TWI648336B - Halogen-free epoxy resin composition and prepreg and laminate using the same - Google Patents

Halogen-free epoxy resin composition and prepreg and laminate using the same Download PDF

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Publication number
TWI648336B
TWI648336B TW106129281A TW106129281A TWI648336B TW I648336 B TWI648336 B TW I648336B TW 106129281 A TW106129281 A TW 106129281A TW 106129281 A TW106129281 A TW 106129281A TW I648336 B TWI648336 B TW I648336B
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Taiwan
Prior art keywords
epoxy resin
halogen
free epoxy
resin composition
weight
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Application number
TW106129281A
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English (en)
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TW201903037A (zh
Inventor
曾憲平
何烈相
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廣東生益科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
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    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

本發明關於一種無鹵環氧樹脂組合物以及使用其之預浸料及層壓板。該無鹵環氧樹脂組合物包含：(A)無鹵環氧樹脂；(B)活性酯樹脂；(C)反應型含磷阻燃劑。使用此種無鹵環氧樹脂組合物製成的預浸料及層壓板，具有高層間黏合力、低熱膨脹係數及高耐濕熱性的優點，且能實現無鹵阻燃。

Description

一種無鹵環氧樹脂組合物以及使用其之預浸料及層壓板
本發明係屬於覆銅板技術領域，尤其關於一種無鹵環氧樹脂組合物以及使用其之預浸料、層壓板及印刷電路板。
一直以來，印刷電路用層壓板通常採用鹵素阻燃劑達到阻燃目的，但鹵素阻燃劑在燃燒時，不但發煙量大，氣味難聞，而且會產生腐蝕性很強的鹵化氫氣體。另有文獻報導指出，近年來鹵素阻燃劑在高溫裂解及燃燒時會產生二噁英、二苯並呋喃等致癌物質，因此，隨著歐盟《關於報廢電氣電子設備指令》及《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，無鹵阻燃型印製電路用層壓板的開發成為業界的重點。
隨著電子材料往輕、薄、短、小的方向發展，更低的損耗及更高的耐熱可靠性成為未來的方向，如此除要求層壓板具有更高的Tg外，亦需具有更好地層間黏合力及低熱膨脹係數。
如何在保持組合物具有實現無鹵阻燃之同時，兼具良好的層間黏合力及低熱膨脹係數以及高耐濕熱性是本領域急待解決的技術問題。
針對先前技術之問題，本發明之目的在於提供一種無鹵環氧樹脂組合物以及使用其之預浸料及層壓板。使用該無鹵環氧樹脂組合物製造的層壓板具有高層間黏合力、低熱膨脹係數及高耐濕熱性的優點，且能實現無鹵阻燃。
本發明人為實現上述目的進行反覆深入的研究，結果發現：藉由將無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑，及其他可選地組分適當混合得到的組合物，可達到上述目的。
一種無鹵環氧樹脂組合物，其包含如下組分：(A)無鹵環氧樹脂；(B)活性酯樹脂；(C)反應型含磷阻燃劑；前述反應型含磷阻燃劑具有如下結構：
其中，R為；X為，其中，Y為取代的苯基、未取代的苯基、取代的萘基或未取代的萘基；Z為無取代基，-CH2-，；n、m獨立選自0~2的整數，例如0、1或2；且n+m為1的整數。
本發明採用反應型含磷阻燃劑，相較於普通含磷酚醛樹脂有較佳的交聯性，可提高交聯密度及反應性。
於本發明中，無鹵環氧樹脂的加入可明顯改善固化物固化交聯密度；活性酯樹脂的加入可有效提升與無鹵環氧樹脂的交聯固化作用。
本發明利用上述三種必要組分之間的相互配合以及相互協同促進作用，得到如上所記載之無鹵環氧樹脂組合物。採用該無鹵環氧樹脂組合物製成的預浸料及層壓板，兼具高層間黏合力、低熱膨脹係數及高耐濕熱性的優點，其層間黏合力可達到0.45以上，熱膨脹係數在2.10%以下，耐濕熱性高達5分鐘以上，且能實現無鹵阻燃。
理想地，前述無鹵環氧樹脂為聯苯酚醛環氧樹脂、DCPD酚醛環氧樹脂、亞烷基酚醛環氧樹脂或雙酚A型酚醛環氧樹脂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：聯苯酚醛環氧樹脂及DCPD酚醛環氧樹脂的混合物，DCPD酚醛環氧樹脂及亞烷基酚醛環氧樹脂的混合物，DCPD酚醛環氧樹脂、亞烷基酚醛環氧樹脂及雙酚A型酚醛環氧樹脂的混合物。
理想地，前述活性酯樹脂為具有如下結構之活性酯，由於該活性酯的特殊結構，其中的苯環、萘環、環戊二烯等剛性結構賦予該活性酯高的耐熱性，同時由於其結構的規整性及與環氧樹脂反應過程中無二次羥基產生，賦予其良好的介電性能及耐濕熱性。
其中，X為苯基或萘基；j為0或1；k為0或1；n表示重複單元，為0.25~1.25，例如0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0、1.05、1.1、1.15、1.2或1.25。
理想地，以無鹵環氧樹脂的添加量為100重量份計，前述活性酯樹脂的添加量為11~37重量份，例如11重量份、12重量份、15重量份、20重量份、25重量份、30重量份、35重量份或37重量份，理想為24~37重量份。
理想地，以無鹵環氧樹脂的添加量為100重量份計，前述反應型含磷阻燃劑的添加量為40~66重量份，例如40重量份、45重量份、48重量份、50重量份、52重量份、55重量份、60重量份、62重量份或66重量份。
理想地，前述無鹵環氧樹脂組合物亦可進一步包含氰酸酯或其預聚物，該組分可提升組合物的玻璃轉化溫度，同時與反應型含磷阻燃劑可共同實現N-P協同阻燃，提高阻燃效率。
理想地，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑 的添加量之和為100重量份計，前述氰酸酯或其預聚物的添加量為10~20重量份，例如10重量份、12重量份、14重量份、16重量份、18重量份或20重量份。
理想地，前述氰酸酯可為雙酚A型氰酸酯等分子中含有至少2個氰氧基的氰酸酯化合物或其預聚物，其可更佳地提升組合物的玻璃轉化溫度。
理想地，前述無鹵環氧樹脂組合物亦可進一步包含固化促進劑，其使樹脂固化並加快樹脂固化速度。
理想地，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述固化劑促進劑的添加量為0.05~1重量份，例如0.05重量份、0.08重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份、0.95重量份或1重量份。
理想地，前述固化促進劑為4-二甲胺基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑或異辛酸鋅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：4-二甲胺基吡啶及2-甲基咪唑的混合物，2-甲基咪唑及2-甲基4-乙基咪唑的混合物，2-苯基咪唑及異辛酸鋅的混合物，2-甲基咪唑、2-甲基4-乙基咪唑及2-苯基咪唑的混合物。
為進一步提高無鹵環氧樹脂組合物的難燃特性，於較佳的情形中，本發明尚可選擇性添加至少一種特定的阻燃性化合物。
理想地，前述阻燃性化合物可以選自阻燃性鹽類，如磷酸鹽 化合物或含氮磷酸鹽化合物，但並不僅限於此。
理想地，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述阻燃性化合物的添加量為0~50重量份且不包含0，例如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重量份或50重量份。
理想地，前述無鹵環氧樹脂組合物亦可進一步包含填料，前述填料為有機或/及無機填料，其主要用來調整組合物的一些物性效果，如降低熱膨脹係數(CTE)、降低吸水率及提高熱導率等。
理想地，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述填料的添加量為0~100重量份且不包含0，例如0.5重量份、1重量份、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、75重量份、80重量份、85重量份、90重量份、95重量份或100重量份，理想為0~50重量份且不包含0。
理想地，前述無機填料可以選自熔融二氧化矽、結晶型二氧化矽、球型二氧化矽、空心二氧化矽、氫氧化鋁、氧化鋁、滑石粉、氮化鋁、氮化硼、碳化矽、硫酸鋇、鈦酸鋇、鈦酸鍶、碳酸鈣、矽酸鈣、雲母或玻璃纖維粉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：熔融二氧化矽及結晶型二氧化矽的混合物，球型二氧化矽及空心二氧化矽的混合物，氫氧化鋁及氧化鋁的混合物，滑石粉及氮化鋁的混合物，氮化硼及碳化矽的混合物，硫酸鋇及鈦酸鋇的混合物，鈦酸鍶及碳 酸鈣的混合物，矽酸鈣、雲母及玻璃纖維粉的混合物，熔融二氧化矽、結晶型二氧化矽及球型二氧化矽的混合物，空心二氧化矽、氫氧化鋁及氧化鋁的混合物，滑石粉、氮化鋁及氮化硼的混合物，碳化矽、硫酸鋇及鈦酸鋇的混合物，鈦酸鍶、碳酸鈣、矽酸鈣、雲母及玻璃纖維粉的混合物。
理想地，前述有機填料可以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至少兩種的混合物，其中典型但非限制性的混合物為：聚四氟乙烯粉末及聚苯硫醚的混合物，聚醚碸粉末及聚四氟乙烯粉末的混合物，聚苯硫醚及聚醚碸粉末的混合物，聚四氟乙烯粉末、聚苯硫醚及聚醚碸粉末的混合物。
理想地，前述填料為二氧化矽，填料之粒徑中度值為1~15μm，例如1μm、2μm、5μm、8μm、10μm、11μm、12μm、13μm、14μm或15μm，理想填料之粒徑中度值為1~10μm。
本發明所記載之「包含」，意指其除前述組份外，亦可包含其他組份，這些其他組份賦予前述無鹵環氧樹脂組合物不同的特性。除此之外，本發明所記載之「包含」，亦可替換為封閉式的「為」或「由……組成」。
例如，前述無鹵環氧樹脂組合物亦可含有各種添加劑，作為具體例，可以列舉抗氧劑、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。
本發明之無鹵環氧樹脂組合物的常規製作方法為：取一容器，先將固體組分放入，接著加入液體溶劑，攪拌直至完全溶解後，加入液體 樹脂、填料、阻燃劑及固化促進劑，繼續攪拌均勻即可，最後用溶劑調整液體固含量至60~80%而製成膠液。
本發明的目的之二在於提供一種預浸料，其包含增強材料及藉由含浸乾燥後附著於其上的如上述之無鹵環氧樹脂組合物。
示例性的增強材料如無紡織物及/或其他織物，例如天然纖維、有機合成纖維以及無機纖維。
使用該膠液含浸增強材料如玻璃布等織物或有機織物，將含浸好的增強材料在155~170℃的烘箱中加熱乾燥5~10分鐘即可得到預浸料。
本發明的目的之三在於提供一種層壓板，其包含至少一張如上述之預浸料。
本發明的目的之四在於提供一種印刷電路板，其包含至少一張如上述之預浸料。
與先前技術相比，本發明至少具有以下功效：
在本發明中，反應型含磷阻燃劑既可作為環氧樹脂的固化劑，又能提供無鹵阻燃特性，且與無鹵環氧樹脂及活性酯樹脂組成的無鹵環氧樹脂組合物中，這三者之間相互配合，具有協同促進作用；利用該無鹵環氧樹脂組合物製作的預浸料、層壓板及覆金屬箔層壓板，不僅具有高達0.45以上的層間黏合力、低至2.10%以下的熱膨脹係數以及高達5分鐘以上的耐濕熱性，且能實現無鹵阻燃。
為便於理解本發明，本發明列舉實施例如下。所屬領域具有通常知識者應該明暸，所記載之實施例僅是幫助理解本發明，不應視為對本發明的具體限制。
根據上述所製成的無鹵環氧樹脂組合物覆金屬箔層壓板，測試其層間黏合力、熱膨脹係數以及燃燒性，如下實施例用於詳細說明與描述，其中有機樹脂的質量份按有機固形物質量份計。
製備例1：反應型含磷阻燃劑B1的製備
於反應釜中投490g雙酚F、324克甲醛水溶液(質量濃度為37%)及24g氫氧化鈉，開啟攪拌，將溫度加熱至40℃，保溫3小時；接著升溫至65℃，保溫3小時後，加入1480g正丁醇，回流12小時；將料溫降至55~60℃，並減壓蒸餾除去1000g左右的正丁醇，得到中間體。
往中間體中加入1080g DOPO(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)，在2小時內將料溫從80℃逐步升溫至190℃，並在120℃時向體系施加減壓以保證正丁醇及時排出體系。在180℃下保溫1小時，接著將料溫降至135℃，加入900g左右的丙二醇甲醚，繼續攪拌0.5小時，放料，得到磷系固化劑A1。
於安裝有溫度計、滴液漏斗、冷凝管、分餾管、攪拌器的燒瓶中加入1mol A2及816g甲基異丁基酮(MIBK)，將體系內減壓氮氣置換，使其溶解。接著，投入0.9mol對苯二甲醯氯，反應2小時，體系內溫度控制在60℃以下；接著，向體系中加入1.2mol苯酚，繼續反應1小時；通氮氣條件下，緩慢滴加189g的20%氫氧化鈉水溶液；在該條件下繼續攪拌1 小時。反應結束後，靜止分液除去水層。於反應物溶解的MIBK相中投入水，攪拌混合，靜止分液，除去水層。重複上述操作直至水層的pH值達到7.0左右。之後藉由傾析器脫去水分，接著減壓蒸餾脫去MIBK，得到反應型含磷阻燃劑B1，酯基當量為223g/mol。
製備例2：反應型含磷阻燃劑B2的製備
於反應釜中投372g二羥基聯苯、324克甲醛水溶液(質量濃度為37%)及24g氫氧化鈉，開啟攪拌，將溫度加熱至40℃，保溫3小時；接著升溫至65℃，保溫3小時後，加入1480g正丁醇，回流12小時；將料溫降至55~60℃，並減壓蒸餾除去1000g左右的正丁醇，得到中間體。
往中間體中加入1080g DOPO(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)，在2小時內將料溫從80℃逐步升溫至190℃，並在120℃時向體系施加減壓以保證正丁醇及時排出體系。在180℃下保溫1小時，接著將料溫降至135℃，加入900g左右的丙二醇甲醚，繼續攪拌0.5小時，放料，得到磷系固化劑A2。
於安裝有溫度計、滴液漏斗、冷凝管、分餾管、攪拌器的燒瓶中加入1mol A2及816g甲基異丁基酮(MIBK)，將體系內減壓氮氣置換，使其溶解。接著，投入0.9mol對苯二甲醯氯，反應2小時，體系內溫度控制在60℃以下；接著，向體系中加入1.2mol苯酚，繼續反應1小時；通氮氣條件下，緩慢滴加189g的20%氫氧化鈉水溶液；在該條件下繼續攪拌1小時。反應結束後，靜止分液除去水層。於反應物溶解的MIBK相中投入水，攪拌混合，靜止分液，除去水層。重複上述操作直至水層的pH值達到7.0左右。之後藉由傾析器脫去水分，接著減壓蒸餾脫去MIBK，得到反應 型含磷阻燃劑B2，酯基當量為226g/mol。
實施例1
取一容器，加入100重量份的7200-H及適量的MEK，攪拌溶解後，加入37重量份的HPC-8000-65T、40重量份製備例1中的反應型含磷阻燃劑及76重量份的矽微粉525及0.76重量份的BYK-W903，攪拌，加入適量的固化促進劑DMAP，繼續攪拌均勻，最後用溶劑調整液體固含量至60~70%而製成膠液。
用玻璃纖維布浸漬上述膠液，即成膠液。用2116規格的玻璃纖維布浸漬上述膠液，並控制至樹脂含量為50%的半固化片，接著烘乾除去溶劑得到預浸料。使用6張所製得之預浸料相互疊合，於其兩側分別壓覆一張銅箔，放進熱壓機中固化製成前述的環氧樹脂覆銅板層壓板。物性數據如表1所示。
實施例2~8：
製作工藝與實施例1相同，配方組成及其物性指標如表1所示。
比較例1~5：
製作工藝與實施例1相同，配方組成及其物性指標如表2所示。
注：表中皆以固體組分重量份計。
表1及表2列舉之材料具體如下：
B1：製備例1得到的反應型含磷阻燃劑。
B2：製備例2得到的反應型含磷阻燃劑。
B3：CN105906785A專利中具有如下結構的物質：
其中R為含有1~8個碳原子的烷基基團或為取代或未取代的苯基。
2812：線性酚醛樹脂(韓國Momentive商品名)。
92741：含磷酚醛樹脂(DOW商品名)。
NC-3000H：聯苯酚醛環氧樹脂(日本化藥商品名)。
7200-H：DCPD型酚醛環氧樹脂(DIC商品名)。
HPC-8000-65T：活性酯樹脂(日本DIC商品名)。
CE01PS：雙酚A型氰酸酯(揚州天啟化學商品名)。
525：二氧化矽填料(矽比科商品名)。
BYK-W903：填料分散劑(BYK商品名)。
DMAP：固化促進劑，4-二甲胺基吡啶(廣榮化學商品名)。
異辛酸鋅：固化促進劑(阿法埃莎商品名)。
以上特性的測試方法如下：
(1)層間黏合力(垂直法)：採用SYL企業標準Q/GDSY6052-2016所規定之垂直拉伸法測試組合物的層間黏合力。
(2)熱膨脹係數：根據熱機械分析法(TMA)，按照IPC-TM-6502.4.24所規定之TMA方法進行測定。
(3)PCT(6h)：將覆銅板表明的銅箔蝕刻後，評價基板：將基板放置壓力鍋中，在120℃、105KPa條件下，處理6個小時：後浸漬於288℃的錫爐中，當基材分層時，記錄相應時間：當基板在錫爐中超過5分鐘還沒出現氣泡或分層時即可結束評價。
(4)燃燒性：依照UL94法規定
從表1及表2的物性數據可知：
(1)將實施例1與比較例1及2相比，實施例1中採用無鹵環氧樹脂7200-H、活性酯樹脂HPC-8000-65T和反應型含磷阻燃劑B1組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.45~0.60，熱膨脹係數為1.90%，經PCT(6h)測定，其耐濕熱性大於5分鐘，並可實現無鹵阻燃，而比較例1及2中採用無鹵環氧樹脂、活性酯樹脂HPC-8000-65T及含磷酚醛樹脂92741組成的無鹵環氧樹脂，其製成的層壓板的層間黏合力為0.20~0.30，遠低於實施例1，熱膨脹係數為2.70%，遠大於實施例1，經PCT(6h)測定，其耐濕熱性為3秒，遠低於實施例1。
以上結果說明，實施例1藉由採用無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑組成的無鹵環氧樹脂組合物，相對比較例1~2採用將反應型含磷阻燃劑替換為含磷酚醛樹脂的無鹵環氧樹脂組合物，其製成 的層壓板具有更高的層間黏合力、更低的熱膨脹係數以及更優異的耐濕熱性，且能實現無鹵阻燃。
(2)將實施例2與比較例3相比，實施例2中採用無鹵環氧樹脂NC-3000H、活性酯樹脂HPC-8000-65T及反應型含磷阻燃劑B1組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.60~0.80，熱膨脹係數為2.10%，其耐濕熱性大於5分鐘，並可實現無鹵阻燃，而比較例3中採用無鹵環氧樹脂NC-3000H、線性酚醛樹脂2812及反應型含磷阻燃劑B1組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.26~0.36，遠低於實施例2，熱膨脹係數為2.80%，遠大於實施例2，經PCT(6h)測定，其耐濕熱性為3秒，遠低於實施例2。
將實施例1與比較例4相比，實施例1中採用無鹵環氧樹脂7200-H、活性酯HPC-8000-65T及反應型含磷阻燃劑B2組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.45~0.60，熱膨脹係數為1.90%，其耐濕熱性大於5分鐘，並可實現無鹵阻燃，而比較例4中採用無鹵環氧樹脂7200-H、線性酚醛樹脂2812及反應型含磷阻燃劑B2組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.27~0.37，遠低於實施例1，熱膨脹係數為2.40%，遠大於實施例1，經PCT(6h)測定，其耐濕熱性為3秒，遠低於實施例1。
以上結果說明，實施例1及2藉由採用無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑組成的無鹵環氧樹脂組合物，相對比較例3~4採用將活性酯樹脂替換為線性酚醛樹脂的無鹵環氧樹脂組合物，其製成的層壓板具有更高的層間黏合力、更低的熱膨脹係數以及更優異的耐濕熱性， 且能實現無鹵阻燃。
(3)將實施例3及5與比較例5相比，實施例3中採用環氧樹脂NC-3000H、活性酯樹脂HPC-8000-65T及反應型含磷阻燃劑B1組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.62~0.82，熱膨脹係數為2.00%，其耐濕熱性大於5分鐘，並可實現無鹵阻燃，實施例5中採用環氧樹脂NC-3000H、活性酯樹脂HPC-8000-65T和反應型含磷阻燃劑B2組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力為0.70~0.90，熱膨脹係數為2.10%，其耐濕熱性大於5分鐘，並可實現無鹵阻燃，而比較例5中採用環氧樹脂NC-3000H、活性酯樹脂HPC-8000-65T及反應型含磷阻燃劑B3組成的無鹵環氧樹脂組合物，其製成的層壓板的層間黏合力僅為0.20~0.30，遠低於實施例3和5，熱膨脹係數為2.80%，遠高於實施例3和5，其耐濕熱性僅為3秒，遠低於實施例3和5。
以上結果說明，實施例3及5藉由採用無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑B1或B2組成的無鹵環氧樹脂組合物，相對比較例5採用將本發明的反應型含磷阻燃劑B1及B2替換CN105906785A中的B3組成的無鹵環氧樹脂組合物，其製成的層壓板具有更高的層間黏合力、更低的熱膨脹係數以及更優異的耐濕熱性，且能實現無鹵阻燃。
(4)藉由實施例1~8可以看出，本發明採用無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑組成的無鹵環氧樹脂組合物中，這三種必要組分之間相互配合並具有協同促進作用，採用該無鹵環氧樹脂組合物製成的預浸料及層壓板，兼具高層間黏合力、低熱膨脹係數和高耐濕熱性的優點，其層間黏合力可達到0.45以上，熱膨脹係數在2.10%以下，耐濕熱 性達到5分鐘以上，且能實現無鹵阻燃。
綜合上述，與一般的層壓板相比，本發明採用由無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑組成的無鹵環氧樹脂組合物而製作的預浸料、層壓板及覆金屬箔層壓板，具有高層間黏合力、低熱膨脹係數以及高耐濕熱性的優點，且能實現無鹵阻燃。
申請人聲明，本發明藉由上述實施例來說明本發明之詳細工藝設備及工藝流程，但本發明並不侷限於上述詳細工藝設備及工藝流程，即不意味著本發明必須依賴上述詳細工藝設備及工藝流程才能實施。所屬技術領域的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及公開範圍之內。

Claims (18)

  1. 一種無鹵環氧樹脂組合物，其特徵在於，前述無鹵環氧樹脂組合物包含如下組分：(A)無鹵環氧樹脂；(B)活性酯樹脂；(C)反應型含磷阻燃劑；前述反應型含磷阻燃劑具有如下結構：
    Figure TWI648336B_C0001
    且，R為
    Figure TWI648336B_C0002
    ；X為
    Figure TWI648336B_C0003
    ，Y為取代的苯基、未取代的苯基、取代的萘基或未取代的萘基；Z為無取代基，
    Figure TWI648336B_C0004
    ，
    Figure TWI648336B_C0005
    ；n、m獨立選自0~2的整數，且n+m為
    Figure TWI648336B_C0006
    1的整數；其中，前述無鹵環氧樹脂為聯苯酚醛環氧樹脂、DCPD型酚醛環氧樹脂、亞烷基酚醛環氧樹脂或雙酚A型酚醛環氧樹脂中的任意一種或至少兩種的混合物；其中，前述活性酯樹脂具有如下結構：
    Figure TWI648336B_C0007
    且，X為苯基或者萘基；j為0或1；k為0或1；n表示重複單元，為0.25~1.25；其中，以無鹵環氧樹脂的添加量為100重量份計，前述活性酯樹脂的添加量為11~37重量份；其中，以無鹵環氧樹脂的添加量為100重量份計，前述反應型含磷阻燃劑的添加量為40~66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，前述無鹵環氧樹脂組合物進一步包含氰酸酯或其預聚物。
  3. 如申請專利範圍第2項所記載之無鹵環氧樹脂組合物，其中，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述氰酸酯或其預聚物的添加量為10~20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進一步包含固化促進劑。
  5. 如申請專利範圍第4項所記載之無鹵環氧樹脂組合物，其中，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述固化劑促進劑的添加量為0.05~1重量份。
  6. 如申請專利範圍第4項所記載之無鹵環氧樹脂組合物，其中，前述固化促進劑為4-二甲胺基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑或異辛酸鋅中的任意一種或至少兩種的混合物。
  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，前述無鹵環氧樹脂組合物進一步包含阻燃性化合物。
  8. 如申請專利範圍第7項所記載之無鹵環氧樹脂組合物，其中，前述阻燃性化合物為阻燃性鹽類。
  9. 如申請專利範圍第7項所記載之無鹵環氧樹脂組合物，其中，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述阻燃性化合物的添加量為0~50重量份且不包含0。
  10. 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含填料。
  11. 如申請專利範圍第10項所記載之無鹵環氧樹脂組合物，其中，前述填料為有機及/或無機填料。
  12. 如申請專利範圍第10項所記載之無鹵環氧樹脂組合物，其中，以無鹵環氧樹脂、活性酯樹脂及反應型含磷阻燃劑的添加量之和為100重量份計，前述填料的添加量為0~100重量份且不包含0。
  13. 如申請專利範圍第11項所記載之無鹵環氧樹脂組合物，其中，前述無機填料為熔融二氧化矽、結晶型二氧化矽、球型二氧化矽、空心二氧化矽、氫氧化鋁、氧化鋁、滑石粉、氮化鋁、氮化硼、碳化矽、硫酸鋇、鈦酸鋇、鈦酸鍶、碳酸鈣、矽酸鈣、雲母或玻璃纖維粉中的任意一種或至少兩種的混合物。
  14. 如申請專利範圍第11項所記載之無鹵環氧樹脂組合物，其中，前述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。
  15. 如申請專利範圍第10項所記載之無鹵環氧樹脂組合物，其中，前述填料為二氧化矽，填料的粒徑中度值為1~15μm。
  16. 一種預浸料，其特徵係其包含增強材料及藉由含浸乾燥後附著於其上之如申請專利範圍第1-15項中任一項所記載之無鹵環氧樹脂組合物。
  17. 一種層壓板，其特徵係其包含至少一張如申請專利範圍第16項所記載之預浸料。
  18. 一種印刷電路板，其特徵係其包含至少一張如申請專利範圍第16項所記載之預浸料。
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