TW201213478A - Adhesive composition and adhesive sheet for fabricating semiconductor package - Google Patents

Adhesive composition and adhesive sheet for fabricating semiconductor package Download PDF

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Publication number
TW201213478A
TW201213478A TW099138786A TW99138786A TW201213478A TW 201213478 A TW201213478 A TW 201213478A TW 099138786 A TW099138786 A TW 099138786A TW 99138786 A TW99138786 A TW 99138786A TW 201213478 A TW201213478 A TW 201213478A
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TW
Taiwan
Prior art keywords
adhesive
adhesive composition
weight
epoxy resin
wafer
Prior art date
Application number
TW099138786A
Other languages
Chinese (zh)
Other versions
TWI448524B (en
Inventor
Sung-Su Kim
Jin-Won Kim
Kwang-Ho Shin
Kyung-Nam Cho
Kyo-Sung Hwang
Chang-Bum Chung
Original Assignee
Kcc Corp
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Publication date
Application filed by Kcc Corp filed Critical Kcc Corp
Publication of TW201213478A publication Critical patent/TW201213478A/en
Application granted granted Critical
Publication of TWI448524B publication Critical patent/TWI448524B/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
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    • H01L21/6835Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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    • H01L23/49513Lead-frames or other flat leads characterised by the die pad having bonding material between chip and die pad
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    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention relates to an adhesive composition which can be used in a semiconductor manufacturing process, and an adhesive material comprising the same which is processed in a sheet form. More specifically, the present invention relates to an adhesive composition which is applied to the surface of a wafer during the semiconductor manufacturing process and used for adhesion of chip and substrate, or chip and chip, and in particular, which has an increased flowability in high-temperature adhesion and thus provides good embedability to structures such as bump and metal wiring, and has improved interface adhesion to a supporting member and thus provides high reliability of a semiconductor device even under high-temperature/high-humidity conditions, and an adhesive sheet comprising the same.

Description

201213478 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種可使用於半導體製程之黏著組成 物’及-種包括該組成物且可加工處理成片狀形式之黏著 材料。更具體地說,本發明係關於一種黏著組成物,以及 包括該組成物之黏著片。該組成物係在半導體製程中施用 於晶,表面及使用於晶片與基板,或晶片與晶片之黏著, 特別是在IBJ溫黏著時具有增加的流動性,因此對於諸如凸 塊及金屬接線等構造提供良好的嵌人性,且對支持構件具 有改進之介面黏著力,因此即使在高溫/高濕狀況下,亦提 供半導體元件高可靠性。 【先前技術】 ^半導體製程中,在印製電路圖案於晶II之程序之後為 將該晶圓切成晶片之切割程序,分割該切割之晶片成個別 ^片之擴充及取晶程序,將該經由取晶程序分割之晶片固 定於基板之黏合程序,晶片與基板電連接用之金屬接線程 序,以及用於保護晶片之環氧模製(epoxy-molding)程序。 如以上所述之方法t,為了易於切割晶圓及易於檢取晶 片’而使用保護晶_黏結片及用於撿取晶>1之黏著組成 物或黏著片。 B曰片接&至基板之慣用方法包含以某種特定圖案施 用液態環氧樹脂組成物於備妥之引線框架或軟性印刷電路 版(MB)並固定晶片’該等晶片係使用保護晶圓用黏合片 預先處理及分割。但是,於施用液體環氧樹脂組成物,在 95048 4 201213478 控制施用厚度均勻性方面有問題,且施用於晶片接合之壓 力易使發生滲出。雖可調整液體黏著組成物之搖變值 (thixotropy index)以控制其流動性,但由於應用於多堆 疊晶片製造之困難度,因而僅限於單晶片製造。 為解決使用液體黏著劑產生的上述問題,建議修改液 體黏著劑成適當的樹脂組成物且以片狀形式提供。此類的 片狀型黏著劑係製成與晶片相似尺寸之細條形式(ri 11 form)然後以使用特定裝置將黏著片切成晶片尺寸並黏合 於基板,再接合分割之晶片之方式使用。但是,此方法需 要特定裝置及額外的程序來切割及黏合黏著片,其利用性 因而減低。 近來的半導體製程,因為黏著片先接合於晶圓之背面 然後施行切割,所以個別晶片係以晶片與黏著片之結合構 造(integrated structure)獲得。此類的黏著片一般可與 接合於此之黏結材料以結合形式供應。在此狀況下,不同 於黏結片係接合於晶圓背面之切割程序,黏著片與黏結片 之結合形式(其中後者層壓於前者之背面)係接合於晶圓, 然後進行其後的步驟。 此類以製備成與黏結片形成結合形式之黏著片接合於 晶圓之背面以簡化半導體製程中自晶圓切割至晶粒黏合之 程序的方法係揭露於韓國專利公開申請案公告(K 〇 r e a201213478 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition which can be used in a semiconductor process, and an adhesive material which can be processed into a sheet form, including the composition. More specifically, the present invention relates to an adhesive composition, and an adhesive sheet comprising the composition. The composition is applied to the crystal in the semiconductor process, the surface and the wafer and the substrate, or the adhesion of the wafer to the wafer, especially when the IBJ is temperature-adhered, so that the structure is such as bumps and metal wiring. Providing good embedding and improved interface adhesion to the support member, thus providing high reliability of the semiconductor element even under high temperature/high humidity conditions. [Prior Art] ^ In the semiconductor manufacturing process, after the process of printing a circuit pattern in the crystal II, a cutting process for cutting the wafer into a wafer is performed, and the diced wafer is divided into individual wafer expansion and crystal extraction programs. A bonding process in which a wafer divided by a crystal pulling process is fixed to a substrate, a metal wiring process for electrically connecting the wafer to the substrate, and an epoxy-molding process for protecting the wafer. As the method t described above, a protective crystal-bonding sheet and an adhesive composition or an adhesive sheet for picking up the crystals>1 are used in order to facilitate the dicing of the wafer and the easy picking of the wafer. A conventional method of bonding a B-chip to a substrate includes applying a liquid epoxy composition in a specific pattern to a prepared lead frame or a flexible printed circuit board (MB) and fixing the wafer. The wafers are protected wafers. Pre-treatment and segmentation with adhesive sheets. However, in the application of the liquid epoxy resin composition, there is a problem in controlling the application of the thickness uniformity at 95048 4 201213478, and the pressure applied to the wafer bonding is liable to cause bleeding. Although the thixotropy index of the liquid adhesion composition can be adjusted to control its fluidity, it is limited to single wafer fabrication due to the difficulty in manufacturing a multi-stack wafer. In order to solve the above problems caused by the use of a liquid adhesive, it is proposed to modify the liquid adhesive into a suitable resin composition and provide it in a sheet form. Such a sheet-like adhesive is formed into a thin strip form (ri 11 form) of a similar size to the wafer and then used to cut the adhesive sheet into a wafer size using a specific device and bond it to the substrate, and then join the divided wafer. However, this method requires a specific device and an additional procedure to cut and bond the adhesive sheet, and its usability is thus reduced. In recent semiconductor processes, since the adhesive sheet is bonded to the back side of the wafer and then cut, individual wafers are obtained by a combined structure of the wafer and the adhesive sheet. Adhesive sheets of this type are generally available in combination with the bonding material bonded thereto. In this case, unlike the cutting process in which the bonded film is bonded to the back side of the wafer, the combination of the adhesive sheet and the adhesive sheet (the latter of which is laminated on the back side of the former) is bonded to the wafer, and then the subsequent steps are performed. A method of attaching an adhesive sheet formed in a bonded form to a bonded sheet to a back surface of a wafer to simplify a process from wafer cutting to die bonding in a semiconductor process is disclosed in Korean Patent Application Publication (K 〇 r e a

Patent Laid-open Publication) No. 10-2006-0021337 及韓國專利(Korea Patent) No. 10-0826420、 10-0646069 、 10-0845092 等。 5 95048 201213478 近來慣用的半導體製程中,為提升半導體封裝件之積 體程度,使用在特定空間垂直堆疊複數層半導體晶片的方 法。利用堆疊半導體元件之技術及使用適用於此類技術之 黏著材料,積體程度可改進為堆疊兩層或更多層晶片於由 引線框架或軟性電路版構成之封裝件。在使用凸塊作為電 連接器之晶片級封裝(CSP)中,使用垂直堆疊晶片於具有焊 接凸塊之基板的技術以提升積體程度。此外,當多層堆疊 複數之晶片以改進積體程度時,為了有效利用晶片空間主 要係使用垂直堆疊相同尺寸晶片的方法。於垂直多層堆疊 相同尺寸晶片,接合晶片於引線框架或板以完成元件之電 連接然後操作金屬接線以電連接晶片與基板或以事先固定 於晶片背面之金屬凸塊接合晶片於基板,之後多層堆疊其 他以同尺寸供應之晶片於其上。在此一連串之程序中,為 要保證半導體元件之可靠性,使用之黏著片在晶片接合之 過程期間須有充分的流動性以嵌入存在於晶片與晶片間之 諸如金屬接線或凸塊之構造,或晶片與基板間不會形成空 隙或破壞構造。此外,須於接合之後經固化過程顯示高介 面黏著度。 半導體之慣用黏著片係藉由下法製成片狀形式:藉由 調配提供可撓性之熱塑性橡膠成分以及具良好之耐熱性黏 著度之固體環氧樹脂組成物,而製備可在室溫處理之片狀 類型之黏著劑,用適當溶劑稀釋該混合物以進行混合,並 進行施用程序。彼等係用於一般晶片接合過程。 但是,在堆疊同尺寸晶片之程序中,此類之慣用黏著 6 95048 201213478 片具低流動性而不足以完全地嵌入金屬接線或金屬凸塊, 因此具有於接合期間產生空隙或因佈置於接合表面之接線 受損而產生瑕疵品之問題。此外,熱塑性橡膠成分及環氧 樹脂組成物間貧乏的相容性造成微小的相分離,且長期暴 露於高溫/高濕狀況下造成橡膠成分之老化由此而減低黏 著度。特別是’除了由構成形成引線框架、接線、凸塊等 的金屬成分提供半導體元件之特性之外,多種不同的有機 材料諸如防焊劑、純化劑等形成保護電路嵌入板及晶片係 同時暴露於要接合之晶片表面’但彼等一般具有比金屬低 之表面能因而使用黏著片之晶片接合可能減低黏著強度。 【發明内容】 [發明欲解決的問題] 為解決如上述之先前技術的問題,本發明的目的係提 供一種黏著組成物以及包括該組成物之黏著片,該組成物 對暴露在欲接合之半導體表面之構造諸如凸塊及金屬接線 提供良好之嵌入性,且對半導體支持構件具有改進之介面 黏著度’而甚至於在高溫/高濕狀況下亦提供半導體元件之 高可靠性。 [技術方法] /為達到如上述之目的,本發明提供一種黏著組成物, 係已括.(A)含有一個或多個反應基之共聚丙烯酸酯化合 物’(β)熱固性環氧樹脂混合物’(c)固化劑,⑼填充料及 ⑻固化促進劑,其中該成分(Α):⑻之重量比率為95 : 5 5 65 : ’ 5亥成分(β)包括一種或多種於15〇。〇具有〇· 1泊 7 95048 201213478 (Pa · s)或較低溶體黏度之環氧樹脂,對每100重量份之該 等成分(A) + (B)KC)之總合,該成分(D)的含量為10至80 重量份,及對每100重量份之該等成分(A) + (B) + (C)之總 合,該成分(E)的含量為0.1至1.4重量份。 本發明另一方面提供製造半導體用之黏著片,其係包 括本發明黏著組成物之塗佈層。 [發明之功效] 當本發明之黏著組成物及黏著片使用於半導體製程 時,可改進對接合對象之介面黏著度且甚至於高溫/高濕狀 況下仍保持黏著特性,藉此可得到高可靠性。此外,由於 高溫流動性,可使暴露於要接合之半導體表面上之構造諸 如凸塊及金屬接線得到良好之嵌入性。 【實施方式】 詳細說明本發明於下。 (A)含有一個或多個反應基之共聚丙烯酸酯化合物 本發明之共聚丙烯酸酯化合物含有一個或多個反應基 (如,極性基),藉此可適當調整其表面能而可形成不同化 合物之分子間交聯或單一分子之分子内交聯,如此可改進 組成物之黏著性能及改進對半導體支持構件中具低表面能 之有機材料之介面黏著特性。當測量其與水之接觸角時, 共聚丙烯酸酯化合物(A)具有之較佳表面能係40達因/公 分(dyne/cm)至50達因/公分(dyne/cm),較佳重量平均分 子量係300,000至1,500,000,及較佳玻璃轉換溫度係 -20°C 至 50°C。 8 95048 201213478 含於共聚丙烯酸酯化合物(A)之反應基的較佳實例包 含一個或多個選自丙稀腈基、環氧基、羥基及叛基者。 具體地,當共聚丙烯酸酯化合物含有環氧基及經基於 一分子,可使用樹脂類諸如SG-PT115(環氧值:0.21當量/ 公斤(eq/kg),羥值:20毫克(mg)KOH/克(g),分子量 800,000),SG-PT134 (環氧值:0.21當量/公斤,經值: 30毫克K0H/克’分子量800, 000)及SG-PT135(環氧值:〇. 21 當量/公斤(kg) ’羥值:400毫克K0H/克,分子量8〇〇, 〇〇〇) 可購自Nagase Chemtex Co.,Ltd.;當共聚丙烯酸酯化合 物含有羧基及丙烯腈基於一分子中,可使用樹脂類諸如Patent Laid-open Publication) No. 10-2006-0021337 and Korean Patent No. 10-0826420, 10-0646069, 10-0845092 and the like. 5 95048 201213478 In a recently used semiconductor process, in order to increase the degree of integration of a semiconductor package, a method of vertically stacking a plurality of semiconductor wafers in a specific space is used. With the technique of stacking semiconductor elements and the use of an adhesive material suitable for such a technique, the degree of integration can be improved by stacking two or more layers of wafers in a package composed of a lead frame or a flexible circuit board. In a wafer level package (CSP) using a bump as an electrical connector, a technique of vertically stacking a wafer on a substrate having solder bumps is used to increase the degree of integration. Further, when a plurality of wafers are stacked in a plurality of layers to improve the degree of integration, a method of vertically stacking wafers of the same size is used in order to effectively utilize the wafer space main line. Stacking wafers of the same size in a vertical stack, bonding the wafer to the lead frame or board to complete the electrical connection of the components, and then operating the metal wiring to electrically connect the wafer to the substrate or bonding the wafer to the substrate with metal bumps previously fixed on the back surface of the wafer, followed by multilayer stacking Other wafers supplied in the same size are mounted thereon. In this series of procedures, in order to ensure the reliability of the semiconductor device, the adhesive sheet used must have sufficient fluidity during the wafer bonding process to embed a structure such as a metal wiring or bump existing between the wafer and the wafer. Or a void or a broken structure is not formed between the wafer and the substrate. In addition, a high interfacial adhesion is exhibited through the curing process after bonding. The conventional adhesive sheet of the semiconductor is formed into a sheet form by the following method: by providing a flexible thermoplastic rubber component and a solid epoxy resin composition having good heat resistance adhesion, the preparation can be processed at room temperature. A sheet-like type of adhesive, which is diluted with a suitable solvent for mixing, and subjected to an application procedure. They are used in general wafer bonding processes. However, in the process of stacking wafers of the same size, such conventional bonding 6 95048 201213478 sheets have low fluidity and are not sufficient to completely embed metal wiring or metal bumps, thus having voids during bonding or due to placement on the bonding surface. The wiring is damaged and the problem of defective products is generated. In addition, the poor compatibility between the thermoplastic rubber component and the epoxy resin composition causes minute phase separation, and long-term exposure to high temperature/high humidity conditions causes deterioration of the rubber component and thus reduces adhesion. In particular, in addition to the characteristics of the semiconductor element provided by the metal component constituting the lead frame, the wiring, the bump, and the like, a plurality of different organic materials such as a solder resist, a purifying agent, and the like are formed to form the protective circuit embedded board and the wafer system simultaneously exposed to the Bonded wafer surfaces 'but they generally have a lower surface energy than metal. Thus wafer bonding using adhesive sheets may reduce adhesion strength. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In order to solve the problems of the prior art as described above, an object of the present invention is to provide an adhesive composition and an adhesive sheet comprising the same, which is exposed to a semiconductor to be bonded Surface construction such as bumps and metal wiring provides good embedding and improved interface adhesion to semiconductor support members' and provides high reliability of semiconductor components even under high temperature/high humidity conditions. [Technical method] / In order to achieve the object as described above, the present invention provides an adhesive composition comprising (A) a polyacrylate compound '(β) thermosetting epoxy resin mixture containing one or more reactive groups' ( c) a curing agent, (9) a filler and (8) a curing accelerator, wherein the weight ratio of the component (Α): (8) is 95: 5 5 65 : '5 hai components (β) include one or more of 15 〇. 〇 环氧树脂 1 泊 950 950 950 950 950 950 950 950 950 950 950 950 950 950 950 950 950 950 950 950 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The content of D) is from 10 to 80 parts by weight, and the content of the component (E) is from 0.1 to 1.4 parts by weight per 100 parts by weight of the total of the components (A) + (B) + (C). Another aspect of the present invention provides an adhesive sheet for producing a semiconductor, which comprises a coating layer of the adhesive composition of the present invention. [Effects of the Invention] When the adhesive composition and the adhesive sheet of the present invention are used in a semiconductor process, the adhesion to the interface of the bonded object can be improved and the adhesive property can be maintained even under high temperature/high humidity conditions, thereby achieving high reliability. Sex. In addition, due to the high temperature fluidity, the embedded structures such as bumps and metal wiring exposed to the surface of the semiconductor to be bonded can be well embedded. [Embodiment] The present invention will be described in detail below. (A) Copolyacrylate compound containing one or more reactive groups The copolyacrylate compound of the present invention contains one or more reactive groups (e.g., polar groups), whereby the surface energy can be appropriately adjusted to form different compounds. Intermolecular cross-linking or intramolecular cross-linking of a single molecule can improve the adhesion properties of the composition and improve the interfacial adhesion properties of organic materials having low surface energy in the semiconductor support member. When the contact angle with water is measured, the copolyacrylate compound (A) has a preferred surface energy of 40 dynes/cm (dyne/cm) to 50 dynes/cm (dyne/cm), preferably a weight average. The molecular weight is 300,000 to 1,500,000, and the preferred glass transition temperature is -20 ° C to 50 ° C. 8 95048 201213478 Preferred examples of the reactive group contained in the copolyacrylate compound (A) include one or more selected from the group consisting of acrylonitrile groups, epoxy groups, hydroxyl groups, and ruthenium groups. Specifically, when the copolyacrylate compound contains an epoxy group and is based on one molecule, a resin such as SG-PT115 (epoxy value: 0.21 equivalent/kg (eq/kg), hydroxyl value: 20 mg (mg) KOH) may be used. / g (g), molecular weight 800,000), SG-PT134 (epoxy value: 0.21 equivalent / kg, value: 30 mg K0H / g 'molecular weight 800,000) and SG-PT135 (epoxy value: 〇. 21 equivalents /kg (kg) 'Hydroxyl value: 400 mg K0H / g, molecular weight 8 〇〇, 〇〇〇) available from Nagase Chemtex Co., Ltd.; when the copolyacrylate compound contains a carboxyl group and acrylonitrile based on one molecule, Resin type such as

Nipol®DN631(丙烤腈:33. 5%’ 密度:〇· 99)及 Nipol®NBR N34 (丙烯腈:27%,密度:〇·98)可購自Zeon Co.,Ltd.;及 當共聚丙烯酸酯化合物含有丙烯腈基於一分子中,可使用 樹脂類諸如那些可購自Hyundai Petrochemical Co.,Ltd. i®SEETEC系列,但不限於此。 於本發明之黏著組成物中,該共聚丙烯駿酯化合物成 分(A):下述之環氧樹脂混合物(B)之重量比率為95 : 5至 65 : 35,及較佳為90 : 1〇至7〇 : 3〇。如果成分(a)以少於 此重量比率蚊義之量使用,則黏著組成物變成太硬因而 在施用期間或切割過程時可能太容易破損。相反的,如果 f分(A)以多於此重量㈣所定義之量制,料能保證黏 者片在黏著及©化後之充分黏㈣度,_此可靠性可能 有問題。 (Β)熱固性環氧樹脂混合物 95048 9 201213478 之於15(TC具有〇 °種或多種从上如下述 j. 〇 1 ' . ' .S)或較低之熔體黏度(如,〇 om 主U.l /白)之環氧樹脂以及 卻υ.ϋϋΐ 包含,例如,簪酪Α刑卢每)—種或夕種之慣用習知者 雙紛A t %氧樹脂、錐必ρ期丨與汾丄 酚S型環氧樹t 雙酚F!衣虱樹脂、雙 樹脂、聯盼之一編美祕刚脂、雙齡八盼醛環氧 化合物之二環氧丙基…, 笪夕pit 叶lc* σ物之一裱氧丙基醚,及該 ’元土代、_化或氫化化合物,多官能環氧樹脂、含 雜環之環氧樹脂等。 更具體地’可使用如商業用實例,雙盼Α型環氧樹脂 諸如 EPICOAT807、EPIC0AT815、EPIC0A而、epic〇AT827、 EPIC0AT828 、 EPIC0AT834 、 EPIC0AT1001 、 EPICOAT1002 、 EPICOAT1003 、 EPICOAT1055 、 EPICOAT1004 、 EPICOAT1004AF 、 EPICOAT1007 、 EPICOAT1009 、 EPI CO AT 10 0 3F、EPI COAT 10 0 4F (商品名,japan Epoxy Res i η Co.,Ltd.),YD01卜 YD-012、YD-013K、YD-014、YD-017、 YD-112 、 YD-113 、 YD-114 、 YD-115 、 YD-127 、 YD-128 (商 品名,Kuk-doChemical Co.,Ltd.),SE-187、SE-187P (商 品名,Shin-wha T&C Co.,Ltd.)等;雙酚F型環氧樹脂 諸如 YDF-161、YDF-162、YDF-170 (商品名,Kuk-do Chemical Co.,Ltd· ) ’ SE-187、SE-187P (商品名 ’ Shin-whaT&CCo·, Ltd.)等;酚系酚醛環氧樹脂諸如EPPN-201、EPPN-501、 10 95048 201213478 EPPN-501HY、EPPN-502 (商品名,Nippon Kayaku Co., Ltd. ) ’ YDPN-63卜 YDPN-636、YDPN-638 (商品名,Kuk-do Chemical Co.,Ltd.)等;及甲酚酚酸·環氧樹脂諸如 YDCN-500-1P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、 YDCN-500-10P、YDCN-500-80P (商品名,Kuk-do Chemical Co.,Ltd.),EOCN-102S、EOCN-103S、EOCN-104S、 EOCN-1012、EOCN-1020、EOCN-1025 及 EOCN-1027 (商品名, Nippon Kayaku Co.,Ltd.)。 環氧樹脂混合物成分(B)包括一種或多種於1501具有 〇.1>自(Pa. s)或較低(如,o.ooi至〇1泊)之溶體黏度之 環氧樹脂。此類環氧樹脂的實例包含γ D c _丨3丨2 (環氧當量:Nipol® DN631 (acrylonitrile: 33.5% 'density: 〇·99) and Nipol® NBR N34 (acrylonitrile: 27%, density: 〇·98) are available from Zeon Co., Ltd.; and when copolymerized The acrylate compound contains acrylonitrile based on one molecule, and resins such as those available from Hyundai Petrochemical Co., Ltd. i® SEETEC series can be used, but are not limited thereto. In the adhesive composition of the present invention, the copolymerized component (A): the epoxy resin mixture (B) described below has a weight ratio of 95:5 to 65:35, and preferably 90:1〇. To 7〇: 3〇. If component (a) is used in an amount less than this weight ratio, the adhesive composition becomes too hard and may be too easily broken during application or during the cutting process. Conversely, if f is (A) is more than the weight defined by the weight (4), it can ensure that the adhesive sheet is sufficiently viscous (four degrees) after adhesion and aging, which may be problematic. (Β) Thermosetting epoxy resin mixture 95048 9 201213478 to 15 (TC has 〇° or more than the following j. 〇1 ' . . . ) or lower melt viscosity (eg, 〇om main Ul / White) Epoxy resin and υ.ϋϋΐ Contains, for example, 簪 Α Α 每 ) — — — — — — — — — — — — — A A A A A A A A A A A A A A A A A A A A A A S-type epoxy tree t bisphenol F! 虱 虱 resin, double resin, one of the hopes of the beauty of the secret fat, the double-epice acetal epoxy compound diepoxypropyl ..., 笪 pit pit leaf lc* σ One of the oxime propyl ethers, and the 'meta-generation, _ or hydrogenated compound, polyfunctional epoxy resin, heterocyclic epoxy resin and the like. More specifically 'can be used as a commercial example, double-anti-type epoxy such as EPICOAT807, EPIC0AT815, EPIC0A, epic〇AT827, EPIC0AT828, EPIC0AT834, EPIC0AT1001, EPICOAT1002, EPICOAT1003, EPICOAT1055, EPICOAT1004, EPICOAT1004AF, EPICOAT1007, EPICOAT1009, EPI CO AT 10 0 3F, EPI COAT 10 0 4F (trade name, japan Epoxy Res i η Co., Ltd.), YD01 Bu YD-012, YD-013K, YD-014, YD-017, YD-112, YD-113, YD-114, YD-115, YD-127, YD-128 (trade name, Kuk-doChemical Co., Ltd.), SE-187, SE-187P (trade name, Shin-wha T&C Co., Ltd.), etc.; bisphenol F type epoxy resin such as YDF-161, YDF-162, YDF-170 (trade name, Kuk-do Chemical Co., Ltd.) 'SE-187, SE-187P ( Trade name 'Shin-whaT&CCo·, Ltd.), etc.; phenolic novolac epoxy resin such as EPPN-201, EPPN-501, 10 95048 201213478 EPPN-501HY, EPPN-502 (trade name, Nippon Kayaku Co., Ltd) . . ' YDPN-63 Bu YDPN-636, YDPN-638 (trade name, Kuk-do Chemical Co., Ltd.), etc.; and cresol phenolic acid ring Resins such as YDCN-500-1P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-10P, YDCN-500-80P (trade name, Kuk-do Chemical Co., Ltd. ), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1020, EOCN-1025, and EOCN-1027 (trade name, Nippon Kayaku Co., Ltd.). The epoxy resin mixture component (B) comprises one or more epoxy resins having a solution viscosity of 1501 from (Pa.s) or lower (e.g., o.ooi to 〇1 poise). Examples of such epoxy resins include γ D c _丨3丨2 (epoxy equivalent weight:

180 克/當量(g/eq),15(TC 時之黏度:〇· 〇1 泊)、YSLV-80XY (環氧當量:195克/當量,丨5(rc時之黏度:〇 〇1泊)及 YSLV-120TE(環氧當量:245克/當量,150°C時之黏度:〇. 1 泊)可購自 Dong-do Chemical Co.,Ltd. ; YX-40〇〇(環氧 當量:192克/當量,^(^時之黏度:0 005泊)可購自180 g / equivalent (g / eq), 15 (viscosity at TC: 〇 · 〇 1 poise), YSLV-80XY (epoxy equivalent: 195 g / equivalent, 丨 5 (viscosity at rc: 〇〇 1 poise) And YSLV-120TE (epoxy equivalent: 245 g / equivalent, viscosity at 150 ° C: 〇. 1 poise) can be purchased from Dong-do Chemical Co., Ltd.; YX-40 〇〇 (epoxy equivalent: 192 Gram / equivalent, ^ (time viscosity of ^: 0 005 poise) can be purchased from

Yukacel Co.,Ltd.;及 xd-1〇〇〇-2L(環氧當量:240 克/ 當量,150°C時之黏度:〇·05泊)以及CER_3〇〇〇-l(環氧當 量:233克/當量’ 150¾時之黏度:〇.〇3泊)可購自Ni卯〇n Kayaku Co·,Ltd. ’ 但不限於此。 環氧樹脂混合物成分(B)中於l5〇〇c具有〇.丨泊(1^· s)或較低之溶體黏度的環氧樹脂之含量並沒有特別限制。 基於100重量%之環氧樹脂混合物成分(B)之量,較佳可使 用5至50重量°/〇 ’但不限於此。 95048 11 201213478 根據本發明之較佳具體例,於丨π。 、u u l具有〇 白式較 := 黏度的環氧樹脂可以上逑量含於環氧樹脂混合物 成“Β)中,而使包括本發明黏著組成物之黏著片具有自 3.0至5.0之對數阻尼比之間之比率,該比率係以流變計 (Rhe〇Vib—T-3_,A&D C〇.,Ltd )分別於航及 120°C於高溫流動性測試進行測量,且於12〇ΐ可具有〇〇ι 至0. 1之對數阻尼比。 、 於包括本發明黏著組成物之黏著片,如果80t/12(rc 之對數阻尼比之比率少於3.0,高溫流動性可能太高因而 在同時要均句地保持上部與底部之間隙時可能在黏合晶片 與基板或晶片與晶片方面有困難。如果12(rc之對數阻尼 比大於0.1 ’當接合於半導體支持構件時流動性可能不足 且因而對暴露於接合表面上之凸塊及金層接線之嵌入性可 能不足。以流變計,PT-3000W所特定之性質的意義說明於 下述評估黏著片之方法中。 本發明之黏著組成物中,該共聚丙烯酸酯化合物成分 (A) ‘環氧樹脂混合物成分(B)之重量比率為95 : 5至65 : 35,較佳為90 : 1〇至: 30。如果成分(B)以多於上述重 里比率所疋義之量使用’則黏著組成物變成太硬且因此在 施用期間或切割過程時可能容易破損。相反的,如果成分 (B) 以少於上述重量比率所定義之量使用’不能保證黏著片 在黏著及固化後之足量黏著強度而可靠性可能有問題。 (C)固化劑 本發明之黏著組成物中,固化劑係使用於固化環氣樹 12 95048 201213478 脂 慣用之固化劑可使用於本發明之黏 可使用選自I系化合物類、胺化合物類、δ'^物。例如, 環氧樹脂用固化劑。較佳可使用具有二_類等慣用的 且羥基當量100克/當量至300克/當量之二兩個以上羥基 酚系酚醛環氧樹脂),而無特別限制。-系樹脂(例如, 本發明之黏著組成物中,固化劑 ⑻之當量比率較佳為0. 8至1.3,更佳為樹脂現合物 果固化劑量遠超出此範圍,未作用之環^ 至1. 1。如 脂可能殘留並於高溫劣化,而可能降低較^或固化剖樹 (D)填充料 一、、#性。 =發明之黏著組成物中,填充料係使用 之耐熱性高溫流動性、加工過程操作性等。碉整黏著片 可使用於本黏著組成物中之填充料並盔 如’可使用氧化硬、氧化銘、銀 &、1]限制。例 黑一'酬、氣化=::鈦:等-=’該等呈球狀且具有10奈米(㈤幻。微米 =尺寸較佳實例為球形氧切其於”組成物令具 义好之分散性並有利於提供高溫流動性。 、於每_重量份之該等成分⑴ΚΒ) +⑹中,本黏著組 成物中^充料(D)之含量係1Q至⑽重量份,較佳為2〇至 60重篁份。如果每重量份之該成分(A) +⑻+⑹中, 填充料量少於10重量份,則黏著片之強度減低而可能易於 發生高溫熱應力Μ之變形。如果填充料量大於80重量 95048 13 201213478 份,黏著片之脆度性問題變得嚴重而加工期間可能易發生 破損,且與黏合膜之黏著力減低,而減低加工過程之可操 作性。 ' (E )固化促進劑 本發明之黏著組成物中,固化促進劑係使用於改進固 化率。 可使用於本黏著組成物中之固化促進劑並無特別限 制。任何固化促進劑均可使用,只要於固化條件之溫度下 月b減少黏者組成物之固化時間者即可。其較佳係使用在製 得黏著月之條件下具低反應性,而在120。(:至18〇°C之固化 溫度下具咼反應性之化合物。例如,可使用2MZ-A、C11Z-A、 2MA-OK、2PHZ 及 2P4MHZ ’ 現可睛自 Sa-kuk Chemical Co., Ltd.;及 TPP、TBP、TBP、TPP-K、TPP-MK、TPPO、DPPE 及 DPPB 現可購自 Hoko Chemical Co.,Ltd.。 於每100重量份之該等成分(A) + (B) + (C)之總量中,本 黏著組成物中固化促進劑(E)之含量係0. 1至1. 4重量份, 較佳為0. 2至1· 0重量份。如果於每1〇〇重量份之該等成 分(A) + (B) + (C)之總量中,固化促進劑量少於〇. 1重量份, 於晶片堆疊後之固化過程中之固化率會不足而底部晶片可 能因其後之晶片堆疊所施加的熱與負荷而搖動,導至瑕疲 品。如果固化促進劑量大於1. 4重量份,由於製造黏著片 過程期間產生的熱可能會發生一些副反應而當產品保存於 室溫時會有減低長期儲藏穩定性之可能性。 除前述成分之外,本黏著組成物可進一步包括其他成 95048 14 201213478 分’其等係慣用於半導體製程之黏著組成物中者,該等其 他成分包含適當量之溶劑諸如丙酮、丁酮、甲苯、乙酸乙 醋等’黏結增強劑、偶合劑、抗靜電劑、快固劑、熱固性 助劑、黏著增強劑、潤濕改善劑、調平(leveling)增強劑 等。本發明之較佳具體例中,具有可黏合於樹脂混合物及 黏著表面兩者之功能基的偶合劑因有助於改進彈性及耐熱 性’而於總量每100重量份之混合物中,可使用3. 0重量 份或較少之量。 製得本黏著組成物之方法沒有特別限制。可以使用慣 用來製備黏著組成物之慣用裝置來製備。根據本發明之具 體例之一 ’本黏著組成物係可於室溫或適當提高之溫度下 以諸如珠磨機等裝置分散及混合上述成分以製得。 本發明另一方面係提供製造半導體用之黏著片,其係 包括如上述之本發明黏著組成物之塗佈層者。 本發明之製造半導體之黏著片之特點為包括本發明黏 著組成物之塗佈層,如果必要,可進一步包括一個或多個 之基底(膜)層’其亦可指離型(膜)層或保護(膜)層,及一 個或多個黏結(膜)層。根據本發明之具體例之一’製造半 導體用之黏著片可具有層狀結構諸如基底層+黏著組成物 廣’基底層+黏著組成物層+基底層;基底層+黏結層+黏著 組成物層;基底層+黏結層+黏著組成物層+基底層等,但不 限於此。 可包含於本發明製造半導體用之黏著片之基底層之材 料並無特別限制。可使用習慣上作為黏著片基底膜之材料 15 95048 201213478 諸如聚對笨二甲酸乙二酯、聚烯烴或聚氣乙烯。至於黏結 詹’可使用慣用於黏著片之黏結材料諸如含有光反應性低 聚物之丙烯酸系材料。 製造半導體用之本黏著片中,黏著組成物塗佈層之乾 厚度並無特別限制,較佳為1〇至2〇〇微米之範圍内。如果 黏著組成物塗佈層之乾厚度小於1〇微求,黏著效力可能不 f二如果乾厚度大於2⑽微米,塗佈操作於塗佈之乾焊過 堆璺矛王度越向時,黏著劊矸飴一 田 φ 在向溫黏合期間自旁邊嵌 出。黏者組成物較佳在125<t 4 二= 一,可以製得本黏著片, 本發月之具體例之 稀釋麵合本黏著組成物至 用於諸如聚對苯二F酸乙二 二乂易於形成塗層,施 施用及乾燥程序,可使用任何可开 並乾燥之。至於 二塗佈、凹版塗佈、刮刀式塗佈;轉法諸如棒 式塗佈、模具娜_屻、=,、滾刀 制。 狹縫式式塗佈等而無限 如上述之本發明黏著片具有 面 提供對於諸如暴露於要接合之表面之凸性且因此 之良好的嵌入性’及對半導趙之切構件具==造 95048 16 201213478 黏著度因此即使在离、、w 高可靠性。 ° μ〜、狀況下亦提供半導體元件之 本發明係以下诚$香 明。但本發明之_料限㈣更仔細地加以說 實施例1 .^;Γ(β42)1;Γ^Γ^ ρ =_b合物(Α1)中,錢 入‘ := 之:丨,氧樹脂-其對環氧樹脂‘ 45重於量=Γ上述製備而得的混合物中,依序加入 里伤之球形氧化矽(D1)作 化促進劑⑻及1.54量份之偶w m里物之固 W為求心之黏度及溶解度,進—步加人有機溶劑丁 _使、'且成物中固體總量為継至35%之量。完成預麟後, 組成物以珠磨机充分再分散然後塗佈於38微米厚並經過 單面離型處理之聚對笨二甲酸乙二酯離型膜上,使成為6〇 微米之乾厚度而製得點著片。 d明於下之評估方法申之黏彈儀試驗(Rheovibron test)之樣本係將上述製得之黏著片於6〇它層壓至厚度 200微米而製得。 實施例2至7 根據顯π於表1之組成比率,黏著組成物及月係以如 實施例1中之相同方法製得。 95048 17 201213478 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 A1(克) 280. 5 0. 0 0. 0 0. 0 0 0 0· 0 0. 0 A2(克) 0. 0 280. 5 0. 0 280. 5 174. 0 412. 6 412. 6 A3(克) 0. 0 0. 0 280. 5 0. 0 0. 0 0. 0 0. 0 81(克) 37. 4 37. 4 37. 4 37. 4 47. 1 14. 6 14. 6 Β2(克) 14. 0 14. 0 14. 0 8. 7 0. 0 0· 0 0. 0 Β3(克) 0, 0 0. 0 0. 0 5. 9 13. 8 11.9 11.9 C(克) 25. 7 25. 7 25. 7 25. 7 32. 2 13. 3 13. 3 於每100重量份上述成分總合t,添加劑之使用量(重量份) D1 45. 0 45. 0 45. 0 0. 0 45. 0 0. 0 0. 0 D2 0.0 0. 0 0. 0 45. 0 0. 0 45. 0 45. 0 E 0· 3 0· 3 〇_ 3 0. 3 0. 3 0. 3 1.0 F 1.5 1.5 1.5 1.5 1.5 1.5 1.5 [表1] A1 : SG-PT115 (Nagase Chemtex,環氡值:〇·21 當量/公斤,羥值:20 毫克 Κ0Η/克) A2 : SG-PT134 (Nagase Chemtex,環氧值:〇_ 21 當量/公斤,羥值:30 毫克 Κ0Η/克) A3 : SG-PT135 (Nagase Chemtex ’ 環氧值:0.21 當量/公斤,羥值:40 毫克 K0H/克) B1 : YDCN-500-4P (Kuk-do Chemical,環氡當量:200 克/當量,軟化點:62°C) B2 : YSLV-80XY(Dong-doChemical ,環氧當量:195 克/當量,15(TC 時之黏度:0. 01 泊) B3 : YX-4000 (Yukacel,環氧當量:192克/當量,150t時之黏度:0· 005泊) C : HF-1M (Meiwha,羥基當量:106克/當量,軟化點:84〇c ) D1 : S0-31R (Datsmori ,平均粒徑:1·24微米,比表面積(S.S.A) : 4.68平方米/克) D2 : FB-3SDX (Denka,平均粒徑:3.3微米,比表面積(s.s A) : 3·9平方米/克) E: 2MA0K-PW (Sa-kuk Chemical,平均粒徑:2 微米,熔點:260。〇 F : KBM-303 (ShinEtsu ,環氧當量:222 克/當量,密度:! 〇6) (A系列:反應性共聚丙烯酸酯化合物,B系列:環氧樹脂,D系列:填充料) 比較例1至9 根據顯示於表2之組成比率,以如實施例1中之相同 95048 18 .201213478 方法製得比較例之黏著組成物及片。 [表2] 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 比較例 7 比較例 8 比較例 9 A2(克) 0. 0 0· 0 113. 5 433. 7 281. 0 278. 3 383. 5 220. 4 280. 5 R1(克) 280. 5 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 R2(克) 0· 0 280. 5 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 BK克) 37. 4 37· 4 54. 1 5. 8 37. 5 37. 0 56. 4 26.4 51.4 B2(克) 14. 0 14. 0 14. 0 10. 5 14. 0 14. 0 13. 9 14. 0 0 C(克) 25. 7 25. 7 34. 1 8. 1 25. 8 25. 5 35. 2 20. 2 25. 7 於每10 0重量份 上述成分總合中, 添加劑之使用量< :重量份) D2 45. 0 45. 0 45. 0 45. 0 45. 0 45. 0 5. 0 85. 0 45. 0 E 0. 3 0. 3 0. 3 0. 3 0. 0 1.5 0. 3 0. 3 0. 3 F 1.5 1.5 1.5 1. 5 1.5 1.5 1. 5 1. 5 1.5 Rl:KNB40M(Kum-ho Petrochemical’丙烯腈_丁二烯橡膠,丙烯腈:41%,門尼黏度 CML+4, l〇〇°c ) : 60) R2:KNB 20LM(Kum-ho Petrochemical,丙烯腈-丁二烯橡膠,丙烯腈:28¾,門尼黏度 (ML+4, l〇〇°c ) : 50) 以上製得之實施例及比較例之黏著片’係根據下述方 法來實行特性評估。 表面能 為評估使用於實施例之反應性共聚丙烯酸酯化合物及 使用於比較例之丙烯腈-丁二烯橡膠之表面能,將各種製得 之黏著組成物以相同的塗佈厚度塗佈於平面硬支持板使 用接觸角測量儀(SE0300A,Surface Electro Optics Co.,Yukacel Co., Ltd.; and xd-1〇〇〇-2L (epoxy equivalent: 240 g/equivalent, viscosity at 150 ° C: 〇·05 poise) and CER_3〇〇〇-l (epoxy equivalent: 233 g / equivalent '1503⁄4 hour viscosity: 〇. 〇 3 poise) is available from Ni卯〇n Kayaku Co., Ltd. 'But not limited to this. The content of the epoxy resin in the epoxy resin mixture component (B) having a viscosity of 〇.丨(1^·s) or a lower solution viscosity in l5〇〇c is not particularly limited. The amount of the epoxy resin mixture component (B) based on 100% by weight is preferably from 5 to 50% by weight, but not limited thereto. 95048 11 201213478 According to a preferred embodiment of the invention, 丨π. , uul has a whitening type: = viscosity of the epoxy resin can be contained in the epoxy resin mixture into a "Β", so that the adhesive sheet comprising the adhesive composition of the present invention has a logarithmic damping ratio of from 3.0 to 5.0 The ratio between the ratios is measured by a rheometer (Rhe〇Vib-T-3_, A& DC〇., Ltd) at a high temperature fluidity test at 120 ° C and at 12 ° C. Having a logarithmic damping ratio of 〇〇ι to 0.1. In the adhesive sheet comprising the adhesive composition of the present invention, if the ratio of the logarithmic damping ratio of 80t/12 is less than 3.0, the high temperature fluidity may be too high and thus It may be difficult to bond the wafer to the substrate or the wafer and the wafer when the gap between the upper portion and the bottom portion is maintained uniformly. If 12 (the logarithmic damping ratio of rc is greater than 0.1', the fluidity may be insufficient when bonded to the semiconductor supporting member and thus The embedding of the bump and gold layer wiring exposed on the bonding surface may be insufficient. The significance of the properties specific to PT-3000W in the rheometer is described in the following method for evaluating the adhesive sheet. , the copolyacrylate The component (A) 'epoxy resin mixture component (B) has a weight ratio of 95:5 to 65:35, preferably 90:1〇 to: 30. If the component (B) is more than the above ratio The amount of derogatory use 'is that the adhesive composition becomes too hard and therefore may be easily broken during application or during the cutting process. Conversely, if the ingredient (B) is used in an amount less than the above-mentioned weight ratio, 'the adhesive sheet cannot be guaranteed The adhesive strength may be problematic after adhesion and curing. (C) Curing agent In the adhesive composition of the present invention, the curing agent is used for curing the ring tree 12 95048 201213478 The curing agent for the fat can be used for the present invention. The adhesive of the invention may be selected from the group consisting of a compound of the I group, an amine compound, and a δ'. For example, a curing agent for an epoxy resin. It is preferred to use a conventional one having a dioxin ratio of from 100 g/eq to 300. The ratio of the equivalent ratio of the curing agent (8) is preferably 0.8 to 1.3. The equivalent ratio of the curing agent (8) is preferably 0.8 to 1.3. More preferably a resin present compound The curing dose is far beyond this range, the unacting ring ^ to 1.1. If the fat may remain and deteriorate at high temperature, it may reduce the hardness of the filler or the cured section (D) filler. In the composition, the filler is heat-resistant high-temperature fluidity, processability, etc. The adhesive sheet can be used for the filler in the adhesive composition and can be used as a hardened, oxidized, silver, and amp. ;, 1] Restriction. Example black one 'remuneration, gasification =:: Titanium: etc. -=' These are spherical and have 10 nm ((5) illusion. Micron = size is preferred as spherical oxygen cut" The composition is well dispersed and helps to provide high temperature fluidity. The content of the charge (D) in the present adhesive composition is from 1Q to (10) parts by weight, preferably from 2 Å to 60 parts by weight, per part by weight of the components (1) ΚΒ) + (6). If the amount of the filler is less than 10 parts by weight per part by weight of the component (A) + (8) + (6), the strength of the adhesive sheet is lowered and deformation of the high-temperature thermal stress 易于 may be liable to occur. If the amount of filler is more than 80 parts 95048 13 201213478 parts, the brittleness problem of the adhesive sheet becomes serious and breakage may occur during processing, and the adhesion to the adhesive film is reduced, thereby reducing the operability of the processing. '(E) Curing accelerator The curing accelerator of the present invention is used to improve the curing rate. The curing accelerator which can be used in the present adhesive composition is not particularly limited. Any curing accelerator can be used as long as the curing time of the adhesive composition is reduced by the month b at the temperature of the curing condition. It is preferably used with a low reactivity under the conditions of the adhesive month, and is at 120. (: compounds with hydrazine reactivity at a curing temperature of 18 ° C. For example, 2MZ-A, C11Z-A, 2MA-OK, 2PHZ and 2P4MHZ can be used. Now available from Sa-kuk Chemical Co., Ltd. And TPP, TBP, TBP, TPP-K, TPP-MK, TPPO, DPPE and DPPB are now available from Hoko Chemical Co., Ltd.. Each component (A) + (B) per 100 parts by weight.至1. 0重量份。 If the content of the curing agent (E) is 0. 1 to 1.4 parts by weight, preferably 0.2 to 1.0 parts by weight. In the total amount of the components (A) + (B) + (C), the curing accelerator dose is less than 0.1 part by weight, and the curing rate during the curing process after the wafer stacking is insufficient. The wafer may be shaken by the heat and load applied by the subsequent wafer stack to lead to fatigue. If the curing acceleration dose is greater than 1.4 parts by weight, some side reactions may occur due to heat generated during the process of manufacturing the adhesive sheet. When the product is stored at room temperature, there is a possibility of reducing long-term storage stability. In addition to the aforementioned components, the adhesive composition may further include other into 9504. 8 14 201213478 is divided into 'adhesive compositions used in semiconductor processes. These other ingredients contain appropriate amounts of solvents such as acetone, methyl ethyl ketone, toluene, ethyl acetate, etc. 'bonding enhancers, coupling agents, antistatic Agent, fast curing agent, thermosetting auxiliary, adhesion enhancer, wetting improver, leveling enhancer, etc. In a preferred embodiment of the invention, it has the function of being adhesive to both the resin mixture and the adhesive surface. The coupling agent of the base may be used in an amount of 3.0 parts by weight or less in a total amount per 100 parts by weight of the total amount of the coupling agent. The method for producing the adhesive composition is not particularly limited. It can be prepared by a conventional apparatus which is conventionally used for preparing an adhesive composition. According to one of the specific examples of the present invention, the present adhesive composition can be dispersed and mixed at room temperature or appropriately elevated temperature by means such as a bead mill. The present invention provides an adhesive sheet for producing a semiconductor, which comprises the coating layer of the adhesive composition of the present invention as described above. The adhesive sheet of the semiconductor is characterized by comprising a coating layer of the adhesive composition of the present invention, and if necessary, further comprising one or more substrate (film) layers, which may also be referred to as a release (film) layer or a protective (film) layer. a layer, and one or more bonding (film) layers. According to one of the specific examples of the present invention, an adhesive sheet for manufacturing a semiconductor may have a layered structure such as a base layer + an adhesive composition wide base layer + an adhesive composition layer + Base layer; base layer + adhesive layer + adhesive composition layer; base layer + adhesive layer + adhesive composition layer + base layer, etc., but is not limited thereto. The material which can be included in the base layer of the adhesive sheet for producing a semiconductor of the present invention is not particularly limited. It is customary to use as a material for the base film of the adhesive sheet. 15 95048 201213478 Such as polyethylene terephthalate, polyolefin or polyethylene. As for the bonding, a bonding material conventionally used for an adhesive sheet such as an acrylic-based material containing a photoreactive oligomer can be used. In the present adhesive sheet for producing a semiconductor, the dry thickness of the coating layer of the adhesive composition is not particularly limited, and is preferably in the range of 1 Å to 2 μm. If the dry thickness of the coating layer of the adhesive composition is less than 1 〇, the adhesion efficiency may not be the same. If the dry thickness is greater than 2 (10) micrometers, the coating operation is applied to the dry soldering of the coated spears.矸饴一田 φ is embedded from the side during the temperature bonding. Preferably, the adhesive composition is at 125 < t 4 ii = one, and the adhesive sheet can be obtained. The diluted surface of the specific example of this month is used for the adhesive composition to be used for, for example, polyethylene terephthalate. It is easy to form a coating, apply and dry, and can be used to open and dry. As for the two coating, the gravure coating, the blade coating; the transfer method such as stick coating, mold 屻, ,, =, hob. Slit-coating, etc., and infinitely as described above, the adhesive sheet of the present invention has a face providing a good embedding property for, for example, exposure to a surface to be joined, and thus a semi-conductive member having a cutting edge == 95048 16 201213478 Adhesion is therefore highly reliable even when it is away from, and w. The present invention is also provided in the state of ° μ~, and the present invention is as follows. However, the limit of the present invention (4) is more carefully described in the example 1. ^; Γ (β42) 1; Γ ^ Γ ^ ρ = _ b compound (Α 1), money into ' : = : 丨, oxygen resin - in the mixture prepared by the above epoxy resin '45 heavy weight = Γ, the spherical cerium oxide (D1) as a chemical accelerator (8) and 1.54 parts of the even wm lining In order to find the viscosity and solubility of the heart, the amount of solids in the organic solvent is increased to 35%. After completion of the pre-strup, the composition was fully redispersed in a bead mill and then coated on a 38 μm thick polybutylene dicarboxylate release film which was subjected to single-sided release treatment to a dry thickness of 6 μm. And made a piece of film. The sample of the Rheovibron test, which is described in the following evaluation method, was prepared by laminating the above-mentioned adhesive sheet to a thickness of 200 μm. Examples 2 to 7 According to the composition ratio of π in Table 1, the adhesive composition and the month were obtained in the same manner as in Example 1. 95048 17 201213478 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 A1 (g) 280. 5 0. 0 0. 0 0. 0 0 0 0 0 0. 0 A2 (克) 0. 0 280. 5 0. 0 280. 5 174. 0 412. 6 412. 6 A3 (g) 0. 0 0. 0 280. 5 0. 0 0. 0 0. 0 0. 0 81( g) 37. 4 37. 4 37. 4 37. 4 47. 1 14. 6 14. 6 Β2 (g) 14. 0 14. 0 14. 0 8. 7 0. 0 0· 0 0. 0 Β3( g) 0, 0 0. 0 0. 0 5. 9 13. 8 11.9 11.9 C (g) 25. 7 25. 7 25. 7 25. 7 32. 2 13. 3 13. 3 per 100 parts by weight of the above Total composition t, amount of additive used (parts by weight) D1 45. 0 45. 0 45. 0 0. 0 45. 0 0. 0 0. 0 D2 0.0 0. 0 0. 0 45. 0 0. 0 45 0 45. 0 E 0· 3 0· 3 〇 _ 3 0. 3 0. 3 0. 3 1.0 F 1.5 1.5 1.5 1.5 1.5 1.5 1.5 [Table 1] A1 : SG-PT115 (Nagase Chemtex, ring value: 〇·21 eq/kg, hydroxyl value: 20 mg Κ0 Η/g) A2 : SG-PT134 (Nagase Chemtex, epoxy value: 〇 _ 21 eq/kg, hydroxyl value: 30 mg Κ 0 Η / gram) A3 : SG-PT135 (Nagase Chemtex ' Epoxy value: 0.21 eq/kg, hydroxyl value: 40 mg K0H/g) B1 : YDCN- 500-4P (Kuk-do Chemical, 氡 equivalent: 200 g / equivalent, softening point: 62 ° C) B2 : YSLV-80XY (Dong-doChemical, epoxy equivalent: 195 g / equivalent, 15 (viscosity at TC) :0. 01 poise) B3 : YX-4000 (Yukacel, epoxy equivalent: 192 g / equivalent, viscosity at 150 t: 0 · 005 poise) C : HF-1M (Meiwha, hydroxyl equivalent: 106 g / equivalent, softened Point: 84〇c) D1: S0-31R (Datsmori, average particle size: 1.24 μm, specific surface area (SSA): 4.68 m 2 /g) D2 : FB-3SDX (Denka, average particle size: 3.3 μm, Specific surface area (ss A): 3·9 m 2 /g) E: 2MA0K-PW (Sa-kuk Chemical, average particle diameter: 2 μm, melting point: 260). 〇F : KBM-303 (ShinEtsu, epoxy equivalent: 222 g / equivalent, density: ! 〇 6) (A series: reactive copolyacrylate compound, B series: epoxy resin, D series: filler) Comparative example 1 to 9 According to the composition ratios shown in Table 2, the adhesive compositions and sheets of the comparative examples were prepared by the same method as in the example of 95048 18 .201213478. [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 A2 (g) 0. 0 0· 0 113. 5 433. 7 281. 0 278. 3 383. 5 220. 4 280. 5 R1(g) 280. 5 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 R2(g) 0· 0 280. 5 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 BK 克) 37. 4 37· 4 54. 1 5. 8 37. 5 37. 0 56. 4 26.4 51.4 B2 (g) 14. 0 14. 0 14. 0 10. 5 14. 0 14. 0 13. 9 14. 0 0 C (g) 25. 7 25. 7 34. 1 8. 1 25. 8 25. 5 35. 2 20. 2 25. 7 The amount of the additive used per 10 parts by weight of the above ingredients, < : parts by weight. D2 45. 0 45. 0 45. 0 45. 0 45. 0 45. 0 5. 0 85. 0 45. 0 E 0. 3 0. 3 0. 3 0. 3 0. 0 1.5 0. 3 0. 3 0. 3 F 1.5 1.5 1.5 1. 5 1.5 1.5 1. 5 1. 5 1.5 Rl: KNB40M (Kum-ho Petrochemical 'acrylonitrile-butadiene rubber, acrylonitrile: 41%, Mooney viscosity CML+4, l〇〇°c) : 60) R2: KNB 20LM (Kum-ho Petrochemical , acrylonitrile-butadiene rubber, acrylonitrile: 283⁄4, Mooney viscosity (ML+4, l〇〇°c): 50) Examples and comparative examples prepared above Adhesive sheet 'characteristic evaluation system implemented according to the following method. The surface energy was evaluated by evaluating the surface energy of the reactive copolyacrylate compound used in the examples and the acrylonitrile-butadiene rubber used in the comparative example, and coating the obtained adhesive compositions on the plane with the same coating thickness. The hard support plate uses a contact angle measuring instrument (SE0300A, Surface Electro Optics Co.,

Ltd.)測量與水的表面能。 95048 19 201213478 黏著強度 黏著強度測量係根據試驗模式JISZ 0237及KSA 1107 (黏著帶及片之試驗方法)使用萬能材料試驗機以90°剝離 試驗來實行。用於黏著強度測量之試驗樣品係以1密耳 (mil)厚之聚醯亞胺膜(IN70,SKC)於65°C熱壓縮於黏著片 之兩面並切割成寬10毫米長150毫米之尺寸而製得。評估 之試驗速度為50毫米/分鐘。 層壓特性 使用膠帶固定設備123〇A,Dynatech c〇·, Ltd.)於65°C以橡膠滚輪來回循環進行壓縮而使各種於實 施例及比較例製得之黏著片與其上具有圖案之8吋晶圓進 行層壓。觀察層壓樣品是否在晶圓與黏著片間產生空隙。 該評估係產生之空隙為總面積之5%或較多時之狀況歸類為 X,產生之空隙少於總面積之5%時之狀況為〇° 高溫流動性及固化特性 各種於實施例及比較例製得之黏著片之南溫流動性係 以測量聚合物流變之設備之黏彈儀(Rheovibron, RPT-3000W,ANDCo.,Ltd.)在 25°C 至 150°C 的加熱條件下 根據流體流動性測量阻尼比以評估。固化特性係根據黏著 片在125°C等溫條件下60分鐘之相轉移(phase transition) 來測量振盡週期以評估。 具體地,將製得之具200微米塗佈厚度之黏著片置於 黏彈儀(Rheovibron)之加熱板上,並將管狀(RBP020)或刀 狀(RBE130)探針浸入黏著片中。然後,在上述測量的條件 20 95048 201213478 力量移開探針,由此改變黏著層内之流體特性 特二由相應改變之擺錘週期、振幅及波數之 期初值纽…皿流動性及固化特性1化特性係以擺錘週 ^刀值與終值間之改變比率(%)計算。高溫流祕係由阻尼 t以下列公式1計算。該評估係將於12(rc具有G ^或較 小對數阻尼比’而於8(rc/靴之阻尼比3· 〇或較大之黏 著片歸類為〇’於12(rc具㈣.丨或較小對數阻尼比作且 有2. 0或較小之8(rc/12(rc阻尼比之黏著片歸類為△,其 他狀況為X。 公式1 △對數阻尼比=[ln(Al/A2) + ln(A2/A3) + ... + ln(An/ A(n+l))]/n 在上列公式中,A1為正弦波中的第一個振幅值,A2為 第一個振幅值’ An為第η個振幅值’ η為總數波。 剪力強度 將各種於實施例及比較例製得之黏著片接合於已完全 • ♦ · -. 形成圖案及鈍化之8叫·,200微米晶圓背面。然後以切割 裝置(DFD6361,DiscoCo.,Ltd.)將晶圓切成2毫米χ2毫 米之晶片。使用黏晶裝置(SDB-30US,SecronCo.,Ltd.) 在120°C ’ 〇· 3兆帕(MPa)及3秒鐘之接合條件下將晶片雙 層堆疊,然後在175°C固化2小時以製得測量剪力強度用 之樣品。將某些製得的樣品分別保存於85Ϊ具85%相對濕 度之恆溫槽24小時以製得暴露於高溫/高濕之樣品。如此 製得的樣品之剪力強度係以黏合測試器(DAGE-4000PXY, 21 95048 201213478 DAG Co.,Ltd.)測量並比較結果。 此外,當剪力強度在上述條件評估10次時,計數顯示 黏結破壞狀態之樣品數,其係在剪切破碎表面上黏著層之 破裂,並以%顯示。 金屬接線嵌入性 在具有自晶片頂部50微米高之金接線作為半導體晶 片與基板間之金屬接線之半導體晶片上’使用黏晶裝置 (SDB-30US,SecronCo.,Ltd.)於 130°C,0.5 兆帕(MPa) 及1秒鐘之條件下,加熱黏合接合有黏著片之第二片晶 片,然後在170°C固化2小時以製得堆疊晶片。研磨製得 之堆疊晶片切面然後觀察接線是否受損及產生任何直徑5 微米或較大之空隙。觀察結果當發生接線受損時以X表示, 當空隙產生時為△及當狀況良好時為〇。 熱收縮抗性 製得實施例及比較例之各種黏著片使具有60微米之 乾厚度及100毫米xl00毫米之尺寸並置於聚對苯二曱酸乙 二酯膜上,該膜係已經過單面離型處理,然後保持於175°C 之固化條件下2小時。測量因熱處理收縮變形之自底面之 歪曲南度並記錄之。 抗濕性 使用於實施例及比較例製得之各種黏著片,將雙層堆 疊晶片於121°C,100%相對濕度及2大氣壓的條件下進行 加壓蒸煮試驗(PCT)達72小時,然後觀察黏著表面以檢查 是否產生任何剝離。觀察結果當狀況良好時以〇表示,當 22 95048 201213478 產生剝離時為χ。 頌干方法所得之結果令,表面能及黏著強度 顯不於下面表3。於實施例及比較例製得之黏著片之評估 結果分別顯示於下面表4及5。 [表3]Ltd.) measures the surface energy of water. 95048 19 201213478 Adhesive strength The adhesion strength measurement was carried out in accordance with the test mode JISZ 0237 and KSA 1107 (test method for adhesive tapes and sheets) using a universal material testing machine with a 90° peel test. The test sample for adhesion strength measurement was heat-compressed on both sides of the adhesive sheet at a temperature of 65 ° C with a 1 mil thick polyimide film (IN70, SKC) and cut into a size of 10 mm wide and 150 mm wide. And made. The test speed was evaluated at 50 mm/min. The lamination characteristics were carried out by using a tape fixing device 123A, Dynatech c., Ltd., and circulating the rubber roller at 65 ° C to compress the adhesive sheets prepared in the examples and the comparative examples. The wafer is laminated. Observe whether the laminated sample creates a gap between the wafer and the adhesive sheet. The condition in which the gap is 5% or more of the total area is classified as X, and the resulting gap is less than 5% of the total area. The condition is 〇° high temperature fluidity and curing characteristics are various in the examples and The south temperature fluidity of the adhesive sheet prepared by the comparative example is based on a viscoelastic apparatus (Rheovibron, RPT-3000W, AND Co., Ltd.) for measuring the rheology of the polymer under the heating condition of 25 ° C to 150 ° C according to Fluid mobility measures the damping ratio to evaluate. The curing characteristics were evaluated by measuring the vibration period according to the phase transition of the adhesive sheet at 125 ° C isothermal conditions for 60 minutes. Specifically, an adhesive sheet having a coating thickness of 200 μm was placed on a hot plate of a Rheivibron, and a tubular (RBP020) or knife-shaped (RBE130) probe was dipped in the adhesive sheet. Then, under the above-mentioned measured conditions 20 95048 201213478, the force is removed, thereby changing the fluid characteristics in the adhesive layer. The second period is the corresponding change of the pendulum period, amplitude and wave number. The 1 characteristic is calculated by the ratio (%) of the change between the value of the pendulum and the final value. The high temperature flow system is calculated from the damping t by the following formula 1. The evaluation will be at 12 (rc has a G ^ or smaller logarithmic damping ratio) and 8 (rc/boot damping ratio 3·〇 or larger adhesive sheet is classified as 〇' at 12 (rc with (4).丨Or a smaller logarithmic damping ratio with 2.0 or less 8 (rc/12 (the rc damping ratio of the adhesive sheet is classified as △, and the other condition is X. Equation 1 △ logarithmic damping ratio = [ln(Al/ A2) + ln(A2/A3) + ... + ln(An/ A(n+l))]/n In the above formula, A1 is the first amplitude value in the sine wave, and A2 is the first The amplitude value 'An is the ηth amplitude value' η is the total number of waves. The shear strength is to bond the various adhesive sheets prepared in the examples and the comparative examples to the complete ♦ · -. Patterning and passivation 8 , 200 μm wafer back side. Then the wafer was cut into 2 mm χ 2 mm wafers by a cutting device (DFD6361, DiscoCo., Ltd.) using a die bonding device (SDB-30US, Secron Co., Ltd.) at 120°. The wafer was double-layered under C' 〇·3 MPa (MPa) and 3 seconds bonding conditions, and then cured at 175 ° C for 2 hours to obtain a sample for measuring shear strength. Some prepared samples were prepared. Stored in 85 cookware with 85% relative humidity The temperature was measured for 24 hours to obtain a sample exposed to high temperature/high humidity. The shear strength of the sample thus obtained was measured by a bonding tester (DAGE-4000PXY, 21 95048 201213478 DAG Co., Ltd.) and the results were compared. Further, when the shear strength was evaluated 10 times in the above conditions, the number of samples showing the state of the adhesion failure was counted, which was broken at the adhesion layer on the shear fracture surface, and was shown in %. The metal wiring embedding was on the top of the wafer. 50 micron high gold wiring on a semiconductor wafer as a metal wiring between a semiconductor wafer and a substrate 'Using a die bonding device (SDB-30US, Secron Co., Ltd.) at 130 ° C, 0.5 MPa (MPa) and 1 second Under the condition, the second wafer of the adhesive sheet is bonded by heat bonding, and then cured at 170 ° C for 2 hours to prepare a stacked wafer. The stacked wafer cut surface is obtained by grinding and then observing whether the wiring is damaged and producing any diameter of 5 μm or Larger gaps. The observation results are indicated by X when the wiring is damaged, Δ when the void is generated, and 〇 when the condition is good. Heat shrinkage resistance is obtained by making various adhesive sheets of the examples and comparative examples. It has a dry thickness of 60 microns and a size of 100 mm x 100 mm and is placed on a polyethylene terephthalate film. The film has been subjected to single-sided release treatment and then maintained at 175 ° C for 2 hours under curing conditions. The measured shrinkage of the bottom surface due to the shrinkage deformation of the heat treatment was recorded and recorded. The moisture resistance was measured using various adhesive sheets prepared in the examples and comparative examples, and the double-layer stacked wafer was irradiated at 121 ° C, 100% relative humidity and 2 A pressure cook test (PCT) was carried out under atmospheric pressure for 72 hours, and then the adhesive surface was observed to check whether any peeling occurred. The observation results are indicated by 〇 when the condition is good, and χ when 22 95048 201213478 is peeled off. The results obtained by the dry method made the surface energy and adhesion strength not as shown in Table 3 below. The evaluation results of the adhesive sheets prepared in the examples and comparative examples are shown in Tables 4 and 5 below, respectively. [table 3]

[表4] 實施例 1 2 3 4 5 6 7 層壓特性 〇 〇 〇 〇 〇 〇 〇 高溫流動性 〇 〇 〇 〇 〇 〇 〇 固化特性 58¾ 66% 67¾ 65¾ 81% 55% 77% 剪力強度1) 17kgf 23kgf 22kgf 18kgf 27kgf 15kgf 18kgf 剪力強度2) 17kgf 21kgf 18kgf 20kgf 24kgf 14kgf 16kgf 剪切表面之黏結破壞 80% 90% 90¾ 80¾ 60¾ 80¾ 70% 金屬接線嵌入性 〇 〇 〇 〇 〇 〇 〇 熱收縮抗性 Omm 0mm Omm Omm 3mm 2mm Omm 抗濕性 〇 〇 〇 〇 〇 〇 〇[Table 4] Example 1 2 3 4 5 6 7 Lamination Characteristics 〇〇〇〇〇〇〇 High Temperature Fluidity 〇〇〇〇〇〇〇 Curing Characteristics 583⁄4 66% 673⁄4 653⁄4 81% 55% 77% Shear Strength 1 17kgf 23kgf 22kgf 18kgf 27kgf 15kgf 18kgf Shear strength 2) 17kgf 21kgf 18kgf 20kgf 24kgf 14kgf 16kgf Bonding damage of sheared surface 80% 90% 903⁄4 803⁄4 603⁄4 803⁄4 70% Metal wiring embedded heat shrinkage resistance Omm 0mm Omm Omm 3mm 2mm Omm Moisture resistance 〇〇〇〇〇〇〇

Kgf :公斤力,mm :毫米 剪力強度1):使用以175°C,2小時固化製得之樣品 剪力強度2):使用以175°C ’ 2小時固化製得且保存於85eC/85%相對濕度24小時之樣 品 23 95048 201213478 [表5] 比較例 1 2 3 4 5 6 7 8 9 層壓特性 〇 〇 〇 〇 〇 X 〇 X 〇 高溫流動性 〇 〇 X X 〇 X 〇 X Δ 固化特性 53% 58% 82¾ 23¾ 18¾ 98% 62¾ 55¾ 77% 剪力強度1) 15kgf 12kgf 19kgf 17kgf 8kgf 13kgf 19kgf 13kgf 22kgf 剪力強度2) 9kgf 7kgf 17kgf 1 7kgf 4kgf 12kgf 18kgf 9kgf 19kgf 剪切表面之黏結破壞 20% 30¾ 10¾ 50% 0¾ 30¾ 70¾ 30¾ 80¾ 金屬接線嵌入性 Δ 〇 Δ Δ 〇 Δ 〇 X X 熱收縮抗性 Omm Omm 5mm Omm 1 Omm Omm 20mm Omm Omm 抗濕性 ..x X 〇 〇 X 〇 X X 〇 ΠΠΠ :毫米 由表3之結果,可見到使用於實施例之反應性共聚丙 烯酸酯化合物與使用於比較例之橡膠成分比較顯示出較高 的表面能及較高的黏著強度。於是,在使用彼等之黏著片 中,對構成半導體支持構件之有機—無機材料於約啊之 固定條件下之初黏性得以改進。 由表4及表5之實施例及比較例之試驗結果,可見到 本實施例之所有黏著片於每—評估項目均顯示良好之特 性,但比較例者則否。 【圖式簡單說明】 益。 【主要元件符號說明】 益。 95048 24Kgf: kg force, mm: mm shear strength 1): shear strength of the sample prepared by curing at 175 ° C for 2 hours 2): using 175 ° C ' 2 hours curing and stored at 85eC / 85 % Relative humidity 24 hours sample 23 95048 201213478 [Table 5] Comparative Example 1 2 3 4 5 6 7 8 9 Lamination characteristics 〇〇〇〇〇X 〇X 〇High temperature fluidity 〇〇XX 〇X 〇X Δ Curing characteristics 53% 58% 823⁄4 233⁄4 183⁄4 98% 623⁄4 553⁄4 77% Shear strength 1) 15kgf 12kgf 19kgf 17kgf 8kgf 13kgf 19kgf 13kgf 22kgf Shear strength 2) 9kgf 7kgf 17kgf 1 7kgf 4kgf 12kgf 18kgf 9kgf 19kgf Bonding surface damage 20% 303⁄4 103⁄4 50% 03⁄4 303⁄4 703⁄4 303⁄4 803⁄4 Metal wiring embedding Δ 〇Δ Δ 〇Δ 〇XX Heat shrinkage resistance Omm Omm 5mm Omm 1 Omm Omm 20mm Omm Omm Moisture resistance ..x X 〇〇X 〇XX 〇ΠΠΠ : From the results of Table 3, it was found that the reactive copolyacrylate compound used in the examples showed higher surface energy and higher adhesion strength than the rubber composition used in the comparative example. Thus, in the use of the adhesive sheets thereof, the initial tackiness of the organic-inorganic material constituting the semiconductor supporting member under the fixed conditions is improved. From the test results of the examples and comparative examples of Tables 4 and 5, it can be seen that all of the adhesive sheets of the present embodiment showed good characteristics in each evaluation item, but the comparative example did not. [Simple description of the schema] Benefits. [Main component symbol description] Benefit. 95048 24

Claims (1)

201213478 七、申請專利範圍: 1. 一種黏著組成物,係包括: (A) s有一個或多個反應基之共聚丙烯酸酯化合物, ⑻熱固性環氧樹脂混合物, (C) 固化劑, (D) 填充料及 (E) 固化促進劑, 其中 該成分(A) : (B)之重量比率為95 : 5至65 : 35, 5亥成分(B)包括一種或多種於150°C具有〇.1泊 (Pa · s)或較低熔體黏度之環氧樹脂, 於每100重量份之該等成分(A)+(B)+(C)之總合 中”亥成分(D)的含量為1 〇至80重量份,及 於每100重量份之該等成分(A) + (;BXC)之總合 中,該成分(E)的含量為〇. 1至1· 4重量份。 2. 3. 如申請專利範圍第1項所述之黏著組成物,其中,該共 聚丙烯S文g曰化合物(A)當測量其與水之接觸角時具有 自40達因/公分(dyne/cm)至50達因/公分之表面能。 如申請專利範圍第1項所述之黏著組成物,其中,該共 聚丙烯酸酯化合物(A)中所含之反應基係一個或多個選 自丙烯腈基、環氧基、羥基及綾基者。 、 ^申請專利範圍第1項所述之黏著組成物,其中,該環 氧樹脂混合物⑻巾所含,於i5(rc具㈣·丨泊或較= 炫體黏度之環氧樹脂量,基於⑽重量%之該環氧樹脂 95048 1 4. 201213478 混合物(β)之量計,為5至50重量%。 5.如_請專利範圍第1項所述之黏著組成物’其t,該固 化劑(C)對該環氧樹脂混合物(B)之當量比率為〇.8至 1.3。 6· 1—種用於製造半導體之黏著片,係包括巾請專利範圍第 1至第5項中任—項所述之黏著組成物之塗佈層者。 95048 201213478 四、指定代表圖:本案無圖式。 ‘(一)本案指定代表圖為:第( )圖。 • (二)本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式: 本案無化學式。 3 95048201213478 VII. Scope of application: 1. An adhesive composition comprising: (A) a copolyacrylate compound having one or more reactive groups, (8) a thermosetting epoxy resin mixture, (C) a curing agent, (D) a filler and (E) a curing accelerator, wherein the component (A): (B) has a weight ratio of 95:5 to 65:35, and 5 components (B) include one or more having a 〇.1 poise at 150 ° C. (Pa · s) or a lower melt viscosity epoxy resin, in a total of 100 parts by weight of the components (A) + (B) + (C), the content of the component (D) is 1 The content of the component (E) is from 0.1 to 1.4 parts by weight per 100 parts by weight of the total of the components (A) + (; BXC). The adhesive composition according to claim 1, wherein the copolymerized polypropylene (A) has a contact angle with water of from 40 dynes/cm (dyne/cm) to The adhesive composition of the invention of claim 1, wherein the reactive group contained in the copolyacrylate compound (A) is one Or a plurality of adhesive compositions selected from the group consisting of acrylonitrile, epoxy, hydroxy, and hydrazine. The adhesive composition of claim 1, wherein the epoxy resin mixture (8) is contained in i5 (rc) (4) The amount of epoxy resin in the anchorage or comparison = viscous viscosity is based on (10)% by weight of the epoxy resin 95048 1 4. 201213478 The amount of the mixture (β) is 5 to 50% by weight. The adhesive composition of the first aspect of the patent range 't, the equivalent ratio of the curing agent (C) to the epoxy resin mixture (B) is 〇.8 to 1.3. 6-1. Adhesive sheet, including the coating layer of the adhesive composition according to any one of the items 1 to 5 of the patent scope. 95048 201213478 IV. Designated representative figure: There is no drawing in this case. '(1) Designation of the case The representative picture is: ( ) picture. • (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: There is no chemical formula in this case. 3 95048
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