TWI750790B - 一種絕緣介質膠膜及其製備方法和多層印刷線路板 - Google Patents
一種絕緣介質膠膜及其製備方法和多層印刷線路板 Download PDFInfo
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- TWI750790B TWI750790B TW109129850A TW109129850A TWI750790B TW I750790 B TWI750790 B TW I750790B TW 109129850 A TW109129850 A TW 109129850A TW 109129850 A TW109129850 A TW 109129850A TW I750790 B TWI750790 B TW I750790B
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Abstract
本發明公開了一種絕緣介質膠膜及其製備方法和多層印刷線路板，其中，所述絕緣介質膠膜包括離型膜以及設置在離型膜表面的絕緣介質層，所述絕緣介質層材料包括飽和聚酯樹脂、氨基樹脂或封閉型異氰酸酯、環氧樹脂、固化劑、無機填料以及固化促進劑。本發明通過在環氧樹脂組合物中引入飽和聚酯樹脂組份，使得制得的絕緣介質膠膜具有介電常數低、介電損耗因數低、不易發生熱膨脹，以及黏著力好的優點。
Description
本發明涉及高密度多層線路板封裝材料領域，尤其涉及一種絕緣介質膠膜及其製備方法、多層印刷線路板。
隨著人工智慧的飛速發展，電子產品也逐漸向薄型化、高密度發展。高密度多層線路板通常作為行動電話、數位相機、手提電腦等可擕式電子產品的封裝基板，IC(積體電路)封裝基板由有芯基板向更薄的無芯基板方向的發展，也使得高密度多層線路板的改進成為研究的熱點。
高密度多層線路板是指在絕緣基板上、傳統雙面板或多層板上，採取玻璃布增強絕緣介質在經化學鍍銅和電鍍銅形成導線及連接孔，如此多次疊加，累積形成所需層數的多層印製線路板。傳統的多層線路板製備工藝是通過在覆銅箔層壓板表面上有選擇性地除去部分銅箔來獲得導電圖形，這種做法工序多、控制難且成本高。
對於多層線路板而言，一般線寬/線間距低於40微米就無法保證線路品質了，而半導體晶片載板普遍線寬/線間距小於15微米。目前解決的方案只有採用半加成法(SAP)或改進型半加工法(MSAP)，這也是當今HDI(高密度互聯多層線路板)最先進的製成工藝。半加成法的技術關鍵便是積層材料-絕緣薄膜材料，也就是日本味之素公司的ABF/GX系列產品，它主要採用環氧及固化
劑以及熱塑性酚氧樹脂來擔當成膜作用。在一定厚度PET承載膜上塗一定厚度膠液後，經過紅外加熱或熱風使溶劑乾燥得到黏性薄膜，但是由於酚氧樹脂是由酚擴鏈環氧而成，其所具有的大量醇羥基會嚴重影響絕緣介質的介電性能，在高頻高速領域應用受限。
中國專利ZL201810631718.9利用聚氨酯丙烯酸酯樹脂、甲基丙烯酸羥乙酯光固化來擔當環氧樹脂成膜組份，採用脂肪族環氧為主體無溶劑塗膠方式來製備絕緣介質膜，然而，無溶劑塗膠方式不太適合配方設計，而且該技術的阻燃性很差，熱膨脹大。
ABF(絕緣介質)薄膜材料所要求的表面低粗化度、低熱膨脹率、低介質損耗及高玻璃轉變溫度等特性，國內目前還無法實現，因此我國的ABF薄膜材料一直依賴於進口，這就大大提高了多層線路板的成本，對我國線路板行業的健康發展極為不利。
因此，現有技術還有待於改進。
鑒於上述現有技術的不足，本發明的目的在於提供一種絕緣介質膠膜及其製備方法和多層印刷線路板，旨在解決現有絕緣介質膠膜柔韌性差、介電常數較高、介電損耗因數高，以及易發生熱膨脹的問題。
本發明的技術方案如下：一種絕緣介質膠膜，其中，包括離型膜以及設置在離型膜表面的絕緣介質層，所述絕緣介質層材料包括飽和聚酯樹脂、氨基樹脂或封閉型異氰酸酯、環氧樹脂、固化劑、無機填料以及固化促進劑。
所述的絕緣介質膠膜，其中，所述絕緣介質層材料按重量份計包括5-30份的飽和聚酯樹脂、0.5-3份的氨基樹脂或封閉型異氰酸酯、45-75份的環氧樹脂、1-25份的固化劑、1-100份的無機填料以及0.1-5份的固化促進劑。
所述的絕緣介質膠膜，其中，所述飽和聚酯樹脂的化學結構式
為：
，其中，n為1-100，R1、R2獨立地選自碳原
子小於20的烷基、苯基、萘基或其組合基團。
所述絕緣介質膠膜，其中，所述氨基樹脂為三聚氰胺或苯代三聚氰胺與甲醛以及有機醇縮聚形成的樹脂。
所述絕緣介質膠膜，其中，所述封閉型異氰酸酯為苯酚封閉的HDI、MDI、TDI以及PDI中的一種或多種；或者，所述封閉型異氰酸酯為己內醯胺封閉的HDI、MDI、TDI以及PDI中的一種或多種。
所述的絕緣介質膠膜，其中，所述環氧樹脂選自雙酚A環氧樹脂、雙酚F環氧樹脂、DCPD環氧樹脂、三酚環氧樹脂、聯苯環氧樹脂、萘酚環氧樹脂和含磷環氧樹脂中的一種或多種。
所述絕緣介質膠膜，其中，所述固化劑選自雙氰胺、芳香胺、酚類化合物、活性酯以及含磷酚醛中的一種或多種。
所述絕緣介質膠膜，其中，所述離型膜的厚度為10-100μm，所述絕緣介質層的厚度為10-200μm。
所述絕緣介質膠膜的製備方法，其中，包括步驟：將氨基樹脂或封閉型異氰酸酯加入飽和聚酯樹脂溶液中，混合制得第一膠液；向所述第一膠液中加入環氧樹脂以及固化劑，混合制得第二膠
液；向所述第二膠液中加入無機填料和固化促進劑，混合制得第三膠液；將所述第三膠液塗覆於離型膜上並進行固化處理，制得所述絕緣介質膠膜。
一種多層印刷線路板，其中，包括本發明所述的絕緣介質膠膜。
有益效果：本發明提供的絕緣介質膠膜包括離型膜以及設置在離型膜表面的絕緣介質層，所述絕緣介質層材料包括飽和聚酯樹脂、氨基樹脂或封閉型異氰酸酯、環氧樹脂、固化劑、無機填料以及固化促進劑。本發明通過在環氧樹脂組合物中引入飽和聚酯樹脂組份，使得制得的絕緣介質膠膜具有介電常數低、介電損耗因數低以及黏著力好等優點。
S10:步驟
S20:步驟
S30:步驟
S40:步驟
圖1為本發明提供的一種絕緣介質膠膜的製備方法較佳實施例的流程圖。
本發明提供一種絕緣介質膠膜及其製備方法和多層印刷線路板，為使本發明的目的、技術方案及效果更加清楚、明確，以下對本發明進一步詳細說明。應當理解，此處所描述的具體實施例僅僅用以解釋本發明，並不用於限定本發明。
本發明實施例提供了一種絕緣介質膠膜，其包括離型膜以及設置在離型膜表面的絕緣介質層，所述絕緣介質層材料包括飽和聚酯樹脂、氨基樹脂或封閉型異氰酸酯、環氧樹脂、固化劑、無機填料以及固化促進劑。
具體來講，現有技術通常採用熱塑型酚氧樹脂與環氧樹脂混合來製備絕緣介質薄膜，然而由於酚氧樹脂是由酚擴鏈環氧而成，其具有大量的醇羥基，所述醇羥基的強極性會影響絕緣介質薄膜的介電性能。本實施例通過在環氧樹脂中引入飽和聚酯樹脂成分，所述飽和聚酯樹脂是由多元醇和多元酸發生聚合反應製備而成，所述飽和聚酯樹脂只在端部含有羥基基團，中間不含有極性的羥基基團，因此所述飽和聚酯樹脂的極性較弱，其與環氧樹脂混合形成的絕緣介質膠膜具有較低的介電常數和較低的介電損耗因數，因而具有較佳的介電性能；同時本實施例還在環氧樹脂中引入了氨基樹脂或封閉型異氰酸酯，所述氨基樹脂或封閉型異氰酸酯可與飽和聚酯樹脂發生交聯反應，既能夠去除飽和聚酯樹脂兩端的羥基，進一步降低飽和聚酯樹脂的極性，提升介電性能，又能夠增加飽和聚酯樹脂的分子量，提升成膜效果。
在一些實施方式中，基於絕緣介質層的工藝性及最終的耐熱、黏著以及介電性能等綜合考慮，本實施例優選所述絕緣介質層材料按重量份計包括5-30份的飽和聚酯樹脂、0.5-3份的氨基樹脂或封閉型異氰酸酯、45-75份的環氧樹脂、1-25份的固化劑、1-100份的無機填料以及0.1-5份的固化促進劑，按本實施例配方制得的絕緣介質層具有優異的介電性能。
在一些實施方式中，所述飽和聚酯樹脂的化學結構式為
，其中，n為1-100，R1、R2獨立地選自碳原子小
於20的烷基、苯基、萘基或其組合基團。本實施例提供的飽和聚酯樹脂具有優
異的成膜性能，且所述飽和聚酯樹脂含有少量的羥基，極性較弱，其與環氧樹脂、氨基樹脂或封閉型異氰酸酯、固化劑、無機填料以及固化促進劑混合制得的絕緣介質層具有較低的介電常數和介電損耗因數。
在一些優選的實施方式中，所述飽和聚酯樹脂的相對分子量為8000-30000。若所述飽和聚酯樹脂的相對分子量小於8000，則不利於成膜，若所述飽和聚酯樹脂的相對分子量大於30000，則分子量過大導致溶解度過低，不利於與環氧樹脂混合成膜。
在一些實施方式中，所述氨基樹脂為三聚氰胺或苯代三聚氰胺與甲醛以及有機醇縮聚形成的樹脂。在本實施例中，氨基樹脂是一種多官能度的聚合物，其作為交聯劑可與端部含有羥基的飽和聚酯樹脂發生交聯反應，從而增加飽和聚酯樹脂的分子量，並降低所述飽和聚酯樹脂的極性，增強絕緣介質層的介電性能。
在一些實施方式中，所述封閉型異氰酸酯為苯酚封閉的HDI、MDI、TDI以及PDI中的一種或多種，但不限於此。在本實施例中，所述封閉性異氰酸酯同樣可作為交聯劑與端部含有羥基的飽和聚酯樹脂發生交聯反應，從而增加飽和聚酯樹脂的分子量，並降低所述飽和聚酯樹脂的極性，增強絕緣介質層的介電性能。
在一些實施方式中，所述封閉型異氰酸酯為己內醯胺封閉的HDI、MDI、TDI以及PDI中的一種或多種，但不限於此。
在一些實施方式中，所述環氧樹脂選自雙酚A環氧樹脂、雙酚F環氧樹脂、DCPD環氧樹脂、三酚環氧樹脂、聯苯環氧樹脂、萘酚環氧樹脂和含磷環氧樹脂中的一種或多種，但不限於此。在一些更優選的實施方式中，所
述環氧樹脂為含磷環氧樹脂，所述含磷環氧樹脂中的磷含量為2-5%，環氧當量為200-600g/mol。
在一些實施方式中，所述固化劑選自雙氰胺、芳香胺、酚類化合物、活性酯以及含磷酚醛中的一種或多種，但不限於此。
在一些實施方式中，所述固化促進劑選自2-甲基咪唑、2-乙基-4甲基咪唑、2-苯基咪唑、DMP-30、吡啶和對甲苯磺酸中的一種或多種，但不限於此。
在一些實施方式中，所述無機填料選自氫氧化鋁、氫氧化鎂、氧化鋁、氮化硼、氮化鋁、碳化矽、沸石、矽灰石、二氧化矽、氧化鎂、矽酸鈣、碳酸鈣、黏土、滑石和雲母中的一種或多種，但不限於此。在本實施例中，所述無機填料的量可以隨使用目的作適當的劑量調整。在一種優選的實施方式中，所述絕緣介質層材料中包括25-100份的無機填料。
在一些實施方式中，所述離型膜的厚度為10-100μm，所述絕緣介質層的厚度為10-200μm。
在一些實施方式中，還提供一種絕緣介質膠膜的製備方法，其中，如圖1所示，包括步驟：步驟S10、將氨基樹脂或封閉型異氰酸酯加入飽和聚酯樹脂溶液中，混合制得第一膠液；步驟S20、向所述第一膠液中加入環氧樹脂以及固化劑，混合制得第二膠液；步驟S30、向所述第二膠液中加入無機填料和固化促進劑，混合制得第三膠液；
步驟S40、將所述第三膠液塗覆於離型膜上並進行固化處理，制得所述絕緣介質膠膜。
在一些實施方式中，所述飽和聚酯樹脂溶液包括有機溶劑以及分散在所述有機溶劑中的飽和聚酯樹脂，所述有機溶劑選自丁酮和環己酮中的一種或兩種。
在一些實施方式中，採用直接加熱或熱風的方式對塗覆在離型膜上的第三膠液進行固化處理，使所述第三膠液形成絕緣介質層。當採用直接加熱的方式對所述第三膠液進行固化處理時，加熱的溫度根據第三膠液中的溶劑沸點來設置，其加熱溫度設置為80-130℃，加熱時間為5-20min。
在一些實施方式中，還提供一種多層印刷線路板，其包括本發明所述的絕緣介質膠膜。
具體來講，將所述絕緣介質膠膜與做好內層線路的PCB板在80-130℃，0.1-1MPa壓力條件下貼合好，然後在真空壓機裡壓制，壓制溫度為150-200℃，硬化時間為30-90分鐘，壓力為0.5~4MPa，制得所述多層印刷線路板。
下面通過實施例對本發明進行詳細說明：
實施例1
取DYNAPOL LH826-05A(德國德固賽商品名，飽和聚酯樹脂)20份，溶於異佛爾酮溶劑中，在常溫或中溫條件下完全溶解後加入HMMM(六甲氧甲基三聚氰胺)1份，攪拌一定時間備用溶液；再加入NPEL-128(二官能環氧樹脂，南亞塑膠工業股份有限公司商品名)30份、XZ 92530含磷環氧樹脂35份，攪拌均勻，將固化劑雙氰胺2.5份溶解於DMF溶劑後加入上述膠液
中，加入球型二氧化矽50份加入上述膠液，充分攪拌分散，最後投入固化促進劑2-乙基-4甲基咪唑和BYK450若干，攪拌均勻待用。選取300×300cm、表面光潔、平整的38μm厚的PET離型膜，離型膜一面均勻塗覆上述膠液，在烘箱中120℃下烘烤7min制得黏著片。將2張絕緣膜疊加，置於真空熱壓機中170℃固化60分鐘得到基材樣品。
實施例2
取DYNAPOL L411 20份，溶於異佛爾酮溶劑中，在常溫或中溫條件下完全溶解後加入HMMM 1份，攪拌一定時間備用溶液；再加入NPEL-128二官能環氧30份、XZ 92530含磷環氧35份，攪拌均勻，將固化劑雙氰胺2.5份溶解於DMF溶劑後加入上述膠液中，加入球型二氧化矽50份加入上述膠液，充分攪拌分散，最後投入固化促進劑2-乙基-4甲基咪唑和BYK450若干，攪拌均勻待用。選取300×300cm、表面光潔、平整的38μm厚的PET離型膜，離型一面均勻塗覆上述膠液，在烘箱中120℃下烘烤7min制得黏著片。將2張絕緣膜疊加，置於真空熱壓機中170℃固化60分鐘得到基材樣品。
實施例3
取DYNAPOL L411 20份，溶於異佛爾酮溶劑中，在常溫或中溫條件下完全溶解後加入Desmodur RL1265 1份，攪拌一定時間備用溶液；再加入NPEL-128二官能環氧30份、XZ 92530含磷環氧35份，攪拌均勻，將固化劑雙氰胺2.5份溶解於DMF溶劑後加入上述膠液中，加入球型二氧化矽50份加入上述膠液，充分攪拌分散，最後投入固化促進劑2-乙基-4甲基咪唑若干，攪拌均勻待用。選取300×300cm、表面光潔、平整的38μm厚的PET離型膜，離型一面均勻塗覆上述膠液，在烘箱中120℃下烘烤7min制得黏著片。將2張絕緣膜疊
加，置於真空熱壓機中170℃固化60分鐘得到基材樣品。
實施例4
取DYNAPOL L411 20份，溶於異佛爾酮溶劑中，在常溫或中溫條件下完全溶解後加入HMMM 1份，攪拌一定時間備用溶液；再加入NPEL-128二官能環氧30份、YEP250含磷環氧35份，攪拌均勻，將固化劑雙氰胺1.5份、DDS 3份溶解於DMF溶劑後加入上述膠液中，加入球型二氧化矽50份加入上述膠液，充分攪拌分散，最後投入固化促進劑2-乙基-4甲基咪唑、三氟化硼乙胺和BYK450若干，攪拌均勻待用。選取300×300cm、表面光潔、平整的38μm厚的PET離型膜，離型一面均勻塗覆上述膠液，在烘箱中120℃下烘烤7min制得黏著片。將2張絕緣膜疊加，置於真空熱壓機中180℃固化60分鐘得到基材樣品。
實施例5
取DYNAPOL L411 20份，溶於異佛爾酮溶劑中，在常溫或中溫條件下完全溶解後加入HMMM 1份，攪拌一定時間備用溶液；再加入NPEL-128二官能環氧30份、YEP250含磷環氧35份，攪拌均勻，將固化劑LA-7052 25份、DDS 3份溶解於PM溶劑後加入上述膠液中，加入球型二氧化矽50份加入上述膠液，充分攪拌分散，最後投入固化促進劑2-乙基-4甲基咪唑、三氟化硼乙胺和BYK450若干，選取300×300cm、表面光潔、平整的38μm厚的PET離型膜，離型一面均勻塗覆上述膠液，在烘箱中120℃下烘烤7min制得黏著片。將2張絕緣膜疊加，置於真空熱壓機中180℃固化60分鐘得到基材樣品。
對比例
取YL6747H30 20份，加入NPEL-128二官能環氧30份、XZ 92530
含磷環氧35份，攪拌均勻，將固化劑雙氰胺2.5份溶解於DMF溶劑後加入上述膠液中，加入球型二氧化矽50份加入上述膠液，充分攪拌分散，最後投入固化促進劑2-乙基-4甲基咪唑若干，攪拌均勻待用。選取300×300cm、表面光潔、平整的38μm厚的PET離型膜，離型一面均勻塗覆上述膠液，在烘箱中120℃下烘烤7min制得黏著片。將2張絕緣膜疊加，置於真空熱壓機中170℃固化60分鐘得到基材樣品。
對上述實施例1-實施例5以及對比例中制得的基材樣本進行性能測試，得到結果如表1所述：
通過上述測試結果可知，本發明實施例提供的絕緣介質膠膜在滿足成膜特性前提下能夠降低介電常數、以及介電損耗因數，同時可滿足玻璃
化溫度，熱膨脹係數不明顯劣化，且鹵素含量在JPCA無鹵標準要求範圍內能達到難燃性試驗UL 94中的V-0的標準。
綜上所述，本發明提供的絕緣介質膠膜包括離型膜以及設置在離型膜表面的絕緣介質層，所述絕緣介質層材料包括飽和聚酯樹脂、氨基樹脂或封閉型異氰酸酯、環氧樹脂、固化劑、無機填料以及固化促進劑。本發明通過在環氧樹脂組合物中引入飽和聚酯樹脂組份，使得制得的絕緣介質膠膜柔韌性極好、介電常數低、介電損耗因數低、不易發生熱膨脹，且黏著力好。。
應當理解的是，本發明的應用不限於上述的舉例，對本領域普通技術人員來說，可以根據上述說明加以改進或變換，所有這些改進和變換都應屬於本發明所附請求項的保護範圍。
S10:步驟
S20:步驟
S30:步驟
S40:步驟
Claims (8)
- 一種絕緣介質膠膜，其特徵在於，包括離型膜以及設置在所述離型膜表面的絕緣介質層，所述絕緣介質層材料按重量份計包括5-30份的飽和聚酯樹脂、0.5-3份的氨基樹脂或封閉型異氰酸酯、45-75份的環氧樹脂、1-25份的固化劑、1-100份的無機填料以及0.1-5份的固化促進劑；所述飽和聚酯樹脂由多元醇和多元酸發生聚合反應製備而成，所述飽和聚酯樹脂只在端部含有羥基基團，中間不含有極性的羥基基團；所述飽和聚酯樹脂的相對分子量為8000~30000，其化學結構式為：，其中，n為1-100，R1、R2獨立地選自碳 原子小於20的烷基、苯基、萘基或其組合基團。
- 如請求項1所述的絕緣介質膠膜，其特徵在於，所述氨基樹脂為三聚氰胺或苯代三聚氰胺與甲醛以及有機醇縮聚形成的樹脂。
- 如請求項1所述絕緣介質膠膜，其特徵在於，所述封閉型異氰酸酯為苯酚封閉的HDI、MDI、TDI以及PDI中的一種或多種；或者，所述封閉型異氰酸酯為己內醯胺封閉的HDI、MDI、TDI以及PDI中的一種或多種。
- 如請求項1所述的絕緣介質膠膜，其特徵在於，所述環氧樹脂選自雙酚A環氧樹脂、雙酚F環氧樹脂、DCPD環氧樹脂、三酚環氧樹脂、聯苯環氧樹脂、萘酚環氧樹脂和含磷環氧樹脂中的一種或多種。
- 如請求項1所述絕緣介質膠膜，其特徵在於，所述固化劑選自雙氰胺、芳香胺、酚類化合物、活性酯以及含磷酚醛中的一種或多種。
- 如請求項1所述絕緣介質膠膜，其特徵在於，所述離型膜的厚度為10-100μm，所述絕緣介質層的厚度為10-200μm。
- 一種如請求項1至6中任一所述絕緣介質膠膜的製備方法，其特徵在於，包括步驟：將氨基樹脂或封閉型異氰酸酯加入飽和聚酯樹脂溶液中，混合制得第一膠液；向所述第一膠液中加入環氧樹脂以及固化劑，混合制得第二膠液；向所述第二膠液中加入無機填料和固化促進劑，混合制得第三膠液；將所述第三膠液塗覆於離型膜上並進行固化處理，制得所述絕緣介質膠膜。
- 一種多層印刷線路板，其特徵在於，包括請求項1至6中任一所述的絕緣介質膠膜。
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