TW201823346A - 一種含有苯並噁嗪的樹脂組合物的製備方法及由其製成的預浸料和層壓板 - Google Patents

一種含有苯並噁嗪的樹脂組合物的製備方法及由其製成的預浸料和層壓板 Download PDF

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TW201823346A
TW201823346A TW106116372A TW106116372A TW201823346A TW 201823346 A TW201823346 A TW 201823346A TW 106116372 A TW106116372 A TW 106116372A TW 106116372 A TW106116372 A TW 106116372A TW 201823346 A TW201823346 A TW 201823346A
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Taiwan
Prior art keywords
benzoxazine
resin
resin composition
weight
epoxy
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TW106116372A
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TWI628223B (zh
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奚龍
李江
許永靜
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廣東生益科技股份有限公司
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Abstract

本發明關於一種含有苯並噁嗪的樹脂組合物的製備方法及由其製成的預浸料和層壓板，前述含有苯並噁嗪的樹脂組合物的製備方法為：向含有苯並噁嗪的樹脂組合物中添加酸性填料；前述含有苯並噁嗪的樹脂組合物中含有苯並噁嗪樹脂以及環氧當量介於150~450之間的環氧樹脂A1和環氧當量介於451~1000之間的環氧樹脂A2。本發明通過在樹脂組合物中添加酸性填料，極大地促進了苯並噁嗪和環氧樹脂的聚合反應，降低苯並噁嗪和環氧聚合所需的固化溫度；使用該添加有酸性填料的樹脂組合物製作的層壓板具有高的抗剝穩定性、高玻璃轉化溫度、低吸水率、高耐熱性、高彎曲強度和良好的工藝加工性，並能實現低熱膨脹係數。

Description

一種含有苯並噁嗪的樹脂組合物的製備方法及由其製成的預浸料和層壓板
本發明關於覆銅板技術領域，尤其關於一種含有苯並噁嗪的樹脂組合物的製備方法及由其製成的預浸料和層壓板。
在電子材料行業，為實現無溴阻燃，業內通常採用含磷的樹脂或阻燃劑，配合含氮的樹脂或阻燃劑實現磷-溴協同高效阻燃。苯並噁嗪樹脂中含有氮元素，與磷元素複配使用時，能以較低的磷含量實現UL 94的V-0等級。加上固化收縮率低，耐濕熱性能佳，得到了廣泛使用。然而，由於苯並噁嗪樹脂結構特點，苯並噁嗪的開環聚合需要較高的溫度，為工業化大量生產帶來困難，成為其應用的難點。
業內學者對上述難題進行了很多研究，其工作主要集中在胺類固化劑，酚醛樹脂，有機酸等物質對苯並噁嗪反應的影響和機理探討。對於印製電路基板(覆銅板，copper clad laminate)行業而言，這些研究成果很難直接進行轉化應用。原因在於：胺類固化劑耐熱性不佳，製成的半成品儲存期限較短；酚醛樹脂雖然耐熱性較好，介電性能較差，剝離強度較低；有機酸對苯並噁嗪的開環作用明顯，在覆銅板生產過程中，最高超過200℃的烘箱溫度促使低沸點酸揮發完畢，在壓合製程無法催化苯並噁嗪 的開環和聚合。而高沸點有機酸則會在樹脂組合物中殘留，在製作過程中增加了PCB板受熱分層爆板的風險。因此，對於苯並噁嗪樹脂的應用，一直存在難題。
基於此，本發明的目的之一在於提供含有苯並噁嗪的樹脂組合物的製備方法及由其製成的預浸料和層壓板。通過在含有苯並噁嗪的樹脂組合物中添加酸性填料，極大地促進了苯並噁嗪和環氧樹脂的聚合反應，降低了苯並噁嗪和環氧聚合所需的固化溫度；使用該添加有酸性填料的組合物製作的層壓板具有高的抗剝穩定性、高玻璃轉化溫度、低吸水率、高耐熱性、高彎曲強度和良好的工藝加工性，並能實現低熱膨脹係數。
發明人為實現上述目的，進行了反復深入的研究，結果發現：通過將酸性填料與含有苯並噁嗪的樹脂組合物適當混合從而進行樹脂組合物的製備，可達到上述目的。
為了實現上述目的，本發明採用了如下技術方案：一種含有苯並噁嗪的樹脂組合物的製備方法，前述方法為：向含有苯並噁嗪的樹脂組合物中添加酸性填料，酸性填料的pH值在2~6之間；前述含有苯並噁嗪的樹脂組合物中含有環氧樹脂和苯並噁嗪樹脂； 前述環氧樹脂含有環氧當量介於150~450之間的環氧樹脂A1和環氧當量介於451~1000之間的環氧樹脂A2。
本發明中通過向含有苯並噁嗪的樹脂組合物中添加酸性填料，可以催化苯並噁嗪和環氧樹脂的開環聚合反應，又能促進苯並噁嗪自身交聯聚合，極大地降低苯並噁嗪和環氧聚合所需的溫度；另外，酸性填料的熔點可高達1000℃以上，在覆銅板生產過程中受熱不會揮發，在PCB加工中也不會分解，解決有機酸和普通無機酸在樹脂中的弱點；此外，酸性填料在樹脂組合物中能降低製品的CTE，其在樹脂組合物中保留下來對製品的可靠性有益。
本發明還採用不同結構和不同環氧當量的環氧樹脂進行配合使用，其在保證樹脂組合物具有較高玻璃轉化溫度，較好的力學性能，較低吸水率的同時，還改善了樹脂組合物機械加工性差的難題。
根據本發明，前述酸性填料的pH值在2~6之間，例如2、2.5、3、3.5、4、5或6，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
本發明中，前述酸性填料的特徵是：將該填料與去離子水按1：9的質量比配製成水溶液，對其進行測定從而得到該填料的pH值在2~6之間。
理想地，前述酸性填料的pH值在4~6之間。
根據本發明，前述酸性填料選自矽微粉、石英粉、雲母粉、黏土、草酸鈣或炭黑中的任意一種或至少兩種的混合物，其中典型但非限制性的混合物為矽微粉和石英粉、黏土和草酸鈣、炭黑和雲母粉。
本發明中，前述酸性填料的粒徑在50nm~50μm之間，例如50nm、60nm、70nm、80nm、90nm、100nm、300nm、500nm、800nm、5μm、10μm、30μm、40μm、45μm或50μm，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
對於前述酸性填料的物理形態，本發明不做特殊限定，例如可以是片材、棒狀、球形、空心球形、粒狀、纖維狀或板狀等；也可以選擇性以矽烷偶聯劑對酸性填料進行處理。
根據本發明，以前述含有苯並噁嗪的樹脂組合物中有機固形物為100重量份計，前述酸性填料的添加量為0.05~100重量份，例如0.05重量份、0.1重量份、1重量份、10重量份、20重量份、30重量份、40重量份、55重量份、60重量份、65重量份、70重量份、80重量份、90重量份或100重量份，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
理想地，以前述含有苯並噁嗪的樹脂組合物中有機固形物為100重量份計，前述酸性填料的添加量為5~60重量份。
本發明採用酸性填料的添加量為5~60作為較佳方式，經發明人研究發現，若前述填料使用量超過60重量份，樹脂組合物整體酸性較強，苯並噁嗪-環氧體系的開環聚合反應明顯加快，會使得樹脂組合物的加工工藝視窗變窄；若前述酸性填料使用量低於5份，樹脂組合物整體酸性較弱，對苯並噁嗪-環氧體系的催化作用不明顯。
根據本發明，前述含有苯並噁嗪的樹脂組合物中，以有機固形物為100重量份計，含有如下組分： (A)環氧樹脂：5~80重量份；(B)苯並噁嗪樹脂：10~80重量份；(C)阻燃劑：1~30重量份；前述環氧樹脂中，環氧樹脂A1和A2的重量比為10：1~1：10，例如10：1、10：2、10：3、10：4、10：5、10：6、10：7、10：8、10：9、1：1、1：2、1：3、1：4、1：5、1：6、1：7、1：8、1：9或1：10，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值，理想為4：1~1：4。
本發明中，前述環氧樹脂的添加量為5~80重量份，例如5重量份、7重量份、10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份或80重量份，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值，理想為20~80重量份。
根據本發明，前述環氧樹脂含有環氧當量介於150~450之間的環氧樹脂A1和環氧當量介於451~1000之間的環氧樹脂A2。
本發明通過採用不同環氧當量的環氧樹脂進行組合，其不僅保證樹脂組合物具有較高的玻璃轉化溫度、較好的力學性能和較低的吸水率，同時還改善樹脂組合物機械性差的問題。
本發明中，前述環氧樹脂A1選自聯苯環氧樹脂、雙環戊二烯環氧樹脂、酚醛型環氧樹脂、含萘環氧樹脂或含蒽環氧樹脂中的任意一種或至少兩種的混合物，且環氧當量介於150~450之間；其中典型但非限制性的混合物為：聯苯環氧樹脂和雙環戊二烯環氧樹脂、雙環戊二烯環氧樹 脂和含萘環氧樹脂、含萘環氧樹脂和含蒽環氧樹脂；前述環氧當量例如可以是150、180、192、200、210、250、315、380、400或450，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
本發明中，前述環氧樹脂A2選自雙酚A環氧樹脂、雙酚F環氧樹脂、羧基丁腈橡膠改性環氧樹脂或含有噁唑烷酮環的環氧樹脂中的任意一種或至少兩種的混合物，且環氧當量介於451~1000之間；其中典型但非限制性的混合物為：雙酚A環氧樹脂和羧基丁腈橡膠改性環氧樹脂、羧基丁腈橡膠改性環氧樹脂和含有噁唑烷酮環的環氧樹脂；前述環氧當量例如可以是451、455、480、492、500、610、720、810、861、900或1000，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
本發明中通過環氧樹脂的選擇搭配，以及酸性填料對苯並噁嗪開環聚合反應的引導和控制，其相互之間產生協同作用，有助於實現較穩定的剝離強度，提升樹脂組合物的可靠性。
根據本發明，前述苯並噁嗪樹脂的添加量為10~80重量份，例如10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份或80重量份，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值，理想為30~65重量份。
本發明中，前述苯並噁嗪樹脂選自雙酚A型苯並噁嗪樹脂、雙環戊二烯型苯並噁嗪樹脂、雙酚F型苯並噁嗪樹脂、酚酞型苯並噁嗪樹脂 或MDA型苯並噁嗪樹脂中的任意一種或至少兩種的混合物，其中典型但非限制性的混合物為：雙酚A型苯並噁嗪樹脂和雙環戊二烯型苯並噁嗪樹脂、雙環戊二烯型苯並噁嗪樹脂和雙酚F型苯並噁嗪樹脂、雙酚F型苯並噁嗪樹脂和酚酞型苯並噁嗪樹脂。
前述雙酚A型苯並噁嗪樹脂單體和雙酚F型苯並噁嗪樹脂單體、酚酞型苯並噁嗪樹脂單體的結構如式(α)所示：
其中，R3為，R4為、-CH2-或中的任意1種。
當R4為時，結構式(α)為雙酚A型苯並噁嗪樹脂單體；當R4為-CH2-時，結構式(α)為雙酚F型苯並噁嗪樹脂單體；當R4為時，結構式(α)為酚酞型苯並噁嗪樹脂單體。
前述MDA型苯並噁嗪樹脂，又稱(4,4’-二胺基二苯甲烷)型苯並噁嗪樹脂，其結構如式(β)所示： 式(β)
前述雙環戊二烯苯並噁嗪樹脂單體的結構式如(γ)所示：
根據本發明，前述阻燃劑的添加量為1~30重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份或30重量份，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值，理想為3~20重量份。
本發明中，前述阻燃劑選自間苯二酚-雙(磷酸二苯酯)、雙酚A-雙(磷酸二苯酯)、間苯二酚-雙(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一種或至少兩種的混合物，其中典型但非限制性的混合物為：間苯二酚-雙(磷酸二苯酯)和雙酚A-雙(磷酸二苯酯)、雙酚A-雙(磷酸二苯酯)和間苯二酚-雙(2,6-二甲苯基磷酸酯)、間苯二酚-雙(2,6-二甲苯基磷酸酯)和甲基磷酸二甲酯、甲基磷酸二甲酯和磷腈化合物。
本發明中，前述含有苯並噁嗪的樹脂組合物中還含有環氧當量大於1000的環氧樹脂，其具體種類在此不做特殊限定。
理想地，前述含有苯並噁嗪的樹脂組合物中還可以含有非酸 性填料。
理想地，前述非酸性填料選自碳酸鈣、硫酸鈣、氧化鋁、硫酸鋇、陶瓷粉、滑石粉或水滑石中的任意一種或至少兩種的混合物，其中典型但非限制性的混合物為：碳酸鈣和硫酸鈣、氧化鋁和硫酸鋇、陶瓷粉和水滑石。
理想地，以有機固形物為100重量份計，前述非酸性填料的添加量為0~100重量份，例如1重量份、5重量份、12重量份、15重量份、24重量份、35重量份、48重量份、56重量份、78重量份、89份或100重量份，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
根據本發明，前述含有苯並噁嗪的樹脂組合物中還可以含有(D)固化促進劑，以前述含有苯並噁嗪的樹脂組合物中有機固形物為100重量份計，前述固化促進劑的添加量為0.1~1重量份，例如0.1重量份、0.2重量份、0.3重量份、0.4重量份、0.5重量份、0.6重量份、0.7重量份、0.8重量份、0.9重量份或1重量份，以及上述數值之間的具體點值，限於篇幅及出於簡明的考慮，本發明不再窮盡列舉前述範圍包括的具體點值。
本發明中，前述固化促進劑選自咪唑類促進劑及其衍生物，吡啶類促進劑，路易士酸類促進劑中的任意一種或至少兩種的混合物，其中典型但非限制性的混合物為咪唑類促進金和吡啶類促進劑、吡啶類促進劑和路易士酸類促進劑、咪唑類促進劑和路易士酸類促進劑。
理想地，前述咪唑類促進劑選自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一種或至少兩種的混合物。
前述固化促進劑有益於環氧樹脂和苯並噁嗪樹脂以及固化劑進行固化反應，形成均勻的三維網狀分子結構，達到較佳的物性。並能促進羥基(-OH)和環氧基等基團濃度的下降，說明樹脂組合物實現較佳的介電性能，降低介電常數和介電損耗。
本發明的目的之二在於提供一種含有苯並噁嗪的樹脂組合物，其含有環氧樹脂、苯並噁嗪樹脂和酸性填料，前述酸性填料的pH值在2~6之間，前述環氧樹脂含有環氧當量介於150~450之間的環氧樹脂A1和環氧當量介於451~1000之間的環氧樹脂A2。
本領域技術人員可以理解，前述含有苯並噁嗪的樹脂組合物中除了包含環氧樹脂、苯並噁嗪樹脂和酸性填料外，還可以任選地含有本發明目的之一前述的阻燃劑、環氧當量大於1000的環氧樹脂、非酸性填料、固化促進劑等組分，且前述樹脂組合物中含有的各個組分和含量均可示例性地參考本發明目的之一所記載的範圍。
本發明前述的「含有」，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樹脂組合物不同的特性。除此之外，本發明前述的「含有」，還可以替換為封閉式的「為」或「由......組成」。
例如，前述含有苯並噁嗪的樹脂組合物可以進一步含有各種添加劑，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。這些添加劑可以單獨使用，也可以兩種或者兩種以上混合使用。
對於本發明中未進一步限定的含有苯並噁嗪的樹脂組合物的製備步驟，本領域技術人員可以參考現有的樹脂組合物的製備方法，結 合實際情況進行選擇，本發明不做特殊限定。
本發明進一步提供一種預浸料，其含有根據本發明目的之一所記載之方法製備得到的樹脂組合物或目的之二前述的樹脂組合物，以及增強材料；所使用的增強材料無特別的限定，可以為有機纖維、無機纖維編織布或無紡布。前述的有機纖維可以選擇芳綸無紡布，前述的無機纖維編織布可以為E-玻纖布、D-玻纖布、S-玻纖布、T玻纖布、NE-玻纖布或石英布。前述增強材料的厚度無特別限定，處於層壓板有良好的尺寸穩定性的考慮，前述編織布及無紡布厚度理想為0.01~0.2mm，且最好是經過開纖處理及矽烷偶聯劑表面處理的，為了提供良好的耐水性和耐熱性，前述矽烷偶聯劑理想為環氧矽烷偶聯劑、胺基矽烷偶聯劑或乙烯基矽烷偶聯劑中的任意一種或至少兩種的混合物。將增強材料通過含浸上述的複合材料，在100~250℃條件下，烘烤1~15分鐘得到前述預浸料。
本發明的印刷電路板用覆銅箔層壓板包括通過加熱和加壓，使兩片或兩片以上的預浸料黏合在一起而製成的層壓板、黏合在層壓板的一面或兩面以上的銅箔；前述的覆銅箔層壓需滿足以下要求：1、層壓的升溫速率通常在料溫80-160℃時的升溫速度應控制在1.0~3.0℃/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300psi左右；3、固化時，控制料溫在185℃，並保溫90min；所覆蓋的金屬箔除銅箔外，亦可以是鎳箔、鋁箔及SUS箔等，其材質不限。
與現有技術相比，本發明至少具有以下功效： (1)本發明通過在樹脂組合物中添加酸性填料，極大地促進苯並噁嗪和環氧樹脂的聚合反應，降低苯並噁嗪和環氧聚合所需的固化溫度，使苯並噁嗪和環氧的反應更完全；(2)本發明通過使用該添加有酸性填料的樹脂組合物製作的層壓板具有高的抗剝穩定性、高玻璃轉化溫度、低吸水率、高耐熱性、高彎曲強度和良好的工藝加工性，並能實現低熱膨脹係數；(3)本發明通過採用不同結構和不同環氧當量的環氧樹脂進行配合，不僅保證樹脂組合物具有較高玻璃轉化溫度，較好的力學性能和較低吸水率，且進一步改善樹脂組合物機械加工性差的難題；(4)本發明通過對環氧樹脂的選擇搭配以及酸性填料的添加，其相互間可產生協同增效作用，從而有助於實現較穩定的剝離強度，提升樹脂組合物的可靠性。
以下透過具體實施方式來進一步說明本發明的技術手段。
以下前述是本發明實施例的具體實施方式，應當指出，對於所屬技術領域之通常知識者而言，在不脫離本發明實施例原理的前提下，可進一步做出若干改進及潤飾，這些改進及潤飾也視為本發明實施例的保護範圍。
下面分多個實施例對本發明實施例進行進一步的說明。本發明實施例不限定於以下的具體實施例。在不改變請求項之範圍內，可以適當的進行變更實施。
下文中如無特別說明，其份代表重量份，其%代表「重量%」。
實施例和對比例中相關的材料及牌號資訊如下：
(A)環氧樹脂：A1：購於日本化藥的型號為NC-3000H的聯苯型環氧樹脂，環氧當量288；A2：購於日本化藥的型號為EPPN-501H的酚醛環氧樹脂，環氧當量166；A3：購於上海勢越的型號為KF21的雙酚F型環氧樹脂，環氧當量540；A4：購於長春樹脂的型號為BE504ELM65的雙酚A型環氧樹脂，環氧當量890；A5：選自新日鐵化學型號為YDF-2004的環氧樹脂，環氧當量1005；
(B)苯並噁嗪樹脂：B1：購於亨斯邁的型號為LZ8290H62的產品；B2：購於東材科技型號為D125的產品；
(C)阻燃劑
C1：購於日本大塚化學株式會社的型號為SPB-100的產品；C2：購於日本大八化學的型號為PX-200的產品；
(D)填料
D1：購於江蘇聯瑞的球形二氧化矽DQ-1030，pH=4.0；D2：購於江蘇聯瑞的球形二氧化矽DQ-1028L，pH=5.8；D3：購於梧州穎豐礦業型號為3000目氣流石英粉，pH=3.0； D4：購於安徽格銳雲母粉GD-2，pH=5.0；D5：購於天津星龍泰化工產品科技有限公司的炭黑，pH=3.0；D6：購於蚌埠鑫源的勃姆石BG-615，pH=6.8；D7：購於矽比科的二氧化矽MEGASIL525，pH=6.5；D8：購於日本admatechs球形矽微粉SC2500-SEJ，pH=8.0；
(E)固化促進劑
E1：購於日本四國化成的2-苯基咪唑。
將實施例和對比例提供的樹脂組合物，按照如下方法製備印製電路用層壓板，並對製備得到的層壓板進行性能測試。
前述印製電路用層壓板的製備方法包括：①通過加熱和加壓作用使一張或一張以上的預浸料黏合在一起，製成的層壓板；②在步驟①製得的層壓板的一面或兩面上黏合金屬箔；③在層壓機中進行層壓；在步驟②的過程中，使用8片預浸料和2片一盎司(35μm厚)的金屬箔疊合在一起；在步驟③的過程中，層壓的操作條件為：料溫80~140℃時，控制升溫速率為1.5~2.5℃/min；外層料溫80-100℃時，施加滿壓，滿壓壓力為350psi左右；固化時，控制料溫在195℃，並保溫60min以上。
實施例和對比例提供的樹脂組合物的配方及性能測試結果見表1~4。
性能測試的專案及具體方法為：
(a)玻璃轉化溫度：根據差示掃描量熱法，按照IPC-TM-650中2.4.25所規定的DSC方法進行測定。
(b)耐燃燒性：依據UL94法測定。
(c)吸水性：按照IPC-TM-650中的2.6.2.1所規定的方法進行測定。
(d)膠水GT
測試溫度174℃。
(e)樹脂DSC反應曲線測試：儀器商：美國TA。N2環境，升溫速率10℃/min。
(f)剝離強度：按照IPC-TM-650中的2.4.8所規定的方法進行測定。
(g)熱膨脹係數：按照IPC-TM-650中的2.4.24所規定的方法進行測定。
物性分析：
(1)從表1~4可以看出，將實施例1與對比例1進行比較， 實施例1中添加酸性填料後，相比對比例1中未添加酸性填料時，樹脂DSC起始溫度和峰值溫度都較低，其製得的板材玻璃轉化溫度較高，耐浸焊時間較長，吸水率較低，剝離強度更高。
將實施例2與對比例2-4進行比較，實施例2中添加pH值在4.0的酸性填料後，相比對比例2-3中添加pH值大於6.0的酸性填料以及對比例4中添加非酸性填料時，樹脂DSC起始溫度和峰值溫度都較低，其製得的板材玻璃轉化溫度較高，耐浸焊時間較長，剝離強度更高。
將實施例2與對比例7進行比較，實施例2中添加酸性填料後，相比對比例7未添加酸性填料時，樹脂DSC起始溫度和峰值溫度都較低，其製得的板材玻璃轉化溫度較高，耐浸焊時間較長，吸水率較低，剝離強度更高。
通過上述實施例1-2和對比例1-4、7可以看出，本發明通過添加pH在2~6之間的酸性填料，相比其他pH值範圍的填料，可以使樹脂DSC起始溫度和峰值溫度都較低，並使板材具有更優異的性能。
(2)從表1~4還可以看出，將實施例2與對比例8-10進行比較，實施例2中添加環氧當量介於150~450之間的環氧樹脂和環氧當量介於451~1000之間的環氧樹脂，相比對比例8和10僅添加環氧當量介於150~450之間的環氧樹脂時，其吸水率更低，具有更優異的剝離強度；相比對比例9中僅添加環氧當量介於451~1000之間的環氧樹脂時，樹脂DSC起始溫度和峰值溫度都較低，其製得的板材玻璃轉化溫度較高，能達到V-0級阻燃，耐浸焊時間較長，吸水率較低，具有更優異的剝離強度。
將實施例4與對比例5-6進行比較，實施例4中採用添加環氧 當量介於150~450之間的環氧樹脂和環氧當量介於451~1000之間的環氧樹脂，相比對比例5中添加兩種環氧當量介於150~450之間的環氧樹脂，其具有更優異的耐浸焊性，吸水率低並且剝離強度更高；相比對比例6中添加兩種環氧當量介於451~1000之間的環氧樹脂，樹脂DSC起始溫度和峰值溫度都較低，其製得的板材玻璃轉化溫度較高，耐浸焊時間較長，吸水率較低，具有更優異的剝離強度。
將實施例8與對比例11-13進行比較，實施例8中採用添加環氧當量介於150~450之間的環氧樹脂和環氧當量介於451~1000之間的環氧樹脂，相比對比例11中添加環氧當量大於1000的環氧樹脂，其樹脂DSC起始溫度和峰值溫度都較低，其製得的板材玻璃轉化溫度較高，吸水率較低；相比對比例12採用環氧當量介於150~450之間的環氧樹脂和環氧當量大於1000的環氧樹脂以及對比例13採用環氧當量介於451~1000之間的環氧樹脂和環氧當量大於1000的環氧樹脂，其樹脂DSC起始溫度和峰值溫度都較低，玻璃轉化溫度較高，吸水率較低。
通過上述實施例2、4、8與對比例5-6和對比例8-13可以看出，本發明中採用添加環氧當量介於150~450之間的環氧樹脂和環氧當量介於451~1000之間的環氧樹脂，這兩種環氧樹脂之間具有協同增效作用，其共同作用使得板材具有更優異的性能。
(3)通過實施例1和3與實施例6和9進行比較可以看出，當實施例1和3中將環氧當量介於150~450之間的環氧樹脂和環氧當量介於451~1000之間的環氧樹脂的重量比控制在4：1~1：4範圍內時，相比實施例6和9中將兩者範圍控制在該範圍之外時，其製得的板材具有更高的玻璃轉化溫 度。
通過上述實施例可以看出，本發明通過在樹脂組合物中添加酸性填料，極大地促進了苯並噁嗪和環氧樹脂的聚合反應，降低了苯並噁嗪和環氧聚合所需的固化溫度，使苯並噁嗪和環氧的反應更完全；本發明通過使用該添加有酸性填料的樹脂組合物製作的層壓板具有高的抗剝穩定性、高玻璃轉化溫度、低吸水率、高耐熱性、高彎曲強度和良好的工藝加工性，並能實現低熱膨脹係數；同時，本發明通過採用不同結構和不同環氧當量的環氧樹脂進行配合，不僅保證了樹脂組合物具有較高玻璃轉化溫度，較好的力學性能和較低吸水率，還進一步改善了樹脂組合物機械加工性差的難題；本發明通過對環氧樹脂的選擇搭配以及酸性填料的添加，其相互間可產生協同增效作用，從而有助於實現較穩定的剝離強度，提升樹脂組合物的可靠性。
應該注意到並理解，在不脫離後述的申請專利範圍所要求的本發明的精神和範圍的情況下，能夠對上述詳細描述的本發明做出各種修改和改進。因此，要求保護的技術方案的範圍不受所給出的任何特定示範教導的限制。
申請人聲明，本發明通過上述實施例來說明本發明的詳細方法，但本發明並不局限於上述詳細方法，即不意味著本發明必須依賴上述詳細方法才能實施。所屬技術領域的技術人員應該理解，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 (20)

  1. 一種含有苯並噁嗪的樹脂組合物的製備方法，其特徵在於：向含有苯並噁嗪的樹脂組合物中添加酸性填料，酸性填料的pH值在2~6之間；前述含有苯並噁嗪的樹脂組合物中含有環氧樹脂和苯並噁嗪樹脂；前述環氧樹脂含有環氧當量介於150~450之間的環氧樹脂A1和環氧當量介於451~1000之間的環氧樹脂A2。
  2. 如申請專利範圍第1項所記載之方法，其中，以前述含有苯並噁嗪的樹脂組合物中有機固形物為100重量份計，前述酸性填料的添加量為0.05~100重量份。
  3. 如申請專利範圍第1項所記載之方法，其中，前述酸性填料選自矽微粉、石英粉、雲母粉、黏土、草酸鈣或炭黑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項所記載之方法，其中，前述酸性填料的粒徑為50nm~50μm。
  5. 如申請專利範圍第1或2項所記載之方法，其中，前述含有苯並噁嗪的樹脂組合物中，以有機固形物為100重量份計，含有如下組分：(A)環氧樹脂：5~80重量份；(B)苯並噁嗪樹脂：10~80重量份；(C)阻燃劑：1~30重量份；前述環氧樹脂中，環氧樹脂A1和A2的重量比為10：1~1：10，理想為4：1~1：4。
  6. 如申請專利範圍第5項所記載之方法，其中，前述環氧樹脂A1選自聯苯環氧樹脂、雙環戊二烯環氧樹脂、酚醛型環氧樹脂、含萘環氧樹脂或含蒽環氧樹脂中的任意一種或至少兩種的混合物，且環氧當量介於150~450之間。
  7. 如申請專利範圍第5項所記載之方法，其中，前述環氧樹脂A2選自雙酚A環氧樹脂、雙酚F環氧樹脂、羧基丁腈橡膠改性環氧樹脂或含有噁唑烷酮環的環氧樹脂中的任意一種或至少兩種的混合物，且環氧當量介於451~1000之間。
  8. 如申請專利範圍第5項所記載之方法，其中，前述苯並噁嗪樹脂選自雙酚A型苯並噁嗪樹脂、雙環戊二烯型苯並噁嗪樹脂、雙酚F型苯並噁嗪樹脂、酚酞型苯並噁嗪樹脂或MDA型苯並噁嗪樹脂中的任意一種或至少兩種的混合物。
  9. 如申請專利範圍第5項所記載之方法，其中，前述阻燃劑選自間苯二酚-雙(磷酸二苯酯)、雙酚A-雙(磷酸二苯酯)、間苯二酚-雙(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一種或至少兩種的混合物。
  10. 如申請專利範圍第5項所記載之方法，其中，前述含有苯並噁嗪的樹脂組合物中進一步含有環氧當量大於1000的環氧樹脂。
  11. 如申請專利範圍第5項所記載之方法，其中，前述含有苯並噁嗪的樹脂組合物中進一步含有非酸性填料。
  12. 如申請專利範圍第11項所記載之方法，其中，前述非酸性填料選自碳酸鈣、硫酸鈣、氧化鋁、硫酸鋇、陶瓷粉、滑石粉或水滑石中的任意一 種或至少兩種的混合物。
  13. 如申請專利範圍第11項所記載之方法，其中，以有機固形物為100重量份計，前述非酸性填料的添加量為0~100重量份。
  14. 如申請專利範圍第5項所記載之方法，其中，前述含有苯並噁嗪的樹脂組合物中進一步含有(D)固化促進劑。
  15. 如申請專利範圍第14項所記載之方法，其中，以前述含有苯並噁嗪的樹脂組合物中有機固形物為100重量份計，前述固化促進劑的添加量為0.1~1重量份。
  16. 如申請專利範圍第14項所記載之方法，其中，前述固化促進劑選自咪唑類促進劑及其衍生物、吡啶類促進劑或路易士酸類促進劑中的任意一種或至少兩種的混合物。
  17. 如申請專利範圍第1-16項中任一項所記載之方法，其中，前述酸性填料的pH值在2~6之間。
  18. 一種含有苯並噁嗪的樹脂組合物，其特徵係藉由如申請專利範圍第1-17項中任一項所記載之方法製備。
  19. 一種預浸料，其特徵係含有根據申請專利範圍第1-17項中任一項所記載之方法製得的樹脂組合物或含有根據申請專利範圍第8項所記載之樹脂組合物。
  20. 一種層壓板或印製電路板，其特徵係包括至少1張如申請專利範圍第19項所記載之預浸料。
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