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TWI555791B - A halogen-free resin composition and a prepreg and laminate produced therefrom - Google Patents

A halogen-free resin composition and a prepreg and laminate produced therefrom Download PDF

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Publication number
TWI555791B
TWI555791B TW104101384A TW104101384A TWI555791B TW I555791 B TWI555791 B TW I555791B TW 104101384 A TW104101384 A TW 104101384A TW 104101384 A TW104101384 A TW 104101384A TW I555791 B TWI555791 B TW I555791B
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TW
Taiwan
Prior art keywords
halogen
parts
epoxy resin
resin
resin composition
Prior art date
Application number
TW104101384A
Other languages
English (en)
Other versions
TW201617398A (zh
Inventor
Hui Li
ke-hong Fang
Original Assignee
Shengyi Technology Co Ltd
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Filing date
Publication date
Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Publication of TW201617398A publication Critical patent/TW201617398A/zh
Application granted granted Critical
Publication of TWI555791B publication Critical patent/TWI555791B/zh

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • B32B15/04—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
    • 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
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    • 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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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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Description

一種無鹵樹脂組合物及用其製作之預浸料與層壓板
本發明涉及層壓板技術領域，具體涉及一種樹脂組合物，尤其涉及一種無鹵樹脂組合物及用其製作之預浸料，層壓板與印刷電路板。
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，並達到了較好的阻燃作用。然而人們對火災現場深入研究後得出結論：雖然含鹵阻燃劑的阻燃效果好，且所需添加量較少，但是採用含鹵阻燃劑的高分子材料在燃燒過程中會產生大量的有毒且具有腐蝕性的氣體和煙霧，容易使人窒息而死，其危害性比大火本身更為嚴重。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，無鹵阻燃印刷線路板的開發成為了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得基材的吸水性變高，耐化學性變差。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及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，具有優良的力學、電學及阻燃性能等。
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、高功能化發展，要求電子元件有更高的訊號傳播速度和傳輸效率，這樣就對作為載體的印刷電路板提出了更高的性能要求，電子產品訊息處理的高速化和多功能化，應用頻率不斷提高，3GHz以上將逐漸成為主流，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的要求會越來越低。
現有的傳統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，而是將與電子組件一起成為PCB和終端廠商設計者提升產品性能的一個重要途徑。因為高介電常數(Dk)會使訊號傳遞速率變慢，高介質損耗(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，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、含磷固化劑複合固化環氧樹脂可以得到一種具有較低介電常數及介質損耗的固化物，但是僅僅以苯乙烯-馬來酸酐來降低材料的介電性能不可避免的會出現很多其他方面的問題，對黏結性影響尤為顯著，因為苯乙烯-馬來酸酐(SMA)分子結構中非極性的苯乙烯結構單元降低了改性基體樹脂的極性，削弱了樹脂與銅箔之間的相互作用力；同時，因為SMA中大量的苯環結構增大了樹脂交聯網絡的脆性，也對動態條件下的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。
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具有較低介電常數及介質損耗的固化物，但以含磷環氧樹脂作為主體樹脂，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，這勢必會對板材的其它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，可以得到一種具有較低介電常數及介質損耗的固化物，但使用普通的苯並噁嗪雖然可以達到固化環氧樹脂及阻燃的目的，但由於普通苯並噁嗪的介電常數較高，往往難以滿足高頻高速傳輸，且胺類固化劑的引入雖然可以提升黏結性，但其存在吸濕性較大及用其固化環氧樹脂耐熱性不足的缺陷，必然會對其在高多層電路板中的使用產生負面影響。
因此，如何生產一種具有低介電常數、低介質損耗，同時保證其耐化學性優良之預浸料及層壓板是目前亟待解決的問題。
本發明的目的在於提供一種樹脂組合物，特別是一種無鹵樹脂組合物及用其製作之預浸料，層壓板與印刷電路板。
為達到此發明目的，本發明採用以下技術手段：
第一方面，本發明提供了一種無鹵樹脂組合物，該組合物按重量份包括如下組分：環氧樹脂50-100份；苯並噁嗪20-70份；聚苯醚5-40份；苯乙烯-馬來酸酐5-30份；無鹵阻燃劑5-40份；固化促進劑0.2-5份；填料20-100份。
本發明的環氧樹脂至少含有一種如下化學結構式所示的具有雙環戊二烯烷基苯酚結構的環氧樹脂： 本發明的環氧樹脂還可以選自雙酚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、三官能環氧樹脂、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中的任意一種或至少兩種的混合物。
本發明的環氧樹脂含量為50-100份，例如可以是50份、55份、60份、65份、70份、75份、80份、85份、90份、95份、100份，較佳係50-90份，更佳係50份。
本發明的環氧樹脂組合物中包含了一種雙環戊二烯烷基苯酚結構的環氧樹脂，該環氧樹脂有利於降低基材的介電性能，同時烷基結構不僅能進一步優化介電性能，並且使基材的吸水率大大降低。
本發明的苯並噁嗪可以為氟化苯並噁嗪樹脂、脂肪族苯並噁嗪樹脂或雙環戊二烯型苯並噁嗪樹脂中的任意一種或至少兩種的混合物。
本發明的氟化苯並噁嗪樹脂為下述化學結構式中的任意一種或至少兩種的混合物：
本發明的脂肪族苯並噁嗪樹脂的化學結構式為：
其中，n為2或3。
本發明的雙環戊二烯型苯並噁嗪樹脂的化學結構式為：
本發明的苯並噁嗪含量為20-70份，例如可以是20份、25份、30份、35份、40份、45份、50份、55份、60份、65份、70份，較佳係40-50份，更佳係45份。
本發明的聚苯醚為低分子量聚苯醚，數量平均分子量在1000-4000。
本發明的聚苯醚含量為5-40份，例如可以是5份、10份、15份、20份、25份、30份、35份、40份，較佳係25份。
本發明的苯乙烯-馬來酸酐的化學結構式為：
其中，x為1-4，6，8；n為1-12；x，n均為整數。
本發明的苯乙烯-馬來酸酐含量為5-30份，例如可以是5份、10份、15份、17份、20份、22份、25份、30份，較佳係10-20份，更佳係20份。
本發明採用苯乙烯-馬來酸酐與苯並噁嗪複合固化環氧組合物，可使基材獲得低的介電常數及介質損耗，較好的耐熱性及耐濕性。
本發明的無鹵阻燃劑可以為磷腈、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、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羥乙基異氰尿酸酯、9，10-二氫-9-氧雜-10-磷雜菲-10-氧化物或含DOPO酚醛樹脂中的任意一種或至少兩種的混合物。
本發明的無鹵阻燃劑含量為5-40份，例如可以是5份、10份、 15份、20份、22份、25份、30份、40份，較佳係20-22份，更佳係22份。
本發明以具有阻燃作用的苯並噁嗪為主要固化劑，同時添加少量含磷阻燃劑，不僅實現了磷氮協同阻燃效應，而且在大大減少組分中磷含量的同時還提高了基材的阻燃性，並且使基材具有較好的耐濕性。
本發明的固化促進劑可以為咪唑類促進劑，所述之咪唑類促進劑為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-氰乙基取代咪唑中的任意一種或至少兩種的混合物。
本發明的固化促進劑含量為0.2-5份，例如可以是0.2份、0.5份、1份、2份、3份、4份、5份。
本發明的填料可以為無機或有機填料；當所述填料為無機填料時，可以為氫氧化鋁、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中的任意一種或至少兩種的混合物；當所述填料為有機填料時，可以為聚四氟乙烯粉末。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。
本發明的二氧化矽可以選擇結晶型、熔融型或球形二氧化矽。
本發明填料的粒徑為0.01-50μm，例如可以是0.01μm、0.05μm、1μm、5μm、10μm、15μm、20μm、25μm、30μm、40μm、50μm，較佳係1-15μm。
本發明的填料含量為20-100份，例如可以是20份、30份、40份、50份、60份、70份、80份、90份、100份，較佳係50份。
為使所述之填料在本發明的樹脂組合物中分散均勻，還可以添加入分散劑，使用的分散劑為氨基矽烷偶聯劑或環氧基矽烷偶聯劑，用來改善無機以及織造玻璃布間的結合性能，從而達到分散均勻的目的，且這類偶聯劑無重金屬存在，不會對人體產生不良影響，使用量為填料的0.5-2%重量份，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。
第二方面，本發明還提供了一種使用如本發明第一方面所述之無鹵樹脂組合物製作之預浸料，該預浸料包括基體材料；與通過浸漬乾燥後附著在其上的無鹵樹脂組合物。
本發明的基體材料為無紡或有紡玻璃纖維布。
第三方面，本發明還提供了一種層壓板，該層壓板包括如本發明第二方面所述之預浸料。
第四方面，本發明還提供了一種印刷電路板，其包含如本發明第三方面所述之層壓板。
與現有技術相對照，本發明具有以下之功效：採用本發明的無鹵樹脂組合物製備得到的層壓板，其介電常數可控制在3.7及以下，介質損耗最高值僅為0.0057，可達到阻燃性試驗UL-94中的V-0標準，PCT吸水率為0.27-0.30；因而，該層壓板在保證無鹵阻燃的同時，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。
下面通過具體實施方式來進一步說明本發明的技術手段。
本領域技術人員應該明瞭，所述實施例僅僅是幫助理解本發明，不應視為對本發明的具體限制。
〔製備例、雙環戊二烯烷基苯酚環氧樹脂的合成〕
在裝有聚四氟乙烯攪拌器、溫度計、冷凝回流器的四口瓶(500mL)中加入270.0g對(1,1,3,3-四甲基)丁基苯酚在水浴加熱中溶化，稱取三氟化硼‧乙醚1.83g，加入500mL四口燒瓶中，在滴液漏斗中加入50.1g雙環戊二烯，控制好滴加速度以便在2h內滴加完所有的雙環戊二烯，升溫至100℃，保溫4h，冷卻至室溫，再加熱至一定溫度蒸餾出過量的雙環戊二烯和對(1,1,3,3-四甲基)丁基苯酚，產物即為雙環戊二烯烷基苯酚樹脂。
將上一步所得到的雙環戊二烯烷基苯酚樹脂放入四口燒瓶中，再稱取100.0g環氧氯丙烷緩慢加入，待其溶解後，開始升溫，並在滴液漏斗中加入1mol的質量分數為33%的KOH溶液，控制速度，使其在1h內滴加完，控制反應溫度在100℃，滴加完後保溫4h，冷卻後水洗，再升溫至120℃蒸餾，蒸出過量環氧氯丙烷，得如下化學結構式所示的具有雙環戊二烯烷基苯酚結構的環氧樹脂：
〔實施例、覆銅箔層壓板的製備方法〕
將環氧樹脂、苯並噁嗪、聚苯醚、聚乙烯-馬來酸酐、無鹵阻燃劑、固化促進劑、填料及溶劑等，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60%-70%而製成膠液，即得到本發明的無鹵樹脂組合物膠液，用2116電子級玻璃纖維布浸漬膠液，經烘箱烘烤成半固化片，取6張2116半固化片，雙面再覆上35μm厚的電解銅箔，在熱壓機作真空層壓，固化190℃/120min，製成覆銅箔層壓板。
實施例1-9以及對比例1-5中所用的各組分及其含量(按重量份計)如表1所示，各組分代號及其對應的組分名稱如下所示：
(A)環氧樹脂
(A-1)製備例中合成的雙環戊二烯烷基苯酚環氧樹脂
(A-2)聯苯型環氧樹脂：NC-3000-H(日本化藥商品名)
(A-3)雙環戊二烯型環氧樹脂：HP-7200H(大日本油墨商品名)
(B)苯並噁嗪
(B-1)脂肪族苯並噁嗪樹脂：KAH-F5404(韓國Kolon商品名)
(B-2)氟化苯並噁嗪：KAH-F5301(韓國Kolon商品名)
(B-3)雙酚F型苯並噁嗪：LZ8280(亨斯曼先進材料)
(B-4)雙環戊二烯苯並噁嗪：LZ8260(亨斯曼先進材料)
(C-1)低分子量聚苯醚：MX90(SABIC Innovative Plastics商品名)，數量平均分子量1000-4000
(C-2)高分子量聚苯醚：Sabic640-111(SABIC Innovative Plastics商品名)數量平均分子量15000-20000
(D)苯乙烯-馬來酸酐低聚物：SMA-EF40(美國Sartomer商品名)
(E)含磷酚醛樹脂：XZ92741(DOW化學商品名)
(F)固化促進劑：2E4MZ(四國化成商品名)
(G)填料：熔融二氧化矽。
實施例1-9和對比例1-5採用的覆銅箔層壓板的製備方法與實施例相同。
採用以下測試方法對實施例1-4和對比例1-4製備的覆銅箔層壓板的玻璃化轉變溫度(Tg)、剝離強度(PS)、介電常數(Dk)與介質損耗角正切值(Df)、阻燃性和PCT 2小時後耐浸焊性及吸水率進行測試，測試結果如表2所示。
各性能參數的測試方法如下：
A玻璃化轉變溫度(Tg)
根據差示掃描量熱法(DSC)，按照IPC-TM-650 2.4.25所規定的DSC方法進行測定；
B剝離強度(PS)
按照IPC-TM-650 2.4.8方法中的“熱應力後”實驗條件，測試金屬蓋層的剝離強度；
C介電常數(Dk)與介質損耗角正切值(Df)
使用條狀線的共振法，按照IPC-TM-650 2.5.5.5測定1GHz下的介電常數(Dk)與介質損耗角正切值(Df)；
D阻燃性
按照UL-94標準進行測試；E PCT 2小時後耐浸焊性及吸水率
將覆銅箔層壓板浸漬在銅蝕刻液中，除去表面銅箔評價基板；將基板放置在壓力鍋中，在121℃，2atm下處理2h，測試吸水率後，浸漬在溫度為288℃的錫爐中，當基材出現起泡或分裂時記錄相應的時間。當基材在錫爐中超過5min還沒有出現起泡或分層時結束評價。
通過表1和表2可以看出以下幾點：
(1)將實施例1與對比例1相比可知，實施例1較對比例1的介電常數、介質損耗和吸水率較對比例1要低，說明實施例1採用其合成的雙環戊二烯烷基苯酚環氧樹脂較對比例1使用聯苯型環氧樹脂可以獲得更低的介電常數、介質損耗以及PCT吸水率；
(2)將實施例2和對比例2相比可知，實施例2較對比例2的玻璃化轉化溫度稍低，但介電常數、介質損耗和PCT吸水率較對比例2都要低，說明實施例2採用實施例1中合成的雙環戊二烯烷基苯酚環氧樹脂較對比例2使用雙環戊二烯型環氧樹脂可以獲得更低的介電常數、介質損耗以及PCT吸水率。
(3)將實施例3和實施例5和對比例3相比可知，實施例實施例3和實施例5較對比例3的玻璃化轉化溫度要高，而其介電常數、介質損耗以及PCT吸水率較對比例3的都要低，阻燃性可達到V-0級，說明實施例3和實施例5分別採用脂肪族苯並噁嗪及氟化苯並噁嗪較對比例3使用雙酚F苯並噁嗪可以獲得更高的玻璃化轉化溫度，更低的介電常數、介質損耗以及PCT吸水率，且阻燃性更高；實施例4和7可知，使用雙環戊二烯苯並噁嗪與脂肪族苯並噁嗪均可實現較高的玻璃化轉變溫度、較低的介電常數，其中使用脂肪族苯並噁嗪具有更高的玻璃化轉變溫度及更低的介電常數。
(4)將實施例4和對比例4相比，實施例4較對比例4具有更低的介電常數、介質損耗和PCT吸水率，說明實施例4採用加入低分子量聚苯醚後較對比例4未加入該組分時可獲得更低的介電常數、介質損耗和PCT吸水率；將實施例1與對比例5相比可知，雖然兩者的綜合性能相當，但使用高分子量 的聚苯醚導致加工性變差。
(5)將實施例1-4相比，實施例1介質損耗、PCT吸水率也最高，實施例4的介質損耗以及PCT吸水率最低，說明隨著製備例中合成的雙環戊二烯烷基苯酚環氧樹脂加入量的增加，介電常數、介質損耗、PCT吸水率均降低。
通過實施例1-9可以得出，在無鹵樹脂組合物中採用雙環戊二烯烷基苯酚環氧樹脂相比本領域常用的環氧樹脂，可以使基材的介電性能更加突出，採用苯乙烯-馬來酸酐與苯並噁嗪複合固化環氧組合物，同時添加少量含磷阻燃劑和低分子量聚苯醚，可以提高基材的阻燃性、黏結性和耐濕性，從而使其獲得更優異的綜合性能，適合在無鹵高多層電路板中使用，具有重要的應用價值。
當然，以上所述之實施例，只是本發明的較佳實例而已，並非用來限制本發明的實施範圍，故凡依本發明申請專利範圍所述之原理所做的等效變化或修飾，均包括於本發明申請專利範圍內。

Claims (13)

  1. 一種無鹵樹脂組合物，其特徵為其係按重量份包括如下組分：環氧樹脂50-100份，且至少含有一種如下化學結構式所示之具有雙環戊二烯烷基結構之環氧樹脂： 苯並噁嗪20-70份；聚苯醚5-40份；苯乙烯-馬來酸酐5-30份；無鹵阻燃劑5-40份；固化促進劑0.2-5份；填料20-100份；所述之苯並噁嗪為氟化苯並噁嗪樹脂或脂肪族苯並噁嗪樹脂中之任意一種或至少兩種的混合物；所述之氟化苯並噁嗪樹脂為下述化學結構式中之任意一種或至少兩種的混合物： 所述脂肪族苯並噁嗪樹脂之化學結構式為： 其中，n為2或3；所述之聚苯醚數量平均分子量在1000-4000；所述之苯乙烯-馬來酸酐之化學結構式為： 其中，x為1-4，6，8；n為1-12；x，n均為整數。
  2. 如申請專利範圍第1項所述之無鹵樹脂組合物，其中，所述之環氧樹脂還可以選自雙酚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、三官能環氧樹脂、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中之任意一種或至少兩種的混合物。
  3. 如申請專利範圍第1項所述之無鹵樹脂組合物，其中，所述之無鹵阻燃劑為磷腈、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、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羥乙基異氰尿酸酯、9，10-二氫-9-氧雜-10-磷雜菲-10-氧化物或含DOPO酚醛樹脂中之任意一種或至少兩種的混合物。
  4. 如申請專利範圍第1項所述之無鹵樹脂組合物，其中，所述之固化促進劑為咪唑類促進劑。
  5. 如申請專利範圍第1項所述之無鹵樹脂組合物，其中，所述之固化促進劑為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-氰乙基取代咪唑中之任意一種或至少兩種的混合物。
  6. 如申請專利範圍第1項所述之無鹵樹脂組合物，其中，所述之填料為無機或有機填料。
  7. 如申請專利範圍第6項所述之無鹵樹脂組合物，其中，所述之填料為無機填料，所述之無機填料為氫氧化鋁、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中之任意一種或至少兩種的混合物。
  8. 如申請專利範圍第6項所述之無鹵樹脂組合物，其中，所述之填料為有機填料，所述之有機填料為聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末中之任意一種或至少兩種的混合物。
  9. 如申請專利範圍第1項所述之無鹵樹脂組合物，其中，所述填料之粒徑為0.01-50μm。
  10. 一種預浸料，其特徵為其係使用如申請專利範圍第1至9項中任一項所述之無鹵樹脂組合物所製成，所述預浸料包括基體材料；和通過浸漬乾燥後附著在其上之無鹵樹脂組合物。
  11. 如申請專利範圍第10項所述之預浸料，其中，所述基體材料為無紡或有紡玻璃纖維布。
  12. 一種層壓板，其特徵為其係包含如申請專利範圍第10項所述之預浸料。
  13. 一種印刷電路板，其特徵為其係包含如申請專利範圍第12項所述之層壓板。
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EP3219757B1 (en) 2019-07-10
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