201031292 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種環氧樹脂組合物，尤指一種具 有複合型環氧樹脂硬化劑之無函素的環氧樹脂組合物。 【先前技術】 目前印刷電路板所應用的範圍及領域相當廣泛，一般 電子產品内的電子元件都插設在印刷電路板上，而現今的 癱印刷電路板為了符合高功率及高熱量之元件的應用範圍， 故在印刷㈣賴功效上進行開發及研究，以提高電 路板的散熱效率及高功率。 而印刷電路板係由含浸膠片（PP)，或含銅箔膠片 (C.er clad lami_，CCL)或銅箱等複數膠片利用熱壓合 而該含浸膠片係將玻璃纖維布浸潰於-環 ，膠中’亚進行乾料後續製程所形成-種薄型膠 片0 ^ 逐漸識的抬頭，許多消費性電子品已 板。基板’而改用無鹵素銅箱基 i，==板多添加有含鱗成分以補償阻燃的效 脂成分結構上;添力;:以應用主樹脂或硬化劑樹 樹㈣内的方添加含軸於 化劑，再添加含磷’搭配苯酚環樹脂硬 備耐燃性，如中華^第=錢所㈣之樹脂膠片具 華民国第293831號及第583258號專利， 201031292 用具有笨并噁嗪環（Benz〇xazine，Bz)之苯酚樹脂硬化 =調和其他酚醛樹脂硬化劑，以製作無鹵樹脂基板。然而 二中的BZ酚搭樹脂硬化劑雖可降低吸水性且具有低的介 =特〖生，但其所製成之基板具有韌性不佳，更有添加過量 二導，耐熱性不足之問題。此外，對於業界採用之基 =壓合製程亦有反應性過慢㈣題，將導致該祕環氧 、脂所製基板的玻璃轉換溫度（Tg)僅能到達16〇度。 緣是，本發明人有感上述缺失之可改善，提出一種設 理且有效改善上述缺失之本發明。 【發明内容】 利用ίίϋ之主要目的’在於提供一種環氧樹脂組合物， :_苯甲基魏酯混摻苯⑽脂硬化劑， 環=之硬化劑，以提升_環她： 致与燮ίί 1 板的玻璃轉換溫度（巧），且不 特=基板之耐熱性及吸水性，而該基板亦具備有阻燃之 環氣^明提供一種環氧樹脂組合物，係包括：組份⑷： d卜 份（6):複合型環氧樹脂硬化劑，其中 =歿σ 3L %氧樹脂硬化劑係由聚^ ^ ^ ^ ^ ^ ^ ^ ^ 化劑及苯酚樹脂硬化劑以_預定_混2 =域月曰硬 .本發明亦提供一種將該玻璃纖維布 乳樹脂組合物中，並經固化、乾 貝於上述的壞 片。 乾知荨步驟後，而形成的膠 本發明更提供一種利用上述膠片 成之印刷電路㈣基板。 “衣程所製 201031292 本發明具有以下有益的效果··本 ?搭配組成-複合型環氧樹脂硬化劑，而使用該複= 壤乳樹脂硬化劑於-主樹财以形成無❹環氧^组 合物之膠液，因此，當玻璃纖維布浸漬於該膠液，以二 硬化的反應料，改善傳祕賴騎㈣㈣作 的壓合溫度過高及時間過長之問題。 為使能更進-步瞭解本發明之特徵及技術内容，請參 閱以下有關本發明之詳細說明與附圖，然提 供參考纽_，鮮絲料發明純限· 【實施方式】 j明係提供-種複合型環氧樹脂硬化劑，將該複 合型環氧樹脂硬化獅加於環氧_旨巾，使玻璃纖維布 在經過含浸（dipping)步驟後得以增加硬化的反應速率， 進而提升酚醛環氧樹脂的樹脂配方之反應性，並提高所製 ，基板的玻璃轉換溫度（Tg)，且不致影響基板之耐熱、 及水f生、並具備阻燃之特性。此外，本發明更進一步改 • 諸f樹月旨硬化劑製作基板壓合溫度過高及時間過長 的問題，再者，本發明更添加適當比例的填充料，以製 作出具有較佳耐燃及耐熱特性的膠片。 t ±該^複合型環氡樹脂硬化劑係主要由聚伸苯曱基磷酸 月曰树知硬化劑及笨酚樹脂硬化劑以一預定比例混合而 f °其中’該聚伸笨甲基磷酸脂樹脂硬化劑係利用聚伸 ，曱基^4酉文酉旨（p〇iyphenyiene methylphosphonate)作為環 氧樹脂之硬化劑應用，聚伸笨曱基磷酸酯可由化學式I 所表示： 201031292201031292 VI. Description of the Invention: [Technical Field] The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition having a composite epoxy resin hardener. [Prior Art] At present, the range and field of application of printed circuit boards are quite extensive. Electronic components in general electronic products are inserted on printed circuit boards, and today's germanium printed circuit boards are designed to meet high power and high heat components. The scope of application, so the development and research on the printing (four) Lai effect, in order to improve the heat dissipation efficiency and high power of the board. The printed circuit board is formed by impregnating film (PP), or a film containing copper foil film (C. er clad lami_, CCL) or a copper box, and the impregnated film is used to impregnate the glass fiber cloth to the ring. In the rubber, the sub-process of the dry material is formed by the subsequent process - a thin film 0 ^ gradually recognized, many consumer electronic products have been plated. Substrate ' instead of halogen-free copper box base i, == plate is added with scaly components to compensate for the flame retardant effect of the fat component structure; add force;: to apply the main resin or hardener tree (4) to add Containing a shafting agent, and then adding a phosphorus-containing phenol ring resin to prepare for fire resistance, such as the resin film of Zhonghua ^Di = (4), Huaminguo No. 293831 and No. 583258, 201031292 with stupid and oxazine The phenol resin of the ring (Benz〇xazine, Bz) is hardened = other phenolic resin hardeners are blended to make a halogen-free resin substrate. However, the BZ phenol resin hardener in the second embodiment can reduce the water absorption and has a low dielectric property, but the substrate produced by the film has poor toughness, and has a problem of insufficient addition of the second conductivity and insufficient heat resistance. In addition, for the industry's base = the reactive process is also too slow (four), the glass transition temperature (Tg) of the substrate made of epoxy and grease can only reach 16 degrees. On the contrary, the present inventors have felt that the above-mentioned deficiency can be improved, and proposes a present invention which is effective in improving the above-mentioned deficiency. SUMMARY OF THE INVENTION The main purpose of utilizing ί 在于 is to provide an epoxy resin composition, : _ benzyl propyl ester mixed with benzene (10) fat hardener, ring = hardener, to enhance _ ring her: to 燮 ί 1 The glass transition temperature of the board is (intelligent), and the heat resistance and water absorption of the substrate are not special, and the substrate is also provided with a flame-retardant ring gas. The epoxy resin composition is provided, which comprises: component (4):卜份(6): a composite epoxy resin hardener, wherein = 殁σ 3L % oxygen resin hardener is composed of a poly- ^ ^ ^ ^ ^ ^ ^ ^ chemical agent and a phenol resin hardener _ predetermined _ mixed 2 = Field Moon Hard. The present invention also provides a bad sheet which is cured and dried in the glass fiber cloth latex resin composition. The present invention further provides a printed circuit (four) substrate using the above film. "King Cheng made 201031292 The present invention has the following beneficial effects ··This combination with the composition-composite epoxy resin hardener, and the use of the complex = latex resin hardener in the main tree to form a flawless epoxy ^ The glue of the composition, therefore, when the glass fiber cloth is immersed in the glue, the two hardened reaction materials are used to improve the problem that the pressure of the transfer is too high and the time is too long. - Steps to understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings, while providing a reference to the new yarn, the invention of the fresh silk material is limited to the limit of the invention. An oxy-resin hardener, the composite epoxy resin hardened lion is added to the epoxy ray towel, so that the glass fiber cloth can increase the reaction rate of hardening after the dipping step, thereby improving the resin formula of the phenolic epoxy resin. Reactability, and improve the glass transition temperature (Tg) of the substrate, without affecting the heat resistance of the substrate, water and flame retardant properties. Moreover, the present invention further changes hardener The problem that the substrate pressing temperature is too high and the time is too long, and further, the present invention further adds a proper proportion of the filler to produce a film having better flame resistance and heat resistance characteristics. t ± The compound type ring-ring resin hardens The agent is mainly composed of a polybenzhydrylphosphoric acid, a sulphuric acid hardener and a phenolic resin hardener, and is mixed at a predetermined ratio and f°, wherein the polyunsaturated methyl phosphate resin hardener is used for stretching, sulfhydryl ^4酉 y 酉 ( ( 〇 〇 〇 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010
ni3n ^ 〇 〇r ] 力、甲基碟酸脂樹脂可以提供較佳的阻辦及 2反應的特性’該聚伸苯甲基魏㈣脂與笨盼 劑月曰^作為—種應用於環氧樹脂的硬化 祕之反應性，並提 二⑽轉換服度（Tg)’再者，所製成之基板的耐執 吸水性、以及阻燃特性均相當優良。 …、 組實=將針對上述之複合魏氧樹脂硬化劑進行多 組成，明藉由複合型環氧樹脂硬化劑之 ―種環氧樹脂组合本發明主要提供 以及組份（BV、*入，ί括. （A):環氧樹脂； 環氣樹骑硬化齊樹脂硬化劑，其中該複合型 苯紛樹腊硬化—本甲基磷酸脂樹脂硬化劑及 預疋比例混合而成，請參考表1。 201031292Ni3n ^ 〇〇r ] Force, methyl benzoate resin can provide better resistance and 2 reaction characteristics 'The phenylmethyl Wei (tetra) grease and the viscous agent 曰 曰 ^ as a kind of epoxy Resin hardening reactivity, and mentioning (10) conversion suitability (Tg)', the substrate obtained by the substrate has excellent water absorption resistance and flame retardant properties. ..., the group = will be multi-component for the above-mentioned composite Wei oxide resin hardener, the invention is mainly provided by the composite epoxy resin hardener epoxy resin combination and the components (BV, * into, ί (A): Epoxy resin; Cyclone tree riding hardening resin hardener, wherein the composite benzene ash wax hardening - this methyl phosphate resin hardener and pre-twist ratio are mixed, please refer to Table 1. 201031292
表1 說明 對照例I Α.環氧樹脂 ' Α1.盼醛環氧樹脂(主劑量份） 100 Β1 ·域敬酷樹脂樹脂硬化劑 ~~Τ' Β2_本盼樹脂硬化劑 Β21 .Βζ樹脂硬化劑(Ρ&) 104 B22.雙酚A酚醛樹脂硬化劑(phr) 吸4 W生（Ρ〇Π21°έ/ϊϊί^ 0.281%" Float 288。。 min 4~5 Tg DMA °c 160 Td(5%) TGA °c 375 UL94 Grade v-l 環氧樹脂係為酚醛樹脂，例如ί '、‘、、、ι〇0篁份，且該 紛-嶋氧樹脂、雙盼氧樹脂、 或兩種以上之混和樹脂，但、曰或上述兩種 環氧樹脂更可以為非_環氧樹脂’該組份Α之 至實施例3主要係改變組份B ，1之實施例1 中的聚伸苯曱基輕脂樹脂硬脂硬化劑 的組成，並針對不同組成之環氧椒樹脂硬化劑 的膠片進行各種特性分析。 物膠液所製成 其中，吸水性又可稱做吸濕性，t 膠片的吸水特性，由於膠片會受環在於判定該 =膨脹變形或吸附水氣。而在該等ς片：二= 過南的情況下，易使所壓製之印刷電路板 的^ 重要特點之-。傳統上，可針對該二的進 201031292 析或熱重量損失法分析，以確認該膠片的吸水性。 耐熱性：即漂錫結果，耐熱實驗係依據產業標準 IPC-TM-650 Method 2.4.13.1，將散熱膠片浸泡於 288°C 錫爐至爆板所需時間（分），其中可得知藉由本發明所提 出的環氧樹脂組合物膠液進行玻璃纖維布浸潰作業之 後製造的膠片具有較高的耐熱性，故爆板所需的時間較 長且符合測試規範。 耐燃性：即難燃性，依據UL 94法測定，係指塑膠 材料耐燃性測試，其以塑膠材料標準試片經火焰燃燒後 ® 之自燃時間、自燃速度、掉落之顆粒狀態來訂定塑膠材 料之耐燃等級。而依耐燃等級優劣，依次是HB、V-2、 V-1、V-0、最高為5V等級。而UL 94測試方法係指塑 膠材料以垂直方式在火燄上燃燒。以每十秒為一測試週 期，其步驟如下：步驟一：將試片放進火焰中十秒再移 開，測定移開之後該試片繼續燃燒時間（τ1);步驟二： 俟試片火焰熄滅後，再放進火焰中十秒再移開，再測定 移開之後該試片繼續燃燒時間（丁2);步驟三：重複數次 φ 貫驗並取其平均值；步驟四：計算Τ1+ Τ2之總合。而 UL 94 V-0等級的要求係為在試片單一燃燒時間丁丨之 平均及T2之平均皆不得超過1〇秒，且其T1與T2的總 合不得超過50秒方符合UL94v_〇要求。 在實施例1至實施例3的組成中，該複合型環氧樹 ，石^化劑中之苯酚樹脂硬化劑係使用Benz〇xazine(BZ) 樹月a ’其具有苯并噁嗪環之苯酚樹脂硬化劑， Benzoxazi^CBZ)樹脂之特性係具有低介電損耗因數、高 彈性率、㊣雜性、低吸水性、高玻璃化溫度、高難燃 201031292 性等特性和沖孔加工性等，而可適當的控制該Bz樹脂 的軟化點，以降低其主架構僵直而缺乏韌性之缺點；^ 時減少外形沖孔時之層間剝離，及提高與多層配線板^ 層電路接觸之樹脂層之黏接力，以改善内層脫落強度之 效果。Table 1 illustrates Comparative Example I Α. Epoxy resin Α1. acetal epoxy resin (main dose portion) 100 Β1 · Domain Jingku resin resin hardener ~~Τ' Β2_ 本盼 resin hardener Β21. Βζ resin hardening Agent (Ρ&) 104 B22. Bisphenol A phenolic resin hardener (phr) Aspirate 4 W (Ρ〇Π21°έ/ϊϊί^ 0.281%" Float 288. min 4~5 Tg DMA °c 160 Td( 5%) TGA °c 375 UL94 Grade vl Epoxy resin is a phenolic resin, such as ί ', ', ,, ι〇0 篁, and the bismuth-oxygen resin, bis-oxygen resin, or more than two Mixed resin, but 曰 or the above two kinds of epoxy resins may be non-epoxy resin'. The component is exemplified to the third embodiment. The polyphenylene fluorenyl group in the embodiment 1 is changed. The composition of the light-fat resin hard fat hardener, and various characteristics analysis of the film of the epoxy resin hardener of different compositions. The glue solution is made of water, which can be called hygroscopicity, and the water absorption of the film. Characteristics, because the film will be subject to the ring to determine the = expansion deformation or adsorption of moisture, and in the case of the slab: two = over the South It is easy to make the important features of the printed circuit board that has been pressed. Traditionally, the analysis of the two can be performed on the 201031292 analysis or the thermal weight loss method to confirm the water absorption of the film. Heat resistance: the result of floating tin, heat resistance The experiment is based on the industry standard IPC-TM-650 Method 2.4.13.1, immersing the heat-dissipating film in the tin furnace at 288 ° C to the time required for the explosion (minutes), wherein the epoxy resin composition proposed by the present invention can be known The film produced after the glass fiber cloth is dipped in the glue has high heat resistance, so the time required for the explosion of the film is long and meets the test specifications. Flame resistance: that is, flame retardancy, measured according to the UL 94 method, refers to The flame resistance test of plastic materials, which sets the flame resistance grade of plastic materials according to the self-ignition time, self-ignition speed and falling particle state of the standard test piece of plastic materials after flame combustion. According to the quality of the fire resistance, HB and V are in turn. -2, V-1, V-0, up to 5V. The UL 94 test method means that the plastic material burns on the flame in a vertical manner. The test cycle is every ten seconds. The steps are as follows: Step 1: The film is placed in the flame for ten seconds and then removed. After the measurement is removed, the test piece continues to burn for a period of time (τ1); Step 2: After the flame of the test piece is extinguished, it is placed in the flame for ten seconds and then removed, and then the measurement is removed. After that, the test piece continues to burn time (D 2); Step 3: Repeat φ test several times and take the average value; Step 4: Calculate the total of Τ1+ Τ2. The requirement of UL 94 V-0 level is test The average burning time of a piece of film and the average of T2 shall not exceed 1 second, and the total of T1 and T2 shall not exceed 50 seconds to meet the requirements of UL94v_〇. In the compositions of Examples 1 to 3, the phenol resin hardener in the composite epoxy resin and the phthalic acid agent is Benzoxazine (BZ), and a phenol having a benzoxazine ring. Resin hardener, Benzoxazi^CBZ) resin has low dielectric loss factor, high modulus of elasticity, positive hybridity, low water absorption, high glass transition temperature, high flame retardancy 201031292 properties, and punching processability. The softening point of the Bz resin can be appropriately controlled to reduce the rigidity of the main structure and lack of toughness; the interlayer peeling during the punching of the profile is reduced, and the adhesion of the resin layer in contact with the circuit of the multilayer wiring board is improved. Relay to improve the effect of the inner layer shedding strength.
因此，依表1所示之實驗結果顯示，實施例i、2、 3匕之環氧樹脂組合物的硬化劑中增加有聚伸笨甲基磷酸 脂樹脂硬化劑，對於所製成的基板之吸水性及耐熱性^ 響不大（相較於對照例1、2)，但因應配合一般1?114^ 合製程（熱壓料溫195Ό以上時間至少30分鐘），由實施 】1 2 3反應出该複合型環氧樹脂硬化劑有加速反庳 之效果，所製成之基板的玻璃轉換溫度（Tg)明顯由 ^提升至185°C以上，換言之，本發明可改善傳統醛類 f脂硬化劑製作基板壓合溫度過高及時間過長的問 題。再一方面，本發明之複合型環氧樹脂硬化劑中之聚 伸笨曱基磷酸脂樹脂與BZ樹脂之配比以1:1〇 (如實施 例1之比例）至3:10 (如實施例3之比例）為佳，二藉 由上述的混合組成，所製成之基板的玻璃轉換溫度（Tg) 可提升至185°C以上，甚至大於200。(：。 另外，實施例4進一步說明複合型環氧樹脂硬化劑 的變化實施態樣，該複合型環氧樹脂硬化劑中之苯酚樹 脂硬化劑更可含酚醛樹脂硬化劑，如實施例4中所添加 的雙盼A齡藤樹脂硬化劑，而利用實施例4之環氧樹脂 組合物所製成之膠片的玻璃轉換溫度（Tg)亦可達18〇 C，因此同樣具有加速反應之效果。 9 201031292 酸脂樹脂硬化劑的用量係;月;::7 :之聚伸苯甲基磷 硬化劑的“係氧樹脂硬化劑中之該苯酚樹脂 該-份。 中該填充料係包括氫氧化=或有填充料，其 組份(D) S t : (Α)的1〇至8。份，以及 份（A)的10至3〇^且。刀（D)之溶劑的用量係為該組 包括有添加物，例如：；中環氧樹脂組合物更 例中’該促進_為咪魏 d ’而在本最佳實施 的〇.4至！份，例如口物’其用量係為該組份⑷ 膠液的硬化時間.而,7、土咪唑，其功用在於加速控制 MEK、PM、環已嗣等之溶劑則為1〇_3〇份之 最佳組成比例，其中， 不該環氧樹脂組合物的 化劑中之聚伸苯^ （Β):複合型環氧樹月旨硬 的18份：量係為該組份⑷ 酚樹脂硬化劑的用吾 ^型级氣樹脂硬化劑中之苯 酚樹脂硬化劑係可為R ^ 且知（Α)的98份，且該苯 或兩者之混合；、^fBZ=硬化劑、祕樹脂硬化劑、 份（A )的30份，曰诗之填充料的用量係為該組 石夕、或兩者之混合·;纟、料係包括氫氧化銘、二氧化 組份（A)的20二’二:⑺）之溶劑的用量係為該 丁_ ; MEK)、丙谷蜊則包括甲基乙基酮（又稱 或兩種以上之混^醇甲鍵（PM)、環己綱、或任兩種 201031292 表2 成分 名稱 說明、特性 ''''------ 總笛兽//二 主樹脂 酚醛主樹脂 鄰甲酚-酚醛環氧樹脂 三者之一或混用 ~ 雙酚A-酚薛環氧樹脂 主劑量(份) 100 酚-酚醛環氧樹脂 複合型環氧 樹脂硬化劑 聚伸苯甲基 磷酸醋樹脂 聚伸苯甲基磷酸醋樹 脂 阻燃、加速反應 相對主劑 量(份） 18 苯酿樹脂硬 化劑 Benzoxazine樹脂硬化 劑 降低吸水性、硬化反應慢；二者 之一或混用 相對主劑 量(份） 98 酚醛樹脂硬化劑 促進劑 咪唑化合物 加速控制膠劑硬化時間 =(¾對主劑 分） 0.4 境充料 氫氧化銘or二氧化 矽 二者之一或混用、阻燃、耐 降低成本 相對總固 30 溶劑 MEK、PM、環己酮 三者之一或混用 呢里、/〇) ^g(%) ---—— 20 —— " ' —----- ---— 本發明更進一步提出一種使用上述環氣樹脂組合 物製造膠片的方法以及所製作成型之膠片。該方法係應 用上述環氧樹脂組合物，其包括組份（A ):環氧樹月^: 組份（B):複合型環氧樹脂硬化劑，其中該複合型環曰J 樹脂硬化劑係由聚伸苯曱基磷酸脂樹脂硬化劑及=氣 樹脂硬化劑以一預定比例混合而成；該環氧樹脂級^酚 更進-步組份（C):填充料，其中該填充料係 化銘、一氧化石夕或兩者之混合；以及組份（d ) :、'^气氣 將一玻璃纖維布浸潰（dipping)於該環氧樹脂組合:。 膠液中，以製成較佳耐燃及耐熱特性的含浸膠片之 或含銅箔膠片（Copper clad laminate，CCL)、或其） 片，且上述膠片可應用製成印刷電路板用之基板，2膠 基板在通過壓合製程時可具有相當良好的反應性。該 综上所述’本發明具有下列諸項優點： 1、本發明主要係利用兩種硬化劑搭配組成一複合型的 11 201031292 ?化劑：而使用該複合型環氧樹脂硬化劑於一主樹 脂，1形成無_素的環氧樹脂組合物膠液，以提升使 肖絲液所製成之膠片的耐祕，也可以兼顧膠片的 低吸水性及耐熱性；同時使㈣複合型環氧樹脂硬 化劑’可以増加所製成之基板的玻璃轉換溫度。 2、另一方面，本發明之環氧樹脂組合物中採用一種含 磷成分之複合型環氧樹脂硬化劑，可以增加基板阻 燃效果；且可進一步提高樹脂硬化的反應速率。 惟以上所述僅為本發明之較佳實施例，非意欲侷限本 發明之專利保護範圍，故舉凡運用本發明說明書及圖式内 容所為之等效變化，均同理皆包含於本發明之權利保護範 圍内，合予陳明。 【圖式簡單說明】 無 【主要元件符號說明】 無 12Therefore, according to the experimental results shown in Table 1, the hardeners of the epoxy resin compositions of Examples i, 2, and 3 were added with a poly(methylphosphonate) resin hardener, for the substrate to be formed. Water absorption and heat resistance ^ is not loud (compared to the control examples 1, 2), but it should be combined with the general 1? 114^ process (hot press temperature 195 Ό or more for at least 30 minutes), by the implementation of 1 2 3 reaction The composite epoxy resin hardener has the effect of accelerating the rumination, and the glass transition temperature (Tg) of the prepared substrate is obviously raised from 185 ° C or higher. In other words, the invention can improve the traditional aldehyde f-hardening. The agent produces a problem that the substrate pressing temperature is too high and the time is too long. In another aspect, the ratio of the polycondensation-based phosphatide resin to the BZ resin in the composite epoxy resin hardener of the present invention is 1:1 〇 (as in the ratio of Example 1) to 3:10 (if implemented) The ratio of the case of Example 3 is preferable, and by the above-mentioned mixing composition, the glass transition temperature (Tg) of the substrate produced can be raised to 185 ° C or more, or even more than 200. (In addition, Example 4 further illustrates a modified embodiment of the composite epoxy resin hardener, wherein the phenol resin hardener in the composite epoxy resin hardener may further contain a phenolic resin hardener, as in Example 4. The added film of the A-year-old rattan resin hardener, and the film made by using the epoxy resin composition of Example 4 can also have a glass transition temperature (Tg) of 18 〇C, and thus has an effect of accelerating the reaction. 9 201031292 The amount of the acid ester resin hardener is; month::: 7: the phenylmethyl phosphorus hardener "the phenol resin in the oxygen resin hardener, the portion of the phenol resin. The filler system includes hydroxide = or a filler, the component (D) S t : (Α) 1〇 to 8 parts, and the part (A) 10 to 3〇^. The amount of the solvent of the knife (D) is The group includes additives, for example:; in the epoxy resin composition, in the example, 'the promotion _ is weiwei d' and in the best practice, 〇.4 to ! parts, such as the mouth' Component (4) Hardening time of the glue. 7., soil imidazole, its function is to accelerate the control of MEK, PM, ring, etc. It is the optimum composition ratio of 1〇3 份, wherein, in the agent of the epoxy resin composition, the benzene (Β): composite epoxy resin is 18 parts: the amount is The component (4) The phenol resin hardener in the phenol resin hardener may be R ^ and 98 parts of the benzene resin, and the benzene or a mixture of the two; ^fBZ = hardener, secret resin hardener, 30 parts of (A), the amount of the stuffing of the poems is the group of Shi Xi, or a mixture of the two; 纟, the system includes the hydroxide, the oxidation group The amount of the solvent of the part (A) of 20 2 '2: (7)) is the amount of the butyl group; the MEK) and the acetaminophen include the methyl ethyl ketone (also known as the two or more kinds of mixed alcohols (PM) ), Cyclohexyl, or any of two 201031292 Table 2 Description of the composition of the name, characteristics ''''------ total flute / / two main resin phenolic main resin o-cresol - phenolic epoxy resin One or mixed ~ bisphenol A-phenol Xue epoxy resin main dose (parts) 100 phenol-phenolic epoxy resin epoxy resin hardener poly benzyl phosphatate resin benzene methyl phosphate vinegar Fat retardant, accelerated reaction relative to main dose (parts) 18 Benzene resin hardener Benzoxazine resin hardener reduces water absorption and slows hardening reaction; either one or a mixture of relative main doses (parts) 98 phenolic resin hardener accelerator imidazole The compound accelerates the control of the hardening time of the gel = (3⁄4 pairs of the main agent) 0.4 The environmental charge of the hydroxide or the cerium dioxide is mixed or mixed, flame retardant, and the cost is reduced relative to the total solid 30 solvent MEK, PM, cyclohexyl One of the ketones or a mixture of ketones, /〇) ^g(%) ---- 20 —— " ' —----- --- — The present invention further proposes the use of the above-mentioned ring gas resin A method of making a film from a composition and a film formed. The method uses the above epoxy resin composition, which comprises the component (A): Epoxy resin: Component (B): a composite epoxy resin hardener, wherein the composite cyclohedral J resin hardener is The polyphenylene phthalate phosphate resin hardener and the = gas resin hardener are mixed at a predetermined ratio; the epoxy resin grade further comprises a step component (C): a filler, wherein the filler system Huaming, oxidized stone or a mixture of the two; and component (d):, '^ air gas dipping a glass fiber cloth in the epoxy resin combination: In the glue, the film is made of impregnated film or copper clad laminate (CCL), or the like, and the film can be applied to a substrate for a printed circuit board, 2 The gum substrate can have fairly good reactivity when passed through a press-bonding process. In summary, the present invention has the following advantages: 1. The present invention mainly utilizes two kinds of hardeners to form a composite type 11 201031292 chemical agent: and the composite epoxy resin hardener is used in one main Resin, 1 forms a non-sugar epoxy resin composition glue to enhance the anti-slip of the film made of the koji liquid, and can also take into account the low water absorption and heat resistance of the film; at the same time make (4) composite epoxy The resin hardener 'can increase the glass transition temperature of the substrate produced. 2. On the other hand, the epoxy resin composition of the present invention employs a composite epoxy resin hardener containing a phosphorus component, which can increase the flame retarding effect of the substrate; and can further increase the reaction rate of the resin hardening. The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Therefore, the equivalents of the present invention and the equivalents of the drawings are all included in the present invention. Within the scope of protection, it is given to Chen Ming. [Simple diagram description] None [Main component symbol description] None 12