TWI662076B - Thermosetable composition and thermoset product prepared thereby - Google Patents
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Abstract
本發明提供一種可固化組成物，其係包含環氧樹脂、含末端不飽和酯基的酚醛樹脂與觸媒，且末端不飽和酯基具有如式(i)所示之結構。藉此，以含末端不飽和酯基的酚醛樹脂作為固化劑，可避免於後續環氧樹脂的固化反應中產生二級醇，且所製得之固化產物具有低介電常數、低介電損失與高玻璃轉移溫度等特性。 The present invention provides a curable composition comprising an epoxy resin, a phenol resin containing a terminal unsaturated ester group, and a catalyst, and the terminal unsaturated ester group has a structure as shown in formula (i). By using the phenolic resin containing a terminal unsaturated ester group as a curing agent, a secondary alcohol can be avoided in the subsequent curing reaction of the epoxy resin, and the obtained cured product has a low dielectric constant and a low dielectric loss. With high glass transition temperature and other characteristics.
Description
本發明是有關於一種可固化組成物及其製備之固化產物，特別是有關於一種包含環氧樹脂與含末端不飽和酯基之酚醛樹脂的可固化組成物及以前述可固化組成物為原料所獲得的固化產物。 The invention relates to a curable composition and a cured product prepared by the same, in particular to a curable composition comprising an epoxy resin and a phenol resin containing a terminal unsaturated ester group, and the aforementioned curable composition is used as a raw material. The obtained cured product.
隨著半導體技術的進步，元件的尺寸也不斷地縮小，而進入微米領域中，單一層導線已經不敷使用，必須朝向三度空間發展，所以必須建構多層金屬內連線，才能滿足發展的需求。在多層金屬內連線製程中，主要有兩個問題會影響其效能，一為金屬導線與介電質層所引起的訊號傳遞延遲(RC delay)，另一為金屬導線配線之間的訊號干擾(Cross talk)，其中訊號傳遞的速度和介電常數(Dielectric Constant；Dk)平方根成反比，而介電損失(Dissipation Factor；Df)越低容易保持訊號的完整性，因此發展低介電材料為現今重要的課題。 With the advancement of semiconductor technology, the size of components has continued to shrink. In the field of micrometers, single-layer wires have become inadequate and must be developed towards three-dimensional space. Therefore, multilayer metal interconnects must be constructed to meet the development needs. . In the multilayer metal interconnection process, there are two main problems that affect its performance. One is the signal transmission delay (RC delay) caused by the metal wire and the dielectric layer, and the other is the signal interference between the metal wire wiring. (Cross talk), where the speed of signal transmission is inversely proportional to the square root of the dielectric constant (Dk), and the lower the dielectric loss (Df), the easier it is to maintain the integrity of the signal. Therefore, the development of low dielectric materials is Important issues today.
現今廣泛採用以環氧樹脂與固化劑為主體的可固化組成物所製備的環氧樹脂固化產物來作為基板的材 料，但若使用目前常見的固化劑，如：酚類化合物，往往會在固化環氧樹脂的過程中產生高極性的二級醇，導致較高的損耗正切，進而使得基板無法滿足實際應用的需求。 Nowadays, an epoxy resin cured product prepared from a curable composition mainly composed of an epoxy resin and a curing agent is widely used as a substrate material. However, if common curing agents such as phenolic compounds are used, they tend to generate highly polar secondary alcohols during the curing process of epoxy resins, resulting in higher loss tangent, which makes the substrate unable to meet the requirements of practical applications. demand.
因此，Nakamura等人研究以具三官能基的活性酯固化劑(如苯三酚醋酸酯；Triacetoxybenzene；TAB)可製得無二級醇的環氧樹脂固化產物，且前述環氧樹脂固化產物較以三酚化合物(如苯三酚；Trihydroxybenzene；THB)作為固化劑所製得之環氧樹脂固化產物有較佳的介電性質。另外，日本石墨(DIC corporation)亦開發有商品名為EPICLON HPC-8000-65T的活性酯固化劑，且後續有其他研究以此活性酯固化劑與環氧樹脂及氰酸酯共聚得到介電損失約8mU的固化產物。 Therefore, Nakamura et al. Studied the use of trifunctional active ester curing agents (such as triacetoxybenzene; TAB) to obtain epoxy resin cured products without secondary alcohol, and An epoxy resin cured product prepared by using a triphenol compound (such as Trihydroxybenzene; THB) as a curing agent has better dielectric properties. In addition, Japan Graphite (DIC corporation) has also developed an active ester curing agent under the trade name EPICLON HPC-8000-65T, and other studies have subsequently been conducted to obtain dielectric loss by copolymerizing the active ester curing agent with epoxy resin and cyanate ester. About 8mU of cured product.
然而，使用前述活性酯固化劑雖可避免習用固化劑的缺失，但亦因在固化環氧樹脂的過程中不產生二級醇，使分子間作用力下降，進而衍生固化產物的熱性質及接著性不足等問題，舉例來說，以前述具三官能基的活性酯固化劑所製得之環氧樹脂固化產物的玻璃轉移溫度較以三酚化合物作為固化劑所製得之環氧樹脂固化產物的玻璃轉移溫度低。是以，如何在導入活性酯作為固化劑的同時不降低固化產物的玻璃轉移溫度與阻燃性實為目前亟欲克服之問題。 However, although the use of the aforementioned active ester curing agent can avoid the lack of conventional curing agents, it also reduces the intermolecular forces because secondary alcohols are not generated during the process of curing the epoxy resin, and the thermal properties of the cured products are further derived. For example, the glass transition temperature of the epoxy resin cured product obtained by using the aforementioned trifunctional active ester curing agent is lower than that of the epoxy resin cured product obtained by using a triphenol compound as a curing agent. The glass transition temperature is low. Therefore, how to introduce the active ester as a curing agent without lowering the glass transition temperature and flame retardancy of the cured product is a problem to be overcome at present.
有鑑於此，本發明旨在於提供一種可固化組成物，其係以含末端不飽和酯基的酚醛樹脂作為固化劑，藉此可避免於後續固化環氧樹脂的反應中產生高極性的二級醇，使得所製得之固化產物具有低介電常數、低介電損失的特性。此外，經由末端不飽和酯基的雙鍵交聯，更可進一步增加固化產物的熱性質與接著強度。 In view of this, the present invention aims to provide a curable composition using a phenolic resin containing a terminal unsaturated ester group as a curing agent, thereby avoiding the generation of highly polar secondary in the subsequent reaction of curing the epoxy resin. Alcohol makes the prepared cured product have the characteristics of low dielectric constant and low dielectric loss. In addition, the double bond cross-linking via the terminal unsaturated ester group can further increase the thermal properties and adhesion strength of the cured product.
依據本發明之一實施方式係在於提供一種可固化組成物，其係包含環氧樹脂、含末端不飽和酯基的酚醛樹脂與觸媒，且末端不飽和酯基具有如式(i)所示之一結構：
依據前述之可固化組成物，其中前述含末端不飽和酯基的酚醛樹脂可具有如式(I)、式(II)、式(III)、式(IV)或式(V)所示之一結構：
依據前述之可固化組成物，其中前述觸媒可包含未共用電子對，且前述觸媒的添加量可為環氧樹脂含量的0.1wt%至5wt%。 According to the foregoing curable composition, the catalyst may include an unshared electron pair, and the amount of the catalyst added may be 0.1 wt% to 5 wt% of the epoxy resin content.
依據前述之可固化組成物，其可更包含一過氧化物起始劑。 According to the aforementioned curable composition, it may further include a peroxide initiator.
依據前述之可固化組成物，其中前述過氧化物起始劑的添加量可為前述含末端不飽和酯基之酚醛樹脂含量的0.1wt%至5wt%。 According to the aforementioned curable composition, the aforementioned peroxide initiator may be added in an amount of 0.1 wt% to 5 wt% of the content of the terminal unsaturated ester group-containing phenolic resin.
依據本發明之另一實施方式係在於提供一種固化產物，其係藉由前述可固化組成物進行一固化反應而得。 According to another embodiment of the present invention, a cured product is provided, which is obtained by performing a curing reaction on the curable composition.
依據前述之固化產物，前述固化反應可藉由加熱前述可固化組成物來完成，且前述固化反應的固化溫度可為180℃至240℃。 According to the aforementioned cured product, the aforementioned curing reaction may be completed by heating the aforementioned curable composition, and the curing temperature of the aforementioned curing reaction may be 180 ° C to 240 ° C.
S102‧‧‧混合步驟 S102‧‧‧ Mixing steps
S104‧‧‧固化步驟 S104‧‧‧Cure step
210、230‧‧‧醇負電 210, 230‧‧‧ alcohol negative
220‧‧‧酚負電 220‧‧‧ Phenol negative
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：第1圖係依據本發明一實施方式之固化產物的製備方法流程圖；第2A圖係本發明實施例1中雙環戊二烯酚醛樹脂在DMSO-d6溶液中分析之氫核磁共振光譜圖；第2B圖係本發明實施例1中固化產物在DMSO-d6溶液中分析之氫核磁共振光譜圖；第3A圖係實施例1中固化反應的反應機構圖之一；第3B圖係實施例1中固化反應的反應機構圖之二；第3C圖係實施例1中固化反應的反應機構圖之三；以及第3D圖係實施例1中固化反應的反應機構圖之四。 In order to make the above and other objects, features, advantages, and embodiments of the present invention more comprehensible, the description of the drawings is as follows: FIG. 1 is a flowchart of a method for preparing a cured product according to an embodiment of the present invention; Fig. 2A is a hydrogen nuclear magnetic resonance spectrum of a dicyclopentadiene phenolic resin analyzed in a DMSO-d 6 solution in Example 1 of the present invention; Fig. 2B is an analysis of a cured product in a DMSO-d 6 solution in Example 1 of the present invention. Fig. 3A is one of the reaction mechanism diagrams of the curing reaction in Example 1; Fig. 3B is the second reaction mechanism diagram of the curing reactions in Example 1; and Fig. 3C is the curing mechanism in Example 1. The third reaction mechanism diagram of the reaction; and FIG. 3D is the fourth reaction mechanism diagram of the curing reaction in Example 1.
本發明提供一種可固化組成物，其係包含環氧樹脂、含末端不飽和酯基的酚醛樹脂與觸媒，且末端不飽和酯基具有如式(i)所示之一結構：
前述環氧樹脂可為雙酚A型環氧樹脂(Diglycidyl ether of Bisphenol A)、酚醛環氧樹脂(Phenol novolac epoxy)、甲基酚醛環氧樹脂(Cresol novolac epoxy)、雙環戊二烯苯酚環氧樹脂(Dicyclopentadiene-phenol epoxy)、含萘環氧樹脂(Naphthalene-containing epoxy)或其混合。換言之，前述環氧樹脂可單獨使用，也可同時使用兩種以上，且當使用兩種以上時，可依任何比例混合。藉此，可藉由選用適當的環氧樹脂，賦予後續固化產物所需的性質。 The aforementioned epoxy resin may be Diglycidyl ether of Bisphenol A, Phenol novolac epoxy, Cresol novolac epoxy, dicyclopentadiene phenol epoxy Dicyclopentadiene-phenol epoxy, Naphthalene-containing epoxy, or a mixture thereof. In other words, the foregoing epoxy resins can be used alone or in combination of two or more kinds, and when two or more kinds are used, they can be mixed in any proportion. Therefore, by selecting an appropriate epoxy resin, desired properties of the subsequent cured product can be imparted.
前述“不飽和酯基”是指同時包含不飽和基團與酯基的官能基，而前述不飽和基團可為有取代基的雙鍵。具體地，前述含末端不飽和酯基的酚醛樹脂可具有如式(I)、式(II)、式(III)、式(IV)或式(V)所示之一結構：
前述觸媒可包含未共用電子對，例如但不限於4-二甲基氨基吡啶(4-Dimethylaminopyridine)、咪唑(Imidazole)、2-甲基咪唑(2-Methylimidazole)或2-乙基-4-甲基咪唑(2-Ethyl-4-methylimidazole)。藉此，觸媒的未共用電子對可與環氧樹脂的環氧基作用而有利於引發後續的固化反應。具體地，前述觸媒的添加量可為環氧樹脂含量的0.1wt%至5wt%。 The aforementioned catalyst may include unshared electron pairs, such as, but not limited to, 4-Dimethylaminopyridine, Imidazole, 2-Methylimidazole, or 2-ethyl-4- Methylimidazole (2-Ethyl-4-methylimidazole). In this way, the unshared electron pair of the catalyst can interact with the epoxy group of the epoxy resin, which is beneficial to initiate the subsequent curing reaction. Specifically, the aforementioned catalyst may be added in an amount of 0.1 wt% to 5 wt% of the epoxy resin content.
再者，前述可固化組成物更可包括一過氧化物起始劑，例如但不限於二叔丁基過氧化物(Di-tert-butyl peroxide；DTBP)、過氧化苯甲醯(Benzoyl peroxide；BPO)、過氧化叔丁醇(Tert-butyl hydroperoxide；TBHP)或叔丁基過氧化異丙苯(Tert-butyl cumyl peroxide；TBCP)。藉此，過氧化物起始劑可促使末端不飽和酯基中的不飽和基團打開聚合，而使固化產物的交聯結構更為緊密，進而提升其熱性質。具體地，過氧化物起始劑的添加量為含末端不飽和酯基之酚醛樹脂含量的0.1wt%至5wt%。 Further, the curable composition may further comprise a peroxide initiator, such as, but not limited to, di-t-butyl peroxide (Di- tert -butyl peroxide; DTBP) , benzoyl peroxide (Benzoyl peroxide; BPO), tert-butyl hydroperoxide (tert -butyl hydroperoxide; TBHP) or t-butyl cumyl peroxide (tert -butyl cumyl peroxide; TBCP) . In this way, the peroxide initiator can promote the opening and polymerization of unsaturated groups in the terminal unsaturated ester groups, so that the crosslinked structure of the cured product is more compact, thereby improving its thermal properties. Specifically, the peroxide initiator is added in an amount of 0.1 wt% to 5 wt% of the content of the phenol resin containing the terminal unsaturated ester group.
本發明進一步提供一種固化產物，其係藉由前述可固化組成物進行一固化反應而得，而前述固化反應參照第1圖簡單說明如下，其中本發明之固化產物的製備方法包含步驟S102與步驟S104。 The present invention further provides a cured product, which is obtained by performing a curing reaction on the curable composition, and the curing reaction is briefly described with reference to FIG. 1. The method for preparing a cured product of the present invention includes steps S102 and steps. S104.
步驟S102是進行一混合步驟，係將環氧樹脂、含末端不飽和酯基的酚醛樹脂與觸媒混合而得到可固化組成物。具體來說，藉由步驟S102，含末端不飽和酯基的酚醛樹脂、環氧樹脂與觸媒可形成含有可固化組成物的一前驅物溶液，並可選擇性地添加過氧化物起始劑至其中，以促使末端不飽和酯基中的不飽和基團打開聚合。此外，前驅物溶液所用之溶劑係用以幫助含末端不飽和酯基的酚醛樹脂與環氧樹脂共混，因此，只要可溶解含末端不飽和酯基的酚醛樹脂、環氧樹脂且不與前述二者反應者，皆可作為步驟S102中的溶劑使用。至於含末端不飽和酯基的酚醛樹脂、環氧樹 脂、觸媒、過氧化物起始劑的細節請參照前文，在此不予以贅述。 Step S102 is a mixing step of mixing an epoxy resin, a phenol resin containing a terminal unsaturated ester group, and a catalyst to obtain a curable composition. Specifically, through step S102, the phenolic resin, epoxy resin, and catalyst containing terminal unsaturated ester groups can form a precursor solution containing a curable composition, and a peroxide initiator can be optionally added. To this, the polymerization of the unsaturated group in the terminal unsaturated ester group is opened. In addition, the solvent used in the precursor solution is used to help the phenolic resin containing the terminal unsaturated ester group and the epoxy resin to be blended. Therefore, as long as the phenolic resin and the epoxy resin containing the terminal unsaturated ester group are soluble, Both of them can be used as the solvent in step S102. As for phenolic resins and epoxy resins containing terminal unsaturated ester groups For details of lipids, catalysts, and peroxide initiators, please refer to the previous sections, and will not be repeated here.
步驟S104是進行一固化步驟，使含末端不飽和酯基的酚醛樹脂與環氧樹脂在觸媒催化下產生交聯以形成固化產物。具體來說，可透過加熱前驅物溶液使含末端不飽和酯基的酚醛樹脂與環氧樹脂在觸媒催化下產生交聯，且加熱之固化溫度可為180℃至240℃，而加熱時間可為1小時至6小時。更具體地，前述加熱方式可採用多段加熱固化方式加熱前驅物溶液，例如，以180℃、200℃、220℃各加熱2小時。關於加熱之固化溫度與加熱時間可隨所使用含末端不飽和酯基的酚醛樹脂與環氧樹脂的種類彈性調整，本發明並不以此為限。 Step S104 is performing a curing step to cause the phenolic resin containing the terminal unsaturated ester group and the epoxy resin to undergo cross-linking under the catalyst catalysis to form a cured product. Specifically, the precursor solution can be heated to cross-link the phenolic resin containing terminal unsaturated ester groups with the epoxy resin under the catalyst catalysis, and the curing temperature of the heating can be 180 ° C to 240 ° C, and the heating time can be For 1 hour to 6 hours. More specifically, the foregoing heating method may use a multi-stage heating curing method to heat the precursor solution, for example, each of the heating is performed at 180 ° C, 200 ° C, and 220 ° C for 2 hours. Regarding the curing temperature and heating time of the heating, the elasticity can be adjusted according to the type of the phenol resin and the epoxy resin containing the terminal unsaturated ester group, and the present invention is not limited thereto.
茲以下列具體實施例進一步示範說明本發明，用以有利於本發明所屬技術領域通常知識者，可在不需過度解讀的情形下完整利用並實踐本發明，而不應將這些實施例視為對本發明範圍的限制，但用於說明如何實施本發明的材料及方法。 The following specific examples are used to further illustrate the present invention for the benefit of the ordinary knowledgeable person in the technical field to which the present invention pertains. The present invention can be fully utilized and practiced without excessive interpretation, and these embodiments should not be regarded as The scope of the present invention is limited, but is used to explain how to implement the materials and methods of the present invention.
首先，在實施例1中，可固化組成物之環氧樹脂係採用市售環氧樹脂HP-7200，含末端不飽和酯基的酚醛樹脂具有式(I)所示之結構，其中A為苯基，R1為甲基，R2與R3為H，觸媒採用4-二甲氨基吡啶，額外添加之過氧化物起始劑則為叔丁基過氧化異丙苯。 First, in Example 1, the epoxy resin of the curable composition is a commercially available epoxy resin HP-7200. The terminal unsaturated ester group-containing phenol resin has a structure represented by formula (I), where A is benzene. Group, R 1 is methyl, R 2 and R 3 are H, the catalyst is 4-dimethylaminopyridine, and the additional peroxide initiator is tert-butyl cumene peroxide.
進一步來說，實施例1之含末端不飽和酯基的酚醛樹脂係由雙環戊二烯酚醛樹脂與甲基丙烯酸酐在4-二甲氨基吡啶催化下反應而得。具體地，如下述反應方程式所示：
請參考第2A圖與第2B圖，第2A圖係本發明實施例1中雙環戊二烯-苯酚加成物(A1)在DMSO-d6溶液中分析之氫核磁共振光譜圖，第2B圖係本發明實施例1中含末端不飽和酯基的酚醛樹脂(I-a)在DMSO-d6溶液中分析之氫核磁共振光譜圖。經由比對第2A圖與第2B圖可知，第2A圖中9.1ppm位置處屬於酚基的特徵峰未見於第2B圖中，但第2B圖中於2.1ppm位置處生成屬於丙烯位置(Allylic position)之甲基上氫的特徵峰，且於5.8ppm及6.3ppm位置處生成屬於乙烯基(Vinyl group)上氫的特徵峰，藉此可進一步證實以雙環戊二烯酚醛樹脂與甲基丙烯酸酐為原料 可在觸媒的催化下製得具甲基丙烯酸苯酯之雙環戊二烯酚醛樹脂。 Please refer to FIG. 2A and FIG. 2B. FIG. 2A is a hydrogen nuclear magnetic resonance spectrum of a dicyclopentadiene-phenol adduct (A1) in a DMSO-d 6 solution in Example 1 of the present invention, and FIG. 2B It is a hydrogen nuclear magnetic resonance spectrum of a phenol resin (Ia) containing a terminal unsaturated ester group in Example 1 of the present invention analyzed in a DMSO-d 6 solution. By comparing Fig. 2A and Fig. 2B, it can be seen that the characteristic peak belonging to the phenol group at the 9.1 ppm position in Fig. 2A is not seen in Fig. 2B, but the propylene position is generated at the position of 2.1 ppm in Fig. 2B. ), A characteristic peak of hydrogen on methyl group, and characteristic peaks belonging to hydrogen on vinyl group (Vinyl group) are generated at the positions of 5.8 ppm and 6.3 ppm, thereby further confirming that the dicyclopentadiene phenol resin and methacrylic anhydride As a raw material, a dicyclopentadiene phenol resin with phenyl methacrylate can be prepared under the catalyst's catalysis.
接著，如第1圖所示之固化產物的製備方法，取0.511克市售環氧樹脂HP-7200與0.5克具甲基丙烯酸苯酯的雙環戊二烯酚醛樹脂，以使前述兩者在當量比1：1的比例下，以二甲基乙醯胺(Dimethylacetamide)為溶劑配置成固含量40wt%的前驅物溶液，並添加0.0025克的4-二甲氨基吡啶與0.005克的叔丁基過氧化異丙苯，接著利用玻璃塗佈機將前驅物溶液塗佈於玻璃上，階段升溫至80℃持續12小時以除去大部分溶劑，再以180℃、200℃、220℃各2小時進行固化，泡水脫模後得到深咖啡色的固化產物。 Next, as in the method for preparing a cured product shown in FIG. 1, 0.511 g of a commercially available epoxy resin HP-7200 and 0.5 g of a dicyclopentadiene phenol resin with phenyl methacrylate are taken so that the foregoing two are equivalent. At a ratio of 1: 1, a precursor solution with a solid content of 40 wt% was prepared using Dimethylacetamide as a solvent, and 0.0025 g of 4-dimethylaminopyridine and 0.005 g of tert-butyl peroxide were added. The cumene was oxidized, and then the precursor solution was coated on glass with a glass coater. The temperature was raised to 80 ° C for 12 hours to remove most of the solvent, and then cured at 180 ° C, 200 ° C, and 220 ° C for 2 hours each. After the foam is released from the mold, a dark brown solidified product is obtained.
後續將進一步藉由第3A圖至第3D圖說明本發明實施例1中具甲基丙烯酸苯酯之雙環戊二烯酚醛樹脂與市售環氧樹脂HP-7200之固化反應的反應機構，其中第3A圖係實施例1中固化反應的反應機構圖之一，第3B圖係實施例1中固化反應的反應機構圖之二，第3C圖係實施例1中固化反應的反應機構圖之三，以及第3D圖係實施例1中固化反應的反應機構圖之四。首先，如第3A圖所示，觸媒DMAP氮上的未共用電子對先攻擊市售環氧樹脂HP-7200(僅繪示局部結構)的環氧基而開環形成帶有醇負電210的中間物(1)。接著，如第3B圖所示，中間物(1)的醇負電210對雙環戊二烯酚醛樹脂(僅繪示局部結構)末端之甲基丙烯酸苯酯上的酯基進行親核取代反應，進而形成中間物(2)及帶有末端酚負電220的中間物(3)。接著，中間物(3)的酚負電220 攻擊中間物(2)中的含氮錯合物以形成產物(4)，並釋放觸媒DMAP，使觸媒DMAP可再回到形成中間物(1)的反應，如第3C圖所示。重複上述反應數次後，形成三維網狀結構。或者，中間物(3)的酚負電220除了攻擊中間物(2)外，也可如第3D圖所示，攻擊起始反應中市售環氧樹脂HP-7200(僅繪示局部結構)的環氧基進行親核開環反應，形成帶有醇負電230的中間物(5)。隨後，醇負電230再對雙環戊二烯酚醛樹脂(僅繪示局部結構)末端之甲基丙烯酸苯酯上的酯基進行親核取代反應，得到產物(4)與帶有末端酚負電220的中間物(3)。 Subsequently, the reaction mechanism of the curing reaction of the dicyclopentadiene phenol resin with phenyl methacrylate and the commercially available epoxy resin HP-7200 in Example 1 of the present invention will be further described with reference to FIGS. 3A to 3D. FIG. 3A is one of the reaction mechanism diagrams of the curing reaction in Example 1, FIG. 3B is the second reaction mechanism diagrams of the curing reaction in Example 1, and FIG. 3C is the third reaction mechanism diagrams of the curing reaction in Example 1. And FIG. 3D is the fourth reaction mechanism diagram of the curing reaction in Example 1. First, as shown in Figure 3A, the unshared electron pair on the nitrogen of the catalyst DMAP first attacks the epoxy group of the commercially available epoxy resin HP-7200 (only a partial structure is shown) and opens a ring with an alcohol negative 210. Intermediate (1). Next, as shown in FIG. 3B, the alcohol negative charge 210 of the intermediate (1) performs a nucleophilic substitution reaction on the ester group on the phenyl methacrylate at the end of the dicyclopentadiene phenol resin (only the partial structure is shown), and further An intermediate (2) and an intermediate (3) with a terminal phenol negative charge 220 are formed. Next, the phenol negative charge of the intermediate (3) is 220 The nitrogen-containing complex in the intermediate (2) is attacked to form the product (4), and the catalyst DMAP is released, so that the catalyst DMAP can return to the reaction to form the intermediate (1), as shown in FIG. 3C. After the above reaction was repeated several times, a three-dimensional network structure was formed. Alternatively, in addition to attacking the intermediate (2), the phenol negative charge 220 of the intermediate (3) may also attack the intermediate (2), as shown in FIG. 3D. The epoxy group undergoes a nucleophilic ring-opening reaction to form an intermediate (5) with an alcohol negative charge of 230. Subsequently, the alcohol negative charge of 230 and then the nucleophilic substitution reaction of the ester group on the phenyl methacrylate at the end of the dicyclopentadiene phenol resin (only the local structure is shown) gave the product (4) and Intermediate (3).
由第3A圖至第3D圖可知，在上述固化反應中，不會產生具有極性的二級醇，有助於降低所製得之固化產物的介電常數。此外，在固化過程中，產物(4)上甲基丙烯酸酯基中的雙鍵在過氧化物起始劑的起始下，可雙鍵聚合形成更緊密的網狀結構而具有如式(VI)所示之局部結構，更可以有效提升固化產物的熱穩定性：
與實施例1不同的是，比較例1之可固化組成物中係採用商品名為EPICLON HPC-8000-65T的活性酯固化劑。至於如環氧樹脂與活性酯固化劑的混合比例、觸媒與溶劑的選用以及固化步驟等條件均與實施例1相同，在此不予以贅述。在固化步驟完成後，泡水脫模即可製得深咖啡色的固化產物。 Unlike Example 1, the curable composition of Comparative Example 1 uses an active ester curing agent with a trade name of EPICLON HPC-8000-65T. As for the conditions such as the mixing ratio of the epoxy resin and the active ester curing agent, the selection of the catalyst and the solvent, and the curing step, the conditions are the same as those in Embodiment 1, and will not be repeated here. After the curing step is completed, a dark brown colored cured product can be obtained by demolding with water.
後續進一步利用熱機械分析法(Thermo-mechanical analysis；TMA)分別量測實施例1所製得之固化產物的玻璃轉移溫度以及比較例1所製得之固化產物的玻璃轉移溫度，其中熱機械分析法的條件為在5℃/min的加熱速率下使用動態機械分析儀(Dynamic Mechanical Analyzer；DMA)來進行。經由分析得知，實施例1所製得之固化產物的玻璃轉移溫度為203℃，而比較例1所製得之固化產物的玻璃轉移溫度為163℃，亦即由本發明所提供之可固化組成物製備而得的固化產物具有較高之玻璃轉移溫度。 Subsequently, the thermo-mechanical analysis (TMA) was used to measure the glass transition temperature of the cured product prepared in Example 1 and the glass transition temperature of the cured product prepared in Comparative Example 1, respectively. The thermo-mechanical analysis The conditions of the method were performed using a Dynamic Mechanical Analyzer (DMA) at a heating rate of 5 ° C / min. It is known through analysis that the glass transition temperature of the cured product obtained in Example 1 is 203 ° C, and the glass transition temperature of the cured product obtained in Comparative Example 1 is 163 ° C, that is, the curable composition provided by the present invention The cured product obtained from the product has a higher glass transition temperature.
再者，進一步利用熱重分析法(Thermo-gravimetric analysis；TGA)量測實施例1之固化產物的5%熱重損失溫度(Td5%)為427℃以及800℃的焦炭殘餘率(Char yield)為2.8%，其中”5%熱重損失溫度”是指固化產物的重量損失達5%的溫度，而”800℃的焦炭殘餘率”是指加熱溫度達800℃時固化產物的殘餘重量比率。此外，前述熱重量分析法的條件是在氮氣氣氛、20℃/min 的加熱速率下使用熱重分析儀來進行。由前述分析可知，實施例1的固化產物具有優良的熱穩定性。 Furthermore, the thermo-gravimetric analysis (TGA) was used to measure the 5% thermogravimetric loss temperature (T d5% ) of the cured product of Example 1 at 427 ° C and 800 ° C (Char yield). ) Is 2.8%, where "5% heat weight loss temperature" refers to the temperature at which the weight loss of the cured product reaches 5%, and "800 ° C coke residue rate" refers to the residual weight ratio of the cured product when the heating temperature reaches 800 ° C . The conditions of the aforementioned thermogravimetric analysis were performed using a thermogravimetric analyzer under a nitrogen atmosphere and a heating rate of 20 ° C / min. It can be known from the foregoing analysis that the cured product of Example 1 has excellent thermal stability.
另以介電常數分析儀測得在頻率為1GHz時，實施例1之固化產物的介電常數(1GHz)與介電損失分別為2.76U與10.4mU，而比較例1之固化產物的介電常數(1GHz)與介電損失分別為為2.86U與11.4mU。由介電分析結果可知，相較於使用市售固化劑所製得之固化產物，實施例1的固化產物確實具有低介電常數與低介電損失的特性。 The dielectric constant analyzer also measured the dielectric constant (1GHz) and dielectric loss of the cured product of Example 1 at a frequency of 1GHz, and the dielectric constant of the cured product of Comparative Example 1 was 2.76U and 10.4mU, respectively. The constant (1GHz) and dielectric loss are 2.86U and 11.4mU, respectively. From the results of the dielectric analysis, it is known that the cured product of Example 1 does have characteristics of low dielectric constant and low dielectric loss compared to the cured product obtained using a commercially available curing agent.
與實施例1不同的是，在實施例2中含末端不飽和酯基的酚醛樹脂具有式(III)所示之結構，其中A為苯基，R1為甲基，R2與R3為H，其他如環氧樹脂同樣採用市售環氧樹脂HP-7200，觸媒仍採用4-二甲氨基吡啶，額外添加之過氧化物起始劑亦為叔丁基過氧化異丙苯。 The difference from Example 1 is that the phenolic resin containing a terminal unsaturated ester group in Example 2 has a structure represented by formula (III), where A is phenyl, R 1 is methyl, R 2 and R 3 are H. Others, such as epoxy resin, also use commercially available epoxy resin HP-7200. The catalyst still uses 4-dimethylaminopyridine, and the additional peroxide initiator is tert-butyl cumene peroxide.
進一步來說，實施例2之含末端不飽和酯基的酚醛樹脂係由酚醛樹脂與甲基丙烯酸酐在4-二甲氨基吡啶催化下反應而得。具體地，如下述反應方程式所示：
接著，取0.511克市售環氧樹脂HP-7200與0.33克具甲基丙烯酸苯酯的酚醛樹脂，以使前述兩者在當量比1：1的比例下，以二甲基乙醯胺為溶劑配置成固含量40wt%的前驅物溶液，並添加0.0025克的4-二甲氨基吡啶與0.003克的叔丁基過氧化異丙苯，接著利用玻璃塗佈機將前驅物溶液塗佈於玻璃上，階段升溫至80℃持續12小時以除去大部分溶劑，再以180℃、200℃、220℃各2小時進行固化，泡水脫模後得到深咖啡色的固化產物。 Next, take 0.511 g of commercially available epoxy resin HP-7200 and 0.33 g of phenolic resin with phenyl methacrylate, so that the foregoing two use dimethylacetamide as a solvent at a ratio of equivalent ratio of 1: 1. Prepare a precursor solution with a solid content of 40% by weight, add 0.0025 g of 4-dimethylaminopyridine and 0.003 g of t-butyl cumene peroxide, and then apply the precursor solution on the glass with a glass coater The temperature was raised to 80 ° C. for 12 hours to remove most of the solvent, and then cured at 180 ° C., 200 ° C., and 220 ° C. for 2 hours each time. After dark-water release, a dark brown solidified product was obtained.
與實施例2不同的是，比較例2之可固化組成物中係採用不包含甲基丙烯酸苯酯的酚醛樹脂作為環氧樹脂的固化劑。至於環氧樹脂與固化劑的混合比例、觸媒與溶劑的選用以及固化步驟等條件均與實施例2相同，在此不予以贅述。在固化步驟完成後，泡水脫模即可製得深咖啡色的固化產物。 Unlike Example 2, the curable composition of Comparative Example 2 uses a phenolic resin that does not contain phenyl methacrylate as a curing agent for the epoxy resin. As for the mixing ratio of the epoxy resin and the curing agent, the selection of the catalyst and the solvent, and the curing step, the conditions are the same as those of the embodiment 2, and will not be repeated here. After the curing step is completed, a dark brown colored cured product can be obtained by demolding with water.
後續同樣利用動態機械分析儀分別測得實施例2所製得之固化產物的玻璃轉移溫度為181℃，而比較例2 所製得之固化產物的玻璃轉移溫度為161℃。由此可知，本發明所提供之可固化組成物製備而得的固化產物具有較高之玻璃轉移溫度。 Subsequently, the glass transition temperature of the cured product obtained in Example 2 was also measured using a dynamic mechanical analyzer, respectively, as compared with 181 ° C, while Comparative Example 2 The glass transition temperature of the obtained cured product was 161 ° C. Therefore, it can be known that the cured product obtained by preparing the curable composition provided by the present invention has a higher glass transition temperature.
接著，再以介電常數分析儀測得在頻率為1GHz時，實施例2之固化產物的介電常數(1GHz)與介電損失分別為2.96U與13.4mU，而比較例2之固化產物的介電常數(1GHz)與介電損失分別為為3.42U與18.4mU。由此可知，本發明中使用具有甲基丙烯酸苯酯的酚醛樹脂作為環氧樹脂的固化劑確實可製得具有低介電常數與低介電損失等特性之固化產物。 Then, the dielectric constant analyzer measured the dielectric constant (1GHz) and dielectric loss of the cured product of Example 2 at a frequency of 1GHz, and the cured product of Comparative Example 2 was 2.96U and 13.4mU, respectively. Dielectric constant (1GHz) and dielectric loss are 3.42U and 18.4mU, respectively. From this, it can be known that the use of a phenolic resin having phenyl methacrylate as the curing agent for the epoxy resin in the present invention can indeed produce a cured product having characteristics such as low dielectric constant and low dielectric loss.
綜上所述，本發明利用含末端不飽和酯基的酚醛樹脂作為固化劑，可在觸媒催化下與環氧樹脂產生交聯而固化，並可避免在固化過程中產生高極性的二級醇，進而製得具有低介電常數、低介電損失等性質，並具有高玻璃轉移溫度的固化產物，而可降低其於產業上應用的限制。 In summary, the present invention utilizes a terminal unsaturated ester group-containing phenolic resin as a curing agent, which can be crosslinked and cured with epoxy resin under catalyst catalysis, and can avoid the generation of highly polar secondary in the curing process. Alcohols, in turn, produce cured products with low dielectric constant, low dielectric loss, and other properties, as well as high glass transition temperatures, which can reduce restrictions on their industrial application.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and retouches without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be determined by the scope of the attached patent application.
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