572926 A7 五、發明說明（ [發明背景] I發明範圍 本發明係有關可對金屬及無機材料產生優越附著性之 環氧樹脂用酚系硬化劑，並有關使用此酚系硬化劑之環氧 樹腊組成物。酚系硬化劑及環氧樹脂組成物可用於電子材 料、塗料、底漆、黏著劑，等等領域，且特別適合用於電 子材料之密封劑、層合物及支架材料。 2 ·先前技藝說明 近年來’電子材料領域上有趨向材料迷你化及減輕重 量之趨勢，而且要預防環境污染、傾向無^素及無銻材料、 無錯銲劑等等。依循這些趨勢之課題即為需要進一步改善 電子材料所使用密封劑、層合物、支架材料等等之性質。 例如：傳統之半導體密封樹脂中使用之環氧樹脂組成 物中’即以酚系酚醛清漆樹脂使酚醛清漆環氧樹脂硬化。 然而’要解決半導體之高集合化需求，就愈需要更小更薄 之包裝。另一方面，當考慮到環境問題時，亦需要傾向無 錯銲劑’而且亦必須解決鉛模框，ppFs(預鍍模框）等等之 發展問題。因此對各種不同性質密封樹脂之需求亦逐年提 高’而傳統之環氧樹脂組成物已很難確保其可靠性（此點主 要依密封樹脂之機械強度而定）。其中一種特定性質之需求 實例為更有效附著半導體晶片及鉛模框上。特定言之，即 使密封樹脂在吸收水份後浸入銲劑中時，亦不會發生破 裂、界面剝落等等現象。 此外’以玻璃基材為主之環氧層合物最常用為印刷電 I 丨丨丨 ι!ί — ^一^ — I (請先閱讀背面之注意事項再填寫本頁) 訂· · 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格⑵Q χ 297公餐） 1 312816 572926 A7 --------^ 五、發明說明（2 ) — — — — — — — — — — I — (請先閱讀背面之注意事項再填寫本頁) 路板之絕緣材料。氰胍通常用於層合物之環氧樹脂用硬化 劑但由於使用無鉛銲劑時需要耐熱性，因此開始著重使 用酚系酚醛清漆樹脂作為硬化劑之方法。然而使用酚系酚 醛清漆樹脂作為硬化劑時之缺點在於對鋼線圈（尤其對多 層板中内層鋼線藺）之附著性遠低於氰胍。 為了改善樹脂與金屬或無機材料之間黏著性而經常採 用之手段為使用矽烷偶合劑處理其表面，或添加矽烷偶合 劑至樹脂中。市面上可取得之環氧型及胺基型矽烷偶合劑 可有效改善黏著性，且已使用多年，但目前的問題在於對 環境之衝擊，及上文曾說明之近來迷你化之趨勢，因此愈 來愈多例子無法符合所需之性質。本發明者因此發展出具 有咪1^坐基或二甲胺基之石夕烧偶合劑（見例如：日本專利申請 案公開公告 Nos· Η05-186479, Η09-012683 及 Η09_ 295988)。現已證明，此等矽烷偶合劑相較於市場上可取得 之碎烧偶合劑更可以大幅改善樹脂與金屬或無機材料之間 之黏著性。 經濟部智慧財產局員工消費合作社印製 然而，上述具有咪唑基或二甲胺基之矽烷偶合劑之缺 點在於若用於整體掺和物時，由於黏度高且水解速度快， 因此很難操作。此外，此等矽烷偶合劑在如··酮類溶劑中 之溶解度差，因此當用於清漆時，出現適用之半衰期短之 缺點，因而限制了此等矽烷偶合劑之用途β [發明概要] 本發明第一個目的為提供一種環氡樹脂硬化劑，供製 造對金屬及無機材料具有優越附著性之環氧樹脂組成物， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 2 312816572926 A7 V. Description of the invention ([Background of the invention] I Scope of the invention The present invention relates to a phenolic hardener for epoxy resins which can have excellent adhesion to metal and inorganic materials, and an epoxy tree using the phenolic hardener Wax composition. Phenolic hardener and epoxy resin composition can be used in the fields of electronic materials, coatings, primers, adhesives, etc., and is especially suitable for sealants, laminates and bracket materials for electronic materials. 2 · Previous technical descriptions In recent years, in the field of electronic materials, there has been a trend toward miniaturization and weight reduction of materials, and to prevent environmental pollution, a trend towards non-ferrous and antimony-free materials, and error-free solders, etc. The topics that follow these trends are: Need to further improve the properties of sealants, laminates, bracket materials, etc. used in electronic materials. For example: In the epoxy resin composition used in traditional semiconductor sealing resins, phenolic novolac resin is used to make novolac epoxy Resin hardening. However, 'to address the high demand for semiconductors, smaller and thinner packages are needed. On the other hand, when considering the environment When it comes to problems, it is also necessary to favor error-free fluxes, and it is also necessary to solve the development problems of lead mold frames, ppFs (pre-plated mold frames), etc. Therefore, the demand for various types of sealing resins is also increasing year by year, while traditional epoxy resins It is difficult for the composition to ensure its reliability (this depends mainly on the mechanical strength of the sealing resin). One example of the demand for specific properties is more effective adhesion to semiconductor wafers and lead mold frames. In particular, even if the sealing resin is in When immersed in the flux after absorbing water, there will be no cracking, interfacial peeling, etc. In addition, 'epoxy laminates based on glass substrates are most commonly used for printed electronics I 丨 丨 丨 ι! — 一^ — I (Please read the notes on the back before filling this page) Order · · Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 size ⑵Q χ 297 public meal) 1 312816 572926 A7 -------- ^ V. Description of the invention (2) — — — — — — — — — — — I — (Please read the precautions on the back before filling out this page) Insulation material for road boards. Cyanoguanidine is usually used as a hardener for epoxy resins for laminates, but since heat resistance is required when using lead-free solders, a method of using a phenolic novolac resin as a hardener has begun to be emphasized. However, the disadvantage of using a phenolic novolac resin as a hardener is that the adhesion to steel coils (especially to the inner steel wire in multi-layer boards) is much lower than that of cyanoguanidine. In order to improve the adhesion between resin and metal or inorganic materials, a method often used is to treat the surface with a silane coupling agent, or add a silane coupling agent to the resin. The epoxy and amine-based silane coupling agents available on the market can effectively improve adhesion and have been used for many years. However, the current problem is the impact on the environment and the recent miniaturization trend described above. More and more examples fail to meet the required properties. The present inventors have thus developed a stone yaki coupler having a 1-methyl group or a dimethylamino group (see, for example, Japanese Patent Application Laid-Open Nos. Η05-186479, Η09-012683, and Η09_295988). It has been shown that these silane coupling agents can significantly improve the adhesion between resins and metal or inorganic materials compared to crushed-coupling couplings available on the market. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, the disadvantages of the above-mentioned silane coupling agents with imidazole or dimethylamine groups are that they are difficult to handle due to their high viscosity and fast hydrolysis rate when they are used in bulk blends. In addition, these silane coupling agents have poor solubility in solvents such as ketones. Therefore, when used in varnishes, they have the shortcoming of short half-life, which limits the use of these silane coupling agents. [Summary of the Invention] This The first object of the invention is to provide a cyclohedral resin hardener for the manufacture of epoxy resin compositions with superior adhesion to metals and inorganic materials. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) ) 2 312816
572926 五、發明說明（3 ) 並提供相應之環氧樹腊組成物及其硬化之材料。此外，另 一個目的為提供容易操作，在闕類溶劑中具有高溶解度， 且適合多種用途（包括清漆）之環氧樹脂硬化劑，並提供使 用此硬化劑之環氧樹脂组成物及其硬化之產品。 本發明者積極實驗方達成上述目的，結果發現，若由 一般酚系硬化劑與具有三級或更高級胺基之矽烷偶合劑混 合時，且當使用此混合物或其反應產物作為硬化劑時，則 可大幅改善環氧樹脂與金屬或無機材料之間黏著性^此 外，亦發現，即使使用具有三級或更高級胺基之矽统偶合 劑’該硬化劑仍很容易操作，而且很容易溶解在所有慣用 之溶劑中。 因此本發明提供一種環氧樹脂用酚系硬化劑，其包 含·· 酚系硬化劑；及 具有二級或更南級胺基之梦烧偶合劑。 吾等認為使用本發明硬化劑改善樹脂與金屬或無機材 料之間附著性之扭轉在於硬化劑中所包含酚系硬化劑之羥 基與硬化劑中所包含具有三級或更高級胺基之矽烷偶合劑 之燒氧砍烧基之間相互反應，因此硬化劑與硬化加速劑二 種功能集結在單一分子f，導致環氧樹脂之硬化反應得以 順利進行。 本發明使用之酚系硬化劑可為每一個分子具有2個或 更多個酚系羥基之任何酚系硬化劑，例如：雙酚A、雙酚 F、聚乙烯酚、苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ϋ ϋ ·1 H ϋ n ·1 ϋ -I I · ϋ I (請先閱讀背面之注意事項再填寫本頁) ·. 經濟部智慧財產局員工消費合作社印製 312816 572926 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 A7 B7 五、發明說明（4 ) 雙酚A酚醛清漆樹脂、雙酚f酚醛清漆樹脂、芳烷基苯齡 樹脂等等。其中，以苯齡樹脂硬化劑特別佳。 具有二級或更鬲級胺基之砍烧偶合劑為具有味嗤基或 其鹽、二甲胺基或其鹽之矽烷偶合劑較佳，且其可作為硬 化加速劑。其實例包括揭示於例如：日本專利申請案公開 &gNos.H05-186479，H09-295988，H05-039295；)H06- 279458, H09-296135, H09-295989, H09-295992, H10- 273492, Hlh092482, H12-226757 及 H1M08246，或由此 等具有咪峻基或二甲胺基之石夕烧偶合劑加上乙酸等等形成 之有機酸鹽。 上述矽烷偶合劑令，以下特別佳。首先為揭示於日本 專利申請案公開公告No· H05-186479之三種咪唑·梦烧化 合物，或其混合物。如日本專利申請案公開公告ν〇η〇5· 186479所揭示者，此等咪唑矽烷化合物為由咪唑化合物與 3-環氧丙氧基丙基矽烷化合物於8〇至2〇〇〇c下反應得到之 二種化合物之混合物（下文中稱此混合物為，，咪唑矽 烷”）。其次為具有二甲胺基之有機矽化合物，其構成日本 專利申請案公開公告No· H09-296135所揭示表面處理劑 之活性成份（下文中稱此等化合物為，，二甲胺基矽烷，，）。揭 示於曰本專利申請案公開公告No. H09_296135之此等二 甲胺基矽烷係由二甲胺與環氧矽烷加熱至20至80^後， 脫除未反應之二甲胺製得。 本發明環氧樹腊之盼系硬化劑可簡單地使用混合物， 但若由上述盼系硬化劑溶解後，在其中攪拌混入如上述具 ^紙張尺度適用中國國家標準（CNS)A4規格（21G x 297公楚)_ 4 犯幻6— --------! 裝--- (請先閱讀背面之注意事項再填寫本頁) 0 572926 A7 -------- B7___ 五、發明說明（5 ) 有三級或更高級胺基之矽烷偶合劑而製得經修飾之酚系硬 化劑時，亦有效。 、 此外，本發明亦提供一種環氧樹脂組成物，其包含0) 環氧樹脂及（b)根據本發明之環氧樹脂用酚系硬化劑。 本發明環氧樹脂组成物中使用之環氧樹脂可為任何環 氧樹脂，但以廣泛用於密封劑及層合物中之環氡樹脂較 佳。其實例包括雙酚A型環氧樹脂、雙酚ρ型環氧樹脂' 雙驗A齡駿清漆型環氧樹脂、苯酚酚醛清漆型環氧樹腊、 甲酚酚醛清漆型環氧樹脂、具有聯苯基架構之環氧樹脂、 具有萘架構之環氧樹脂、具有三苯基甲烷架構之環氧樹 脂’及此等環氧樹脂結構中有些氫原子被自素置換之環氧 樹脂。此外，本發明環氧樹脂組成物中所含環氧樹脂及環 氧樹脂用酚系硬化劑之量最好使混合比例（羥基/環氧基） 在0.2至1·2之範圍内。 本發明環氧樹脂组成物可另包含無機填料。密封劑中 常用之任何無機填料均可使用，但以雜質濃度低且平均粒 子直徑不超過30微米之矽石粉末較佳。無機填料佔樹脂组 成物總量之相對比例為25至90重量％較佳。 若需要時，可在本發明環氧樹脂組成物中適當添加釋 模劑如：天然蠟、合成蠟、直鏈脂肪酸之金屬鹽、酸醯胺、 酯及鏈烷烴，阻燃劑如：三氧化銻，著色劑如：碳黑，發 烧偶合劑、各種硬化加速劑、提供低應力之製劑如：橡膠 與矽酮等等。 本發明環氧樹脂組成物適用於層合物之清漆。此外， (請先閱讀背面之注意事項再填寫本頁) 裝 訂： 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） 5 312816 572926572926 V. Description of the invention (3) and provide corresponding epoxy wax composition and its hardened material. In addition, another object is to provide an epoxy resin hardener which is easy to handle, has high solubility in 阙 solvents, and is suitable for various uses (including varnishes), and provides an epoxy resin composition using the hardener and its hardened resin. product. The present inventors have actively experimented to achieve the above-mentioned object, and found that if a general phenolic hardener is mixed with a silane coupling agent having a tertiary or higher amine group, and when this mixture or a reaction product thereof is used as a hardener, It can greatly improve the adhesion between epoxy resin and metal or inorganic materials ^ In addition, it has been found that the hardener is easy to handle and easy to dissolve even when using a silicon-based coupling agent with a tertiary or higher amine group In all customary solvents. Accordingly, the present invention provides a phenol-based hardener for epoxy resins, which contains a phenol-based hardener; and a dream-fired coupling agent having a secondary or southern amine group. We believe that the use of the hardener of the present invention to improve the adhesion between the resin and the metal or inorganic material is that the hydroxyl group of the phenolic hardener contained in the hardener and the silane coupler having tertiary or higher amine groups contained in the hardener The oxygen-burning and oxygen-burning groups of the mixture react with each other, so the two functions of the hardener and the hardening accelerator are combined in a single molecule f, which causes the hardening reaction of the epoxy resin to proceed smoothly. The phenolic hardener used in the present invention may be any phenolic hardener having two or more phenolic hydroxyl groups per molecule, for example: bisphenol A, bisphenol F, polyvinyl phenol, phenol novolac resin, methyl alcohol Phenolic novolac resin, this paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ϋ ϋ · 1 H ϋ n · 1 ϋ -II · ϋ I (Please read the precautions on the back before filling in this Page) ·. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 312816 572926 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention (4) Bisphenol A novolac resin, bisphenol f novolac resin, aromatic Alkylbenzene age resin and so on. Among them, benzene-based resin hardeners are particularly preferred. The chopped-coupling agent having a secondary or higher amine group is preferably a silane coupling agent having a miso group or a salt thereof, a dimethylamine group or a salt thereof, and it can be used as a hardening accelerator. Examples thereof are disclosed in, for example: Japanese Patent Application Publication & gNos. H05-186479, H09-295988, H05-039295;) H06-279458, H09-296135, H09-295989, H09-295992, H10-273492, Hlh092482 , H12-226757 and H1M08246, or the organic acid salt formed by the ishibuya coupling agent which has miconyl or dimethylamino group plus acetic acid and the like. The above-mentioned silane coupling agent is particularly preferable in the following. First, there are three kinds of imidazole · dream burning compounds disclosed in Japanese Patent Application Laid-Open Publication No. H05-186479, or a mixture thereof. As disclosed in Japanese Patent Application Publication No. ν〇〇〇 · 186479, these imidazole silane compounds are obtained by reacting an imidazole compound with a 3-glycidoxypropylsilane compound at 80 to 2000c. A mixture of the two compounds obtained (hereinafter, this mixture is referred to as "imidazole silane"). Next is an organic silicon compound having a dimethylamine group, which constitutes the surface treatment disclosed in Japanese Patent Application Laid-Open Publication No. H09-296135 Active ingredients of the agent (hereinafter, these compounds are referred to as, dimethylaminosilane, etc.). These dimethylaminosilanes disclosed in Japanese Patent Application Publication No. H09_296135 are composed of dimethylamine and a ring. The oxysilane is heated to 20 to 80 ^, and is obtained by removing unreacted dimethylamine. The hope-based hardener of the epoxy resin of the present invention can be simply used as a mixture, but if the hope-based hardener is dissolved, the Among them, the mixture is mixed with the paper size as described above, which is applicable to the Chinese National Standard (CNS) A4 specification (21G x 297 Gongchu) _ 4 Guiren 6 — --------! Loading --- (Please read the back (Please fill in this page again) 0 572926 A7 -------- B7___ V. Description of the invention (5) It is also effective when a modified phenolic hardener is obtained by using a silane coupling agent of a tertiary or higher amine group. In addition, the present invention also provides an epoxy resin composition, It contains 0) epoxy resin and (b) phenolic hardener for epoxy resin according to the present invention. The epoxy resin used in the epoxy resin composition of the present invention may be any epoxy resin, but is widely used as a sealant. Cycloplast resins in laminates and laminates are preferred. Examples include bisphenol A epoxy resin, bisphenol ρ-type epoxy resin 'double-test A-age varnish-type epoxy resin, phenol novolac-type epoxy resin wax , Cresol novolac epoxy resin, epoxy resin with biphenyl structure, epoxy resin with naphthalene structure, epoxy resin with triphenylmethane structure, and some hydrogen atoms in these epoxy resin structures Epoxy resin replaced by self-priming. In addition, the amount of epoxy resin and phenolic hardener for epoxy resin contained in the epoxy resin composition of the present invention is preferably such that the mixing ratio (hydroxyl / epoxy group) is 0.2 to Within the range of 1.2. The epoxy resin composition of the present invention The material may further include an inorganic filler. Any inorganic filler commonly used in sealants can be used, but silica powder having a low impurity concentration and an average particle diameter of not more than 30 microns is preferred. The relative proportion of the inorganic filler to the total resin composition It is preferably 25 to 90% by weight. If necessary, a mold release agent such as natural wax, synthetic wax, metal salt of linear fatty acid, ammonium acid, ester and chain may be appropriately added to the epoxy resin composition of the present invention. Alkanes, flame retardants such as antimony trioxide, colorants such as carbon black, fever coupling agents, various hardening accelerators, low stress agents such as rubber and silicone, etc. The epoxy resin composition of the present invention is applicable Laminated varnish. In addition, (please read the notes on the back before filling out this page) Binding: Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297) Gongchu) 5 312816 572926
五、發明說明（6 本發明環氧樹脂组成物亦可浸入基材内’用為預浸料，或 可用在由此等預浸料堆疊成之層合物t，此外，與金屬粉 末捏摔混合時’本發明環氧樹脂組成物亦適用為半導體晶 片支架材料。S此本發明環氧樹脂组成物有許多用途。 加熱本發明環氧樹脂组成物時，亦形成硬化之環氧樹 脂。此硬化材料適用於半導體密封裝置，其中使用硬化之 材料密封半導遨晶片。 本發明另一方面提供一種製造環氧樹脂用酚系硬化劑 之方法，其包括： 熔化酚系硬化劑；及 在其中攪拌混合具有三級或更高級胺基之石夕烧偶合 劑’得到經修飾之盼系硬化劑。 製造本發明環氧樹脂用酚系硬化劑之方法中，具有三 級或更焉級胺基之珍燒偶合劑之比例為每1份重量比紛系 硬化劑使用0.001至1份重量比較佳，以0 01至〇 5份重 量比更佳。若具有三級或更高級胺基之砍燒偶合劑用量太 馬時’則會發生膠凝，若太低則無法改善附著性。 若酚系硬化劑為固體時，混合酚系硬化劑與具有三級 或更高級胺基之矽烷偶合劑之較佳混合法為事先熔化驗系 硬化劑’然後逐漸攪拌熔化物同時添加矽烷偶合劑β苯驗 樹脂之羥基與矽烷之烷氧矽烷基則反應形成醇。 [圖式之簡單說明] 第1圖說明使用實例所製造樹脂共同結合之銅合金板 之抗切變強度之測定法。 --裝--- (請先閱讀背面之注咅？事項再填寫本頁) 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） 6 312816 572926 A7 ------—~ 五、發明說明（7 ) [具體實施例之說明] 下文透過實例特別說明本發明。然而，本發明不受限 於此等實例。首先，在製造本發明環氡樹脂用酚系硬化劑 之前，先製備咪唑_矽烷或二甲胺基矽烷；此作法說明於下 述合成實例1及合成實例2。應注意，實例中述及之混合 比例單位係以重量計。 (合成實例1) 如日本專利申請案公開公告No· Η05-1 86479所述，首 先製造咪唑-矽烷。製備3·4克（〇·〇5莫耳）咪唑於95°c之溶 化物’以超過30分鐘時間，在氬蒙氣下，攪拌滴注H 8 克（0.05莫耳）3-環氧丙氧基丙基三甲氧砍院。滴注完成 後’反應績於95 °C溫度下進行1小時。所得咪峻-碎烧為 三種成份之混合物。 (合成實例2) 依曰本專利申請案公開公告No. Η09-296135所述，製 造二甲胺基矽烧。取13.5克（0.3莫耳）二甲胺與17.3克（0.07 莫耳）3-環氧丙氧基三甲氧矽烷置入氮蒙氣下之高壓釜 中，二種成份於150°C下加熱反應1小時。反應後，使用 蒸發器排除反應混合物中過量二甲胺，得到19.9克二甲胺 基矽烷。 (實例1) 依下列方法，使用來自合成實例1之咪唑-矽燒製造根 據本發明環氧樹脂用之酚系硬化劑。取所製得35克苯紛紛 醛清漆樹脂（羥基當量104)加熱至l〇〇°C，製成熔化物。逐 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） 7 312816 —— — — — — — — — II —^^1 · I I (請先閱讀背面之注意事項再填寫本頁) 上*0 · 經濟部智慧財產局員工消費合作社印製 572926V. Description of the invention (6 The epoxy resin composition of the present invention can also be immersed in a substrate 'used as a prepreg, or can be used in a laminate t stacked with such prepregs, and in addition, it can be crushed with metal powder When mixed, the epoxy resin composition of the present invention is also suitable as a semiconductor wafer holder material. This epoxy resin composition of the present invention has many uses. When the epoxy resin composition of the present invention is heated, a hardened epoxy resin is also formed. The hardened material is suitable for a semiconductor sealing device, in which a semiconductor material is sealed with a hardened material. Another aspect of the present invention provides a method for manufacturing a phenolic hardener for epoxy resin, comprising: melting a phenolic hardener; and therein Stirring the Shibuya coupling agent having a tertiary or higher amine group is obtained by stirring to obtain a modified hope-based hardener. The method for producing a phenolic hardener for an epoxy resin of the present invention has a tertiary or higher amine group The ratio of the Zhizheng coupling agent is 0.001 to 1 part by weight per 1 part by weight of the hardener, and more preferably 0.01 to 0.5 parts by weight. If it has a third or higher amine group, When the amount of the coupling agent is too high, gelation will occur, and if it is too low, the adhesion will not be improved. If the phenolic hardener is solid, the phenolic hardener is mixed with a silane coupling agent having a tertiary or higher amine group. The preferred mixing method is to melt the test hardener in advance and then gradually stir the melt while adding the hydroxy group of the silane coupling agent β benzene test resin and the alkoxysilyl group of the silane to react to form an alcohol. [Simplified description of the diagram] Figure 1 Describe the method for determining the shear strength of copper alloy plates combined with resins produced by use cases. --- --- (Please read the note on the back? Matters before filling out this page) Employees ’Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs The printed paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 χ 297 mm) 6 312816 572926 A7 ---------- ~ 5. Description of the invention (7) [Description of specific embodiments] The following examples The present invention is particularly illustrated. However, the present invention is not limited to these examples. First, before manufacturing the phenol-based hardener for the cyclofluorene resin of the present invention, an imidazole-silane or dimethylaminosilane is first prepared; this method It is shown in the following Synthesis Example 1 and Synthesis Example 2. It should be noted that the mixing ratio units mentioned in the examples are by weight. (Synthesis Example 1) As described in Japanese Patent Application Publication No. · 05-1 86479, first Manufacture of imidazole-silane. Prepare 3.4 g (0.05 mol) of a solution of imidazole at 95 ° C for more than 30 minutes under stirring in an argon atmosphere, and instill H 8 g (0.05 mol) with stirring. 3-glycidoxypropyltrimethoxytriol. After completion of the instillation, the reaction was performed at a temperature of 95 ° C for 1 hour. The obtained micon-crush was a mixture of three components. (Synthesis Example 2) Yi Yue As disclosed in this Patent Application Publication No. Η09-296135, dimethylaminosilicon is manufactured. Take 13.5 g (0.3 mol) of dimethylamine and 17.3 g (0.07 mol) of 3-glycidoxytrimethoxysilane in an autoclave under nitrogen atmosphere, and heat the two components at 150 ° C for reaction 1 hour. After the reaction, an excessive amount of dimethylamine in the reaction mixture was removed using an evaporator to obtain 19.9 g of dimethylamine silane. (Example 1) A phenol-based hardener for an epoxy resin according to the present invention was produced by using the imidazole-silicon fired from Synthesis Example 1 according to the following method. 35 g of the benzene aldehyde novolak resin (hydroxyl equivalent weight 104) obtained was heated to 100 ° C to prepare a melt. Chinese paper standard (CNS) A4 specification (210x 297 mm) is applied on a paper-by-paper scale 7 312816 —— — — — — — — — II — ^^ 1 · II (Please read the precautions on the back before filling this page) Top * 0 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 572926
漸添加！克合成實例1之，唾·矽烷，添加後，反應現合物 ㈣5分鐘’然後冷卻β冷卻後’所得固體磨成粉得到 — — — — — — — — — — — I · I I f請先閱讀背面之注音？事項再填寫本頁} 經咪唑-矽烷修飾之苯酚酚醛清漆樹脂（硬化劑1}，係環氧 樹脂用之酚系硬化劑。 (實例2) 依實例1之相同方法，但改用！克合成實例2之二甲 胺基矽烷替代1克合成實例i之咪唑_矽烷，得到二甲胺基 矽烷修飾之苯酚酚醛清漆樹脂（硬化劑2)，係環氧樹脂用酚 系硬化劑。 (實例3至14) 實例3至14中，依下列方法，使用實例丨之硬化劑！ 或實例2之硬化劑2製造環氧樹脂組成物。依下表丨所示 比例，於室溫下混合鄰甲酚酚醛清漆型環氧樹脂（環氡基當 量210)及其他材料。如表！所示，適當時可添加溶凝矽石 粉末（平均粒子直徑14微米）、2-乙基-4-甲基咪唑及3_環氧 丙氧基丙基三甲氧矽烷作為添加物。所得混合物再於9〇 至l〇〇°C下捏拌，冷卻後，磨成粉，得到環氧樹脂組成物。 經濟部智慧財產局員工消費合作社印製 使用上述付到之各環氧樹腊組成物，如第1圖所干， 將二片銅合金板（C-7025, 50毫米X 25毫米）共同結合在一 起’使環氧樹脂組成物於175°C下硬化8小時。採用第j 圖所示結構作為試驗板，採用張力測試器，依第丨圖所示 箭頭方向拉開試驗板，測定抗切變強度。拉開之速度為j 毫米/分鐘。其結果示於下表2。 (對照實例1至3) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 8 312816 572926 A7 B7 五、發明說明（9) 對照實例1至3中，採用苯酚酚醛清漆樹脂作為硬化 劑替代根據本發明環氧樹脂用之酚系硬化劑。亦即使用表 1所示之材料及混合比例，除此以外，均如實例3至14所 示製造環氧樹脂組成物。此外，使用所得到之環氧樹脂組 成物，依實例3至14所示測定抗切變強度。測定結果示於 下表2。 表1 實倒 對照實例 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 鄰甲酚紛联清漆型環乘 樹麻 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 硬化劑1 55 55 55 5S 55 55 硬化刺2 55 55 55 55 55 55 - - - 笨酚轮媒清漆樹磨 54 54 54 路凝矽石粉末 — 600 600 細 600 600 一 600 600 一 600 600 讎 600 600 2-乙基-4-甲基咪唑 3-環氡丙氧基丙基-三甲軋基矽烷 咪喳矽烷 1.5 表2 實例 對照實例 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 黏著性抗 切變強度 (公斤/公 分， 82 34 j 15 86 ► 37 38 80 32 36 81 35 37 60 25 形成凝集物 ! 實例3至14各具有充份黏著性抗切變強度，其中即使 用根據本發明硬化劑。實例3、6、9與12未使用熔凝矽石 粉末作為添加物，且具有高度黏著性抗切變強度，為80 公斤/公分2或以上。相對於對照實例1，其中未使用根據 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） 312816 訂 經濟部智慧財產局員工消費合作社印製 572926 A7 ------ B7 五、發明說明（10) 本發明硬化劑且未含有熔凝矽石粉末，強度則不足，為60 公斤/公分2。實例4、5、7、8、10、11、13與14則包含 了溶凝砍石粉末，其黏著性抗切變強度為32公斤/公分2 或以上。相對於對照實例2與3，同樣地包含熔凝矽石粉 末’但未使用根據本發明硬化劑，其強度則低，為25公斤 /公分2，或則形成凝集物，不可能結合。 (實例15與16) 實例15與16中，使用來自實例1之硬化劑1製造清 漆’使用此等清漆得到預浸料及鍍銅層合物。首先，依表 3所示比例混合溴化雙酚a型環氧樹脂（Br含量215%，環 氧基當量480)、鄰甲酚酚醛清漆型環氧樹脂（環氧基當量 210)、來自實例]之硬化劑丨（咪唑-矽烷修飾之酚醛清漆樹 脂）及下表3所示之其他材料。添加丙酮至各混合物令，製 成清漆。 其次’使各清漆浸入規格7628型玻璃纖維編織基材中 (係一種用於層合物之非鹼性平面編織玻璃布），使樹脂含 量約50%，乾燥，得到預浸料。將至多8張各預浸料堆疊 在一起’在每一面放上鋼箔（厚35微米），於40公斤/公分 2下加壓90分鐘，同時加熱至i75t，得到鍍銅之層合物。 為了評估各鍍銅之層合物之黏著力，使用寬1公分之鋼線 測定抗剝落強度。結果示於下表4。 (對照實例4與5) 對照實例4與5中，依表3所示比例使用表3所示材 料，但改用苯酚酚醛清漆樹脂（羥基當量1〇4)替代根據本發 — — — — — — — — — I — · I I (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（21〇x297公釐） 10 312816 572926 A7 --B7 —------^ 五、發明說明（U) 明硬化劑。除此之外，均依實例15與16製得鍛鋼層合物， 亦測定抗剝落強度。測定結果示於下表4。 (對照實例6) 對照實例6中，依表3所示比例使用表3所示材料， 但不使用根據本發明硬化劑。前述實例只使用丙酮來製備 清漆，但對照實例6中，除了丙酮外，尚必需使用二甲基 甲醢胺及甲基溶纖劑來製備清漆。除此之外，均依實例15 與16製備鍍銅層合物，測定抗剝落強度。測定結果示於下 表4 〇 --t— (請先閱讀背面之注意事項再填寫本頁) 表3 ............. ....... '—-- 實例 η 15 16 4 5 6 > 溴化雙酚Α型環氧樹脂 ^ 90 90 90 90^ 鄰甲紛紛搭清漆型環氧樹腊 10 10 10 10 10> 硬化劑i 27 27 一 — 一 苯酚酚醛清漆樹脂 — 27 27 1 胍 ' ^- 一 一 一 — 2-乙基-4-甲基-咪唑 — 0.2 0.2 0.2 0.厂 咪唑-矽烷 — 一 *— 0.4 卜· ---—^^. 訂· 經濟部智慧財產局員工消費合作社印製 本 表4 實例 ’~ 對照實飞i ^~^ 15 16 4 5 6 ^ 抗剝落強度（公斤/公分） 2.0 1.9 L7 於清漆中形成凝集物 2.0 ' --- 相 儘管只使用丙酮作為溶劑，仍得到充份抗剝落強度。相對 於對照實例4與5，其中未使用根據本發明硬化劑，且只 使用丙_作為溶劑’其強度則低，或則在清漆中形成凝莽 物。此外已發現，實例15與16具有充份抗剝落強度， 當於使用氰胍硬化劑（對L照實例6)時。 ^張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐）Gradually added! Grams of Synthesis Example 1, sialane. After the addition, the reaction solid was ㈣5 minutes 'then cooled and then cooled after β cooling'. The obtained solid was ground into powders. — — — — — — — — — — — I f Zhuyin on the back? Please fill in this page again}} Phenolic novolac resin (hardener 1) modified with imidazole-silane, a phenolic hardener for epoxy resin. (Example 2) The same method as in Example 1 was used, but used instead! The dimethylaminosilane of Example 2 was substituted for 1 g of the imidazole_silane of Synthesis Example i to obtain a dimethylaminosilane-modified phenol novolac resin (hardener 2), which is a phenolic hardener for epoxy resins. (Example 3) (14 to 14) In Examples 3 to 14, the hardener of Example 丨 was used according to the following method! Or the hardener 2 of Example 2 was used to make the epoxy resin composition. According to the proportion shown in the following table, o-cresol was mixed at room temperature. Novolac epoxy resin (cyclohexyl equivalent 210) and other materials. As shown in the table !, fused silica powder (average particle diameter 14 microns), 2-ethyl-4-methylimidazole can be added when appropriate And 3-glycidoxypropyltrimethoxysilane as an additive. The resulting mixture was kneaded at 90 to 100 ° C, cooled and ground into a powder to obtain an epoxy resin composition. Ministry of Economic Affairs wisdom Printing and use of epoxy resin wax The finished product, as shown in Figure 1, combines two copper alloy plates (C-7025, 50 mm X 25 mm) together to 'harden the epoxy resin composition at 175 ° C for 8 hours. Use the j The structure shown in the figure is used as a test plate. A tensile tester is used to pull the test plate in the direction of the arrow shown in the figure to determine the shear strength. The speed of pulling is j mm / min. The results are shown in Table 2 below. (Comparative Examples 1 to 3) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 8 312816 572926 A7 B7 V. Description of the invention (9) Comparative Examples 1 to 3 use phenol novolac resin The phenolic hardener for the epoxy resin according to the present invention is replaced as a hardener. That is, the materials and mixing ratios shown in Table 1 are used, and epoxy resin compositions are manufactured as shown in Examples 3 to 14. Using the obtained epoxy resin composition, the shear strength was determined as shown in Examples 3 to 14. The measurement results are shown in Table 2 below. Table 1 Comparative Example 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 O-cresol varnished ring-shaped hemp 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Hardener 1 55 55 55 5S 55 55 Hardened spines 2 55 55 55 55 55 55---Phenol varnish varnish tree mill 54 54 54 Road condensed silica powder — 600 600 Fine 600 600 600 600 600 600 600 600 600 2-Ethyl-4-methylimidazole 3-Cycloproxypropoxypropyl-trimethylsilyl imidazine 1.5 Table 2 Examples Comparative Examples 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 Adhesive Shear Strength (kg / cm, 82 34 j 15 86 ► 37 38 80 32 36 81 35 37 60 25 Form agglomerates! Examples 3 to 14 each have sufficient adhesion Shear resistance, in which the hardener according to the invention is used. Examples 3, 6, 9 and 12 did not use fused silica powder as an additive and had a high adhesive shear strength of 80 kg / cm2 or more. Relative to Comparative Example 1, which does not use the Chinese National Standard (CNS) A4 specification (210 x 297 mm) according to this paper size. 312816 Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative 572926 A7 ------ B7 5. Description of the invention (10) The hardener of the present invention, which does not contain fused silica powder, has insufficient strength, which is 60 kg / cm2. Examples 4, 5, 7, 8, 10, 11, 13, and 14 contain coagulation chopped stone powder, which has an adhesive shear strength of 32 kg / cm2 or more. Relative to Comparative Examples 2 and 3, fused silica powder was similarly contained, but the hardener according to the present invention was not used, and its strength was low at 25 kg / cm2, or agglomerates were formed, and bonding was impossible. (Examples 15 and 16) In Examples 15 and 16, the varnish was produced using the hardener 1 from Example 1 '. These varnishes were used to obtain a prepreg and a copper-plated laminate. First, according to the ratio shown in Table 3, brominated bisphenol a type epoxy resin (215% Br content, epoxy equivalent 480), o-cresol novolac epoxy resin (epoxy equivalent 210), from the example ] Hardener 丨 (imidazole-silane-modified novolak resin) and other materials shown in Table 3 below. Add acetone to each mixture to make a varnish. Secondly, each varnish is dipped into a 7628 type glass fiber woven base material (a non-alkali flat woven glass cloth used for laminates), the resin content is about 50%, and the prepreg is obtained. Stack up to 8 sheets of each prepreg 'on each side. Place steel foil (35 microns thick) on each side, press at 40 kg / cm 2 for 90 minutes, and heat to i75t at the same time to obtain a copper-plated laminate. In order to evaluate the adhesion of each copper-plated laminate, the peel resistance was measured using a steel wire 1 cm wide. The results are shown in Table 4 below. (Comparative Examples 4 and 5) In Comparative Examples 4 and 5, the materials shown in Table 3 were used in the proportions shown in Table 3, but a phenol novolak resin (hydroxyl equivalent 104) was used instead of according to the present invention — — — — — — — — — I — · II (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (21 × 297 mm) 10 312816 572926 A7 --B7 —-- ---- ^ V. Description of the invention (U) Ming hardener. In addition, forged steel laminates were prepared according to Examples 15 and 16, and the peel resistance was also measured. The measurement results are shown in Table 4 below. (Comparative Example 6) In Comparative Example 6, the materials shown in Table 3 were used in the proportions shown in Table 3, but the hardener according to the present invention was not used. The foregoing example uses only acetone to prepare the varnish, but in Comparative Example 6, in addition to acetone, it is necessary to use dimethylformamide and methyl cellosolve to prepare the varnish. Except that, copper plating laminates were prepared according to Examples 15 and 16, and the peel resistance was measured. The measurement results are shown in the following table 4 〇--t— (Please read the precautions on the back before filling in this page) Table 3 ............. ....... '- -Example η 15 16 4 5 6 > Brominated bisphenol A epoxy resin ^ 90 90 90 90 ^ o-methyl varnish epoxy epoxy wax 10 10 10 10 10 > hardener i 27 27 mono-phenol Novolac resin — 27 27 1 Guanidine '^-one one one — 2-ethyl-4-methyl-imidazole — 0.2 0.2 0.2 0. Factory imidazole-silane — one * — 0.4 BU · --- — ^. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, this table 4 Example '~ Comparative real flying i ^ ~ ^ 15 16 4 5 6 ^ Peeling strength (kg / cm) 2.0 1.9 L7 Forming agglutinates in varnish 2.0' --- Although the phase uses only acetone as a solvent, it still has sufficient peeling strength. In contrast to Comparative Examples 4 and 5, where the hardener according to the present invention was not used, and only propylene was used as the solvent ', its strength was low, or a rash was formed in the varnish. In addition, Examples 15 and 16 have been found to have sufficient peel resistance when using a cyanoguanidine hardener (as in Example 6 for L). ^ The scale is applicable to China National Standard (CNS) A4 (210 X 297 mm)