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TWI555793B - 一種熱固性樹脂組合物及用其製作之預浸料與層壓板 - Google Patents

一種熱固性樹脂組合物及用其製作之預浸料與層壓板 Download PDF

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Publication number
TWI555793B
TWI555793B TW104101388A TW104101388A TWI555793B TW I555793 B TWI555793 B TW I555793B TW 104101388 A TW104101388 A TW 104101388A TW 104101388 A TW104101388 A TW 104101388A TW I555793 B TWI555793 B TW I555793B
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Taiwan
Prior art keywords
parts
epoxy resin
weight
resin composition
thermosetting resin
Prior art date
Application number
TW104101388A
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English (en)
Other versions
TW201617400A (zh
Inventor
Hui Li
ke-hong Fang
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Shengyi Technology Co Ltd
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Priority claimed from CN201410633141.7A external-priority patent/CN104371321B/zh
Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Publication of TW201617400A publication Critical patent/TW201617400A/zh
Application granted granted Critical
Publication of TWI555793B publication Critical patent/TWI555793B/zh

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Description

一種熱固性樹脂組合物及用其製作之預浸料與層壓板
本發明涉及層壓板技術領域，具體涉及一種樹脂組合物，尤其涉及一種熱固性樹脂組合物及用其製作之預浸料，層壓板與印刷電路板。
隨著電子工業的飛速發展，電子產品向輕、薄、短小、高密度化、安全化、高功能化發展，要求電子元件有更高的訊號傳播速度及傳輸效率，因此就對作為載體的印刷電路板提出了更高的性能要求，電子產品訊息處理的高速化及多功能化，應用頻率不斷提高，3GHz以上將逐漸成為主流，除了保持對層壓板材料的耐熱性有更高的要求外，對其介電常數及介質損耗值要求會越來越低。
現有的傳統FR-4很難滿足電子產品的高頻及高速發展的使用需求，同時基板材料不再是扮演傳統意義下的機械支撐角色，而將與電子組件一起成為PCB及終端廠商設計者提升產品性能的一個重要途徑。因為高Dk會使訊號傳遞速率變慢，高Df會使訊號部分轉化為熱能損耗在基板材料中，因此具有低介電常數，低介質損耗的高頻傳輸，尤其是無鹵高頻板材的開發已成為覆銅箔層壓板行業的重點。
目前，含鹵阻燃劑(特別是溴系阻燃劑)被廣泛用於高分子 阻燃材料，並達到了較好的阻燃作用。然而人們對火災現場深入研究後得出結論：雖然含鹵阻燃劑的阻燃效果好，且所需添加量較少，但是採用含鹵阻燃劑的高分子材料在燃燒過程中會產生大量的有毒且具有腐蝕性的氣體和煙霧，使人窒息而死，其危害性比大火本身更為嚴重。因此，隨著歐盟《關於報廢電氣電子設備指令》和《關於在電氣電子設備中限制使用有害物質指令》於2006年7月1日的正式實施，無鹵阻燃印製線路板的開發成為了業內開發工作的重點，各覆銅箔層壓板的廠家都紛紛推出自己的無鹵阻燃覆銅箔層壓板。
為了解決上述問題，CN101796132B提出了使用環氧樹脂、低分子化的苯酚改性聚苯醚及氰酸酯組合物，該環氧樹脂組合物具備優異的介電特性，而且能夠維持阻燃性並具有高耐熱性。但該環氧組合物使用溴系阻燃劑阻燃，雖然具有較優異的綜合性能，但這些含有溴成份的阻燃劑於產品製造、使用甚至回收或丟棄時都很容易對環境造成污染，難以滿足綠色環保的使用要求。
CN103013110A提出了使用氰酸酯、苯乙烯-馬來酸酐、聚苯醚、雙馬來醯亞胺的固化物，並使用磷氮基化合物作阻燃劑可達到低介電常數、低介電損耗、高耐熱性及高耐燃性，但雙馬來醯亞胺固化溫度高，且其固化物較脆，在加工及使用過程中有許多不足。
因此，如何生產一種具有低介電常數、低介質損耗，同時保證其耐化學性優良之預浸料及層壓板是目前亟待解決的問題。
本發明的目的在於提供一種樹脂組合物，特別是一種熱固性樹脂組合物及用其製作之預浸料，層壓板與印刷電路板。
為達到此發明目的，本發明採用以下技術手段：第一方面，本發明提供了一種熱固性樹脂組合物，該組合物按重量份包括如下組分：氰酸酯50-150份；環氧樹脂30-100份；苯乙烯-馬來酸酐5-70份；聚苯醚20-100份；無鹵阻燃劑30-100份；固化促進劑0.05-5份；填料50-200份；本發明所採用的環氧樹脂至少含有一種如下化學結構式所示的具有雙環戊二烯烷基結構的環氧樹脂： 除了包含上述結構的環氧樹脂，本發明還可以選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、聯苯環氧樹脂、烷基酚醛環氧樹脂、雙環戊二烯環氧樹脂、雙酚A型酚醛環氧樹脂、鄰甲酚型酚醛環氧樹脂、苯酚型酚醛環氧樹脂、三官能環氧樹脂、四官能環氧樹脂、異氰酸酯改性環氧樹脂、萘型環氧樹 脂或含磷環氧樹脂中的任意一種或至少兩種的混合物。
在本發明中，所述環氧樹脂的含量為30-100重量份，例如可以是30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份、100重量份。
本發明的熱固性樹脂組合物中由於混入了環氧樹脂，可大大改善加工性能，該環氧樹脂組合物中包含了一種雙環戊二烯烷基結構的環氧樹脂，該環氧樹脂的雙環戊二烯結構的高度對稱及大體積結構有利於降低基材的介電性能，同時烷基結構的非極性及疏水性能不僅能進一步優化介電性能，且使基材吸水率大大降低。
本發明所採用的氰酸酯選自具有下述化學結構式中的至少一種： 其中X1、X2各自獨立為至少一個R、Ar、SO2或O；R選自-C(CH3)2-、-CH(CH3)-、-CH2-或經取代或未經取代的二環戊二烯基；Ar選自經取代或未經取代的苯、聯苯、萘、酚醛、雙酚A、雙酚A酚醛、雙酚F或雙酚F酚醛的任意一種；n為大於或等於1的整數；Y為脂肪族官能基或芳香族官能基。
在本發明中，所述氰酸酯的含量為50-150重量份，例如可以是50重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份、100重量份、105重量份、110重量份、115重量份、120重量份、125重量份、130重量份、135重量份、140重量份、145重量份、150重量份。
本發明的熱固性樹脂組合物中通過添加氰酸酯能顯著提升體系的耐熱性及介電性能。
本發明所採用的苯乙烯-馬來酸酐的化學結構式為：
其中，x為1-4，6，8；n為1-12；x，n均為整數。
在本發明中，所述苯乙烯-馬來酸酐的含量為5-70重量份，例如可以是5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份。
本發明所採用的聚苯醚為低分子量聚苯醚，數量平均分子量在1000-4000。
在本發明中，所述聚苯醚的含量為20-100重量份，例如可以是20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份、100重量份。
本發明的熱固性樹脂組合物通過添加聚苯醚可大大降低板材的介電常數及介質損耗，另外聚苯醚的使用還可以改善板材的韌性，對板材在高頻多層電路板中的使用有正面影響。
本發明所採用的無鹵阻燃劑為磷腈、聚磷酸銨、三(2-羧乙基)膦、三(異丙基氯)磷酸鹽、三甲基磷酸鹽、二甲基-甲基磷酸鹽、間苯二酚雙二甲苯基磷酸鹽、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羥乙基異氰尿酸酯、9，10-二氫-9-氧雜-10-磷雜菲-10-氧化物或含DOPO酚醛樹脂中的任意一種或至少兩種的混合物。
在本發明中，所述無鹵阻燃劑的含量為30-100重量份，例如可以是30重量份、35重量份、40重量份、45重量份、50重量份、60重量份、70重量份、80重量份、90重量份、100重量份。
本發明所採用的固化促進劑為咪唑、金屬鹽、三級胺或呱啶類化合物中的任意一種或至少兩種的混合物。
理想地，所述之固化促進劑為2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、1-氰乙基取代咪唑、苄基二甲基胺、乙醯丙酮鈷、乙醯丙酮銅或異辛酸鋅中的任意一種或至少兩種的混合物。
在本發明中，所述固化促進劑的含量為0.05-5重量份，例如可以是0.05重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份。
本發明所採用的填料為無機或有機填料。
理想地，所述之填料為無機填料，所述之無機填料為氫氧化鋁、氧化鋁、氫氧化鎂、氧化鎂、三氧化二鋁、二氧化矽、碳酸鈣、氮化鋁、氮化硼、碳化矽、二氧化鈦、氧化鋅、氧化鋯、雲母、勃姆石、煅燒滑石、滑石粉、氮化矽或煅燒高嶺土中的任意一種或至少兩種的混合物。
理想地，所述之填料為有機填料，所述之有機填料為聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末中的任意一種或至少兩種的混合物。
理想地，所述填料的粒徑為0.01-50μm，例如可以是0.01μm、0.05μm、1μm、5μm、10μm、15μm、20μm、25μm、30μm、40μm、50μm，較佳係為1-15μm，更佳係1-5μm。
為使所述之填料在本發明的樹脂組合物中分散均勻，還可以加入分散劑，使用的分散劑為氨基矽烷偶聯劑或環氧基矽烷偶聯劑，用來改善無機以及織造玻璃布間的結合性能，從而達到分散均勻的目的，且這類偶聯劑無重金屬存在，不會對人體產生不良影響，使用量為無機填料的 0.5-2%重量份，若使用量太高，則加快反應，影響儲存時間，用量太小，則無顯著改善結合穩定性的效果。
第二方面，本發明還提供了一種使用如本發明第一方面所述之熱固性樹脂組合物製作之預浸料，該預浸料包括基體材料；與通過浸漬乾燥後附著在其上的熱固性樹脂組合物。
本發明的基體材料為無紡或有紡玻璃纖維布。
第三方面，本發明還提供了一種層壓板，該層壓板包括如本發明第二方面所述之預浸料。
第四方面，本發明還提供了一種印刷電路板，其包含如本發明第三方面所述之層壓板。
與現有技術相對照，本發明具有以下之功效：採用本發明的熱固性樹脂組合物製作之預浸料及層壓板具有低介電常數及低介質損耗，其介電常數可控制在3.6以下，介質損耗在0.0041-0.0044之間，同時具有優異的阻燃性、耐熱性、耐濕性等綜合性能，其阻燃性可達到阻燃性試驗UL-94中的V-0標準，PCT吸水率為0.28-0.32，適合在無鹵高頻多層電路板中使用。
下面通過具體實施方式來進一步說明本發明的技術手段。
本領域技術人員應該明瞭，所述實施例僅僅是幫助理解本發明，不應視為對本發明的具體限制。
〔製備例、雙環戊二烯烷基苯酚環氧樹脂的合成〕
在裝有聚四氟乙烯攪拌器、溫度計、冷凝回流器的四口瓶(500mL)中加入270.0g對(1，1，3，3-四甲基)丁基苯酚在水浴加熱中溶化，稱取三氟化硼．乙醚1.83g，加入500mL四口燒瓶中，在滴液漏斗中加入50.1g雙環戊二烯，控制好滴加速度以便在2h內滴加完所有的雙環戊二烯，升溫至100℃，保溫4h，冷卻至室溫，再加熱至一定溫度蒸餾出過量的雙環戊二烯及對(1，1，3，3-四甲基)丁基苯酚，產物即為雙環戊二烯烷基苯酚樹脂。
將上一步所得雙環戊二烯烷基苯酚樹脂放入四口燒瓶，再稱取100.0g環氧氯丙烷緩慢加入，待其溶解後，開始升溫，並在滴液漏斗中加入1mol的質量分數為33%的KOH溶液，控制速度，使其在1h內滴加完，控制反應溫度在100℃，滴加完後保溫4h，冷卻後水洗，再升溫至120℃蒸餾，蒸出過量環氧氯丙烷，得到如下化學結構式所示的具有雙環戊二烯烷基苯酚環氧樹脂：
〔實施例、覆銅箔層壓板的製備方法〕
將氰酸酯、環氧樹脂、苯乙烯-馬來酸酐、聚苯醚、無鹵阻燃劑、固化促進劑、填料及溶劑等，放入容器中，攪拌使其混合均勻，製成膠水，用溶劑調整溶液固體含量至60%-70%而製成膠液，即得到熱固性樹脂組合物膠液，用2116電子級玻纖布浸漬膠水，經烘箱烘烤成半固化片，取6張2116半固化片，雙面再覆上35μm厚電解銅箔，在熱壓機作真空層壓，固化190℃/120min，製成覆銅板。
實施例1-6以及對比例1-5中所用的各組分及其含量(按重量份計)如表1所示，各組分代號及其對應的組分名稱如下所示：
(A)氰酸酯：HF-10(上海慧峰科貿商品名)
(B)環氧樹脂
(B-1)製備例中合成的雙環戊二烯烷基苯酚環氧樹脂
(B-2)聯苯型環氧樹脂：NC-3000-H(日本化藥商品名)
(B-3)雙環戊二烯型環氧樹脂：HP-7200H(大日本油墨商品名)
(C)苯乙烯-馬來酸酐低聚物：SMA-EF40(美國Sartomer商品名)
(D-1)低分子量聚苯醚：MX90(SABIC Innovative Plastics商品名)， 數量平均分子量1000-4000
(D-2)高分子量聚苯醚：Sabic640-111(SABIC Innovative Plastics商品名)數量平均分子量15000-20000
(E)無鹵阻燃劑
(E-1)PX-200(日本大八化學株式會社商品名)
(E-2)SPB-100(大塚化學株式會社商品名)
(G)固化促進劑
(H)填料：熔融二氧化矽
實施例1-6與對比例1-5採用的覆銅箔層壓板的製備方法與實施例相同。
採用以下方法對實施例1-6與對比例1-5製備的覆銅箔層壓板的玻璃化轉變溫度(Tg)、剝離強度(PS)、介電常數(Dk)及介質損耗角正切值(Df)、阻燃性和PCT2小時後耐浸焊性及吸水率進行測試，測試結果如表2所示。
各性能參數的測試方法如下：
A玻璃化轉變溫度(Tg)
根據差示掃描量熱法(DSC)，按照IPC-TM-650 2.4.25所規定的DSC方法進行測定；
B剝離強度(PS)
按照IPC-TM-650 2.4.8方法中的“熱應力後”實驗條件，測試金屬蓋層的剝離強度；
C介電常數(Dk)與介質損耗角正切值(Df)
使用條狀線的共振法，按照IPC-TM-650 2.5.5.5測定1GHz下的介電常數(Dk)與介質損耗角正切值(Df)；
D阻燃性
按照UL-94標準進行測試；E PCT 2小時後耐浸焊性及吸水率
將覆銅箔層壓板浸漬在銅蝕刻液中，除去表面銅箔評價基板；將基板放置在壓力鍋中，在121℃，2atm下處理2h，測試吸水率後，浸漬在溫度為288℃的錫爐中，當基材出現起泡或分裂時記錄相應的時間。當基材在錫爐中超過5min還沒有出現起泡或分層時結束評價。
從表1及表2的數據可以看出以下幾點：(1)通過實施例1-3可以看出，實施例1-3的PCT吸水率分別為0.32、0.31和0.28，實施例3的PCT吸水率最低，由此可以得出，隨著環氧樹脂(對應組分代號為B-1)含量的增加，基材的PCT吸水率逐漸下降，使其吸水率明顯改善；(2)通過實施例2與比較例1可以看出，實施例2的介電常數、介質損耗和PCT吸水率都低於比較例1，由此可以得出，實施例2採用本發明合成的雙環戊二烯烷基苯酚環氧樹脂相比比較例1中採用聯苯型環氧樹脂可以獲得更低的介電常數、介質損耗和PCT吸水率；(3)通過實施例3與比較例2可以看出，實施例3的介電常數、介質損耗及PCT吸水率都低於比較例2，由此可以得出，實施例3採用本發明合成的雙環戊二烯烷基苯酚環氧樹脂相比比較例2中採用商品化的雙環戊二烯環氧樹脂可以獲得更低的介電常數、介質損耗及PCT吸水率；(4)通過實施例5、實施例6與比較例3可以看出，所用組分需控制在一定重量份範圍才能使基材具有較優異的綜合性能，比較例3的介電性能與實施例5和實施例6相差不大，但不能通過2小時PCT測試，由此可以看出，比較例3在使用環氧樹脂低於30重量份時會影響到基材的2小時PCT測試；(5)通過實施例2與比較例4可以看出，實施例2的介電常數、介質損耗及PCT吸水率都低於比較例4，而且比較例4不能通過2小時PCT測試，由此可以看出，實施例2添加低分子量聚苯醚後相比比較例4未添加時，介電性能明顯改善，且能通過2小時PCT測試。將實施例2與對比例5相比可知，雖然兩者的綜合性能相當，但使用高分子量的聚苯醚導致加工性變差。
通過實施例1-6可以得出，採用本發明的熱固性樹脂組合物製備得到的層壓板，其介電常數可控制在3.6以下，介質損耗在0.0041-0.0044之間，同時具有優異的阻燃性、耐熱性、耐濕性等綜合性能，其阻燃性可達到阻燃性試驗UL-94中的V-0標準，PCT吸水率為0.28-0.32，適合在無鹵高頻多層電路板中使用。
綜上所述，本發明所提供的熱固性樹脂組合物，在保證無鹵阻燃的同時具有低介電常數、低介質損耗、優異的耐熱性、黏結性等綜合性能，適合在無鹵高頻多層電路板中使用。
當然，以上所述之實施例，只是本發明的較佳實例而已，並非用來限制本發明的實施範圍，故凡依本發明申請專利範圍所述之原理所做的等效變化或修飾，均包括於本發明申請專利範圍內。

Claims (13)

  1. 一種熱固性樹脂組合物，其特徵為其係按重量份包括如下組分：氰酸酯50-150份；環氧樹脂30-100份；苯乙烯-馬來酸酐5-70份；聚苯醚20-100份；無鹵阻燃劑30-100份；固化促進劑0.05-5份；填料50-200份；所述之環氧樹脂至少含有一種如下化學結構式所示之具有雙環戊二烯烷基結構之環氧樹脂： 所述之氰酸酯係選自具有下述化學結構式中的至少一種： 其中X1、X2各自獨立為至少一個R、Ar、SO2或O；R選自-C(CH3)2-、-CH(CH3)-、-CH2-或經取代或未經取代的二環戊二烯基；Ar選自經取代或未經取代的苯、聯苯、萘、酚醛、雙酚A、雙酚A酚醛、雙酚F或雙酚F酚醛的任意一種；n為大於或等於1的整數；Y為脂肪族官能基或芳香族官能基；所述之苯乙烯-馬來酸酐的化學結構式為： 其中，x為1-4，6，8；n為1-12；x，n均為整數；所述之聚苯醚數量平均分子量在1000-4000。
  2. 如申請專利範圍第1項所述之熱固性樹脂組合物，其中，所述之環氧樹脂還可以選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、聯苯環氧樹脂、烷基酚醛環氧樹脂、雙環戊二烯環氧樹脂、雙酚A型酚醛環氧樹脂、鄰甲酚型酚醛環氧樹脂、苯酚型酚醛環氧樹脂、三官能環氧樹脂、四官能環氧 樹脂、異氰酸酯改性環氧樹脂、萘型環氧樹脂或含磷環氧樹脂中的任意一種或至少兩種的混合物。
  3. 如申請專利範圍第1項所述之熱固性樹脂組合物，其中，所述之無鹵阻燃劑為磷腈、聚磷酸銨、三(2-羧乙基)膦、三(異丙基氯)磷酸鹽、三甲基磷酸鹽、二甲基-甲基磷酸鹽、間苯二酚雙二甲苯基磷酸鹽、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羥乙基異氰尿酸酯、9，10-二氫-9-氧雜-10-磷雜菲-10-氧化物或含DOPO酚醛樹脂中的任意一種或至少兩種的混合物。
  4. 如申請專利範圍第1項所述之熱固性樹脂組合物，其中，所述之固化促進劑為咪唑、金屬鹽、三級胺或呱啶類化合物中的任意一種或至少兩種的混合物。
  5. 如申請專利範圍第1項所述之熱固性樹脂組合物，其中，所述之固化促進劑為2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、1-氰乙基取代咪唑、苄基二甲基胺、乙醯丙酮鈷、乙醯丙酮銅或異辛酸鋅中的任意一種或至少兩種的混合物。
  6. 如申請專利範圍第1項所述之熱固性樹脂組合物，其中，所述之填料為無機或有機填料。
  7. 如申請專利範圍第6項所述之熱固性樹脂組合物，其中，所述之填料為無機填料，所述之無機填料為氫氧化鋁、氧化鋁、氫氧化鎂、氧化鎂、三氧化二鋁、二氧化矽、碳酸鈣、氮化鋁、氮化硼、碳化矽、二氧化鈦、氧化鋅、氧化鋯、雲母、勃姆石、煅燒滑石、滑石粉、氮化矽或煅燒高嶺土中的任意一種或至少兩種的混合物。
  8. 如申請專利範圍第6項所述之熱固性樹脂組合物，其中，所述之填料為有機填料，所述之有機填料為聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末中的任意一種或至少兩種的混合物。
  9. 如申請專利範圍第1項所述之熱固性樹脂組合物，其中，所述填料的粒徑為0.01-50μm。
  10. 一種使用如申請專利範圍第1至9項中任一項所述之熱固性樹脂組合物製作之預浸料，其特徵為所述預浸料係包括基體材料；與通過浸漬乾燥後附著在其上的熱固性樹脂組合物。
  11. 如申請專利範圍第10項所述之預浸料，其中，所述基體材料為無紡或有紡玻璃纖維布。
  12. 一種層壓板，其特徵為其係包含如申請專利範圍第10項所述之預浸料。
  13. 一種印刷電路板，其特徵為其係包含如申請專利範圍第12項所述之層壓板。
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US20170253013A1 (en) 2017-09-07
JP2018502938A (ja) 2018-02-01
TW201617400A (zh) 2016-05-16
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JP6420479B2 (ja) 2018-11-07
AU2014411037A1 (en) 2017-06-08
CN104371321A (zh) 2015-02-25
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