在下文中，將更詳細地描述本發明。 根據本發明的一個實施例之用於黏晶之環氧樹脂組合物包括環氧樹脂、彈性體、固化劑、填充劑及溶劑，其中該彈性體包括具有環氧基的彈性體，且該固化劑包括固態胺化合物。 在本發明的一個實施例中，環氧樹脂係用於賦與黏著力及提高耐久性的組份，且在一個分子內具有至少兩個或更多個環氧基。 環氧樹脂之實例包括雙酚類環氧樹脂，諸如雙酚A、雙酚E、雙酚F、雙酚M、雙酚S及雙酚H；縮水甘油醚類環氧樹脂；縮水甘油胺類環氧樹脂；酚酚醛清漆類環氧樹脂、甲酚酚醛清漆類環氧樹脂；經二聚體酸改質之環氧樹脂及其類似物。此等樹脂可單獨或以兩種或更多種之組合的形式使用，且對混合時的混合比率不存在特定限制。 在本發明的一個實施例中，以環氧樹脂組合物之總重量計，可包含2至20重量%之量的環氧樹脂。當環氧樹脂之含量低於2%重量時，可減少黏著力，從而對可靠性造成影響。當環氧樹脂之含量超過20重量%時，可增加玻璃轉移溫度及彈性模數，藉此導致晶粒開裂。 在本發明的一個實施例中，環氧樹脂在高溫下與醯亞胺樹脂合併時可呈現極好的黏結強度。 醯亞胺樹脂之實例包括4,4-雙順丁烯二醯亞胺二苯醚、4,4-雙順丁烯二醯亞胺二苯基甲烷、4,4-雙順丁烯二醯亞胺-3,3'-二甲基二苯基甲烷、4,4-雙順丁烯二醯亞胺二苯基碸、雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]醚、雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]甲烷、雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]氟甲烷、雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]碸、雙順丁烯二醯亞胺寡聚物及其類似物。 由在固化後提高黏結強度，同時保持組合物之儲存穩定性之觀點來看，當使用時，以環氧樹脂之100重量份計，醯亞胺樹脂之混合量可為1至200重量份。 此外，為了促進醯亞胺樹脂之固化，可使用自由基聚合引發劑。自由基聚合引發劑之實例包括過氧化乙醯基環己基磺醯基、過氧化異丁醯基、過氧化苯甲醯、過氧化辛醯基、過氧化乙醯基、過氧化二異丙苯、氫過氧化異丙苯、偶氮二異丁腈及其類似物。以100重量份之醯亞胺樹脂計，自由基聚合引發劑可以0.01至3.0重量份之量使用。 在本發明的一個實施例中，彈性體用於藉由向黏晶物質賦與彈性以吸收內應力之目的，且包括具有環氧基的彈性體。 具有環氧基之彈性體的實例包括B-Tough A3 (由Croda製造的環氧基官能性反應性韌化劑)、KR系列 (由Kukdo Chemical Co., Ltd.製造)、PB3600及PB4700(由Daicel Japan製造)及其類似物。 在本發明的一個實施例中，以環氧樹脂組合物之總重量計，可含有30至50重量%之量的彈性體。當彈性體之含量低於30%重量時，增加玻璃轉移溫度及彈性模數，藉此發生晶粒開裂。在彈性體之含量大於50重量%時，增加黏度，藉此對操作性產生影響，或玻璃轉移溫度變得太低，藉此在高溫下進行的後續操作期間發生晶粒移位現象。 在本發明的一個實施例中，固化劑係與環氧樹脂反應以進行組合物之固化的組份，且包括固態胺化合物。 可使用(但不限於)氰基胍、三聚氰胺、咪唑及其類似物作為固態胺化合物，其在室溫下係固體。 在本發明的一個實施例中，以環氧樹脂組合物之總重量計，可含有1至3%重量之量的固化劑。當固化劑之含量低於1重量%時，交聯密度降低且吸濕率增加，藉此對可靠性造成影響。當含量大於3%重量時，適用期可縮短且因此可在溶劑乾燥過程中發生固化。 在本發明的一個實施例中，填充劑係用於控制組合物之流動性及黏度的組份，且其實例包括二氧化鈦、硫酸鋇、碳酸鈣、二氧化矽、氧化鋁及其類似物。此等物質可單獨或以兩種或更多種之組合的形式使用。在本發明的一個實施例中，可藉由包括矽酮粉末作為填充劑來賦與彈性。 在本發明的一個實施例中，以環氧樹脂組合物之總重量計，可含有25至45%重量之量的填充劑。當填充劑之含量低於25%重量時，黏度及搖變減黏性較低，且因此黏晶物質在印刷期間無法維持其形狀且出現崩潰現象。當填充劑之含量超過45%重量時，黏度變得較高，藉此在印刷時發生表面變得不光滑的現象。 在本發明的一個實施例中，溶劑之實例包括二甘醇二甲醚、三伸乙甘醇二甲醚、二甘醇乙醚、2-(2-甲氧基乙氧基)乙醇、γ-丁內酯、異佛爾酮(isophorone)、卡比醇(carbitol)、乙酸卡比醇、1,3-二甲基-2-咪唑啶酮、乙酸2-(2-丁氧基乙氧基)乙酯、乙基溶纖劑、乙酸乙基溶纖劑、丁基溶纖劑、二噁烷、環己酮、苯甲醚及其類似物。此等溶劑可單獨或以兩種或更多種之組合的形式使用。 在本發明的一個實施例中，以環氧樹脂組合物之總重量計，可含有15至30%重量之量的溶劑。當溶劑之含量低於15%重量時，可增加黏度，對操作性造成影響。當溶劑之含量大於30%重量時，可降低黏度且需要較長時間來進行溶劑乾燥過程，其間可進行環氧化物固化反應。 根據本發明之一個實施例的環氧樹脂組合物可進一步包括固化催化劑。 使用固化催化劑來改良組合物之固化率，且其實例包括二乙基三胺(DETA)、乙二胺(EDA)、三伸乙基四胺(TETA)、四伸乙基五胺(TEPA)、二乙基胺基丙胺(DEAPA)、甲烷二胺(MDA)、N-胺基乙基哌啶(N -AEP)、間二甲苯二胺(m-XDA)、1,3-雙胺基甲基環己烷(1,3-AC)、異佛爾酮二胺、二胺基環己烷、N,N-二乙基-1,3-丙二胺、N-(2-羥基乙基)-1,3-戊二胺、N,N-二正丁基-1,3-丙二胺、經改質之多元胺及其類似物。 以100重量份之環氧樹脂計，固化催化劑可以1至20重量份之量使用。當固化催化劑之含量低於1重量份時，固化催化劑之活性降低且因此不進行固化。當固化催化劑之含量大於20重量份時，固化催化劑之活性變得極高且因此存在儲存穩定性劣化的問題。 此外，只要未不利地影響本發明之目的，根據本發明之一個實施例的環氧樹脂組合物可視需要進一步包括添加劑，諸如黏著促進劑、分散劑、抗發泡劑、消泡劑及離子清除劑。 根據本發明之一個實施例的環氧組合物可藉由在真空消泡後，使用混合攪拌棒充分地分散每一組份來製備。較佳在製備之後8小時內在-20至-40℃下儲存於冰箱內，且使用時，其必須在適用期內使用。 本發明之一個實施例提供使用用於黏晶之環氧樹脂組合物製造的半導體裝置。 製造根據本發明之一個實施例之半導體裝置的方法包括以下步驟：將用於黏晶的環氧樹脂組合物塗覆至支撐基板上、乾燥所塗覆的樹脂組合物以實現B階段、在B階段樹脂組合物上安置半導體元件及使上面安置半導體元件之樹脂組合物固化。 支撐基板不受特定限制，且舉例而言，諸如42合金引線框架或銅引線框架之引線框架；聚醯亞胺樹脂、環氧樹脂之塑膠膜及其類似物；包含諸如玻璃或非編織物之基底材料的基板，其中注入含有聚醯亞胺樹脂、環氧樹脂及其類似物的樹脂組合物且隨後硬化(預浸體)；或由陶瓷(諸如氧化鋁)製得的支撐部件。 作為將用於黏晶之環氧樹脂組合物供應且塗覆至支撐基板上的方法，印刷方法係較佳的。作為印刷方法，舉例而言，可使用網版印刷。 作為乾燥所塗覆的樹脂組合物以實現B階段之方法，加熱可作為實例提及。本發明之用於黏晶的環氧樹脂組合物含有特定溶劑，但大多數溶劑在B階段揮發。 借助於B階段，在支撐基板上形成具有足夠小的空隙的低黏性或無黏性黏晶層。 作為半導體元件(晶粒)，IC、LSI及其類似物可作為實例提及。可安置半導體元件以形成DRAM、SRAM、快閃記憶體及其類似物。此時，有可能在加熱條件下，藉由施加負載進行樹脂組合物的暫時黏結。或者，有可能藉由進一步加熱來進行樹脂組合物之固化。 在本發明的一個實施例中，較佳對上面安置有半導體組件之樹脂組合物(黏晶層)進行後固化。 樹脂組合物之此後固化可與密封材料之後固化步驟組合，其限制條件為在安置及組裝過程中不出現問題。 在下文中，將參考實例、比較實例及實驗實例更具體地描述本發明。熟習此項技術者將顯而易見，此等實例、比較實例及實驗實例僅用於說明本發明且本發明之範疇並不限於此。實例 1 以 及比較實例 1 及 2 ： 製備用於黏晶之環氧樹脂組合物
混合各別組份與以下表1中展示之組合物以製備用於黏晶的環氧樹脂組合物(單位：重量%)。 [表1]
1) Hypro 1300X13NA CTBN (CVC thermoset specialties) 2) B-Tough A3 (Croda) 3) EOCN-1020 (Nippon kayaku) 4) YDCN-500-4P (Kukdo Chemical) 5) CNE80208 (KCC) 6) MEH-7800SS (Meiwa) 7) DICY (Air product) 8) Carbitol acetate (Samchun Chemical) 9) AEROSIL R 972 (EVONIK) 10) SFP-30M (Denka) 11) EP-2601 (Dow corning) 12) IXEPLAS-A1 (Toagosei) 13) IXE-600 (Toagosei) 14) LC550 (SHIN-A T&C) 15) BYK110 (BYK Additive & Instruments ) 16) BYK-085 (BYK Additive & Instruments ) 17) BYK-A501 (BYK Additive & Instruments ) 18) S-510 (CHISSO)實驗實例 1 ：
藉由以下方法量測在實例1以及比較實例1及2中製備之環氧樹脂組合物的物理性質，且結果展示於以下表2中。 (1) 黏度及搖變減黏指數 獲得大約0.5 ml之組合物樣品且在布洛克菲爾德錐形/板黏度計(Brookfield cone/plate viscometer)中使用軸CP-51在0.5 rpm及25 rpm之旋轉速度下量測在25℃下的黏度。獲得在5 rpm下所量測的值作為黏度值，且搖變減黏指數計算為在0.5 rpm及5 rpm下所量測的兩個黏度值的比率，亦即，在0.5 rpm下所量測的值/在5 rpm下所量測的值。 (2) 玻璃轉移溫度(Tg)及彈性模數 組合物的樣品以0.2 mm之厚度塗佈且在125℃/30 min及175℃/120 min下固化，且隨後使用Perkin ELmer DMA 8000以拉伸模式進行量測。 (3) 實驗室剪切強度 根據ISO 4587測試方法在20℃下測試五個樣品，且展示平均值。樣品係與鋁板連接的金屬。 (4) 黏性 塗有100 μm之厚度的組合物的測試樣本在烘箱中於125℃下揮發30分鐘，且隨後使用質構儀(Texture Analyzer)用5N之力按壓5秒以量測分離力。 [表2]
如可由以上表2發現，證實與不含彈性體及胺化合物的比較實例1及2相比，含有具有環氧基之彈性體作為彈性體且含有固態胺化合物作為固化劑之實例1的環氧樹脂組合物在B階段之後具有較高黏結強度且顯示較低黏性。 儘管已展示且描述本發明之特定實施例，熟習此項技術者應理解，其並非意欲將本發明限於該等較佳實施例，且熟習此項技術者將顯而易見，可在不背離本發明之精神及範疇的情況下作出不同變化及改變。 因此，本發明之範疇藉由隨附申請專利範圍及其等效物界定。Hereinafter, the present invention will be described in more detail. An epoxy resin composition for die bonding according to an embodiment of the present invention includes an epoxy resin, an elastomer, a curing agent, a filler, and a solvent, wherein the elastomer includes an elastomer having an epoxy group, and the curing The agent includes a solid amine compound. In one embodiment of the present invention, an epoxy resin is used for imparting adhesion and improving durability, and has at least two or more epoxy groups in one molecule. Examples of the epoxy resin include bisphenol epoxy resins such as bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, and bisphenol H; glycidyl ether epoxy resins; glycidylamines Epoxy resin; phenol novolac epoxy resin, cresol novolac epoxy resin; dimer acid modified epoxy resin and the like. These resins may be used singly or in combination of two or more kinds, and there is no particular limitation on the mixing ratio at the time of mixing. In one embodiment of the invention, the epoxy resin may be included in an amount of from 2 to 20% by weight based on the total weight of the epoxy resin composition. When the content of the epoxy resin is less than 2% by weight, the adhesion can be reduced, thereby affecting the reliability. When the content of the epoxy resin exceeds 20% by weight, the glass transition temperature and the modulus of elasticity can be increased, thereby causing grain cracking. In one embodiment of the invention, the epoxy resin exhibits excellent bond strength when combined with a quinone imine resin at elevated temperatures. Examples of the quinone imine resin include 4,4-bis-butylene diimide diphenyl ether, 4,4-bis-s-butylene diimide diphenylmethane, 4,4-bis-butenylene dioxime Imine-3,3'-dimethyldiphenylmethane, 4,4-bissuccinimide diphenyl fluorene, bis[4-(4-m-butylene imidate phenoxy) Phenyl]ether, bis[4-(4-maleoximine phenoxy)phenyl]methane, bis[4-(4-m-butyleneimine phenoxy)phenyl] Fluoromethane, bis[4-(4-maleoximine phenoxy)phenyl]anthracene, bis-n-butylenediamine oligomers and the like. From the viewpoint of improving the bonding strength after curing while maintaining the storage stability of the composition, when used, the amount of the quinone imine resin may be 1 to 200 parts by weight based on 100 parts by weight of the epoxy resin. Further, in order to promote the curing of the quinone imine resin, a radical polymerization initiator may be used. Examples of the radical polymerization initiator include etidylcyclohexylsulfonyl peroxide, isobutylphosphonium peroxide, benzammonium peroxide, octadecyl peroxide, ethoxylated oxime, dicumyl peroxide, hydroperoxide Cumene, azobisisobutyronitrile and the like. The radical polymerization initiator may be used in an amount of 0.01 to 3.0 parts by weight based on 100 parts by weight of the quinone imine resin. In one embodiment of the invention, the elastomer is used for the purpose of imparting internal stress by imparting elasticity to the viscous material, and includes an elastomer having an epoxy group. Examples of the epoxy group-containing elastomer include B-Tough A3 (epoxy functional reactive toughening agent manufactured by Croda), KR series (manufactured by Kukdo Chemical Co., Ltd.), PB3600, and PB4700 (by Daicel Japan) and the like. In one embodiment of the invention, the elastomer may be included in an amount of from 30 to 50% by weight based on the total weight of the epoxy resin composition. When the content of the elastomer is less than 30% by weight, the glass transition temperature and the modulus of elasticity are increased, whereby grain cracking occurs. When the content of the elastomer is more than 50% by weight, the viscosity is increased, whereby the operability is affected, or the glass transition temperature becomes too low, whereby the grain shift phenomenon occurs during the subsequent operation at a high temperature. In one embodiment of the invention, the curing agent is a component that reacts with the epoxy resin to effect curing of the composition, and includes a solid amine compound. As the solid amine compound, it is possible to use, but is not limited to, cyanoguanidine, melamine, imidazole and the like as a solid amine compound which is solid at room temperature. In one embodiment of the invention, the curing agent may be included in an amount of from 1 to 3% by weight based on the total weight of the epoxy resin composition. When the content of the curing agent is less than 1% by weight, the crosslinking density is lowered and the moisture absorption rate is increased, thereby affecting the reliability. When the content is more than 3% by weight, the pot life can be shortened and thus curing can occur during solvent drying. In one embodiment of the present invention, the filler is a component for controlling the fluidity and viscosity of the composition, and examples thereof include titanium oxide, barium sulfate, calcium carbonate, cerium oxide, aluminum oxide, and the like. These materials may be used singly or in combination of two or more. In one embodiment of the invention, the elasticity can be imparted by including an anthrone powder as a filler. In one embodiment of the invention, the filler may be included in an amount of from 25 to 45% by weight based on the total weight of the epoxy resin composition. When the content of the filler is less than 25% by weight, the viscosity and the shake-reducing property are low, and thus the viscous material cannot maintain its shape and collapse during printing. When the content of the filler exceeds 45% by weight, the viscosity becomes higher, whereby the surface becomes unsmooth at the time of printing. In one embodiment of the present invention, examples of the solvent include diglyme, triethylene glycol dimethyl ether, diethylene glycol ethyl ether, 2-(2-methoxyethoxy)ethanol, γ- Butyrolactone, isophorone, carbitol, carbitol acetate, 1,3-dimethyl-2-imidazolidinone, 2-(2-butoxyethoxy) acetate Ethyl ester, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, anisole and the like. These solvents may be used singly or in combination of two or more. In one embodiment of the invention, the solvent may be included in an amount of from 15 to 30% by weight based on the total weight of the epoxy resin composition. When the content of the solvent is less than 15% by weight, the viscosity can be increased to affect the workability. When the content of the solvent is more than 30% by weight, the viscosity can be lowered and it takes a long time to carry out a solvent drying process in which an epoxide curing reaction can be carried out. The epoxy resin composition according to an embodiment of the present invention may further include a curing catalyst. A curing catalyst is used to improve the curing rate of the composition, and examples thereof include diethyltriamine (DETA), ethylenediamine (EDA), triethylidenetetramine (TETA), tetraethylidene pentaamine (TEPA). , diethylaminopropylamine (DEAPA), methane diamine (MDA), N-aminoethylpiperidine (N-AEP), m-xylenediamine (m-XDA), 1,3-diamine Methylcyclohexane (1,3-AC), isophoronediamine, diaminocyclohexane, N,N-diethyl-1,3-propanediamine, N-(2-hydroxyethyl Base) - 1,3-pentanediamine, N,N-di-n-butyl-1,3-propanediamine, modified polyamines and the like. The curing catalyst may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the epoxy resin. When the content of the curing catalyst is less than 1 part by weight, the activity of the curing catalyst is lowered and thus curing is not performed. When the content of the curing catalyst is more than 20 parts by weight, the activity of the curing catalyst becomes extremely high and thus there is a problem that storage stability is deteriorated. Further, the epoxy resin composition according to an embodiment of the present invention may further include additives such as an adhesion promoter, a dispersant, an antifoaming agent, an antifoaming agent, and an ion scavenging as needed, as long as the object of the present invention is not adversely affected. Agent. The epoxy composition according to one embodiment of the present invention can be prepared by sufficiently dispersing each component using a mixing stir bar after vacuum defoaming. It is preferably stored in the refrigerator at -20 to -40 ° C within 8 hours after preparation, and when used, it must be used during the applicable period. One embodiment of the present invention provides a semiconductor device fabricated using an epoxy resin composition for die bonding. A method of manufacturing a semiconductor device according to an embodiment of the present invention includes the steps of: coating an epoxy resin composition for die bonding onto a support substrate, drying the applied resin composition to achieve a B-stage, at B The semiconductor element is placed on the stage resin composition and the resin composition on which the semiconductor element is placed is cured. The support substrate is not particularly limited, and is, for example, a lead frame such as a 42 alloy lead frame or a copper lead frame; a polyimide film, a plastic film of an epoxy resin, and the like; and includes, for example, a glass or a non-woven fabric. A substrate of a base material in which a resin composition containing a polyimide resin, an epoxy resin, and the like is injected and then hardened (prepreg); or a support member made of a ceramic such as alumina. As a method of supplying an epoxy resin composition for a die bond and applying it to a support substrate, a printing method is preferred. As the printing method, for example, screen printing can be used. As a method of drying the applied resin composition to achieve the B stage, heating can be mentioned as an example. The epoxy resin composition for a die bond of the present invention contains a specific solvent, but most of the solvent is volatilized in the B stage. By means of the B-stage, a low-viscosity or non-viscous, viscous layer having a sufficiently small void is formed on the support substrate. As the semiconductor element (die), an IC, an LSI, and the like can be mentioned as an example. Semiconductor components can be placed to form DRAMs, SRAMs, flash memories, and the like. At this time, it is possible to temporarily bond the resin composition by applying a load under heating. Alternatively, it is possible to cure the resin composition by further heating. In one embodiment of the invention, the resin composition (adhesive layer) on which the semiconductor component is placed is preferably post-cured. This post-cure curing of the resin composition can be combined with the post-curing step of the sealing material with the proviso that no problems occur during placement and assembly. Hereinafter, the present invention will be more specifically described with reference to examples, comparative examples, and experimental examples. It will be apparent to those skilled in the art that these examples, comparative examples and experimental examples are merely illustrative of the invention and the scope of the invention is not limited thereto. Examples 1 and 2 and Comparative Example 1: Preparation of die-bonding of the epoxy resin composition for mixing the individual components with the epoxy resin composition is shown in Table 1 The composition was prepared for sticky crystals (unit: weight%). [Table 1] 1) Hypro 1300X13NA CTBN (CVC thermoset specialties) 2) B-Tough A3 (Croda) 3) EOCN-1020 (Nippon kayaku) 4) YDCN-500-4P (Kukdo Chemical) 5) CNE80208 (KCC) 6) MEH-7800SS (Meiwa) 7) DICY (Air product) 8) Carbitol acetate (Samchun Chemical) 9) AEROSIL R 972 (EVONIK) 10) SFP-30M (Denka) 11) EP-2601 (Dow corning) 12) IXEPLAS-A1 (Toagosei 13) IXE-600 (Toagosei) 14) LC550 (SHIN-A T&C) 15) BYK110 (BYK Additive & Instruments) 16) BYK-085 (BYK Additive & Instruments) 17) BYK-A501 (BYK Additive & Instruments ) 18 S-510 (CHISSO) Experimental Example 1 : The physical properties of the epoxy resin compositions prepared in Example 1 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 2 below. (1) Viscosity and shake reduction index obtained approximately 0.5 ml of the composition sample and rotated at 0.5 rpm and 25 rpm using a shaft CP-51 in a Brookfield cone/plate viscometer The viscosity at 25 ° C was measured at speed. The value measured at 5 rpm was obtained as the viscosity value, and the rocking viscosity reduction index was calculated as the ratio of the two viscosity values measured at 0.5 rpm and 5 rpm, that is, measured at 0.5 rpm. Value / value measured at 5 rpm. (2) The glass transition temperature (Tg) and the sample of the elastic mold array were coated at a thickness of 0.2 mm and cured at 125 ° C / 30 min and 175 ° C / 120 min, and then stretched using Perkin ELmer DMA 8000. The mode is measured. (3) Laboratory shear strength Five samples were tested at 20 ° C according to the ISO 4587 test method and the average value was shown. The sample is a metal that is attached to an aluminum plate. (4) A test sample having a composition coated with a thickness of 100 μm was volatilized in an oven at 125 ° C for 30 minutes, and then pressed with a force of 5 N for 5 seconds using a Texture Analyzer to measure the separation force. . [Table 2] As can be found from Table 2 above, it was confirmed that the epoxy containing the elastomer having an epoxy group as an elastomer and containing a solid amine compound as a curing agent was compared with Comparative Examples 1 and 2 containing no elastomer and an amine compound. The resin composition has a higher bonding strength after the B stage and shows a lower viscosity. While a particular embodiment of the invention has been shown and described, it will be understood by those skilled in the art Different changes and changes are made in the context of the spirit and scope. Therefore, the scope of the invention is defined by the scope of the appended claims and their equivalents.