸水率係由處理前後之樣品的重量變化求得。此外,比較例1及6在成形時產生了空隙,故無法製造疊層板。因此,比較例1及6未進行低吸水性的評價。
[電特性]
在獲得之5片預浸體的上下兩面配置銅箔(三井金屬礦業(股)公司製「3EC-VLP」,厚度12μm),以壓力30kgf/cm2
、溫度220℃之條件實施100分鐘的疊層成形(熱硬化),獲得具有由預浸體形成之絕緣層、與銅箔的覆銅箔疊層板。該覆銅箔疊層板之絕緣層的厚度為約400~450μm。將獲得之覆銅箔疊層板之表面銅箔利用蝕刻除去。之後,利用切割鋸裁切成大小100mm×1mm×0.4mmt,得到測定用樣品。使用該測定用樣品,利用擾動法空洞共振器(Agilent(股)製品,Agilent8722ES)測定1GHz及10GHz之介電率(Dk)及1GHz及10GHz之介電損耗正切(Df)。此外,比較例1及6在成形時產生了空隙,故無法製造疊層板。因此,比較例1及6未進行電特性的評價。
[阻燃性]
使用[電特性]之項目中獲得之測定用樣品,依據UL94垂直燃燒試驗法實施阻燃性試驗。此外,比較例1及6在成形時產生了空隙,故無法製造疊層板。因此,比較例1及6未進行阻燃性的評價。
由實施例1~3及比較例2之結果可知如下情事。首先,可知即使如實施例1~3般將環狀碳二亞胺化合物(D)摻合至清漆,流動特性亦不會惡化。又,可知清漆中摻合有環狀碳二亞胺化合物(D)之實施例1~3,相較於清漆中未摻合有環狀碳二亞胺化合物(D)之比較例2,可使玻璃轉移溫度、耐藥品性及電特性(低介電損耗正切性)的特性得到改善。又,可知該等特性有隨著環狀碳二亞胺化合物(D)的摻合量增大而得到改善的傾向。又,與使用了非環狀碳二亞胺化合物(鏈狀碳二亞胺化合物)的比較例3進行比較,流動特性、電特性雖為實施例同等程度,但耐熱性及耐除膠渣性未改善,吸水性差。由此可認為:非環狀碳二亞胺化合物雖與各種熱硬化性樹脂反應,但其結構上未形成交聯,故電特性雖得到改善,但耐熱性及耐除膠渣性不會改善。又,耐熱性及吸水率的惡化據推測係因為非環狀碳二亞胺化合物的反應末端化合物,但本發明並不限定於該推測。
本申請案係基於2018年8月9日向日本專利廳提申的日本專利申請案(特願2018-150563),其內容援引於此作為參照。
[產業上利用性]
本發明作為印刷配線板用之樹脂組成物具有產業上之可利用性。
1:第1絕緣層
2:第2絕緣層
3:第1導體層、第2導體層
[圖1]係顯示多層無芯基板之面板之一例的構成的部分剖面圖。
Claims (16)
- 一種印刷配線板用樹脂組成物,含有苯酚化合物(A)、馬來醯亞胺化合物(B)、環氧化合物(C)、環狀碳二亞胺化合物(D)、無機填充材(E)、及硬化促進劑(F), 該無機填充材(E)之含量,相對於樹脂固體成分100質量份為100~250質量份。
- 如申請專利範圍第1項之印刷配線板用樹脂組成物,其中,該環狀碳二亞胺化合物(D)之含量,相對於樹脂固體成分100質量份為2.0~15質量份。
- 如申請專利範圍第1或2項之印刷配線板用樹脂組成物,其中,該環狀碳二亞胺化合物(D)之含量,相對於樹脂固體成分100質量份為2.5~12.0質量份。
- 如申請專利範圍第1或2項之印刷配線板用樹脂組成物,其中,該馬來醯亞胺化合物(B)之含量,相對於樹脂固體成分100質量份為10~30質量份。
- 如申請專利範圍第1或2項之印刷配線板用樹脂組成物,其中,該環狀碳二亞胺化合物(D)包含1分子內含有2個以上之碳二亞胺基的多價環狀碳二亞胺化合物。
- 如申請專利範圍第1或2項之印刷配線板用樹脂組成物,其中,該硬化促進劑(F)包含咪唑化合物及/或有機磷化合物。
- 如申請專利範圍第1或2項之印刷配線板用樹脂組成物,其中,該無機填充材(E)含有選自於由二氧化矽、軟水鋁石、及氧化鋁構成之群組中之1種以上。
- 一種預浸體,包含: 基材,及 含浸或塗布於該基材的如申請專利範圍第1至11項中任一項之印刷配線板用樹脂組成物。
- 一種疊層板,具有如申請專利範圍第12項之預浸體。
- 一種覆金屬箔疊層板,具有: 如申請專利範圍第12項之預浸體,及 配置於該預浸體之單面或兩面的金屬箔。
- 一種印刷配線板,包含: 由如申請專利範圍第12項之預浸體形成的絕緣層,及 形成於該絕緣層之表面的導體層。
- 一種多層印刷配線板,具有: 多個絕緣層,係由第1絕緣層、與疊層在該第1絕緣層之單面側的1個或多個第2絕緣層構成;及 多個導體層,係由配置在該多個絕緣層中的各絕緣層之間的第1導體層、與配置在該多個絕緣層之最外層之表面的第2導體層構成; 該第1絕緣層及該第2絕緣層分別具有如申請專利範圍第12項之預浸體。
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TW201638141A (zh) * | 2015-02-13 | 2016-11-01 | 三井化學股份有限公司 | 高分子壓電膜及其製造方法 |
TW201726801A (zh) * | 2015-08-04 | 2017-08-01 | 信越化學工業股份有限公司 | 熱硬化性環氧樹脂組成物 |
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US9078365B2 (en) | 2006-04-28 | 2015-07-07 | Hitachi Chemical Co., Ltd. | Resin composition, prepreg, laminate, and wiring board |
WO2010071213A1 (ja) | 2008-12-15 | 2010-06-24 | 帝人株式会社 | 環状カルボジイミドを含有する樹脂組成物 |
SG10201502708PA (en) | 2010-04-08 | 2015-05-28 | Mitsubishi Gas Chemical Co | Resin composition, prepreg, and laminated sheet |
JP5734604B2 (ja) * | 2010-08-30 | 2015-06-17 | 太陽ホールディングス株式会社 | 硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
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JP2014122326A (ja) * | 2012-11-22 | 2014-07-03 | Toyo Ink Sc Holdings Co Ltd | フェノール性水酸基含有ポリアミド、及びその熱硬化性樹脂組成物 |
JP6370073B2 (ja) | 2013-04-26 | 2018-08-08 | 積水化学工業株式会社 | ポリビニルアセタール系樹脂組成物 |
SG11201701852VA (en) | 2014-09-11 | 2017-04-27 | Teijin Ltd | Thermosetting resin composition |
JP6766360B2 (ja) | 2016-01-15 | 2020-10-14 | 住友ベークライト株式会社 | 樹脂組成物 |
JP2017179311A (ja) * | 2016-03-31 | 2017-10-05 | 日立化成株式会社 | 樹脂組成物、プリプレグ、樹脂シート及び積層板 |
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JP6642342B2 (ja) | 2016-09-02 | 2020-02-05 | 信越化学工業株式会社 | 熱硬化性エポキシ樹脂組成物 |
JP7102093B2 (ja) * | 2016-09-28 | 2022-07-19 | 味の素株式会社 | 樹脂組成物、樹脂シート、回路基板及び半導体チップパッケージ |
EP3730552A4 (en) * | 2017-12-22 | 2021-08-25 | Teijin Limited | COMPOSITION OF THERMOSETTING RESIN |
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TW201638141A (zh) * | 2015-02-13 | 2016-11-01 | 三井化學股份有限公司 | 高分子壓電膜及其製造方法 |
TW201726801A (zh) * | 2015-08-04 | 2017-08-01 | 信越化學工業股份有限公司 | 熱硬化性環氧樹脂組成物 |
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