TWI613254B - 一種熱固性樹脂組成物 - Google Patents
一種熱固性樹脂組成物 Download PDFInfo
- Publication number
- TWI613254B TWI613254B TW105141169A TW105141169A TWI613254B TW I613254 B TWI613254 B TW I613254B TW 105141169 A TW105141169 A TW 105141169A TW 105141169 A TW105141169 A TW 105141169A TW I613254 B TWI613254 B TW I613254B
- Authority
- TW
- Taiwan
- Prior art keywords
- polyphenylene ether
- resin composition
- thermosetting
- thermosetting resin
- ether resin
- Prior art date
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- NMVQCYQENRLEOX-UHFFFAOYSA-N CCCP1(Oc2ccccc2-c2c1cccc2)=O Chemical compound CCCP1(Oc2ccccc2-c2c1cccc2)=O NMVQCYQENRLEOX-UHFFFAOYSA-N 0.000 description 1
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Abstract
一種熱固型樹脂組成物,採用由末端基經過苯乙烯改質的苯乙烯型聚苯醚以及末端基經過壓克力改質的壓克力型聚苯醚為主樹脂,且此兩種聚苯醚的重量比例介於0.5~1.5之間,使得熱固型樹脂組成物具有優異的耐熱性、流動性及填膠性,並且採用多種不同半衰期溫度之過氧化物,組合成複式交聯起始劑,在熱硬化過程中可有效提升交聯密度;硬化後的熱固型樹脂組成物,具有低介電常數、低介電損耗、高Tg及高剛性,且應用供補強材浸漬成浸漬片(prepreg),具有極佳裁切性。
Description
本發明為一種熱固性樹脂組成物,尤其是一種含有交錯型熱固性聚苯醚樹脂的熱固性樹脂組成物。
傳統印刷電路板中使用之絕緣材料主要為環氧樹脂,其固化後具有良好之絕緣性及耐化性,且具有成本優勢,因此環氧樹脂已廣泛被用作電路板絕緣層主要材料。然而近年來高頻及寬頻通訊裝置及設備發展迅速,訊號傳輸速度及數據處理量倍增,加上電子設備及電子組裝趨向高密度化,印刷電路板之發展亦隨之朝向更細之線寬線距(pitch)、板數更高(high layer counts)、板厚變薄、無鹵素化之發展趨勢,環氧樹脂所具有之電性、吸水性、耐燃性、尺寸穩定性等均已不敷需求。
美國第5223568號專利揭露一種用於電路載板的可模製熱塑性組成物(moldable thermosetting composition),由選用在室溫下呈液體且分子量少於5,000的聚丁二烯樹脂或聚異戊二烯(polyisoprene)樹脂的其中一種、再與含有熱塑性彈性體(thermoplastic elastomer)的固體丁二烯(butadiene)或異戊二烯(isoprene)的其中一種混合而成。此專利除了需要高溫硬化(即,熱壓溫度>250℃)外,對於聚丁二烯黏性大且導致銅箔基板生產時,難以連續自動化生產的問題,仍然沒有解決,且聚丁二烯易燃,需要添加更多耐燃劑,才能達到UL-94V0之水準。
聚苯醚樹脂具有極佳之絕緣性、耐酸鹼性、及優良之介電常數(dielectric constant)及介電損耗(dielectric dissipation facotr),因此相較於環氧樹脂,聚苯醚樹脂具有更優異之電氣特性,更能符合電路板絕緣材料之需求。但市售聚苯醚樹脂多為熱塑性且分子量過大(數均平均分子量>20,000),對於溶劑之溶解性不佳,不易直接導入應用在電路板上。因此,許多研究開發工作即是針對上述缺點進行改善,以期能將聚苯醚樹脂改質為可固化、且更具相容性、更具加工性之樹脂材料,同時亦能保留有聚苯醚樹脂優異之電氣特性。
美國第7858726號專利揭露以分子量再分配方式將大分子量聚苯醚樹脂轉化為小分子量聚苯醚樹脂,溶解度雖可改善,但分子鏈末端為羥基,雖可硬化,但因其極性基特性,會造成介電損耗升高;且平均每個聚苯醚分子具有之羥基數目小於2,可提供硬化之活性基比例不足,交聯密度不足,易因活性基數目若不足,造成硬化後交聯度不足,耐熱性變差的問題。
美國第7141627號專利提及關於以羥基進行硬化之缺點,也就是,羥基雖可用作硬化之活性基,但若羥基數目過高又會在硬化過程中,反應不完全,會有羥基殘留,造成硬化後板材之介電損耗偏高,吸水性過高等問題,因此對於有低介電常數及低介電損耗之需求之材料,因此以羥基進行硬化並無法根本改善其電性及吸水性。
美國第2014/4255711號公開案揭露一種末端改質為不飽和基之聚苯醚樹脂,並與bismaleimide共同硬化,可縮短膠化時間。其實施例中採用具有苯乙烯基之聚苯醚,雖可使耐熱性提高,但往往因為苯乙烯基屬
於硬質結構,造成受熱硬化過程中,流動性變差,且Bis-maleimide往往因溶解度不佳,加工時容易析出,造成分散性的問題。
WO2015/054626公開案揭示一種樹脂組成物,採用末端為OH基及甲基丙烯酸酸酯及丙烯酸酸酯基團之聚苯醚。末端OH基之聚苯醚,往往因為極性偏高,導致吸水率增加,影響電性。丙烯酸酯基團可提供軟質結構,雖可提供硬化過程中較佳之流動性,但無法提供較佳之耐熱性、耐燃性及機械強度。例如,美國第2014/141188號公開案揭露一種壓克力樹脂之無鹵耐燃組成,其目的就是為了提升壓克力樹脂之耐燃性。
Journal of Polymer Science(Vol.XI,No.5,p.491-506,1953)教示苯乙烯結構較穩定,具有較高之活化能,遇熱時結構較為穩定。而壓克力結構活化能較低,遇熱時更容易發生裂解。
更具體而言,現有技術中,美國第5223568號專利使用聚丁二烯樹脂,有加工條件不易控制及聚丁二烯樹脂結構耐燃性不佳的缺點,為彌補其耐燃性質,就必須添加更多的耐燃劑,但額外添加的耐燃劑,會影響造成其他重要物性受到影響,例如耐熱性不足、玻璃轉移溫度(Tg)降低、電性偏高等問題。
聚苯醚含大量苯環的結構,與聚丁二烯樹脂相較,穩定性高,且具有較佳耐燃性。所以,美國第7858726號專利採用小分子量聚苯醚樹脂,改善了溶解度不佳的問題,但其耐熱性較差。若將小分子量聚苯醚樹脂的末端,進一步改質為具有特定官能基之熱固性聚苯醚樹脂,經熱硬化後,交聯度提升,耐熱性亦提升,可增加應用空間。
美國第7141627號專利教示熱固性聚苯醚樹脂之末端基,可
為羥基,但其缺點為在硬化過程中會產生極性基團,不利於硬化後板材之介電常數及介電損耗,並且因為吸水率升高,易產生爆板及耐熱性問題。
但,熱固性當聚苯醚樹脂之末端基,經研究,以非極性基團(如不飽和基團之烯基、炔基等)進行改質,再進行熱硬化,硬化過程就不會有產生極性基,硬化後也無極性基殘留,可以降低Dk(介電常數)及Df(介電損耗)值,更可降低吸水率。
熱固性當聚苯醚樹脂之末端基,以壓克力基進一步改質時,屬於非極性基,硬化過程及硬化後不會產生極性基,可以獲得較佳之電性及較低之吸水率。但壓克力基本身結構屬於碳氫鍵結構,屬於軟質結構,受熱硬化時,流動性會較佳。但,Journal of Polymer Science(Vol.XI,No.5,p.491-506,1953)教示碳氫鍵的穩定性較差,遇熱易裂解,耐熱性較差。
然而,經研究,當聚苯醚樹脂之末端基結構,以苯乙烯基進一步改質時,因亦屬於非極性基團,硬化過程不會有產生極性基,硬化後也無極性基殘留,可以降低電性及吸水率。而且,苯乙烯基具有苯環結構,屬於硬質結構,因電子共振效應,結構穩定性高,耐熱性也高。但其缺點在於,受熱硬化時,流動性較差。尤其是應用在厚銅(2 oz以上)之多層板壓合製程時,常會因流動性較差,導致較差的線路填膠效果。
為解決上述問題,本發明之主要目的在於公開一種熱固型樹脂組成物,其中包含聚苯醚樹脂,且化學結構具有更多非極性不飽和官能基團,最佳結構是在聚苯醚樹脂之主鏈末端位置,賦與一個可硬化之不
飽和反應官能基團,且無極性基團存在,可使介電常數及介電損耗大幅降低,吸水率也可以降低。
本發明之另一目的在於提供一種熱固型樹脂組成物,其主樹脂為熱固性聚苯醚樹脂組合物,且具有按一定比例組合的苯乙烯基聚苯醚樹脂及壓克力基聚苯醚樹脂,其特性兼顧流動性及耐熱性,不但保留壓克力結構的耐熱性,並且改善了苯乙烯結構的流動性。
本發明之又一目的在於提供一種熱固型樹脂組成物,其成分包含:(a)熱固性聚苯醚樹脂,佔全部樹脂組成物固含量的35~60wt%,為苯乙烯基聚苯醚樹脂及壓克力基聚苯醚樹脂的組合,其中含苯乙烯基聚苯醚樹脂:壓克力基聚苯醚樹脂之重量比例,介於0.5~1.5之間;(b)無機粉體(填充劑),佔全部樹脂組成物固含量的20~50wt%;(c)阻燃劑,佔全部樹脂組成物固含量的5~25wt%;(d)交聯劑,佔全部樹脂組成物固含量的5~20wt%;(e)複合式交聯起始劑,佔全部樹脂組成物固含量的0.1~3wt%。
本發明之另一目的在於提供一種熱固性聚苯醚樹脂,包含交錯型熱固性聚苯醚樹脂,硬化後,其特性具備低介電常數、低介電損耗、高Tg、高耐熱性、高耐燃性之特點,且對於溶劑之溶解度佳,對於其他樹脂之相容性優良,充分展現該熱固性聚苯醚樹脂組合物之優點;該硬化性組成物在1GHz頻率下,具有介電常數(Dk)<3.0、介電損耗(Df)<0.0020之優良電氣特性,亦兼具高於210℃以上之玻璃轉移溫度(Tg)及288
℃耐焊錫耐熱性達600秒以上。
本發明公開的熱固性樹脂組成物,加工性優良,對於溶劑之溶解度佳,環氧樹脂之相容性亦佳,可應用在供印刷電路板使用的半固化膠片及固化片,或供玻纖布浸漬後再與銅箔壓合成銅箔基板,或進一步採用該銅箔基板製成高規格的印刷電路板。
本發明公開的熱固性樹脂組成物,具有下列有益效果:1.適用於低溫壓合加工;2.供預浸片浸漬後不會偏軟,且具優異裁切性,生產時不須常換刀具,增加成本;3.使用到銅箔基板上且經過硬化後,具有較佳之剛性,在伺服器等須多層化之印刷電路板應用上具有其優勢。
本發明揭露一種熱固型樹脂組成物,以熱固性聚苯醚樹脂為主樹脂,而且,所述熱固性聚苯醚樹脂的成分,是由末端基經過苯乙烯改質的聚苯醚(下稱苯乙烯型聚苯醚)以及末端基經過壓克力改質的聚苯醚(下稱壓克力型聚苯醚)此兩種聚苯醚依一定重量比例混合而成。
其中,所述苯乙烯型聚苯醚之結構,如結構式(A)所示:
其中,R1~R8為烯丙基、氫基或C1~C6烷基,或選自上述群組中的一種或多種;
X為:O(氧原),,,,,,-C-,,,
P1為苯乙烯基或;n=1~99之整數。
本發明的熱固性聚苯醚樹脂,有二種製造方法,但不以此兩種方法為限。
第一種製造方法為氧化聚合法,係由2,6-二甲基酚(2,6-Dimethyl Phenol,簡稱2,6-DMP)與氧(O2)或空氣(Air)在有機溶劑與銅和胺類所形成的配位錯合物催化劑存在下,經碳、氧原子C-O之氧化聚合而得。另外,2,6-DMP亦可以與具有官能基之酚物進行共聚合而達到改質效果。
經氧化聚合法所得之聚苯醚樹脂分子鏈末端仍具有一定數量之羥基,可進一步藉由末端接枝反應,賦予不同之反應官能基。
第二種製造方法為透過酚物與過氧化物之裂解反應,將未官能基化之較高分子量聚苯醚樹脂裂解成較低分子量之聚苯醚,經裂解法所得之聚苯醚樹脂分子鏈末端仍具有一定數量之羥基,可進一步藉由末端接枝反應,賦予不同之反應官能基。或透過不同官能基之二酚,賦予較低分子量之聚苯醚具有不同之反應官能基。
本發明的熱固性聚苯醚樹脂,是在製程中再對聚苯醚樹脂分子鏈末端之羥基進行進一步接枝改質。接枝反應機制是基於親核性取代反應(Nucleophilic Substitution)原理進行。具體實施方式是先將小分子量聚苯醚樹脂之末端羥基進行鈉鹽化或鉀鹽化,形成末端酚鹽(phenoxide)。
所述末端酚鹽的反應性高,可與鹵化物、酸鹵化物或酸酐類等單體進行反應。本發明的具體實施方式,是在相轉移觸媒的存在下,投入具有不飽和活性基(如烯基、炔基)之鹵化物、酸鹵化物或酸酐類等酸性單體作為封端接枝單體,經接枝反應後,上述單體之殘基會與聚苯醚主鏈末端之氧原子接上,進而形成本發明之交錯型熱固性聚苯醚樹脂。
本發明的熱固型樹脂組成物,以本發明的熱固性聚苯醚樹脂為主樹脂,且由下列(a)~(e)成分共同調配而成:其中,(a)熱固性聚苯醚樹脂,佔全部樹脂組成物固含量的35~60wt%,為苯乙烯型聚苯醚樹脂及壓克力型聚苯醚樹脂的組合,其中含苯乙烯基聚苯醚樹脂:壓克力基聚苯醚樹脂之重量比例,介於0.5~1.5之間,優選的較佳比
例為介於0.75~1.25之間;(b)無機粉體(填充劑),佔全部樹脂組成物固含量的20~50wt%;(c)阻燃劑,佔全部樹脂組成物固含量的5~25wt%;(d)交聯劑,佔全部樹脂組成物固含量的5~20wt%;(e)複合式交聯起始劑,佔全部樹脂組成物固含量的0.1~3wt%。
所述熱固性聚苯醚樹脂的苯乙烯型聚苯醚樹脂,為具備上述結構式(A)的聚苯醚樹脂;所述熱固性聚苯醚樹脂的壓克力型聚苯醚樹脂,為具備上述結構式(B)的聚苯醚樹脂。
本發明的熱固性聚苯醚樹脂,其數均分子量(Mn)較佳範圍為1,000以上且25,000以下,更佳範圍為2,000以上且10,000以下,可得到較佳之物性,如玻璃轉移溫度(Tg)、介電常數及介電損耗。
更具體而言,本發明的熱固性聚苯醚樹脂,其末端最少含有一個或一個以上的不飽和活性官能基,末端接枝官能基之多寡可由量測OH價進行評判。OH價量測依據中華民國國家標準CNS6681規範測得,其方法為配置25vol.%無水醋酸酐之吡啶溶液,配製成乙醯化試劑。精秤將待測樣品數克及乙醯化試劑5mL混合完全,並加熱使其完全溶解後,添加酚酞作指示劑,以0.5N之氫氧化鉀乙醇溶液進行標定得之。
本發明的熱固性聚苯醚樹脂,其OH價較佳範圍為小於3.0mgKOH/g,更佳範圍為小於2.0mgKOH/g,OH價最小可為0.001mgKOH/g,以確保有足夠的官能基參予反應,以得到較佳的玻璃轉移溫度(Tg)及耐熱性等物性。OH價大於10.0mgKOH/g時,代表其末端接枝之官能基數量不足,會導致硬化後之物性,包括:玻璃轉移溫度(Tg)或耐熱性等特性不符
合預期,且應用於製作銅箔基板時經常會發生爆板情形。
本發明的熱固型聚苯醚樹脂,其OH價愈低,代表配方中所使用的聚苯醚樹脂有足夠之官能基參予反應,組合物壓板溫度可較低,在150~200℃壓板均可達到所要求之物性。
所述熱固型樹脂組成物的無機粉體(填充劑),用於改善樹脂組成物硬化後的機械強度及其尺寸安定性。所述無機粉體選自球型或不規則二氧化矽(SiO2)、二氧化鈦(TiO2)、氫氧化鋁(Al(OH)3)、氧化鋁(Al2O3)、氫氧化鎂(Mg(OH)2)、氧化鎂(MgO)、碳酸鈣(CaCO3)、氧化硼(B2O3)、氧化鈣(CaO)、鈦酸鍶(SrTiO3)、鈦酸鋇(BaTiO3)、鈦酸鈣(CaTiO3)、鈦酸鎂(2MgO.TiO2)、二氧化鈰(CeO2)或燻矽石(fume silica)的其中一種或一種以上。
所述無機粉體的平均粒徑介於0.01~20微米。其中,所述燻矽石為一種多孔奈米級(nano-sized)矽石粒子,其添加比例為0.1~10wt%,平均粒徑為1至100奈米(nm);當燻矽石的添加比例大於10wt%,會造成樹脂組成物黏度提昇,加工困難。其中二氧化矽可為熔融型及結晶型,考量組成物之介電特性,優選為熔融型二氧化矽,如寶琳之525ARI。
所述熱固型樹脂組成物的阻燃劑,選自溴系阻燃劑或磷系阻燃劑。其中,所述溴系阻燃劑選自美商Albemarle Corporation(雅寶公司)的商品名Saytex BT 93W(ethylene bistetrabromophthalimide)阻燃劑、Saytex BT阻燃劑、93Saytex 120(tetradecabromodiphenoxy benzene)阻燃劑、Saytex 8010(Ethane-1,2-bis(pentabromophenyl))阻燃劑或Saytex 102(decabromo diphenoxy oxide)阻燃劑。
所述磷系阻燃劑選自磷酸脂類、磷腈類、聚磷酸銨類、磷酸三聚氰胺類(Melamine Polyphosphate)、氰尿酸三聚氰胺類(Melamine Cyanurate)、含鋁次磷酸脂類或DOPO類阻燃劑中的一種或多種。
所述磷酸脂類阻燃劑選自三苯基磷酸脂(TPP)、間苯二酚雙磷酸脂(RDP)、雙酚A二(二苯基)磷酸脂(BPAPP)、雙酚A二(二甲基)磷酸脂(BBC)、二磷酸間苯二酚酯(CR-733S)或間苯二酚-雙(二-2,6-二甲基苯基磷酸酯)(PX-200)中的一種或多種。
所述DOPO類阻燃劑選自DOPO(具下列結構式式(C))、DOPO-HQ(具下列結構式(D))或雙DOPO衍生結構(具下列結構式(E))中的一種或二種以上組合。
聚苯醚樹脂的玻璃轉移溫度,以添加溴系阻燃劑較磷系阻燃劑為高。
所述熱固型樹脂組成物的交聯劑,用於提高熱固性樹脂的交聯度,並調整基材之剛性及韌性,並調整加工性。所述交聯劑選自1,3,5-三聚氰酸三烯丙基酯(triallyl cyanurate,TAC)、三烯丙基異氰脲酸酯(triallyl isocyanurate,TAIC)、三甲代烯丙基異氰脲酸酯(trimethallyl isocyanurate,TMAIC),鄰苯二甲酸二烯丙酯(diallyl phthalate)、二乙烯苯(divinylbenzene)或1,2,4-苯三甲酸三烯丙酯(1,2,4-Triallyl trimellitate)中的一種或一種以上組合。
所述熱固型樹脂組成物的複式交聯起始劑,為有機過氧化物,用於在不同溫度下加速交聯反應。當本發明的樹脂組合物被加熱時,在特定的溫度下,起始劑分解形成自由基,開始引發自由基交聯聚合反應。隨溫度升高,過氧化物會消耗越快。因此,過氧化物與樹脂組合物
間,會有搭配性問題。若過氧化物分解溫度太低,低於聚合反應之活化能,會產生交聯度不足問題。
本發明的熱固性樹脂組合物,採用苯乙烯型聚苯醚以及壓克力型聚苯醚依一定重量比例混合而成。苯乙烯基及壓克力基的反應活化能不同,故需要採用複式交聯起始劑來啟始反應,達到最佳物性結果,起始劑依兩種樹脂的比例混合,其交聯度最完全。
常見的過氧化物中,選自叔丁基異丙苯基過氧化物、過氧化二異丙苯(DCP)、過氧化苯甲醯(BPO)、2,5-二甲基-2,5-雙(叔丁基過氧基)己烷、2,5-二甲基-2,5-二(叔丁基過氧基)己炔、1,1-二(叔丁基過氧基)-3,3,5-三甲基環己烷或過氧化氫異丙苯中的一種或多種。
本發明的複式交聯起始劑,係指以過氧化物之1小時半衰期溫度為依據,組合多種交聯起始劑,使本發明所述的熱固型樹脂組合物,在加溫硬化過程中,可以在不同溫度階段,由複式交聯起始劑來啟動多重交聯反應,使樹脂組合物可以交聯更完全,得到更好的耐熱性及物性。
本發明的複式交聯起始劑,以過氧化物中含有的活性氧比例大於5%為較佳,選自過氧化二異丙苯(活性氧:5.86%,1小時半衰期溫度:137℃)、1,4雙叔丁基過氧異丙基苯(活性氧:9.17%,1小時半衰期溫度:139℃)、以2,5-二甲基-2,5-二(叔丁基過氧基)己烷(活性氧:10.25%,1小時半衰期溫度:140℃)、二叔戊基過氧化物(活性氧:8.81%,1小時半衰期溫度:143℃)、二(叔丁基)過氧化物(活性氧:10.78%,1小時半衰期溫度:149℃)或過氧化氫異丙苯(活性氧:9.14%,1小時半衰期溫度:188℃)中的一種或二種以上組合,優選的組合為1,4雙叔丁基過氧異丙基苯及過氧
化氫異丙苯,用量依樹脂的混合比例調整,產生的硬化物玻璃轉移溫度、剛性等物理性最佳。
除此之外,本發明的熱固性樹脂組合物,可以利用添加偶合劑來改善無機粉體樹脂間的介面親合性。偶合劑可以直接添加入樹脂混合物中,或事先將無機粉體以偶合劑預先處理後,再製成本發明的樹脂混合物。
本發明的熱固性樹脂組合物,可供補強材浸漬及形成預浸體及硬化物。其中,預浸體為複合材料,在常溫15~40℃下,經過含浸製程使補強材浸漬所述熱固性樹脂組合物而構成,本發明的預浸體,包含補強材10~50wt%及含浸樹脂混合物50~90wt%。其中,所述補強材選自玻璃纖維布(glass cloth)、玻璃纖維蓆(non-woven glass cloth)、有機纖維布(organic fiber cloth)、有機纖維蓆(non-woven organic fiber cloth)、紙(paper)、非織性液晶聚合物布料、合成纖維布、碳纖維布、PP布、PTFE布或不織布。
本發明的預浸體,經過溫度100~140℃的烘乾製程後,可製得供印刷電路板使用的半固化膠片及固化片。選用玻璃纖維布為補強材,所製得的玻纖布預浸體,經上下壓合銅箔後,可製成供高頻印刷電路板使用的銅箔基板。
所述銅箔基板的製法,可以連續自動化生產,包括取一片或二片以上(含二片)的本發明預浸體,經層層相疊後,再於最上面及最下面各置入一片35μm厚的銅箔,在25kg/cm2壓力及溫度85℃下,保持恒溫20分鐘,再以3℃/min的加溫速率,加溫到150℃~190℃後,再保持恒溫120
分鐘,接著慢慢冷卻到130℃,以製得厚度0.8mm以上的銅箔基板。
本發明的熱固性樹脂組合物,使用前面所述之交錯型熱固性聚苯醚樹脂,硬化後的特性,具有低介電常數、低介電損耗、高Tg、高耐熱性及高耐燃性之特點,可充分展現熱固性聚苯醚樹脂的優點。因此,使用本發明的玻纖布預浸體與銅箔壓合後,可製成供高階規格的印刷電路板使用的銅箔基板。
茲列舉以下實施例及比較例來闡明本發明的效果,但本發明的權利範圍不是僅限於實施例的範圍。
各實施例及比較例所製成的銅箔基板,係根據下述方法進行物性評估:
1.玻璃轉移溫度(℃):以動態機械分析儀(DMA)測試。
2.吸水率(%):試樣在120℃及2atm壓力鍋中加熱120分鐘後計算加熱前後重量變化量。
3.288℃耐焊錫耐熱性(秒):試樣在120℃及2atm壓力鍋中加熱120分鐘後浸入288℃焊錫爐,記錄試樣爆板分層所需時間。
4.銅箔剝離強度(lb/in):測試銅箔與電路載板之間的剝離強度。
5.介電常數Dk(1GHz):以介電分析儀(Dielectric Analyzer)HP Agilent E4991A測試在頻率3G Hz時的介電常數Dk。
6.介電損耗Df(1GHz):以介電分析儀(Dielectric Analyzer)HP Agilent E4991A測試在頻率1G Hz時的介電損耗Df。
7.聚苯醚樹脂分子量測定:以定量之聚苯醚樹脂溶於THF溶劑中,以配
製成1%之溶液,再加熱至溶液澄清後,進行GPC(凝膠滲透層析法)分析並計算特性鋒面積而得。分析之檢量線是以不同分子量之聚苯乙烯標準品進行多點標定,建立檢量線後便可得待測品之分子量數據。
8.OH價測定:配置25vol.%無水醋酸酐之吡啶溶液,配製成乙醯化試劑。精秤將待測樣品數克及乙醯化試劑5mL混合完全,並加熱使其完全溶解後,添加酚酞作指示劑,以0.5N之氫氧化鉀乙醇溶液進行標定得之。
9.剛性:使用動態機械分析儀(DMA)測試,以50℃時之G’值(儲存模數,GPa)表示。
按表1所示的熱固性樹脂組合物,使用甲苯混合成清漆(Varnish),將上述清漆在常溫下以南亞玻纖布(南亞塑膠公司,布種型號7628)進行浸漬,然後於110℃(含浸機)乾燥數分鐘後即得樹脂含量43wt%之預浸體,最後將4片預浸漬體層層相疊於二片35μm厚之銅箔間,在25kg/cm2壓力及溫度85℃下,保持恒溫20分鐘,再以3℃/min的加溫速率,加溫到185℃後,再保持恒溫120分鐘,接著慢慢冷卻到130℃以取得0.8mm厚的銅箔基板。
測試所製成的銅箔基板的物性,其結果詳如表1所示。結果:比較表1的實施例1~13及比較例1~4的結果後,可以得到以下結論:
1.實施例1~6電路基板均具有優良的介電常數(Dk)及介電損耗(Df),介電常
數均小於3.0,介電損耗均小於0.0020,且玻璃轉移溫度(Tg)亦均高於205℃;此外其他物性方面,包含:銅箔剝離強度、吸水率、288℃耐焊錫耐熱性、耐燃性等亦維持良好之特性,尤其預浸漬片(Prepreg)裁切性佳,更為其特性。
2.比較例1中,採用末端為壓克力基之聚苯醚,其剛性較低,Tg也較低,耐熱性略差,但線路填膠性OK。而比較例2中,採用末端為苯乙烯基之聚苯醚,基板物性較佳,但線路填膠性NG。此與末端基結構有關,壓克力基屬於軟質結構,耐熱性較差,但流動性較佳。而苯乙烯基結構穩定,屬於硬質結構,耐熱性較佳,但不易流動。
3.實施例1~3,採用不同比例之末端壓克力基聚苯醚及末端苯乙烯基聚苯醚混合為主樹脂,並採用複式交聯起始劑,線路填膠特性及耐熱性均可通過。
4.實施例2,4及5中,採用不同結構之DOPO類阻燃劑,並搭配壓克力基之聚苯醚及苯乙烯基之聚苯醚,使用複式交聯起始劑,結果耐熱性,電性,線路填膠性等均通過。
5.實施例6為配方中採用溴系耐燃劑,結果Tg較磷系耐燃劑更高。
6.比較例5~6為採用單一交聯起始劑。由於採用兩種不同末端基之聚苯醚樹脂,其硬化反應之活化能不同,反應後之交聯度較差,影響Tg,耐熱性等。
7.比較例3使用末端OH基之聚苯醚樹脂,由於末端未官能基化,OH價高達47mgKOH/g,造成硬化後玻璃轉移溫度(Tg)偏低,且耐熱性不佳,基板剝離強度偏低及介電常數、介電損耗偏高(>0.0035)。
8.比較例4中,配方多添加聚丁二烯樹脂,介電常數及介電損耗下降,但因聚丁二烯樹脂屬於耐熱性較差之樹脂,易燃,造成耐燃性NG,Tg偏低。
*3.OH價(mgKOH/g):配置25vol.%無水醋酸酐之吡啶溶液,配製成乙醯化試劑。精秤將待測樣品數克及乙醯化試劑5mL混合完全,並加熱使其完全溶解後,添加酚酞作指示劑,以0.5N之氫氧化鉀乙醇溶液進行標定得之。
*4.分子量測定:以定量之聚苯醚樹脂溶於THF溶劑中,以配製成1%之溶液,再加熱至溶液澄清後,進行GPC(凝膠滲透層析法)分析並計算特性鋒面積而得。分析之檢量線是以不同分子量之聚苯乙烯標準品進行多點標定,建立檢量線後便可得待測品之分子量數據。
*7.使用動態機械分析儀(DMA)測試,tanδ值為最大時之溫度(波峰值)。
*8.試樣在120℃及2atm壓力鍋中加熱120分鐘,計算前後之重量差。
*9.試樣在120℃及2atm壓力鍋中加熱120分鐘後浸入288℃焊錫爐,記錄試樣爆板分層所需時間,>600表示高於600秒。
*10.使用動態機械分析儀(DMA)測試,以100℃時之G’值(儲存模數)表示。
*11.基板:含玻纖布之硬化後組成物。
*12.以1080規格電子級玻纖布6張,樹脂含量(RC):70%,與厚銅線路板壓合。壓合後以切片方式檢驗線路是否完全填滿。
*13.預浸漬片(Prepreg)裁切性:○:裁切正常;△:不易裁斷;╳:無法裁切。
Claims (10)
- 一種熱固型樹脂組成物,其特徵在於,由下列(a)~(e)成分共同調配而成,且基於樹脂組成物的固含量:(a)熱固性聚苯醚樹脂,佔35~60wt%,且數均分子量(Mn)介於1,000~25,000,依末端基經過苯乙烯改質且具下列結構式(A)的苯乙烯型聚苯醚樹脂:末端基經過壓克力改質且具下列結構式(B)的壓克力型聚苯醚樹脂的重量比介於0.5~1.5混合而成;
- 如申請專利範圍第1項所述之熱固型樹脂組成物,其中,所述熱固性聚苯醚樹脂的數均分子量(Mn)介於2,000~10,000。
- 如申請專利範圍第1項所述之熱固型樹脂組成物,其中,所述熱固性聚苯醚樹脂的OH價,小於3.0mgKOH/g。
- 如申請專利範圍第1項所述之熱固型樹脂組成物,其中,苯乙烯型聚苯醚樹脂:壓克力型聚苯醚樹脂之重量比例,介於0.75~1.25之間。
- 如申請專利範圍第1項所述之熱固型樹脂組成物,其中,所述阻燃劑係由十溴二苯乙烷及1,2-雙(四溴鄰苯二甲醯亞胺)乙烷所組成群組中選擇的一種或兩種。
- 如申請專利範圍第1項所述之熱固型樹脂組成物,其中,所述阻燃劑係由磷酸脂類、磷腈類、聚磷酸銨類、磷酸三聚氰胺類、氰尿酸三聚氰胺 類、含鋁次磷酸脂類及DOPO類阻燃劑所組成群組中選擇的一種或多種。
- 如申請專利範圍第1項所述之熱固型樹脂組成物,其中,所述複合式交聯起始劑為1,4雙叔丁基過氧異丙基苯及過氧化氫異丙苯的組合。
- 一種印刷電路板,其特徵在於,使用申請專利範圍第1項之熱固型樹脂組成物為絕緣層。
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TWI686436B (zh) * | 2018-08-28 | 2020-03-01 | 台燿科技股份有限公司 | 無鹵素低介電樹脂組合物,以及使用該組合物所製得之預浸漬片、金屬箔積層板與印刷電路板 |
TWI688607B (zh) * | 2018-10-04 | 2020-03-21 | 台光電子材料股份有限公司 | 樹脂組合物及由其製成之物品 |
CN109504062B (zh) * | 2018-11-22 | 2021-07-16 | 南亚塑胶工业股份有限公司 | 一种热固性树脂组合物 |
CN113366041A (zh) * | 2019-01-31 | 2021-09-07 | 松下知识产权经营株式会社 | 热固性树脂组合物、树脂片、层压体和印刷线路板 |
TWI794445B (zh) * | 2019-03-12 | 2023-03-01 | 台燿科技股份有限公司 | 樹脂組合物及其應用 |
TWI758602B (zh) * | 2019-04-12 | 2022-03-21 | 南亞塑膠工業股份有限公司 | 熱固性樹脂組成物及包含其之印刷電路板 |
KR102231991B1 (ko) * | 2019-10-30 | 2021-03-25 | 주식회사 서연이화 | 테일게이트 인너 판넬용 폴리프로필렌 수지 조성물 및 이의 성형품 |
CN113337098A (zh) * | 2021-06-28 | 2021-09-03 | 广东生益科技股份有限公司 | 一种热固性树脂组合物及其应用 |
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CN115716981A (zh) * | 2021-08-24 | 2023-02-28 | 南亚塑胶工业股份有限公司 | 树脂组成物 |
CN114149678B (zh) * | 2022-01-10 | 2023-10-10 | 南亚新材料科技股份有限公司 | 热固性树脂组合物、增强材料、覆金属层压板及其应用 |
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