201242995 六、發明說明： 【發明所屬之技術領域】 ^發明_於錄料⑽旨減物 薄膜覆晶封裝伽p,FilmPaekage)时=關^於 封的液狀環氧樹脂組成物。 等體疋件之密 【先前技術】 在屬於可對! 审、佳—本古今Λ 置之配線箄夕 '问密度化、高輸出化的半導體元件安 C0F(ChipGnFilra)封裝等半導體封裝中，係利:式的 接合（flip Chip bonding)。一般而言，倒褒晶片接j片 係以凸塊（bump)接合半導體元件與基板，並 °中’ =rri—狀半導體密封-封半= 近年來，為了對應液晶驅動IC之高密度化、言 化之要求，正朝搭載液晶驅動IC之配線圖型（⑻丨:出 pattern)之間距密集（fine pitch)化發展。由於該間^巨1呢 集化，而使液晶驅動ic之運作溫度逐漸上昇。在距密 密封之半導體封裝中，若於配線間賦予電位差= 會發生遷移（migration)。遷移，係指配線圖型之金屬、'曰 化學反應而溶出，而導致配線間之電阻值降低的現象因電 為了抑制該遷移，而有報告提出包含金屬離子、纟士人 之底填劑。該底填劑係將因電化學反應而溶出的金屬_】 以金屬離子結合劑固定化，藉此而試圖抑制遷移。 子 然而，若在底填劑中含有金屬離子結合劑，則會使广 323915 4 201242995 降::::劑之玻_移溫度降低等使 • [先前技術文獻] [專利文獻] [專利文獻1]日本_ 2齡卿85號公報 【發明内容】 (發明欲解決之課題） 導體=之:題係防止於使用液狀環氧樹脂組成物之半 之辦，且抑制液狀環氧樹脂組成物於保存時 本發明之目㈣提供—種保存特性優異、在 硬紐化f之耐遷移性優異之高可靠性之液狀環氧樹脂組成物。 (解決課題之手段） 本發明係關於藉由具有以下之構成而解決上述問題 之液狀環氧樹脂組成物。 [1] 一種液狀環氧樹脂組成物，其含有：⑴含有胺基紛 (ami卿heru^)型環氧樹脂之液狀環氧樹脂、⑻酸針硬化 劑、及（C)咪唾化合物； 其中，相對於（㈣分⑽重量份，含有胺絲型環氧樹脂 5至90重量份。 [2] 如上述⑴所述之液狀環氧樹脂組成物，其中，⑷成 分所含有之胺級型環氧樹脂為式⑴所表示者： 1>-\ /-=\ /-<1201242995 VI. Description of the invention: [Technical field to which the invention pertains] ^Invention_Recording (10) Reducing material When the film is covered with a crystal chip, the liquid epoxy resin composition is sealed. The density of the body parts [previous technique] In the semiconductor package such as the C0F (ChipGnFilra) package for the density and high output of the wiring, which is available for the review, Lee: Flip Chip bonding. In general, the flip chip is connected to the substrate by a bump, and the '=rri-like semiconductor seal-sealing half in the middle of the film. In recent years, in order to cope with the high density of the liquid crystal driver IC, In the meantime, the fine pitch is developed in the wiring pattern ((8): out pattern) in which the liquid crystal driver IC is mounted. Due to the integration of the ^1 giant, the operating temperature of the liquid crystal driving ic gradually rises. In a semiconductor package that is hermetically sealed, if a potential difference is given between the wirings, migration will occur. The migration refers to the metal of the wiring pattern, the dissolution of the chemical reaction, and the decrease in the resistance value between the wirings. In order to suppress this migration, it has been reported that a metal ion and a gentleman's underfill are proposed. This underfill is intended to suppress migration by immobilizing a metal eluted by an electrochemical reaction with a metal ion binder. However, if a metal ion binder is contained in the underfill, the 323915 4 201242995 is lowered: the glass transition temperature of the ::: agent is lowered, etc. [Prior Art Document] [Patent Literature] [Patent Document 1 Japanese _ 2nd Anniversary No. 85 [Invention] (The subject to be solved by the invention) Conductor =: The problem is to prevent the use of a liquid epoxy resin composition and to suppress the liquid epoxy resin composition. The object (4) of the present invention at the time of storage provides a highly reliable liquid epoxy resin composition which is excellent in storage characteristics and excellent in migration resistance in hard bonding. (Means for Solving the Problem) The present invention relates to a liquid epoxy resin composition which solves the above problems by having the following constitution. [1] A liquid epoxy resin composition comprising: (1) a liquid epoxy resin containing an amine-based epoxy resin, (8) an acid needle hardener, and (C) a sodium salium compound The liquid epoxy resin composition as described in the above (1), wherein the (4) component contains an amine, in the liquid epoxy resin composition of the above-mentioned (1). The grade epoxy resin is represented by the formula (1): 1>-\ /-=\ /-<1
323915 5 (1) 201242995 [3] 如上述[1]賴之餘錢樹㈣祕，復含有⑻彈 性體（elastomer)。 [4] 如上述[1]所述之餘魏樹職成物，復含有（e)石夕 烷偶合劑（silane coupling agent)。 [5] 如上述[1]所述之液狀環氧樹驗成物，其中，相對於 (Α)成分1當量，（Β)成分為〇 6至i 2當量之比率。 [6] 如上述[1]所述之錄環氧樹驗成物，其中，相對於 (A)成分100質量份，（C)成分為〇 〇5至1〇質量份。 [7] 如上述[3]所述之綠環氧樹缝祕，其巾，相對於 (A)成分100質量份，（D)成分為1至3〇質量份。 [8] 如上述[1]所述之液狀環氧樹脂組成物，纟24小 之黏度上昇率為300%以下。 [9] 如上述⑴所述之綠環氧樹驗成物，其係藉由使 (C)成分分散在將胺聽型環氧樹脂除外之⑴成分之至少 :部分中’作成母料（master batch)後，將包含胺基盼型 環氧樹脂的（A)成分之剩餘部分與⑻成分混合至母 而得到者。 薄膜覆晶封裝用密㈣，其包含上述⑴所述之 液狀裱氧樹脂組成物。 導體裝置，其係使用上述叫所述之薄膜覆晶 封裝用达、封劑而經密封者。 [12] -種如上述⑴所述之液狀環氧樹脂、喊物之製造方 法、-係使（C)成分分散在將胺基酴型環氧樹脂除外之⑴ 成刀中^乍成母料後，將胺基紛型環氧樹脂與⑻成分混合 323915 ⑧ 6 201242995 至母料中。 (發明之效果） 依據本發明[1] ’可提供一種保存特性優異、硬化後 耐遷移性優異之液狀環氧樹脂組成物。 依據本發明[11]，可容易地提供一種耐遷移性優異之 高可靠性之半導體零件。 ” 依據本發明[12]，可提升耐遷移性優異之環氧樹脂組 成物之保存特性。 、 【實施方式】 [液狀環氧樹脂組成物] 本發明之液狀環氡樹脂組成物係含有：（A)含有胺基 紛型環氧樹脂之液狀環氧樹脂、⑻賴硬化劑、及（〇米 唑化合物；其中，相對於（A)成分100重量份，含有胺基齡 型環氧樹脂5至90重量份。 係藉由形成交 胺基酚型環氧 2個官能基者 α(Α)成分所含有之胺基酚型環氧樹脂， ^费度高之樹脂骨架，財卩制遷移的發生。 树月曰係以式（2)所表示之於鄰位或對位具有323915 5 (1) 201242995 [3] As mentioned above [1] Lai Yu Yu Shu (4) secret, complex contains (8) Elastomer (elastomer). [4] The eucalyptus compound as described in the above [1], which further comprises (e) a silane coupling agent. [5] The liquid epoxy resin composition according to the above [1], wherein the (Β) component is a ratio of 〇 6 to i 2 equivalents per equivalent of the (Α) component. [6] The epoxy resin composition according to the above [1], wherein the component (C) is 〇 5 to 1 〇 by mass based on 100 parts by mass of the component (A). [7] The green epoxy resin according to the above [3], wherein the towel has a component (D) of 1 to 3 parts by mass based on 100 parts by mass of the component (A). [8] The liquid epoxy resin composition according to the above [1], wherein the viscosity increase rate of the crucible 24 is 300% or less. [9] The green epoxy resin test composition according to (1) above, which is obtained by dispersing the component (C) in at least a portion of the component (1) excluding the amine-type epoxy resin as a masterbatch (master) After batch), the remainder of the component (A) containing the amine-based epoxy resin and the component (8) are mixed to the mother. The film-on-film encapsulation is dense (4), which comprises the liquid oxime resin composition described in the above (1). The conductor device is sealed by using the above-mentioned film-coated package for sealing and sealing. [12] A liquid epoxy resin according to the above (1), a method for producing a shim, and a component (C) dispersed in (1) a metal-based oxime-type epoxy resin After the material, the amine-based epoxy resin was mixed with the component (8) in 323915 8 6 201242995 to the master batch. (Effect of the Invention) According to the invention [1]', a liquid epoxy resin composition excellent in storage characteristics and excellent in migration resistance after curing can be provided. According to the invention [11], it is possible to easily provide a highly reliable semiconductor component excellent in migration resistance. According to the invention [12], the storage characteristics of the epoxy resin composition excellent in migration resistance can be improved. [Embodiment] [Liquid epoxy resin composition] The liquid cyclic resin composition of the present invention contains (A) a liquid epoxy resin containing an amine-based epoxy resin, (8) a sizing hardener, and (a carbazole compound; wherein, with respect to 100 parts by weight of the component (A), an amine-based epoxy resin is contained. 5 to 90 parts by weight of the resin. The aminophenol-based epoxy resin contained in the α (Α) component of the two functional groups of the aminophenol-based epoxy resin, the resin skeleton having a high degree of cost, and the financial system The occurrence of migration. The tree scorpion is represented by the formula (2) to the ortho or para position.
(2) 耐遷移性之觀點 而從硬化性、耐熱性'接著性、耐久性 來看，以式（1)所表示者為特佳： 323915 201242995(2) From the viewpoint of migration resistance, in terms of hardenability, heat resistance, adhesion, and durability, it is particularly excellent in the formula (1): 323915 201242995
ο >-〇 (1) 市售品可列舉三菱化學製之 ’ (grade) : _0、__等。里環氧樹脂（品級 胺基朌型環氧樹脂以外之（A)成分，可列舉··液 酚A型環氧樹脂、液狀雙酚F 雙 ^ 孓衣氧樹脂、液狀萘型環氧 嶋趣旨、液狀雁環式環氧樹腊、 ^狀^型城樹脂、液狀環狀脂肪族型環氧樹脂、液狀 第里％氧樹脂、液狀錢烧系環氧樹脂等；從硬化性 熱性、接著性、収性錢點㈣，叹輕W型 2、液狀雙㈣型環氧樹脂、液㈣氧燒系環氧樹脂為 較佳。此外，從黏度調整之觀點來看，環氧當量以8〇至 250g/eq為較佳。市售品可列舉新日鐵化學製雙盼F型产 氧樹脂（品名：YDF8170)、DIC製雙酚A型環氧樹脂（品名， EXA-850CRP)、DIC製萘型環氧樹脂（品名：Hp4〇32D)、ο >-〇 (1) Commercial products can be cited by Mitsubishi Chemical's (grade): _0, __, etc. (A) component other than the epoxy resin (grade amine-based epoxy resin), liquid phenol A type epoxy resin, liquid bisphenol F double oxime epoxy resin, liquid naphthalene type ring Oxygen sputum, liquid geese ring-shaped epoxy tree wax, ^ shape ^ city resin, liquid cyclic aliphatic epoxy resin, liquid Terry % oxygen resin, liquid money burning epoxy resin, etc.; From the point of viscosity adjustment, from the point of view of viscosity adjustment, from the viewpoint of viscosity adjustment, heat resistance, adhesion, and replenishment (4), sigh, W type 2, liquid double (tetra) type epoxy resin, and liquid (tetra) oxy-fired epoxy resin. The epoxy equivalent is preferably from 8 Å to 250 g/eq. Commercially available products include Nippon Steel Chemical Co., Ltd., a double-fat F-type oxygen generating resin (product name: YDF8170), and DIC bisphenol A type epoxy resin (product name, EXA-850CRP), DIC naphthalene epoxy resin (product name: Hp4〇32D),
Momentive Performance Materials 製矽氧烷系環氧樹脂 (品名· TSL9906)等。胺基酚型環氧樹脂以外之（A)成分， 可為單獨使用或將2種以上併用。 從耐遷移性之觀點來看，相對於（A)成分1〇〇重量份， 以含有5至90重量份胺基盼型環氧樹脂為較佳。 (B)成分係賦予良好的反應性（硬化速度）、適度的黏 性。（B)成分可列舉：四氫酞酸酐、六氫酞酸酐、曱基四氣 酞酸酐 '甲基丁烯基四氫酞酸酐、甲基六氫酞酸酐、烷基 323915 8 201242995 化四氫酞酸酐、六氫酞酸酐、甲基海米酸酐（methyl HIMIC anhydride)、經稀基取代之玻珀酸酐、曱基納迪克酸針 (methyl nadic anhydride)、氫化曱基納迪克酸酐、三烧 基四氫酞酸酐、曱基環己烯四曱酸二酐、酞酸酐、苯偏三 曱酸酐、苯均四曱酸酐、二苯基酮四曱酸二酐、乙二醇雙 脫水苯偏三曱酸酯（ethylene glycol bis-anhydrotrimellitate)、丙三醇雙（脫水苯偏三曱酸酯） 單乙酸醋、十二烯基琥珀酸酐、氣橋酸酐（chl〇rendic anhydride)、脂肪族二元酸聚酐、戊二酸酐等；以曱基丁 烯基四虱欧酸軒為較佳。市售品可列舉：三菱化學製酸肝 (品級：YH306、YH307)等。（B)成分可為單獨使用或將2 種以上併用。 (C)成分為硬化促進劑，（c)成分可列舉：2_曱基味β坐、 2-十一基咪唑、2-十七基咪唑、2-乙基-4-曱基咪唑、2_ 笨基咪唑、2-苯基-4-曱基咪唑等咪唑化合物；2, 4-二胺基 一6~[2’-曱基咪唑基_(1，）]乙基一均三啡等三畊化合物； 1，8-二氮雜雙環[5,4,〇]十一烯_7(DBU)、三伸乙二胺、二 曱基苄胺（benzyldimethylamine)、三乙醇胺等三級胺化合 物；三苯基膦、三丁基膦、三（對曱基笨基）膦、三（壬基苯 基）膦等填系硬化促進劑。⑹成分可為單獨使用或將2種 以上併用。 相對於（A)成分1當量，（b)成分較佳為Q 6至u當 =之比率，更佳為0.6至10當量。（A)成分之當量為環氧 當·$，（B)成分之當量為酸酐當量。若為〇 6以上，則反應 323915 9 201242995 性、硬化後的液狀環氧樹脂組成物於PCT試驗之耐濕可靠 性、耐遷移性良好；另一方面，若為12以下，則增黏倍 率不會變得過高’會抑制孔洞（void)的產生。 相對於（A)成分1〇〇質量份，所含有之（C)成分較佳為 0.05至15質量份’更佳為〇·05至1〇質量份，又更佳為 0.05至8質量份’又再更佳為〇. 1至5質量份，特佳為〇 3 至3.0質量份。若為〇·05質量份以上，則反應性良好；若 為15質量份以下’則耐濕可靠性良好，並且增黏倍率安 定。 從液狀環氧樹脂組成物之應力緩和之觀點來看，液狀 環氧樹脂組成物係以復含有屬於（D)成分之彈性體為較 佳。（D)成分可列舉··聚矽氧橡膠（silicone rubber)、丁 二烯橡膠、聚稀烴橡膠、核殼（core shell)橡膠等。（d) 成分可使用固體者。形態並無特別限定，可使用例如粒子 狀、粉末狀、片（pellet)狀者，當為粒子狀時，例如平均 粒徑係10至200nm，較佳為30至100nm，更佳為50至 80nm。（D)成分亦可使用在常溫下為液狀者，例如平均分子 量較低的聚二有機石夕氧烧（口〇17(1丨〇巧31105丨1(^8116)、聚丁 二烯、乙烯丙稀（ethylene propylene)、苯乙缚丁二稀、 丙稀腈丁二稀、異戊二埽。此外，（D)成分可使用於末端具 有會與環氧基反應之基者，該等可為固體、液狀之任一形 態。市售品可列舉宇部興產製ATBN、CTBN1008-SP等。（D) 成分係可為單獨使用或將2種以上併用。 從密著性之觀點來看，液狀環氧樹脂組成物以復包含 323915 1〇 ⑧ 201242995 (E)成分為較佳。（E)成分可列舉：3-縮水甘油氧基丙基三 甲氧基矽烷、3-胺基丙基三甲氧基石夕烷、乙烯基三曱氧基 石夕烧、對苯乙烯基三甲氧基石夕燒、曱基丙烯醯氧基丙基 曱基三曱氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3〜 脲基丙基三乙氧基石夕烧、3-疏基丙基三甲氧基石夕烧、雙（三 乙氧基矽基丙基）四硫化物、3·~異氰酸酯丙基三乙氧基矽烷 等，較佳為3-縮水甘油氧基丙基三甲氧基矽炫、3-胺基丙 基三甲氧基矽烷。市售品可列舉信越化學工業製ΚΒΜ4〇3、 ΚΒΕ903 、 ΚΒΕ9103 等。 相對於（Α)成分100質量份，所含有之（D)成分較佳為 1至30質量份，更佳為1至25質量份。（D)成分若為！質 量份以上，則緩和液狀環氧樹脂組成物之硬化物之應力； 若為30質量份以下，則液狀環氧樹脂組成物之硬化後的耐 濕可靠性不會降低。 相對於（A)成分100質量份，所含有之（E)成分為〇. 〇5 至10質量份，較佳為0.05至5.0質量份，更佳為〇.丨至 3.0質量份。若為〇· 05質量份以上，則密著性會提升，於 PCT試驗之耐濕可靠性會變得更良好，若為5 〇質量份以 下，則會抑制液狀樹脂組成物的發泡。 於不損及本發明目的之範圍内，本發明之液狀環氧樹 脂組成物中可再依需要而調配調平劑、氧化矽填料 filler)、消泡劑、搖變劑、抗氧化劑、顏料、染料等添1^ 劑。 】σ 從注入性之觀點來看，液狀環氧樹脂組成物於溫度 323915 11 201242995 25°C之黏度係以5G至麵―· s為較佳，若為$ lOOOmPa·項為更佳。在此，黏度係以東機產業 型黏度計（型號：TVE-22H)測定。 此外，就液狀環氧樹脂組成物而言，24小時後之黏声 上昇率k佳為獅％以下，48小時後之黏度上昇率較佳 600%以下。在此，黏度上昇率係測定將液狀環氧樹脂組点 物於室溫保管24小時、48小時後之黏度，以⑵或仏小 時後之勒度）/(起始黏度）作為黏度上昇率（單位：幻。 本發明之環氧樹脂組成物，係適合作為利用倒裴晶片 接合（fllpchipbonding)之半導體元件的密封劑，而特 適合作為薄臈覆晶封裝用密封劑。 [液狀％氧樹脂組成物之製造方法] 本發明之液狀環氧樹脂組成物之製造方法的特徵為： 使（C)成分分散在將胺基酚型環氧樹脂除外之（A)成分之至 少一部分中’作成母料後，包含胺絲氧樹脂的（A) 成分之剩餘部分與（B)成分混合至母料中。 本發月之液狀環氧档十脂組成物的著眼重點係：藉由胺 基Μ環氧樹脂而使高溫下之樹脂組成物之彈性模數維持 高值。然而，若併用胺基酶型環氧樹脂與味唆化合物，則 會由於胺基盼型環氧樹脂與咪錢合物之高度反應性而使 黏度决速增加’導致注人性劣化，故無法使用於薄膜覆晶 用等密封劑。 因此，本發明中’係使咪嗤成分預先分散於胺基紛型 環氧樹知以外之液狀壤氧樹脂（例如液狀雙紛Α型環氧樹 323915 ⑧ 12 201242995 脂或液狀雙射型環氧樹脂）中，作成母料（高濃度分散體） 後，混合胺基酚型環氧樹脂，藉此而解決在使用胺基酚裂 環氧樹脂時所發生的問題。 因此’本發明之液狀環氧樹脂組成物係可藉由使（〇 成分分散在將胺基酚型環氧樹脂除外之（A)成分之至少一 部分中，作成母㈣，將包切絲㈣氧樹㈣（A)成分 之剩餘部分與⑻成分混合至母射，而加以製造。 在此，在製作母料時，相對於（c)成分 100質量份， 與（C)成分混合之將絲_環氧樹麟外之（A)成分較佳 為10至1000質£份，若為50至剛質量份則更佳。 製作母料時’可依所需，藉由-邊予以加熱處理，一 邊進打攪拌、溶融、混合、分散而得到。該等之混合、攪 拌、分散等之裝置’並無特別限定，可使用具備授摔、加 熱裝置之擂潰機、3輥研磨機、球磨機、行星式攪掉機 (planetary mixer)、珠磨機等。此外，亦可將該等裝置適 當組合使用。 f匕s知基紛型環氧樹脂的（A)成分之剩餘部分與（b) 成刀此口至母料中時，混合順序並無特別限定。進行現合 之方法係可與製作母料時相同。 .本發明之液狀環氧樹脂組成物，係以分注器 (dispenser)、印刷等而形成/塗佈在基板之所期望的位 置在此’液狀壤氧樹脂組成物係在可撓性配線基板等基 板與半導體το件之間，以至少―部分相接於基板的配線上 之方式而形成。 323915 13 201242995 本發明之液㈣脂組成物之硬化，較佳_ _ C進行30至細秒；從提升作為薄膜覆晶封農用密封劑使 用時之生產性之觀點來看’特佳為於200秒以内使之硬化。 又，半導體元件、基板雖可使用所期望者，但以倒穿 晶片接合之半導體元件與C0F封裝用基板之組合為較佳： 如此，本發明之液狀樹脂組成物非常適合作為液狀半 導體密封劑，而具有使_液狀半導體密封劑崎封的倒 裝晶片型半導體元件之半導體零件係耐遷純及耐引線腐 钱性優異，為高可靠性者。 (實施例） 雖藉由實施例而說明本發明’惟本發明並非限定於該 等者。又，以下實施例中之「份」、「％」若無特別註明，即 係表示質量份、質量％。 [實施例1至21、比較例1至3、參考例1至1〇] ，依表1至4所示之調配方式’製作液狀樹脂組成物（以 下稱為「樹脂組成物」）。在實施例i至2卜比較例i至3、 參考例1至6巾’先將雙酴jr型環氧樹脂與⑹成分進行混 合，作成母料後，再加入其他成分。在參考例7至9中， 先將胺基酴型環氧樹脂與⑹成分進行混合，作成母料後， 再加入其他成分。在參考例10至12中，係同時加入全部 成分。所製作之樹脂組成物，除了比較例2以外皆為液狀。 比較例2中’⑹成分溶解不完全而成為殘留有固形分之狀 態，而未能製作均勻的液狀環氧樹月旨組成物。 [黏度之評估] 201242995 以東機產業公司製E型黏度計（型號：TVE-22H)測定 剛製作後（30分鐘以内）的樹脂組成物之黏度（起始黏度， 單位：mPa · s)。於表1至4，表示起始黏度之測定結果。 此外’測定將樹脂組成物於室溫保管24小時、48小時後 之黏度’將（24或48小時後之黏度）/(起始黏度）作為黏度 上昇率（單位：％)。結果係表示於表1至4。 [膠化時間之評估] 樹脂組成物的膠化時間之評估係以下述方式進行。在 150±2<>c之加熱板上，以針（needle)滴下約3mmp之樹脂組 成物’一邊使針適度地接觸樹脂組成物，一邊以馬錶測定 直到樹脂組成物變成不會呈拔絲狀為止之時間，以作為膠 化時間。膠化時間之評估結果係表示於表1至4。 [吸水率之評估] 將所製作之樹脂組成物經150Ϊ硬化60分鐘而成之試 料之起始重量設為^(g)，於PCT試驗槽（121t±2°c/濕度 100%/2atm之槽）中放置2〇小時後，將冷卻至室溫而得到 的試驗片之重量設為Wl(g)，並以下述式求出吸水率（單 位：％)。 吸水率= (Wi-W〇)/W〇x 100(%) 吸水率之評估結果係表示於表1至4。 [彎曲彈性模數之評估] 將所製作之樹脂組成物挾在塗佈有脫模劑之玻璃板 與玻璃板間’於150t使其硬化60分鐘而成為35〇em之 膜片狀’使用萬能試驗機（島津製作所股份有限公司製-323915 15 201242995 AG-Ι)求出於室溫下之弯曲彈性模數。又 _ 定，採用其平均值。此外，試驗片之 =n=3進行測 點測定，將平均值用於計算值。彎曲彈性模行5 至4· 2GPp f曲彈性模數之評估結果她^為2· 0 [萃取C1離子量之評估] '、表不於表1至4。 將所製作之樹脂組成物於職進行硬化6〇分鐘 碎成5職平方左右。對於硬化塗膜 ： =放Γ2〇ΓΓ錢槽(12rc，濕度― 作^式驗;r # B後’令部至室溫’以所得到之萃取液 層析儀，測定以上述流程而得到的 濃度。“el離子量之評估結果係表示 於表1至4。 [注入性之評估] 上第1U)至第1(c)®係表示說明樹脂組成物的注入性 的-平估方法之不思圖。首先’如第圖所示，於基板2〇 上設置20_之間隙40，固定玻璃板3〇以取代半導體元 件’而料試驗H，隸縣板取代可撓性基板 以作為基板20。其次’將該試驗片放置在設定於U(rc之 力^板上，如f 1⑻圖所示般在玻璃板3〇 一端之側塗佈 所製作之樹脂組成物1〇，並測定直到如第丨圖⑹所示般 以樹月日組成物11填滿間隙4q為止之時間，以在9()秒以下 即填滿之情形為「H人性之評估結果絲示於表i 至4。 [耐遷移性之評估] 323915 201242995 • f施高溫高濕偏壓試驗，以評估樹驗成物之耐離子 ‘遷移性。試驗方法係如以下所述。在具備經锡鑛覆（〇·2+ • 0』5/zm)之銅配線（圖型寬度1〇Ρ、線間寬度15_、圖 型間距25_)之聚酿亞胺膠帶（polyimide tape)基材上， 塗佈所製作之樹脂级成物為厚度2〇_，以15代處理3〇 分鐘，使密封劑硬化而製作試驗片。對該試驗片使用離子 遷移評估系統（espec公司製），測定於11〇ΐ/濕度85%、 及200。(： /濕度〇%之條件下施加DC6〇v之電壓時之電阻值變 化，並將在11(TC/濕度85%、或是20(TC/濕度〇%中之至少 任一者之條件下.，以電阻值低於丨.〇〇χ1〇7Ω之時間點設為 閾值’§平估銅配線之遷移（單位：小時）。而電阻值未低於 閣值者，以超過1 〇 〇小時之時間點為試驗結束。耐遷移性 之評估結果係表示於表1至4。 323915 17 201242995 [表l] 1比較例2 I in 〇 ti) 丨 195 1 ! 2.58 I 10 T-· CQ CQ Ο 〇 1 1 1 I 1 1 1 1 I I 實施例7 〇 σ> Ο 产 ! 190 1 2.58 1 _______ 10 CO CD C) 〇 1 1 424 tn 0) CD 00 cJ <o.i」 1 153 I I 178 I >100 >100 |實施例6 I ΙΛ CO ΙΩ [187 I 2.58 in ¢9 GQ d 〇 1 1 456 100 r· 2.9 <0.1 151 179 >100 >100 |實施例_5 I ο 卜 Ο CO I 12§1 Z.58 in CO 0Q d 〇 1 1 495 102 c〇 r- ci <o.t | 155 176 ! >100 >100 1實施例4 I ο ΙΟ ο ID [158 I 2.58 to C9 00 d 〇 1 1 518 105 n C3 <0.1 L 153 I 179 I >100 I >100 1實施例3 I s Ο 00 134 Z5Q in ** CO ¢0 d 0 I 1 588 118 3,2 | 寸 〇 <0.1 149 172 >100 1 >100 實施例2 o 严 Ο σ> 127 2.58 in T- C9 CO O’ 0 1 1 630 120 r- ci CO <0.1 151 175 >100 >100 L實施例1 1 ΙΩ ΙΩ σ> 122 2.58 ΙΩ t- w 0.8 0 1 1 647 120 1 3.2 I 3.3 <0.1 l_ 142 ' 175 1 <Ά >100 >100 1比較倒U C9 卜 σ> 121 Z58 ID r- CO CX8 〇 1 1 650 121 ri 3.4 <0.1 148 1 172 I 20-70 10-30 調配物 胺基酚型環氡樹脂υ (質量份） 雙酚F型環氧樹鹿《(質量份） /-Ν Μ V-/ C7 W Jj 右 咪唑4> (質量份） 核殼橡鏐6)(質量份） 偶合射6Ϊ(質量份） (B)成分之酸酐當量/(A)成分之環氧當量 |缒|硬化促進糾雙W型環氧賴所製 1當使用由硬化促進射+胺基酚型環氧樹脂所製 造之MB時 1__ 未使用母料時 黏度（mPae8) 膠化時間（ε) I吸水率（蚱） 彆曲彈性數（GPa) 萃取Cl離子量（ppm) 24h黏度上升率（％) 48h黏度上升率（％> _ ― ! 耐遷移特性(h)丨10°C/溼度85Χ條件下 耐遷移特性(h)200°c/溼度0«條件下 (Α)成分 (Β)成分 | (C)成分1 1 (D)成分1 (E)成分 母料(MB) 製造方法 評估結果 ε〇 寸 smM:M06,^备^硪^川^叱蝴祐《中^埋-£辆械4卧：1>獾^(9 dwIsoinzml0:^08，轫^蘇敢怀(w Z5寸dzg:08,^炉砩如—呀—蝴^丨^睞嗜爸圃^^寸 woo 卜 £αΛ: 3rtB,^^ α3Ί0ε9αω? 3ΤΒ8Ζ鉍蚌 q·'-槲 Μ (t 18 323915 201242995 [表2] 實施例1 6 I 8 s 1彻Ί [14.90 1 io r· η Τ* 0 1 1 418 [ 3 TO cj o 1 342 I ^89 I m >100 1 >100 1 實施例15 S s 198 |2J98 1 10 r~ <0 Τ· 0 1 1 I 402 I 丨 i3S 1 ¢0 屮 fO o 155 ：229 | >100 1 >100 1 實施例14 S g 198 1 10 T— ¢0 0 1 1 352 1 ^57 1 C0 寸 C9 1 <0.1 | 130 188 | >!〇〇 1 >100 1 賁施例13 S s 158 1 12.90 I to T— η «? Ο 0 1 1 559 τ- (0 CO ! <o.i | 328 I >!〇〇 | >!〇〇 Ί 實施例12 s 158 I 2.53 ： 10 T— CO CO d 0 1 1 518 1 105 1 ο ci to <0.1 | 153 179 | >!〇〇 | >100 | 實施例” 〇 IP s 158 I 0-13 10 r— <0 § 0 1 1 501 3 0J CO 卜 CO 丨 <<u | 131 187 J >100 | >100 實施例10 〇 s 120 8 T- u> r- ο 0 1 1 598 r- ci I L—0.2 J 335 ^_475 I —>咖」 >100 | 實施例9 ο 10 o 10 120 I 2^0 10 产 η <P d 0 1 1 541 | 101 J n (0 1— d 155 221 J >100 J >100 | |實施例8 s g I 120 I 0.11 LO r· ο (D 0 0 1 1 508 I 393 I CO Qi r- d ! 132 丨 185 I ：>!〇〇 I >100 1麥考例3 s s 100 I 10.00 10 r· η 叫 Ο 0 1 1 '1111 00 C5 丨—42 I — 322 I 454 I 10-80 | 5-加1 1參考例2 s 8 100 2.00 IQ r- ο ir> d 0 1 1 983 OJ <0 4.2 一 I o 157 224 I 5-60 I 0-20 |參考例1 s s 100 | 0.10 I 10 产 ο 10 d 0 1 1 955 I 298 I (0 5 T" ! 136 i 185 I η Τ u> 〇 I 調配物 胺基酴型環氣樹鹿υ(質量份） ! 1雙酚F型環氧樹脂2)(質量份） 酸酐硬化劑3)(質量份） I咪嗤4)(質量份） I 核殼橡味s)(質量份） 偶合射e)(質量份） | (B)成分之酸酐當量/(A)成分之環氧杳量 | 當使用由硬化促進劑+雙酚F型環氣樹脂所製 造之MB時 當使用由硬化促進劑+胺基酚型環氧樹脂所製 造之MB蒔 1未使用母料時 I 黏度（ίηΡβ·β) 膠化時間（S〉 I I吸水丰（％) i彎曲彈性棋數（GPa) I 萃取Cl離子量（ppm> | 24h黏度上升率(％) I 48h黏度上升半〔％> I 注入性… 耐遷移特性OO1101C/溼度85¾條件下 I «ί邊移特性(h)20〇r/溼度〇%條件下 | (Α)成分 (B)成分 | (c)成分； (D)成分1 (Ε)成分 1 母料（MB) 製造方法 評估結果 19 323915 201242995 [表3] CO 磁 〇 〇 〇 r— □0 to r- 00 ip csi in <0 00 d 1 1 1 寸 C0 〇 ω λ OJ cd ο CO (Ο 00 8 〇 /\ flK 〇 /V § i r— CM 诺 ίΚ 〇 to 〇 ΙΟ Φ 10 r- 00 w oi O 〇 〇 00 〇 〇 1 1 00 00 C0 σ> σ> Ν C0 04 cd ο V* Μ ΙΟ r— 对 00 f— 〇 τ— /\ ο r^ y\ S 革 ο ΙΩ 〇 to ω ΙΟ r- 00 in CM o CO CD 〇 GD d 0 1 1 兮 ID 0) 00 Ο γ· Μ C0 ΓΗ cj τ— ο CO 寸 τ— in t- 〇 /S Ο X i Ο ΙΟ 〇 to 00 to r- 00 ii) CNi o (0 〇 Q0 d 〇 1 1 00 〇 CO Ο Ο Γ- CO CO ο CO in r- in 00 τ— § Λ. § 八 〇0 r* ο ΙΩ ο in αο (Ο r- 00 i〇 cvj 10 产 〇 r- 〇 ω d 〇 1 1 αο Ο) 吋 ΙΟ ο γ- Ο CO r— CO ο 0> 寸 d) r· 1— 〇 A Ο ✓V i 埃 Ο ΙΟ ο in αο in τ— 00 10 ?>i ΙΩ r- Ο 〇 α〇 d 〇 1 1 cvi CVJ to CO ο γ— Γ ΟΟ o cd ο o ΙΩ r- r- σΰ Γ- 〇 A ο ▼» A <(ίι» φ; 鉍 V»/ 严》 Γ" 奘 Μ 甭 蝴 /-N φΐ 3 w Ci, /-Ν Φ φι! 鉍 δ -ϋ ϊ /^N 每 ΦΊ 妒 Ψ /-N 拿 φ| & 一 s 酪 雖 雄 φί φ 茶 /-\ Φ4 ”1 味 φ4 %s Q \ •φ® fe 铋 £ 餘 b 洛 制 + «/ ji3 Ϊ ®齿 OP Ρ3 蝴 + m Λ3 5 S世 ㈣ 隹· 本 CB CL E *w>· S? 酋 jj i 求 齋 O 0. s 钵 t 故 « δί* Ε 8： φ| JM W ^-Η ϊ 坤· «w* 聲 ifl Tf^r 匀 CM 李 條 τ^ν β < 卜 漤 a? LO 00 ㈣1 、 P 〇 Γ·\ <5 ϊ 概 t t 维 、 P ο s Λ S 錐 概 尨. < ta 2 Φ: ts s <w» S 'w* 1 S'丧 e柃 鉍蚺Η濂滢采4α 323915 20 ⑧ 201242995 [表4] <N 2 S 00 1^ 产 ο σ> cJ 产 in 09 00 6 1 I 〇 0) 00 CO 03 ο r- N ri 5 ο ο A Ο ο A 〇 〇 X έ 沄 g 0Q in 产 □Q in cJ in 1» P? GQ O 1 1 〇 10 LA 00 r— 00 in CO GO ri 〇 Ο Ο /\ ο ο 〇 X 〇 ο ¥ S 00 in τ— d ΙΑ TO 00 d 1 1 〇 寸 \ί) CO τ~ CO N C9 ci d V ο ο X ο ο X 〇 Λκ 〇 a> 5 % S 〇 ΙΩ 00 in r— o σ> w »— in 严 C9 CD d 1 〇 1 ο in cvj τ— 00 严 r· C9 寸 d V ο ο Λ ο ο ο X ό Κ 〇0 暫 S Ο to oo to 严 00 U) cj in τ- C9 CO d 1 〇 1 产 00 ο 严 寸 C9 00 C3 d V ο ο X ο ο /Λ ο X 〇 咿 S ο U) GO ΙΩ τ— C9 产 d in C0 oo d 1 〇 1 t*" ύ〇 in to σ> c^ CO ID ci d α ο " ο ο <a ο 〇 A ① %» S ο ΙΟ σ> CO CM to O) CD 产 in r~ CO Oi T~ 〇 1 1 CO r- 寸 ΙΟ 严 产 严 ir> cJ 5 V σϊ 寸 ο 寸 ο 下 ι〇 〇 CJJ ο ΙΛ S s CD CO CJ 0) CO w in .户 c? C4 r- 〇 1 1 οα eg CO to c〇 c*? 0) T~ ο m ιη τ* CO Μ CM 凼 S ιλ ο ό S s σ> 3 ^- d in T~ CO OJ r· 0 1 1 0) 00 C\1 00 σ> LD r* C9 d V Ο Μ r- ο 00 Λ ό C0 ο 碁 <π (Η r"\ S-/ 海 锗 Vw^ Μ 璉 s 解 C&. 洛 制 _ W « 右 /—s 〇W w r-\ 每 φ| ΐο 餘 雄 /-N © w 筚 咖 鋼 r-\ φ) 猫 V Φ 嗜 £ 斜 率 C&, 洛 ¥ + W $ •δ曾 qc-CQ m 洛 蝴 + 在 Λ3 S當 ¢1 齿 1# < « a a. 2 宙 Δ3 «"~S # Ϊ <0 Q. S 琏 瞭 电 Ε a cH Η' 旛 ι-Η i « -Μ Cs) •w> 价 -Μ 雜 tl m 00 、 P 〇 — % 铕 t 轴 、 Ρ 〇 A m 苜. 链 < 堪 £ 世 «-s, υ 堪 堪 21¾¾ $柃 实衔 ㈣ it 21 323915 201242995 從表1至4可知，實施例1至21皆為黏度上昇率低、 注入性良好、耐遷移性優異，且彎曲彈性模數為所期望之 值。相對於此’（A)成分之胺基酚型環氧樹脂含量少之比較 例1中，耐遷移性為不良。（A)成分中不含胺基酚型環氧樹 脂並藉由添加苯并三唑而試圖抑制遷移之比較例3中，48 小時後之黏度上昇率變高為1〇〇〇%以上，2〇〇<t/濕度⑽之 耐遷移特性為劣。此外，相對於（A)成分1當量其（b)成分 為〇. 5當量之比率的參考例1至3中，耐遷移性為不良； 其比率為1.2當量之參考例4至6中’耐遷移性亦為不良。 另外，參考例1至3中，被認為係源自原料之（A)成分的萃 取C1離子量為多，放置於室溫而可見黏度上昇。此外，以 胺基紛型環氧樹脂製作母料之參考例7中，不僅相對於⑷ 成分100質量份其⑹成分為〇 13 f量份而為少，並且黏 度上昇率亦為高。含有較多⑹成分之參考例8、9中，起 ”也高，膠化時間短’注入性為劣，而黏度上昇 率向。若將調配量相同之實施例4與參考例8進行比較， 則參考例8之起始減為實闕4之約2.丨倍 :1〇至12 ’起始黏度顯著為高，膠化時間短， 4二:9而黏度上昇率高。若將調配量相同之實施例 例Γ之^ 1 較，則參考例12之起喊度為實施 特別是⑹成ί之含量為12.9質量份之 1 ，起始黏度顯著為高。在此，當黏度上昇率兔 323915 存安定性會變差。此外，將環氧樹脂組成物作為 薄膜覆4裝用密_制時，其可料間錢短，而造Momentive Performance Materials A non-oxygenated epoxy resin (product name: TSL9906). The component (A) other than the aminophenol type epoxy resin may be used alone or in combination of two or more. From the viewpoint of migration resistance, it is preferred to contain 5 to 90 parts by weight of an amine-based epoxy resin based on 1 part by weight of the component (A). The component (B) imparts good reactivity (hardening rate) and moderate viscosity. The component (B) may, for example, be tetrahydrophthalic anhydride, hexahydrophthalic anhydride, decyl tetraphthalic anhydride 'methylbutenyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, alkyl 323915 8 201242995 tetrahydroquinone Anhydride, hexahydrophthalic anhydride, methyl HIMIC anhydride, thin-substituted capric anhydride, methyl nadic anhydride, hydrogenated quinonedic anhydride, tricarbyl Hydrophthalic anhydride, mercaptocyclohexene tetradecanoic acid dianhydride, phthalic anhydride, benzene trimellitic anhydride, benzene tetraphthalic anhydride, diphenyl ketone tetraphthalic acid dianhydride, ethylene glycol bis-dehydrated trimellitic acid Ethylene glycol bis-anhydrotrimellitate, glycerol bis (dehydrated benzotridecanoate) monoacetic acid vinegar, dodecenyl succinic anhydride, chl〇rendic anhydride, aliphatic dibasic acid polyanhydride , glutaric anhydride, etc.; preferably decylbutenyl sulfonate. Commercially available products include: acid liver produced by Mitsubishi Chemical (grade: YH306, YH307). The component (B) may be used alone or in combination of two or more. The component (C) is a hardening accelerator, and the component (c) is exemplified by 2 曱 味 β β sit, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-mercaptoimidazole, 2_ An imidazole compound such as streptozolyl imidazole or 2-phenyl-4-mercaptoimidazole; 2,4-diamino- 6-[2'-nonylimidazolyl-(1,)]ethyl-mono-trientene a cultivating compound; a tertiary amine compound such as 1,8-diazabicyclo[5,4,fluorene]undecene-7 (DBU), triethylenediamine, benzyldimethylamine or triethanolamine; A hardening accelerator such as triphenylphosphine, tributylphosphine, tris(p-indolyl)phosphine or tris(nonylphenyl)phosphine. (6) The components may be used singly or in combination of two or more. The component (b) is preferably a ratio of Q 6 to u when = relative to 1 equivalent of the component (A), more preferably 0.6 to 10 equivalents. The equivalent of the component (A) is an epoxy. The equivalent of the component (B) is an acid anhydride equivalent. In the case of 〇6 or more, the liquid epoxy resin composition of the reaction 323915 9 201242995 and the cured resin is excellent in moisture resistance reliability and migration resistance in the PCT test. On the other hand, if it is 12 or less, the viscosity increase ratio is increased. Will not become too high 'will inhibit the generation of voids (void). The component (C) is preferably 0.05 to 15 parts by mass with respect to 1 part by mass of the component (A), more preferably 〇·05 to 1 part by mass, still more preferably 0.05 to 8 parts by mass. Further preferably, it is from 1 to 5 parts by mass, particularly preferably from 3 to 3.0 parts by mass. When the amount is 〇·05 parts by mass or more, the reactivity is good, and when it is 15 parts by mass or less, the moisture resistance reliability is good, and the viscosity increasing ratio is stabilized. From the viewpoint of stress relaxation of the liquid epoxy resin composition, the liquid epoxy resin composition is preferably an elastomer containing the component (D). Examples of the component (D) include silicone rubber, butadiene rubber, polysulfide rubber, and core shell rubber. (d) The ingredients may be solid. The form is not particularly limited, and for example, in the form of a pellet, a powder or a pellet, when it is in the form of particles, for example, the average particle diameter is 10 to 200 nm, preferably 30 to 100 nm, more preferably 50 to 80 nm. . The component (D) may also be used in the form of a liquid at a normal temperature, for example, a polydiorganophosphorus oxide having a lower average molecular weight (mouth 〇 17 (1丨〇31105丨1 (^8116), polybutadiene, Ethylene propylene, styrene dibutyl, acrylonitrile dibutyl, isoprene dichloride. In addition, the component (D) can be used for a group having a terminal which reacts with an epoxy group. For the commercially available product, ATBN, CTBN1008-SP, etc., which are manufactured by Ube Industries, Ltd., may be used. (D) The components may be used alone or in combination of two or more. From the viewpoint of adhesion It is preferable that the liquid epoxy resin composition contains a compound of 323915 1〇8 201242995 (E). The component (E) may, for example, be 3-glycidoxypropyltrimethoxydecane or 3-aminopropylpropane. Trimethoxy-oxanthene, vinyl trimethoxy oxy-stone, p-styryl trimethoxy sinter, decyl propylene methoxy propyl decyl tridecyl decane, 3-propenyl methoxy propyl Trimethoxy decane, 3~ ureidopropyl triethoxy sulphur, 3-sodium propyl trimethoxy sulphur, bis (triethoxy fluorenyl) Base) tetrasulfide, 3·-isocyanate propyl triethoxy decane, etc., preferably 3-glycidoxypropyltrimethoxyoxime, 3-aminopropyltrimethoxydecane. Commercial product The component (D) is preferably contained in an amount of from 1 to 30 parts by mass, more preferably from 1 to 25 parts by mass, per 100 parts by mass of the (Α) component. When the component (D) is at least a part by mass, the stress of the cured product of the liquid epoxy resin composition is alleviated; if it is 30 parts by mass or less, the moisture resistance reliability of the liquid epoxy resin composition after curing is not The component (E) is contained in an amount of 〇. 5 to 10 parts by mass, preferably 0.05 to 5.0 parts by mass, more preferably 〇. 丨 to 3.0 parts by mass, based on 100 parts by mass of the component (A). When the amount is 5% by mass or more, the adhesion is improved, and the moisture resistance reliability in the PCT test is further improved. When the amount is 5 parts by mass or less, the foaming of the liquid resin composition is suppressed. The liquid epoxy resin composition of the present invention can be further required as needed within the scope of the object of the present invention. To prepare a leveling agent, a cerium oxide filler, an antifoaming agent, a rocking agent, an antioxidant, a pigment, a dye, etc. 】 σ From the viewpoint of injectability, a liquid epoxy resin composition The viscosity at a temperature of 323915 11 201242995 at 25 ° C is preferably 5G to ― s s, and is preferably more than 10,000 parts. Here, the viscosity is an industrial grade viscometer (Model: TVE-22H) In addition, in the case of the liquid epoxy resin composition, the viscosity increase rate k after 24 hours is preferably less than lion%, and the viscosity increase rate after 48 hours is preferably 600% or less. Here, the viscosity increase rate is measured by the viscosity of the liquid epoxy resin group stored at room temperature for 24 hours and 48 hours, and the viscosity is increased by (2) or after the hour (/ initial viscosity). (Unit: Magical. The epoxy resin composition of the present invention is suitable as a sealant for a semiconductor device using flip chip bonding, and is particularly suitable as a sealing agent for a thin-film flip chip package. [Liquid % oxygen Method for Producing Resin Composition] The method for producing a liquid epoxy resin composition of the present invention is characterized in that: (C) component is dispersed in at least a part of the component (A) excluding the aminophenol type epoxy resin' After the masterbatch is prepared, the remainder of the component (A) containing the amine silk oxide resin and the component (B) are mixed into the masterbatch. The focus of the liquid epoxy epoxide composition of this month is: by amine Based on the epoxy resin, the elastic modulus of the resin composition at a high temperature is maintained at a high value. However, if an amino-based epoxy resin and a miso compound are used in combination, an amine-based epoxy resin and a microphone are used. High reactivity of the compound to make the viscosity The increase in speed is caused by deterioration of the injectability, and therefore it cannot be used for a sealing agent such as a film for flip chip. Therefore, in the present invention, the liquid component is prepared by dispersing the amidine component in advance in the liquid epoxy resin other than the amine-based epoxy resin. (For example, liquid double-type epoxy resin 323915 8 12 201242995 grease or liquid bijective epoxy resin), after preparing a masterbatch (high concentration dispersion), mixing an aminophenol type epoxy resin The problem that occurs when the aminophenol phenolic epoxy resin is used is solved. Therefore, the liquid epoxy resin composition of the present invention can be obtained by dispersing the bismuth component in the epoxy phenol epoxy resin ( In at least a part of the component A), the mother (4) is prepared, and the remainder of the component (A) of the oxygen tree (4) (A) and the component (8) are mixed to the mother particle to be produced. Here, when the master batch is produced, (c) 100 parts by mass of the component, and the component (A) which is mixed with the component (C) is preferably 10 to 1000 parts by weight, more preferably 50 to just parts by mass. When the masterbatch is used, it can be heated by the side while stirring. It is obtained by melting, mixing, and dispersing. The apparatus for mixing, stirring, dispersing, etc. is not particularly limited, and a crucible having a drop and a heating device, a 3-roll mill, a ball mill, and a planetary agitator can be used. (planetary mixer), bead mill, etc. In addition, these devices may be used in combination as appropriate. The remaining part of the component (A) of the epoxy resin and (b) the knife to the mother In the case of the material, the order of mixing is not particularly limited. The method of performing the mixing can be the same as in the case of preparing the master batch. The liquid epoxy resin composition of the present invention is formed by a dispenser, printing, or the like. / Applying to a desired position on the substrate, the liquid-liquid oxy-resin composition is disposed between the substrate such as the flexible wiring substrate and the semiconductor material, at least partially in contact with the wiring of the substrate. form. 323915 13 201242995 The liquid (4) of the present invention is hardened, preferably _ _ C for 30 to fine seconds; from the viewpoint of productivity when used as a film-sealing agricultural sealant, 'excellent for 200 Harden it within seconds. Further, although a semiconductor element or a substrate can be used as desired, a combination of a semiconductor element which is reversed by wafer bonding and a substrate for SOC packaging is preferable. Thus, the liquid resin composition of the present invention is very suitable as a liquid semiconductor sealing. The semiconductor component having a flip-chip type semiconductor device in which the liquid semiconductor sealing agent is sealed is excellent in resistance to migration and lead rot, and is highly reliable. (Embodiment) The present invention has been described by way of examples, but the invention is not limited thereto. In addition, "parts" and "%" in the following examples represent the parts by mass and mass% unless otherwise specified. [Examples 1 to 21, Comparative Examples 1 to 3, and Reference Examples 1 to 1], a liquid resin composition (hereinafter referred to as "resin composition") was prepared according to the mixing method shown in Tables 1 to 4. In Examples i to 2, Comparative Examples i to 3, and Reference Examples 1 to 6, the bismuth jr type epoxy resin and the component (6) were first mixed to prepare a master batch, and then other components were added. In Reference Examples 7 to 9, the amine fluorene type epoxy resin and the component (6) were first mixed to prepare a master batch, and then other components were added. In Reference Examples 10 to 12, all the components were simultaneously added. The resin composition produced was liquid except for Comparative Example 2. In Comparative Example 2, the component (6) was incompletely dissolved and remained in a solid form, and a uniform liquid epoxy resin composition could not be produced. [Evaluation of Viscosity] 201242995 E-type viscometer (Model: TVE-22H) manufactured by Edo Industries Co., Ltd. The viscosity (starting viscosity, unit: mPa · s) of the resin composition immediately after production (within 30 minutes) was measured. Tables 1 to 4 show the results of the measurement of the initial viscosity. Further, 'the viscosity of the resin composition after storage at room temperature for 24 hours and 48 hours' was measured (viscosity after 24 or 48 hours) / (starting viscosity) as the viscosity increase rate (unit: %). The results are shown in Tables 1 to 4. [Evaluation of Gelation Time] The evaluation of the gelation time of the resin composition was carried out in the following manner. On a hot plate of 150±2<>c, a resin composition of about 3 mmp was dropped by a needle, and while the needle was appropriately contacted with the resin composition, it was measured with a horse watch until the resin composition became not drawn. The time until the shape is used as the gelation time. The evaluation results of the gelation time are shown in Tables 1 to 4. [Evaluation of water absorption rate] The starting weight of the sample obtained by hardening the resin composition prepared by curing for 150 minutes for 60 minutes was set as ^(g) in a PCT test tank (121t ± 2 ° c / humidity 100% / 2 atm) After leaving the tank for 2 hours, the weight of the test piece obtained by cooling to room temperature was Wl (g), and the water absorption rate (unit: %) was calculated by the following formula. Water absorption rate = (Wi-W 〇) / W 〇 x 100 (%) The evaluation results of water absorption are shown in Tables 1 to 4. [Evaluation of Bending Elastic Modulus] The resin composition produced was kneaded between a glass plate coated with a release agent and a glass plate to be cured at 150 t for 60 minutes to become a film of 35 〇em. The test machine (manufactured by Shimadzu Corporation, Ltd. -323915 15 201242995 AG-Ι) was used to obtain the bending elastic modulus at room temperature. Also _, the average value is used. In addition, the test piece was measured with =n=3, and the average value was used to calculate the value. The evaluation result of the elastic modulus of the bending elastic modulus 5 to 4·2GPp f is ^2 0 [Evaluation of the amount of extracted C1 ions], and is not shown in Tables 1 to 4. The resin composition produced is hardened for 6 minutes in a job and broken into 5 squares. For the hardened coating film: = put the 2 〇ΓΓ 2 trough (12 rc, humidity - test; r # B after the 'order to room temperature' to obtain the extract liquid chromatograph, determine the above process Concentration. "Evaluation results of the amount of el ions are shown in Tables 1 to 4. [Evaluation of Injectability] The first to the first (1) to the first (c) of the resin indicate the injectability of the resin composition. First, as shown in the figure, a gap 40 of 20_ is placed on the substrate 2, the glass plate 3 is fixed to replace the semiconductor element, and the test H is replaced by a sub-plate to replace the flexible substrate as the substrate 20. Next, the test piece was placed on a U (rc force plate), and the resin composition prepared was coated on the side of one end of the glass plate as shown in the figure of f 1 (8), and measured until As shown in Fig. 6 (6), the time until the gap 4q is filled with the tree-month composition 11 is "9" or less, that is, "the evaluation result of H humanity is shown in Tables i to 4. [Evaluation of migration resistance] 323915 201242995 • F high-temperature and high-humidity bias test to evaluate the ion-to-migration resistance of the tree test substance. The system is as follows. The copper wiring (the width of the pattern is 1〇Ρ, the width between the lines is 15_, and the distance between the patterns is 25_) is covered by tin-coated (〇·2+ • 0』5/zm). On a polyimide tape substrate, the resin composition prepared by coating was a thickness of 2 Å, and treated for 15 minutes in 15 passages to cure the sealant to prepare a test piece. Ion migration evaluation was used for the test piece. The system (manufactured by Espec Co., Ltd.) measures the change in resistance at a voltage of DC6〇v under conditions of 11〇ΐ/humidity 85% and 200. (:/humidity 〇%, and will be at 11 (TC/humidity 85). %, or 20 (TC/humidity 〇% under any of the conditions. The resistance value is lower than 丨.〇〇χ1〇7Ω is set as the threshold value' § Evaluate the migration of copper wiring (unit :hour). If the resistance value is not lower than the value of the cabinet, the time point of more than 1 hour is the end of the test. The evaluation results of migration resistance are shown in Tables 1 to 4. 323915 17 201242995 [Table l] 1Comparative Example 2 I in 〇ti) 丨195 1 ! 2.58 I 10 T-· CQ CQ Ο 11 1 1 I 1 1 1 1 II Example 7 〇σ> Ο Production! 190 1 2.58 1 _____ __ 10 CO CD C) 〇1 1 424 tn 0) CD 00 cJ <oi" 1 153 II 178 I >100 >100 |Example 6 I ΙΛ CO ΙΩ [187 I 2.58 in ¢9 GQ d 〇1 1 456 100 r· 2.9 <0.1 151 179 >100 >100 |Example _5 I ο Ο Ο CO I 12§1 Z.58 in CO 0Q d 〇1 1 495 102 c〇r- ci < Ot | 155 176 ! >100 >100 1 Embodiment 4 I ο ΙΟ ο ID [158 I 2.58 to C9 00 d 〇1 1 518 105 n C3 <0.1 L 153 I 179 I >100 I >100 1 Embodiment 3 I s 00 00 134 Z5Q in ** CO ¢ 0 d 0 I 1 588 118 3, 2 | inch 〇 <0.1 149 172 > 100 1 > 100 Example 2 o Severe σ > 127 2.58 In T- C9 CO O' 0 1 1 630 120 r- ci CO < 0.1 151 175 > 100 > 100 L Example 1 1 Ι Ω Ι Ω σ > 122 2.58 Ι Ω t- w 0.8 0 1 1 647 120 1 3.2 I 3.3 <0.1 l_ 142 ' 175 1 <Ά >100 >100 1Comparative inverted U C9 卜σ> 121 Z58 ID r- CO CX8 〇1 1 650 121 ri 3.4 <0.1 148 1 172 I 20- 70 10-30 Formulation Aminophenol-based cyclic resin υ (parts by mass) Bisphenol F-type epoxy tree deer "(parts by mass) /-Ν Μ V-/ C7 W Jj omnizazole 4&g t; (mass) Core-shell rubber 6) (mass parts) Coupling shot 6 Ϊ (mass parts) (B) Component anhydride equivalent / (A) component epoxy equivalent | 缒 | Hardening promotes double W type epoxy Lai made 1 When using MB made of hardening-promoting + aminophenol type epoxy resin 1__ When the masterbatch is not used, the viscosity (mPae8) Gelation time (ε) I Water absorption rate (蚱) GPa) Extraction of Cl ions (ppm) 24h viscosity increase rate (%) 48h viscosity increase rate (%> _ ― ! Resistance to migration characteristics (h) 丨 10 ° C / humidity 85 Χ under conditions of migration resistance (h) 200 ° c/humidity 0« (Α) component (Β) component | (C) component 1 1 (D) component 1 (E) component masterbatch (MB) Manufacturing method evaluation result ε〇 inch smM: M06, ^备^硪^川^叱蝶佑"中^埋-£车械4卧:1>獾^(9 dwIsoinzml0:^08,轫^苏敢怀(w Z5 inch dzg:08,^炉砩如—呀—蝴蝶^丨^睐爱爸圃^^寸woo 卜£αΛ: 3rtB,^^ α3Ί0ε9αω? 3ΤΒ8Ζ铋蚌q·'-槲Μ (t 18 323915 201242995 [Table 2] Example 1 6 I 8 s 1 Ί [ 14.90 1 io r · η Τ * 0 1 1 418 [ 3 TO cj o 1 342 I ^89 I m > 100 1 > 100 1 Example 15 S s 198 | 2J98 1 10 r~ <0 Τ· 0 1 1 I 402 I 丨i3S 1 ¢0 屮fO o 155 :229 | >100 1 >100 1 Example 14 S g 198 1 10 T— ¢0 0 1 1 352 1 ^57 1 C0 inch C9 1 <0.1 | 130 188 | >!〇〇1 >100 1 Example 13 S s 158 1 12.90 I to T— η «? Ο 0 1 1 559 Τ- (0 CO ! <oi | 328 I >!〇〇| >!〇〇Ί Example 12 s 158 I 2.53 : 10 T—CO CO d 0 1 1 518 1 105 1 ο ci to < 0.1 | 153 179 | >!〇〇| >100 | Example 〇IP s 158 I 0-13 10 r— <0 § 0 1 1 501 3 0J CO Bu CO 丨<<u | 131 187 J >100 | > 100 Example 10 〇s 120 8 T-u> r- ο 0 1 1 598 r- ci IL-0.2 J 335 ^_475 I —> Coffee >100 | Example 9 ο 10 o 10 120 I 2^0 10 η < P d 0 1 1 541 | 101 J n (0 1 - d 155 221 J > 100 J > 100 | | Example 8 sg I 120 I 0.11 LO r· ο (D 0 0 1 1 508 I 393 I CO Qi r- d ! 132 丨185 I :>!〇〇I >100 1 McC. 3 ss 100 I 10.00 10 r· η Ο Ο 0 1 1 '1111 00 C5 丨—42 I — 322 I 454 I 1 0-80 | 5-plus 1 1 Reference Example 2 s 8 100 2.00 IQ r- ο ir> d 0 1 1 983 OJ <0 4.2 I I 157 224 I 5-60 I 0-20 | Reference Example 1 ss 100 | 0.10 I 10 ο 10 d 0 1 1 955 I 298 I (0 5 T" ! 136 i 185 I η Τ u> 〇I Formulation Amine-based 环 type 气 树 υ 质量 (mass)! 1 pair Phenol F type epoxy resin 2) (mass parts) Anhydride hardener 3) (mass parts) I 嗤 4) (mass parts) I Core shell rubber s) (mass parts) Coupled shot e) (mass parts) | (B) The anhydride equivalent of the component / The amount of epoxy oxime of the component (A) | When using the MB made of the hardening accelerator + bisphenol F type ring gas resin, when using the hardening accelerator + aminophenol type epoxy When the MB莳1 made of resin does not use the masterbatch I viscosity (ίηΡβ·β) gelation time (S> II water absorption (%) i bending elastic number (GPa) I extract Cl ion amount (ppm> | 24h viscosity Increasing rate (%) I 48h viscosity increase half [%> I injectability... migration resistance OO1101C/humidity 852⁄4 condition I «b edge shift characteristic (h) 20〇r/humidity 〇% condition | (Α) component (B) Ingredients | (c) Ingredients; (D) Ingredient 1 (Ε) Ingredient 1 Masterbatch (MB) Method evaluation result 19 323915 201242995 [Table 3] CO magnetic 〇〇〇 r □ □ 0 to r 00 ip csi in < 0 00 d 1 1 1 inch C0 〇 ω λ OJ cd ο CO (Ο 00 8 〇 / \ flK 〇/V § ir— CM 诺诺Κ 〇to 〇ΙΟ Φ 10 r- 00 w oi O 〇〇00 〇〇1 1 00 00 C0 σ>σ> Ν C0 04 cd ο V* Μ ΙΟ r—for 00 F— 〇τ— /\ ο r^ y\ S ο Ι 〇 〇 to ω ΙΟ r- 00 in CM o CO CD 〇GD d 0 1 1 兮ID 0) 00 Ο γ· Μ C0 ΓΗ cj τ— ο CO寸τ— in t- 〇/S Ο X i Ο ΙΟ 〇to 00 to r- 00 ii) CNi o (0 〇Q0 d 〇1 1 00 〇CO Ο Ο Γ- CO CO ο CO in r- in 00 τ —§ Λ. § 八〇0 r* ο ΙΩ ο in αο (Ο r- 00 i〇cvj 10 〇r- 〇ω d 〇1 1 αο Ο) 吋ΙΟ ο γ- Ο CO r— CO ο 0> Inch d) r· 1—〇A Ο ✓V i Ο ΙΟ ο in αο in τ— 00 10 ?>i ΙΩ r- Ο 〇α〇d 〇1 1 cvi CVJ to CO ο γ— Γ ΟΟ o cd ο o Ι r r r r r r r r r r r r r r r r r r r r r r Φ Φ φι! 铋δ -ϋ ϊ /^N Every ΦΊ 妒Ψ /-N Take φ| & a s cheese although φί φ tea /-\ Φ4 ”1 φ4 %s Q \ •φ® fe 铋£余b 洛+{/ ji3 Ϊ ®tooth OP Ρ3 Butterfly+ m Λ3 5 S (4) 隹· This CB CL E *w>· S? Emirates jj i Seek O 0. s 钵t 故 « δί* Ε 8 : φ| JM W ^-Η 坤 Kun· «w* sound ifl Tf^r uniform CM Li τ^ν β < 卜漤 a? LO 00 (4) 1 , P 〇Γ · \ <5 ϊ tt tt P ο s Λ S cone outline. < ta 2 Φ: ts s <w» S 'w* 1 S' 柃铋蚺Η濂滢e柃铋蚺Η濂滢 mining 4α 323915 20 8 201242995 [Table 4] <N 2 S 00 1^ Produced ο σ> cJ Produced in 09 00 6 1 I 〇0) 00 CO 03 ο r- N ri 5 ο ο A Ο ο A 〇〇X έ 沄g 0Q in Production □Q in cJ in 1» P? GQ O 1 1 〇10 LA 00 r— 00 in CO GO ri 〇Ο Ο /\ ο ο 〇X 〇ο ¥ S 00 in τ— d ΙΑ TO 00 d 1 1 inch \ί) CO τ~ CO N C9 ci d V ο ο X ο ο X 〇Λκ 〇a> 5 % S 〇Ι Ω 00 in r — o σ> w »—in strict C9 CD d 1 〇1 ο in cvj τ— 00 严 r· C9 inch d V ο ο Λ ο ο ο X ό Κ 〇0 Temporary S Ο to oo to 00 00 U) cj in τ- C9 CO d 1 〇1 00 ο 严 寸 C9 00 C3 d V ο ο X ο ο /Λ ο X 〇咿S ο U) GO Ι Ω τ — C9 produces d in C0 oo d 1 〇 1 t*" ύ〇in to σ> c^ CO ID ci d α ο " ο ο <a ο 〇A 1 %» S ο ΙΟ σ> CO CM to O) CD production in r~ CO Oi T~ 〇1 1 CO r- inch ΙΟ strict production strict ir> cJ 5 V σϊ inch ο inch ο ι〇〇CJJ ο ΙΛ S s CD CO CJ 0) CO w in .户 c? C4 r- 〇1 1 οα eg CO to c〇c*? 0) T~ ο m ιη τ* CO Μ CM 凼S ιλ ο ό S s σ> 3 ^- d in T~ CO OJ r· 0 1 1 0) 00 C\1 00 σ> LD r* C9 d V Ο Μ r- ο 00 Λ ό C0 ο 碁<π (Η r"\ S-/ 海锗Vw^ Μ 琏s Solution C&. 洛__ «Shift _ W r W w r-\ per φ| ΐο 余雄/-N © w 筚 钢 steel r-\ φ) Cat V Φ 奇 £ Slope C&, Luo ¥ + W $ •δ曾qc-CQ m 洛毛+ at Λ3 S当¢1 tooth 1# < « a a. 2 宙Δ3 «"~S # Ϊ <0 Q. S 琏 Ε a cH Η ' 幡ι-Η i « -Μ Cs) •w> Price-Μ Miscellaneous tl m 00 , P 〇 % % % % % % % 链 链 « « « « « « « « « « « « 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 it it it it it it it it it it it it it it it it it it it it it it it it 21 has a low viscosity increase rate, good injectability, excellent migration resistance, and a bending elastic modulus is a desired value. In Comparative Example 1 in which the content of the aminophenol-based epoxy resin of the component (A) was small, the migration resistance was poor. In Comparative Example 3, in which the amino acid-based epoxy resin was not contained in the component (A) and the migration was attempted to be inhibited by the addition of benzotriazole, the viscosity increase rate after 48 hours was increased to 1% or more, 2 The migration resistance of 〇〇<t/humidity (10) is inferior. Further, in Reference Examples 1 to 3 in which the ratio (b) of the component (b) was (e) equivalent to 5 parts, the migration resistance was poor; the ratio was 1.2 equivalents in Reference Examples 4 to 6 Migrability is also bad. Further, in Reference Examples 1 to 3, it is considered that the amount of extracted C1 ions derived from the component (A) derived from the raw material is large, and the viscosity is increased when left at room temperature. In addition, in the reference example 7 in which the master batch is made of the amine-based epoxy resin, the component (6) is less than 100 parts by mass of the component (4), and the viscosity increase rate is also high. In Reference Examples 8 and 9 containing a large number of (6) components, the "high", the gelation time was short, and the injectability was inferior, and the viscosity was increased. If the formulation amount was the same, Example 4 was compared with Reference Example 8. Then, the initial value of Reference Example 8 is reduced to about 2. The 黏 times: 1 〇 to 12 ′, the initial viscosity is remarkably high, the gelation time is short, 4 2: 9 and the viscosity increase rate is high. In the case of the same example, the degree of squeaking of the reference example 12 is particularly high in the content of (6) ί, which is 12.9 parts by mass, and the initial viscosity is remarkably high. Here, when the viscosity rise rate is rabbit 323915 The stability of storage and storage will be worse. In addition, when the epoxy resin composition is used as a film cover 4, it can be used for a short period of time.
22 201242995 成使用上的問題。另外，當注入性為劣時，除了注入性之 問題以外’造成孔洞的可能性會變高，而造成使用上的問 題。 (產業上之可利用性） 如上所述，本發明之液狀樹脂組成物可抑制液狀樹脂 組成物在保存時之增黏，^可防止硬化後切狀樹脂組成 物之遷移，而特別適於包含倒裝晶片型半導體元件之半導 體零件。 【圖式簡單說明】 第1圖（A)至（C)係說明樹脂組成物的注入性的評估方 法之不意圖。 【主要元件符號說明】 10、11 樹脂組成物 基板 30 玻螭板 4〇 間隙 32391522 201242995 The problem with the use. In addition, when the injectability is inferior, in addition to the problem of injectability, the possibility of causing a hole becomes high, causing problems in use. (Industrial Applicability) As described above, the liquid resin composition of the present invention can suppress the viscosity of the liquid resin composition during storage, and can prevent migration of the cut resin composition after hardening, and is particularly suitable. For semiconductor components including flip chip type semiconductor devices. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (A) to (C) are diagrams for explaining an evaluation method of the injectability of a resin composition. [Description of main component symbols] 10, 11 Resin composition Substrate 30 Glass plate 4〇 Clearance 323915