Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/91537
標題: 低介電銅箔基板用之苯乙烯化磷系酚醛樹脂
Phosphinated novolacs with styrenic linkages for low-dielectric copper clad laminate
作者: Chih Yao Hou
侯智耀
關鍵字: no;無
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摘要: 
本實驗室於中華民國專利I432445中揭露一種製備磷系酚醛樹脂(P-BPN)之方法,其係利用DOPO與bisphenolAnovolac(BPN)透過acid-fragmentation之機制進行反應而得。然而,此方法將降低該產物之分子量,使其環氧樹脂固化物之玻璃轉移溫度大幅下降。本篇論文試圖以兩種方式改善其固化物之熱性質,第一,將磷含量3%之磷系酚醛樹脂(P3)與不同莫耳比例之4-vinylbenzylchloride於鹼性環境催化下進行反應,獲得一系列乙烯苯基醚化之磷系酚醛樹脂P3-Sx(其中x為改質之比例)。透過導入剛硬之苯乙烯結構,可大幅提升固化物之熱性質。另一方面,此方式能夠直接減少與環氧樹脂固化過程中所產生之二級醇,並且形成低極性且具疏水性之聚苯乙烯結構以減低二級醇對介電性質所產生之負面效應。因此,P3-Sx系列硬化劑之環氧樹脂固化物皆具有高玻璃轉移溫度、高熱穩定性、低介電性質以及低吸水率。然而,該固化物雖於UL-94測試中依然達到V-0等級,惟兩次燃燒時間相加已將近10秒,顯示磷含量之不足。為使耐燃性能夠進一步提升且利於業界調控配方,因此於第二個方式中,將磷含量5%之磷系酚醛樹脂(P5)與不同莫耳比例之paraformaldehyde於酸性環境催化下進行反應,獲得一系列高分子量之磷系酚醛樹脂P5-Ny(其中y為paraformaldehyde之添加比例)。
其係透過SEAr之機制使paraformaldehyde脫水形成亞甲基架橋,以增加產物之分子量。由於硬化劑之分子量提升,其環氧樹脂固化物皆具有相當優異之熱性質。最後,再利用方法一之概念,將P5-N3導入苯乙烯結構,得到P5-N3-Sx系列高分子量之乙烯苯基醚化之磷系酚醛樹脂硬化劑,其固化物結合了高熱性質、低介電性質、低吸水率及更優異之耐燃性之優點。透過上述兩種方式所製備之磷系環氧樹脂硬化劑,其固化物於UL-94測試中皆達到V-0等級,顯示其優異之耐燃性。綜合上述優異之性質,P3-Sx、P5-Ny及P5-N3-Sx系列硬化劑於銅箔基板之發展及製造上,將具有相當良好之前景。

In our previous work, the patented method1 for preparation of phosphinated epoxy curing agents (P-BPN) from bisphenol A novolac (BPN) via acid-fragmentation led to dramatically decreasing in glass transition temperature of the thermosets. In the thesis, two proaches are demonstrated for improving the thermal properties of the thermosets. In the first approach, the curing agent with 3 % phosphorus content (P3) is reacted with various molar ratio of 4-vinylbenzyl chloride under base-catalyzed environment to form ether linkages with styrenic structures, and the products are abbreviated as P3-Sx (where x is the proportion of functionalization). The rigid segments, styrene, in P3-Sx leads to enhance thermal properties of the resulting epoxy thermosets. Moreover, incorporating styrenic structures into P3 not only directly reduce the formation of the secondary alcohols during curing process, but abate the adverse impact of them by forming non-polar, hydrophobic polystyrene-structures. Therefore, the thermosets cured with P3-Sx possess high glass transition temperature, high thermal stability, low dielectric properties, and low moisture absorption. However, the characteristic of flame-resistance in P3-Sx slightly decreased due to functionalization. Therefore, in the second approach, the curing agent with 5 % phosphorus content (P5) is reacted with various molar ratio of paraformaldehyde in acid-catalyzed environment to lengthen its molecular chain according to the chemistry in preparation of phenolic novolacs. The products are abbreviated as P5-Ny (where y is the amount of paraformaldehyde added), and the resulting epoxy thermosets possess higher glass transition temperature due to larger molecular weight in P5-Ny series curing agents. And then, P5-N3 were chosen and functionalized into P5-N3-Sx series curing agents similar to the first approach. The resulting thermosets of P5-N3-Sx combine various advantages just mentioned above. Finally, all the thermosets of both approaches achieve UL-94 V-0 rating, showing great flame-retardancy. Due to various impressive properties, P3-Sx, P5-Ny and P5-N3-Sx series curing agents have promising prospects in development of copper clad laminates.
URI: http://hdl.handle.net/11455/91537
其他識別: U0005-0607201513564600
Rights: 同意授權瀏覽/列印電子全文服務,2018-07-16起公開。
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