TWI651361B - Ｄｏｐｏ衍生物與環氧樹脂組合物於高頻基板上應用 - Google Patents

Ｄｏｐｏ衍生物與環氧樹脂組合物於高頻基板上應用 Download PDF

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TWI651361B
TWI651361B TW104127955A TW104127955A TWI651361B TW I651361 B TWI651361 B TW I651361B TW 104127955 A TW104127955 A TW 104127955A TW 104127955 A TW104127955 A TW 104127955A TW I651361 B TWI651361 B TW I651361B
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weight
parts
compound
epoxy resin
resin composition
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謝東穎
沈琦
呂榮哲
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大陸商江蘇雅克科技股份有限公司
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Abstract

一種複合材料、用其製作的高頻電路基板及其製作方法。該複合材料包含固體組分如下：DOPO(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)衍生化合物10-70重量份，固化劑10-50重量份，一種或多種環氧樹脂10-90重量份以及無機填充材10-40重量份。本發明的無鹵低介電樹脂組合物，採用了高純度的DOPO(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)衍生物以細微小顆粒分散於組成物中，不僅不會降低組合物的交聯程度，反而增加耐熱性與耐燃性。用該樹脂組合物所製成的印刷電路板用預浸料和覆銅箔層壓板，具有優良的介電性能，高玻璃化轉變溫度，可以滿足印刷電路覆銅板行業電子信號傳輸的高頻化和資訊處理的高速化需求。

Description

DOPO衍生物與環氧樹脂組合物於高頻基 板上應用
本發明涉及化學材料領域的阻燃劑，以DOPO的衍生化合物，用固化劑與環氧樹脂的環氧基進行反應，獲得對環境友好、低介電特性、耐熱性能優異的無鹵阻燃環氧樹脂固化組合物。
環氧樹脂本身的化學結構決定了其在反應性、強韌性、柔軟性等方面均有優異的性能，且具有良好的機械性能、電氣性能和尺寸穩定性；對於不同的基材而言，其粘結性也相當優越，固化後的環氧樹脂不僅能保持基材原來的特性，而且對於水、氣及化學物質更具阻隔性，且具有質輕、成本低等優點，所以環氧樹脂被廣泛應用於電子和航太工業，特別是半導體封裝材與印刷電路板基材等領域。另一方面，隨著科技日新月異，許多電腦資訊產業、通訊業及消費性電子產品，其變化非常的快。綜觀整個電子產業，其發展特色具有：1.使用的頻率越來越高；2.製造技術層次越來越高。
以印刷電路板而言，將朝低介電、低熱膨脹化、多層化、高耐熱化等方向發展，同時為符合環境友好之要求，電子、通訊產品亦趨向輕、薄、短小、高可靠度、多功能化與環保之需求。隨著無線網路、通訊器材使用的高頻化，高頻基板必成為未來發展趨勢。高頻通訊基板所使用的材料要求不外乎能夠快速傳送資料，並且在傳送的過程不會造成資料的損失或被干擾，因此在選取製作高頻通訊器材時必須具有以下幾個基本特性：(1)介電常數小而且穩定；(2)介電消耗因數必須小；(3)低吸水率；(4)抗化性佳；(5)耐熱性良好；(6)無鹵阻燃性需求。
相對來說，有機磷系阻燃劑因發煙量低，不易形成有毒氣體和腐蝕性氣體，具有環境友好性，被公認為可替代鹵系阻燃劑的重要品種。在環氧樹脂和板材領域，反應型的有機磷系阻燃劑，如DOPO衍生物，應用較為常見，它們透過共價鍵的方式連接到環氧樹脂上面，對材料的性能本身影響較小。而作為添加型的有機磷系阻燃劑，在環氧樹脂領域的應用則相對較少，因為它對阻燃劑的熔點和穩定性要求較高，一般的阻燃劑難以達到要求。
作為添加型的阻燃劑，以醚鍵連接的DOPO衍生物雖然有少量專利報導(參見日本專利申請特開平11[1999] -106619和日本專利申請特開P2001-270993A)。但對其合成方法研究得較少，且該製備方法產率低成本高。將其作為環氧樹脂組合物的阻燃劑應用在高頻載板上，也從未見報導。
本發明針對現有技術的不足，不僅提供了一種簡單、高效的DOPO衍生物製備方法，衍生物變得易於提純，且收率高、成本低。再將其透過與環氧樹脂組合物的搭配，可生產出具有低介電常數，高耐熱、耐燃性佳的電子材料可應用於印刷電路板使用。
DOPO衍生物的製備，其特徵在於化合物(B)與化合物(C)在催化劑、夾帶劑、溶劑的存在下，在一個大氣壓、150-220℃下脫水反應4-30小時制得化合物(A)。
化合物(A)的分子式為：
其中，R1，R2為氫、烷基、芳基或者雜環取代基(取代基上均不能與醇羥基反應的位點)；X為氧原子或無取代基，m和n分別為1-8；化合物(B)的分子式為：
其中，R1和R2的定義與上述相同；化合物(C)的分子式為：
其中，m、n和X的定義與上述相同。
反應式為：
化合物(C)和化合物(B)的投料莫耳比優選為0.4到3.0。比例太低，則化合物(B)轉換率難以提高；比例過高時，則單取代物增多，且面臨著化合物(C)的回收問題。
反應式中，催化劑為適用於脫水反應或著Arbuzov反應的催化劑，包含烷基鹵化物、鹼金屬鹵化物、鹼土金屬鹵化物、過度金屬鹵化物或者酸催化劑。具體的包含碘化鈉、溴化鈉、碘化鉀、溴化鉀、氯化鋰、溴化鋰、碘化鋰、C1-C6的烷基碘化物，C1-C6的烷基溴化物，氯化鐵、溴化鐵、氯化亞鐵、溴化亞鐵、氯化鎂、氯化鎳、溴化鎳、氯化鋁、氯化鈦、氯化錫、氯化鋅、銅粉、氯化銅、氯化鈷、溴化鍶、硫 酸、鹽酸、氯酸、高氯酸、磷酸、氫溴酸、氫氟酸，硝酸、草酸、烷基磺酸、聚合物磺酸的一種或組合。催化劑的用量為化合物(B)莫耳量的0.1-7.0%。
反應所需之溶劑為高沸點溶劑，也就是在常壓下 沸點大於150℃；熔點大於-100℃。具體包含二苯甲烷、二苯乙烷、二苯丙烷、聯苯、二苯醚、環乙基苯、乙二醇二甲醚、乙二醇二乙醚，或者上述化合物的混合物。
反應所需之夾帶劑為低沸點溶劑，即常壓下其沸 點小於150℃，具體包含苯、甲苯、二甲苯、二氯乙烷、氯仿、四氯化碳、戊烷、己烷、庚烷、辛烷、環己烷，或者它們的混合物。
化合物(A)的合成是透過化合物(B)的P-H鍵與化 合物(C)的-OH兩個活性位點之間進行反應，而化合物(B)的取代基R1與R2不參與反應，同時化合物(C)中的烷氧基鏈也不參與反應，因此R1、R2以及m、n的變化對反應條件都沒有太大影響。
在另一個實施方案中，反應後之DOPO衍生物可 為化合物(A-1)，結構式如下：
在另一個實施方案中，反應後之DOPO衍生物可 為化合物(A-2)，結構式如下：
在另一個實施方案中，反應後之DOPO衍生物可 為化合物(A-3)，結構式如下：
本發明複合材料樹脂組合物中，其所用之固化劑 包含酚類固化劑、胺類固化劑、酸類或酸酐固化劑，酯類固化劑，含磷固化劑中的一種或多種。
本發明複合材料樹脂組合物中，其所用之環氧樹 脂包含以下化合物中的至少一種：
(1)雙官能環氧樹脂，其包含雙酚A型環氧樹脂，雙酚F型環氧樹脂，聯苯型環氧樹脂，萘環型環氧樹脂，雙環戊二烯型環氧樹脂，氰酸酯型環氧樹脂。
(2)酚醛環氧樹脂，其包含本酚酚醛環氧樹脂，雙酚A酚醛環氧樹脂，鄰甲基酚醛環氧樹脂。
(3)含磷環氧樹脂，其包含二氫氧雜磷菲氧化物(DOPO)改性環氧樹脂，10-(2,5-二羥基萘基)二氫氧雜磷菲氧化物。
(4)萘環環氧樹脂。
(5)聯苯環氧樹脂。
上述環氧樹脂可根據用途單獨使用或混合使用，如使用聯苯型環氧樹脂、萘環型或鄰甲基酚醛型環氧樹脂則固化物具有較高的玻璃化轉變溫度與較好的耐熱性能。
本發明複合材料樹脂組合物中，其所用之無機填充材包含氫氧化鋁、沸石、矽灰石、二氧化矽、氧化鎂、矽酸鈣、碳酸鈣、粘土、滑石及雲母中的一種或多種。
使用該上述的複合材料樹脂組合物磷含量控制在1-5%，以該組合物制得預浸料，包含基料與透過含浸泡乾燥後附著其上的複合材料樹脂組合物，其使用織物或無紡織物為基料，例如天然纖維，有機合成纖維以及無機纖維均可採用。本發明組合物為常規的製備方法，先行將固形物放入，然後加溶劑，所用溶劑可以是丙酮、丁酮、環己酮、乙二醇甲醚、丙二醇甲醚、丙二醇甲醚醋酸酯等中的一種或多種，攪拌直到完全溶解後，再加入液態樹脂，繼續攪拌均勻平衡即可。將上述的組合物加到一個容器中，將促進劑、固化劑先溶解在一定的丁酮溶劑中，用丁酮溶劑適當調整溶液的固體含量65%至75%而製成膠液，使用玻璃纖維布等之物或有機物韓進該膠液，將浸好的玻璃纖維布在170℃的烘箱中烘3-5分鐘，即製成預浸料。
上述複合材料組合物製作的覆銅箔層壓板，包含多個疊合的預浸料，每一個預浸料包含基料及透過含浸泡乾燥之後附著在基料上面的複合材料樹脂組合物。
本發明的印刷電路板用覆銅箔層壓板，透過加熱 和加壓，使用兩片或兩片以上的預浸料粘合在一起而製成的層壓板，在層壓板的一面或兩面覆合上銅箔製成。所述的覆銅層壓板須滿足以下要求：1.層壓的升溫速率通常在料溫80-170℃時的升溫速率應控制在1-3℃/min；2.層壓的壓力設置，外層料溫在80-100℃時施加滿壓，滿壓壓力為250psi左右；3.固化時，控制料溫在180℃，並持溫120min；所覆蓋的金屬箔除銅箔外，還可以是鋁箔等，其材質不限。
具體實施製成的印刷電路用覆銅箔層壓板(8片 黏結片)測其界電損耗因數，耐熱性、吸水性、玻璃化轉變溫度、阻燃性等性能，如下述實施例進一步給予詳加說明與描述。
為了使本揭示內容的敘述更加詳盡與完備，下文 針對了本發明的實施態樣與具體實施例提出了說明性的描述；但這並非實施或運用本發明具體實施例的唯一形式。以下所揭露的各實施例，在有益的情形下可相互組合或取代，也可在一實施例中附加其他的實施例，而無須進一步的記載或說明。在以下描述中，將詳細敘述許多特定細節以使讀者能夠充分理解以下的實施例。然而，可在無此等特定細節之情況下實踐本發明之實施例。
茲將本實施例詳細說明如下，但本發明並非局限 在實施例範圍。
實施例與比較例中所用的各成分詳述如下：
環氧化聚丁二烯：
(A)環氧化聚丁二烯
苯并噁嗪：
(B)烯丙基苯并噁嗪
環氧樹脂：
(C-1)鄰甲基酚醛環氧樹脂
(C-2)雙環戊二烯環氧樹脂
硬化劑：
(D-1)苯乙烯-馬來酸酐低聚物SMA-FE40
(D-2)含磷固化劑DHP-60H
添加型阻燃劑：
(E-1)苯氧基磷晴SPB-100
(E-2)化合物(A-1)
(E-3)化合物(A-2)
(E-4)化合物(A-3)
(E-5)磷酸酯阻燃劑OP-935
固化促進劑：
(F)2-甲基-4乙基咪侳
無機填充材：
(G)球型矽微粉
膠水組合物配方：
物性評估表：
以上物性的測試方法如下：
(1)玻璃化轉移溫度：使用升溫速率=20℃/min微差掃瞄熱分析儀(DSC)測試。
(2)剝離強度：將試片裁為長方形，放入測試設備中，以一定速度與拉力測試金屬覆蓋層的剝離強度。
(3)耐燃性：試片裁成0.5in×4.7in長方形，以焰高2cm之藍色火焰燃燒10秒後移開，共燒兩次後，紀錄火焰移開後之自熄時間。
(4)熱安定性：將試片裁切磨平後，放入熱重分析儀(TMA)測試。
(5)吸水性：試樣在120℃及2atm高壓鍋中加熱30分鐘。
(6)電氣特性：將已蝕刻後基板裁成5cm2正方形試片，於105℃烘箱內烘2hr後，取出以板厚測定儀量測試片三處的板厚。再將試片夾入介電測量儀中，測三點的資料後取平均值。
(7)T288爆板：試樣在120℃及2atm高壓鍋中加熱120分鐘後，浸在288℃的焊錫槽中20秒，以肉眼觀察有無分層。
綜合上述結果可知，依照本發明可達到低介電， 耐燃佳，吸水率低的特性。本發明同時也充分利用環氧化聚丁二烯、苯並惡螓、環氧樹脂、硬化劑之協同效應，而且應用無鹵素板材，也能符合環保要求。以上所述，僅為本發明的較佳實施例，對於本領域的普通技術人員來說，可根據本發明的技術方案與構思做出其他各種相應的變化，而這些變化都屬於本發明權利要求的保護範圍。

Claims (4)

  1. 一種複合材料樹脂組合物，其包含：DOPO衍生化合物8-9重量份，其中該DOPO衍生化合物具有以下結構： 其中，R1，R2為氫、烷基、芳基或者雜環取代基(取代基上均不能與醇羥基反應的位點)；X無取代基(碳-碳係直接相連)，當m為1-8時，n為8，或當m為8時，n為1-8；其中，所述DOPO衍生化合物是由化合物(B)與化合物(C)在催化劑、夾帶劑、溶劑的存在下，在1-6個大氣壓、150-220℃下脫水反應製備；其中，化合物(B)具有以下結構： 其中，R1和R2的定義與上述相同；其中，化合物(C)的具有以下結構： 其中，m、n和X的定義與上述相同，所述的催化劑 為適用於脫水反應或者Arbuzov反應的催化劑；環氧化聚丁二烯15-50重量份；烯丙基苯并噁嗪22-42重量份；固化劑18重量份，其中該固化劑包含苯乙烯-馬來酸酐低聚物；環氧樹脂12-24重量份，其中該環氧樹脂包含鄰甲基酚醛環氧樹脂及雙環戊二烯環氧樹脂；以及無機填充材10-40重量份。
  2. 一種利用如請求項1所述之複合材料樹脂組合物製作的預浸料，包含基料以及透過包含浸泡乾燥後附著其上的複合材料樹脂組合物。
  3. 如請求項2所述之預浸料，其中該基料為織物或無紡織物。
  4. 一種利用如請求項2所述之複合材料樹脂組合物製作的預浸料製備的覆銅層壓板，包含多個疊合的預浸料，及壓覆在疊合的預浸料的一面或兩面上的銅箔，每一預浸料包含基料及透過含浸泡乾燥之後附著在基料上的複合材料樹脂組合物。
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