201012887 六、發明說明： 【發明所屬之技術領域】 本發明係關於包含（甲基）丙烯酸系樹脂與環氧樹脂 ，且於將半導體晶片接著於基板上時可減低孔隙發生之接 著劑組成物，以及使用該接著劑組成物之接著用薄片及切 割•黏晶接著薄膜。 0 【先前技術】 半導體裝置係藉由例如下製造：（i)以切割（切斷 )步驟將形成有1C電路之大直徑矽晶圓切成半導體晶片 ，（π )以硬化性液狀接著劑等作爲固晶材將該晶片熱壓 著於導線框上，且使該接著劑硬化而固定（安裝）該晶片 ，（：iii)對電極間打線接合，隨後，（iv)藉由封裝以提 升操作性及保護免於受外部環境影響。封裝形態最普遍使 用樹脂之轉注成型（transfer molding)法，因此方法係量 • 產性優異且低價之故。 近年來，伴隨著半導體裝置之高機能化，用以搭載半 導體晶片之支撐基板（基材）亦要求高密度化、細微化。 於該等狀況下，使用液狀接著劑作爲上述固晶材料時，接 著劑於搭載半導體晶片時會自晶片端溢出而造成電極污染 ，且由於接著劑層之厚度不均勻造成晶片之傾斜，而容易 產生打線接合。因此，爲改善該等缺點而期望接著劑薄膜 化。 另一方面，基板存在有因配線等之電路要素產生之凹 -5- 201012887 凸部，於將半導體晶片熱壓著在該等基板上時，作爲固晶 材之接著薄膜，亦即固晶薄膜無法將凹部完全埋入，該未 被埋入之部份成爲孔隙殘留，該孔隙於回焊爐加熱時膨脹 ，使接著劑層遭破壞而有損及半導體裝置信賴性之情況。 尤其，近年來，成爲要求對應於無鉛焊錫之高溫（265°C )下之耐回焊性，防止孔隙形成之重要性變高。以下，將 未殘留孔隙而埋入基板上凹部之性能稱爲「埋入性能」。 爲解決上述問題，思及以使熔融之固晶薄膜流入存在 @ 於基板上之凹部並埋入之方式，以具有低熔融黏度之固晶 薄膜將半導體晶片熱壓著於基板上，極力使之不形成孔隙 ，但無法完全避免孔隙形成，且由於熱壓著需要長時間， 且要求高的壓力，因此產生對生產性造成不良影響之問題 。而且’固晶薄膜自晶片端大量溢出，亦有造成電極污染 之問題。 用以解決上述問題之一方法有藉由封裝樹脂在高溫高 壓下進行模製’使殘存之孔隙以樹脂封裝步驟加熱、壓縮 @ ，以使孔隙之體積變小之狀態下進一步吸收於固晶薄膜中 ’或者，使孔隙之體積變得很小並使固晶薄膜加熱硬化， 藉此去除孔隙之方法。該方法並不需要.特殊之步驟，於製 造面上有利。 然而’過去作爲固晶之上述接著劑，具體而言，已開 發出包含接著性優異之樹脂的丙烯酸系樹脂、環氧樹脂， 其硬化劑的酚樹脂及觸媒之低彈性率材料（例如專利文獻 1~3)。因此’儘管該等接著劑之接著性能優異，但使用 [£]- -6- 201012887 該接著劑之接著薄膜若使用於硬化反應之進行快速，以樹 脂封裝步驟去除孔隙之上述方法中，由於樹脂封裝步驟前 之打線接合步驟中之加熱而使薄膜熔融黏度上升速度變大 ’因此於樹脂封裝步驟中難以去除孔隙。亦即，熔融黏度 變大之結果’無法使孔隙體積充分變小，且無法將孔隙吸 收於樹脂中。據此，過去之接著劑難以充分埋入基板上之 凹部’而要求改良埋入性能。 ❹ [專利文獻1]特開平10-163391號公報 [專利文獻2]特開平11-12545號公報 [專利文獻3 ]特開2 0 0 0 - 1 5 4 3 6 1號公報 【發明內容】 [發明欲解決之課題] 本發明之目的係提供一種不僅接著性優異且埋入性能 及耐熱性均優異之接著劑組成物，以及使用該接著劑組成 〇 物之接著用薄片及切割•黏晶接著薄膜。 [用以解決課題之手段] 因此，本發明人等針對包含丙烯酸系樹脂及環氧樹脂 之接著劑組成物進行各種檢討，發現下述之接著劑組成物 與過去者相較，可保持優異之接著性，同時發揮耐熱性優 異且良好之埋入性能。 換言之’本發明第一目的係提供一種接著劑組成物， 其係包含 201012887 (A) 重量平均分子量爲50,000~1,500,000，且含有 對下述（B)及（C)成份之一或二者具有反應性之官能基 之（甲基）丙烯酸系樹脂， (B) 重量平均分子量爲5 000以下之環氧樹脂，及 (C) 芳香族聚胺化合物。 本發明第二目的係提供一種接著用薄片，其具備基材 及設於該基材上之由上述接著劑組成物所成之層。又，由 該接著劑組成物所成之層即使於自基材剝離之狀態，在室 ❿ 溫下亦保有薄膜形狀，亦即相當於接著薄膜。 本發明之第三目的係提供一種切割·黏晶接著薄膜， 其具備具有基材及設於其上之黏著劑層之切割薄膜，與設 於該切割薄膜之黏著劑層上之由上述接著劑組成物所成之 層。 [發明效果] 本發明之接著劑組成物由於抑制於打線接合步驟中因 ® 加熱造成之熔融黏度上升，具有於樹脂封裝步驟中可使孔 隙完全消失之熔融黏度，且由於可容易地將孔隙完全去除 ，因而具有優異之埋入性能。又，該接著劑組成物藉由加 熱硬化，可獲得對各種基材具有高接著力且爲低彈性率且 耐熱性優異之接著劑硬化物層。據此，該接著劑組成物可 用以製造信賴性高的半導體裝置。 【實施方式】 -8 - 201012887 以下詳細說明本發明。又，本說明書中，所謂「重量 平均分子量」意指以凝膠滲透層析（GPC)測定並換算成 聚苯乙烯之重量平均分子量。 本發明之接著劑組成物包含上述（A )〜（C )成份， 且由於在室溫下保有形狀，例如可形成薄膜狀薄膜，另一 方面，藉由加熱成爲可塑狀態，進而以該狀態長時間保存 ，藉此發揮優異之埋入性能。該組成物之硬化物相對於基 φ 材具有高的接著性同時爲低彈性率且具有優異之耐熱性。 [(A)(甲基）丙烯酸系樹脂] (A)成份爲重量平均分子量50,000〜1，500,000，且 含有對下述（B)及（C)成份之一或二者具有反應性之官 能基之（甲基）丙烯酸系樹脂。本說明書中所謂（甲基） 丙烯酸系樹脂意指包含源自由丙烯酸、丙烯酸衍生物、甲 基丙烯酸及甲基丙烯酸衍生物所組成之（甲基）丙烯酸系 〇 單體之單體單位之聚合物。（A)成份可單獨使用一種亦 可組合兩種以上使用。組合兩種以上使用時，（A)成份 亦可爲含有上述官能基之（甲基）丙烯酸系樹脂與不含上 述官能基之（甲基）丙烯酸系樹脂之混合物。 (A)成份可列舉例如上述（甲基）丙烯酸系單體之 均聚物或共聚物或該（甲基）丙烯酸系單體與其他單體之 共聚物，重量平均分子量爲 50,〇〇〇〜1,500,000，且含有對 下述（B)及（C)成份之一或二者具有反應性之官能基之 聚合物。（甲基）丙烯酸系單體與其他單體之共聚物中， -9 - 201012887 源自其他單體之單體單位之含量相對於（A 單體單位，較好爲0〜50莫耳％，更好爲0〜 甲基）丙烯酸系單體與其他單體之共聚物中 自可以單獨一種使用亦可組合兩種以上使用 上述丙烯酸衍生物可列舉例如丙烯酸甲 酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸2_ 烯酸月桂酯等丙烯酸烷酯；丙烯酸羥基乙酯 丙酯等丙烯酸羥基烷酯；丙烯酸苄酯等含有 丙烯酸酯；二甲基丙烯醯胺等丙烯醯胺；醯 TO-1 492 (商品名，東亞合成工業製造）等 之丙烯酸酯；丙烯酸縮水甘油酯等含有環氧 :丙烯腈。 上述甲基丙烯酸衍生物可列舉例如甲基 甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙 甲基丙烯酸2-乙基己酯、甲基丙烯酸月桂醋 烷酯；甲基丙烯酸羥基乙酯、甲基丙烯酸羥 丙烯酸羥基烷酯；甲基丙烯酸苄酯等含有芳 基丙烯酸酯；二甲基甲基丙烯酸醯胺等甲基 醯亞胺甲基丙烯酸酯等含有醯亞胺基之甲基 基丙烯酸縮水甘油酯等含有環氧基之甲基丙 上述其他單體可列舉例如苯乙烯、丁二 生物（烯丙基醇、乙酸烯丙酯等）。 本發明較佳之實施形態中’ （A )成份 表示之單位之共聚物： )成份中之總 3 0莫耳％。（ ，該等單體各 〇 酯、丙烯酸乙 -乙基己酯、丙 、丙烯酸羥基 芳香族烴基之 Φ 亞胺丙烯酸酯 含有醯亞胺基 基之丙烯酸酯 丙烯酸甲酯、 烯酸異丁酯、 等甲基丙烯酸 基丙酯等甲基 @ 香族烴基之甲 丙烯酸醯胺； 丙烯酸酯；甲 烯酸酯。 烯、烯丙基衍 爲含有以下式 -10- 201012887 【化1】201012887 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition comprising a (meth)acrylic resin and an epoxy resin and capable of reducing pore formation when a semiconductor wafer is attached to a substrate, And the use of the adhesive composition followed by a sheet and a cut/sticky film followed by a film. 0 [Prior Art] A semiconductor device is manufactured by, for example, manufacturing: (i) cutting a large-diameter 矽 wafer formed with a 1C circuit into a semiconductor wafer by a dicing (cutting) step, (π) as a hardening liquid adhesive And pressing the wafer as a solid crystal material on the lead frame, and hardening the adhesive to fix (mount) the wafer, (:iii) wire bonding between the electrodes, and then (iv) lifting by encapsulation Operational and protection from external environment. The most common form of packaging is the transfer molding method using a resin. Therefore, the method is excellent in productivity and low in cost. In recent years, with the increase in the functionality of semiconductor devices, the support substrate (substrate) on which the semiconductor wafer is mounted is also required to be denser and finer. In such a case, when a liquid adhesive is used as the above-mentioned solid crystal material, the adhesive may overflow from the wafer end when the semiconductor wafer is mounted to cause electrode contamination, and the wafer is tilted due to uneven thickness of the adhesive layer. It is easy to produce wire bonding. Therefore, it is desirable to thin the adhesive in order to improve these disadvantages. On the other hand, the substrate has a concave -5 - 201012887 convex portion which is generated by a circuit element such as a wiring, and when the semiconductor wafer is heat-pressed on the substrate, the bonding film as a solid crystal material, that is, a solid crystal film The recess cannot be completely buried, and the unburied portion becomes a void residue which expands when heated in the reflow furnace to damage the adhesive layer and impair the reliability of the semiconductor device. In particular, in recent years, the reflow resistance at a high temperature (265 ° C) corresponding to lead-free solder has been demanded, and the importance of preventing void formation has become high. Hereinafter, the performance of embedding the recess in the substrate without leaving pores is referred to as "buriing performance". In order to solve the above problem, it is considered that the molten solid crystal film is poured into the concave portion existing on the substrate and buried, and the semiconductor wafer is heat-pressed on the substrate by a solid crystal film having a low melt viscosity. No pores are formed, but pore formation cannot be completely avoided, and it takes a long time due to hot pressing, and high pressure is required, thereby causing a problem of adversely affecting productivity. Moreover, the 'solid crystal film overflows a large amount from the wafer end, and there is also a problem of causing electrode contamination. One of the methods for solving the above problems is to mold the resin at a high temperature and pressure by encapsulating the resin by heating and compressing the remaining pores in a resin encapsulating step to further absorb the solid crystal film in a state where the volume of the pores is reduced. Medium 'or a method of making the volume of the pores small and heat-hardening the solid crystalline film, thereby removing the pores. This method does not require a special step and is advantageous on the manufacturing surface. However, in the past, as the above-mentioned adhesive agent for solid crystal, specifically, an acrylic resin or an epoxy resin containing a resin excellent in adhesion, a phenol resin of a hardener, and a low modulus material of a catalyst (for example, a patent) have been developed. Literature 1~3). Therefore, 'although the adhesion performance of the above-mentioned adhesives is excellent, the use of the adhesive film of [£]- -6- 201012887 is used in the above method of removing the pores by the resin encapsulation step if the film is used for the hardening reaction rapidly, due to the resin The heating in the wire bonding step before the encapsulation step increases the film melt viscosity increase rate. Therefore, it is difficult to remove the voids in the resin encapsulation step. That is, as a result of the increase in the melt viscosity, the pore volume is not sufficiently reduced, and the pores cannot be absorbed into the resin. Accordingly, it has been difficult for the past adhesive to be sufficiently buried in the recessed portion on the substrate, and it is required to improve the embedding performance. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide an adhesive composition which is excellent not only in adhesion but also excellent in embedding property and heat resistance, and an adhesive sheet and a cut/adhesive crystal which are formed using the adhesive. film. [Means for Solving the Problem] The inventors of the present invention conducted various reviews on the composition of an adhesive containing an acrylic resin and an epoxy resin, and found that the following adhesive composition can be excellent compared with the past. The adhesive property is excellent in both heat resistance and good embedding performance. In other words, the first object of the present invention is to provide an adhesive composition comprising 201012887 (A) having a weight average molecular weight of 50,000 to 1,500,000 and containing a reaction to one or both of the following (B) and (C) components. a (meth)acrylic resin having a functional group, (B) an epoxy resin having a weight average molecular weight of 5,000 or less, and (C) an aromatic polyamine compound. A second object of the present invention is to provide a sheet for subsequent use comprising a substrate and a layer formed of the above-mentioned adhesive composition provided on the substrate. Further, even if the layer formed of the adhesive composition is peeled off from the substrate, the film shape is maintained at room temperature, that is, it corresponds to the film. A third object of the present invention is to provide a dicing paste-bonding film comprising a dicing film having a substrate and an adhesive layer disposed thereon, and the above-mentioned adhesive agent disposed on the adhesive layer of the dicing film The layer formed by the composition. [Effect of the Invention] The adhesive composition of the present invention has a melt viscosity which is caused by the heating of the ® in the wire bonding step, and has a melt viscosity which completely disappears in the resin encapsulation step, and since the pores can be easily completed It is removed and thus has excellent embedding properties. Further, the adhesive composition is cured by heating, and an adhesive cured layer having high adhesion to various substrates and having low modulus of elasticity and excellent heat resistance can be obtained. Accordingly, the adhesive composition can be used to manufacture a highly reliable semiconductor device. [Embodiment] -8 - 201012887 The present invention will be described in detail below. In the present specification, the "weight average molecular weight" means a weight average molecular weight measured by gel permeation chromatography (GPC) and converted into polystyrene. The adhesive composition of the present invention contains the above components (A) to (C), and since it has a shape at room temperature, for example, a film-like film can be formed, and on the other hand, it is made into a plastic state by heating, and further in this state. Time is saved, thereby achieving excellent embedding performance. The cured product of the composition has high adhesion to the base material while being low in modulus and having excellent heat resistance. [(A) (Meth)Acrylic Resin] The component (A) has a weight average molecular weight of 50,000 to 1,500,000 and contains a functional group reactive with one or both of the following (B) and (C) components. (meth)acrylic resin. The term "(meth)acrylic resin" as used herein means a polymer comprising a monomer unit of a (meth)acrylic fluorene monomer composed of a source of free acrylic acid, an acrylic acid derivative, a methacrylic acid, and a methacrylic acid derivative. . (A) The components may be used singly or in combination of two or more. When two or more types are used in combination, the component (A) may be a mixture of a (meth)acrylic resin containing the above functional group and a (meth)acrylic resin containing no such functional group. The component (A) may, for example, be a homopolymer or a copolymer of the above (meth)acrylic monomer or a copolymer of the (meth)acrylic monomer and another monomer, and have a weight average molecular weight of 50, 〇〇〇 a polymer of ~1,500,000 and having a functional group reactive with one or both of the following (B) and (C) components. In the copolymer of the (meth)acrylic monomer and the other monomer, the content of the monomer unit derived from the other monomer is -9 - 201012887 with respect to (A monomer unit, preferably 0 to 50 mol%, More preferably, the copolymer of the 0-methyl)acrylic monomer and the other monomer may be used alone or in combination of two or more. The above-mentioned acrylic acid derivative may, for example, be methyl acrylate, butyl acrylate or butyl acrylate. An alkyl acrylate such as an ester or a lauryl acrylate; a hydroxyalkyl acrylate such as hydroxyethyl acrylate; an acrylate such as benzyl acrylate; an acrylamide such as dimethyl acrylamide; 醯TO-1 492 ( Acrylate such as trade name, manufactured by Toagosei Co., Ltd.; glycidyl acrylate or the like containing epoxy: acrylonitrile. The methacrylic acid derivative may, for example, be ethyl methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauric methacrylate or hydroxyethyl methacrylate; And hydroxyalkyl hydroxy acrylate; aryl acrylate such as benzyl methacrylate; methyl quinone imine methacrylate such as dimethyl methacrylate The epoxy group-containing methyl acrylate such as glycidyl acrylate may, for example, be styrene or butyl acetyl (allyl alcohol, allyl acetate or the like). In a preferred embodiment of the invention, the total amount of the copolymer of the unit represented by the '(A) component: ) is 30% by mole. (The oxime esters of the monomers, ethyl hexyl acrylate, propylene, hydroxy aryl aromatic acrylates, acrylonitrile acrylates containing phthalimido-based acrylate methyl acrylate, isobutyl acrylate, Methyl@ aryl hydrocarbon group such as methacrylic acid propyl amide; acrylate; methacrylate. The olefin and allylic derivatives contain the following formula-10-201012887 [Chemical 1]
CN 該共聚物可藉由使用丙烯腈作爲單體而製造。該情況 下，丙烯腈之含量相對於總單體量較好爲1〜50莫耳％，更 好爲3〜40莫耳％，最好爲5〜30莫耳％。 (A )成份中之官能基就所得接著劑硬化物層之接著 性方面而言，以環氧基、羧基或其組合較佳。（A )成份 ® 中之官能基可例如藉由使用含有該官能基之單體作爲（A )成份之原料而使用之單體之至少一部份合成（A )成份 ，而導入（A)成份中。含有該官能基之單體可列舉例如 丙烯酸、甲基丙烯酸、含有環氧基之丙烯酸衍生物（例如 、丙烯酸縮水甘油酯）、含有環氧基之甲基丙烯酸衍生物 (例如，甲基丙烯酸縮水甘油酯），該等單體可單獨使用 一種亦可組合兩種以上使用。 (A)成份中之官能基含量，每100克之（A)成份 ❹ 較好爲0.002〜0.1莫耳，更好爲0.005〜0.05莫耳。該含量 在0.002〜0.1莫耳之範圍內時，可易於獲得具有充分埋入 性能之組成物及具有充分接著力之接著劑硬化物層。 (A )成份之重量平均分子量通常爲50,000〜1,500,000 ，較好爲 1 00,000〜1，〇〇〇,0〇〇。上述分子量若未達50,000 ，則有所得接著劑硬化物層之接著性強度降低之情況。上 述分子量若超過1，500,000，則有所得組合物之黏度過高 造成操作性變差之情況。 又，（A)成份之（甲基）丙烯酸系樹脂以熱機械分 -11 - 201012887 析（TMA)測疋之玻璃轉移點（Tg)較好爲_4〇。〇〜1〇〇。〇 ，更好爲-10〜70°c。 [(B)環氧樹脂] (B)成份爲重量平均分子量在5000以下，較好 150〜3000之環氧樹脂，且較好爲每一分子中具有至少兩個 環氧基者。上述分子量若超過5000，則（B)成份對（A )成份之溶解及分散任一方或二者變成不充分，而有兩成 φ 份分離之可能性。（B )成份可單獨使用—種亦可組合兩 種以上使用。 再者’使用本發明之接著劑組成物作爲接著用薄片時 ’尤其，所貼合之矽晶圓較薄時，爲能夠防止龜裂發生及 翹起，且可在更低溫及更低壓下壓著上述接著用薄片，（ B)成份較好在室溫下爲液狀，且以環球法（jis-K7234) 測定之軟化溫度爲1 〇〇 °C以下。 (B)成份可列舉例如雙（4 -羥基苯基）甲烷、2,2’- 參 雙（4_羥基苯基）丙烷或該等之鹵化物之二縮水甘油醚及 該等之聚縮合物（亦即雙酚F型環氧樹脂、雙酚A型環氧 樹脂等）：丁二烯二環氧化物、乙烯基環己烯二環氧化物 ;1,2-二羥基苯之二縮水甘油醚、間苯二酚之二縮水甘油 醚、1,4-雙（2,3-環氧基丙氧基）苯、4,4’-雙（2,3-環氧基 丙氧基）二苯基醚、1，4-雙（2,3-環氧基丙氧基）環己烯 等之二縮水甘油醚；雙（3,4-環氧基-6-甲基環己基甲基） 己二酸酯；使多價酚或多價醇與表氯醇縮合獲得之聚縮水 iS] -12- 201012887 甘油酯；使酚酚醛清漆、甲酚酚醛清漆等之酚醛清漆型酚 樹脂或鹵化之酚醛清漆型酚樹脂與表氯醇縮合獲得之環氧 基酚醛清漆（亦即，酚酚醛清漆型環氧樹脂、甲酚酚醛清 漆型環氧樹脂等之酚醛清漆型環氧樹脂）；以過氧化法環 氧化之環氧化聚烯烴或環氧化聚丁二烯；含有萘環之環氧 樹脂；聯苯型環氧樹脂；酚芳烷基型環氧樹脂；聯苯芳烷 基型環氧樹脂；環戊二烯型環氧樹脂等。 φ 作爲（B)成份，除上述之每一分子中具有至少兩個 環氧基之環氧樹脂以外，亦可適當的倂用單環氧化合物。 單環氧化合物可列舉例如苯乙烯環氧化物、環己烯環氧化 物、環氧丙烷、甲基縮水甘油醚、乙基縮水甘油醚、苯基 縮水甘油醚、烯丙基縮水甘油醚、環氧辛烷、環氧十二烷 等。 其中’以雙酚F型環氧樹脂、雙酚A型環氧樹脂、甲 酚酚醛清漆樹脂型環氧樹脂或其組合較佳。 φ (B)成份之調配量相對於1〇〇質量份之（A)成份較 好爲5~3 00質量份，更好爲1〇〜200質量份。使上述調配 量在5~300質量份之範圍內時，可容易地獲得具有充分埋 入性能之組成物，由該組成物獲得之接著劑硬化物層容易 成爲接著力優異’彈性率上升獲得抑制，且具有充分柔軟 性者。 [(C)芳香族多元胺化合物] (C)成份之芳香族多元胺化合物爲具有芳香環且具 -13- 201012887 有至少兩個直接鍵結於該芳香環之胺基之化合物，且具有 作爲環氧樹脂用硬化劑及觸媒之機能者。芳香族多元胺化 合物由於具有融點，且在打線接合步驟之加熱下爲固體， 因此含有芳香族多元胺化合物之組成物之硬化反應得以緩 慢進行。因此，該組成物可有效的抑制因加熱硬化造成之 熔融黏度上升。另外，使含有芳香族多元胺化合物之組成 物經加熱硬化獲得之硬化物之耐熱性優異。據此，包含（ C)成份之芳香族多元胺化合物之本發明組成物與過去者 馨 相比較’埋入性能被改善，且容易使硬化後之耐熱性變成 優異者。（C)成份可單獨一種使用亦可組合兩種以上使 用。 存在於（C)成份中之芳香環可爲芳香族烴環亦可爲 芳香族雜環。至於芳香族烴環可列舉例如苯環、萘環、蒽 環等。芳香族雜環可列舉例如吡啶環、喹啉環、異喹啉環 等。 (C)成份之芳香族多元胺化合物只要具有作爲環氧 參 樹脂用硬化劑及觸媒之機能即無特別限制，但就所得硬化 物之耐熱性觀點而言’以具有磺醯基之芳香族多元胺化合 物較佳。 (C )成份之具體例舉例爲間-苯二胺、對-苯二胺、 1，2-二胺基苯、4,4，-二胺基二苯基甲烷、2,2_雙（4_胺基 苯基）丙烷、雙（4-(4 -胺基苯氧基）苯基）楓、雙（4_ (3 -胺基苯氧基）苯基）碾、4,4’_二胺基二苯基丙院、 4,4’-二胺基二苯基亞楓、4,4，_二胺基二苯基颯、3,3，_二 t S 1 -14- 201012887 胺基二苯基楓、3，4’-二胺基二苯基醚、4,4’-二胺基二苯基 醚、4,4’-雙（4-胺基苯氧基）聯苯、2,6·二胺基吡啶、雙 (3-胺基苯基）二乙基矽烷、4,4’-二胺基二苯基二乙基矽 烷、聯苯胺、3，3’-二氯聯苯胺、3,3，-二甲氧基聯苯胺、 4,4’-二胺基二苯甲酮、N，N-雙（4-胺基苯基）-正丁基胺 、N，N-雙（4-胺基苯基）甲基胺、丨，5_二胺基萘、3,3’-二 甲基-4,4’ -二胺基聯苯、4 -胺基苯基-3-胺基苯甲酸酯、 φ Ν,Ν-雙（4-胺基苯基）苯胺、雙（對-点-胺基-第三丁基苯 基）醚、對-雙（2-甲基-4-胺基戊基）苯' 對-雙（i，l-二 甲基-5-胺基戊基）苯、（1,3-雙（4·胺基苯氧基））苯、 間·二甲苯二胺、對-二甲苯二胺、4,4’-二胺基二苯基醚氧 化膦、4,4’-二胺基二苯基Ν-甲基胺、4,4’·二胺基二苯基 Ν -苯基胺等。該等中，就所得硬化物之耐熱性之觀點而言 ，以具有磺醯基之芳香族多元胺化合物的4,4’-二胺基二 苯基颯及3,3’-二胺基二苯基颯等較佳。該等芳香族多元 φ 胺化合物爲公知作爲環氧樹脂硬化劑者，可使用市售品。 (C )成份之調配量較好爲（C )成份中之胺基相對於 本發明組成物中之全部環氧基之莫耳比成爲0.6〜1.4之量 ，更好成爲〇.8~ 1.2之量。於本發明組成物中調配上.述莫 耳比成爲〇.6〜1.4之量之（C)成份時，由於該組成物可 充分進行交聯，因此所得硬化物之硬化特性容易變得良好 ，且可有效地提升接著力及耐焊錫回焊性。另外，爲了使 (C)成份不易以未反應物殘留於該硬化物中而不會變成 浪費，故易於實現省資源化，而較經濟。 -15- 201012887 本發明之組成物中除（B)成份之環氧樹脂以外’由 於調配有含有環氧基作爲官能基之（A)成份及含有環氧 基之其他成份，故本發明組成物中之所謂全部環氧基意指 (B)成份中之環氧基，與含有環氧基作爲官能基之（A) 成份中之環氧基，及含有環氧基之其他成份中之環氧基之 合計。（B)成份中之環氧基與含有作爲官能基之環氧基 之（A)成份中之環氧基之合計，相對於本發明組成物中 之全部環氧基之莫耳比較好爲0.6〜1，更好爲0.8~1。另外 參 ，（B)成份中之環氧基相對於本發明組成物中之全部環 氧基之莫耳比較好爲0.6〜1，更好爲0.8~0.95。其中，本 發明組成物中，除（B)成份及含有環氧基作爲官能基之 (A)成份以外不含有具有環氧基之成份時，（C)成份之 調配量，較好爲使（C)成份中之胺基相對於（B)成份中 之環氧基與含有環氧基作爲官能基之（A)成份中之環氧 基之合計之莫耳比成爲0.6~1.4之量，更好成爲0.8〜1.2 之量。另外’本發明組成物中除（B)成份以外未含具有 參 環氧基之成份時，（C )成份之調配量，較好爲使（C )成 份中存在之胺基相對於（B)成份中存在之環氧基之莫耳 比成爲0.6〜1_4之量，更好爲成爲0.8〜1.2之量。 [其他成份] 本發明之組成物中，除上述（A)〜（C)成份以外， 在不損及本發明之接著劑組成物特性之範圍內亦可調配其 他成份。至於該其他成份可列舉例如（C )成份以外之觸 t S1 -16- 201012887 媒；（C)成份以外之硬化劑；塡充劑；接著助劑；顏料 、染料等著色劑；潤濕增進劑；抗氧化劑；熱安定劑等。 <(C)成份以外之觸媒> (C )成份以外之觸媒可使用慣用者，其實例可列舉 三苯基鱗等之磷系觸媒、2-苯基-4,5-二羥基甲基咪唑等之 咪唑系觸媒等。（C)成份以外之觸媒可單獨使用一種， φ 亦可兩種以上倂用。 < (C )成份以外之硬化劑> (C)成份以外之硬化劑並無特別限制，可使用過去 習知之各種者。該硬化劑可單獨使用一種，亦可依據該等 硬化劑之硬化性能等倂用兩種以上。至於該硬化劑可使用 過去習知之各種者，可列舉例如二伸乙基三胺、三伸乙基 四胺、二乙胺基丙基胺、N-胺基乙基哌嗪、雙（4-胺基-3-❹ 甲基環己基）甲烷、間二甲苯二胺、甲烷二胺、3,9-雙（ 3-胺基丙基）-2,4,8，10-四氧雜螺（5,5)十一烷等之（C) 成份以外之胺系化合物；環氧樹脂-二伸乙基三胺加成物 、胺-環氧乙烷加成物、氰基乙基化多元胺等之改質脂肪 族多元胺；雙酚A、三羥甲基烯丙氧基酚、低聚合度之酚 酚醛清漆樹脂、環氧化或丁基化之酚樹脂或 Super Beckcitel 001 (日本Reich Holding化學工業（股）製造 )、Hitanol 4010 ((日立製作所（股）製造）、Scado form L.9 (荷蘭 Scado Zwoll 公司製造）、Methyl on 75108 -17- 201012887 (美國奇異電子公司製造）等之以商品名知悉之酚樹脂等 中之分子中含有至少兩個酚性羥基之酚系樹脂； Beck amine P. 138 (日本 Reich Hoi ding 化學工業（股）製 造）、Meran (日立製作所（股）製造）、U-VanlOR (東 洋高壓工業（股）製造）等之以商品名知悉之碳樹脂；三 聚氰胺樹脂、苯胺樹脂等之胺基樹脂；以式： HS(C2H4OCH2OCH2OC2H4SS)LC2H4OCH2OC2H4SH (式中， L=1〜10之整數）表示之聚硫醚樹脂等之一分子中具有至 少兩個锍基之聚硫醚樹脂；苯二甲酸酐、六氫苯二甲酸酐 、四氫苯二甲酸酐、均苯四酸酐、甲基耐地酸、十二烷基 琥珀酸酐、氯菌酸酐等之有機酸或其酐（酸酐）等。該等 中，由於酚系樹脂（尤其是酚酚醛清漆樹脂）可對所得組 成物賦予良好成形作業性且可對所得硬化物層賦予優異之 耐濕性，且沒有毒性、比較便宜，因此較適宜。 使用（C)成份以外之硬化劑時，其使用量相對於 100質量份之（B)成份之環氧樹脂，較好爲0.1 ~50質量 份。該使用量在0.1〜50質量份之範圍內時，所得接著劑 組成物易成爲埋入性能良好者。 <塡充劑> 本發明組成物中亦可調配塡充劑。塡充劑並無特別限 制，可使用習知者。塡充劑可單獨使用一種亦可組合兩種 以上使用。塡充劑之調配量相對於（A)〜（C)成份之合 計100質量份，較好爲0-9 00質量份，更好爲〇〜5 00質量 201012887 份。 至於塡充劑可列舉例如二氧化矽微粉末、氧化鋁、氧 化鈦、碳黑、銀粒子等其他導電性粒子等之無機系塡充劑 ;聚矽氧微粒子等之有機系塡充劑。該等中，以二氧化矽 微粉末、聚矽氧微粒子較佳。以下針對二氧化矽微粒子及 聚矽氧微粒子更詳細說明。CN The copolymer can be produced by using acrylonitrile as a monomer. In this case, the content of acrylonitrile is preferably from 1 to 50 mol%, more preferably from 3 to 40 mol%, most preferably from 5 to 30 mol%, based on the total monomer. The functional group in the component (A) is preferably an epoxy group, a carboxyl group or a combination thereof in terms of the adhesion of the resulting cured layer of the adhesive. The functional group in the component (A) can be synthesized by, for example, synthesizing the component (A) by using at least a part of the monomer used as the raw material of the component (A), and introducing the component (A). in. Examples of the monomer containing the functional group include acrylic acid, methacrylic acid, an epoxy group-containing acrylic acid derivative (for example, glycidyl acrylate), and an epoxy group-containing methacrylic acid derivative (for example, methacrylic acid shrinkage). Glyceride), these monomers may be used alone or in combination of two or more. The content of the functional group in the component (A) is preferably from 0.002 to 0.1 mol per 100 g of the component (A), more preferably from 0.005 to 0.05 mol. When the content is in the range of 0.002 to 0.1 mol, a composition having sufficient embedding property and an adhesive hardened layer having sufficient adhesion can be easily obtained. The weight average molecular weight of the component (A) is usually from 50,000 to 1,500,000, preferably from 1,00,000 to 1, 〇〇〇, 0 〇〇. If the molecular weight is less than 50,000, the adhesive strength of the obtained cured layer of the adhesive may be lowered. When the molecular weight exceeds 1,500,000, the viscosity of the resulting composition is too high, resulting in deterioration of workability. Further, the glass transition point (Tg) of the (meth)acrylic resin of the component (A) measured by thermomechanical -11 - 201012887 (TMA) is preferably _4 Å. 〇~1〇〇. Oh, better for -10~70°c. [(B) Epoxy Resin] The component (B) is an epoxy resin having a weight average molecular weight of 5,000 or less, preferably 150 to 3,000, and preferably at least two epoxy groups per molecule. When the above molecular weight exceeds 5,000, either or both of the (B) component is insufficient for the dissolution and dispersion of the component (A), and there is a possibility that two parts of φ are separated. (B) The components may be used singly or in combination of two or more. In addition, when the adhesive composition of the present invention is used as a sheet for subsequent use, in particular, when the bonded wafer is thin, cracks can be prevented from occurring and lifted, and the laminate can be pressed at a lower temperature and a lower pressure. The above-mentioned subsequent sheet is used, and the component (B) is preferably liquid at room temperature, and the softening temperature measured by the ring and ball method (jis-K7234) is 1 〇〇 ° C or less. The component (B) may, for example, be bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)propane or a diglycidyl ether of such a halide and the like. (ie bisphenol F type epoxy resin, bisphenol A type epoxy resin, etc.): butadiene diepoxide, vinyl cyclohexene diepoxide; 1,2-dihydroxybenzene diglycidyl Ether, diglycidyl ether of resorcinol, 1,4-bis(2,3-epoxypropoxy)benzene, 4,4'-bis(2,3-epoxypropoxy)di a diglycidyl ether of phenyl ether, 1,4-bis(2,3-epoxypropoxy)cyclohexene or the like; bis(3,4-epoxy-6-methylcyclohexylmethyl) An adipate; a polycondensation water obtained by condensing a polyvalent phenol or a polyvalent alcohol with epichlorohydrin iS] -12- 201012887 glyceride; a novolak type phenol resin such as a phenol novolak or a cresol novolak or halogenated An epoxy phenol novolak obtained by condensing a novolac type phenol resin with epichlorohydrin (that is, a novolak type epoxy resin such as a phenol novolak type epoxy resin or a cresol novolak type epoxy resin); Epoxidized epoxy Polyolefin or epoxidized polybutadiene; epoxy resin containing naphthalene ring; biphenyl type epoxy resin; phenol aralkyl type epoxy resin; biphenyl aralkyl type epoxy resin; cyclopentadiene type Epoxy resin, etc. φ As the component (B), a monoepoxy compound may be appropriately used in addition to the epoxy resin having at least two epoxy groups in each of the above molecules. Examples of the monoepoxy compound include a styrene epoxide, a cyclohexene epoxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, and a ring. Oxyoctane, epoxy dodecane, and the like. Among them, bisphenol F type epoxy resin, bisphenol A type epoxy resin, cresol novolac resin type epoxy resin or a combination thereof is preferred. The amount of the φ (B) component is preferably from 5 to 300 parts by mass, more preferably from 1 to 200 parts by mass, per part by mass of the component (A). When the amount of the above-mentioned compounding amount is in the range of 5 to 300 parts by mass, a composition having sufficient embedding property can be easily obtained, and the cured layer of the adhesive obtained from the composition is likely to be excellent in adhesion, and the increase in modulus of elasticity is suppressed. And have sufficient flexibility. [(C) Aromatic Polyamine Compound] The aromatic polyamine compound of the component (C) is a compound having an aromatic ring and having at least two amine groups directly bonded to the aromatic ring in the range of -13 to 201012887, and having Hardener and epoxy resin for epoxy resin. Since the aromatic polyamine compound has a melting point and is solid under heating by the wire bonding step, the hardening reaction of the composition containing the aromatic polyamine compound is gradually progressed. Therefore, the composition can effectively suppress the increase in the melt viscosity due to heat hardening. Further, the cured product obtained by heat-hardening the composition containing the aromatic polyamine compound is excellent in heat resistance. According to this, the composition of the present invention containing the aromatic polyamine compound of the component (C) is improved in embedding performance as compared with the past, and it is easy to make the heat resistance after hardening excellent. The component (C) may be used alone or in combination of two or more. The aromatic ring present in the component (C) may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The aromatic hydrocarbon ring may, for example, be a benzene ring, a naphthalene ring or an anthracene ring. The aromatic heterocyclic ring may, for example, be a pyridine ring, a quinoline ring or an isoquinoline ring. The aromatic polyamine compound of the component (C) is not particularly limited as long as it has a function as a curing agent and a catalyst for the epoxy resin, but it has an aromatic group having a sulfonyl group from the viewpoint of heat resistance of the obtained cured product. Polyamine compounds are preferred. Specific examples of the component (C) are m-phenylenediamine, p-phenylenediamine, 1,2-diaminobenzene, 4,4,-diaminodiphenylmethane, 2,2_bis (4) _Aminophenyl)propane, bis(4-(4-aminophenoxy)phenyl) maple, bis(4-(3-aminophenoxy)phenyl), 4,4'-diamine Diphenylpropanoid, 4,4'-diaminodiphenyl sulfite, 4,4,-diaminodiphenyl fluorene, 3,3,_di t S 1 -14- 201012887 Amino Phenyl maple, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 2, 6. Diaminopyridine, bis(3-aminophenyl)diethyldecane, 4,4'-diaminodiphenyldiethyldecane, benzidine, 3,3'-dichlorobenzidine, 3,3,-dimethoxybenzidine, 4,4'-diaminobenzophenone, N,N-bis(4-aminophenyl)-n-butylamine, N,N-double ( 4-aminophenyl)methylamine, anthracene, 5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4-aminophenyl-3-amine Benzoate, φ Ν, Ν-bis(4-aminophenyl)aniline, bis(p-dod-amino-tert-butylphenyl) ether, p-Bis(2-methyl-4-aminopentyl)benzene 'p-bis(i,l-dimethyl-5-aminopentyl)benzene, (1,3-bis(4.amino) Phenoxy))benzene, m-xylenediamine, p-xylenediamine, 4,4'-diaminodiphenyl ether phosphine oxide, 4,4'-diaminodiphenylfluorene-A Alkylamine, 4,4'-diaminodiphenylanthracene-phenylamine, and the like. Among these, 4,4'-diaminodiphenylanthracene and 3,3'-diaminodiyl group having an aromatic polyamine compound having a sulfonyl group, from the viewpoint of heat resistance of the obtained cured product Phenylhydrazine or the like is preferred. These aromatic polyvalent φ amine compounds are known as epoxy resin hardeners, and commercially available products can be used. The amount of the component (C) is preferably such that the molar ratio of the amine group in the component (C) to the total epoxy group in the composition of the present invention is from 0.6 to 1.4, more preferably 〇.8 to 1.2. the amount. When the component (C) having a molar ratio of from 66 to 1.4 is blended in the composition of the present invention, since the composition can be sufficiently crosslinked, the cured property of the obtained cured product tends to be good. And can effectively improve the adhesion and solder reflow resistance. Further, in order to make it difficult for the component (C) to remain as an unreacted material in the cured product without being wasteful, it is easy to realize resource saving and economical. -15- 201012887 In the composition of the present invention, in addition to the epoxy resin of the component (B), the composition of the present invention is composed of the component (A) containing an epoxy group as a functional group and other components containing an epoxy group. The term "all epoxy groups" means an epoxy group in the component (B), an epoxy group in the component (A) containing an epoxy group as a functional group, and an epoxy group in other components containing an epoxy group. The sum of the bases. The total of the epoxy groups in the component (B) and the epoxy group in the component (A) containing the epoxy group as the functional group is preferably 0.6 with respect to all the epoxy groups in the composition of the present invention. ~1, preferably 0.8~1. Further, the epoxy group in the component (B) is preferably 0.6 to 1, more preferably 0.8 to 0.95, based on the total of the epoxy groups in the composition of the present invention. In the composition of the present invention, when the component (B) and the component containing the epoxy group as the functional group (A) do not contain a component having an epoxy group, the compounding amount of the component (C) is preferably such that The molar ratio of the amine group in the component to the total of the epoxy group in the component (B) and the epoxy group in the component (A) having the epoxy group as a functional group is 0.6 to 1.4, more Good to be 0.8 to 1.2. Further, when the composition of the present invention contains no component having a cyclooxy group other than the component (B), the amount of the component (C) is preferably such that the amine group present in the component (C) is relative to (B) The molar ratio of the epoxy group present in the component is from 0.6 to 1-4, more preferably from 0.8 to 1.2. [Other components] In the composition of the present invention, in addition to the above components (A) to (C), other components may be blended within a range not detracting from the characteristics of the adhesive composition of the present invention. As the other component, for example, a touch other than the component (C), a hardener other than the component (C); a hydrazine; a auxiliaries; a colorant such as a pigment or a dye; a wetting improver; ; antioxidants; thermal stabilizers, etc. <Catalyst other than the component (C)> The catalyst other than the component (C) can be used as a catalyst, and examples thereof include a phosphorus-based catalyst such as triphenyl scale, and 2-phenyl-4,5-di. An imidazole-based catalyst such as hydroxymethylimidazole. The catalyst other than the component (C) may be used alone or in combination of two or more. <(C) Hardener other than the component (C) The hardener other than the component (C) is not particularly limited, and any of the conventional ones can be used. The curing agent may be used singly or in combination of two or more kinds depending on the hardening properties of the curing agents. As the hardener, various conventionally used ones may be used, and examples thereof include di-ethyltriamine, tri-ethylidenetetraamine, diethylaminopropylamine, N-aminoethylpiperazine, and bis(4- Amino-3-indolylmethylcyclohexyl)methane, m-xylylenediamine, methanediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro 5,5) an amine compound other than the component (C) such as undecane; an epoxy resin-diethylidene triamine adduct, an amine-ethylene oxide adduct, and a cyanoethylated polyamine Such as modified aliphatic polyamine; bisphenol A, trimethylol allyloxyphenol, low polymerization degree phenol novolac resin, epoxidized or butylated phenol resin or Super Beckcitel 001 (Japan Reich Holding Chemical Industrial (stock) manufacturing), Hitanol 4010 (made by Hitachi, Ltd.), Scado form L.9 (made by Scado Zwoll, the Netherlands), Methyl on 75108 -17- 201012887 (made by American Singular Electronics Co., Ltd.) a phenolic resin containing at least two phenolic hydroxyl groups in a molecule such as a phenol resin; Beck amine P. 138 (Reich Hoi ding Chemical Co., Ltd., Japan) (manufactured by Hitachi, Ltd.), a carbon resin known by the name of Meran (manufactured by Hitachi, Ltd.), U-VanlOR (manufactured by Toyo Kogyo Co., Ltd.), and an amine-based resin such as melamine resin or aniline resin; Formula: HS(C2H4OCH2OCH2OC2H4SS) LC2H4OCH2OC2H4SH (wherein, an integer of L = 1 to 10) represents a polythioether resin having at least two mercapto groups in one molecule such as a polythioether resin; phthalic anhydride, hexahydrobenzene An organic acid such as dicarboxylic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl acid acid, dodecyl succinic anhydride or chloric anhydride or an anhydride thereof (anhydride), etc. The resin (especially the phenol novolak resin) can provide good moldability to the obtained composition, and can impart excellent moisture resistance to the obtained cured layer, and is not toxic and relatively inexpensive, and therefore is preferable. When the amount of the curing agent other than the curing agent is 0.1 to 50 parts by mass based on 100 parts by mass of the epoxy resin of the component (B), the resulting adhesive agent is used in an amount of 0.1 to 50 parts by mass. Composition In the composition of the present invention, the chelating agent may be formulated. The chelating agent is not particularly limited, and a conventional one may be used. The chelating agent may be used alone or in combination. The compounding amount of the chelating agent is preferably from 0 to 00 parts by mass, more preferably from 〇 to 50,000 by mass, of 201012887 parts, based on 100 parts by mass of the total of the components (A) to (C). Examples of the chelating agent include inorganic ruthenium agents such as cerium oxide micropowder, alumina, titanium oxide, carbon black, and silver particles; and organic ruthenium agents such as polyfluorene fine particles. Among these, cerium oxide micropowder and polythene oxide fine particles are preferred. The following is a more detailed description of the cerium oxide microparticles and the polythene oxide microparticles.
•二氧化矽微粉末• cerium oxide micropowder
物所成之層的熔融黏度，可抑制於樹脂封裝步驟中晶片流 動，降低所得接著劑硬化物層之吸水率及線膨脹率。二氧 化矽微粉末並無特別限制，可使用習知者。二氧化矽微粉 末就所得組成物之流動性方面而言，較好爲經有機烷氧基 矽烷、有機氯矽烷、有機矽氮烷、低分子量矽氧烷等有機 矽化合物等進行表面處理者。二氧化矽微粉末可單獨使用 @ —種亦可組合兩種以上使用。 二氧化矽微粒子之平均粒徑較好爲10//m以下，更好 爲5/zm以下。該平均粒徑在10/zni以下時，本發明之接 著用薄片容易維持表面平滑性。另外，二氧化矽微粉末之 最大粒徑較好爲20/xm以下。再者，本說明書中所謂「平 均粒徑」係指使用雷射光繞射法，藉由粒度分佈測定裝置 求得相當於累積分佈之50%之體積基準之平均粒徑。另外 ’所謂「最大粒徑」爲求得上述平均粒徑時所測定的累積 分佈中粒徑之最大値。 -19- 201012887 二氧化矽微粉末可列舉例如發煙二氧化矽、沉降性二 氧化矽等補強性二氧化矽；石英等結晶性二氧化矽。具體 而言例示爲日本Aerosil公司製造之Aerosil R972、R974 、R976; ADOMA技術（股）公司製造之SE-2050、SC-2050 、 SE-1050 、 SO-E1 、 SO-C1 、 SO-E2 ' SO-C2 、 SO-E3 、SO-C3、SO-E5、SO-C5;信越化學工業公司製造之 Musil 120A、Musil 130A 等。 二氧化矽微粉末之調配量較好係一方面將塡充劑整體 @ 之調配量調整在上述範圍內，另一方面爲組成物總質量之 5〜80質量％，最好爲10〜60質量％。上述調配量在5〜80 質量％之範圍內時，可有效地降低所得接著劑硬化物層之 吸水率及線膨脹率，又，容易抑制彈性率上升。 •聚矽氧微粒子 聚矽氧微粒子較好藉由與上述二氧化矽微粉末倂用， 使所得接著劑硬化物層之彈性率及吸水率降低。聚矽氧微 參 粒子並沒有特別限制，可使用習知者，可列舉例如，聚矽 氧橡膠微粒子、聚矽氧樹脂微粒子等。聚矽氧微粒子可單 獨使用一種亦可組合兩種以上使用。 聚矽氧微粒子之平均粒徑較好爲0.1〜l〇；zm，更好爲 0_5〜5a m。該平均粒徑在0.1-10# m之範圍內時，容易維 持本發明之接著用薄片之平滑性。另外，聚矽氧微粒子之 最大粒徑較好爲20//m以下，更好爲10gm以下。 至於聚矽氧微粒子以複合聚矽氧橡膠微粒子較佳。複 t S3 -20- 201012887 合聚矽氧橡膠微粒子爲在聚矽氧橡膠微粒子表面上之至少 一部份，以藉由在該表面上之聚合反應所生成之聚有機倍 半砂氧院樹脂之微小體存在之粒子。複合聚砂氧橡膠微粒 子爲例如可依據特開平7- 1 96 8 1 5號公報中所述之方法製 備者。亦即，於平均粒徑0.1〜10/zm之球狀聚矽氧橡膠微 粒子之水性分散液中，直接添加鹼性物質或添加其鹼性水 溶液與有機三烷氧基矽烷，在球狀聚矽氧橡膠微粒子之表 φ 面上，使有機三烷氧基矽烷水解並聚合，接著使之乾燥， 獲得複合聚矽氧橡膠微粒子。聚有機倍半矽氧烷樹脂之含 量相對於100質量份之球狀聚矽氧橡膠微粒子，以1~500 質量份較佳，更好爲2〜100質量份。該含量在1〜500質量 份時，複合聚矽氧橡膠微粒子在所得接著劑組成物中之分 散性易變得良好，且可容易地獲得組成均勻之接著用薄片 。又，易於成爲所得硬化物層之彈性率上升受到抑制者。 複合聚矽氧橡膠微粒子可使用例如信越化學工業公司 φ 製造之 KMP-600、KMP-605、X-52-7030 等。 聚矽氧微粒子之調配量較好爲一方面將塡充劑全部之 調配量調整在上述範圍內，一方面成爲組成物總質量之 5~30質量％，且更好成爲10〜20質量％。上述調配量在 5〜30質量％之範圍內時，所得接著劑硬化物層之彈性率及 吸水率可被有效地降低，又，容易抑制線膨脹率之增加、 強度之下降。 <接著助劑> -21 - 201012887 本發明之組成物中，爲了提升接著性，亦可添加接著 助劑。接著助劑可單獨使用一種，亦可組合兩種以上使用 。至於接著助劑可使用例如含矽之偶合劑（矽烷偶合劑） 。接著助劑之例可舉例爲商品名爲信越化學工業公司製造 之 ΚΒΜ-403、ΚΒΜ-402、ΚΒΜ-803、KBM-8 02、KBM-903 、KBM-902、KBM-503、KBM5103 或者 X-12-414，或者 該等之部份水解物等。 [組成物之調製] 本發明之接著劑組成物可藉由以慣用之混合手段在室 溫下混合上述（A) ~(C)成份及視需要之其他成份而調 製。 [組成物之用途] 本發明之接著劑組成物可用於接著兩種被接著物。該 等被接著物並無特別限制，但作爲一被接著物可列舉例如 @ 矽晶片、玻璃、陶磁等。另一被接著物可列舉例如ΒΤ基 板等之樹脂基板；由金、銀、銅、鎳等所構成之導線框基 板；矽基板。 例如，以適當濃度將本發明之接著劑組成物溶解於溶 劑中且塗佈於一被接著物上，經乾燥後，將另一被接著物 壓著於塗佈有該接著劑組成物之該被接著物表面上，且使 該接著劑組成物加熱硬化，可使該等二個被接著物接著在 —起。上述溶劑可列舉例如甲基乙基酮、甲苯、環己酮、 1 S3 -22- 201012887 N-甲基吡咯啶酮（NMP )等之非質子性極性溶劑。乾燥係 在室溫至200°C ’尤其是在80〜150°C下進行1分鐘〜1小 時，特別是3至10分鐘較佳。壓著以在〇.〇1〜10MPa，特 別是 0.05~2MPa之壓力下進行較佳。加熱硬化以在 100〜200°C，尤其是在120〜180°C之溫度下進行30分鐘〜8 小時，尤其是1〜7小時較佳。 另外，本發明之接著劑組成物亦可在成形成薄膜之狀 φ 態下用於二個被接著物之接著。例如，可使用具備有基材 與設置於該基材上之由本發明之接著劑組成物所成之層（ 以下有時稱爲接著劑組成物層）之接著用薄片，使上述二 個被接著物接著。更具體而言，例如，可自該接著用薄片 剝離該接著劑組成物層，且將該接著劑組成物層以層狀夾 在二個被接著物之間並經壓著加熱硬化，使該二個被接著 物接著。壓著及加熱硬化之條件係與上述相同。 上述接著用薄片可藉由將本發明之接著劑組成物以與 參 上述相同之適當濃度溶解於溶劑中，且塗佈於基材上並經 乾燥’形成接著劑組成物層而獲得。溶劑之例及乾燥條件 係與上述相同。接著劑組成物層之膜厚並無特別限制，可 依據目的選擇，但以10〜500/zm較佳，最好爲15〜lOOym 。上述基材通常爲薄膜狀，例如聚乙烯薄膜、聚丙烯薄膜 、聚酯薄膜、聚醯胺薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺 薄膜、聚醚醯亞胺薄膜、聚四氟乙烯薄膜、紙、金屬箔等 基材’或可使用表面經脫模處理之上述基材。上述基材之 厚度較好爲10〜l〇〇#m，更好爲25~50ym。 -23- 201012887 半導體製造之領域中’由本發明之接著劑組成物所成 之層（接著劑薄膜）可作爲將矽晶片接著於基板上之所謂 的固晶薄膜使用。使用該接著薄膜將矽晶片固晶於基板上 之後’經歷打線接合步驟及封裝步驟製造半導體裝置時， 固晶後未埋入之部份’在該接著薄膜硬化獲得之接著劑硬 化物層與基板之間之接著力將因打線接合步驟中之加熱而 下降。上述未埋入之部份在打線接合步驟之後將藉封裝步 驟而埋入。爲了使如此般經樹脂封裝之半導體裝置具有信 參 賴性’即使於該接著劑硬化物層與基板之間有接著力下降 之部份’但整體維持足夠之接著力仍屬必要。據此成爲必 要之接著力在26〇°C下測定時，通常至少爲lMPa。據此， 在打線接合步驟之加熱條件下將以層狀挾持在矽晶片與基 板之組合等之二個被接著物間之接著薄膜加熱後，以半導 體封裝樹脂在封裝步驟中之加熱/加壓條件下熱壓著，再 經加熱硬化成爲層狀之硬化物（接著劑硬化物層）之後， 在260°C下測定該二個被接著物間之剪切接著力時，該剪 ❹ 切接著力通常至少爲1 MPa。打線接合步驟之加熱條件有 各種條件，但通常爲在17〇t下30分鐘以上。另外，以上 述半導體封裝樹脂之封裝步驟中之加熱/加壓條件通常爲 在160〜180°C/5〜lOMPa下10~150秒之間。加熱硬化之條 件係與上述相同。 本發明之接著劑組成物可用於本發明之切割·黏晶接 著薄膜中。亦即，本發明之切割•黏晶接著薄膜爲具備具 有基材及設於其上之黏著劑層之切割薄膜，與設置於該切 ί S] -24- 201012887 割薄膜之黏著劑層之上之由本發明之接著劑組成物所成之 層之切割·黏晶接著薄膜。上述基材通常爲薄膜狀，可使 用例如聚四氟乙烯（PTFE )薄膜、聚對苯二甲酸乙二酯（ PET)薄膜、聚乙烯（PE)薄膜、聚丙烯（PP)薄膜、聚 醯亞胺薄膜、該等經改質之塑膠薄膜。上述基材之厚度較 好爲60~500# m，更好爲80~200//m。形成上述黏著劑層 之黏著劑可列舉例如感壓黏著劑、紫外線照射前維持黏著 φ 力，且藉由照射紫外線使黏著力下降之黏著劑等。上述黏 著劑層之厚度較好爲2~10ym，更好爲5〜10ym。 本發明之切割•黏晶接著薄膜可藉由例如於切割薄膜 之黏著劑層上層合本發明之接著用薄片中之接著劑組成物 層而製造。另外，可藉由使本發明之接著劑組成物以與上 述相同之適當濃度溶解於溶劑中且塗佈於切割薄膜之黏著 劑層上並經乾燥，形成接著劑組成物層而得。溶劑之例、 乾燥條件及接著劑組成物層之膜厚係與上述相同。切割薄 φ 膜可使用例如感壓類型之切割薄膜、紫外線硬化類型之切 割薄膜。 本發明之接著劑組成物不僅可用於半導體裝置等之電 子零件製造中，亦可用於包含接著步驟之各種製品之製造 中，例如LED零件 '感應器、液晶零件等之製造。 [實施例] 以下，藉由實施例及比較例進一步說明本發明，但本 發明並不受該等實施例之限制。 -25- 201012887 [接著劑組成物之調製] 將下列（A )〜（D )成份及其他成份依表1所示之調 配量（質量份）饋入自轉•公轉方式之混合機（THIN KY (股）製造）中，接著，添加甲基乙基酮、甲苯或環己嗣 以使該等成份之合計濃度成爲20質量％，經混合調製接著 劑組成物。 (A)(甲基）丙烯酸系樹脂 .SG-P3:具有環氧基之丙嫌腈系樹脂（NAGASE CHEMTEX公司製造），含有0.021莫耳/100克之環氧基 ，Tg=12°C，重量平均分子量=85萬。The melt viscosity of the layer formed by the object suppresses the flow of the wafer in the resin encapsulation step, and reduces the water absorption rate and the linear expansion ratio of the obtained cured layer of the adhesive. The fine powder of cerium oxide is not particularly limited, and those skilled in the art can be used. The cerium oxide fine powder is preferably subjected to surface treatment with respect to the fluidity of the obtained composition, such as an organic alkoxy decane, an organic chlorodecane, an organic decane, or an organic ruthenium compound such as a low molecular weight siloxane. The cerium oxide micropowder can be used alone or in combination of two or more. The average particle diameter of the cerium oxide microparticles is preferably 10/m or less, more preferably 5/zm or less. When the average particle diameter is 10/zni or less, the subsequent sheet of the present invention easily maintains surface smoothness. Further, the maximum particle diameter of the ceria fine powder is preferably 20/xm or less. In the present specification, the "average particle diameter" means an average particle diameter corresponding to a volume basis of 50% of the cumulative distribution by a particle size distribution measuring apparatus using a laser light diffraction method. Further, the "maximum particle diameter" is the maximum 粒径 of the particle diameter in the cumulative distribution measured when the average particle diameter is obtained. -19- 201012887 The cerium oxide micropowder may, for example, be a reinforcing cerium oxide such as fumed cerium oxide or sedimentary cerium oxide; or crystalline cerium oxide such as quartz. Specifically, it is exemplified by Aerosil R972, R974, and R976 manufactured by Japan Aerosil Co., Ltd.; SE-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO-E2 'SO manufactured by ADOMA Technology Co., Ltd. -C2, SO-E3, SO-C3, SO-E5, SO-C5; Musil 120A, Musil 130A, etc. manufactured by Shin-Etsu Chemical Co., Ltd. The amount of the fine powder of the cerium oxide is preferably adjusted to the above range on the one hand, and 5 to 80% by mass, preferably 10 to 60% by mass of the total mass of the composition on the other hand. %. When the amount of the above compound is in the range of 5 to 80% by mass, the water absorption ratio and the coefficient of linear expansion of the obtained cured layer of the adhesive can be effectively lowered, and the increase in the modulus of elasticity can be easily suppressed. • Polyoxynene fine particles The polyoxynene fine particles are preferably used in combination with the above-mentioned ceria micropowder to reduce the modulus of elasticity and water absorption of the resulting cured layer of the adhesive. The polyoxymethylene microparticles are not particularly limited, and those skilled in the art can be used, and examples thereof include polyoxyphthalocide fine particles and polyoxynoxy resin fine particles. The polyoxynene fine particles may be used singly or in combination of two or more. The average particle diameter of the polyoxynene fine particles is preferably 0.1 to 1 Torr; zm, more preferably 0 to 5 to 5 mA. When the average particle diameter is in the range of 0.1 to 10 m, the smoothness of the sheet for subsequent use of the present invention can be easily maintained. Further, the maximum particle diameter of the polyoxynene fine particles is preferably 20/m or less, more preferably 10 gm or less. As for the polyoxynene fine particles, the composite polyoxyxene rubber fine particles are preferred. Complex t S3 -20- 201012887 The polyoxyxene rubber microparticles are at least a part of the surface of the polyoxyxene rubber microparticles, and the polyorganic sesquifer oxide resin formed by the polymerization reaction on the surface Particles in which tiny bodies are present. The composite polyaerte rubber fine particles are prepared, for example, by the method described in Japanese Laid-Open Patent Publication No. Hei 7-96 8 1 5 . That is, in an aqueous dispersion of spherical polyoxynized rubber fine particles having an average particle diameter of 0.1 to 10/zm, a basic substance or an alkaline aqueous solution and an organic trialkoxy decane are added directly to the spherical polyfluorene. On the φ surface of the oxy rubber fine particles, the organotrialkoxydecane is hydrolyzed and polymerized, followed by drying to obtain composite polyoxyxene rubber fine particles. The content of the polyorganosilsesquioxane resin is preferably from 1 to 500 parts by mass, more preferably from 2 to 100 parts by mass, per 100 parts by mass of the spherical polyoxyxene rubber fine particles. When the content is from 1 to 500 parts by mass, the dispersibility of the composite polyoxyxene rubber fine particles in the obtained adhesive composition tends to be good, and a sheet having a uniform composition can be easily obtained. Moreover, it is easy to suppress the increase in the elastic modulus of the obtained cured layer. For the composite polyoxyethylene rubber fine particles, for example, KMP-600, KMP-605, X-52-7030, etc. manufactured by Shin-Etsu Chemical Co., Ltd. φ can be used. The blending amount of the polyoxynene fine particles is preferably such that the total amount of the chelating agent is adjusted within the above range, and on the other hand, it is 5 to 30% by mass, and more preferably 10 to 20% by mass based on the total mass of the composition. When the compounding amount is in the range of 5 to 30% by mass, the elastic modulus and water absorption of the obtained cured layer of the adhesive can be effectively lowered, and the increase in the linear expansion ratio and the decrease in strength are easily suppressed. <Adjunct aid> -21 - 201012887 In the composition of the present invention, in order to improve the adhesion, a further auxiliary agent may be added. Then, the auxiliary agents may be used alone or in combination of two or more. As the auxiliary agent, for example, a coupling agent containing ruthenium (a decane coupling agent) can be used. Examples of the auxiliary agent can be exemplified by ΚΒΜ-403, ΚΒΜ-402, ΚΒΜ-803, KBM-8 02, KBM-903, KBM-902, KBM-503, KBM5103 or X- manufactured by Shin-Etsu Chemical Co., Ltd. 12-414, or a portion of the hydrolyzate, etc. [Preparation of Composition] The adhesive composition of the present invention can be prepared by mixing the above components (A) to (C) and other components as needed at room temperature by a conventional mixing means. [Use of Composition] The adhesive composition of the present invention can be used for the following two kinds of substrates. The material to be attached is not particularly limited, but examples of the material to be attached include, for example, @矽 wafer, glass, ceramic, and the like. The other substrate may, for example, be a resin substrate such as a ruthenium substrate; a lead frame substrate made of gold, silver, copper, nickel or the like; or a tantalum substrate. For example, the adhesive composition of the present invention is dissolved in a solvent at an appropriate concentration and applied to an adherend, and after drying, another adherend is pressed against the composition coated with the adhesive. On the surface of the substrate, and the adhesive composition is heat-hardened, the two substrates can be brought together. The solvent may, for example, be an aprotic polar solvent such as methyl ethyl ketone, toluene, cyclohexanone or 1 S3 -22-201012887 N-methylpyrrolidone (NMP). The drying is preferably carried out at room temperature to 200 ° C ', especially at 80 to 150 ° C for 1 minute to 1 hour, particularly 3 to 10 minutes. The pressing is preferably carried out under a pressure of 〜1〇10 MPa, particularly 0.05~2 MPa. The heat curing is carried out at a temperature of from 100 to 200 ° C, especially at a temperature of from 120 to 180 ° C for from 30 minutes to 8 hours, particularly preferably from 1 to 7 hours. Further, the adhesive composition of the present invention may be used in the form of a film to form a film in the φ state for subsequent use of the two substrates. For example, a sheet having a substrate and a layer formed of the adhesive composition of the present invention (hereinafter sometimes referred to as an adhesive composition layer) provided on the substrate may be used, so that the two are followed. Things go on. More specifically, for example, the adhesive composition layer may be peeled off from the subsequent sheet, and the adhesive composition layer is sandwiched between the two substrates by pressing and hardened by pressing heat. The two are followed by the next. The conditions of pressing and heat hardening are the same as described above. The above-mentioned subsequent sheet can be obtained by dissolving the adhesive composition of the present invention in a solvent at a suitable concentration as described above, and applying it to a substrate and drying to form an adhesive composition layer. Examples of the solvent and drying conditions are the same as above. The film thickness of the subsequent composition layer is not particularly limited and may be selected according to the purpose, but is preferably 10 to 500 / zm, more preferably 15 to 100 μm. The above substrate is usually in the form of a film, such as a polyethylene film, a polypropylene film, a polyester film, a polyamide film, a polyimide film, a polyimide film, a polyether quinone film, a polytetrafluoroethylene film. A substrate such as a vinyl film, paper, or metal foil may be used. The above substrate having a surface subjected to release treatment may be used. The thickness of the above substrate is preferably from 10 to 1 Å #m, more preferably from 25 to 50 μm. -23- 201012887 In the field of semiconductor manufacturing, a layer (adhesive film) composed of the adhesive composition of the present invention can be used as a so-called solid crystal film in which a germanium wafer is attached to a substrate. After the tantalum wafer is crystallized on the substrate by using the adhesive film, the portion which is not embedded after the solid crystal is formed when the semiconductor device is manufactured by the wire bonding step and the packaging step, and the adhesive hardened layer and the substrate obtained by hardening the adhesive film The adhesion between them will decrease due to the heating in the wire bonding step. The above unburied portion will be buried by the packaging step after the wire bonding step. In order to make the resin-encapsulated semiconductor device have a reliability - even if there is a portion where the adhesion between the adhesive layer and the substrate is lowered, it is necessary to maintain a sufficient adhesion as a whole. According to this, it is necessary to measure the force at 26 ° C, usually at least 1 MPa. According to this, under the heating condition of the wire bonding step, the film is sandwiched between the two substrates after the combination of the wafer and the substrate, and the film is heated, and the semiconductor package resin is heated/pressurized in the packaging step. After the heat is pressed under conditions, and then hardened by heating to form a layered cured product (adhesive hardened layer), the shearing force between the two substrates is measured at 260 ° C. The force is usually at least 1 MPa. The heating conditions for the wire bonding step are various, but are usually 30 minutes or more at 17 Torr. Further, the heating/pressurizing conditions in the encapsulating step of the above semiconductor encapsulating resin are usually between 160 and 180 ° C / 5 to 10 MPa for 10 to 150 seconds. The conditions for heat hardening are the same as described above. The adhesive composition of the present invention can be used in the dicing/bonding film of the present invention. That is, the dicing die-bonding film of the present invention is a dicing film having a substrate and an adhesive layer disposed thereon, and an adhesive layer disposed on the dicing layer of the dicing film The dicing/bonding film of the layer formed by the adhesive composition of the present invention. The above substrate is usually in the form of a film, and for example, a polytetrafluoroethylene (PTFE) film, a polyethylene terephthalate (PET) film, a polyethylene (PE) film, a polypropylene (PP) film, or a polyphthalate can be used. Amine film, such modified plastic film. The thickness of the above substrate is preferably from 60 to 500 #m, more preferably from 80 to 200/m. The pressure-sensitive adhesive which forms the pressure-sensitive adhesive layer may, for example, be a pressure-sensitive adhesive, an adhesive which maintains a pressure of φ before ultraviolet irradiation, and an adhesive which is lowered by irradiation with ultraviolet rays. The thickness of the above adhesive layer is preferably from 2 to 10 μm, more preferably from 5 to 10 μm. The dicing die-bonding film of the present invention can be produced by laminating, for example, an adhesive layer of a dicing film, a layer of an adhesive composition in a subsequent sheet of the present invention. Further, the adhesive composition of the present invention can be obtained by dissolving the adhesive composition of the present invention in a solvent at the same concentration as described above, applying it to the adhesive layer of the dicing film, and drying it to form an adhesive composition layer. The solvent, the drying conditions, and the film thickness of the adhesive composition layer are the same as described above. The thin film of φ can be used, for example, a dicing film of a pressure sensitive type or a cut film of an ultraviolet curing type. The adhesive composition of the present invention can be used not only in the manufacture of electronic components such as semiconductor devices, but also in the manufacture of various products including the subsequent steps, such as the manufacture of LED parts 'inductors, liquid crystal parts and the like. [Examples] Hereinafter, the present invention will be further illustrated by examples and comparative examples, but the present invention is not limited by the examples. -25- 201012887 [Preparation of the composition of the adhesive] The following (A) to (D) components and other components are fed into the mixer of the rotation/revolution mode according to the mixing amount (parts by mass) shown in Table 1 (THIN KY ( In the production), methyl ethyl ketone, toluene or cyclohexane was added so that the total concentration of the components was 20% by mass, and the adhesive composition was prepared by mixing. (A) (meth)acrylic resin. SG-P3: an acrylic acid-based acrylic resin (manufactured by NAGASE CHEMTEX Co., Ltd.) containing 0.021 mol/100 g of epoxy group, Tg = 12 ° C, weight The average molecular weight = 850,000.
• SG-P3-43 :具有環氧基之丙燦腈系樹脂（NAGASE CHEMTEX公司製造），含有0.050莫耳/loo克之環氧基 ，Tg=12°C，重量平均分子量=85萬。 (B )環氧樹脂 _ • RE-310S:雙酚A型環氧樹脂（日本環氧樹脂公司 製造），重量平均分子量=600 • EOCN-1〇2〇:甲酚酚醛清漆型環氧樹脂（日本化藥 公司製造），重量平均分子量=1200 (C)芳香族多元胺化合物 • 4,4’-DDS: 4,4’-二胺基二苯基颯（和歌山精化公司 製造），具有磺醯基之芳香族多元胺 i S1 -26- 201012887 • 3,3’-DDS. 3,3 - —•胺基一本基楓（和歌山精化公司 製造），具有磺醯基之芳香族多元胺 .DDM: 4,4’-二胺基二苯基甲烷（和歌山精化公司製 造），芳香族多元胺 (其他成份）芳香族多元胺化合物以外之觸媒 • 2PHZ: 2-苯基-4,5_二羥基甲基咪唑（四國化成製造 _ ) (其他成份）芳香族多元胺化合物以外之硬化劑 •酚樹脂：KA-1160(大日本油墨化學公司製造） (其他成份）塡充劑 •二氧化矽微粉末：SE-2050 (ADAMA TECHS公司 製造），球狀二氧化矽，平均粒徑 〇 •複合聚矽氧橡膠微粒子：X-52_7030(信越化學工 業公司製造），平均粒徑 (其他成份）接著助劑 •偶合劑：X-12-414(信越化學工業公司製造），锍 系矽烷偶合劑 [接著用薄片之製作] 接著，將接著劑組成物塗佈於塗覆有氟系聚砂氧脫模 -27- 201012887 劑之厚度50//m PET薄膜上，且在110 °C下加熱乾燥10 分鐘，製作具備厚度約25/zm之接著劑組成物層之接著用 薄片。 [試驗] 針對所得接著用薄片進行下述試驗。結果示於表1。 (1 )楊氏模數 參 將接著用薄片中之自PET薄膜剝離之接著劑組成物層 8片重叠，且在7〇 °C下熱層合後’在175 °C下加熱6小時 硬化。切割成40mmxl0mmx200Vm之薄膜作爲試驗片， 使用動態黏彈性測定裝置’以拉伸模式’夾具間距離 10mm，測定溫度_80~300°C，測定頻率1Hz之條件下測定 楊氏模數。 (2)初期之接著性 參 將厚度450；am之矽晶圓切割成2mmx2mm之晶片， 隨後在經切割之晶圓背面’以使接著劑組成物層接觸之方 式在100°C下熱壓著接著用薄片。接著，將接著用薄片切 割成與晶片相同之形狀，獲得貼附接著用薄片之矽晶片。 自該矽晶片剝離PET薄膜，獲得貼附接著劑組成物層之矽 晶片。接著，將塗佈並硬化有光阻劑AUS3 08 (太陽油墨 (股）公司製造）之10mmxl0mm之BT基板或砂基板上 ，以使附著有接著劑組成物層之面接觸之方式’載置所得 ί S1 -28- 201012887 之貼附接著劑組成物層之矽晶片，且在170 °C、0.1 MPa之 條件下熱壓著2秒而固定。使如此固定有矽晶片之基板在 1 75 °c下加熱6小時使接著劑組成物層硬化製備試驗片（ 接著試驗片）。使用該接著試驗片，藉由黏合試驗機（ DAGE公司製造，4000PXY )，測定在260 °C下之接著劑 硬化物層與基板之間之剪切接著力。 φ ( 3 )濕熱後之接著性 使上述（2)之接著試驗片在85°C/60%RH之條件下 維持168小時，接著通過260 °C之回焊爐3次後，如上述 (2)般測定2 60°C下之剪切接著力。 (4 )埋入性能 在直徑8英吋、厚度75/zm之矽晶圓之一面上，以使 接著劑組成物層接觸之方式在70°C下熱壓著接著用薄片。 φ 自經熱壓著之接著用薄片剝離PET薄膜獲得之貼附接著劑 組成物層之晶圓之接著劑組成物層面上，以與該感壓切割 薄膜之黏著劑層接觸之方式貼附感壓切割薄膜。在下述切 割條件下將該矽晶圓切割成邊長9mm之矽晶片。接著’ 將如此獲得之9mm邊長之矽晶片自背面貼附有接著劑組 成物層之上述感壓切割薄膜之黏著劑層剝離。藉由NEC 機器公司製造之固晶裝置（BESTEM-D02-Type C)，在形 成有5〜15//m寬之長條狀電路圖案之50mmx5〇mmx厚度 250#m之樹脂基板（塗佈有光阻AUS308之硬化BT基板 -29 · 201012887 )上以接著劑組成物層接觸之方式配置該矽晶片，且在 13 0°c、0.1 MPa之條件下熱壓著1秒鐘。該方面以圖i ( 埋入性能試驗中顯示矽晶片配置之圖）爲準具體加以說明 ，在每邊50mm之正方形樹脂基板2上以3mm之間隔分成 4行4列配置16個每邊9mm之正方形矽晶片1，且使配 置於最外側之矽晶片1與樹脂基板2之外緣之間隔成爲 2.5mm。將如此作法之矽晶片經熱壓著的樹脂基板以相當 於打線接合步驟中之加熱溫度之170°C加熱90分鐘後，自 _ 樹脂基板上以600/zm厚之模製材料KMC2500LM1 B (信 越化學工業公司製造）經樹脂封裝（175 °C，封裝壓力 6.9MPa，90秒），使該模製材料在175 °C下加熱硬化4小 時。以超音波畫像測定裝置觀察如此般獲得之半導體封裝 內部，檢查是否有孔隙。 又，除將在相當於打線接合步驟中之加熱溫度之170 °C下之加熱時間自90分鐘變更成150分鐘以外，於與上 述相同，檢查是否有孔隙。 @ 藉由超音波畫像測定裝置觀察未確認到半導體封裝內 部有孔隙時，評價爲埋入性能充分。另一方面，藉由以超 音波畫像測定裝置觀察確認到半導體封裝內部有孔隙時， 評價爲埋入性能不足。表1中，「〇」係表示埋入性能充 分，「X」係表示埋入性能不足。 切割條件： 切割裝置：DAD-341 (DISCO公司製造） 切斷方式：單次切斷 ί £1 -30- 201012887 轉子旋轉數·· 40000rPm 切割刀：NBC-ZH 104F 27HEEE (DISCO 公司製造） (5 )封裝之信賴性 在上述（4 )中切離經樹脂封裝之矽晶片所得之合計 16個封裝在85 °C /60 %RH之條件下放置168小時，接著通 過最高到達溫度260 °C之焊錫回焊爐3次後，藉由超音波 φ 畫像測定裝置觀察矽晶片與基板之間是否有剝離。表1中 ，「〇」代表1 6個封裝均未觀察到剝離，「X」代表1 6 個封裝中觀察到1個剝離。 -31 - 201012887 [表1]• SG-P3-43: an acrylonitrile-based resin having an epoxy group (manufactured by NAGASE CHEMTEX Co., Ltd.) containing 0.050 mol/look of epoxy group, Tg = 12 ° C, and a weight average molecular weight = 850,000. (B) Epoxy resin _ • RE-310S: bisphenol A epoxy resin (manufactured by Nippon Epoxy Co., Ltd.), weight average molecular weight = 600 • EOCN-1〇2〇: cresol novolac type epoxy resin ( Manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight = 1200 (C) Aromatic polyamine compound • 4,4'-DDS: 4,4'-diaminodiphenyl hydrazine (manufactured by Wakayama Seiki Co., Ltd.), sulphur Aromatic polyamines of sulfhydryl i S1 -26- 201012887 • 3,3'-DDS. 3,3 -••Amino-based Benfeng (manufactured by Wakayama Seiki Co., Ltd.), aromatic polyamine with sulfonyl group .DDM: 4,4'-diaminodiphenylmethane (manufactured by Wakayama Seiki Co., Ltd.), a catalyst other than aromatic polyamine (other components) aromatic polyamine compound • 2PHZ: 2-phenyl-4, 5_Dihydroxymethylimidazole (Manufactured by Shikoku Chemicals Co., Ltd.) (Other Ingredients) Hardener other than aromatic polyamine compound • Phenolic resin: KA-1160 (manufactured by Dainippon Ink Chemicals Co., Ltd.) (Other Ingredients) Tamping Agent • Antimony dioxide fine powder: SE-2050 (manufactured by ADAMA TECHS), spherical cerium oxide, average particle size 〇•复Polyoxynized rubber microparticles: X-52_7030 (manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size (other components) followed by additives and coupling agents: X-12-414 (manufactured by Shin-Etsu Chemical Co., Ltd.), lanthanide coupling agent [Subsequent production of a sheet] Next, the adhesive composition was applied onto a 50//m PET film coated with a fluorine-based polysilicon oxide mold release -27-201012887, and dried at 110 ° C. After 10 minutes, a subsequent sheet having an adhesive composition layer having a thickness of about 25/zm was produced. [Test] The following test was carried out with respect to the obtained sheet. The results are shown in Table 1. (1) Young's modulus The 8 layers of the adhesive composition layer which was peeled off from the PET film in the sheet were laminated, and after heat lamination at 7 ° C, the film was hardened by heating at 175 ° C for 6 hours. A film cut into 40 mm x 10 mm x 200 Vm was used as a test piece, and the Young's modulus was measured using a dynamic viscoelasticity measuring apparatus in a tensile mode, a distance between the jigs of 10 mm, a temperature of _80 to 300 ° C, and a measurement frequency of 1 Hz. (2) The initial adhesive step is to cut the wafer of thickness 450; am into a 2mm x 2mm wafer, and then heat-press at 100 ° C on the back side of the cut wafer in contact with the layer of the adhesive composition. Then use a sheet. Next, the sheet is then cut into the same shape as the wafer to obtain a wafer to which the subsequent sheet is attached. The PET film was peeled off from the tantalum wafer to obtain a tantalum wafer to which an adhesive composition layer was attached. Next, a 10 mm×10 mm BT substrate or a sand substrate coated with a photoresist AUS3 08 (manufactured by Sun Ink Co., Ltd.) was applied and hardened, and the surface of the adhesive composition layer was placed in contact with each other. ί S1 -28- 201012887 The wafer of the composition layer of the adhesive is attached and fixed by pressing at 170 ° C and 0.1 MPa for 2 seconds. The substrate thus fixed with the tantalum wafer was heated at 1, 75 ° C for 6 hours to harden the adhesive composition layer to prepare a test piece (following the test piece). Using this test piece, the shear adhesion force between the adhesive layer of the adhesive at 260 ° C and the substrate was measured by a bonding tester (manufactured by DAGE, 4000 PXY). φ ( 3 ) Adhesion after damp heat, the test piece of the above (2) was maintained at 85 ° C / 60% RH for 168 hours, and then passed through a reflow oven at 260 ° C for 3 times, as described above (2) The shear adhesion force at 60 ° C was measured as usual. (4) Buried property On one side of a wafer having a diameter of 8 inches and a thickness of 75/zm, the sheet was heat-pressed at 70 ° C in such a manner as to contact the composition layer of the subsequent agent. Φ affixed to the adhesive composition layer of the wafer to which the adhesive composition layer is attached by peeling off the PET film by heat-pressing, in contact with the adhesive layer of the pressure-sensitive dicing film Press-cut film. The tantalum wafer was cut into a tantalum wafer having a side length of 9 mm under the following cutting conditions. Next, the thus obtained 9 mm long side wafer was peeled off from the pressure-sensitive adhesive layer of the above-mentioned pressure-sensitive dicing film to which the adhesive composition layer was attached. A resin substrate (coated with a 50 mm x 5 mm x 50 mm thickness) of a long strip-shaped circuit pattern of 5 to 15/m width is formed by a die bonding apparatus (BESTEM-D02-Type C) manufactured by NEC Machine Co., Ltd. The tantalum wafer was placed on the hardened BT substrate -29 · 201012887 of the photoresist AUS308 by contact with the adhesive composition layer, and heat-pressed for 1 second at 130 ° C and 0.1 MPa. This aspect is specifically described in Fig. i (the diagram showing the arrangement of the germanium wafer in the embedding performance test). The square resin substrate 2 of 50 mm on each side is divided into 4 rows and 4 columns at intervals of 3 mm, and 16 sides of each side are 9 mm. The square wafer 1 was placed in a square, and the distance between the outermost wafer 1 and the outer edge of the resin substrate 2 was 2.5 mm. After the heat-pressed resin substrate of the wafer thus heated is heated at 170 ° C for the heating temperature in the wire bonding step for 90 minutes, the molding material KMC2500LM1 B is applied to the resin substrate at 600/zm thickness (Shin-Etsu The chemical industry company was packaged by resin (175 ° C, package pressure 6.9 MPa, 90 seconds), and the molding material was heat-hardened at 175 ° C for 4 hours. The inside of the thus obtained semiconductor package was observed by an ultrasonic image measuring device to check whether or not there was a void. In addition, the presence or absence of voids was examined in the same manner as described above except that the heating time at 170 ° C corresponding to the heating temperature in the wire bonding step was changed from 90 minutes to 150 minutes. @ When it was observed by the ultrasonic image measuring apparatus that there was no void in the inside of the semiconductor package, it was evaluated that the embedding performance was sufficient. On the other hand, when it was confirmed by the ultrasonic image measuring apparatus that there was a void in the inside of the semiconductor package, it was evaluated that the embedding performance was insufficient. In Table 1, "〇" indicates that the embedding performance is sufficient, and "X" indicates that the embedding performance is insufficient. Cutting conditions: Cutting device: DAD-341 (manufactured by DISCO) Cutting method: single cutting ί £1 -30- 201012887 Rotor rotation number · 40000rPm Cutting knife: NBC-ZH 104F 27HEEE (manufactured by DISCO) (5 The reliability of the package is set in the above (4), and the total of 16 packages obtained by cutting off the resin-coated silicon wafer are placed at 85 ° C / 60 % RH for 168 hours, and then passed through the solder having a maximum temperature of 260 ° C. After three reflow ovens, the ultrasonic φ image measuring device was used to observe whether or not there was peeling between the silicon wafer and the substrate. In Table 1, "〇" represents no peeling observed in 16 packages, and "X" represents one peel observed in 16 packages. -31 - 201012887 [Table 1]
m m 比較例 1 2 3 4 5 6 7 8 1 2 3 A成份 SG-P3 59.5 59.5 59.5 59.5 34.0 42.4 52.5 59.5 59.5 59.5 SG-P3 43 59.5 B成份 RE310S 19.1 19.1 20.1 38.2 7.1 16.9 24.2 15.5 EOCN1020 19.5 19.5 24.2 C成份 4,4’-DDS 6.0 6.4 6.4 12.8 4.5 5.6 3,3，-DDS 6.0 DDM 5.4 其他 2PHZ 1.3 1.3 0.1 KA-1160 9.9 SC2050 15 15 15 15 15 15 40 15 15 15 15 KMP600 10 X-12-414 1 楊氏模數（MPa) 680 590 640 610 630 850 950 480 620 600 580 接著性（MPa) Si基板 初期 2.2 2.5 3.4 2.2 1.9 3.0 4.0 3.8 1.2 1.3 2.8 濕熱後 2.2 2.3 3.7 2.1 1.6 3.2 3.8 3.7 1.6 1.4 2.5 接著性（MPa) BT基板 初期 5.0 5.2 4.2 5.1 3.1 5.3 5.5 5.2 2.3 2.3 3.4 濕熱後 4.8 5.1 4.8 5.3 2.8 5.0 5.4 5.2 2.5 2.4 3.3 埋入性能 17(TC下加熱90分鐘後 〇 〇 〇 〇 〇 〇 〇 〇 X X x 17〇°C下加熱150分鐘後 〇 〇 〇 〇 X 〇 X X X X X 封裝信賴性 170°C下加熱90分鐘後 〇 〇 〇 〇 〇 〇 〇 〇 X X X 170°C下加熱150分鐘後 〇 〇 〇 〇 X 〇 〇 〇 X X X 相對於本發明之組成物（實施例1 ~8 )之使用芳香族 多元胺化合物作爲觸媒及硬化劑’於比較例1及2之組成 物係使用咪唑觸媒替代芳香族多元胺化合物作爲觸媒，且 未使用硬化劑，比較例3之組成物係使用咪唑觸媒替代芳 香族多元胺化合物作爲觸媒’使用酚樹脂替代芳香族多元 [S 1 -32- 201012887 胺化合物作爲硬化劑。如表1中所示，本發明之組成物相 較於比較例1〜3之組成物，埋入性能優異，且自本發明之 組成物所得之硬化物層相較於自比較例1〜3之組成物所得 之硬化物層，其在吸濕下之封裝信賴性高。 [產業上之可能利用性] 本發明之接著劑組成物之埋入性能優異，自該接著劑 0 組成物所得之接著劑硬化物層之接著性優異，同時爲低彈 性率且耐熱性優異。據此，該接著劑組成物可使用作爲用 以製造信賴性高之半導體裝置之接著用薄片及切割•黏晶 接著薄膜中之接著劑組成物層。 【圖式簡單說明】 圖1爲顯示埋入性能試驗中之矽晶片配置圖。 Φ 【主要元件符號說明】 1 :矽晶片 2 :樹脂基板 I S：} -33-Mm Comparative Example 1 2 3 4 5 6 7 8 1 2 3 A component SG-P3 59.5 59.5 59.5 59.5 34.0 42.4 52.5 59.5 59.5 59.5 SG-P3 43 59.5 B component RE310S 19.1 19.1 20.1 38.2 7.1 16.9 24.2 15.5 EOCN1020 19.5 19.5 24.2 C Ingredients 4,4'-DDS 6.0 6.4 6.4 12.8 4.5 5.6 3,3,-DDS 6.0 DDM 5.4 Others 2PHZ 1.3 1.3 0.1 KA-1160 9.9 SC2050 15 15 15 15 15 15 40 15 15 15 15 KMP600 10 X-12-414 1 Young's modulus (MPa) 680 590 640 610 630 850 950 480 620 600 580 Subsequent (MPa) Si substrate initial 2.2 2.5 3.4 2.2 1.9 3.0 4.0 3.8 1.2 1.3 2.8 After damp heat 2.2 2.3 3.7 2.1 1.6 3.2 3.8 3.7 1.6 1.4 2.5 Subsequent (MPa) BT substrate initial 5.0 5.2 4.2 5.1 3.1 5.3 5.5 5.2 2.3 2.3 3.4 After damp heat 4.8 5.1 4.8 5.3 2.8 5.0 5.4 5.2 2.5 2.4 3.3 Buried performance 17 (after heating for 90 minutes at TC) 〇〇 XX x 17〇°C heating for 150 minutes, 〇〇〇〇X 〇XXXXX package reliability after heating at 170°C for 90 minutes〇 〇〇〇〇〇〇 XXX at 170 ° C for 150 minutes, 〇〇〇〇X 〇〇〇XXX relative to the composition of the present invention (Examples 1 to 8) using an aromatic polyamine compound as a catalyst and hardening The composition of the agents 'Comparative Examples 1 and 2 used an imidazole catalyst instead of an aromatic polyamine compound as a catalyst, and no hardener was used. The composition of Comparative Example 3 used an imidazole catalyst instead of an aromatic polyamine compound. Catalyst 'uses phenolic resin instead of aromatic poly [S 1 -32- 201012887 amine compound as a hardener. As shown in Table 1, the composition of the present invention was excellent in embedding performance as compared with the compositions of Comparative Examples 1 to 3, and the cured layer obtained from the composition of the present invention was compared with Comparative Examples 1 to 3. The cured layer obtained from the composition has high packaging reliability under moisture absorption. [Industrial Applicability] The adhesive composition of the present invention is excellent in embedding performance, and has excellent adhesion to the adhesive cured layer obtained from the composition of the adhesive 0, and has low elasticity and excellent heat resistance. According to this, the adhesive composition can be used as a binder layer for manufacturing a highly reliable semiconductor device and an adhesive composition layer in a dicing paste. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing a germanium wafer in a buried performance test. Φ [Description of main component symbols] 1 : 矽 wafer 2 : resin substrate I S:} -33-