201127864 六、發明說明： 【發明所屬之技術領域】 本發明係於半導體的覆晶’尤其是c 〇F (薄膜覆晶） 型的覆晶的封閉用之高可靠度、高絕緣性及高操作性的半 導體封閉用環氧樹脂組成物及使用該組成物而成之半導體 裝置。 【先前技術】 作爲搭載液晶驅動器1C的半導體裝置，已知有在撓性 基板上搭載半導體晶片（元件）的COF或TCP (膠帶式承 載封閉）等。此外，COF係定義爲在具有配線的撓性基板 上搭載半導體晶片等的構造之半導體裝置。近年來液晶驅 動器的多輸出化等的要求變強，配線圖案的細微化優異之 C Ο F安裝變多。但是’由於細微配線圖案使配線間窄間距 化及因驅動電壓的高電壓化’而容易發生電流流經配線圖 案時使配線中的金屬離子化而遷移，析出堆積在不是本來 的配線位置之處而引起配線間的絕緣惡化及電路短路之遷 移。因此’在確保半導體裝置的可靠度上，防止C〇F長時 間產生遷移變得非常重要。 作爲半導體裝置的封閉劑’多使用環氧樹脂組成物， 但在COF安裝中’於半導體晶片（積體電路）之下塡充封 閉劑而封閉時’爲防止因封閉劑中的溶劑揮發而產生孔洞 ’係使用無ί谷劑的環氧樹脂組成物。然而，由防止伴隨近 年來的乍間隙化、窄間距（例如3 〇 μ m以下）化所產生的遷 201127864 移，或由安裝時的操作性等方面來看，要求 脂組成物的低黏度化。 使用酸酐作爲硬化劑時，可減低環氧樹 度，惟在於COF安裝中，影響COF型半導體 的耐濕性，特別是耐遷移性的不足受到重視 酹醛樹脂作爲硬化劑時，則有使環氧樹脂組 高的傾向，故有降低操作性之情形。 作爲硬化劑之芳香族胺，相對較容易使 物低黏度化而操作性佳，可提供黏著性、耐 均優良之組成物，惟硬化需要高溫與長時間 差的問題。爲加快硬化速度而有添加咪唑、 試，惟低黏度化變得困難而容易引起操作性 起離子性雜質增加及耐濕性惡化之情形。此 子性雜質及水分有成爲離子遷移的原因之情 媒的選擇、組成物調製時額外需要緻密的工 管理。 因此，有用於防止環氧樹脂組成物的遷 提案。例如，有對環氧樹脂，調配聚乙烯對 基-4,6-二胺基-s-三嗪及咪唑化合物之封閉 (專利文獻1 ):對阻焊劑（環氧樹脂等） 屬離子結合劑之苯并三唑類、三嗪類、以及 酸加成物之封閉用樹脂組成物（專利文獻2 ) 但是，該等遷移防止劑爲固體或粉末時 調整粒徑和粒度，亦難以於環氧樹脂中均勻 無溶劑環氧樹 脂組成物的黏 裝置之可靠度 。此外，使用 成物的黏度變 環氧樹脂組成 熱性、耐濕性 ，有生產性較 三級胺等的嘗 的下降，有引 外，由於該離 形，故硬化觸 程管理、品質 移之添加劑之 苯酚、2-乙烯 用樹脂組成物 ，調配作爲金 該等之異氰尿 之提案。 ，即使精密地 地分散。遷移 -6- 201127864 防止劑未均勻地分散時，即使將封閉用樹脂組成物使用於 半導體裝置，並無法得到所期望的遷移防止效果。 遷移防止劑爲液狀的或溶液時，雖可均勻地分散，但 由於會增加與環氧樹脂的均勻性使反應快速進行，而有難 以作爲一液型封閉用樹脂組成物使用之新問題。 此外，以提升半導體封閉用環氧樹脂組成物於室溫之 儲存安定性爲主要的目的，提案有包含：有機矽烷、有機 矽氧烷、具有水解性基的矽化合物等的矽化合物，及由乙 醯丙酮酯錯合物等的有機金屬化合物所構成之硬化觸媒， 及芳香族胺硬化劑之組成物（專利文獻3 )。但是，該硬 化觸媒，在硬化性與儲存安定性的平衡有問題，且可靠度 並不充分。於專利文獻3，作爲環氧樹脂，記載有雙酚A等 的縮水甘油醚型環氧樹脂、雙酚A等的縮水甘油酯型環氧 樹脂、脂環式環氧樹脂等，惟並未記載關於具有環狀矽氧 烷骨架之環氧樹脂及環氧樹脂組成物的遷移。 如以上所述，爲防止遷移等，雖有硬化劑的選擇、使 用硬化觸媒、使用遷移防止劑等的提案，現狀並不存在可 以使近年來於COF安裝所嚴格要求之低黏度（操作性）與 耐遷移性並存之環氧樹脂組成物。 [專利文獻1 ]日本特開昭6 1 - 1 2 7 2 2號公報 [專利文獻2]日本特開2005_3 3 3 08 5號公報 [專利文獻3]日本專利第3775773公報 【發明內容】 201127864 [發明所欲解決的課題] 本發明之目的係提供先前的半導體封閉用環氧樹脂組 成物所沒有之可並存耐濕性與耐遷移性，並且操作性亦優 良的半導體特別是COF型半導體封閉用環氧樹脂組成物， 及使用該組成物作爲封閉劑之半導體裝置，特別是COF型 半導體裝置。 [用以解決課題的手段] 爲達成本發明目的之本發明係如下（1) - (15)所述 〇 (1 ) 一種半導體封閉用環氧樹脂組成物，其係包含201127864 VI. Description of the Invention: [Technical Field] The present invention is based on the high reliability, high insulation and high operation of the flip chip of a semiconductor, especially the c 〇F (film-coated) type flip chip. An epoxy resin composition for semiconductor encapsulation and a semiconductor device using the same. [Prior Art] As a semiconductor device in which the liquid crystal driver 1C is mounted, COF or TCP (tape-type load-carrying) in which a semiconductor wafer (element) is mounted on a flexible substrate is known. Further, the COF is defined as a semiconductor device having a structure in which a semiconductor wafer or the like is mounted on a flexible substrate having wiring. In recent years, the demand for multi-output of liquid crystal drives has become strong, and the C Ο F mounting with excellent wiring pattern is increased. However, when the current is passed through the wiring pattern, the metal in the wiring is ionized and migrates due to the narrow pitch of the wiring between the wiring lines and the high voltage of the driving voltage. The deposition is deposited in a place other than the original wiring. This causes deterioration of insulation between wirings and migration of short circuits. Therefore, it is very important to prevent the migration of C〇F for a long period of time in securing the reliability of the semiconductor device. As a sealing agent for a semiconductor device, an epoxy resin composition is often used, but in a COF mounting, when a sealing agent is filled under a semiconductor wafer (integrated circuit), it is closed to prevent evaporation of a solvent in a blocking agent. The hole 'is an epoxy resin composition without a gluten. However, it is required to prevent the migration of the fat composition, the narrow pitch (for example, 3 〇μm or less), or the operability at the time of installation, and the low viscosity of the lipid composition. . When an acid anhydride is used as the curing agent, the degree of epoxy resin can be reduced. However, in the COF mounting, the moisture resistance of the COF-type semiconductor is affected, and in particular, the lack of migration resistance is emphasized. When the furfural resin is used as a curing agent, the ring is formed. Since the oxygen resin group tends to be high, there is a case where the workability is lowered. The aromatic amine which is a hardener is relatively easy to be made into a low-viscosity and has excellent handleability, and can provide a composition excellent in adhesion and resistance, but hardening requires a problem of high temperature and long time. In order to increase the rate of hardening, imidazole is added, and it is difficult to cause low viscosity, which may cause an increase in operability and deterioration of moisture resistance. This impurity and water have a tendency to become a cause of ion migration, and an additional labor management is required for composition modulation. Therefore, there is a proposal for preventing the migration of the epoxy resin composition. For example, there is a sealing of a polyethylene-based 4,6-diamino-s-triazine and an imidazole compound for an epoxy resin (Patent Document 1): an ion bond for a solder resist (epoxy resin, etc.) Resin composition for blocking benzotriazoles, triazines, and acid addition products (Patent Document 2) However, when the migration preventing agents are solid or powder, the particle size and particle size are adjusted, and it is also difficult to be epoxy. The reliability of the adhesive device of the uniform solvent-free epoxy resin composition in the resin. In addition, the viscosity of the product is changed to the heat resistance and moisture resistance of the epoxy resin, and the productivity is lower than that of the tertiary amine. However, due to the release, the hardening contact management and the quality shifting additive are used. The resin composition of phenol and 2-ethylene is formulated as a hetero-cyanide of gold. Even if it is precisely dispersed. Migration -6-201127864 When the preventive agent is not uniformly dispersed, even if the resin composition for sealing is used in a semiconductor device, a desired migration preventing effect cannot be obtained. When the migration preventing agent is in the form of a liquid or a solution, it can be uniformly dispersed. However, since the reaction with the epoxy resin is increased to make the reaction proceed rapidly, it is difficult to use it as a one-liquid type sealing resin composition. In addition, in order to improve the storage stability of the epoxy resin composition for semiconductor encapsulation at room temperature, an antimony compound including an organic decane, an organic decane, a hydrazine compound having a hydrolyzable group, and the like are proposed. A curing catalyst composed of an organometallic compound such as an acetamylacetone complex or a composition of an aromatic amine curing agent (Patent Document 3). However, this hard catalyst has a problem in balance between hardenability and storage stability, and reliability is not sufficient. In the case of the epoxy resin, a glycidyl ether type epoxy resin such as bisphenol A, a glycidyl ester type epoxy resin such as bisphenol A, or an alicyclic epoxy resin is described as the epoxy resin, but it is not described. The migration of an epoxy resin and an epoxy resin composition having a cyclic siloxane skeleton. As described above, in order to prevent migration, etc., there are proposals for the selection of a curing agent, the use of a curing catalyst, and the use of a migration preventing agent. However, there is no low viscosity (operability) that can be strictly required in recent years in the installation of COF. An epoxy resin composition that is compatible with migration resistance. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. OBJECTS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a semiconductor which is excellent in operability and which is not compatible with the conventional epoxy resin composition for semiconductor encapsulation, and which is excellent in handleability, particularly for COF type semiconductor encapsulation. An epoxy resin composition, and a semiconductor device using the composition as a blocking agent, particularly a COF type semiconductor device. [Means for Solving the Problems] The present invention for achieving the object of the present invention is as follows (1) - (15) 〇 (1) A resin composition for encapsulating a semiconductor, which comprises
環氧樹脂（A)、芳香族胺硬化劑（B)、金屬錯合物（C )、及可藉由水解產生矽烷醇基之矽化合物（D)之半導 體封閉用環氧樹脂組成物，其特徵在於：作爲環氧樹脂（ A) ’使用具有環狀矽氧烷骨架之多官能脂環式環氧樹脂 〇 (2 )如（1 )所述的半導體封閉用環氧樹脂組成物， 其中環氧樹脂（A )係對4員〜8員環狀矽氧烷之矽加成具有 環己烯氧基之官能基之環氧樹脂。 (3 )如（2 )所述的半導體封閉用環氧樹脂組成物， 其中環氧樹脂（A)係於骨架具有4員環狀矽氧烷之環氧樹 脂。 (4 )如（3 )所述的半導體封閉用環氧樹脂組成物， 其中環氧樹脂（A)係以構造式（1)所示之環氧樹脂。 -8 - 201127864 【化1】An epoxy resin (A), an aromatic amine curing agent (B), a metal complex (C), and an epoxy resin composition for semiconductor encapsulation which can produce a sterol group-based oxime compound (D) by hydrolysis, The epoxy resin (A) is used as a polyfunctional alicyclic epoxy resin having a cyclic siloxane chain (2), and the epoxy resin composition for semiconductor encapsulation according to (1), wherein the ring The oxygen resin (A) is an epoxy resin obtained by adding a functional group having a cyclohexenyloxy group to a group of 4 to 8 membered cyclic oxiranes. (3) The epoxy resin composition for semiconductor encapsulation according to (2), wherein the epoxy resin (A) is an epoxy resin having a 4-membered cyclic oxirane in the skeleton. (4) The epoxy resin composition for semiconductor encapsulation according to (3), wherein the epoxy resin (A) is an epoxy resin represented by the structural formula (1). -8 - 201127864 【化1】
(1) (5)如（1)〜（4)之任何一項所述的半導體封閉用 環氧樹脂組成物，其中芳香族胺硬化劑（B )係具有伸烷 基二苯胺構造之芳香族胺。 (6 )如（5 )所述的半導體封閉用環氧樹脂組成物， 其中芳香族胺硬化劑（B )係4,4'-伸甲基雙（2-乙基苯胺 )° (7 )如（1 )〜（6 )之任何一項所述的半導體封閉用 環氧樹脂組成物’其中金屬錯合物（C )係選自由鋁、鐵 、鋅、銦及鎂所組成之群之至少一種金屬的錯合物。 (8 )如（1 )〜（7 )之任何一項所述的半導體封閉用 環氧樹脂組成物’其中金屬錯合物（C )係乙醯丙酮錯合 物。 (9 )如（1 )〜（8 )之任何一項所述的半導體封閉用 環氧樹脂組成物，其中金屬錯合物（C)係選自由三乙醯 丙酮鋁及雙乙醯乙酸乙酯•單乙醯丙酮鋁所組成之群之至 -9- 201127864 少一種。 (1 〇 )如（1 )〜（9 )之任何一項所述的半導體封閉 用環氧樹脂組成物，其中藉由水解產生矽烷醇基之矽化合 物（D)係矽烷偶合劑。 (11 )如（1 )〜（9 )之任何一項所述的半導體封閉 用環氧樹脂組成物，其中藉由水解產生矽烷醇基之矽化合 物（D )係以構造式（2 )所表示之矽化合物： 【化2】(1) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (4) wherein the aromatic amine hardener (B) has an aromatic structure of an alkyl diphenylamine structure. amine. (6) The epoxy resin composition for semiconductor encapsulation according to (5), wherein the aromatic amine hardener (B) is 4,4'-methyl bis(2-ethylaniline) ° (7 ) The epoxy resin composition for semiconductor encapsulation of any one of (1), wherein the metal complex (C) is at least one selected from the group consisting of aluminum, iron, zinc, indium, and magnesium. A complex of metal. (8) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (7) wherein the metal complex (C) is an acetamidineacetone complex. The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (8) wherein the metal complex (C) is selected from the group consisting of aluminum triacetate and ethyl acetoacetate • One group consisting of monoethyl acetonide and aluminum -9- 201127864. (1) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (9), wherein the decyl alcohol-based ruthenium compound (D) is a decane coupling agent by hydrolysis. (11) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (9), wherein the oxime compound (D) which generates a stanol group by hydrolysis is represented by the structural formula (2)矽 compound: [Chemical 2]
Rn—Si—(〇R.)4-n (2) (式中，R係碳數1〜10之直鏈狀或分支狀的烷基，R’係碳 數1〜2的烷基，n係1〜3之整數）。 (1 2 )如（1 1 )所述的半導體封閉用環氧樹脂組成物 ，其中藉由水解產生矽烷醇基之矽化合物（D)係乙烯基 三甲氧基矽烷或乙烯基三乙氧基矽烷。 (1 3 )如（1 )〜（1 2 )之任何一項所述的半導體封閉 用環氧樹脂組成物，其中芳香族胺硬化劑（Β )的胺基比 例係相對於環氧樹脂（Α)之環氧基1當量爲〇.8~1.5當量 〇 (1 4 )—種半導體裝置，其係以（1 )〜（1 3 )之任何 一項所述的半導體封閉用環氧樹脂組成物封閉而成。 (15 ) —種COF型半導體裝置，其係以（1)〜（13) 之任何一項所述的半導體封閉用環氧樹脂組成物封閉而成 -10- 201127864 [發明之效果] 本發明的半導體封閉用環氧樹脂組成物係低黏度，而 黏著性、耐熱性、耐濕性等優良。此外，由於該組成物係 無溶劑而低黏度，故特別是對COF型半導體元件的安裝時 之環境並無影響，亦不會產生孔洞，操作性優良。因此， 可作爲底膜使用係毋庸置疑，亦可使用於先塗佈方式（ NCP )。此外，使用該組成物安裝的半導體裝置，由於耐 濕性及耐遷移性優良，故不會有配線間絕緣惡化及電路短 路。並且，亦無外觀不良的問題。 【實施方式】 (環氧樹脂組成物） 本發明之半導體封閉用環氧樹脂組成物（以下，亦記 載爲樹脂組成物），係屬於環氧樹脂（A )-芳香族胺硬化 劑（B )-金屬錯合物（c )系半導體封閉用樹脂組成物， 作爲環氧樹脂，使用具有環狀矽氧烷骨架的多官能脂環式 環氧樹脂（以下，亦記載爲脂環式環氧樹脂（A，）），進 一步藉由調合藉由水解產生矽烷醇基之矽化合物（D )( 以下’亦記載爲水解性矽化合物），可充分地發揮脂環式 環氧樹(A’）的特性。此可推定係藉由金屬錯合物（c )與水解性砂化合物（D )之水解所產生的矽烷醇基之反 應所起始的觸媒作用，引起包含脂環式環氧樹脂（A，）之 環氧樹脂（A )與芳香族胺硬化劑（B )之加成反應（硬化 )之故°然後’藉由芳香族胺硬化劑（B )顯現良好的密 -11 - 201127864 著性，藉由金屬錯合物（C )與矽烷醇基使硬化性良好。 此外，由於脂環式環氧樹脂（A’）、金屬錯合物（C)及 水解性矽化合物（D )的離子性雜質含量少，故可推斷不 會引起對半導體裝置等的金屬腐蝕及於高溫下之熱惡化、 電氣特性的下降，而使耐遷移性優良。 本發明的環氧樹脂組成物的黏度在1 00 °C爲0.5〜7 0.0 mPa.s，以 0.5〜65.0 mPa.s爲佳，以 0.5~60.0 mPa.s更佳 。超過70.0 mPa · s，則注入時間變得過長，或產生未注入 部分，而降低生產效率與發生外觀、可靠度的惡化。未滿 0.5 mPa · s，則發生流出到注入部分以外或形狀保持力的 下降，導致污染的產生或外觀、可靠度的惡化。此外，該 環氧樹脂組成物之的增黏率（於常溫放置24小時後的黏度 增加率），由操作性之面以未滿2.0爲佳，以1.5以下更佳 (環氧樹脂） 具有環狀矽氧烷骨架的多官能脂環式環氧樹脂（A·) 係本發明之樹脂組成物之主劑、基劑。脂環式環氧樹脂（ A’），只要是作爲環氧樹脂組成物時，可調整爲可侵入窄 間距配線部及窄間隙部之黏度之範圍，則以液狀、固形均 可’以容易低黏度化之液狀樹脂爲佳。具體而言，可列舉 對4員〜8員環狀矽氧烷之矽加成具有環己烯氧基官能基之 環氧樹脂、對4員〜8員環狀甲基矽氧烷之矽加成具有環己 燃氧基官能基之環氧樹脂、4員〜8員環狀矽氧烷以層狀鍵 -12- 201127864 結矽氧烷，並且，對該環狀矽氧烷之矽加成具有環己烯氧 基官能基之環氧樹脂等。亦可倂用複數種脂環式環氧樹脂 (A')。 對4員環狀甲基砂氧院之砂加成具有環己稀氧基官能 基之環氧樹脂之代表例係以構造式（1 )表示之環氧樹脂 【化3】Rn—Si—(〇R.)4-n (2) (wherein R is a linear or branched alkyl group having 1 to 10 carbon atoms, and R′ is an alkyl group having 1 to 2 carbon atoms, n Is an integer from 1 to 3). (1) The epoxy resin composition for semiconductor encapsulation according to (1), wherein the oxime compound (D) which is hydrolyzed to produce a stanol group is vinyltrimethoxydecane or vinyltriethoxydecane. . (1) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (1), wherein an amine group ratio of the aromatic amine hardener (Β) is relative to an epoxy resin (Α) An epoxy resin composition for semiconductor encapsulation according to any one of (1) to (1), wherein the epoxy group is one equivalent of 8.8 to 1.5 equivalents of ruthenium (1 4). Closed. (15) A COF-type semiconductor device, which is obtained by sealing the epoxy resin composition for semiconductor encapsulation according to any one of (1) to (13) - 201127864 [Effects of the Invention] The epoxy resin composition for semiconductor encapsulation is low in viscosity, and excellent in adhesion, heat resistance, moisture resistance, and the like. Further, since the composition has a low viscosity without a solvent, it has no influence on the environment at the time of mounting the COF-type semiconductor element, and does not cause voids, and is excellent in workability. Therefore, it can be used as a base film, and it can be used in the first coating method (NCP). Further, since the semiconductor device mounted using the composition is excellent in moisture resistance and migration resistance, there is no deterioration in insulation between wirings and short circuit. Moreover, there is no problem of poor appearance. [Embodiment] (Epoxy Resin Composition) The epoxy resin composition for semiconductor encapsulation of the present invention (hereinafter also referred to as a resin composition) belongs to an epoxy resin (A)-aromatic amine curing agent (B). - a metal complex (c) is a resin composition for semiconductor encapsulation, and a polyfunctional alicyclic epoxy resin having a cyclic siloxane skeleton (hereinafter also referred to as an alicyclic epoxy resin) is used as the epoxy resin. (A,)) Further, by blending a ruthenium compound (D) which produces a stanol group by hydrolysis (hereinafter also referred to as a hydrolyzable ruthenium compound), the alicyclic epoxy tree (A') can be sufficiently exhibited. characteristic. This is presumed to be caused by the catalytic action initiated by the reaction of the metal complex (c) with the stanol group produced by the hydrolysis of the hydrolyzable sand compound (D), resulting in the inclusion of an alicyclic epoxy resin (A, ) the addition reaction (hardening) of the epoxy resin (A) and the aromatic amine hardener (B). Then, the aromatic amine hardener (B) shows good density - 201127864, The hardenability is improved by the metal complex (C) and the stanol group. Further, since the alicyclic epoxy resin (A'), the metal complex (C), and the hydrolyzable ruthenium compound (D) have a small content of ionic impurities, it is estimated that corrosion of a metal such as a semiconductor device or the like is not caused. The heat deterioration at a high temperature and the deterioration of electrical characteristics make the migration resistance excellent. The viscosity of the epoxy resin composition of the present invention is 0.5 to 7 0.0 mPa·s at 100 ° C, preferably 0.5 to 65.0 mPa·s, more preferably 0.5 to 60.0 mPa·s. When it exceeds 70.0 mPa · s, the injection time becomes too long, or an uninjected portion is generated, and the production efficiency and appearance and reliability are deteriorated. When it is less than 0.5 mPa · s, the outflow to the outside of the injection portion or the decrease in the shape retaining force occurs, resulting in the occurrence of contamination or deterioration in appearance and reliability. In addition, the viscosity-increasing rate of the epoxy resin composition (the viscosity increase rate after standing at room temperature for 24 hours) is preferably less than 2.0 from the operability side, more preferably 1.5 or less (epoxy resin). The polyfunctional alicyclic epoxy resin (A·) having a siloxane skeleton is a main component and a base of the resin composition of the present invention. When the alicyclic epoxy resin (A') is used as an epoxy resin composition, it can be adjusted to a range in which the viscosity of the narrow-pitch wiring portion and the narrow gap portion can be infiltrated, and it is easy to be liquid or solid. A low viscosity liquid resin is preferred. Specifically, an epoxy resin having a cyclohexenyloxy functional group is added to a fluorene of 4 to 8 membered cyclic oxiranes, and a cyclic methyl oxane of 4 to 8 members is added. An epoxy resin having a cyclohexyloxy functional group, a 4-member to 8-membered cyclic oxirane as a layered bond -12-201127864 decane oxane, and a ruthenium addition to the cyclic oxirane An epoxy resin or the like having a cyclohexenyloxy functional group. A variety of alicyclic epoxy resins (A') can also be used. A representative example of an epoxy resin having a cyclohexyloxy functional group added to a 4-membered cyclic methyl oxalate is an epoxy resin represented by the structural formula (1).
(1) 以式（1)表示之環氧樹脂之乙基環己烯氧基以外， 亦可列舉具有後述官能基R之環己烯氧基。 4員〜8員環狀矽氧烷以層狀鍵結，並且，於該環狀矽 氧烷之矽具有環己烯氧基官能基之環氧樹脂之代表例係以 構造式（3 )表示： 201127864 【化4】(1) In addition to the ethylcyclohexenyloxy group of the epoxy resin represented by the formula (1), a cyclohexenyloxy group having a functional group R to be described later may also be mentioned. A representative of an epoxy resin having a cyclohexenyloxy group functional group of 4 to 8 members is bonded in a layered manner, and a representative example of the epoxy resin having a cyclohexenyloxy group in the cyclic azide is represented by the structural formula (3) : 201127864 【化4】
(式中R係具有以構造式（4)表示之環己嫌氧基之官能基 【化5】(wherein R is a functional group having a cyclohexyloxy group represented by the structural formula (4).
ch3 叫）。，一。"^> (4) 以加成環己烯氧基之情形爲佳。 可於不損及脂環式環氧樹脂（A1 )之特性的範圍，倂 用其他的環氧樹脂。具體而言，以環氧樹脂（A)全體爲 1 0 0 w t %，脂環式環氧樹脂（A')的調配量以3 0 w t %以上爲 佳，以5 0 w t %以上更佳。 可倂用的環氧樹脂，係雙酚A、雙酚F等的縮水甘油醚 之雙酚型環氧樹脂：二縮水甘油基苯胺、二縮水甘油基鄰 甲苯胺、對胺基苯酣型環氧樹脂等的液狀縮水甘油胺型環 氧樹脂；（3'，4'-環氧環己烷）甲基_3,4_環氧環己基羧酸 醋、1-甲基-4- (2 -甲基環氧乙烷基）-7_氧雜雙環[4,10]庚 院#的脂環式環氧樹脂；2,2 -雙（4-經基環己基）丙院二 -14- 201127864 縮水甘油基醚等的氫化型環氧樹脂；丨，3 _雙（3 _縮水甘油 氧基丙基）-1，1，3,3-四甲基二矽氧烷等具有環氧基之環己 烷寡聚物；酚醛型環氧樹脂等。 較佳爲液狀雙酣型環氧樹脂、液狀縮水甘油胺型環氧 樹脂、具有環氧基的環己烷寡聚物，特佳爲液狀雙酚A型 環氧樹脂、液狀雙酚F型環氧樹脂、液狀對胺基苯酚型環 氧樹脂' 1，3 -雙（3-縮水甘油氧基丙基）m3—四甲基 二矽氧烷、液狀雙酚A型環氧樹脂之氫化物、（3，，4'-環氧 環己院）甲基-3，4 -環氧環己基羧酸酯、12:8,9-:環氧樹 脂（l，2:8,9-diepoxynen)。 (芳香族胺硬化劑） 芳香族胺硬化劑（B )係環氧樹脂（a )之硬化劑。芳 香族胺硬化劑（B )’只要是作爲環氧樹脂組成物時，可 調整爲可侵入窄間距配線部及窄間隙部之黏度之範圍，則 以液狀、固形均可’從侵入速度等的觀點以容易使樹脂組 成物低黏度化之液狀爲佳。固形時，加熱使之液化後與環 氧樹脂混合爲佳。 芳香族胺硬化劑（B )以具有伸烷基二苯胺構造之芳 香族胺爲佳，以於芳香環至少具有一個取代基的芳香族胺 爲佳。取代基以甲基、乙基等的低級烷基、甲氧基等的低 級烷氧基爲佳。芳香族胺硬化劑（B )，即使含有於其合 成時所副產之寡聚物等亦無妨。芳香族胺硬化劑（B )可 以單獨使用，亦可倂用複數種。當然，只要不損及芳香族 -15- 201127864 胺硬化劑（B )之特性，亦可倂用其他胺硬化劑。 芳香族胺硬化劑（B )，具體而言’可列舉：間苯二 胺、1,3-二胺基甲苯、1,4-二胺基甲苯、2,4-二胺基甲苯、 3,5-二乙基-2,4-二胺基甲苯、3,5-二乙基-2,6-二胺基甲苯 、2,4-二胺基苯甲醚等之1個芳香環之胺硬化劑；2,4-二胺 基二苯基甲烷、4,4-二胺基二苯基颯、4,4-二胺基二苯基 颯、4,4·-亞甲基雙（2-乙基苯胺）、3，3’-二乙基-4,4’-二胺 基苯基甲烷、3,3’，5,5'-四甲基-4,4'-二胺基苯基甲烷、 3,3，，5,5'-四乙基-4,4’ -二胺基苯基甲烷等之2個芳香環的胺 硬化劑；該胺硬化劑之水解縮合物；聚氧化四亞甲基二-對-胺基安息香酸酯、聚氧化四亞甲基二-對-胺基苯甲酸酯 等的芳香族胺硬化劑；芳香族二胺與環氧氯丙烷之縮合物 或芳香族二胺與苯乙烯之反應生成物等。 以具有伸烷基二苯胺構造之芳香族胺爲佳，由反應性 等之方面觀之，以液狀4,4'-伸甲基雙（2-乙基苯胺）特別 佳。 此外，由可形成黏度低的環氧樹脂組成物而言，較 好倂用3,5-二乙基-2,4-二胺基甲苯、3,5-二乙基-2,6-二胺 基甲苯。此外在於N C P用組成物之情形，從降低增黏率的 觀點而言，亦較好使用例如液狀4,4'-伸甲基雙（2-乙基苯 胺）。 芳香族胺硬化劑（B )，係以其胺基對環氧樹脂（A ) 之環氧基1當量，以〇.8~1.5當量的比例調配，較佳爲0.9〜 1 .2當量。若在於上述範圍外，則有引起樹脂組成物對半 -16- 201127864 導體元件之黏著強度下降或玻璃轉移點下降等問題之情況 (金屬錯合物） 金屬錯合物（C )係與藉由水解產生矽烷醇基之矽化 合物（D )協同促進環氧樹脂（A )之硬化之觸媒成分。 金屬錯合物（C)，只要是具有硬化促進作用者，並無特 別限定，較好爲於所期望的加熱溫度顯現硬化促進作用， 可作爲一液型組成物使用，不阻礙耐遷移性者。 作爲金屬，可列舉鋁、鐵、鋅、銦、鎂等，以鋁爲佳 〇 作爲配位基，可列舉乙醯丙酮鹽、吡啶、三苯膦、乙 二胺、乙二胺四醋酸等’以乙醯丙酮鹽爲佳。以鋁的乙醯 丙酮鹽錯合物特別佳。 當然，亦可倂用兩種以上金屬錯合物（C )。此外， 只要不損及金屬錯合物（C )的特性，亦可倂用其他的金 屬錯合物。 鋁的乙醯丙酮鹽錯合物’可列舉三乙醯丙酮銘、三（ 十八烷基乙醯丙酮）鋁、三（十六烷基乙醯丙酮）鋁、乙 基乙醯丙酮鋁 '雙乙醯乙酸乙酯•單乙醯丙酮鋁等，惟由 硬化性、一液性等的方面觀之，以三乙醯丙酮鋁、雙乙醯 乙酸乙酯.單乙醯丙酮鋁爲佳。當然，亦可倂用該等之二 種以上。 金屬錯合物（C )由於係與水解性砂化合物（d )協同 -17- 201127864 做觸媒作用，故無法一槪地決定其調配量，惟金屬錯合物 (C)的標準，對環氧樹脂（A)與芳香族胺硬化劑（B) 之合計量100質量份爲〇.1〜2質量份，以0.2〜1·8質量份爲佳 。少於該範圍，則環氧樹脂組成物的硬化性變差，多於該 範圍，則環氧樹脂組成物的儲存安定性會惡化。 (水解性矽化合物） 藉由水解產生矽烷醇基之矽化合物（D )係作爲促進 環氧樹脂（A)利用芳香族胺硬化劑（Β )之加成反應（硬 化）之觸媒成分，與金屬錯合物（C)協同作用。 水解性矽化合物（D )，可列舉矽烷偶合劑及以構造 式（2)表示之矽化合物： 【化6】Ch3 is called). ,One. "^> (4) It is preferable to add cyclohexeneoxy group. Other epoxy resins can be used without damaging the properties of the alicyclic epoxy resin (A1). Specifically, the total amount of the epoxy resin (A) is 100%, and the blending amount of the alicyclic epoxy resin (A') is preferably 30 w t % or more, more preferably 50 w t % or more. Epoxy resin which can be used as a bisphenol type epoxy resin of glycidyl ether such as bisphenol A or bisphenol F: diglycidyl aniline, diglycidyl o-toluidine, p-aminophenyl hydrazine ring Liquid glycidylamine type epoxy resin such as oxygen resin; (3', 4'-epoxycyclohexane) methyl_3,4_epoxycyclohexylcarboxylic acid vinegar, 1-methyl-4- ( 2 -Methyl oxiranyl)-7_oxabicyclo[4,10] Gengyuan# alicyclic epoxy resin; 2,2-bis(4-cyclohexyl)propyl broth II-14 - 201127864 Hydrogenated epoxy resin such as glycidyl ether; oxime, 3 _bis(3 _ glycidoxypropyl)-1,1,3,3-tetramethyldioxane, etc. a cyclohexane oligomer; a phenolic epoxy resin or the like. It is preferably a liquid bismuth-type epoxy resin, a liquid glycidylamine type epoxy resin, a cyclohexane oligomer having an epoxy group, particularly preferably a liquid bisphenol A type epoxy resin, a liquid double Phenol F type epoxy resin, liquid p-aminophenol type epoxy resin ' 1,3 - bis(3-glycidoxypropyl) m3 - tetramethyldioxane, liquid bisphenol A ring Hydroxide hydride, (3,4'-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, 12:8,9-: epoxy resin (l, 2:8) , 9-diepoxynen). (Aromatic Amine Curing Agent) The aromatic amine curing agent (B) is a curing agent for the epoxy resin (a). The aromatic amine curing agent (B) can be adjusted to a viscosity that can penetrate into the narrow-pitch wiring portion and the narrow gap portion as long as it is an epoxy resin composition, and can be in a liquid or solid shape. The viewpoint is preferably a liquid which is easy to make the resin composition low in viscosity. In the case of solid form, it is preferred to heat and liquefy it and mix it with an epoxy resin. The aromatic amine hardener (B) is preferably an aromatic amine having an alkylenediphenylene structure, and preferably an aromatic amine having at least one substituent in the aromatic ring. The substituent is preferably a lower alkyl group such as a methyl group or an ethyl group or a lower alkoxy group such as a methoxy group. The aromatic amine curing agent (B) may contain an oligomer or the like which is by-produced at the time of its synthesis. The aromatic amine hardener (B) may be used singly or in combination of plural kinds. Of course, other amine hardeners may be used as long as they do not detract from the characteristics of the aromatic -15-201127864 amine hardener (B). The aromatic amine hardener (B), specifically, may be exemplified by m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, and 3, An aromatic ring amine such as 5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene or 2,4-diaminoanisole Hardener; 2,4-diaminodiphenylmethane, 4,4-diaminodiphenylanthracene, 4,4-diaminodiphenylanthracene, 4,4·-methylene double (2 -ethylaniline), 3,3'-diethyl-4,4'-diaminophenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminobenzene An amine hardener of two aromatic rings such as methane, 3,3,5,5'-tetraethyl-4,4'-diaminophenylmethane; a hydrolysis condensate of the amine hardener; polyoxidation An aromatic amine hardener such as tetramethylene di-p-amino benzoate or polyoxytetramethylene di-p-aminobenzoate; condensate of aromatic diamine and epichlorohydrin Or a reaction product of an aromatic diamine and styrene. The aromatic amine having an alkylenediphenylene structure is preferred. From the viewpoint of reactivity and the like, it is particularly preferable that the liquid 4,4'-methyl-bis(2-ethylaniline) is excellent. In addition, from the epoxy resin composition which can form a low viscosity, it is preferred to use 3,5-diethyl-2,4-diaminotoluene or 3,5-diethyl-2,6-di. Aminotoluene. Further, in the case of the composition for N C P , from the viewpoint of lowering the viscosity-increasing ratio, for example, liquid 4,4'-methyl-bis(2-ethylaniline) is preferably used. The aromatic amine curing agent (B) is formulated in an amount of from 8. 8 to 1.5 equivalents, preferably from 0.9 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy group (A). If it is outside the above range, there is a problem that the adhesion of the resin composition to the semi--16-201127864 conductor element is lowered or the glass transition point is lowered (metal complex) metal complex (C) and The hydrazine compound (D) which hydrolyzes to produce a stanol group synergistically promotes the hardening of the epoxy resin (A). The metal complex (C) is not particularly limited as long as it has a curing-promoting effect, and it is preferred to exhibit a curing-promoting action at a desired heating temperature, and it can be used as a one-liquid type composition, and does not inhibit migration resistance. . Examples of the metal include aluminum, iron, zinc, indium, and magnesium. The aluminum is preferably used as a ligand, and examples thereof include acetamidine acetone, pyridine, triphenylphosphine, ethylenediamine, and ethylenediaminetetraacetic acid. Ethyl acetonide is preferred. The aluminum acetonide alkoxide complex is particularly preferred. Of course, it is also possible to use two or more metal complexes (C). Further, other metal complex compounds may be used as long as the characteristics of the metal complex (C) are not impaired. The aluminum acetamidine alkoxide complex can be exemplified by triacetone acetone, tris(octadecylacetone)aluminum, tris(hexadecylacetammonium)aluminum, ethylethylammonium acetonate-a double Ethyl acetate, ethyl acetonide, aluminum acetonate, etc., but it is preferably made of triacetic acid aluminum acetonate, ethyl acetoacetate, ethyl acetonate, and aluminum acetonate. Of course, it is also possible to use more than two of these. Since the metal complex (C) acts synergistically with the hydrolyzable sand compound (d) -17-201127864, it is impossible to determine the amount of the compound, but the standard of the metal complex (C), the ring 100 parts by mass of the total amount of the oxygen resin (A) and the aromatic amine curing agent (B) is preferably 0.1 to 2 parts by mass, preferably 0.2 to 1.8 parts by mass. When the amount is less than this range, the hardenability of the epoxy resin composition is deteriorated. When the amount is more than this range, the storage stability of the epoxy resin composition is deteriorated. (Hydrolyzable oxime compound) The ruthenium compound (D) which produces a stanol group by hydrolysis is used as a catalyst component for promoting the addition reaction (hardening) of the epoxy resin (A) using an aromatic amine curing agent (Β), and The metal complex (C) synergistically. The hydrolyzable hydrazone compound (D) may, for example, be a decane coupling agent or a hydrazine compound represented by the formula (2):
Rn—Si—(OR')4.n (2) (式中R係碳數1~1〇之直鏈狀或分支狀烷基、R'係碳數1~2 之烷基，η係1〜3之整數）。 矽烷偶合劑，有乙烯基系、縮水甘油氧基系、甲基丙 烯酸系、胺基系、毓系等，惟與其他的矽烷偶合劑相比， 乙烯基矽烷偶合劑與金屬錯合物（C )組合時，不會引起 樹脂組成物之硬化物膨脹等的外觀不良故而較佳。由於鹵 素爲遷移原因之一，故含有鹵素之矽烷偶合劑並不佳。 乙烯基矽烷偶合劑，可列舉乙烯基三（β-甲氧基乙氧 基）矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等 ’最好爲乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等特 -18- 201127864 別佳。亦可倂用該等。 縮水甘油氧基矽烷偶合劑，可列舉γ-縮水甘油氧基丙 基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷等。以γ-縮水甘油氧 基丙基三甲氧基矽烷爲佳。 胺基矽烷偶合劑，可列舉Ν-β (胺基乙基）γ-胺基丙 基三甲氧基矽烷、Ν-β (胺基乙基）γ-胺基丙基甲基二甲 氧基矽烷、γ -胺基丙基三乙氧基矽烷、Ν -苯基- γ-胺基丙基 三甲氧基矽烷、N-(l，3-二甲基亞丁基）-3-(三甲氧基矽 烷基）-1-丙基胺、Ν-( 1,3·二甲基亞丁基）-2-(三甲氧 基矽烷基）-1-丙基胺、N-(l，3-二甲基亞丁基）-3-(三 乙氧基矽烷基）-1-丙基胺、N-(l，3-二甲基亞丁基）_2· (三乙氧基矽烷基）-1-丙基胺等及該等的水解縮合物。以 Ν- ( 1,3 -二甲基亞丁基）-3-(三乙氧基矽烷基）-1-丙基 胺爲佳。 毓基矽烷偶合劑，以γ-锍基丙基三甲氧基矽烷、γ-氯 丙基三甲氧基矽烷等爲佳。 以構造式（2)表示之烷氧基矽烷係三苯基甲氧基矽 烷、三苯基乙氧基矽烷、二苯基甲基甲氧基矽烷等的單烷 氧基矽烷；二苯基二甲氧基矽烷、二苯基二乙氧基矽烷等 二烷氧基矽烷；三（對甲氧基苯基）矽烷、對甲基苄基三 甲氧基矽烷等三烷氧基矽烷等。以二苯基二甲氧基矽烷、 二苯基二乙氧矽烷等的二烷氧基矽烷爲佳。亦可將該等倂 用。此外，該等烷氧基矽烷亦可與矽烷偶合劑倂用。 -19- 201127864 水解性矽化合物（D )由於係與金屬錯合物（C )協同 做觸媒使用’故無法一槪地決定其調配量，惟水解性矽化 合物（D )之標準，係相對於環氧樹脂（a )與芳香族胺 硬化劑（B )之合計量1〇〇質量份，於底部充塡用時爲〇.5〜 4質量份，以0.8〜3質量份爲佳，於NCP用時爲1〜8質量份， 以2〜5質量份爲佳。少於該範圍則環氧樹脂組成物的硬化 性變差’多於該範圍則環氧樹脂組成物的儲存安定性會惡 化。 (其他的調配劑） 可對含有上述必須成分（A )〜（D )的環氧樹脂組成 物’調配勻化劑、著色劑、離子捕捉劑、消泡劑、塡充劑 '難燃劑等。各調配劑的種類、調配量如一般方法。此外 ，亦可調配氧雜環丁烷、丙烯酸酯、雙馬來醯亞胺等的熱 硬化性樹脂、熱塑性樹脂、彈性體等。 塡充劑，只要考慮樹脂組成物的黏性、流動性、塡充 性等進行選擇即可，並無特別限定，一般爲二氧化矽、玻 璃、滑石、氧化鋁、矽酸鈣、碳酸鈣、硫酸鋇、氧化鎂、 氮化矽、氮化硼、氮化鋁等。以二氧化矽爲佳。塡充劑， 對除塡充劑之外的樹脂組成物之全體量1〇〇質量份，以50 質量份以下調配》 (樹脂組成物的調製） 本發明之樹脂組成物，係將成分（A )〜（D )及其他 -20- 201127864 的調配劑混合、攪拌而調製。混合攪拌’可使用滾輪硏磨 機進行，當然，並非限定於此。環氧樹脂（A )爲固體時 ’可藉由加熱等使之液狀化或流動化後進行混合爲佳。 將各成分同時混合，亦可先將一部分的成分混合後， 再將剩餘成分混合等，可適宜變更。 (半導體裝置） 半導體裝置，係如圖1所示其1例之剖面圖，以於基材 (可撓式膜）1配置多數的配線5 (障壁層2、導體層3及鍍 錫層4所組成）之配線基板6，及將搭載於該配線基板6之 半導體晶片7以封閉劑8結合之構造爲基本。配線基板6， 係於基材1依多數配線5，阻焊劑9之順序層合之構造，配 線5之一端可與所搭載之半導體晶片7連接，另一端與外部 機器連接。阻焊劑9，係藉由覆蓋並保護基材1上之配線5 ，防止短路及斷線。再者，基板1爲撓性膜時爲COF。 (半導體晶片的安裝） 半導體晶片的安裝，可以於撓性配線基板與半導體晶 片之間，塡充環氧樹脂組成物之底部充塡方式實施，亦可 於撓性配線基板上塗佈環氧樹脂組成物之後，將半導體晶 片黏著的方式，亦可以其他方式實施。 底部充塡方式之情形，可例如以如下順序實施。 (1 )將撓性配線基板6與具有金凸塊（突起電極） 10之半導體晶片7接合。再者，於配線5的表面不與半導體 -21 - 201127864 晶片7接合的部分以阻焊劑9覆蓋保護。 (2 )於該接合後，於半導體晶片7與撓性配線基板6 之間塡充封閉劑8 (封閉用環氧樹脂組成物），加熱硬化 ，製造半導體裝置1 1。 NCP方式之情形，可例如以如下順序實施。 於撓性配線基板6上供給先塗佈用樹脂，將具有金凸 塊（突起電極）1 〇的半導體晶片7放在撓性配線基板6上， 藉由加熱·加壓使撓性配線基板6與半導體晶片7連接的同 時使樹脂硬化，製造半導體裝置11» [實施例] (實施例1~26、比較例1〜5 ) 將下述成分，以表1〜3所示量量取，將一倂混合之混 合物以3滾輪硏磨機混練，得到均勻的樹脂組成物。將該 樹脂組成物放置於減壓下，去除樹脂組成物中的氣泡，作 爲評估用試料。將該樹脂組成物及該樹脂組成物之硬化物 的儲存安定性（增黏率）、硬化性' PCT剝離性（剝離時 間）及耐遷移性（絕緣阻抗値）以下述裝置、方法予以測 定、評估。將評估結果示於表1〜3。 (環氧樹脂） •對4員環狀甲基矽氧烷之矽加成乙基環己烯氧化物 ，以構造式（1 )表示之環氧樹脂 •雙酚F型環氧樹脂（環氧當量160) -22- 201127864 •雙酚A型環氧樹脂（環氧當量185 ) •對胺基苯酚型環氧樹脂（環氧當量94 ) •1，3-雙（3-縮水甘油氧基丙基）-1，1，3,3-四甲基二矽 氧烷 (胺硬化劑） • 4,4'-伸甲基雙（2-乙基苯胺） •3,5-二乙基-2,6-二胺基甲苯（胺當量44.6§) •環己基胺·無水物（胺當量49.6g) •二甲基胺基丙基胺（胺當量51.lg) (金屬錯合物） •三乙醯丙酮鋁 •雙乙醯乙酸乙酯·單乙醯丙酮鋁 •三乙醯丙酮鐵 •二乙醯丙酮鋅 •三乙醯丙酮銦 •二乙醯丙酮鎂 (水解性矽化合物） •乙烯基三甲氧基矽烷 • γ-縮水甘油氧基丙基三甲氧基矽烷 • γ-胺基丙基三甲氧基矽烷 •二苯基二甲氧基矽烷 -23- 201127864 •二苯基二乙氧矽烷 •苯基三甲氧基矽烷 •3-三乙氧基矽烷基-N- ( 1，3-二甲基 之水解縮合物 (其他的調配劑） •馬來醯化別羅勒烯 .2-苯基-4-甲基咪唑 (黏度、增黏率） 使用E型黏度計（東機產業（股）製 形），以液溫2 5 °C、1 〇rpm測定評估用試料 將該評估用試料灌入密閉容器（樹脂製注象 (25°C、濕度25% )放置24小時之後，測定 放置前後之黏度求得增黏率。該增黏率爲 存安定性良好而爲合格（〇），2 · 0以上之 性不良而爲不合格（X )。 (硬化性） 以與黏著在聚醯亞胺薄膜上之矽晶片 )之長邊側面接觸之方式塗佈1 0 m g評估用盡 入烘箱，以1 50°C加熱，使環氧樹脂硬化。 驗片垂直豎起以目視觀察評估用試料的垂1 下之硬化時間。下垂的時間未滿1 0分鐘時， 丁基）丙基胺 型式 TVE-22H 的初期黏度。 1"器），以室溫 :黏度。由室溫 未滿2.0時，儲 情形儲存安定 (2x20x0.75mm ζ料之試驗片放 使加熱後的試 :、測定不再垂 視爲硬化性良 -24- 201127864 好而評估爲合格（〇），1 0分鐘以上之情形視爲硬化性不 良而評估爲不合格（X )。 (絕緣阻抗値） 於形成於聚醯亞胺薄膜上的梳型電極（材質：在銅上 鍍錫，圖案間距：30μηι、電極寬：1 5μιη )上塗佈評估用 試料，以1 5 (TC加熱9 0分鐘，使之硬化製造試驗片。將加 熱後的試驗片放入8 5 °C、濕度8 5 %的槽（E S P E C (股）製 、模式SH-641)，於電極間施加40V的直流電壓，測定電 極間的電阻。電阻値以1 X 1 08 Ω以上持續5 0 0小時以上時， 視爲絕緣性良好而評估爲合格（〇），未滿500小時時視 爲絕緣性不良而評估爲不合格（X )。然後，絕緣性合格 時’判定爲具有不影響實用性之絕緣保持特性（耐遷移性 (PCT剝離時間） 對剝離試驗用配線板〔日立超L S I系統（股）製之 30μηι間距、直接凸塊配線的c〇F用PKG型TEG ( Phase 6 30 )〕塗佈評估用試料5.0mg ’以1 5(TC加熱、硬化90分鐘。 確認沒有初期剝離，使用E S P E C (股）公司製E H S - 4〗0 Μ， 放置於P C Τ ( 1 2 1 °C '相對溼度！ 〇 〇 %、2大氣壓）3 〇 〇小時 後’觀察有無剝離。3 00小時後完全沒有剝離之情形爲合 格（〇）’於2〇〇小時後只要有一點點剝離之情形爲不合 格（X )，評估耐濕性。 -25- 201127864 (實施例27〜29 ) 將下述成分’以表4所示量加以量取，將一倂混合之 混合物以3滾輪硏磨機混練，得到均勻的樹脂組成物。將 該樹脂組成物放置於減壓下，去除樹脂組成物中的氣泡， 作爲評估用試料。將該樹脂組成物及該樹脂組成物之硬化 物的儲存安定性（增黏率）及硬化性以上述裝置、方法予 以測定、評估。惟從N P C用組成物的觀點，該增黏率爲未 滿2.0時，則儲存安定性良好而爲合格（〇），2.0以上之 情形儲存安定性不良而爲不合格（X)。再者，關於硬化 性以如下方法評估。 於150°C的熱板上，供給液狀半導體封閉劑5mg±lmg， 藉由攪拌棒如畫圓般地攪拌，由供應開始一邊攪拌一邊拿 起攪拌棒，拉離時拉絲成5mm以下之時間爲未滿80秒視爲 硬化性良好而評估爲合格（〇），80秒以上的情形視爲硬 化性不良而評估爲不合格（X)。 (黏著性） 以下述方法測定、評估該樹脂組成物之硬化物之黏著 性。將評估結果示於表4。 使用安裝基板進行接合（2 0 0 °c x 3 0秒），放入烘箱進 行後固化（1 6 0 t X 9 0分鐘）。以目視觀察該p KG之撓性基 板6與矽晶片7的連接部，於連接部沒有龜裂.剝離等缺陷 者爲合格（〇），只要梢微有缺陷者爲不合格（X) ’評 -26- 201127864 估黏著性。於安裝基板使用i.GmmxIS.SmmxSSOpm厚， L/S=20pm者。 •對4員環狀甲基矽氧烷之矽加成乙基環己烯氧化物 ，以構造式（1)表示之環氧樹脂 • 4,4’-伸甲基雙（2-乙基苯胺） •3-三乙氧基矽烷基-N-( 1,3-二甲基亞丁基）丙基胺 水解縮合物（市售品） •三乙醯丙酮鋁 • γ-縮水甘油氧基丙基三甲氧基矽烷 由實施例1與比較例1、2之對比，環氧樹脂（Α)爲具 有環狀矽氧烷骨架之多官能脂環式環氧樹脂之情形，與具 有非環狀矽氧烷構造之多官能脂環式環氧樹脂之情形相比 ，至發生PCT剝離之時間較長。 由實施例I與比較例3〜4之對比，芳香族胺系硬化劑之 情形’與非芳香族胺系硬化劑之情形相比，可知儲存安定 性較優良。 此外，由實施例1與實施例3之電阻値之經時變化（圖 3及圖4 )，及比較例5之電阻値之經時變化（圖2 )之對比 ’明顯可知芳香族胺系硬化劑之情形，相較於沒有包含胺 系硬化劑之情形，高溫耐濕可靠度明顯地優良。 -27- 201127864 實施例7 50.64 47.06 d CO 〇 »〇 ο 寸 00 〇 〇 〇 〇 實施例6 66.71 30.99 o 〇 r-H ο 〇 〇 〇 〇 實施例5 I 84.60 | 13.10 in o »η m ο in ο 〇 〇 〇 〇 寸 ±i I 78.21 | 1 19.49 1 in O «ο m d ο s 〇 〇 〇 X 比較例3 78.67 | I 19.03 | d m o Ο S X 〇 X X 比較例2 58.49 39.41 d in 〇 r«H 〇 <Ν ι〇 Ο m 〇 X 〇 〇 比較例1 70.16 | 1 27.74 1 d 〇 d (Ν in ο m U^) 〇 X 〇 〇 寸 *=Γ> 镯 75.98 15.84 00 <N o ο (Ν m d ο Ο irj ο CN 〇 〇 〇 〇 實施例3 74.82 23.08 O yn ο ο (Ν »Λϊ Ο CO 〇 〇 〇 〇 實施例2 I 29.74 1 ί 29.74 31.62 in o m O iTi Ο S 〇 〇 〇 〇 實施例1| I 74.59 | 23.11 ^T) o »r> m d ί—Η *Ti ο 寸 00 〇 〇 〇 〇 am ΠΧ! 嘁 m •N 涨 φπ 遯 m « & am mg 祕 m 嫠 到 Ρη 慈 am Π33 奪 嘁 m 副 浒 糊 狴 a rA ί 祕 Μ φπ ^ΝΡ 5祕 S汽 iy i 擀 A Κ) (N s w E- «： 4 浒 ffi- m 狴 II v〇 <N m K1 II r^T 環己基胺 狴 稍 ϋ 鏗 m η- 11 三乙醯丙酮鋁 雙乙醯乙酸乙酯·單乙酿丙酮鋁 三乙醯丙酮鐵 二乙醯丙酮鋅 三乙醯丙酮銦 二乙醯丙酮鎂 乙烯基三甲氧基矽烷 w ii i- m 稍 m 嘁 M 扣 1 卜 m 祕 E- 1)1 1E 寧 m 嫲 E- 11 枨 11 祕 K) II m 浒 II 稍 祕 B- II] S 卜 m — 1丨1糊 cAE： ο ι-Η /^ν PQ D o o ? Q |ϊ n m i 黯 m #1 黯 Η m S 齒 1? Μ k 龌 區分 胺硬 化劑 B < 赔口 物C 矽化 合物 D 質量 比 評估 -28- 201127864 i 握 Ιϋ 74.59 1 23.11 ΙΛ1 Ο »〇 m Ο v〇 Ο s 〇 〇 〇 〇 1實施例14 1 74.59 | 23.11 Ο ν*ί rn ο d 〇 〇 〇 〇 習 in I 74.59 | | 23.11 | Ο m ο ό ο 〇 〇 〇 〇 實施例12」 I 74.59 | | 23.11 | ο <Τ) m ο d 寸 00 〇 〇 〇 〇 -U -1A | 18.00 | 〇 卜 I 19.90 | 〇 寸 o d (Ν 1 1 X X 〇 Ο 實施例111 Γ 74.59 | | 23.11 ] i/Ί· Ο Ο u-1 ΙΟ Ο s 〇 〇 〇 〇 〇 i 辑 IK 丨 74.59 1 | 23.11 1 irt Ο m d «Ο ο 寸 00 〇 〇 〇 〇 實施例9 [74.59 1 | 23.11 | in ο cn ο 1〇 ο 〇 〇 〇 〇 00 辑 U | 74.59 | 1 23.11 | ο rn ο «ο ο 寸 00 〇 〇 X 〇 m 蕕 HS m 涨 遯 m 訟 m & 1雙酚F型液狀環氧樹脂 1 am TO Μ 嘁 Μ 装 到 < ΙΜ ni m 副 擀 埋 1,3-雙(3-縮水甘油氧基丙基)-1，1，3,3-四甲基 二砂氧院 CEC3 擗 K] CN 枨 埕 11 CN m hO π ΓΛ ro m 狴 m IE m 11 线 m m 嵌 a| i2-苯基-4-甲基咪唑 1 DO r m 111 r n 餾 K] 趦 N3 鹽 K] 1三乙醯丙酮鐵 Ί 二乙醯丙酮鋅 Π m 匾 r 魍 hO HI 二乙酿丙酮鎂 爾 祕 Π1 K) m IE nf M 扭 躍 1 £S 槭 m m tE • m H-11 浒 11 嫲 hO 11 淋 11 1苯基三甲氧基Ϊ夕烷 1 tE i 卜 κι 1 ΓΛ Ν—✓ ζ 師 δ躍 啤 cA糊 ο ο 又 + < D o 3< S' Q ϋ V_^ 迤 m 鍵 Μ 黯 Η UEJ S 龌 Φ ήι 環氧 樹脂 A 胺硬 化劑 B 其他 金屬 錯合 物C 矽化 合物 D 4¾) 1 -1 1¾^ 評估 -29- 201127864 實施例26 29.89 29.89 I 6.61 31.78 00 ο 丨 1.02 I I 0.81 I 〇 〇 〇 〇 實施例25 29.28 29.28 I 6.51 I 31.13 I (N in m d 2.08 〇 〇 〇 〇 I實施例24] | 29.44 | I 29.44 | 6.54 I 31.28 I CN r—· m 〇 2.06 1.34 〇 〇 〇 〇 遐 29.44 29.44 | 6.54 I 31.28 I in m 〇 1.55 1.86 〇 〇 〇 〇 賓施例22 29.59 29.59 丨 6.58 | 31.44 | cn 〇 1.54 ； CO CO 〇 〇 〇 〇 實施例2! 29.59 29.59 | 6.58 31.44 in m c> 1.03 1.85 〇 〇 〇 〇 實施例20 29.74 29.74 | 6.61 | 31.61 | m 〇 I 1.02 | rn 〇 〇 〇 〇 實施例i 91 29.89 29.89 6.64 31.78 〇 〇 I 0.51 | <N rn 〇 〇 〇 〇 實施例1 si 29.86 29.86 6.63 31.75 oo I 0.10 | I 1.83 | 〇 〇 〇 〇 實施例i7i 30.01 30.01 1 6.67 I 31.91 | rn I 0.10 | 1 1.31 1 〇 〇 〇 〇 實施例i6j 30.16 30.16 1 6.70 Γ3Ι081 d 00 d 0.10 0.80 〇 〇 〇 〇 m 祕 m •μ 涨 遯 m δ w Ε- 蚺 4 am 033 m 燦 到 m am Π33 M 嫲 m 装 副 < 祕 m 到 浒 ή & a (Λ CO s E： 補 祕 思 in NP 餿遯 逛 浒 m Κ) CN ίκ ffi- ffi- ftl 狴 11 <N m Κ] 11 環己基胺 狴 H- 11 三乙醯丙酮鋁 1E 翻 K3 螂 • 餾 N] 氍 K1 m K) ti 二乙醯丙酮鋅 m 慮 膣 κι in 疆 曙 m K) HI <ilL/ 匾 m K) 1] 乙烯基三甲氧基砂烷 ui in m IE 祕 矩 扣 躍 1 m 嘁 HI w κ S 狴 1 糊 祕 11 m 擀 II m ui Κ] 11 稍 枨 II m 祕 H- 111 m S Η « Β- ^1 口 rAlE 〇 D o 玄 PQ 务 Q II 'w/ a i 黯 S 黯 Η im / 1$ 丨區分丨 1 1! 樹脂 A 胺硬 化劑 Β 1 <s it φ曰口 物c 化合 物D 質量 jj 評估 -30- 201127864 [表4] 表4 區分 實施例27 實施例28 實施例29 環氧 樹脂 A 含有環狀甲基矽氧烷骨架之環氧樹月旨 57.5 57.4 56.9 雙酚F型液狀環氧樹脂 雙酚A型液狀環氧樹脂 對胺基苯酚型環氧樹月旨 1，3-雙(3-縮水甘油氧基丙基)-1，1，3,3-四甲基二矽 氧院 胺硬 化劑 B 4,4’-伸甲基雙(2-乙基苯胺） 38.4 38.3 38.1 3,5-二乙基-2,6-二胺基甲苯 環己基胺 二甲基胺基丙基胺 金屬 錯合 物C 三乙醯丙酮鋁 1.0 1.0 1.0 雙乙醯乙酸乙酯·單乙醯丙酮鋁 三乙醯丙酮鐵 二乙醯丙酮鋅 三乙醯丙酮銦 二乙醯丙酮鎂 矽化 乙烯基三甲氧基矽烷 r -縮水甘油氧基丙基三甲氧基矽烷 3.0 3.0 3.0 r-胺基丙基三甲氧基砂院 二苯基二甲氧基矽烷 合物 D 二苯基二乙氧基矽烷 苯基三甲氧基矽烷 3-三乙氧基矽院基-N-0,3-二甲基亞丁基)丙基胺 之水解縮合物 0.1 0.3 1.0 質量 比 C/(A+B)xl00 1.04 1.04 1.05 D/(A+B)xl00 3.23 3.45 4.21 評估 絕緣性(電阻値） 〇 〇 〇 PCT剝離性(剝離時間） 〇 〇 〇 硬化性 〇 〇 〇 儲存安定性(增黏率） 〇 〇 〇 黏著性 〇 〇 〇 -31 - 201127864 【圖式簡單說明】 圖1係本發明之半導體裝置之1例之剖面圖。 圖2係表示比較例5之環氧樹脂組成物之電阻値之經時 變化之圖表。 圖3係表示實施例1之環氧樹脂組成物之電阻値之經時 變化之圖表。 圖4係表示實施例3之環氧樹脂組成物之電阻値之經時 變化之圖表。 【主要元件符號說明】 1 :基材（可撓式膜） 2 :障壁層 3 :導體層 4 :鍍錫層 5 :配線 6 :配線基板 7 :半導體晶片（元件） 8 :環氧樹脂組成物（封閉劑） 9 :阻焊劑 1 〇 :凸塊（突起電極） 1 1 :半導體裝置 •32-Rn—Si—(OR′)4.n (2) (In the formula, R is a linear or branched alkyl group having 1 to 1 carbon atoms, R' is an alkyl group having 1 to 2 carbon atoms, and η is 1 An integer of ~3). The decane coupling agent may be a vinyl group, a glycidoxy group, a methacrylic acid group, an amine group or a fluorene type, but a vinyl decane coupling agent and a metal complex (C) compared with other decane coupling agents. When it is combined, it is preferable because the appearance of the cured product of the resin composition is not deteriorated. Halogen-containing decane coupling agents are not preferred because halogens are one of the causes of migration. Examples of the vinyl decane coupling agent include vinyl tris(β-methoxyethoxy)decane, vinyl trimethoxy decane, vinyl triethoxy decane, etc., preferably vinyl trimethoxy decane, ethylene. Base triethoxy decane and other special -18- 201127864 is better. You can also use these. Examples of the glycidyloxydecane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxypropylmethyldiethoxylate. Decane and so on. Preferably, γ-glycidoxypropyltrimethoxydecane is used. The amino decane coupling agent may, for example, be Ν-β(aminoethyl)γ-aminopropyltrimethoxydecane or Ν-β(aminoethyl)γ-aminopropylmethyldimethoxydecane. , γ-Aminopropyltriethoxydecane, Ν-phenyl-γ-aminopropyltrimethoxydecane, N-(l,3-dimethylbutylidene)-3-(trimethoxydecane 1-propylamine, Ν-(1,3,3-dimethylbutylene)-2-(trimethoxydecyl)-1-propylamine, N-(l,3-dimethylarylene 3-(triethoxydecyl)-1-propylamine, N-(l,3-dimethylbutylene)_2·(triethoxydecyl)-1-propylamine, etc. And the hydrolysis condensate. Preferably, Ν-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine is preferred. The decyl decane coupling agent is preferably γ-mercaptopropyltrimethoxydecane, γ-chloropropyltrimethoxydecane or the like. a monoalkoxydecane represented by the structural formula (2), alkoxy decane, triphenylmethoxy decane, triphenyl ethoxy decane, diphenylmethyl methoxy decane, etc.; a dialkoxy decane such as methoxy decane or diphenyldiethoxy decane; a trialkoxy decane such as tris(p-methoxyphenyl)decane or p-methylbenzyltrimethoxydecane; and the like. The dialkoxysilane such as diphenyldimethoxydecane or diphenyldiethoxysilane is preferred. You can also use these options. Further, the alkoxydecane may also be used in combination with a decane coupling agent. -19- 201127864 The hydrolyzable ruthenium compound (D) is used in combination with the metal complex (C) as a catalyst, so it is impossible to determine the amount of the compound, but the standard of the hydrolyzable ruthenium compound (D) is relative. The total amount of the epoxy resin (a) and the aromatic amine curing agent (B) is 1 part by mass, and when the bottom is charged, it is preferably 5 to 4 parts by mass, preferably 0.8 to 3 parts by mass. The NCP is used in an amount of 1 to 8 parts by mass, preferably 2 to 5 parts by mass. When the amount is less than this range, the hardenability of the epoxy resin composition deteriorates. If the ratio is more than this range, the storage stability of the epoxy resin composition deteriorates. (Other preparation agents) The epoxy resin composition containing the above-mentioned essential components (A) to (D) can be formulated with a leveling agent, a coloring agent, an ion scavenger, an antifoaming agent, a sputum filling agent, a flame retardant, and the like. . The type and amount of each formulation are as follows. Further, a thermosetting resin such as oxetane, acrylate or bismaleimide, a thermoplastic resin, an elastomer or the like may be blended. The chelating agent is not particularly limited as long as it is selected in consideration of viscosity, fluidity, and sufficiency of the resin composition, and is generally cerium oxide, glass, talc, alumina, calcium citrate, calcium carbonate, Barium sulfate, magnesium oxide, cerium nitride, boron nitride, aluminum nitride, and the like. Preferably, cerium oxide is used. The amount of the resin composition of the present invention is adjusted to 50 parts by mass or less based on the total amount of the resin composition other than the hydrazine. (Preparation of Resin Composition) The resin composition of the present invention is a component (A) ) ~ (D) and other -20- 201127864 formula mixing and stirring to prepare. The mixing and agitation can be carried out using a roller honing machine, of course, without being limited thereto. When the epoxy resin (A) is a solid, it may be liquidized or fluidized by heating or the like and then mixed. When the components are mixed at the same time, a part of the components may be mixed first, and then the remaining components may be mixed or the like, and may be appropriately changed. (Semiconductor device) The semiconductor device is a cross-sectional view of one example as shown in FIG. 1 , and a plurality of wirings 5 (the barrier layer 2, the conductor layer 3, and the tin-plated layer 4) are disposed on the substrate (flexible film) 1 The wiring board 6 of the composition) and the structure in which the semiconductor wafer 7 mounted on the wiring board 6 is bonded by the sealing agent 8 are basically used. The wiring board 6 is formed by laminating the substrate 1 in a plurality of wirings 5 and a solder resist 9, and one end of the wiring 5 is connectable to the semiconductor wafer 7 to be mounted, and the other end is connected to an external device. The solder resist 9 prevents the short circuit and the disconnection by covering and protecting the wiring 5 on the substrate 1. Further, when the substrate 1 is a flexible film, it is COF. (Installation of Semiconductor Wafer) The mounting of the semiconductor wafer can be performed between the flexible wiring substrate and the semiconductor wafer, and the bottom of the epoxy resin composition can be filled, or the epoxy resin can be coated on the flexible wiring substrate. After the composition, the manner in which the semiconductor wafer is adhered may be implemented in other manners. The case of the bottom filling method can be implemented, for example, in the following order. (1) The flexible wiring board 6 is bonded to the semiconductor wafer 7 having gold bumps (protruding electrodes) 10. Further, a portion where the surface of the wiring 5 is not bonded to the semiconductor -21 - 201127864 wafer 7 is covered with a solder resist 9 to protect it. (2) After the bonding, the sealing agent 8 (the epoxy resin composition for sealing) is filled between the semiconductor wafer 7 and the flexible wiring board 6, and heat-hardened to manufacture the semiconductor device 11. The case of the NCP mode can be implemented, for example, in the following order. The resin for the first application is supplied onto the flexible wiring board 6, and the semiconductor wafer 7 having the gold bumps (protruding electrodes) 1 is placed on the flexible wiring board 6, and the flexible wiring board 6 is heated and pressurized. The resin is cured while being bonded to the semiconductor wafer 7 to produce a semiconductor device 11» [Examples] (Examples 1 to 26, Comparative Examples 1 to 5) The following components were measured in amounts shown in Tables 1 to 3, and The mixed mixture was kneaded in a 3-roll honing machine to obtain a uniform resin composition. The resin composition was placed under reduced pressure to remove bubbles in the resin composition, and used as an evaluation sample. The storage stability (tackifying ratio), the curability PCT peeling property (peeling time), and the migration resistance (insulation resistance 値) of the resin composition and the cured product of the resin composition were measured by the following apparatus and method. Evaluation. The evaluation results are shown in Tables 1 to 3. (Epoxy Resin) • Addition of ethyl cyclohexene oxide to 4-membered cyclic methyl oxane, epoxy resin represented by formula (1) • Bisphenol F epoxy resin (epoxy Equivalent 160) -22- 201127864 • Bisphenol A epoxy resin (epoxy equivalent 185) • P-aminophenol epoxy resin (epoxy equivalent 94) • 1,3-bis(3-glycidoxypropane 1,1,1,3,3-tetramethyldioxane (amine hardener) • 4,4'-methyl bis(2-ethylaniline) •3,5-diethyl-2 ,6-Diaminotoluene (amine equivalent 44.6 §) • Cyclohexylamine·anhydride (amine equivalent 49.6 g) • Dimethylaminopropylamine (amine equivalent 51.lg) (metal complex) • Three Ethyl acetonide • Ethyl acetonate ethyl acetate • Monoethyl acetonide aluminum • Triethylene acetonide iron • Diethyl acetonide zinc • Triethylene acetonate indium • Diethyl acetonate magnesium (hydrolyzable hydrazine compound) • Vinyl Trimethoxydecane • γ-glycidoxypropyltrimethoxydecane • γ-Aminopropyltrimethoxydecane • Diphenyldimethoxydecane-23- 201127864 • Diphenyldiethoxydecane • Phenyltrimethoxydecane•3- Triethoxy decyl-N- (hydrogen condensate of 1,3-dimethyl (other formulating agents) • Maleic acid, oleylene, 2-phenyl-4-methylimidazole (viscosity, increase) Viscosity) Using an E-type viscometer (Dongji Industry Co., Ltd.), the evaluation sample was measured at a liquid temperature of 2 5 ° C and 1 rpm. The evaluation sample was poured into a closed container (resin-made image (25). °C, humidity 25%) After standing for 24 hours, the viscosity before and after the placement was measured to determine the viscosity increase rate. The viscosity increase rate was good and the test was good (〇), and the hardness of 2·0 or more was unqualified. (X) (hardenability) Apply 10 mg of the evaluation to the side of the long side of the tantalum wafer adhered to the polyimide film, and exhaust it into the oven at 150 ° C to make the epoxy The resin was hardened. The test piece was vertically erected to visually observe the hardening time of the evaluation sample. The initial viscosity of the butyl propylamine type TVE-22H was less than 10 minutes after the drooping time. 1"), to room temperature: viscosity. When the room temperature is less than 2.0, the storage condition is stable. (2x20x0.75mm test piece is placed in the test after heating: the measurement is no longer considered to be hardenability -24-201127864, and the evaluation is qualified (〇) , 10 minutes or more is considered to be unsatisfactory (X) due to poor hardenability. (Insulation resistance 値) Comb electrode formed on polyimide film (material: tinned on copper, pattern pitch : 30 μηιη, electrode width: 15 μιη) was coated with the evaluation sample, and the test piece was cured by heating at 1500 (TC for 90 minutes). The heated test piece was placed at 85 ° C, humidity of 85 %. The groove (ESPEC system, mode SH-641), a DC voltage of 40 V is applied between the electrodes, and the resistance between the electrodes is measured. When the resistance 1 is 1 X 1 08 Ω or more and lasts for 500 hours or more, it is regarded as insulation. It is evaluated as qualified (〇) when it is good, and it is considered as unqualified (X) when it is less than 500 hours. Then, when the insulation is qualified, it is judged to have insulation retention characteristics (migration resistance) that does not affect practicality. (PCT stripping time) for the peeling test wiring board [ The sample of the evaluation value of 5.0 μm of the PKG type TEG (Phase 6 30 ) coated with the 30 μηι pitch and the direct bump wiring made by the LSI system was used to heat and harden for 90 minutes. There is no initial peeling, use ESP - 4 〖0 Μ made by ESPEC Co., Ltd., placed on PC Τ (1 2 1 °C 'relative humidity! 〇〇%, 2 atmospheres) 3 hrs later 'observe whether there is peeling. 3 The case where there is no peeling after 00 hours is qualified (〇)', and the moisture resistance is evaluated as long as there is a slight peeling after 2 hours, and the moisture resistance is evaluated. -25- 201127864 (Examples 27 to 29) The following components were weighed in the amounts shown in Table 4, and the mixed mixture was kneaded in a 3-roll honing machine to obtain a uniform resin composition. The resin composition was placed under reduced pressure to remove the resin composition. The air bubbles in the product are used as evaluation samples. The storage stability (tackification ratio) and hardenability of the resin composition and the cured product of the resin composition are measured and evaluated by the above-described apparatus and method. Material point of view, the viscosity increase rate is not When it is 2.0, the storage stability is good and it is acceptable (〇), and in the case of 2.0 or more, the storage stability is poor and it is unqualified (X). Further, the hardenability is evaluated by the following method. The hot plate at 150 °C The liquid semiconductor sealing agent is supplied with 5 mg ± 1 mg, and the stirring rod is stirred as a circle, and the stirring rod is picked up while stirring, and the drawing is performed for 5 mm or less for less than 80 seconds. The hardenability was good and it was evaluated as acceptable (〇), and the case of 80 seconds or more was regarded as poor in hardenability and evaluated as unacceptable (X). (Adhesiveness) The adhesion of the cured product of the resin composition was measured and evaluated by the following method. The evaluation results are shown in Table 4. Bonding was carried out using a mounting substrate (200 ° C x 30 0 seconds) and post-curing in an oven (1 60 t X 90 minutes). The connection portion between the flexible substrate 6 of the p KG and the tantalum wafer 7 was visually observed, and there was no crack at the joint portion. Defects such as peeling were acceptable (〇), and those who were slightly defective were defective (X) -26- 201127864 Estimated adhesion. For the mounting substrate, use i.GmmxIS.SmmxSSOpm thick, L/S=20pm. • Adding ethylcyclohexene oxide to a 4-membered cyclic methyl oxane to form an epoxy resin of the formula (1) • 4,4′-methyl bis(2-ethylaniline) • 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine hydrolysis condensate (commercially available) • Triethyl acetonide aluminum • γ-glycidoxypropyl Trimethoxy decane is the same as Comparative Example 1 and 2, and the epoxy resin (Α) is a polyfunctional alicyclic epoxy resin having a cyclic siloxane skeleton, and has a non-cyclic oxime In the case of a polyfunctional alicyclic epoxy resin of alkane structure, the time until PCT peeling occurs is longer. From the comparison between Example I and Comparative Examples 3 to 4, the case of the aromatic amine-based curing agent was better than that of the case of the non-aromatic amine-based curing agent. Further, the time-dependent change of the electric resistance 实施 of the first embodiment and the third embodiment (Fig. 3 and Fig. 4) and the time-dependent change of the electric resistance 比较 of the comparative example 5 (Fig. 2) clearly show that the aromatic amine-based hardening In the case of the agent, the high-temperature moisture resistance reliability is remarkably excellent as compared with the case where the amine-based hardener is not contained. -27- 201127864 Example 7 50.64 47.06 d CO 〇»〇ο inch 00 〇〇〇〇Example 6 66.71 30.99 o 〇rH ο 〇〇〇〇Example 5 I 84.60 | 13.10 in o »η m ο in ο 〇 ±±i I 78.21 | 1 19.49 1 in O «ο md ο s 〇〇〇X Comparative Example 3 78.67 | I 19.03 | dmo Ο SX 〇XX Comparative Example 2 58.49 39.41 d in 〇r«H 〇< Ν ι〇Ο m 〇X 〇〇Comparative example 1 70.16 | 1 27.74 1 d 〇d (Ν in ο m U^) 〇X 〇〇 inch*=Γ> Bracelet 75.98 15.84 00 <N o ο (Ν md ο Ο irj ο CN 〇〇〇〇 Example 3 74.82 23.08 O yn ο ο (Ν »Λϊ Ο CO 〇〇〇〇 Example 2 I 29.74 1 ί 29.74 31.62 in om O iTi Ο S 〇〇〇〇 Example 1| I 74.59 | 23.11 ^T) o »r> md ί—Η *Ti ο inch 00 〇〇〇〇am ΠΧ! 嘁m •N up φπ 遁m « & am mg secret m Ρ 慈 Π 狴 狴 r r r r r φ φ φ φ φ 秘 秘 秘 秘 秘 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( K1 II r^T Cyclohexylamine 狴 slightly 铿m η- 11 triethyl hydrazine acetone aluminum acetoacetate ethyl acetate · single ethyl acetonide aluminum triacetone acetone iron diethyl acetonide acetone zinc triacetone acetone indium two醯Acetone magnesium vinyltrimethoxy decane w ii i- m slightly m 嘁M buckle 1 卜m secret E- 1)1 1E 宁 m 嫲E- 11 枨11 secret K) II m 浒II slightly secret B-II] S 卜 m — 1丨1 paste cAE: ο ι-Η /^ν PQ D oo ? Q |ϊ nmi 黯m #1 黯Η m S Tooth 1? Μ k 龌Different amine hardener B <矽Compound D mass ratio evaluation -28- 201127864 i Grip 74.59 1 23.11 ΙΛ1 Ο »〇m Ο v〇Ο s 〇〇〇〇1Example 14 1 74.59 | 23.11 Ο ν*ί rn ο d Habits In I 74.59 | | 23.11 | Ο m ο ό ο 〇〇〇〇 Example 12" I 74.59 | | 23.11 | ο <Τ) m ο d inch 00 〇〇 〇-U -1A | 18.00 | I I I 19.90 | 〇 inch od (Ν 1 1 XX 实施 Example 111 Γ 74.59 | | 23.11 ] i/Ί· Ο Ο u-1 ΙΟ Ο s 〇〇〇〇〇i IK 丨74.59 1 | 23.11 1 irt Ο md «Ο ο 00 00 〇〇〇〇 Example 9 [74.59 1 | 23.11 | in ο cn ο 1〇ο 〇〇〇〇00 Series U | 74.59 | 1 23.11 | Rn ο «ο ο 00 00 〇〇X 〇m 莸HS m up 遁m litigation m & 1 bisphenol F liquid epoxy resin 1 am TO Μ 装 Installed to < ΙΜ ni m Deputy burial 1, 3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyl oxalate CEC3 擗K] CN 枨埕11 CN m hO π ΓΛ ro m 狴m IE m 11 line Mm inlaid a| i2-phenyl-4-methylimidazole 1 DO rm 111 rn distillation K] 趦N3 salt K] 1 triacetone acetone iron bismuth acetonide zinc hydrazine m 匾r 魍hO HI Magnesium secret 1 K) m IE nf M torsion 1 £S maple mm tE • m H-11 浒11 嫲hO 11 leaching 11 1 phenyl trimethoxy oxime 1 tE i κ ι 1 ΓΛ Ν—✓ ζ δ δ 跃 跃 c c 又 又 + + < D o 3< S' Q ϋ V_^ 迤m key Μ 黯Η UEJ S 龌Φ ήι Epoxy resin A amine hardener B Other metal mismatch Compound C 矽 compound D 43⁄4) 1 -1 13⁄4^ Evaluation -29- 201127864 Example 26 29.89 29.89 I 6.61 31.78 00 ο 丨 1.02 II 0.81 I 〇〇〇〇 Example 25 29.28 29.28 I 6.51 I 31.13 I (N in md 2.08 〇〇〇〇I Example 24] | 29.44 | I 29.44 | 6.54 I 31.28 I CN r—· m 〇2.06 1.34 〇〇〇〇遐29.44 29.44 | 6.54 I 31.28 I in m 〇1.55 1.86 〇〇〇〇宾Example 22 29.59 29.59 丨6.58 | 31.44 | cn 〇1.54 ; CO CO 〇〇〇〇 Example 2! 29.59 29.59 | 6.58 31.44 in m c> 1.03 1.85 〇〇〇〇Example 20 29.74 29.74 | 6.61 | 31.61 | m 〇I 1.02 | rn 〇〇〇〇Example i 91 29.89 29.89 6.64 31.78 〇〇I 0.51 | <N rn 〇〇〇〇Example 1 si 29 .86 29.86 6.63 31.75 oo I 0.10 | I 1.83 | 〇〇〇〇Example i7i 30.01 30.01 1 6.67 I 31.91 | rn I 0.10 | 1 1.31 1 〇〇〇〇Example i6j 30.16 30.16 1 6.70 Γ3Ι081 d 00 d 0.10 0.80 〇〇〇〇m 秘m •μ 遁m δ w Ε- 蚺4 am 033 m to m am Π33 M 嫲m 装副< 秘m to 浒ή & a (Λ CO s E: 补秘思In NP 浒 浒m Κ) CN ίκ ffi- ffi- ftl 狴11 <N m Κ] 11 Cyclohexylamine hydrazine H- 11 Triethylene acetonide aluminum 1E Turn K3 螂• Distillation N] 氍K1 m K) Ti diacetyl acetonide zinc m 膣 κι in 曙 曙 m K) HI <ilL/ 匾m K) 1] vinyl trimethoxy sulane ui in m IE secret moment leap 1 m 嘁 HI w κ S 狴1 糊密11 m 擀II m ui Κ] 11 枨II m 秘 H- 111 m S Η « Β- ^1 口 rAlE 〇D o 玄 PQ Q Q ' '//i 黯S 黯Η im / 1$丨Different 丨1 1! Resin A amine hardener Β 1 <s it φ gargle c Compound D Quality jj Evaluation -30- 201127864 [Table 4] Table 4 Differentiation Example 27 Example 28 Example 29 Epoxy Resin A Epoxy Tree Containing Cyclic Methyl Oxane Skeleton 57.5 57.4 56.9 Bisphenol F Type Liquid Epoxy Resin Bisphenol A Liquid Epoxy Resin to Aminophenol Type epoxy tree 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldioxanine hardener B 4,4'-extension methyl double (2-ethylaniline) 38.4 38.3 38.1 3,5-Diethyl-2,6-diaminotoluenecyclohexylamine dimethylaminopropylamine metal complex C triethylammonium acetone 1.0 1.0 1.0 Ethyl acetate, ethyl acetonate, acetone, aluminum, triethyl hydrazine, acetone, iron, diethyl acetonide, zinc ethoxide, triethylene sulfonium, acetone, indium, diethyl acetonide, acetone, magnesium hydride, vinyl trimethoxy decane, r-glycidoxypropyltrimethoxy Decane 3.0 3.0 3.0 r-Aminopropyltrimethoxy sand diphenyldimethoxydecane D Diphenyldiethoxydecanephenyltrimethoxydecane 3-triethoxyanthracene - Hydrolyzed condensate of N-0,3-dimethylbutylidene)propylamine 0.1 0.3 1.0 Mass ratio C/(A+B)xl00 1.04 1.04 1.05 D/(A+B)xl00 3.23 3.45 4.21 Evaluation of insulation (resistance 値) 〇〇〇 PCT peelability (peeling time) 〇〇〇 hardenability 〇〇〇 storage stability (tackifying ratio) 〇〇〇 adhesion 〇 〇〇-31 - 201127864 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention. Fig. 2 is a graph showing the change with time of the electric resistance of the epoxy resin composition of Comparative Example 5. Fig. 3 is a graph showing the change with time of the electric resistance of the epoxy resin composition of Example 1. Fig. 4 is a graph showing the change with time of the electric resistance of the epoxy resin composition of Example 3. [Description of main component symbols] 1 : Substrate (flexible film) 2 : Barrier layer 3 : Conductor layer 4 : Tin plating layer 5 : Wiring 6 : Wiring substrate 7 : Semiconductor wafer (element) 8 : Epoxy resin composition (blocking agent) 9 : solder resist 1 〇: bump (protrusion electrode) 1 1 : semiconductor device • 32-