TWI593746B - 一種無鹵環氧樹脂組合物以及含有其之預浸料、層壓板和印刷電路板 - Google Patents

一種無鹵環氧樹脂組合物以及含有其之預浸料、層壓板和印刷電路板 Download PDF

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Publication number
TWI593746B
TWI593746B TW105115621A TW105115621A TWI593746B TW I593746 B TWI593746 B TW I593746B TW 105115621 A TW105115621 A TW 105115621A TW 105115621 A TW105115621 A TW 105115621A TW I593746 B TWI593746 B TW I593746B
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Taiwan
Prior art keywords
epoxy resin
halogen
resin composition
weight
parts
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TW105115621A
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English (en)
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TW201720869A (zh
Inventor
Hui Li
ke-hong Fang
Yong-Jing Xu
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Shengyi Technology Co Ltd
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Publication of TW201720869A publication Critical patent/TW201720869A/zh
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Description

一種無鹵環氧樹脂組合物以及含有其之預浸料、層壓板和印刷電路板
本發明屬於覆銅板技術領域，具體係關於一種無鹵環氧樹脂組合物以及含有其之預浸料、層壓板和印刷電路板。
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，並有較好的阻燃作用。隨著人們環保意識的提高及歐盟一系列指令的頒布，無鹵阻燃印刷線路板的開發成為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。
目前工業上普遍使用含磷樹脂來實現阻燃效果，但過多磷的引入會使基材吸水性高及耐化學性差等諸多問題。
近年來，以苯並噁嗪作為基體樹脂用於無鹵基材的開發越來越受到重視。苯並噁嗪是一類由氧原子和氮原子構成的苯並六元雜環體系，具有開環聚合的特點，聚合時無小分子釋放，聚合後形成類似酚醛樹脂的網狀結構，製品的固化收縮小，孔隙率低，有優良的力學、電學和阻燃性能。
另一方面，隨著電子工業的飛速發展，電子產品向輕、薄、短小、高密度化、安全化及高功能化發展，要求電子元件有更高的訊號傳 播速度及傳輸效率，這樣就對作為載體的印刷電路板提出了更高的性能要求。電子產品資訊處理的高速化及多功能化，應用頻率不斷提高，除了保持對層壓板材料的耐熱性有更高的要求外，對其介電常數和介質損耗值要求會越來越低。
現有之傳統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，而將與電子元件一起成為PCB和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及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。
為了解決上述問題，CN101684191B提出了使用苯並噁嗪、苯乙烯-馬來酸酐(SMA)、含磷固化劑複合固化環氧樹脂可以得到一種較低介電常數及介質損耗的固化物，SMA用量過多，雖然可以降低材料的介電常數值，但不可避免的會出現很多其他方面的問題，對黏結性影響尤其顯著，因為SMA分子結構中非極性的苯乙烯結構單元含量降低了改性基體樹脂的極性，削弱了樹脂與銅箔之間相互作用力；同時，因為SMA中大量的苯環結構增大了樹脂交聯網路的脆性，也對動態條件下黏結性能產生不利影響，從而降低了基材之間及基材與銅箔的黏結強度，且隨著電子工業的發展，對基材的耐熱性提出了更高的要求。
CN100523081C提出了使用苯並噁嗪、苯乙烯-馬來酸酐和其他固化劑複合固化含磷及無鹵無磷環氧組合物可以得到一種較低介電常數及介質損耗的固化物，但以含磷環氧作為主體樹脂，雖然可以達到優異的 阻燃性，但磷的過多引入，必然對基材的吸水性產生極大影響，這勢必會對基材的很多性能有負面影響。
CN103131131A提出了使用苯並噁嗪、苯乙烯-馬來酸酐和胺類固化劑複合固化環氧樹脂，可以得到一種較低介電常數及介質損耗的固化物，胺類固化劑的引入雖然可以提升基材的黏結性，但是勢必會造成基材耐熱性的下降，難以滿足高多層應用的需求。
CN103881302A提供了一種樹脂組合物及應用其的銅箔基板及印刷電路板。前述樹脂組合物包含環氧樹脂、苯並噁嗪樹脂、苯乙烯馬來酸酐共聚物以及聚酯，使用聚酯雖然具有較好的介電性能，但聚酯價格貴，且前述樹脂組合物使用了較多的苯並噁嗪，會使基材的脆性增加。
而且，以上苯並噁嗪、苯乙烯-馬來酸酐複合固化環氧樹脂的現有技術均沒有考慮苯並噁嗪及苯乙烯馬來酸酐的用量對預浸料在不同固化溫度條件下介質損耗值(Df)穩定性的影響，而穩定的Df值對與基材在終端的應用中訊號的穩定性傳輸具有重要意義。
針對現有技術的不足，本發明的目的之一在於提供一種無鹵環氧樹脂組合物，其通過將苯並噁嗪和苯乙烯-馬來酸酐(SMA)的量控制在合適的範圍，在保持低介電常數和低介質損耗的同時，確保了預浸料在不同固化溫度條件下Df值的穩定性，克服了目前苯並噁嗪和苯乙烯-馬來酸酐固化環氧樹脂體系Df隨固化溫度發生變化的缺點。
為了實現上述目的，本發明採用了以下技術手段： 一種無鹵環氧樹脂組合物，其特徵係其按重量份數包括如下組分：
環氧樹脂 60重量份
苯並噁嗪樹脂 15~28重量份
苯乙烯-馬來酸酐 10~20重量份。
本發明透過選擇15~28重量份的苯並噁嗪樹脂和10~20重量份的苯乙烯-馬來酸酐固化60重量份的環氧樹脂，可以在保持低介電常數、低介質損耗的同時，確保了預浸料在不同固化溫度條件下Df值的穩定性，克服了目前苯並噁嗪樹脂和苯乙烯-馬來酸酐固化環氧樹脂體系Df隨固化溫度發生變化的缺點。
苯並噁嗪樹脂有利於提高固化後樹脂及其製成的基材所需的阻燃性能、吸濕性、耐熱性、力學性能及介電性能。本發明通過對其添加量的選擇，使在所得基材具有上述性能的前提下，進一步保證了預浸料在不同固化溫度條件下Df值的穩定性，克服了目前苯並噁嗪和苯乙烯-馬來酸酐固化環氧樹脂體系Df隨固化溫度發生變化的缺點。在本發明中，前述苯並噁嗪樹脂的含量例如為16重量份、17重量份、18重量份、19重量份、20重量份、21重量份、22重量份、23重量份、24重量份、25重量份、26重量份、27重量份或28重量份。苯並噁嗪樹脂的添加量不足15重量份，則Tg和介電性能不佳，超過28重量份，則基材脆性增加且Df值會隨固化溫度而發生變化，Df值的穩定性降低。理想地，前述苯並噁嗪樹脂的添加量為20-25重量份。
在本發明中，前述苯乙烯-馬來酸酐的添加量例如為10重量 份、11重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份或20重量份。在本發明中，苯乙烯-馬來酸酐有利於改善基材的介電性能，在10至20重量份添加範圍內的苯乙烯-馬來酸酐含量，可使該無鹵環氧樹脂組成物具有較好的綜合性能。若苯乙烯-馬來酸酐的含量不足10重量份，則Tg低且達不到改善介電性能的作用，若超過20重量份，一方面會使基材的黏結性及阻燃性變差，另一方面基材Df值也會隨固化溫度而發生變化，Df值的穩定性降低。理想地，前述苯乙烯-馬來酸酐的添加量為15~18重量份。
理想地，前述無鹵環氧樹脂組合物，其按重量份數包括如下組分：
環氧樹脂 60重量份
苯並噁嗪樹脂 20~25重量份
苯乙烯-馬來酸酐 15~18重量份。
採用該理想的無鹵環氧樹脂組合物得到的基材除具有上述性能外，進一步具有更低的Df值以及更高的Tg。
理想地，前述無鹵環氧樹脂組合物進一步包括含磷阻燃劑。
理想地，前述含磷阻燃劑為含磷酚醛和磷氮基化合物。
理想地，前述含磷阻燃劑為10~40重量份的含磷酚醛和10~50重量份的磷氮基化合物。
在本發明中，前述含磷酚醛的含量例如為10重量份、11重量份、14重量份、17重量份、20重量份、23重量份、26重量份、29重量份、32重量份、35重量份或38重量份。含磷酚醛在低於10重量份時，阻燃性能 達不到V-0等級，而高於40重量份時，雖然能確保阻燃，但基材吸水率增加、Tg降低，且會影響基材的PCT性能。
在本發明中，前述磷氮基化合物的含量例如為10重量份、11重量份、14重量份、17重量份、20重量份、23重量份、26重量份、29重量份、32重量份、35重量份、38重量份、41重量份、44重量份、47重量份或49重量份。磷氮基化合物的添加量不足10重量份，則阻燃性不佳，超過50重量份則成本增加，而且，基材玻璃轉化溫度降低。
在本發明中，理想地，前述環氧樹脂包括選自雙酚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、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所成群中的任意一種或者至少兩種的混合物。
理想地，前述苯並噁嗪樹脂選自具有如下結構的苯並噁嗪樹脂中的任意一種或者至少兩種的組合：
其中，R2及R3為單取代或多取代，R2及R3各自獨立地為氫、甲基、烯丙基或醛基，R1為-CH2-、-O-、-C(CH3)2-、-SO2-、-C(CF3)2-、-CH2CH2-或雙環戊二烯基中的任意一種或者至少兩種的組合，R4及R5各自獨立地為烯丙基、未取代或取代的苯基、未取代或取代的碳原子數為1~8的烷基或未取代或取代的環烷基中的任意一種或者至少兩種的組合。
理想地，前述苯乙烯-馬來酸酐結構式為：
其中，x：n=0.8~19：1，理想為1~15：1，進一步理想為1~12：1。
理想地，前述苯乙烯馬來酸酐共聚物的數均分子量為1000~50000，理想為1500~45000，進一步理想為2000~40000。
示例性的苯乙烯-馬來酸酐如商品名SMA-1000、SMA-2000、SMA-3000、EF-30、EF-40、EF-60和EF-80等的馬來酸酐。
理想地，前述含磷酚醛選自9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)改性酚醛樹脂、10-(2,5-二羥基苯基)9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-HQ)改性酚醛樹脂或10-(2,9-二羥基萘基)9,10-二 氫-9-氧雜-10-膦菲-10-氧化物(DOPO-NQ)改性酚醛樹脂所成群中的任意一種或者至少兩種的混合物。
在本發明中，前述磷氮基化合物，是含有磷和氮原子的化合物，理想為具有如下結構的磷氮基化合物，其具有阻燃功能。無鹵樹脂組合物固化後形成的基材在燃燒時，該磷氮基化合物的磷原子會形成焦炭狀磷酸覆蓋於基材表面並阻隔空氣繼續進入，以阻斷燃燒。
其中，n為大於1的正整數。
在本發明的無鹵樹脂組成物中，添加磷氮基化合物的優點在於，可增加該無鹵環氧樹脂組成物及其固化物的阻燃性。本發明使用磷氮基化合物作為阻燃劑的主要優點在於，該磷氮基化合物不具有游離羥基(OH基)，因而添加在樹脂組成物內不會對該樹脂組成物的介電性能有負面影響。此外，該磷氮基化合物亦具有高磷含量(13%)、大於350℃的熱裂解溫度、良好的耐濕穩定性和低吸濕性，相較於傳統使用的一般含磷阻燃劑效果更好。
為進一步提高無鹵環氧樹脂組成物的阻燃性，理想地，本發明除了磷氮基化合物外，可進一步選擇性再添加如下無鹵阻燃劑，前述無鹵阻燃劑可選自聚磷酸銨、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、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯或三-羥乙基異氰尿酸酯所成群中的任意一種或者至少兩種的組合。
理想地，前述無鹵環氧樹脂組合物進一步包括20~100重量份的填料。前述填料的含量例如為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重量份或95重量份。
理想地，前述填料為有機或/及無機填料，主要起改善介電性能、降低熱膨脹係數、改善導熱性及降低成本的作用。
理想地，前述無機填料選自氫氧化鋁、氧化鋁、氫氧化鎂、氧化鎂、三氧化二鋁、二氧化矽(包括結晶型、熔融型、球形二氧化矽)、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所成群中的任意一種或者至少兩種的混合物。
理想地，前述有機填料選自聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末所成群中的任意一種或者至少兩種的混合物。
理想地，在本發明中，填料的粒徑為0.01~50μm。
為使前述填料在無鹵環氧樹脂組合物中分散均勻，可進一步添加分散劑，使用的分散劑為胺基矽烷偶聯劑或/和環氧基矽烷偶聯劑，用來改善無機以及織造玻璃布等增強材料間的結合性能，從而達到分散均勻的目的。而且，這類偶聯劑無重金屬存在，不會對人體產生不良影響，其使用量為填料重量的0.5-2%。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。
理想地，前述無鹵環氧樹脂組合物進一步包含固化促進劑，該固化促進劑選自咪唑類促進劑，理想地選自2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑所成群中的任意一種或者至少兩種的組合。
本發明前述的“包括”，意指其除前述組份外，還可以包括其他組份，這些其他組份賦予前述環氧樹脂組合物不同的特性。除此之外，本發明前述的“包括”，還可以替換為封閉式的“為”或“由......組成”。
例如，前述環氧樹脂組合物還可以含有各種添加劑，作為具體例，可以舉出抗氧劑、熱穩定劑、抗靜電劑、紫外線吸收劑、顏料、著色劑或潤滑劑等。這些各種添加劑可以單獨使用，也可以兩種或者兩種以上混合使用。
在本發明中，理想地，前述環氧樹脂組合物不包括胺類固化劑。這主要是由於，胺類固化劑的引入雖然可以提升基材的黏結性，但是會造成基材耐熱性的下降，難以滿足高多層應用的需求。
本發明的目的之二在於提供一種使用前述的無鹵環氧樹脂組合物製作的預浸料，前述預浸料包括增強材料及通過含浸乾燥後附著在增強材料上的如前述的無鹵環氧樹脂組合物。
前述增強材料為無紡或有紡玻璃纖維布等。
本發明的目的之三在於提供一種印刷電路板，其包括至少一張疊合的如上前述的預浸料。
本發明進一步提供了一種使用前述的預浸料製作的覆銅箔 層壓板，前述覆銅箔層壓板包括至少一張疊合的預浸料以及壓覆在疊合後的預浸料一側或兩側的銅箔。每一張預浸料包括增強材料及通過含浸乾燥後附著在增強材料上的無鹵環氧樹脂組合物。
與現有技術相比，本發明具有如下功效：
①本發明透過選擇15~28重量份的苯並噁嗪樹脂和10~20重量份的苯乙烯-馬來酸酐固化60重量份的環氧樹脂，可以在保持低介電常數和低介質損耗的同時，確保了預浸料在不同固化溫度條件下Df值的穩定性，克服了目前苯並噁嗪樹脂和苯乙烯-馬來酸酐固化環氧樹脂體系Df隨固化溫度發生變化的缺點。
②本發明以具有阻燃作用的苯並噁嗪樹脂作為固化劑，同時添加含磷酚醛和吸水率低的磷氮基化合物實現磷氮協同阻燃效應，在大大減少組分磷含量的同時提高了基材的阻燃性，且使基材具有較好的耐濕性。
③使用該樹脂組合物製備的預浸料及層壓板，具有低介電常數(1GHZ，3.9)、低介質損耗、優異的阻燃性(V-0或V-1)、耐熱性(Tg，DSC，178℃)、黏結性(剝離強度1.25N/mm)、低的吸水率(0.36%)及優異的耐濕性等綜合性能，克服了目前無鹵層壓板介電常數偏高、耐熱性不足以及耐濕性差等缺點，適合在無鹵高多層電路板中使用。
下面通過具體實施方式來進一步說明本發明的技術手段。
針對上述發明的預浸料及層壓板用樹脂組合物，測試200℃固化120min程序下的固化基材的剝離強度、玻璃轉化溫度、阻燃性、PCT 兩小時後耐浸焊極限、吸水率以及介電常數，測試不同固化溫度條件下的介質損耗性能，如下述實施例進一步給予說明與描述。
將含有環氧樹脂、苯並噁嗪、苯乙烯-馬來酸酐、含磷酚醛、磷氮基化合物、填料及其他助劑放入容器中，攪拌使其混合均勻，製成膠水，用溶劑調整溶液固體含量至60wt%-70wt%而製成膠液，即得到本發明樹脂組合物膠液。用2116電子級玻纖布浸漬膠水，經烘箱烘烤成預浸料，取6張2116預浸料，雙面再覆上35μm厚電解銅箔，在熱壓機作真空層壓，選擇的固化程序分別為190℃、200℃和210℃條件下固化120min，製成覆銅板。
實施例及比較例中所用各組分詳述如下：
(A)環氧樹脂
(A-1)NC-3000-H(日本化藥商品名)
(A-2)HP-7200H(大日本油墨商品名)
(B)苯並噁嗪
(B-1)D-125(四川東材科技集團股份有限公司商品名)
(B-2)LZ8280(亨斯曼先進材料商品名)
(C)苯乙烯-馬來酸酐低聚物：SMA-EF40(美國Sartomer商品名)
(D-1)雙氰胺：DICY(寧夏大榮商品名)
(D-2)聚酯：EXB-9460
(E)含磷酚醛樹脂
(E-1)XZ92741(DOW化學商品名)
(E-2)LC-950(SHIN-A公司商品名)
(F)磷氮基化合物：SPB-100(大塚化學商品名)
(G)填料：熔融二氧化矽
從表1~表3可以看出以下幾點：
透過實施例1和實施例2、7、8可知，固化劑優化後的配方具有更低的Df值及更高的Tg。
透過實施例2、7、8和實施例3可知，固化劑優化後的配方雖然Tg稍低但具有更高的剝離強度和更低的吸水率，即從實施例1-3、7、8可看出固化劑優化後的配方具有更好的綜合性能。
透過對比實施例2和實施例4、9可知，雖然添加含磷酚醛和磷氮基化合物後Tg稍降，但可以確保阻燃可達V-0而對其他性能影響不大，而添加填料對基材性能影響不大。
透過實施例4和比較例1-2可看出，苯並噁嗪在低於15重量份時Tg偏低，且介電性能較差，而高於28重量份時雖然具有較高的Tg，但加工性差且Df不穩定，隨固化溫度的升高而升高。
透過實施例5和對比例3-4可知，苯乙烯-馬來酸酐在低於10重量份時Tg不足，介質損耗性能較差，還會影響基材的加工性，而高於20重量份時雖然能提高Tg但阻燃不足，吸水率增加且Df不穩定，隨固化溫度的升高而升高。
透過實施例6和對比例5-6可知，含磷酚醛在低於10重量份時阻燃性能達不到V-0等級，而高於40重量份時雖然能確保阻燃，但會是基材吸水率增加、Tg降低，且會影響基材的PCT性能。
透過實施例5和對比例7-8可知，磷氮基化合物在低於10重量份時阻燃性能達不到V-0等級，而高於50重量份時雖然能保證阻燃，但會是基材Tg降低，且會影響基材的PCT性能及加工性。
對比例9
對比例9為CN 101684191B公開的實施例4。
對比例10
對比例10為CN103131131A公開的實施例1。
對比例11
對比例11為CN 103881302A公開的實施例2。
透過實施例1-9可以得出，採用本發明的無鹵樹脂組合物製備得到的層壓板，其介電性能較好，介質損耗值不隨固化溫度的升高而發生變化，達到阻燃性試驗UL-94中的V-0標準，因而，該層壓板在確保無鹵阻燃的同時，還具有低介電常數、低介質損耗、優異的耐熱性、黏結性及耐濕性等綜合性能，適合在無鹵高多層電路板中使用。即使用本發明樹脂組合物製備的預浸料及層壓板，具有低介電常數、低介質損耗、優異的阻 燃性、耐熱性、黏結性及耐濕性等綜合性能，克服了目前無鹵層壓板介電常數偏高，耐熱性不足，耐濕性差等缺點，適合在無鹵高多層電路板中使用。
申請人聲明，本發明透過上述實施例來說明本發明的詳細方法，但本發明並不侷限於上述詳細方法，即不意味著本發明必須依賴上述詳細方法才能實施。所屬技術領域之通常知識者應該明瞭，對本發明的任何改進，對本發明產品各原料的等效替換及輔助成分的添加、具體方式的選擇等，均落在本發明的保護範圍和公開範圍之內。

Claims (21)

  1. 一種無鹵環氧樹脂組合物，其特徵係其按重量份數包括如下組分：環氧樹脂 60重量份苯並噁嗪樹脂 15~28重量份苯乙烯-馬來酸酐 10~20重量份。
  2. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述苯並噁嗪樹脂的添加量為20-25重量份。
  3. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述苯乙烯-馬來酸酐的添加量為15~18重量份。
  4. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述無鹵環氧樹脂組合物，其按重量份數包括如下組分：環氧樹脂 60重量份苯並噁嗪樹脂 20~25重量份苯乙烯-馬來酸酐 15~18重量份。
  5. 如申請專利範圍第1或2項所記載之無鹵環氧樹脂組合物，其中，前述無鹵環氧樹脂組合物進一步包括含磷阻燃劑；前述含磷阻燃劑為含磷酚醛及磷氮基化合物。
  6. 如申請專利範圍第5項所記載之無鹵環氧樹脂組合物，其中，前述含磷阻燃劑為10~40重量份的含磷酚醛及10~50重量份的磷氮基化合物。
  7. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述環氧樹脂選自包括雙酚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、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所成群中的任意一種或者至少兩種的混合物。
  8. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述苯並噁嗪樹脂選自具有如下結構的苯並噁嗪樹脂中的任意一種或者至少兩種的組合： 其中，R2及R3為單取代或多取代，R2及R3各自獨立地為氫、甲基、烯丙基或醛基，R1為-CH2-、-O-、-C(CH3)2-、-SO2-、-C(CF3)2-、-CH2CH2-或雙環戊二烯基中的任意一種或者至少兩種的組合，R4及R5各自獨立地為烯丙基、未取代或取代的苯基、未取代或取代的碳原子數為1-8 的烷基或未取代或取代的環烷基中的任意一種或者至少兩種的組合。
  9. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述苯乙烯-馬來酸酐結構式為： 其中，x：n=0.8~19：1。
  10. 如申請專利範圍第9項所記載之無鹵環氧樹脂組合物，其中，前述苯乙烯馬來酸酐共聚物的數均分子量為1000~50000。
  11. 如申請專利範圍第5項所記載之無鹵環氧樹脂組合物，其中，前述含磷酚醛選自9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物改性酚醛樹脂、10-(2,5-二羥基苯基)9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物改性酚醛樹脂或10-(2,9-二羥基萘基)9,10-二氫-9-氧雜-10-膦菲-10-氧化物改性酚醛樹脂所成群中的任意一種或者至少兩種的混合物。
  12. 如申請專利範圍第5項所記載之無鹵環氧樹脂組合物，其中，前述磷氮基化合物為具有如下結構的磷氮基化合物： 其中，n為大於1的正整數。
  13. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述無鹵環氧樹脂組合物進一步包括無鹵阻燃劑，前述無鹵阻燃劑為選自聚磷酸銨、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、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯或三-羥乙基異氰尿酸酯所成群中的任意一種或者至少兩種的組合。
  14. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述無鹵環氧樹脂組合物進一步包括20~100重量份的填料；前述填料為有機或/及無機填料。
  15. 如申請專利範圍第14項所記載之無鹵環氧樹脂組合物，其中，前述無機填料選自氫氧化鋁、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所成群中的任意一種或者至少兩種的混合物；前述有機填料選自聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末中的任意一種或者至少兩種的混合物。
  16. 如申請專利範圍第14項所記載之無鹵環氧樹脂組合物，其中，填料的粒徑為0.01~50μm。
  17. 如申請專利範圍第1項所記載之無鹵環氧樹脂組合物，其中，前述無鹵環氧樹脂組合物包含固化促進劑，前述固化促進劑選自咪唑類促進劑。
  18. 如申請專利範圍第17項所記載之無鹵環氧樹脂組合物，其中，前述固化促進劑選自2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑所成群中的任意一種或者至少兩種的組合。
  19. 一種預浸料，其特徵係其包括增強材料及通過含浸乾燥後附著在增強材料上的如申請專利範圍第1至18項中任一項所記載之無鹵環氧樹脂組合物。
  20. 一種層壓板，其特徵係其包括至少一張疊合的如申請專利範圍第19項所記載之預浸料。
  21. 一種印刷電路板，其特徵係其包括至少一張疊合的如申請專利範圍第19項所記載之預浸料。
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