TW201207960A - Fabricating method of semiconductor wafer with adhsive layer, photosensitive adhsion agent and semiconductor device - Google Patents

Fabricating method of semiconductor wafer with adhsive layer, photosensitive adhsion agent and semiconductor device Download PDF

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TW201207960A
TW201207960A TW100127206A TW100127206A TW201207960A TW 201207960 A TW201207960 A TW 201207960A TW 100127206 A TW100127206 A TW 100127206A TW 100127206 A TW100127206 A TW 100127206A TW 201207960 A TW201207960 A TW 201207960A
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resin
semiconductor wafer
photosensitive adhesive
photosensitive
mass
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TW100127206A
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Chinese (zh)
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Shuichi Mori
Shinjirou Fujii
Kazuyuki Mitsukura
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means 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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means 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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2924/181—Encapsulation

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)

Abstract

This invention provides a fabricating method of semiconductor wafer with adhesive layer including the following steps: coating a whole surface of one side of a semiconductor wafer with a photosensitive adhesion agent using a screen print method to form a photosensitive adhesion agent layer, exposing the photosensitive adhesion agent layer to process the photosensitive adhesion agent layer to B-stage.

Description

201207960. 六、發明說明： 【發明所屬之技術領域】201207960. VI. Description of the invention: [Technical field to which the invention belongs]

本發明是有關於-種附接著劑層的半導體晶圓的制造 =法、感光性接著劑及半導體裝置。更詳細而言，本^明 疋有關於作為將積體電路（integratecj circujt，π )、大A 積體電路（large scale integration，LSI)等半導體元件盥， 線框架、絕雜支躲板等支娜件或者半_ 彼5 積層時的接合材料（晶粒黏合材）來使用的晶粒黏 光性接著劑’使職晶粒黏合用感級接著劑 ^ ^ 圓的製造方法及半導體裝置。 等體曰曰 【先前技術】 n^、LSI科導體元件與支持構件的接合材料或者將 +導體晶片彼此積層時的接合材料，已知使的酿 著膜、於特定的聚醜亞胺樹脂中添 性填料或無機填料的晶粒黏合用接著膜。 電 近年來，正在研究藉由在半導體晶圓（以下有 化。ίΠ上總括地進行半導體裝置的組裝步驟而效率 化㈣6 ’隨著半導體晶片的積層，日日日圓的厚度存在薄膜 的步驟 '或者利用旋轉塗 /曰曰;_合祕著舰佈於半導體晶圓上的步驟。 整個==:步方法等:於半導_ 驟而留Η儿層堡切割用支持膜，藉由切割步 基板或半導體有接著膜的半導體晶片貼附於半導體 3 201207960. 由高====著劑的方法亦廣泛知曉藉 旋轉塗佈法。 的液狀接著劑塗佈於整個面的 =使用薄膜晶圓的步驟中，存在晶圓的強度下降的傾 ，°因此’於晶圓的背面研磨步驟之後，較理想為於貼人 有为面研磨带的狀態下，塗佈晶粒黏合用接著劑而進行 階段化。 先前技術文獻 專利文獻 專利文獻1 :日本專利特開2008-98213號公報 專利文獻2:日本專利特公平5-54262號公報 然而，於使用接著膜的情況，在將接著膜層壓於晶圓 上的步驟中容易於晶圓以外的部分產生接著膜的浪費。另 外，於使用旋轉塗佈法的情況，亦必需向半導體晶圓上不 斷供給、廢棄接著劑，直至形成均勻的接著劑的層為止， 容易產生接著劑的浪費。 進而’背面研磨帶的耐熱性為80。(：〜l〇〇t：左右，藉 由100°C以上的加熱，背面研磨帶收縮。背面研磨帶的收 縮可成為半導體晶圓的龜曲的原因。即便是以下的加 熱’亦由於背面研磨帶的熱膨脹率、與半導體晶圓的熱膨 脹率的差，而存在加熱後的冷卻過程中半導體晶圓翹曲的 傾向。 【發明内容】 本發明是鑒於上述情況而形成，目的在於提供一種可The present invention relates to a semiconductor wafer fabrication method, a photosensitive adhesive, and a semiconductor device. In more detail, this is a semiconductor component such as an integrated circuit (integratecj circujt, π), a large scale integration (LSI), a wire frame, and a miscellaneous support. A method of manufacturing a crystal grain-adhesive adhesive for use in a bonding material (grain bonding material) in the case of a bonding material (a die bonding material) or a semiconductor device. Equivalent 曰曰 [Prior Art] n^, a bonding material of a LSI-based conductor element and a supporting member, or a bonding material when a +-conductor wafer is laminated to each other, a known brewing film, in a specific poly-imine resin The grain bonding of the additive filler or the inorganic filler is carried out using an adhesive film. In recent years, research is being conducted to improve the efficiency of semiconductor devices by semiconductor semiconductor wafers (4) 6 'with the lamination of semiconductor wafers, the step of thin film of the thickness of the Japanese yen' or The step of using a spin coating/曰曰; _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Or a semiconductor wafer with a semiconductor film attached to the semiconductor 3 201207960. The method of high ==== implantation is also widely known by the spin coating method. The liquid adhesive is applied to the entire surface = using a thin film wafer In the step of the wafer, the strength of the wafer is lowered. Therefore, after the back surface polishing step of the wafer, it is preferable to apply the die bonding adhesive in a state where the surface is polished. In the case of using an adhesive film, in the case of using an adhesive film, the film layer is used in the case of using an adhesive film. In the step on the wafer, it is easy to waste the adhesive film on the portion other than the wafer. In addition, in the case of using the spin coating method, it is necessary to continuously supply and discard the adhesive onto the semiconductor wafer until a uniform formation is formed. Further, the layer of the agent is likely to be wasteful of the adhesive agent. Further, the heat resistance of the back surface polishing tape is 80. (: ~ l〇〇t: left and right, the back surface polishing tape is shrunk by heating at 100 ° C or higher. The shrinkage can be the cause of the tortuosity of the semiconductor wafer. Even if the following heating is due to the difference between the thermal expansion coefficient of the backside polishing tape and the thermal expansion coefficient of the semiconductor wafer, there is a semiconductor wafer warpage during the cooling process after heating. The present invention has been made in view of the above circumstances, and an object thereof is to provide a

S 4 201207960 *^一 * 知 ρΐί 在膜厚均自且接著劑力浪的情況下於半 成接著綱，鼓可避免由用於接著劑層❹階^ ^ 熱所引起的半導體晶_曲_接著劑 鬥σ 製造方法；該製造方法中所❹的感紐接^體^^ 利用該製造綠來製造_接著_ 體裝置及網版印感光性接著劑。 日日0的+導 本發明提供―種附接著劑層的半導體晶 法，包括以下步驟：於半導體晶圓的— ^^ 用酿印刷法塗佈感光性接著劑以形成感光性利 以及藉由曝光將感光性接著劑層進行8階段化。"·曰， 依據上述本發明的製造方法， x 的浪費少的情況下於彻晶圓上形成接:劑;且 =於接著劑層❹階段化的加心:半= 性化==:包含熱硬化性樹脂、放射線聚合 上述感光性接著劑可更包含熱硬化起始劑。 上述感光性接著劑的坑下的S 4 201207960 *^一* 知ρΐί In the case where the film thickness is self-contained and the adhesive force is applied, the drum can avoid the semiconductor crystal _ _ caused by the heat applied to the adhesive layer. Then, the manufacturing method of the hopper σ; the sensation of the 纽 ^ 该 该 该 利用 利用 利用 利用 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The invention provides a semiconductor crystal method of a kind of adhesive layer, comprising the steps of: coating a photosensitive adhesive on a semiconductor wafer by a brewing method to form a photosensitive property and by Exposure The photosensitive adhesive layer was subjected to eight stages. "·曰, according to the manufacturing method of the present invention described above, when the waste of x is small, the bonding agent is formed on the wafer; and = the centering of the adhesive layer is half-centered: half = sexualization ==: The thermosetting resin is contained, and the above-mentioned photosensitive adhesive agent for radiation polymerization may further contain a thermosetting initiator. Under the pit of the above photosensitive adhesive

Pa.s ’上述感光性接著劑的觸變指數可為 本發明的感光性接著劑包含熱硬化性 合性化合物及光聚合起始劑u射料 成感光性接著劑層。 於上这製造方法中用於形 驟的3而5明ί供—種半導體裝置，利用包括以下步 驟的方法喊付·將_上述本發_製造方法而獲制The thixotropy index of the above-mentioned photosensitive adhesive can be such that the photosensitive adhesive of the present invention contains a thermosetting compound and a photopolymerization initiator u to form a photosensitive adhesive layer. The semiconductor device for use in the above-described manufacturing method is obtained by a method including the following steps:

201207960.^ I 附接著劑層的半導體晶圓單片化，獲得附接著劑層的半導 體晶片；以及將附接著劑層的半導體晶圓的半導體晶片接 著於支持構件或者其他半導體晶片上。 進而’本發明提供一種網版印刷用感光性接著劑，包 含熱硬化性樹脂、放射線聚合性化合物及光聚合起始劑， 且25C下的黏度為1 Pa.s〜100 Pa.s’觸變指數為1 〇〜3.〇。 [發明的效果] 依據本發明’提供一種可在膜厚均勻且接著劑的浪費 少的情況下於半導體晶圓上形成接著劑層，而且可避免由 用於接著劑層的B階段化的加熱所引起的半導體晶圓翹曲 的附接著劑層的半導體晶圓的製造方法；該製造方法中所 使用的感光性接著劑；包括可利用該製造方法而製造的半 導體晶圓的半導體裝置及網版印刷用感光性接著劑。 【實施方式】 以下，一邊參照圖式，一邊對本發明的附接著劑層的 半導體晶圓的製造方法、感光性接著劑、半導體裝置及網 版印刷用感光性接著劑的較佳一實施形態進行詳細說明。 但，本發明並不限定於以下的實施形態。 本實施形態的半導體裝置的製造方法包括以下步驟： 於半導體晶圓的一側的表面整體，利用網版印刷法塗佈感 光性接著劑而形成感光性接著劑層（感光性接著劑層形成 步驟）；藉由曝光將感光性接著劑層進行B階段化（B階 段化步驟）；以及將半導體晶圓與經B階段化的感光性接 著劑層一起切開分割（切割步驟）。 201207960. (感光性接著劑層形成步驟） 圖1所示的半導體晶圓6是用於形成内藏於半導體封 裝體（半導體裝置）（圖6)中的半導體晶片I3a及半導體 晶片13b (圖6)。半導體晶圓6通常為矽晶圓。半導體晶 圓6上可已藉由前步驟而形成有電路。感光性接著劑層形 •成步驟中，例如，如圖1所示，於半導體晶圓6的與形成 有電路的面相反側的面（背面）’利用網版印刷法塗佈（印 刷）感光性接著劑5。藉此，如圖2所示，於半導體晶圓6 的背面上形成厚度均勻的感光性接著劑層7。 網版印刷法通常包括以下的兩種工法。其中一種是使 用在平坦的金屬板上設置有經圖案化的開口部的所謂金屬 印刷版的工法。5玄工法中，精由在欲印刷的對象上設置金 屬印刷版，以稱為刮漿板的金屬板掃去搭載於金屬印刷版 上的油墨而塗佈油墨。藉由該步驟，油墨經塗佈成設置於 金屬印刷版上的開口圖案的形狀。 、 另一網版印刷法有使用在將不鏽鋼、尼龍、及聚酯等 的紗編織而準備的網眼中，僅殘留欲塗佈的部分而以樹脂 等填埋的所謂網眼印刷版的工法。該工法中，以稱為到^ 的樹脂製或者金屬製的板掃去搭载於網眼印刷版上的油 墨。藉由該步驟，油墨渗透至網眼印刷版的未經樹脂等所 填埋的開口部。接著，使用以聚胺基㈣醋或石夕橡膠等所 形成的到襞板在網眼印刷版上到掃。藉由該步驟，渗透至 開口部的油墨經轉印至印刷對象上，印刷步驟結束二 本實施形態中，任-種印刷工法令均可僅於所需的位 201207960. 置、區域選擇性地塗佈接著劑，因此可減少接著劑的浪費， 材料良率優異。 若以使用金屬印刷版的工法，於比較廣的範圍内進行 印刷’則由於在開口部無任何構件，故而不會產生開口部 的與到激板的壓力相對的來自印刷版的應力。因此，存在 壓力集中於到漿板的中央，刮漿板中央部強烈地擠入開口 部’於開口部的中央感光性接著劑層的膜厚下降的傾向。 即’通常存在開口部越廣，刮漿板的中央部越強烈地擠入， 中央的感光性接著劑層的膜厚越降低的傾向。 另方面’使用網眼印刷版的工法中，由於開口部亦 有網、’y、，故而產生與刮聚板的壓力相對的來自網眼印刷版 的應力。即，於到漿板中央部，亦由於位於開口部的網紗 可作為支持構件而發揮功能，故而並無刮漿板強烈地擠入 開口部的情況。因此，於刮漿板中央部，膜厚亦不下降， 可獲得均勻的感光性接著劑層。 本貫施形態的網版印刷法中，就於晶圓的表面整體之 類的比較廣的_設置麟均自的感紐接著_點 而言’較佳為使用網眼印刷版的工法。 (B階段化步驟） 上述感光性接著劑層7是於藉由曝光而經B階段化後 具有對被黏附體的接著性的感光性接著劑層。對所塗佈的 感光性接義層7，利用曝絲置騎可見域紫外線，、 將構成感光性接著劑層7的感光性接著劑5進行B产俨 化。藉此，進行感光性接著劑5中所含的光聚合起始^ 8 201207960 放射線聚合性化合物的聚合反應，經B階段化的感光性接 著劑層8具有適當的黏著性及接著性。具體而言，感光性 接巧層8固紐半導體晶圓6上。如此，並非藉由加熱， 而是錯由曝光來進行感光性接著劑層7的B階段化， 於將背面研磨帶貼合於半導體晶圓6的狀態下，可進^ 光性接著劑5的塗佈及感紐接著_ 7的B階段化。〜 一就避免由氧引起的綠合反應的阻礙的觀點而言，曝 光較佳為純氣環境下或真^條件下，或者域光性接^ 劑層7上層壓有透明的覆蓋膜的狀態下進行。更詳細而 言’藉由曝光而經B階段化的感光性接著劑層8具有告 ?藉由切割的單片化及切割時可自支持體上剝離的適二 著f生與對半導體晶#及玻璃基板等被黏附體的接著性。 下文對具有上述魏的感紐接著騎8的詳細情況進行 說明。 藉由經曝光的感光性接著劑層8M3(rc下 力（表面黏力）為· gw以下，可確認感光性接^ 層8經B階段化。 劑 “若3〇。(：下的表面黏力超過2〇〇 gf/cm2，則存在感光性 接著劑層8的室溫下的表面的黏著性提高，操作性下降的 傾向。進而，存在切割後的與切割膜的剝離性下降，拾 性下降的傾向。另外’若30。(：下的表面黏力為i gfW以 下，則存在感光性接著劑的黏著性降低，切割時於感光眭 接著劑與切割膜的界面渗人水，產生晶片飛出的傾向。 經曝光的感光性接著劑層8的12〇°CT的表面黏力較 201207960., 佳為200 gfW以上。^ 12Gt下的表面黏力小於2〇〇 gf/cm2 ’财在熱㈣性妓，鎌著喊纽隙，熱壓 著溫度高溫化等傾向。另外，於12(rc下的表面黏力為備 gf/cm2以上的情況，存在熱壓著時感光性接著劑過度濕潤 擴散，於晶片侧面滲出感光性接著劑的傾向。 上述表面黏力是以如下方式測定而得的值。利用網版 印刷法將感級接著劑塗佈抑晶圓上，對所得的塗膜， 使用高精度平行曝光機（〇RC製作所製造、， 「ΕΧ=ΐη2·Β_〇〇」（商品名））’於氣氣環境下以麵 mJ/cm進行曝光。然後，使用灿⑽公司製造的探針黏 性試驗機，以探針直徑為5>1 _、剝離速度為ig mm/s、 接觸荷重為l〇〇gf/cm2、接觸時間為ls的條件測定抓 及120Ϊ下的感級接著_ 8的表_黏力。亦可使用 平行曝光機（Luminas股份有限公司製造，「ml_2i〇fm Mask Aligner」（商品名））來代替上述高精度平行曝光機。 (切割步驟） 接著，將具有半導體晶圓6及形成於其背面上的感光 ^接^層8的附接著劑層的半導體晶圓2G自晶圓側切 割’製作經單片化的半導體晶片n (圖4)。即， 切斷半導體晶圓6，半導體晶圓6被切開分割為 體晶片i卜於該切割步驟之前，較佳為於形成有 ^述感光性接著_ 8的半導體㈣6的背面貼附切割膜 。貝附可視需要-邊加熱-邊進行。例如，較佳為於利 刀。1膜10將整體固定於框架（切片）9上的狀態下（圖 201207960. / ^.pif 3) ’使用切割刀片12來進行（圖4)。經單片化的附 性接著劑層的半導體^ U是使用晶粒黏合I置等來才t 取（圖5 )。 。 如圖6所示，將藉由切割步驟而獲得的半導體晶 配置於另行準備的支持構件μ上。或者，將與半導體晶片a 13a不同的另一半導體晶月別配置於預先接合於支 件14的半導體晶片13a上。此時，藉由感光性接著劑層 16及感光性接著劑層17熱壓著，半導體晶片13a血支^ 構件14、以及半導體晶片別與半導體晶片…接^半 導體晶片13a及半導體晶片13b與支持構件… 片13a接著固定。 〒販日日 然後’半導體晶片13a及半導體晶片13b上的接合墊 與支持構件14是由接合線18所連接，半導體晶片&及 f導體晶片13b是與接合線18 一起由密封材15所密封， 藉此完成如圖6所示的半導體封裝（半導體裝置）。 依據以上所說明的半導體裝置的製造方法，用以將半 導體晶片13a與支持構件14、或者半導體晶片13&及半導 體晶片l；3b彼此接著的感光性接著劑5可利用網版印刷法 而僅塗佈於半導體晶圓6上。藉此’不論感光性接著劑5 的組成如何，均可藉由變更印刷版而塗佈成所需的膜厚。 因此’可減少半導縣置或者附接著劑層的半導體晶圓的 製造方法巾難著綱浪費，可以單—的接著髓佈成多 種膜厚。 接著’對本實施形態的感光性接著劑的較佳實施形態 11 201207960 jyz/zpif 進行說明。該感光性接著劑可適宜用作上述半導體裝置的 製造方法中的上述感光性接著劑5。 本實施形態的感光性接著劑包含（A)熱硬化性樹脂、 (B)放射線聚合性化合物、及（C)光聚合起始劑。 (A)熱硬化性樹脂只要是包含藉由加熱而產生交聯 反應的反應性化合物的成分，則無特別限定，例如可列舉： 環氧（epoxy)樹脂、氰酸酯（cyanate ester)樹脂、順丁 烯二醯亞胺（maleimide)樹脂、烯丙基耐地醯亞胺（allyl nadimide)樹脂、苯酚（phenol)樹脂、脲（urea)樹脂、 三聚氰胺（melamine)樹脂、醇酸（alkyd)樹脂、丙稀酸 樹脂（acrylic resin)、不飽和聚酯（p〇lyester)樹脂、鄰苯 二甲酸二烯丙酯（diallyl phthalate )樹脂、聚矽氧（siiicone ) 樹脂、間苯二紛曱酸（resorcinol formaldehyde)樹脂、二 曱苯（xylene)樹脂、呋喃（furan)樹脂、聚胺基甲酸酯 (polyurethane)樹脂、酮（ketone)樹脂、三聚氰酸三稀 丙酯（triallyl cyanurate )樹脂、聚異氰酸酯（polyisocyanate ) 樹脂、含有異三聚氰酸三（2-羥基乙基）酯 (tris(2-hydroxyethyl)isocyanurate)的樹脂、含有偏苯三曱 酸三稀丙酯（triallyl trimellitate )的樹脂、由環戊二烯 (cyclopentadiene )合成的熱硬化性樹脂、及藉由芳香族 二氰亞胺（dicyanamide)的三聚物化而得的熱硬化性樹 脂。其中，與聚醯亞胺樹脂的組合中，就可使其具有高溫 下的優異接著力的方面而言，較佳為環氧樹脂、順丁烯二 醯亞胺樹脂及烯丙基耐地醯亞胺樹脂。此外，該些熱硬化 12 201207960. jyz/zpif 性樹脂可翔制丨種或者將2彻上 較佳為分子咕含至少2_上的環氧基， 就熱[者性、硬錄及硬化物特性的方面而言，更 盼的縮水甘_型的環氧樹脂。此種樹關 :二型(或者AD型、s型、的縮水甘油二: 又齡&的縮水甘細、環氧乙烧加成物雙^型的縮水 丙烧加成物雙盼A型的縮水甘_、苯賴 酸树月曰的縮水甘㈣、甲祕_脂的縮水甘_、雙紛 A祕樹脂的縮水甘㈣、萘樹脂的縮水甘_、3官能 4 ^型）的縮水甘⑽、二環戊二稀苯齡樹脂 的縮水甘_、二聚酸的縮水甘油酯、3官能型（或者4 _水甘油胺及萘樹脂的縮水甘油胺。該些樹脂 可早獨使用1種或者將2種以上組合使用。 作為環氧樹脂，就防止電遷移或防止金屬導體電路的 ^的觀點而言，難為使㈣作為㈣離子的驗金屬離 土類金屬離子、鹵素離子、特別是氯離子或水解性 氣4減少至300 ppm以下的高純度品。 =對於感紐接著·量，環氧樹料熱硬化性樹脂 二，佳為1G質量百分比（mass%)〜⑽刪s%，就感光 性接者劑的可靠性的觀點而言，更佳為2() _%〜6〇 °若該量超過8G mass% ’則存在感光性接著劑的黏 度提，，印刷性下降的傾向。另—方面，若該量小於1〇 mass/。’則存在無法獲得充分的熱壓著性及高溫接著性的 傾向。相對於感紐接著劑總量，熱硬化性樹脂的量的上 13 201207960. 限值及下限值亦可為 10 mass%、2〇 mass%、33 mass%、42.5 mass%、60 mass% 或 80 mass%。 作為（A)熱硬化性樹脂，5%質量減少溫度較佳為 150°C以上，更佳為18(rc以上，進而更佳為2〇〇ΐ以上。 此處，所謂5%質量減少溫度，是指對熱硬化性樹脂，使 用示差熱熱重量同時測定裝置（sn Nan〇techn〇1〇gy製造： TG/DTA6300 ) ’ 於升溫速度 i 〇°c /min、氮氣流（4〇〇 ) 下測定時的5%質量減少溫度。藉由應用5%質量減少溫度 ，的熱硬化性樹脂，可於熱壓著或熱硬化時抑制熱硬化性 樹脂揮發。具有此種耐熱性的熱硬化性樹脂可列舉分子内 具有芳香環的環氧樹脂，就接著性、耐熱性的觀點而言， 特佳為使用3官能型（或者4官能型）的縮水甘油胺、雙 紛A型（或者AD型、Ss、F3〇的縮水甘油鱗。 本實施形態的感光性接著劑較佳為含有熱硬化 (硬化促進劑）。熱硬化起始劑只要是藉由加熱而促進環氧 樹脂的硬化或者聚合的化合物，舰無制關，例如可 列舉：_化合物、脂肪族胺、脂環族胺、芳香族聚胺、 聚醯胺、脂肪族酸酐、脂環族酸酐、芳香族酸酐、二氰二 胺（dicyandiamide)、有機酸二醯肼、三氟化硼胺錯合物、 咪=(imidazoie)類、二氰二胺衍生物、二甲酸二酿耕、 二苯基膦、四苯基鱗四苯基石猶鹽、2_乙基冰〒基味唾_ 四苯基破鹽、甲基丙稀酸2_[(3,5_H㈣基)幾基胺 基]乙醋、甲基丙烯酸2-(0讲甲基亞丙基胺基]縣胺基） 乙酯、1，8-二氮雜雙環[5,4,〇]十一烯四苯基爛酸鹽及三級 201207960 Ξ二==:含溶劑時的溶解性、分散性的觀 5〇質量份。另外，就接著性、耐敎性 里伤〜 =化咪销。相對於熱硬化性樹脂二質量^點 rf日 =值及下限值可為⑽質量二 0.67質1伤、i質罝份或者5〇質量份。 作為咪唑類，反應開始溫度較佳為 ，最佳為贈c以上。若反應開始溫度小於=為 接著劑的保存穩紐下降，因此存在感光性接著 1、站又上升，膜厚的控制變得輯的傾向。4 咪蝴交佳為使用平均粒徑較 ί 以下、最佳為5 _以下的化合物。藉由使用3 並且可抑制咪侧沈降的變化’ 薄膜時，可藉由減少表面的凹凸卜而c生接著劑的 為可減少逸出2 !硬化均句地進行，故而認 解性的呼唑叮瘅〜自，糟由使用缺乏對環氧樹脂的溶 解性的Μ，可獲得良好的保存穩定性。 用此i呼可於31氧樹脂中的咪唾類。藉由使 的表= 料少形錢紐接著_薄膜時 的表面的凹凸。此種咪唑_ τ _〜他基4=== 曱基11 米唑、1 t美r其0 # 1鼠基乙基_2_乙基-4- 卞坐i亂基乙基_2一笨基·、1¥基_2_甲基味〇坐、 15 201207960 jyz /zpif 1-苄基-2-苯基味n坐等。 人从f*光轉著劑可含麵系化合物作為硬化劑。紛系化 I μΪ為分子中具有至少2個以上雜減的紛系化合 物二匕種化合物例如可列舉：苯盼祕、㈣祕、第三 Ζ、—環戍二婦甲齡_、二環戊二稀苯紛驗 -丄伸本4基改f苯盼祕、萘_化合物、三苯紛系 ^物、四苯盼祕、雙紛A祕、聚_對乙縣苯紛及 本料烧基樹脂。該些化合物中，較佳為數量平均分子量 為400 4G0G的範圍内的化合物。藉此於半導體裝置的 組裝中的加_，可抑魏為半導體元件或者裝置等的污 木，原因的加熱時的逸出氣體。相對於熱硬化性樹脂刚 質篁份’料、化合物#量較佳為5G f量份〜⑶質量份， 更佳為70質量份〜1〇〇質量份。 ⑻放射線聚合性化合物可列舉具有乙烯性不飽和 基的化合物’乙職不飽和基可_ :乙烯基、稀丙基、 丙炔基了烯基、乙块基、苯基乙炔基、順丁稀二酿亞胺 基二耐地醯亞胺基、（甲基)丙_基等。就反應性的觀點 而吕，較佳為（甲基）丙烯醯基，較佳為包含單官能（甲基) 丙烯酸醋。藉由添加單官能（甲基)㈣酸g|，尤其可於用 以B階段㈣曝光畴低感紐接著劑較聯密度，可使 曝光壓著性、低應力性及接著性成為良好的狀態。 單官能（甲基）丙烯酸醋的5%質量減少溫度較佳為 100°c以上，更佳為12(rCm，尤佳為15(rc以上，最佳 為180°c以上。此處，所謂5%質量減少溫度，是指對單官 201207960, 能（曱基）丙烯酸酯，使用示差熱熱重量同時測定裝置（SII Nanotechnology 製造：TG/DTA6300 )，於升溫速度 10°C/min、氣氣流（400 ml/min)下測定時的5%質量減少 溫度。藉由應用5%質量減少溫度高的單官能（曱基)丙烯酸 酯’可抑制藉由曝光而B階段化後所殘存的未反應的單官 能（曱基)丙烤酸醋在熱壓著或者熱硬化時揮發。 只要是此種單官能（曱基）丙烯酸酯，則並無特別限 定’可使用：含縮水甘油基的（曱基）丙烯酸酯、苯酚EO 改質（甲基)丙烯酸酯、笨酚PO改質（曱基）丙烯酸酯、壬基 苯酚EO改質（甲基）丙烯酸酯、壬基苯酚p〇改質（曱基)丙 烯酸酯、含酚性羥基的（曱基）丙烯酸酯、含羥基的（曱基) 丙烯酸酯、苯基苯酚縮水甘油醚（曱基)丙烯酸酯、及（曱基) 丙烤S文本氧基乙g旨專方香族系（曱基）丙烤酸醋、含酿亞胺 基的（曱基)丙烯酸酯、含羧基的（甲基）丙烯酸酯、含異冰片 基的（曱基)丙烯酸酯、含二環戊二烯基的（曱基)丙烯酸酯、 以及（曱基)丙烯酸異冰片酯等。 就B階段化後的與被黏附體的密著性、硬化後的接著 性、耐熱性的觀點而言，單官能（曱基）丙烯酸酯較佳為具 有胺基曱酸酯基、異三聚氰酸基、醯亞胺基或者羥基，特 佳為分子内具有醯亞胺基的單官能（曱基)丙烯酸酯。 亦可較佳地使用具有環氧基的單官能（曱基）丙烯酸 ，。作為具有環氧基的單官能（曱基）丙烯酸酯，就保存穩 定性、接著性、低逸出氣體性、耐熱可靠性及耐濕可靠性 的觀點而言，5%質量減少溫度較佳為15(TC以上，尤佳為 17 201207960. 〇yz/^,pif 180°C以上，最佳為·。c以上。此種具有環氧基的單官能 (甲基)丙烯酸醋並無特別限定，但藉由使用5%質量減少溫 度為15G°C以上的多官能環氧樹脂作為原料，可滿足上 财熱性。 八有環氧基的單官能（甲基）丙稀酸酯並無特別限定， 除了甲基丙烯酸縮水甘油s旨、丙触縮水甘油酯、丙稀酸 4-經基丁g旨縮水甘油㈣、甲基丙烯酸4嚷基丁g旨縮水甘油 醚以外’可列舉使具有與環氧基反應的官能基及乙稀性不 飽，基的化合物與多官能環氧樹脂進行反應而獲得的化合 物等。上述與環氧基反應的官能基並無特別限定，可列舉 異氰酸酯基、羧基、酚性羥基、羥基、酸酐、胺基、硫醇 基、醯胺基等。該些化合物可單獨使用丨種，或者將2種 以上組合使用。 具有環氧基的單官能（甲基）丙烯酸酯，例如藉由在三 苯基膦或四丁基溴化銨的存在下，使丨分子中具有至少2 個以上環氧基的多官能環氧樹脂、與相對於環氧基丨當量 而為0.1當量〜0.9當量的（曱基)丙烯酸進行反應而獲^。 另外，藉由在二月桂酸二丁基錫的存在下，使多官能異氰 酸酯化合物與含羥基的（甲基）丙烯酸酯及含羥基的^氧化 合物進行反應，或者使多官能環氧樹脂與含異氰酸酯基的 (曱基)丙烯酸酯進行反應，而獲得含縮水甘油基的胺基甲 酸酯（曱基)丙烯酸酯等。 ι 具有環氧基的單官能（曱基)丙烯酸酯就保存穩定性、 接著性、半導體裝置的組裝加熱時及半導體裝置的組裝後 201207960. j^z/zpif 的揮發二感=== :孔====== 應的成八捏路0〇c以上，就可抑制回流焊時由於未反 2:。。:上。此剝離的方面而言’最佳為 為分子咐晴細輪較佳 進而，作為具有環氧基的單官能（曱基)丙烯酸醋，就 pf止電遷移或防止金轉體電路的脑的觀㈣言，較佳 ，使用將作為雜質離子的驗金屬離子、驗土類金屬離子、 、素離=、制是氣離子或水解性氣等減少至刪口帅 以下的向純度品。例如，藉由使用減少鹼金屬離子、鹼土 類金屬離子、s素離子等的多官能環氧樹脂作為原料，可 滿足上述雜質離子濃度。總氣含量可依據JIS K7243-3來 測定。 + 滿足上述耐熱性及純度的具有環氧基的單官能（甲基) 丙烯酸酯成分並無特別限定，可列舉將以下化合物作為原 料的成分：雙酚A型（或者AD型、S型、F型）的縮水 甘油醚、氫化雙酚A型的縮水甘油醚、環氧乙烷加成物雙 盼A及/或F型的縮水甘油趟、環氧丙烧加成物雙盼a及/ 或F型的縮水甘油醚、苯酚酚醛樹脂的縮水甘油醚、甲盼 酚醛樹脂的縮水甘油醚、雙酚A酚醛樹脂的縮水甘油醚、 19 201207960. j wpif 萘樹脂的縮水甘油醚、3官能型（或者4官能蜇）的縮水 甘油醚、二環戊二烯苯酚樹脂的縮水甘油醚、二聚酸的縮 水甘油酯、3官能型（或者4官能型）的縮水甘油胺以及 萘樹脂的縮水甘油胺等。 特別是為了改善熱壓著性、低應力性及接著性，較佳 為環氧基及乙烯性不飽和基的數量分別為3個以下，特佳 為乙稀性不飽和基的數量為2個以下。此種化合物並無特 別限定’較佳為使用下述通式（1)、通式（2)、通式（3)、 通式（4)或通式（5)所表示的化合物等。下述通式（1) =式5 * ’Ru及r16表示氮原子或甲基’r1〇、r11、 及R表示2價的有機基，r15、r17&r1S表示具有環 ^或乙驗不餘和基的有機基。f表示整數。f例如為i 201207960201207960.^ I The semiconductor wafer with the adhesive layer is singulated to obtain a semiconductor wafer with an adhesive layer; and the semiconductor wafer of the semiconductor wafer with the adhesive layer is attached to a supporting member or other semiconductor wafer. Further, the present invention provides a photosensitive adhesive for screen printing comprising a thermosetting resin, a radiation polymerizable compound, and a photopolymerization initiator, and has a viscosity of 1 Pa.s to 100 Pa.s' thixotropic at 25 C. The index is 1 〇~3.〇. [Effect of the Invention] According to the present invention, it is provided that an adhesive layer can be formed on a semiconductor wafer with a uniform film thickness and a low waste of an adhesive agent, and heating by B-stage for the adhesive layer can be avoided. A method of manufacturing a semiconductor wafer with an adhesive layer caused by warpage of a semiconductor wafer; a photosensitive adhesive used in the manufacturing method; and a semiconductor device and a network including a semiconductor wafer which can be manufactured by the manufacturing method A photosensitive adhesive for printing. [Embodiment] Hereinafter, a preferred embodiment of a method for producing a semiconductor wafer with an adhesive layer of the present invention, a photosensitive adhesive, a semiconductor device, and a photosensitive adhesive for screen printing will be described with reference to the drawings. Detailed description. However, the present invention is not limited to the following embodiments. The method for manufacturing a semiconductor device according to the present embodiment includes the steps of: applying a photosensitive adhesive to a whole surface of one side of a semiconductor wafer by a screen printing method to form a photosensitive adhesive layer (photosensitive adhesive layer forming step) The B-stage of the photosensitive adhesive layer is exposed by exposure (B-stage step); and the semiconductor wafer is cut and divided together with the B-staged photosensitive adhesive layer (cutting step). 201207960. (Photosensitive adhesive layer forming step) The semiconductor wafer 6 shown in FIG. 1 is used to form a semiconductor wafer I3a and a semiconductor wafer 13b embedded in a semiconductor package (semiconductor device) (FIG. 6) (FIG. 6) ). The semiconductor wafer 6 is typically a germanium wafer. An electrical circuit can be formed on the semiconductor wafer 6 by the previous step. In the photosensitive adhesive layer formation step, for example, as shown in FIG. 1, the surface (back surface) of the semiconductor wafer 6 opposite to the surface on which the circuit is formed is coated (printed) by screen printing. Sexual adhesive 5. Thereby, as shown in FIG. 2, a photosensitive adhesive layer 7 having a uniform thickness is formed on the back surface of the semiconductor wafer 6. Screen printing usually includes the following two methods. One of them is a method of using a so-called metal printing plate provided with a patterned opening on a flat metal plate. In the mysterious method, a metal printing plate is set on an object to be printed, and an ink plated on a metal printing plate is swept by a metal plate called a squeegee to apply ink. By this step, the ink is applied in the shape of an opening pattern provided on the metal printing plate. In another screen printing method, a so-called mesh printing plate in which a portion to be coated is left in a mesh prepared by knitting a yarn such as stainless steel, nylon, or polyester, and is filled with a resin or the like is used. In this method, the ink plated on the screen printing plate is swept by a resin or metal plate called ?. By this step, the ink penetrates into the opening portion of the mesh printing plate which is not filled with the resin or the like. Next, a rubbed plate formed of polyamine-based (iv) vinegar or Shishi rubber or the like is used to sweep onto the screen printing plate. By this step, the ink that has penetrated into the opening portion is transferred to the printing target, and the printing step is completed. In the present embodiment, any of the printing tools can be used only in the desired position 201207960. By applying an adhesive, the waste of the adhesive can be reduced, and the material yield is excellent. If the printing is carried out in a relatively wide range by the method using a metal printing plate, since there is no member in the opening portion, the stress from the printing plate in the opening portion opposite to the pressure on the plate is not generated. Therefore, there is a tendency that the pressure concentrates on the center of the pulp sheet, and the center portion of the squeegee plate strongly pushes into the opening portion. The thickness of the central photosensitive adhesive layer in the opening portion tends to decrease. In other words, the wider the opening portion is, the stronger the center portion of the squeegee is pushed in, and the film thickness of the photosensitive adhesive layer at the center tends to decrease. On the other hand, in the method of using a screen printing plate, since the opening portion also has a net, 'y, a stress from the screen printing plate opposite to the pressure of the scraping plate is generated. In other words, since the mesh located in the opening portion functions as a supporting member in the center portion of the pulp sheet, there is no case where the squeegee plate is strongly pushed into the opening portion. Therefore, the film thickness does not decrease in the center portion of the squeegee, and a uniform photosensitive adhesive layer can be obtained. In the screen printing method of the present embodiment, it is preferable to use a method of using a mesh printing plate in a relatively wide range of the surface of the wafer. (B-stage step) The photosensitive adhesive layer 7 is a photosensitive adhesive layer having an adhesive property to the adherend after being B-staged by exposure. To the applied photosensitive layer 7, the ultraviolet light in the visible region is placed by the exposure wire, and the photosensitive adhesive 5 constituting the photosensitive adhesive layer 7 is subjected to B production. Thereby, the polymerization reaction of the photopolymerization starting compound contained in the photosensitive adhesive 5 is carried out, and the B-staged photosensitive adhesive layer 8 has appropriate adhesiveness and adhesion. Specifically, the photosensitive layer 8 is bonded to the semiconductor wafer 6. In this manner, the B-stage of the photosensitive adhesive layer 7 is not performed by heating, but the bonding of the back surface polishing tape to the semiconductor wafer 6 is performed, and the adhesive 5 can be applied. The coating and the sensation are followed by the B-stage of -7. - In the case of avoiding the inhibition of the greening reaction caused by oxygen, the exposure is preferably in a pure gas atmosphere or under a true condition, or a state in which a transparent cover film is laminated on the domain photopolymer layer 7. Go on. More specifically, the photosensitive adhesive layer 8 which is B-staged by exposure has a singulation by dicing and a peeling from the support when dicing and dicing. And the adhesion of the adhered body such as a glass substrate. The details of the sense of the above-mentioned Wei and then the ride 8 will be described below. It was confirmed that the photosensitive interface layer 8 was B-staged by the exposed photosensitive adhesive layer 8M3 (the rc lower force (surface viscosity) was less than gw. The agent "if 3 〇. (: under the surface adhesion) When the force exceeds 2 〇〇gf/cm2, the adhesion of the surface of the photosensitive adhesive layer 8 at room temperature is improved, and the workability tends to be lowered. Further, the peeling property with the dicing film after dicing is lowered, and the detachability is improved. The tendency to decrease. In addition, if 30. (The surface adhesion is below i gfW, the adhesion of the photosensitive adhesive is lowered, and the interface between the photosensitive adhesive and the dicing film is infiltrated when cutting, and the wafer is generated. The tendency to fly out. The surface adhesion of the exposed photoresist layer 8 of 12〇°CT is better than 201207960. It is better than 200 gfW. The surface adhesion at 12Gt is less than 2〇〇gf/cm2. The heat (four) sex 镰 镰 喊 纽 , , , , , , , , , , , , , , , , , rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc Wet diffusion, a tendency to bleed out a photosensitive adhesive on the side of the wafer. The above surface viscosity is The value obtained by the following method was applied to the wafer by a screen printing method, and the obtained coating film was produced by a high-precision parallel exposure machine (manufactured by 〇RC, "ΕΧ=ΐη2· Β 〇〇 ( (product name)) 'Exposure in a mJ/cm surface in an air atmosphere. Then, using a probe viscosity tester manufactured by Can Co., Ltd., with a probe diameter of 5 gt. The speed is ig mm / s, the contact load is l〇〇gf / cm2, the contact time is ls, the condition is measured and the level of sensitivity is 120 接着. _ 8 table _ adhesion. Parallel exposure machine can also be used (Luminas limited stock) The company manufactures "ml_2i〇fm Mask Aligner" (trade name) instead of the high-precision parallel exposure machine. (Cutting step) Next, the semiconductor wafer 6 and the photosensitive layer 8 formed on the back surface thereof are provided. The semiconductor wafer 2G with the adhesive layer is cut from the wafer side to produce a singulated semiconductor wafer n (Fig. 4). That is, the semiconductor wafer 6 is cut, and the semiconductor wafer 6 is cut and divided into bulk wafers. Before the cutting step, it is preferred to form the photosensitive property A dicing film is attached to the back surface of the semiconductor (4) 6 of _8. The scallop is visually required to be heated-side. For example, it is preferably a sharp knife. The film 10 is integrally fixed to the frame (slice) 9 ( Figure 201207960. / ^.pif 3) 'Use the dicing blade 12 to perform (Figure 4). The singulated adhesive layer of the semiconductor is used to obtain the semiconductor bond I (Figure 5) As shown in Fig. 6, the semiconductor crystal obtained by the dicing step is disposed on a separately prepared support member μ. Alternatively, another semiconductor crystal different from the semiconductor wafer a 13a is placed in advance to be bonded to the support. On the semiconductor wafer 13a of the device 14. At this time, the photosensitive wafer layer 16 and the photosensitive adhesive layer 17 are heat-pressed, and the semiconductor wafer 13a is supported by the semiconductor member 14 and the semiconductor wafer and the semiconductor wafer are connected to the semiconductor wafer 13a and the semiconductor wafer 13b. Member... Sheet 13a is then fixed. The bonding pad and the supporting member 14 on the semiconductor wafer 13a and the semiconductor wafer 13b are connected by the bonding wires 18, and the semiconductor wafer & and the f-conductor wafer 13b are sealed together with the bonding wires 18 by the sealing material 15 Thereby, the semiconductor package (semiconductor device) as shown in FIG. 6 is completed. According to the method of manufacturing a semiconductor device described above, the photosensitive adhesive 5 for bonding the semiconductor wafer 13a and the supporting member 14 or the semiconductor wafer 13 & and the semiconductor wafer 1; 3b to each other can be coated by the screen printing method only Illustrated on the semiconductor wafer 6. Thus, regardless of the composition of the photosensitive adhesive 5, the desired film thickness can be applied by changing the printing plate. Therefore, it is difficult to reduce the manufacturing method of the semiconductor wafer which can reduce the semi-conducting county or the adhesive layer, and it is possible to form a plurality of film thicknesses. Next, a preferred embodiment of the photosensitive adhesive of the present embodiment 11 201207960 jyz/zpif will be described. The photosensitive adhesive can be suitably used as the photosensitive adhesive 5 in the method for producing a semiconductor device described above. The photosensitive adhesive of the present embodiment contains (A) a thermosetting resin, (B) a radiation polymerizable compound, and (C) a photopolymerization initiator. (A) The thermosetting resin is not particularly limited as long as it is a component containing a reactive compound which generates a crosslinking reaction by heating, and examples thereof include an epoxy resin and a cyanate ester resin. Maleimide resin, allyl nadimide resin, phenol resin, urea resin, melamine resin, alkyd resin , acrylic resin, unsaturated polyester (p〇lyester) resin, diallyl phthalate resin, siiicone resin, isophthalic acid ( Resorcinol formaldehyde) resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, Polyisocyanate resin, resin containing tris(2-hydroxyethyl)isocyanurate, and tree containing triallyl trimellitate Thermosetting resins from cyclopentadiene (cyclopentadiene) synthesized by the aromatic and dicyanimide (dicyanamide) obtained trimer of thermosetting resin. Among them, in combination with a polyimine resin, an epoxy resin, a maleimide resin, and an allyl-resistant mantle are preferable in terms of excellent adhesion at a high temperature. Imine resin. In addition, the thermosetting 12 201207960. jyz / zpif resin can be used to prepare the seed or 2 is preferably a molecular group containing at least 2 - on the epoxy group, on the heat [humanity, hard recording and hardening In terms of properties, it is more desirable to shrink the epoxy resin. This kind of tree is closed: type II (or AD type, s type, glycidol two: ageing & shrinkage, epoxy Ethylene burn adduct double type of shrinking acrylic burn adduct double wish type A The shrinking water _, the phthalic acid tree 曰 曰 缩 ( 四 四 四 四 四 四 四 四 ( ( ( ( ( ( ( ( ( ( ( ( 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂 脂Glycine (10), dicyclopentadiene benzoate resin, glycidyl, dimer acid glycidyl ester, trifunctional (or 4 _ glacial glycerylamine and naphthalene resin glycidylamine. These resins can be used alone 1 It is difficult to use (4) as a (tetra) ion metal-free metal ion, a halogen ion, especially as an epoxy resin, in order to prevent electromigration or prevent a metal conductor circuit. Chloride or hydrolyzed gas 4 is reduced to a high purity product of 300 ppm or less. = For the amount of sensitivities, epoxy resin thermosetting resin 2, preferably 1 G mass% (mass%) ~ (10) s%, From the viewpoint of the reliability of the photosensitive connector, it is more preferably 2 () _% to 6 〇 ° if the amount exceeds 8 G mass % ' In the viscosity of the photosensitive adhesive, the printability tends to decrease. On the other hand, if the amount is less than 1 〇mass/, there is a tendency that sufficient heat-compression and high-temperature adhesion cannot be obtained. The total amount of the bonding agent, the amount of the thermosetting resin is 13 201207960. The limit and the lower limit may also be 10 mass%, 2 〇 mass%, 33 mass%, 42.5 mass%, 60 mass% or 80 mass%. The (A) thermosetting resin preferably has a 5% mass reduction temperature of 150 ° C or more, more preferably 18 (rc or more, still more preferably 2 Å or more. Here, a 5% mass reduction temperature For the thermosetting resin, use a differential thermal mass simultaneous measuring device (sn Nan〇techn〇1〇gy: TG/DTA6300) ' at a heating rate i 〇 °c / min, nitrogen flow (4 〇〇) The 5% mass reduction temperature at the time of the measurement. The thermosetting resin which is 5% by mass reduction temperature can suppress the volatilization of the thermosetting resin at the time of hot pressing or thermal curing. The resin may be an epoxy resin having an aromatic ring in its molecule, and it is adhesive and heat resistant. In view of the above, it is particularly preferred to use a trifunctional (or tetrafunctional) glycidylamine or a double-type A (or an anti-glycidol scale of AD type, Ss, or F3). The photosensitive adhesive of the present embodiment is preferably used. In order to contain a thermosetting (hardening accelerator), the thermosetting initiator is a compound which promotes hardening or polymerization of an epoxy resin by heating, and the ship is not controlled, and examples thereof include: a compound, an aliphatic amine, and an alicyclic ring. Amines, aromatic polyamines, polyamines, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamides, organic acid diterpenes, boron trifluoride amine complexes, microphones (imidazoie), dicyandiamide derivative, dicarboxylic acid, diphenyl phosphating, diphenylphosphine, tetraphenyl quaternary tetraphenyl sulphate, 2 ethyl glacial sulphate, salicyl _ tetraphenyl sulphate, Acrylic acid 2_[(3,5_H(tetra)yl)-ylamino]ethyl acetoacetate, 2-(0-methyl propylamino)amine, ethyl methacrylate, 1,8-diaza Bicyclo[5,4,anthrene]undecene tetraphenyl sulphonate and tertiary grade 201207960 Ξ2 ==: 5 parts by mass of solubility and dispersibility in the case of solvent. In addition, the susceptibility to the susceptibility to the sputum is ~ yummy. The mass value rf day = value and the lower limit value of the thermosetting resin may be (10) mass two, 0.67 mass 1 injury, i mass component or 5 mass parts. As the imidazole, the reaction initiation temperature is preferably, and it is preferably a c or more. When the reaction start temperature is less than =, the storage stability of the subsequent agent is lowered, so that the photosensitivity is maintained. Then, the station rises again, and the control of the film thickness tends to be complicated. 4 The product is preferably a compound having an average particle diameter of 5% or less, preferably 5 Å or less. By using 3 and suppressing the change in the microside sedimentation' film, it is possible to reduce the escape of the surface by reducing the unevenness of the surface.叮瘅~自,, by using a ruthenium lacking solubility in epoxy resin, good storage stability can be obtained. Use this to call the sodium saliva in 31 oxygen resin. By making the table = material, the surface of the film is uneven. This imidazole _ τ _ ~ heptyl 4 === thiol 11 imiazole, 1 t beautiful r its 0 # 1 鼠基乙_2_ethyl-4- 卞 sit i chaotic ethyl _2 a stupid Base·1¥ base_2_methyl miso sitting, 15 201207960 jyz /zpif 1-benzyl-2-phenyl-flavor n sitting. A person from a f* light transfer agent may contain a facial compound as a hardener. The compound I μΪ is a compound of the diterpenoid compound having at least two or more impurities in the molecule, for example, benzophenone, (four) secret, third Ζ, 戍 戍 戍 、 、, dicyclopentan Diluted benzene has been tested - 丄 本 本 4 4 4 4 4 4 4 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Resin. Among these compounds, a compound having a number average molecular weight of 400 4 G0G is preferred. Thereby, the addition of _ in the assembly of the semiconductor device suppresses the contamination of the semiconductor element or the device, and the escape of gas during heating. The amount of the raw material 、 part and the compound # with respect to the thermosetting resin is preferably 5 parts by weight to (3) parts by mass, more preferably 70 parts by mass to 1 part by mass. (8) The radiation-polymerizable compound may, for example, be a compound having an ethylenically unsaturated group, which may be an ethylenically unsaturated group: a vinyl group, a propyl group, a propynyl group, an alkenyl group, an ethyl group, a phenylethynyl group, a butadiene group. Di-iminoimine di-resistant quinone imine group, (meth) propyl group and the like. From the viewpoint of reactivity, it is preferably a (meth)acrylonitrile group, preferably a monofunctional (meth)acrylic acid vinegar. By adding a monofunctional (meth)(tetra) acid g|, especially in the B-stage (four) exposure domain low-sensing binder, the exposure density, low stress and adhesion can be made into a good state. . The 5% mass reduction temperature of the monofunctional (meth)acrylic acid vinegar is preferably 100 ° C or more, more preferably 12 (rCm, particularly preferably 15 (rc or more, preferably 180 ° C or more. Here, 5) % mass reduction temperature refers to the use of a differential thermogravimetric simultaneous measurement device (manufactured by SII Nanotechnology: TG/DTA6300) for a single official 201207960, capable of (meth) acrylate, at a heating rate of 10 ° C / min, gas flow ( 5% mass reduction temperature at 400 ml/min. The unreacted residual after B-stage by exposure can be suppressed by applying a 5% mass-low temperature monofunctional (fluorenyl) acrylate. The monofunctional (fluorenyl) propylene vinegar volatilizes when hot pressed or thermally hardened. There is no particular limitation as long as it is such a monofunctional (fluorenyl) acrylate. 'Can be used: glycidyl group-containing (fluorenyl group) Acrylate, phenol EO modified (meth) acrylate, phenol phenol modified (mercapto) acrylate, nonyl phenol EO modified (meth) acrylate, nonyl phenol p 〇 modified (fluorenyl) Acrylate, phenolic hydroxyl-containing (fluorenyl) acrylate, hydroxyl-containing ( Acrylate, phenylphenol glycidyl ether (mercapto) acrylate, and (fluorenyl) propylene-baked S-text oxy-ethylene ethoxylate glucosyl acetonide (mercapto) acrylate, carboxyl group-containing (meth) acrylate, isobornyl-based (fluorenyl) acrylate, dicyclopentadienyl-containing (fluorenyl) acrylate, and (fluorenyl) Isobornyl acrylate or the like. The monofunctional (fluorenyl) acrylate preferably has an amine group from the viewpoint of adhesion to the adherend after B-stage, adhesion after curing, and heat resistance. An acid ester group, an iso-trisocyanate group, a quinone imine group or a hydroxyl group, particularly preferably a monofunctional (fluorenyl) acrylate having a quinone imine group in the molecule. It is also preferred to use a single group having an epoxy group. Functional (fluorenyl) acrylate, as a monofunctional (fluorenyl) acrylate having an epoxy group, from the viewpoints of storage stability, adhesion, low gas evolution, heat resistance reliability, and moisture resistance reliability, The 5% mass reduction temperature is preferably 15 (TC or more, especially preferably 17 201207960. 〇yz/^, pif 180 °C In the above, the monofunctional (meth)acrylic acid vinegar having an epoxy group is not particularly limited, but a polyfunctional epoxy resin having a 5% mass reduction temperature of 15 G ° C or more is used. As a raw material, it can satisfy the above-mentioned heat. The monofunctional (meth) acrylate having an epoxy group is not particularly limited, except for glycidyl methacrylate, propyl glycidyl ester, and acrylic acid 4- In addition to glycidyl (tetra), glycidyl methacrylate, and glycidyl ether, the compound having a functional group reactive with an epoxy group and an ethylenically unsaturated group, and a polyfunctional epoxy are exemplified. A compound obtained by reacting a resin or the like. The functional group reactive with the epoxy group is not particularly limited, and examples thereof include an isocyanate group, a carboxyl group, a phenolic hydroxyl group, a hydroxyl group, an acid anhydride, an amine group, a thiol group, and a decylamino group. These compounds may be used singly or in combination of two or more. A monofunctional (meth) acrylate having an epoxy group, for example, a polyfunctional epoxy having at least 2 or more epoxy groups in a ruthenium molecule in the presence of triphenylphosphine or tetrabutylammonium bromide The resin is reacted with (indenyl)acrylic acid in an amount of 0.1 equivalent to 0.9 equivalent based on the equivalent of the epoxy group. Further, the polyfunctional isocyanate compound is reacted with a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing oxy-compound in the presence of dibutyltin dilaurate, or a polyfunctional epoxy resin and an isocyanate-containing group are allowed to be reacted. The (mercapto) acrylate is reacted to obtain a glycidyl group-containing urethane (mercapto) acrylate or the like. ι Monofunctional (fluorenyl) acrylate having an epoxy group for storage stability, adhesion, assembly heating of a semiconductor device, and assembly of a semiconductor device 201207960. The volatilization of j^z/zpif === : hole ====== If it is more than 0〇c, it can suppress the reflow soldering because it is not reversed 2:. . :on. In terms of the exfoliation, the best is the molecular fine-grain fine wheel, and further, as a monofunctional (fluorenyl) acrylic vinegar having an epoxy group, the pf stop electromigration or the brain of the gold-return circuit is prevented. (4) It is preferable to use a metal ion to be used as an impurity ion, a metal ion of a soil test, a metal ion, a gas ion or a hydrolyzable gas, and the like to be reduced to a purity product. For example, the above impurity ion concentration can be satisfied by using a polyfunctional epoxy resin which reduces alkali metal ions, alkaline earth metal ions, s-ion ions or the like as a raw material. The total gas content can be determined in accordance with JIS K7243-3. The monofunctional (meth) acrylate component having an epoxy group which satisfies the above heat resistance and purity is not particularly limited, and examples thereof include a bisphenol A type (or AD type, S type, F). Type) glycidyl ether, hydrogenated bisphenol A type glycidyl ether, ethylene oxide adduct double hope A and / or F type of glycidol, propylene propylene oxide adducts and / or F-type glycidyl ether, glycidyl ether of phenol novolac resin, glycidyl ether of phenolic resin, glycidyl ether of bisphenol A phenolic resin, 19 201207960. j wpif glycidyl ether of naphthalene resin, trifunctional ( Or a tetrafunctional glycidyl ether, a glycidyl ether of a dicyclopentadiene phenol resin, a glycidyl ester of a dimer acid, a trifunctional (or tetrafunctional) glycidylamine, and a glycidylamine of a naphthalene resin. Wait. In particular, in order to improve the hot stamping property, the low stress property and the adhesion property, the number of the epoxy group and the ethylenically unsaturated group is preferably 3 or less, and particularly preferably the number of the ethylenically unsaturated group is 2. the following. The compound is not particularly limited. It is preferred to use a compound represented by the following formula (1), formula (2), formula (3), formula (4) or formula (5). The following general formula (1) = formula 5 * 'Ru and r16 represent a nitrogen atom or a methyl group 'r1〇, r11, and R represent a divalent organic group, and r15, r17&r1S means having a ring ^ or an undetected And the organic group of the base. f represents an integer. f is for example i 201207960

Ry-^yc„-〇-°^ ⑸ R，8 ^~每 相對於（B)放射線聚合性化合物’上述单官能（曱基) 丙烯酸酯的量較佳為20 mass%〜100 mass%，更佳為40 mass%〜100 mass% ’ 最佳為 50 mass%〜1〇〇 mass%。藉由 將單官能（曱基)丙烯酸酯設為上述量，可提高B階段化後 的與被黏附體的密著性及熱壓著性。 (B)放射線聚合性化合物可含有2官能以上的（曱基) 丙烯酸酯。此種丙烯酸酯並無特別限制，可列舉：二乙二 醇二丙稀酸自旨、三乙二醇二丙稀酸g旨、四乙二醇二丙缚酸 S旨、二乙二醇二甲基丙烯酸g旨、三乙二醇二甲基丙稀酸賴、 四乙二醇二曱基丙騎g旨、三m曱基丙烧二㈣酸酿、三 羥甲基丙烷二丙烯酸酯、三羥曱基丙烷二曱基丙烯酸酯、 21 201207960 ^y^/zpif 二經甲基丙院三甲基丙烯酸g旨、M•丁二醇二㈣酸酉旨、 1，6-己二醇二丙烯酸函旨、Μ_τ二醇二甲基丙騎^ & 己二醇二甲基丙稀酸S旨、季戊四醇三丙稀酸醋、季戊四 四丙烯_、季細醇三甲基㈣義、季細醇四甲臭 丙稀酸酯、二季戊四醇六__、二季細醇六甲義二 烯酸酯、苯乙烯、二乙烯基苯、4_乙烯基甲苯、‘乙$美 t定（4-vinyipyridine)、N_乙烯基轉咬嗣、丙婦酸^ 基乙醋、甲基丙烯酸2·經基乙自旨、以丙騎基氧基趣 基丙烧、1，2·甲基丙烯轉氧基·2•祕賊、亞甲基雙丙 烯醯胺、N，N-二曱基丙埽醯胺、N_經甲基丙稀酿胺、^三 聚氰酸二(β-羥基乙基)酯的三丙烯酸酯、下述通式（6)所 表示的化合物、胺基曱酸酯丙烯酸酯、胺基甲酸酯曱基丙 稀酸酯、及尿素丙稀酸醋等。 [化2]Ry-^yc„-〇-°^ (5) R, 8 ^~ per amount of the (B) radiation-polymerizable compound 'the above-mentioned monofunctional (fluorenyl) acrylate is preferably 20 mass% to 100 mass%, more Preferably, 40 mass% to 100 mass% 'best is 50 mass% to 1 mass%. By setting the monofunctional (fluorenyl) acrylate to the above amount, the B-staged and adherends can be improved. (B) The radiation polymerizable compound may contain a bifunctional or higher (fluorenyl) acrylate. The acrylate is not particularly limited, and examples thereof include diethylene glycol diacrylic acid. Self-purpose, triethylene glycol diacrylic acid g, tetraethylene glycol dipropyl acid S, diethylene glycol dimethacrylate g, triethylene glycol dimethyl acrylate, tetraethyl Glycol dimercapto-propyl ketone, tri-m-mercaptopropene bis (four) acid brewing, trimethylolpropane diacrylate, trihydroxymethyl propane dimercapto acrylate, 21 201207960 ^y^/zpif Methyl propyl trimethacrylate g, M • butanediol di(tetra) phthalate, 1,6-hexanediol diacrylic acid, Μττ diol dimethyl propylene riding & hexane diol Acrylic acid S , pentaerythritol triacetic acid vinegar, pentaerythritol propylene, quaternary alcohol trimethyl (tetra), quaternary alcohol tetramethyl acrylate, dipentaerythritol hexamethacrylate hexamethacrylate , styrene, divinylbenzene, 4_vinyltoluene, '4-vinyipyridine', N_vinyl turn bite, propyl ethyl acetoacetate, methacrylic acid 2.乙自意,以丙基基基基丙,1,2·Methyl propylene tooxy·2• Secret thief, methylene bis acrylamide, N,N-dimercaptopropylamine , N_methacrylic acid, triacrylate of bis(β-hydroxyethyl) cyanurate, a compound represented by the following formula (6), an amino phthalate acrylate, Amino phthalate acrylate, and urea acrylate vinegar, etc. [Chemical 2]

上述通式（6)中，R19及r2〇分別獨立地表示氫原子 或曱基’ g及h分別獨立地表示1〜2〇的整數。 該些放射線聚合性化合物可單獨使用1種，或者將2 種以上組合使用。其中’具有上述通式（6)所表示的二醇 骨架的放射線聚合性化合物，就可充分賦予硬化後的耐溶 劑性，且低黏度，具有高的5%質量減少溫度的方面而言 較佳。 22 S, 201207960^. 藉由使用官能基當量高的放射線聚合性化合物，可更 有效果地抑制對半導體晶圓施加的應力（低應力化），抑制 半導體晶圓的輕曲（低翹曲化）。官能基當量高的放射線聚 合性化合物較佳為聚合官能基當量為200 eq/g以上，更佳 為300 eq/g以上，最佳為4〇〇eq/g以上。藉由使用具有聚 合官能基當量為200 eq/g以上的醚骨架、胺基曱酸酯基及/ 或異二聚氰酸基的放射線聚合性化合物，可提高感光性接 著劑的接著性，且可低應力化、低輕曲化。亦可將聚合官 能基當量為200 eq/g以上的放射線聚合性化合物與聚合官 能基當量小於200 eq/g的放射線聚合性化合物併用。 相對於感光性接著劑總量，（B)放射線聚合性化合物 的量較佳為10 mass%〜95 mass% ’就晶片壓著時的濕潤擴 散性的觀點而言，更佳為2〇 mass%〜9〇 mass%，就b階 段化後的形狀保持的觀點而言，最佳為4〇 mass%〜9〇 mass%。若（B)成分小於1〇 mass%，則存在B階段化後 的黏力增大的傾向，若超過95 mass%，則存在熱硬化後的 接著強度下降的傾向。相對於感光性接著劑總量，放射線 聚合性化合物的量的上限值及下限值亦可為1Q画以、2〇 mass%、40 mass%、56.7 職辦、66 職以、％ 脱ss%或 95 mass%。 。（B)放射線聚合性化合物較佳為於室溫（15它〜 30 C )下為液狀，|考慮到感光性接著劑自網眼印刷版的 脫洛性，則黏度幸父佳為50〇〇mPa.s以下若進一步考慮到 印刷後的自身雜所引起的平坦化，則更佳為靡mpa s 23 201207960 乃z/zpif 以下。若黏度超過5000 mPa.s，則存在感光性接著劑的黏 度上升，印刷性下降的傾向。 作為（B)放射線聚合性化合物，5%質量減少溫度較 佳為120°C以上，更佳為150°C以上，進而更佳為i80〇C以 上。此處，所謂5%質量減少溫度，是指對放射線聚合性 化合物’使用示差熱熱重量同時測定裝置（sn Nanotechnology 製造：TG/DTA6300 )，於升溫速度 1 〇°C /min、氮氣流（400 ml/min )下測定時的5%質量減少 溫度。藉由應用5%質量減少溫度高的放射線聚合性化合 物’可抑制未反應的放射線聚合性化合物在熱壓著或者熱 硬化時揮發。 作為（C)光聚合起始劑（光起始劑），就光聚合的感 度提尚的方面而言’對波長為365 nm的光的分子吸光係 數較佳為100 ml/g.cm以上，更佳為200 ml/g.cm以上。此 外’分子吸光係數是藉由製備樣品的0.001 mass%乙腈溶 液，對該溶液使用分光光度計（Hitachi High-Technologies 公司製造’「U-3310」（商品名）），測定吸光度而求出。 此種（C)成分例如可列舉：2-节基-2-二甲基胺基-1-(4-嗎琳 基苯基 ）- 丁酮 -1 (2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butan 〇ne-l )、2,2-二曱氧基-l，2-二苯基乙烷-1-酮 (2,2-dimethoxy-1，2-diphenylethane-1 -one )、卜羥基-環己基 -苯基-酉同（1-hydroxy-cyclohexyl-phenyl-ketone)、2-曱基 -1-(4-(曱硫基）苯基）-2-嗎啉基丙酮-1 24 201207960. (2-methyl-1 -(4-(methylthio)phenyl)-2-morpholinopropanon e-1 )、2,4-二乙基°塞"頓酿J ( 2,4-diethylthioxanthone)、2-乙基 蒽酉昆（2-ethylanthraquinone )及菲酿（phenanthrenequinone ) 等芳香族酮；苄基二甲基縮酮（benzyl dimethyl ketal)等 苄基衍生物；2-(鄰氣苯基)-4,5-二苯基咪唑二聚物、2-(鄰 氯苯基)-4,5-二（間曱氧基苯基）味唑二聚物、2-(鄰氟苯 基)-4,5-苯基咪唑二聚物、2-(鄰曱氧基苯基)-4,5-二苯基咪 唑二聚物、2-(對曱氧基苯基)_4,5_二苯基咪唑二聚物、2,4-二(對曱氧基苯基)-5-苯基咪唑二聚物及2-(2,4-二曱氧基苯 基)-4,5-二苯基咪唑二聚物等2,4,5-三芳基咪唑二聚物；9-苯基吖啶（9-phenyl acridine)及1,7-雙(9,9，-吖啶基)庚烷等 吖啶衍生物；雙(2,6-二曱氧基苯曱醯基)_2,4,4-三甲基-戊基 氧化膦及雙(2,4,6，-三曱基苯甲醯基)_苯基氧化膦等雙醢基 氧化膦（bisacyl phosphine oxide);以及具有順丁烯二醯亞 胺的化合物等。該些化合物可單獨使用丨種或者將2種以 上組合使用。 上述光聚合起始劑中，就不含溶劑的感光性接著劑中 的溶解性的方面而言，較佳為使用22_二曱氧基4,2二苯 基乙烧-1，、2-¥基_2-二甲基胺基小(4_嗎琳基苯基)丁 _ -1、2,2-二曱氧基_ι，2-二苯基乙烷_丨_酮及2曱基·^(4兴曱硫 基)苯基)-2-嗎琳基丙院七_。另外，就即便在空氣環境 下，亦可藉由曝光而使感光性接著劑層進行B階段化的方 面而言，紐為顧2_¥基_2_二曱基絲邻·㈣基苯 基>丁酮]、2,2-二甲氧基]，2_二苯基乙燒小酉同及2·甲基 25 201207960. o^z/zpif -1-(4-(曱硫基)苯基)_2_嗎啉基丙烷+酮。 π 一（C)成分亦可包含藉由放射線的照射而表現出促進 %氧樹脂的聚合及/或反應的功能的光起始劑。此種光起始 劑例如可列舉藉由放射線照射而產生鹼的光鹼產生劑、藉 由放射線照射而產生酸的光酸產生劑等，特佳為光鹼產生 劑。 藉由使用光驗產生劑，可進一步提高感光性接著劑對 被黏附體的尚溫時的接著性（高溫接著性）及耐濕性。其 原因可列舉：藉由利用光鹼產生劑生成的鹼作為環氧樹脂 的硬化觸媒而效率良好地發揮作用，可進一步提高交聯密 度；另外，所生成的硬化觸媒腐蝕基板等的情況少。藉由 使感光性接著劑中含有光鹼產生劑，可提高交聯密度，可 進一步減少高溫放置時的逸出氣體。進而，認為可使硬化 製程的溫度低溫化、短時間化。 光驗產生劑只要是在放射線照射時產生鹼的化合物， 則可不受特別限制地使用。就反應性、硬化速度的方面而 言’所產生的鹼較佳為強鹼性化合物。 此種放射線照射時所產生的鹼例如可列舉：咪唑、2，4 _ 二甲基味唾及1 -甲基咪唑等咪唑衍生物；哌嗪（piperazine) 及2,5- —曱基°底嗪等°底唤衍生物；派咬（piperidine)及1，2-二甲基哌啶等哌啶衍生物；脯胺酸（pr〇Hne)衍生物、三 甲基胺、三乙基胺及三乙醇胺等三烷基胺衍生物；4_甲基 胺基吡啶（4-methylaminopyridine)及4-二甲基胺基吡啶 等在4位取代有胺基或烷基胺基的吡啶衍生物；吡咯啶In the above formula (6), R19 and r2〇 each independently represent a hydrogen atom or a fluorenyl group, and g and h each independently represent an integer of 1 to 2 Å. These radiation-polymerizable compounds may be used alone or in combination of two or more. Among them, the radiation polymerizable compound having the diol skeleton represented by the above formula (6) can be sufficiently provided with solvent resistance after curing, and has a low viscosity and a high 5% mass reduction temperature. . 22 S, 201207960^. By using a radiation polymerizable compound having a high functional group equivalent, it is possible to more effectively suppress stress applied to a semiconductor wafer (low stress) and suppress light warpage of a semiconductor wafer (low warpage) ). The radiation-polymerizable compound having a high functional group equivalent weight preferably has a polymerization functional group equivalent of 200 eq/g or more, more preferably 300 eq/g or more, and most preferably 4 〇〇eq/g or more. By using a radiation polymerizable compound having an ether skeleton having a polymerization functional group equivalent of 200 eq/g or more, an amino phthalate group, and/or a heterodicentocyanate group, the adhesion of the photosensitive adhesive can be improved, and It can be low in stress and low in lightness. Further, a radiation polymerizable compound having a polymerization functional group equivalent of 200 eq/g or more may be used in combination with a radiation polymerizable compound having a polymerization functional group equivalent of less than 200 eq/g. The amount of the (B) radiation polymerizable compound is preferably from 10 mass% to 95 mass% with respect to the total amount of the photosensitive adhesive agent. It is more preferably 2 〇 mass% from the viewpoint of wet diffusibility at the time of wafer pressing. ～9〇mass%, from the viewpoint of shape retention after b-stage, the optimum is 4〇mass%~9〇mass%. When the component (B) is less than 1% by mass, the adhesive strength after the B-stage tends to increase, and if it exceeds 95 mass%, the strength after the thermal hardening tends to decrease. The upper limit and the lower limit of the amount of the radiation polymerizable compound with respect to the total amount of the photosensitive adhesive agent may be 1Q draw, 2 〇 mass%, 40 mass%, 56.7, 66 jobs, and % ss % or 95 mass%. . (B) The radiation polymerizable compound is preferably liquid at room temperature (15 to 30 C), and the viscosity is good for 50 考虑 considering the detachment property of the photosensitive adhesive from the screen printing plate. 〇mPa.s If the flattening caused by the self-mixing after printing is further taken into consideration, it is more preferable that 靡mpa s 23 201207960 is z/zpif or less. When the viscosity exceeds 5,000 mPa.s, the viscosity of the photosensitive adhesive increases, and the printability tends to decrease. As the (B) radiation polymerizable compound, the 5% mass reduction temperature is preferably 120 ° C or higher, more preferably 150 ° C or higher, and still more preferably i 80 ° C or higher. Here, the 5% mass reduction temperature means that the radiation-polymerizable compound 'is a differential thermogravimetric simultaneous measurement device (manufactured by Sn Nanotechnology: TG/DTA6300) at a temperature increase rate of 1 〇 ° C / min, and a nitrogen flow (400 5% mass reduction temperature at the time of measurement under ml/min). By using a radiation polymerizable compound having a high 5% mass reduction temperature, the unreacted radiation polymerizable compound can be suppressed from volatilizing during hot pressing or heat curing. As the (C) photopolymerization initiator (photoinitiator), the molecular absorption coefficient of light having a wavelength of 365 nm is preferably 100 ml/g.cm or more in terms of sensitivity of photopolymerization. More preferably, it is 200 ml/g.cm or more. Further, the molecular absorption coefficient was determined by preparing a 0.001 mass% acetonitrile solution of the sample, and measuring the absorbance using a spectrophotometer (manufactured by Hitachi High-Technologies, Inc., "U-3310" (trade name)). Examples of such a component (C) include 2-benzyl-2-dimethylamino-1-(4-morphinylphenyl)-butanone-1 (2-benzyl-2-dimethylamino-1 - (4-morpholinophenyl)-butan 〇ne-l ), 2,2-dimethoxy-l,2-diphenylethane-1-one (2,2-dimethoxy-1,2-diphenylethane-1 - One), 1-hydroxy-cyclohexyl-phenyl-ketone, 2-mercapto-1-(4-(indolylthio)phenyl)-2-morpholinyl Acetone-1 24 201207960. (2-methyl-1 -(4-(methylthio)phenyl)-2-morpholinopropanon e-1 ), 2,4-diethyl °" &St; J (2,4-diethylthioxanthone) , an aromatic ketone such as 2-ethylanthraquinone and phenanthrenequinone; a benzyl derivative such as benzyl dimethyl ketal; 2-(o-phenylene) -4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-decyloxyphenyl) oxazole dimer, 2-(o-fluorophenyl) -4,5-phenylimidazole dimer, 2-(o-nonyloxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)_4,5_2 Phenylimidazole dimer, 2,4-di(p-nonyloxyphenyl)-5-benzene 2,4,5-triarylimidazole dimer such as imidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; 9-phenylindole Acridine derivatives such as 9-phenyl acridine and 1,7-bis(9,9--acridinyl)heptane; bis(2,6-dimethoxyphenylphenyl)_2,4, Bisylyl phosphine oxide such as 4-trimethyl-pentylphosphine oxide and bis(2,4,6,-trimercaptobenzylidene)-phenylphosphine oxide; and having a cis-butene a compound of diimine and the like. These compounds may be used alone or in combination of two or more. Among the above photopolymerization initiators, in terms of solubility in a solvent-free photosensitive adhesive, it is preferred to use 22-dimethoxy 4,2 diphenylethene-1, 2- ¥2-dimethylamino small (4-cylinylphenyl) butyl-1,1,2,2-dimethoxyoxy_ι,2-diphenylethane_丨-one and 2曱Base · ^ (4 曱 曱 thio) phenyl) -2- 琳 基 丙 丙 七 七. In addition, even in the air environment, the photosensitive adhesive layer can be B-staged by exposure, and the ruthenium is 2 ¥ 基 _ _ _ & & & & & & & & &&; butanone], 2,2-dimethoxy], 2_diphenylethyl acetonide and 2·methyl 25 201207960. o^z/zpif -1-(4-(indolyl)benzene Base)_2_morpholinopropane + ketone. The π-(C) component may also contain a photoinitiator which exhibits a function of promoting polymerization and/or reaction of the % oxygen resin by irradiation of radiation. Examples of such a photoinitiator include a photobase generator which generates an alkali by radiation irradiation, a photoacid generator which generates an acid by irradiation with radiation, and the like, and a photobase generator is particularly preferred. By using a photoinitiator, it is possible to further improve the adhesion (high temperature adhesion) and moisture resistance of the photosensitive adhesive to the adherend at room temperature. The reason for this is that the alkali generated by the photobase generator acts as a curing catalyst for the epoxy resin, and the crosslinking density is further improved, and the generated curing catalyst corrodes the substrate or the like. less. By including a photobase generator in the photosensitive adhesive, the crosslinking density can be increased, and the evolved gas at the time of high temperature deposition can be further reduced. Further, it is considered that the temperature of the hardening process can be lowered and shortened. The photoreceptor can be used without particular limitation as long as it is a compound that generates a base upon irradiation with radiation. The base produced in terms of reactivity and rate of hardening is preferably a strongly basic compound. Examples of the base produced by such radiation irradiation include imidazole derivatives such as imidazole, 2,4-dimethylsaphed saliva and 1-methylimidazole; piperazine and 2,5-fluorenyl group. a derivative such as piperidine and piperidine derivatives such as 1,2-dimethyl piperidine; a derivative of prion Hne, trimethylamine, triethylamine and a trialkylamine derivative such as triethanolamine; a pyridine derivative in which an amino group or an alkylamine group is substituted at the 4-position, such as 4-methylaminopyridine and 4-dimethylaminopyridine; Pyridine

S 26 201207960 jyz/zpif (pyrrolidine)及正曱基吡咯啶等吡咯啶衍生物；二氫吡啶 衍生物、三伸乙基二胺及1，8-二氮雜雙環(5,4,0)十一稀-1 (l，8-diazabiscyclo(5,4,0)undecene-l，DBU)等脂環式胺 衍生物；以及苄基甲基胺、苄基二曱基胺及苄基二乙基胺 等苄基胺衍生物。 如上所述的藉由放射線照射而產生驗的光驗產生劑例 如可使用 Journal of Photopolymer Science and Technology 第12卷第313項〜第314項（1999年）或Chemistry 〇f Materials第11卷第170項〜第176項（ 1999年）等中記 載的四級銨鹽衍生物。該些四級銨鹽衍生物由於藉由活性 光線（放射線）的照射而生成高驗性的三烧基胺，因此最 適合於環氧樹脂的硬化。 光驗產生劑亦可使用Journal of American Chemical Society 第 118 卷第 12925 頁（1996 年）或 P〇lymer Journal 第28卷第795頁（ 1996年）等中記載的胺曱酸衍生物。 藉由活性光線的照射而產生驗的光驗產生劑可使用： 2,4-一甲氧基-1，2-二苯基乙烧-1-酮、l，2-辛二酮、ι_[4-(苯 硫基)-2·(鄰苯曱醢基肟)]或乙酮、及ι_[9_乙基_6_(2_曱基笨 曱醯基)-9Η-咔唑-3-基]-1-(鄰乙醯基肟）等肟衍生物；或作 為光自由基產生劑而銷售的2-节基-2-二曱基胺基-1-(4-嗎 琳基笨基)-丁酮-1、2,2-二甲氧基-l，2-二苯基乙烧_ι_酮、2-曱基小(4_(曱硫基)苯基)_2-嗎琳基丙烧小酮、2_苄基·2·二 曱基胺基-1-(4-嗎淋基苯基)-丁酮-1、六芳基雙咪嗤衍生物 (鹵素、烧氧基、硝基及氰基等取代基可取代於苯基上）、 27 201207960t ^ t Λ^^Ιί 以及苯并異噁唑酮（benzoisooxazol〇ne)衍生物等 光驗產生劑亦可使用在高分子的主鏈及/或側鍵導入 有產生鹼的基團的化合物。就作為感光性接著劑的接 性、流動性及财熱性的觀點而言，此時的分子量較佳為重 量平均分子量為1000〜100000，更佳為5〇〇〇〜3〇〇〇〇。 上述光鹼產生劑由於在未曝光的狀態下未與環氧樹脂 表現出反應性，故而室溫下的儲存穩定性非常優異。曰 相對於放射線聚合性化合物100質量份，光聚合起始 劑的量可為5質量份以上或1質量份以上。相對於放射^ 聚合性化合物100質量份，光聚合起始劑的量可為〇 i質 量份以下或1質量份以下。 本實施形態的感光性接著劑可視需要而併用增感劑。 5亥增感劑例如可列舉·掉腦酿i ( camphorquinone )、苯偶酿 (benzil)、雙乙醯（diacetyl)、苄基二曱基縮酮、节基二 乙基細3同、> 基一(2-甲氧基乙基)縮g同、4,4’-二曱基节基_ 二曱基縮酮、蒽醌、1-氣蒽醌、2-氯蒽醌、1，2_苯并蒽醌、 1- 羥基蒽醌、1-甲基蒽醌、2-乙基蒽醌、1-溴蒽醌、噻噸酮、 2- 異丙基噻噸酮、2-硝基噻噸酮、2-甲基噻噸酮、2,4-二甲 基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮、2-氯 -7-三氟甲基°塞°頓酮、嗟嘲酮_1〇，1〇_二氧化物、嗟嘲_·ι〇_ 氧化物、安息香曱醚、安息香乙醚、異丙醚、安息香異丁 醚、二苯甲酮、雙(4-二曱基胺基苯基)酮、4,4，-雙二乙基胺 基二苯甲酮及含有疊氮基的化合物。該些增感劑可單獨使 用1種或者將2種以上併用而使用。S 26 201207960 jyz/zpif (pyrrolidine) and pyrrolidine derivatives such as n-decyl pyrrolidine; dihydropyridine derivatives, tri-ethylenediamine and 1,8-diazabicyclo(5,4,0) An alicyclic amine derivative such as 1,1-diazabiscyclo(5,4,0)undecene-l, DBU; and benzylmethylamine, benzyldidecylamine and benzyldiethyl A benzylamine derivative such as an amine. The photoreceptor generating the test by radiation irradiation as described above can be, for example, Journal of Photopolymer Science and Technology, Vol. 12, No. 313 to No. 314 (1999) or Chemistry 〇f Materials, Vol. 11, No. 170. The quaternary ammonium salt derivative described in Item 176 (1999). These quaternary ammonium salt derivatives are most suitable for the hardening of epoxy resins because they generate highly detectable trialkylamine by irradiation with active rays (radiation). The photoinitiator can also be used in the Journal of American Chemical Society, Vol. 118, p. 12925 (1996) or P. Lymer Journal, Vol. 28, p. 795 (1996). The photoreceptor produced by the irradiation of active light can be used: 2,4-methoxy-1,2-diphenylethen-1-one, l,2-octanedione, ι_[ 4-(phenylthio)-2·(o-phenylhydrazinyl)] or ethyl ketone, and ι_[9_ethyl_6_(2_indolyl)-9Η-carbazole-3- An anthracene derivative such as -1-(o-ethylindenyl) or a 2-mercapto-2-didecylamino-1-(4-morphinyl) group sold as a photoradical generator )-butanone-1,2,2-dimethoxy-l,2-diphenylethene-y-ketone, 2-mercapto-small (4-(indolylthio)phenyl)_2-morphinyl Propylene ketone, 2-benzyl-2,didecylamino-1-(4-phosphonylphenyl)-butanone-1, hexaaryldiamine derivative (halogen, alkoxy, Photoreceptors such as nitro and cyano substituents may be substituted on the phenyl group, 27 201207960 t ^ t Λ^^Ιί and benzoisooxazol〇ne derivatives may also be used in the polymer. A compound having a base generating group is introduced into the main chain and/or the side bond. The molecular weight at this time preferably has a weight average molecular weight of from 1,000 to 100,000, more preferably from 5 to 3 Torr, from the viewpoints of the properties of the photosensitive adhesive, fluidity, and heat. Since the photobase generator does not exhibit reactivity with an epoxy resin in an unexposed state, the storage stability at room temperature is extremely excellent.曰 The amount of the photopolymerization initiator may be 5 parts by mass or more or 1 part by mass or more based on 100 parts by mass of the radiation polymerizable compound. The amount of the photopolymerization initiator may be hereinafter less than 1 part by mass or less than 1 part by mass relative to 100 parts by mass of the radiation-polymerizable compound. The photosensitive adhesive of the present embodiment may be used in combination with a sensitizer as needed. Examples of the 5 sensitizing agent include camphorquinone, benzil, diacetyl, benzyldidecyl ketal, and benzyldithioacetate, and > Base one (2-methoxyethyl) condensed g, 4,4'-diindenyl group ketone dimethyl ketal, hydrazine, 1- gas hydrazine, 2-chloro hydrazine, 1, 2 _Benzoindole, 1-hydroxyindole, 1-methylindole, 2-ethylhydrazine, 1-bromoindole, thioxanthone, 2-isopropylthioxanthone, 2-nitrothiazide Tons of ketone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7 -Trifluoromethyl ° ° 顿 酮 嗟 嗟 嗟 嗟 嗟 嗟 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物, benzophenone, bis(4-didecylaminophenyl) ketone, 4,4,-bisdiethylaminobenzophenone, and azide-containing compound. These sensitizers may be used alone or in combination of two or more.

28 S 201207960. oy^ci ^pif 、本實施形態的感光性接著劑中，就提高低應力性、與 被黏附體的岔著性、熱壓著性的方面而言，亦可含有（D) 熱塑性樹脂。（D )成分的玻璃轉移溫度（Tg )較佳為i卿 以下，更佳為120。(：以下，進而更佳為100〇c以下，最佳為 80°C以下。於該Tg超過15(TC的情況，存在感光性接著劑 的黏度上升的傾向。另外，當熱壓著於被黏附體上時，存 在需要15G°C以上的高溫’半導體晶圓容易產生編的傾 向。 此處’所謂「Tg」，是指經膜化的（D)成分的主分散 峰值溫度。使用Rheometrics公司製造的黏彈性分析儀 「RSA-2」（商品名），以膜厚為1〇〇 μιη、升溫速度為 5°C/min、頻率為i Ηζ、測定溫度為_15〇χ：〜3〇〇t：的條件 進行測定’此時於Tg附近觀測到的tan3峰值溫度為主分 散峰值溫度。 (D)成分的重量平均分子量較佳為控制在5〇〇〇〜 500000的範圍内，就高度兼顧熱壓著性與高溫接著性的方 面而& ’更佳為10000〜300000。此處，所謂「重量平均 分子量」’是指使用島津製作所公司製造的高效液相層析儀 C R4 A」（商品名），以聚本乙稀換算而測定時的重量平 均分子量。 作為（D)成分，除了可列舉：聚酯樹脂、聚醚樹脂、 聚醯亞胺樹脂、聚酿胺樹脂、聚醯胺醯亞胺樹脂、聚喊酿 亞胺樹脂、聚胺基曱酸酯樹脂、聚胺基曱酸酯醯亞胺樹脂、 聚胺基曱酸酯醯胺醯亞胺樹脂、矽氧烷聚醯亞胺樹脂、聚 29 201207960 ^yz/zpif 酯醯亞胺樹脂、該些樹脂的共聚物、該些樹脂的前驅物（聚 醯胺酸等）以外，可列舉：聚苯并噁唑樹脂、苯氧基樹脂、 聚砜樹脂、聚醚砜樹脂、聚苯硫醚樹脂、聚酯樹脂、聚醚 樹脂、聚碳酸s旨樹脂、聚__樹脂、重量平均分子量為1 萬〜100萬的（曱基）丙烯酸共聚物、酚醛樹脂及苯酚樹脂 等。該些樹脂可單獨使用1種或者將2種以上組合使用。 另外，亦可為於該些树月曰的主鍵及/或側鍵上賦予了乙二醇 及丙一醇專·一醇基、緩基及/或經基的樹脂。 該些樹脂中，就高溫接著性、耐熱性的觀點而言，（D) 成刀較佳為具有酿亞胺基的樹脂。具有酿亞胺基的樹脂例 如可列舉：聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞 胺樹月曰、聚胺基曱酸g旨酿亞胺樹脂、聚胺基甲酸酉旨酿胺酿 亞胺樹脂、矽氧烷聚醯亞胺樹脂、聚酯醯亞胺樹脂、及該 些樹脂的共聚物，例如聚醢亞胺樹脂可利用公知方法使四 羧酸二酐與二胺進行縮合反應而獲得。即，有機溶劑中， 使四竣酸—酐與二胺以等莫耳，或者視需要相對於四缓酸 二酐的合計1.0 mol，對二胺的合計以較佳為〇 5 m〇1〜2 〇 mol、更佳為〇.8 m〇i〜1.〇 m〇i的範圍調整組成比（各成分 的添加順序為任意），於反應溫度80°C以下、較佳為〇〇c〜 6〇C下進行加成反應。隨著反應進行，反應液的黏度緩緩 上升，生成作為聚醯亞胺樹脂的前驅物的聚醯胺酸。此外， 為了抑制感光性接著劑的諸特性的下降，上述四敌酸二軒 較佳為以乙酸酐進行藉由再結晶的純化處理的四羧酸二 酐。 一 201207960 •3 wpif —關於上述縮合反應中的四羧酸二酐與二胺的組成比， 右相對於四驗二賴合計1Q mGl，二胺的合計超過2 〇 則有於所得聚醯亞胺樹脂中，具有胺末端的聚酿亞 物，増多的傾向。進而，有聚醢亞胺樹脂的重量 鑤j刀子量降低，包括感光性接著劑的耐熱性的各種特性 二侍不充分的傾向。另—方面，若相對於四紐二軒的合 1·〇 mol，一胺的合計小於〇 5 m〇1，則存在具有酸末端 羧基末端）的聚醯亞胺樹脂寡聚物的量增多的傾向。進 :，在聚醯亞胺樹脂的重量平均分子量降低，包括感光 *生接著劑的耐熱性的各種特性變得不充分的傾向。〜 、聚醯亞胺樹脂可藉由使上述反應物（聚醯胺酸）進行 =欠閉環而獲得。脫水閉環可利用進行加熱處理的熱閉環 决、使用脫水劑的化學閉環法等來進行。 … 作為聚醯亞胺樹脂的原料來使用的四羧酸二酐並無特 別限制，例如可列舉··均苯四甲酸二酐、3,3，，4,4，_聯苯基 四甲酸一酐、2,2’，3,3’·聯笨基四曱酸二酐、2,2_雙(3,4_二羧 ^苯基)丙烧二針、2,2_雙(2,3_讀絲基)秘二軒、u_ 雙(2,3-二幾基苯基)乙烧二酐、u•雙(3,4二幾基笨基)乙烧 雙(2,3-二縣苯基）甲烧二酐、雙(Me縣苯基) _元一肝、雙(3,4-二縣苯基)石風二酐、3,4,9，1〇-花四甲酸 「軒、雙(3,4-二叛基笨基)鱗二肝、苯四甲酸二軒、 ，4,3’，4’-二苯甲酮四甲酸二酐、2,3,2，，3，·二苯甲酮四甲酸二 厂、3,3,3’，4’_二苯甲_四甲酸二針、以从萘四甲酸二肝、 ，4,5,8-萘四▼酸二酐、如义萘四甲酸二酐彳如萘四 31 201207960 〆 am r 曱酸一酐、2,6-二氣萘-1，4,5,8-四曱酸二酐、2,7-二氯萘 -1，4,5,8-四曱酸二酐、2,3,6,7_四氣萘四曱酸二酐： 菲-l，8,9，l〇-四曱酸二酐、吡嗪·2,3 5 6_四甲酸二酐、噻吩 -2,3,5,6-四曱酸二酐、2,3,3·，4·-聯苯基四曱酸二酐、3 4 3,,4，_ 聯苯基四甲酸二酐、2,3,2，,3，·聯苯基四甲酸二酐、雙(3’，4_ 二羧基苯基)二曱基矽烷二酐、雙(3,4_二羧基苯基）曱基苯 基矽烷二酐、雙(3,4-二羧基苯基)二苯基矽烷二酐、154_雙 (3,4_一幾基苯基二曱基石夕烧基)笨二酐、1，3_雙(3,4-二緩基 苯基)-1，1，3,3-四曱基二環己烷二酐、對伸苯基雙(偏苯三曱 酸酐酯）、伸乙基四甲酸二酐、^冬丁烷四甲酸二酐、十 氫萘-1，4,5,8-四甲酸二酐、4,8·二曱基_1，2,3,5,6,7-六氫萘 _1，2,5,6-四曱酸二酐、環戊烧-1，2,3,4-四曱酸二酐、吡咯啶 -2,3,4,5-四甲酸二酐、ι，2,3,4-環丁烷四曱酸二酐、雙（外_ 雙環[2,2，1]庚烷-2,3-二曱酸二酐、雙環_[2,2,2]_辛·7_烯 _2,3,5,6-四曱酸二酐、2,2·雙(^工羧基苯基)丙烷二酐、22_ 雙[4-(3,4>二羧基苯基)苯基]丙烧二酐、之，2雙(3,4_二竣基苯 基)六氟丙烷二酐、2,2_雙[4-(3,4-二羧基苯基)苯基]六氟丙 烧一酐、4,4-雙(3,4-一緩基苯氧基)二苯基硫喊二酐、ι，4_ 雙(2-羥基六氟異丙基)苯雙(偏苯三曱酸酐）、丨，3-雙(2羥基 六氟異丙基）苯雙(偏苯三曱酸酐）、5_(2,5·二氧四氫呋喃 基)-3-曱基-3-環己烯-1，2-二甲酸二針、四氫〇夫喃·2,3,4,5-四 曱酸二針及下述通式（7)所表示的四叛酸二針。下述通式 (7)中，a表示2〜20的整數。 [化3]28 S 201207960. oy^ci ^pif In the photosensitive adhesive of the present embodiment, the low stress property, the adhesion to the adherend, and the hot pressability may be included (D). Thermoplastic resin. The glass transition temperature (Tg) of the component (D) is preferably at most i, more preferably at most 120. (The following is more preferably 100 〇c or less, and most preferably 80 ° C or less. When the Tg exceeds 15 (in the case of TC, the viscosity of the photosensitive adhesive tends to increase. In addition, when the heat is pressed against the quilt In the case of adhering a body, there is a need for a high temperature of 15 G ° C or higher. The semiconductor wafer tends to be knitted. Here, "Tg" means the peak temperature of the main dispersion of the film (D). Using Rheometrics The viscoelastic analyzer "RSA-2" (trade name) manufactured has a film thickness of 1 μm η, a heating rate of 5 ° C/min, a frequency of i Ηζ, and a measurement temperature of _15 〇χ: 〜3 〇 The condition of 〇t: is measured. The peak temperature of tan3 observed near Tg at this time is the main dispersion peak temperature. The weight average molecular weight of the component (D) is preferably controlled within the range of 5 〇〇〇 to 500,000. In addition, it is more preferably 10,000 to 300,000. In this case, the "weight average molecular weight" is a high performance liquid chromatography C R4 A manufactured by Shimadzu Corporation. (product name), measured in terms of poly-ethylene The weight average molecular weight. As the component (D), a polyester resin, a polyether resin, a polyimide resin, a polyamine resin, a polyamidimide resin, a polyacrylamide resin, and a poly Amino phthalate resin, polyamino phthalate yttrium imide resin, polyamine phthalate amide amine imide resin, decyl oxynimide resin, poly 29 201207960 ^yz/zpif ester 醯Examples of the amine resin, the copolymer of these resins, and the precursor of these resins (polylysine, etc.) include polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, and poly a phenyl sulfide resin, a polyester resin, a polyether resin, a polycarbonate resin, a poly-_resin, a (fluorenyl)acrylic copolymer having a weight average molecular weight of 10,000 to 1,000,000, a phenol resin, a phenol resin, and the like. These resins may be used singly or in combination of two or more kinds. In addition, ethylene glycol and propanol monool may be added to the primary and/or side bonds of the sap. Base and / or warp resin. Among these resins, high temperature adhesion, heat resistance In general, the (D) forming knife is preferably a resin having a brewing imine group. Examples of the resin having a brewing imine group include a polyimine resin, a polyamidimide resin, and a polyether quinone. Arachis, polyamino phthalic acid g, imine resin, polyamine urethane resin, fluorinated imine resin, polyester phthalimide resin, and these resins The copolymer, for example, a polyimine resin can be obtained by a condensation reaction of a tetracarboxylic dianhydride with a diamine by a known method. That is, in an organic solvent, a tetradecanoic acid-anhydride and a diamine are equimolar, or The total amount of the diamine is 1.0 mol, and the total of the diamine is preferably 〇5 m〇1 to 2 〇mol, more preferably 〇.8 m〇i~1.〇m〇i The composition ratio is adjusted (the order of addition of each component is arbitrary), and the addition reaction is carried out at a reaction temperature of 80 ° C or lower, preferably 〇〇 c 6 6 ° C. As the reaction progresses, the viscosity of the reaction liquid gradually rises, and polyglycine which is a precursor of the polyimide resin is formed. Further, in order to suppress the deterioration of the properties of the photosensitive adhesive, the above-mentioned tetrahydro acid is preferably a tetracarboxylic dianhydride which is subjected to purification treatment by recrystallization from acetic anhydride. A 201207960 •3 wpif—about the composition ratio of tetracarboxylic dianhydride to diamine in the above condensation reaction, the right is 1Q mGl in total with respect to the four tests, and the total amount of diamines exceeds 2 〇. Among the resins, there is a tendency to have a large amount of agglomerates having an amine terminal. Further, the weight of the polyimide resin is reduced, and the various properties including the heat resistance of the photosensitive adhesive tend to be insufficient. On the other hand, if the total amount of monoamines is less than 〇5 m〇1, the amount of polyimine resin oligos having acid terminal carboxy terminal groups is increased relative to the combination of 纽 〇 四 四 四 四 四 四 四 四tendency. Further, the weight average molecular weight of the polyimide resin is lowered, and various properties including the heat resistance of the photosensitive material and the raw adhesive tend to be insufficient. ~ Polyimide resin can be obtained by subjecting the above reactant (polyglycolic acid) to under-closed ring. The dehydration ring closure can be carried out by a thermal ring closure method using a heat treatment or a chemical ring closure method using a dehydrating agent. The tetracarboxylic dianhydride used as a raw material of the polyimine resin is not particularly limited, and examples thereof include pyromellitic dianhydride and 3,3,4,4,-biphenyltetracarboxylic acid. Anhydride, 2,2',3,3'·biphenyltetracarboxylic acid dianhydride, 2,2_bis(3,4-dicarboxyphenyl)propane, two needles, 2,2_double (2, 3_read silk base) secret two Xuan, u_ bis (2,3-diylphenyl) ethylene dianhydride, u• double (3,4 bis group stupid) acetylene double (2,3-two County phenyl)methyst dianhydride, double (Me county phenyl) _Yuan Yigan, bis (3,4-two phenyl) stone dianhydride, 3,4,9,1 〇-flower tetracarboxylic acid Xuan, Shuang (3,4- 2 ruthenium base) scale liver, benzene tetracarboxylic acid dixanthine, 4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,2,,3 , benzophenone tetracarboxylic acid second plant, 3,3,3',4'_dibenzoic acid-tetracarboxylic acid two needles, from naphthalene tetracarboxylic acid dihepatic, 4,5,8-naphthalene tetrahydro acid Anhydride, such as naphthalene tetracarboxylic acid dianhydride, such as naphthalene four 31 201207960 〆am r decanoic acid anhydride, 2,6-di-naphthalene-1,4,5,8-tetradecanoic acid dianhydride, 2,7-two Chloronaphthalene-1,4,5,8-tetradecanoic acid dianhydride, 2,3,6,7_tetra-naphthalene tetraphthalic acid dianhydride: phenanthrene-l,8,9,l-tetradecanoic acid dianhydride Pyr · 2,3 5 6_tetracarboxylic dianhydride, thiophene-2,3,5,6-tetradecanoic dianhydride, 2,3,3·,4·-biphenyltetradecanoic dianhydride, 3 4 3 ,,4,_biphenyltetracarboxylic dianhydride, 2,3,2,3,bisbiphenyltetracarboxylic dianhydride, bis(3',4-dicarboxyphenyl)didecyldecane dianhydride, double (3,4-dicarboxyphenyl)nonylphenyl decane dianhydride, bis(3,4-dicarboxyphenyl)diphenylnonane dianhydride, 154_bis(3,4-polyphenylene)曱基石夕)) dianhydride, 1,3_bis(3,4-dibuylphenyl)-1,1,3,3-tetradecylbicyclohexane dianhydride, p-phenylene (trimellitic anhydride ester), ethyltetracarboxylic dianhydride, butane butane tetracarboxylic dianhydride, decalin-1,4,5,8-tetracarboxylic dianhydride, 4,8·didecyl _1,2,3,5,6,7-hexahydronaphthalene_1,2,5,6-tetradecanoic acid dianhydride, cyclopentane-1,2,3,4-tetradecanoic acid dianhydride, pyrrole Pyridine-2,3,4,5-tetracarboxylic acid dianhydride, iota, 2,3,4-cyclobutane tetradecanoic acid dianhydride, bis(exo-bicyclo[2,2,1]heptane-2,3 - Diphthalic acid dianhydride, bicyclo-[2,2,2]-octyl 7-ene-2,3,5,6-tetradecanoic dianhydride, 2,2·bis(^-carboxyphenyl)propane Dihydride, 22_bis[4-(3,4>dicarboxyphenyl)phenyl]propane dianhydride , 2 bis(3,4-diphenyl) hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]hexafluoropropanone, 4 , 4-bis(3,4-hexyl phenoxy)diphenyl sulfonate, iota, 4_bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), hydrazine, 3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 5-(2,5-dioxotetrahydrofuryl)-3-indolyl-3-cyclohexene-1,2-di Two needles of formic acid, tetrahydrofurfuran, two needles of 2,3,4,5-tetradecanoic acid, and four needles of tetrazolium represented by the following formula (7). In the following general formula (7), a represents an integer of 2 to 20. [Chemical 3]

S 32 201207960^S 32 201207960^

上述通式（7)所表示的四羧酸二酐例如可由偏苯三曱 酸酐單氣化物及所對應的二醇來合成。具體而言可列舉： 1，2-(伸乙基)雙(偏苯三曱酸酐酯）、1，3-(三亞甲基)雙(偏苯 三曱酸酐酯）、1，4-(四亞曱基)雙(偏苯三曱酸酐酯）、1,5-(五 亞曱基)雙(偏苯三曱酸酐酯）、1，6-(六亞甲基)雙(偏苯三曱 酸酐酯）、1，7-(七亞曱基)雙(偏苯三甲酸酐酯）、1,8-(八亞曱 基)雙(偏苯三曱酸酐酯）、1，9-(九亞曱基)雙(偏苯三甲酸酐 酯）、1,10-(十亞曱基)雙(偏苯三曱酸酐酯）、1,12-(十二亞甲 基)雙(偏苯三曱酸酐酯）、1，16-(十六亞曱基)雙(偏苯三曱酸 酐酯)及1，18-(十八亞甲基)雙(偏苯三曱酸酐酯）。 就賦予對溶劑的良好溶解性及耐濕性、對波長為365 nm的光的透明性的觀點而言，四羧酸二酐較佳為下述式 (8)或式（9)所表示的四羧酸二酐。 [化4] 33 201207960. / ^.pifThe tetracarboxylic dianhydride represented by the above formula (7) can be synthesized, for example, from a trimellitic anhydride monovapor and a corresponding diol. Specific examples thereof include 1,2-(extended ethyl)bis(trimellitic anhydride), 1,3-(trimethylene)bis(trimellitic anhydride), and 1,4-(four Yttrium) bis(trimellitic anhydride), 1,5-(pentamethylene) bis(trimellitic anhydride), 1,6-(hexamethylene) bis(p-benzotrifluoride) Anhydride ester), 1,7-(heptylene) bis(trimellitic anhydride), 1,8-(octadecyl)bis(trimellitic anhydride), 1,9-(nine) Mercapto) bis(trimellitic anhydride), 1,10-(decindolyl) bis(trimellitic anhydride), 1,12-(dodecyl)bis (trimellitic anhydride) Ester), 1,16-(hexadecanoyl)bis(trimellitic anhydride) and 1,18-(octadecyl)bis(trimellitic anhydride). The tetracarboxylic dianhydride is preferably represented by the following formula (8) or formula (9) from the viewpoint of imparting good solubility to a solvent and moisture resistance and transparency to light having a wavelength of 365 nm. Tetracarboxylic dianhydride. [化4] 33 201207960. / ^.pif

如上所述的四羧酸二酐可單獨使用1種，或者將2種 以上組合使用。 就進一步提高接著強度的方面而言，（D)成分可使用 含羧基及/或酚性羥基的聚醯亞胺樹脂。作為上述含羧基及 /或羥基的聚醯亞胺樹脂的原料而使用的二胺較佳為包含 下述式（10)、式（11)、式（12)或式（13)所表示的芳 香族二胺。 [化5]The tetracarboxylic dianhydride as described above may be used alone or in combination of two or more. In terms of further improving the strength of the adhesive, the (D) component may be a polyimine resin containing a carboxyl group and/or a phenolic hydroxyl group. The diamine used as a raw material of the carboxyl group-containing and/or hydroxyl group-containing polyimine resin preferably contains a fragrance represented by the following formula (10), formula (11), formula (12) or formula (13). Group diamine. [Chemical 5]

S 34 201207960.S 34 201207960.

作為上述聚醯亞胺樹脂的原料而使用的其他二胺並無 特別限制’例如可列舉：鄰伸笨基二胺、間伸苯基二胺、 對伸苯基二胺、3,3，_二胺基二苯基醚、3,4，-二胺基二苯基 鱗、4,4'·二胺基二苯基醚、3,3，-二胺基二苯基曱烷、3,4，-二胺基二苯基曱烷、4,4，-二胺基二笨基曱烷、雙(4-胺基-3,5-二甲基苯基）甲烷、雙(4-胺基-3,5-二異丙基苯基）甲烷、3,3，· 二胺基二苯基二氟甲烷、3,4，-二胺基二苯基二氟曱烷、4,4，_ 二胺基二苯基二氟甲烷、3,3，-二胺基二苯基砜、3,4，-二胺 基二苯基砜、4,4’-二胺基二苯基砜、3,3，-二胺基二苯基硫 鱗、3,4'-二胺基二苯基硫醚、4,4，-二胺基二苯基硫鱗、3,3，-二胺基二苯基酮、3,4’-二胺基二苯基酮、4,4，-二胺基二笨 基酮、2,2-雙(3-胺基苯基）丙烷、2,2，-(3,4，-二胺基二苯基) 丙烷、2,2_雙(4_胺基苯基)丙烷、2,2-雙(3-胺基苯基)六氟丙 35 201207960 烷、2,2-(3,4’-二胺基二苯基)六I丙烷、2,2_雙(4胺基苯基) ，氟丙烷、1，3_雙(3_胺基苯氧基)苯、丨，‘雙胺基苯氧基) 苯、1,4-雙(4-胺基苯氧基)苯、3,3’-(1，4-伸笨基雙(i_甲基亞 乙基))雙苯胺、3,4'-(1，4-伸苯基雙(1_曱基亞乙基))雙苯胺、 4,4^(1，4-伸苯基雙(1_甲基亞乙基))雙苯胺、22雙(4_(3_胺 基苯氧基)苯基)丙烷、2,2_雙(4-(3-胺基苯氧基)苯基)六氟丙 烷γ 2,2-雙(4-(4-胺基苯氧基)苯基)六氟丙烷、雙胺基 烯氧基）苯基)硫醚、雙(4-(4-胺基烯氧基）苯基)硫醚、雙 (4-(3_胺基烯氧基)苯基)砜、雙(4_(4_胺基烯氧基)苯基)砜、 3,3 -一羥基-4,4’-二胺基聯苯及3,5-二胺基苯曱酸等芳香族 一胺，1，3-雙(胺基曱基)環己烷、2,2_雙(4-胺基苯氧基苯基） 丙烷、下述通式（14)所表示的脂肪族醚二胺、以及下述 通式（15)所表示的石夕氧烧二胺。 上述二胺中，就賦予與其他成分的相容性的方面而 5，較佳為下述通式（14)所表示的脂肪族趟二胺，更佳 為乙二醇及/或丙二醇系二胺。下述通式（14)中，Rl、r2 及R3分別獨立地表示碳數！〜！〇的伸烷基，b表示2〜8〇 的整數。 [化6] H2N—·R1—^〇—R2 卜 〇一R3—νη2 (14) 此種脂肪族醚二胺具體而言可列舉：Sun Techn〇The other diamine used as a raw material of the above-mentioned polyimine resin is not particularly limited, and examples thereof include, for example, anthracene diamine, meta-phenylenediamine, p-phenylenediamine, 3,3,_ Diaminodiphenyl ether, 3,4,-diaminodiphenyl scale, 4,4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl decane, 3, 4,-Diaminodiphenyl decane, 4,4,-diaminodiphenyl decane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amine 3-,5-diisopropylphenyl)methane, 3,3,diaminodiphenyldifluoromethane, 3,4,-diaminodiphenyldifluorodecane, 4,4, _ Diaminodiphenyldifluoromethane, 3,3,-diaminodiphenyl sulfone, 3,4,-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3,-diaminodiphenylsulfanium scale, 3,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenylsulfide scale, 3,3,-diamine group Diphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4,-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2, -(3,4,-diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl) Fluoropropyl 35 201207960 alkane, 2,2-(3,4'-diaminodiphenyl)hexapropane, 2,2-bis(4-aminophenyl), fluoropropane, 1,3_bis (3) _Aminophenoxy)benzene, anthracene, 'diaminophenoxy" benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-extended base Bis(i-methylethylidene))diphenylamine, 3,4'-(1,4-phenylenebis(1-fluorenylethylene))diphenylamine, 4,4^(1,4- Phenyl bis(1-methylethylidene))diphenylamine, 22bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy) Phenyl) hexafluoropropane γ 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, bisaminoalkenyloxy)phenyl) sulfide, bis (4- (4-Aminoalkenyloxy)phenyl) sulfide, bis(4-(3-amino)oxy)phenyl)sulfone, bis(4-(4-amino)oxy)phenyl)sulfone, An aromatic monoamine such as 3,3-hydroxy- 4,4'-diaminobiphenyl and 3,5-diaminobenzoic acid, 1,3-bis(aminomercapto)cyclohexane, 2 , 2_bis(4-aminophenoxyphenyl)propane, an aliphatic ether diamine represented by the following formula (14), and an anthraquinone diamine represented by the following formula (15) . The diamine is imparted with compatibility with other components, and is preferably an aliphatic quinone diamine represented by the following formula (14), more preferably ethylene glycol and/or propylene glycol. amine. In the following general formula (14), R1, r2 and R3 each independently represent the carbon number! ~! The alkyl group of hydrazine, b represents an integer of 2 to 8 。. H2N—·R1—^〇—R2 Bu 〇R3—νη2 (14) Such an aliphatic ether diamine can be specifically listed as: Sun Techn〇

Chemical (股）製造的 jeffamine d-230、Jeffamine D-400、 s 36 201207960Chemicals made by jeffamine d-230, Jeffamine D-400, s 36 201207960

Jeffamine D-2000、Jeffamine D-4000、Jeffamine ED-600、 Jeffamine ED-900、Jeffamine ED-2000、Jeffamine EDR-148 ; BASF (製造）聚醚胺D-230、聚醚胺D-400及 聚醚胺D-2000等聚氧伸烷基二胺等脂肪族二胺。該些二 胺較佳為總二胺的20莫耳百分比（m〇l%)以上，就可高 度兼顧與（A)熱硬化性樹脂或（B)放射線聚合性化合物 等其他調配成分的相容性、以及熱壓著性與高溫接著性的 方面而言，更佳為50 mol%以上。 就賦予室溫下的密著性、接著性的方面而言，上述二 胺較佳為下述通式（15)所表示的石夕氧烧二胺。下述通式 〇5)中，R4及R9分別獨立地表示碳數i〜5的伸烷基或 者可具有取代基的伸苯基，R5、R6、R7及R8分別獨立地 表示碳數1〜5的烧基、苯基或者笨氧基，d表示卜 [化7]Jeffamine D-2000, Jeffamine D-4000, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2000, Jeffamine EDR-148; BASF (manufactured) polyetheramine D-230, polyetheramine D-400 and polyether An aliphatic diamine such as an amine D-2000 such as a polyoxyalkylene diamine. These diamines are preferably at least 20 mol% (m〇l%) or more of the total diamine, and are compatible with other compounding ingredients such as (A) thermosetting resin or (B) radiation polymerizable compound. It is more preferably 50 mol% or more in terms of properties, hot pressing properties and high temperature adhesion properties. The diamine is preferably an anthracycline diamine represented by the following formula (15) from the viewpoint of imparting adhesion to the room temperature and adhesion. In the following formula 〇5), R4 and R9 each independently represent an alkylene group having a carbon number of i to 5 or a phenyl group which may have a substituent, and R5, R6, R7 and R8 each independently represent a carbon number of 1~ 5 calcined, phenyl or stupidoxy, d represents Bu [Chemical 7]

〜80 mol%，就可 5而言，尤佳為1 政果降低，若高於80 mol%， 'mc)1%，則添加矽氧烧二胺的 則存在與其他成分的相容性、 37 .π 201207960 高溫接著性下降的傾向β 犬(:533:15)所表示的石夕氧貌二胺，具體而言， 夕氧燒二胺可列舉：1，W·四甲基 -，其=胺基絲)二發纽、u，3,3，苯氧基·丨，3雙(4_ 二魏烷:/，1，3,3-四苯基]，3_雙(2_胺基乙基)二 1^3元、^3,3_四:基-1，3~雙(3，基丙基)二石夕氧燒、 ϋ Γ 胺基乙基氧烧、丨，1，3,3,甲 基又(3_胺基丙基)二石夕氧貌、U 3,3四曱基丄 胺f7基)二魏敍以二甲基_1，3·二甲氧基#雙(4_ 胺基:基)二魏料。式（15)中的d為2㈣氧燒二胺 可列舉：U，3,3,5,5_六甲基巧，5•雙(4胺基苯基)三石夕氧燒、 U，5,5-四笨基_3,3_二甲基^雙^胺基丙基)三石夕氧燒、 U，5,5-四苯基·3,3_二甲氧基4,5•雙(4胺基丁基）三矽氧 烷、U，5,5-四苯基_3,3_二曱氧基]，5雙(5胺基戊基)三矽 氧烧、1，1，5,5-四甲基_3,3_二甲氧基_15_雙(2·胺基乙基)三 矽氧院、1，1，5,5·四甲基_3,3_二甲氧基_1，5_雙(4_胺基丁基） ^石夕氧烧、1，1，5,5-四曱基_3,3_二甲氧基'5-雙(5_胺基戊基) 三矽氧烷、1，1，3,3,5,5-六甲基-1，5-雙(3-胺基丙基）三矽氧 烷、U，3,3,5,5_六乙基_1，5_雙（3_胺基丙基）三矽氧烷及 I1，3,3,5,5·六丙基-1，5-雙(3-胺基丙基)三矽氧烷等。 上述二胺可單獨使用1種，或者將2種以上組合使用。 上述聚醯亞胺樹脂可單獨使用1種，或者視需要將2 種以上混合（摻合）而使用。 如上所述’當決定聚醯亞胺樹脂的組成時，較佳為設~80 mol%, as far as 5 is concerned, especially 1 is reduced. If it is higher than 80 mol%, 'mc) is 1%, the addition of xenon diamine is compatible with other components. 37 . π 201207960 The tendency of high temperature adhesion decline β 氧 oxygen oxime represented by β dog (: 533: 15), specifically, oxime diamine can be exemplified by 1, W · tetramethyl - = amine silk) dinuclear, u, 3, 3, phenoxy oxime, 3 bis (4-diweines: /, 1,3,3-tetraphenyl), 3 bis (2-amino) Ethyl) 2 1 3 3 , 3 3 , 3 4 4 : yl 1 , 3 bis ( 3 , propyl ) oxazepine , ϋ 胺 胺 胺 胺 氧 丨 1 1 1 1 1 , 3, methyl (3_aminopropyl) bismuth oxide, U 3,3 tetradecyl decylamine f7) diwei s dimethyl 1,3 · dimethoxy # double (4_Amino: base) diwe. The d in the formula (15) is 2 (tetra) oxydiamine: U, 3, 3, 5, 5 hexamethyl, 5 • bis (4 aminophenyl) trichost, U, 5, 5-tetraphenyl _3,3-dimethyl^bis-aminopropyl) trichosting, U,5,5-tetraphenyl·3,3-dimethoxy 4,5•double ( 4 aminobutyl)trioxane, U,5,5-tetraphenyl-3,3-dimethoxyl,5-bis(5-aminopentyl)trioxane, 1,1,5 ,5-tetramethyl-3,3-dimethoxy_15_bis(2.aminoethyl) trioxane, 1,1,5,5·tetramethyl-3,3-di Oxyl-1,5_bis(4-aminobutyl)^石石, 1,1,5,5-tetradecyl_3,3-dimethoxy '5-bis(5-amine Pentyl) trioxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trioxane, U, 3, 3, 5 ,5_hexaethyl_1,5-bis(3-aminopropyl)trioxane and I1,3,3,5,5·hexapropyl-1,5-bis(3-aminopropyl Base) trioxane and the like. These diamines may be used alone or in combination of two or more. The above-mentioned polyimine resin may be used singly or in combination of two or more kinds as needed. As described above, when determining the composition of the polyimide resin, it is preferred to

S 38 201207960 計成聚醯亞胺樹脂的Tg成為150°C以下，作為聚醯亞胺樹 脂的原料的二胺特佳為使用上述通式（14)所表示的脂肪 族喊二胺。 合成上述聚醯亞胺樹脂時，藉由將如下述式（16)、式 (17)或式（18)所表示的化合物之類的單官能酸針及/ 或單官能胺投入至縮合反應液中，可向聚合物末端導入酸 酐或二胺以外的官能基。另外’藉此，可降低聚合物的分 子量，降低感光性接著劑的黏度，提高熱壓著性。 [化8]S 38 201207960 The Tg of the polyimine resin is not more than 150 ° C, and the diamine which is a raw material of the polyimine resin is preferably an aliphatic shirodiamine represented by the above formula (14). When the polyimine resin is synthesized, a monofunctional acid needle and/or a monofunctional amine such as a compound represented by the following formula (16), formula (17) or formula (18) is introduced into the condensation reaction liquid. Among them, an acid anhydride or a functional group other than a diamine may be introduced into the polymer terminal. Further, by this, the molecular weight of the polymer can be lowered, the viscosity of the photosensitive adhesive can be lowered, and the hot stamping property can be improved. [化8]

含咪唑的聚醯亞 胺可以下述方式獲得。 。可使用如下㈣構式所示的含咪嗅 Λ/c Ά I 、I、*··· · · 基的二胺而獲得―部分作為上述所示的二 [化9] 胺成分。 39 201207960 丨The imidazole-containing polyimine can be obtained in the following manner. . The diamine containing the olfactory oxime / c Ά I, I, *, ····· group as shown in the following (4) configuration can be used to obtain a moiety as the above-mentioned bis [9] amine component. 39 201207960 丨

C11HC11H

nh2Nh2

上述聚醯亞胺樹脂就可均勻地進行B階段化的方面而 5，當將厚度成形為30 μηι時對波長為365 nm的光的穿 透率較佳為10%以上，就可以更低的曝光量進行B階段化 的方面而έ更佳為20%以上。此種聚醯亞胺樹脂例如可藉 由使上述通式（7)所表示的酸酐、與上述通式（14)所表 示的脂肪族趟二胺及/或上述通式（15)所表示的石夕氧烧二 胺進行反應而合成。 就抑制黏度的上升，進一步減少感光性接著劑中的溶 解殘留的方面而言，（D)熱塑性樹脂較佳為使用在常溫 (25 C )下為液狀的液狀熱塑性樹脂。此種熱塑性樹脂可 不使用溶劑而加熱來進行反應，不應用如本實施形態之類 的溶劑的感光性接著劑中，就溶劑去除的步驟的削減、殘 存溶劑的減少、再沈澱步驟的削減的方面而言有用。另外， 液狀熱塑性樹脂亦容易自反應爐中取出。此種液狀熱塑性 樹脂並無特別限定，可列舉：聚丁二烯、丙烯腈_丁二烯寡 聚物、聚異戊二烯及聚丁烯等橡膠狀聚合物；聚烯烴、丙 烯酸聚合物、聚矽氧聚合物、聚胺基甲酸酯、聚醯亞胺、 以及聚酿胺酿亞胺等。其中較佳為使用聚醯亞胺樹脂。 201207960 -----pu 液狀的聚醯亞胺樹脂例如藉由使上述酸肝、與脂肪族 醚二胺或矽氧烷二胺進行反應而獲得。作為合成方法，是 藉由不添加溶劑’使酸酐分散於脂肪族醚二胺或矽氧烷二 胺中，進行加熱而獲得。 本實施形態的感光性接著劑較佳為使用高精度平行曝 光機（〇RC製作所製造，「ΕΧΜ-1172-Β·〇〇」（商品名））進 行曝光後，2〇t〜30(TC下的最低熔融黏度為3〇〇〇〇 Pa.s 以下的感光性接著劑。亦可使用平行曝光機（Luminas股 份有限公司製造，「ML-21OFM Mask Aligner」（商品名）） 來代替上述高精度平行曝光機。 本說明書巾，所謂「最健雜度」，是表示對利用光 ，為1000 mJ/cm2的光進行曝光後的樣品，使用黏彈性測 疋裝置 ARES (Rheometrics Scientific F.E.(股）製造）進 行測定時的2(rc〜3G(rc下的熔_度的最低值二此外， 測定板是使用直徑為8 mm的平行板。設為升溫速度為 5C/mm、測定溫度為20〇C〜300t、頻率為丨Hz的測定 上述最低熔融黏度較佳為2〇〇〇〇 Pa.s以下，更佳 i_o Pa.s以下，進而更佳為15_ Pa.s以下。_由且有 上述範_的最低縣减，可確縣分的低溫^麼 性，對具有凹凸的基板等亦可賦予良好的密著性 低溶融減的下限值縣_奴，賴作 = 言，較佳為10Pa.s以上。 π 本實施形態的感光性接著劑可視f要使用熱自由基產 201207960 生劑。熱自由基產生劑較佳為有機過氧化物。有機過氧化 物較佳為1分鐘半衰期溫度為8(rc以上，更佳為1〇〇1以 亡，最佳為12(TC以上。有機過氧化物是考慮到感光性接 著劑的製備條件、製膜溫度、硬化（貼合）條件、其他製 程條件、儲存穩定性等來選擇。可使用的有機過氧化物並 無特別限定，例如可列舉：2,5_二曱基_2,5-二（第三丁基過 氧化己烧）、一異丙笨基過氧化物、過氧化-2-乙基己酸第 三丁酯、過氧化-2-乙基己酸第三己酯、ι，ι·雙（第三丁基過 氧化)-3,3,5·三曱基環己烷、U-雙(第三己基過氧化)_3,3,5_ 三曱基環己烷及雙(4-第三丁基環己基)過氧化二碳酸酯’， 可將該些過氧化物中的丨種單獨使用，或者將2種以上混 合使用。藉由包含有機過氧化物，可使曝光後所殘存的未 反應的放射線聚合性化合物進行反應，可實現逸出氣體的 減少（低逸出氣體化）、高接著化。 相對於放射線聚合性化合物的總量，熱自由基產生劑 的3：較佳為0.01 mass%〜20 mass%，尤佳為ο] mass%〜 10 mass〇/°，最佳為 〇·5 mass%〜5 mass%。若小於 〇.〇1 mass% ’則存在硬化性下降’由添加帶來的效果變小的傾 向，若超過5 mass%，則存在看到逸出氣體量的增加、保 存穩定性的下降的傾向。 熱自由基產生劑只要是1分鐘半衰期溫度為8〇〇c以上 的化合物’則並無特別限定’例如可列舉：Perhexa 25B (曰 油公司製造）、2,5-二曱基-2,5-二(第三丁基過氧化己烷）（i 勿在里半衣期溫度：180°C )、Percumyl D (曰油公司製造）The above-mentioned polyimine resin can uniformly perform the B-staged aspect. 5, when the thickness is formed into 30 μm, the transmittance of light having a wavelength of 365 nm is preferably 10% or more, which can be lower. The amount of exposure is more preferably 20% or more in terms of B-stage. Such a polyimine resin can be represented, for example, by the acid anhydride represented by the above formula (7), the aliphatic anthraquinone diamine represented by the above formula (14), and/or the above formula (15). Shixi oxygen is diamined and reacted to synthesize. The (D) thermoplastic resin is preferably a liquid thermoplastic resin which is liquid at normal temperature (25 C) in terms of suppressing the increase in viscosity and further reducing the residual solubility in the photosensitive adhesive. The thermoplastic resin can be reacted without heating with a solvent, and in the photosensitive adhesive which does not apply the solvent of this embodiment, the reduction of the solvent removal step, the reduction of the residual solvent, and the reduction of the reprecipitation step are possible. Useful. Further, the liquid thermoplastic resin is also easily taken out from the reaction furnace. The liquid thermoplastic resin is not particularly limited, and examples thereof include rubbery polymers such as polybutadiene, acrylonitrile-butadiene oligomer, polyisoprene, and polybutene; and polyolefins and acrylic polymers. , polyoxyl polymers, polyurethanes, polyimine, and polyamines. Among them, a polyimide resin is preferably used. 201207960 ----- pu The liquid polyimine resin is obtained, for example, by reacting the above-mentioned sour liver with an aliphatic ether diamine or a decyl diamine. The synthesis method is obtained by dispersing an acid anhydride in an aliphatic ether diamine or a decane diamine without adding a solvent, and heating. The photosensitive adhesive of the present embodiment is preferably subjected to exposure using a high-precision parallel exposure machine ("ΕΧΜ-1172-Β·〇〇" (trade name)) manufactured by 〇RC, 2 〇t~30 (TC The minimum melt viscosity is a photosensitive adhesive of 3 〇〇〇〇Pa.s or less. A parallel exposure machine ("ML-21OFM Mask Aligner" (trade name) manufactured by Luminas Co., Ltd.) can also be used instead of the above-mentioned high precision. Parallel exposure machine. The "the most robustness" in this manual is a sample obtained by exposing light of 1000 mJ/cm2 to light using a viscoelastic measuring device ARES (Rheometrics Scientific FE). 2 at the time of measurement (rc~3G (the lowest value of the melt_degree under rc). In addition, the measurement plate is a parallel plate having a diameter of 8 mm. The temperature rise rate is 5 C/mm, and the measurement temperature is 20 〇C. The measurement of the lowest melting viscosity of 〜300t and the frequency of 丨Hz is preferably 2〇〇〇〇Pa.s or less, more preferably i_o Pa.s or less, and even more preferably 15_Pa.s or less. The lowest county of _ is reduced, but the low temperature of the county is correct. The uneven substrate or the like can also provide a lower limit value of good adhesion and low melting reduction. _ slave, = =, say, preferably 10 Pa.s or more. π The photosensitive adhesive of the present embodiment can be used. The free radical is produced in 201207960. The thermal radical generating agent is preferably an organic peroxide. The organic peroxide preferably has a one-minute half-life temperature of 8 (rc or more, more preferably 1 〇〇 1 to death, preferably 12 (TC or more. The organic peroxide is selected in consideration of preparation conditions of the photosensitive adhesive, film forming temperature, curing (bonding) conditions, other process conditions, storage stability, etc. Organic peroxides can be used. It is not particularly limited, and examples thereof include 2,5-dimercapto-2,5-di(t-butylperoxyhexanone), isopropylidene peroxide, and peroxy-2-ethylhexanoic acid. Third butyl ester, third hexyl peroxy-2-ethylhexanoate, ι, ι·bis(t-butylperoxy)-3,3,5·trimethylcyclohexane, U-double ( Third hexyl peroxy) _3,3,5-trimethylcyclohexane and bis(4-t-butylcyclohexyl)peroxydicarbonate', which can be used in the peroxides By using an organic peroxide, the unreacted radiation-polymerizable compound remaining after the exposure can be reacted, and the escape gas can be reduced (low-emission gasification). The thermal radical generating agent 3 is preferably 0.01 mass% to 20 mass%, more preferably ο] mass% 〜 10 mass 〇 / °, and most preferably the total amount of the radiation polymerizable compound. 〇·5 mass%~5 mass%. If it is less than 〇.〇1 mass% ', the curability decreases, and the effect by the addition tends to be small. When it exceeds 5 mass%, there is a tendency to see an increase in the amount of evolved gas and a decrease in storage stability. . The thermal radical generating agent is not particularly limited as long as it is a compound having a one-minute half-life temperature of 8 〇〇 c or more. For example, Perhexa 25B (manufactured by Oyster Sauce Co., Ltd.), 2,5-dimercapto-2,5 - bis (tertiary butyl peroxy hexane) (i not in the half-coating temperature: 180 ° C), Percumyl D (manufactured by Oyster Oil Co., Ltd.)

S 42 201207960 及二呉丙本暴過氧化物〔1分鐘半衰期溫度：175。〇）。 本實施形態的感光性接著劑中，為了賦予保存穩定 性、製程適應性或者抗氧化性，可於不損及感光性接著劑 的硬化性的範_進-步添加_、多祕類、賴、亞 磷酸酯類及硫類等聚合抑制劑或者抗氧化劑。 進而，本實施形態的感光性接著劑中亦可適當含有填 料。填料例如可列舉：銀粉、金粉、銅粉及錄粉等金屬填 1 ’氧化紹、氫氧㈣、氫氧化鎂、碳酸妈、碳酸镁、石夕 =鈣：矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、結晶 切、非晶性二氧切、氮_、氧化鈦、玻璃、 等無機填料，以及碳及橡膠系填料等有機填 枓’=，形狀等如何，可無特別限制地使用。 填料是為了對感光性接著劍使用。例如’金屬 等的目的而添加。非金屬電性、導熱性及觸變性 劑層賦予導触為了賊光性接著 加，有機填料是為了對及低吸濕性等的目的而添 而添加。 ％ 接者劑層賦予韌性等的目的 種，上或者有機填料可單獨使用1 裝置用接著材料所要求“電性其可賦予對半導體 的方面而言，触為金 〜、性或者低吸濕特性 緣性的方面而言，較佳為.绦7者…、機填料，就可賦予絕 緣性的填料t，就對‘接=填料。無機填料或者絕 4生接讀的分散性良好且可職予 43 201207960 · 熱時=接著力的方面而言，更佳為二氧化石夕填料。 30 平均粒徑為1〇μΐΏ以下且最大粒徑為 :=若平二 === 相對= 真是根據所賦予的特性或者功能來決定， 的量 f纽#)與填料的合計，上述填料 1δ〇ί 050 mass〇/o 9 1 mass%-4° 低α仆供 咖娜〜3〇職祝。藉由使填料增量， :二=匕、高彈性模數化得以實現，可有效地提 率）、熱時的刀接著強刀Γ切斷性）'打線接合性（超音波效 必要以上’則存在感光性接著劑的黏 熱==向，_ :通的填料的量。使用填:時的混== 組合而進^。'擂賴、三輥機及球磨機等分散機適當 的界的3性接著射’為了使不同種材料間 高的方“言，心:=為=S 42 201207960 and dipyridamole peroxide [1 minute half-life temperature: 175. 〇). In the photosensitive adhesive of the present embodiment, in order to impart storage stability, process suitability, or oxidation resistance, it is possible to add _, a secret, and a remedy without impairing the curability of the photosensitive adhesive. , polymerization inhibitors such as phosphites and sulfurs or antioxidants. Further, the photosensitive adhesive of the present embodiment may contain a filler as appropriate. Examples of the filler include silver powder, gold powder, copper powder, and recording powder. The metal is filled with 1 'oxidized salt, hydrogen and oxygen (four), magnesium hydroxide, carbonic acid mother, magnesium carbonate, and stone=calcium: magnesium citrate, calcium oxide, magnesium oxide. , alumina, aluminum nitride, crystal cut, amorphous dioxotomy, nitrogen _, titanium oxide, glass, and other inorganic fillers, as well as carbon and rubber-based fillers, such as organic filling '=, shape, etc., no special Use restricted. The filler is used for the sensitivity of the sword. For example, it is added for the purpose of metal or the like. The non-metal electrical, thermal conductivity, and thixotropic agent layer are added to the guide for the slick light addition, and the organic filler is added for the purpose of, and low hygroscopicity. % The carrier layer imparts a target species such as toughness, and the upper or the organic filler can be used alone. 1 The device is required to be used as a material. The electrical property can be imparted to the semiconductor, and the contact is gold-, or low-absorbent. In terms of the edge, it is preferable to use the 绦7, the machine filler, and the insulating filler t can be provided, and the dispersion of the 'attachment|filler. The inorganic filler or the raw material can be read and used. To 43 201207960 · In terms of heat = adhesion, it is better to be a dioxide dioxide filler. 30 The average particle size is less than 1〇μΐΏ and the maximum particle size is: = if Ping 2 === Relative = Really The characteristics or functions assigned are determined by the amount of F. #) and the total of the filler, the above-mentioned filler 1δ〇ί 050 mass〇/o 9 1 mass%-4° low α servant for the service of the company. Increment of the filler, : 2 = 匕, high elastic modulus can be achieved, can effectively increase the rate), the knife when hot, then the strong knife Γ cutting property) 'wire bonding (over the ultrasonic effect necessary above) exists The heat of the photosensitive adhesive == direction, _: the amount of the filler. Use the mixture == combination when filling Into the ^. "Dry, three-roller and ball mill and other dispersing machines, the appropriate boundary of the three-sex shot" in order to make the difference between the different kinds of materials "word, heart: = =

S 44 201207960, ，熱硬化性宫能基或甲基㈣義及/或 線聚合性官能基的化合物。上述 ：u曰等放射 咬分解、umh⑽ K糸偶合劑的彿點及/ 或刀解恤度&佳為15QC以上，更佳為⑽。c以上 佳，2〇〇C以上。即，最佳為使料點及/或分解溫 2〇(TC以上，且具有環氧基等熱硬化性官能基或甲基=酸 醋及/或關酸轉放射線聚合性官能基的料系偶人 劑。就上舰果或耐齡从本的方面而言，上述偶^ 的量相對於所使用的感光性接著劑100質量份，較佳為設 為0.01質量份〜20質量份。 本實施形態的感光性接著劑中，為了吸附離子性雜質 而使吸濕時的絕緣可靠性良好，亦可進—步添加離子捕獲 劑。此種離子捕獲劑並無特別限制，例如可列舉：三嗪硫 醇化合物、酚系還原劑等作為用以防止銅產生離子化而溶 出的銅毒抑制劑而為人所知的化合物；粉末狀的鉍系、銻 系、鎂系、鋁系、鍅系、鈣系、鈦系、念珠系及該些的混 合系等無機化合物。具體例並無特別限定’有東亞合成（股） 製造的無機離子捕獲劑：商品名ΙΧΕ-300(銻系）、ΙΧΕ-50〇 (絲系）、ΙΧΕ-600 (銻、鉍混合系）、ΐχΕ-700 (鎂、鋁混 合系）' ΙΧΕ-800 (锆系）、ΙΧΕ-1100 (鈣系）等。該些離子 捕獲劑可單獨使用1種，或者將2種以上混合使用。就由 添加帶來的效果或耐熱性、成本等方面而言，上述離子捕 獲劑的量相對於感光性接著劑100質量份，較佳為0.01質 量份〜10質量份。 就當在印刷前向網眼印刷版的開口部供給感光性接著 45 201207960 满穩疋地供⑺的賴而言，就印刷時感紐接著 眼開口部的脫洛的觀點而言，以及就藉由上述感光性、“ 劑自發地流動而在印刷後使感光性接著 ，者 =跡平坦化的觀點而言，感光性接著= 為1.0〜3_0。若上述觸變指數為i 〇以上 佳 用印刷法而供給及塗佈的上述感光性接著J產：下： 荨，可使印刷形狀保持良好的傾向。進而，若該 ，3.0以下’則存在可抑制利用印刷法而供給:2 ，生接著劑中產生「缺損」或飛白等的傾向。= =者劑的觸變指數的上限值及下限值可為1()、1 2、’^或 ，作餅將感紐接著劑供給至印舰上等的感光性 =者劑的㈣的觀點而言，就印刷時感紐 自 ::的脫落的觀點而言，以及就藉由感光性接= 也=動而使印刷㈣紐接著㈣的氣、;认魏的痕跡平 pt〜ιΓΓ言、’感光性接著_ 25tT的黏度較佳為1 下二π·:。感光性接著劑的25ΐ下的黏度的上限值及 ! Pa-s>8.5P,s. 12.8 P，s^ 16.0 P,s^ l00P,s〇 以黏度是使用E型旋轉職計（東京計器製造）， 觸邮*、25C、轉速G·5聊的條件進行測定時的值。 =:數疋以利用Ε型旋轉黏度計，以坑、轉速i啊 们収時的值與以坑、轉速1G rpm的條件進 丁疋時的制比蚊義（觸變指數=(UPm下的黏度） / UOrpm下的黏度））。S 44 201207960, a compound of thermosetting sclerosing or methyl (tetra) and/or linear polymerizable functional groups. The above: : u曰 and other radiation bite decomposition, umh (10) K 糸 coupling agent of the Buddha's point and / or knife release degree & preferably 15QC or more, more preferably (10). More than c, 2〇〇C or more. That is, it is preferable to use a material having a temperature of 2 〇 or more (TC or higher and having a thermosetting functional group such as an epoxy group or a methyl group; a vinegar and/or a transesterification functional group) In the aspect of the present invention, the amount of the above-mentioned particles is preferably 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of the photosensitive adhesive to be used. In the photosensitive adhesive of the embodiment, the ion-trapping agent may be further added in order to adsorb the ionic impurities to improve the insulation reliability during moisture absorption. The ion-trapping agent is not particularly limited, and examples thereof include: a compound known as a copper poison inhibitor for preventing the generation of ionization of copper by a sulfinyl thiol compound, a phenolic reducing agent, or the like; a powdery lanthanide, lanthanide, magnesium, aluminum, or lanthanide An inorganic compound such as a calcium-based, titanium-based, rosary-based or mixed system. The specific example is not particularly limited to an inorganic ion-trapping agent produced by East Asia Synthetic Co., Ltd.: trade name ΙΧΕ-300 (锑), ΙΧΕ -50〇(silk),ΙΧΕ-600 (锑,铋 mixed system) ΐχΕ-700 (a mixture of magnesium and aluminum) 'ΙΧΕ-800 (zirconium), ΙΧΕ-1100 (calcium), etc. These ion trapping agents may be used singly or in combination of two or more. The amount of the ion trapping agent is preferably 0.01 parts by mass to 10 parts by mass based on 100 parts by mass of the photosensitive adhesive, in terms of the effect of addition, heat resistance, cost, etc. The photosensitive portion of the printing plate is supplied with light sensitivity. Next, for the purpose of the detachment of the opening of the eye, the sensitivity is "spontaneous". From the viewpoint of smoothness after printing, the photosensitivity is then 1.0 to 3_0. The above-mentioned thixotropic index is i 〇 or more and is preferably supplied and coated by the printing method. Photosensitive property: J: Lower: 荨, the printing shape tends to be good. Further, if it is 3.0 or less, it can be suppressed by the printing method: 2, "defective" or whitening occurs in the raw adhesive. Tendency of the == agent The upper limit value and the lower limit value may be 1 (), 1 2, '^ or, for the purpose of supplying the sensor to the photosensitive agent of the printing ship (4), Sense New: From the point of view of detachment, and by the photosensitive connection = also = moving to make the printing (four) continuation (four) of the gas; the trace of the recognition of Wei pt ~ ι ΓΓ, 'photosensitive _ 25tT The viscosity is preferably 1 下2 π: The upper limit of the viscosity at 25 感光 of the photosensitive adhesive and Pa-s>8.5P, s. 12.8 P, s^ 16.0 P, s^ l00P, s〇 The viscosity is measured using the E-type rotation meter (manufactured by Tokyo Keiki Co., Ltd.), and is measured under the conditions of contact*, 25C, and rotation speed G·5. =: The number of 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋Viscosity) / viscosity at UOrpm)).

S 46 201207960〆 [實例] 以下，列舉實例’對本發明進行更具體的說明。但本 發明不受以下實例的限定。 (感光性接著劑的調整） 首先’將熱硬化性樹脂及放射線聚合性化合物，於設 置於油浴中的四口可分離式燒瓶中’於氮氣環境下一邊加 熱至60°C —邊攪拌，使其溶解。向所得的溶液中分別添加 熱硬化起始劑及光聚合起始劑，加入擂潰機中，混練後， 於5 Torr以下進一步進行1小時脫泡混練。進而，藉由進 行放射線聚合性化合物的添加及脫泡混練來調整黏度，獲 得各成分為表1所示的比例的感光性接著劑。各感光性接 著劑的25°C下的黏度及觸變指數示於表i。 (感光性接著劑層的形成） 使用設置有V-screen V160網眼印刷版（NBc Meshtec 股份有限公司製造）的MK-838SV印刷機（Minami股份 有限公司製造）’將所得的感光性接著劑於尺寸為8英忖 φ、厚度為50 μιη的矽晶圓的背面上印刷塗佈成6英吋φ 的圓形狀。以目視確έ忍印刷後的感光性接著劑的情況，名士 果為無飛白等’可設置均勻的感光性接著劑層。 (Β階段化後的感光性接著劑層的表面的黏力測定） 作為實例1〜實例4,對利用網版印刷法而形成於石夕晶 圓上的感光性接著劑層，使用平行曝光機（Luminas股^ 有限公司製造，「ML-21OFM Mask Aligner」（商品名；)），於 氮氣環i兄下以1000 mJ/cm進行曝光，將感光性接著劑層 47 201207960 .η 進行Β階段化。進而’作為比較例1，準備印刷有與實例 1相同的感光性接著劑的矽晶圓，於loot:的乾燥機中投入 一小時，藉由加熱進行B階段化。B階段化後，使用Rhesca 么司製造的探針黏性試驗機’以探針直徑為5.1 mm、剝離 速度為10 mm/s、接觸荷重為1〇〇 gf/cm2、接觸時間為1 s 的條件，來測定30它下的感光性接著劑層的表面黏力。β 階段化後的表面黏力示於表1。 (B階段化後的矽晶圓的翹曲的觀察） 對上述「B階段化後的感光性接著劑層的表面的黏力 測定」中獲得的B階段化後的矽晶圓進行觀察，結果為， 於實例1〜實例4中獲得的形成有感光性接著劑層的石夕晶 圓上未看到翹曲。但是，於比較例1中獲得的形成有感光 性接著劑層的矽晶圓上看到伴隨加熱的矽晶圓的纽曲，石夕 晶圓的端部與中央部的高低差為1.5 cm左右。B階段化後 的矽晶圓的翹曲的觀察結果示於表1。 (拾取性） 於利用網版印刷法而形成有感光性接著劑層的石夕晶圓 的矽晶圓側層壓切割帶，設置於切片上後，使用切割裝置 (Disco股份有限公司製造，「DAD-322〇」（商品名）），切 割為10 mmxlO mm見方。實例1〜實例4中，確認切割後 的矽晶圓的情況，結果為不缺乏矽晶片，可切割。另外， 自切割帶上拾取10個石夕晶片，結果為感光性接著劑未轉印 至切割帶上，拾取性亦良好。另一方面，比較例1中，B P白^又化後的感光性接者劑層的黏力過強’無法進行切叫。S 46 201207960 〆 [Examples] Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited by the following examples. (Adjustment of Photosensitive Adhesive) First, the thermosetting resin and the radiation polymerizable compound were stirred while being heated to 60 ° C in a nitrogen atmosphere in a four-neck separable flask provided in an oil bath. Let it dissolve. A thermosetting initiator and a photopolymerization initiator were added to the obtained solution, and the mixture was placed in a crucible machine, and after kneading, the mixture was further degassed and kneaded at 5 Torr or less for 1 hour. Further, the viscosity was adjusted by the addition of the radiation polymerizable compound and the defoaming and kneading, and a photosensitive adhesive having a ratio of each component shown in Table 1 was obtained. The viscosity and the thixotropic index at 25 ° C of each photosensitive adhesive are shown in Table i. (Formation of photosensitive adhesive layer) The obtained photosensitive adhesive was used in a MK-838SV printing machine (manufactured by Minami Co., Ltd.) provided with a V-screen V160 mesh printing plate (manufactured by NBc Meshtec Co., Ltd.) The back surface of a tantalum wafer having a size of 8 inches φ and a thickness of 50 μm was printed and coated into a circular shape of 6 inches φ. In the case where the photosensitive adhesive after printing is visually confirmed, the name is not white or the like, and a uniform photosensitive adhesive layer can be provided. (Measurement of Viscosity on Surface of Photosensitive Adhesive Layer After Staged) As Examples 1 to 4, a parallel exposure machine was used for a photosensitive adhesive layer formed on a Shiyue wafer by a screen printing method. (Manufactured by Luminas Co., Ltd., "ML-21OFM Mask Aligner" (trade name;)), exposed at 1000 mJ/cm under nitrogen gas, and the photosensitive adhesive layer 47 201207960 .η was staged. . Further, as Comparative Example 1, a tantalum wafer on which the same photosensitive adhesive as in Example 1 was printed was prepared, and it was placed in a loot: dryer for one hour, and B-staged by heating. After the B-stage, the probe viscosity tester manufactured by Rhesca was used with a probe diameter of 5.1 mm, a peeling speed of 10 mm/s, a contact load of 1〇〇gf/cm2, and a contact time of 1 s. The conditions were measured to determine the surface tack of the photosensitive adhesive layer underneath. The surface adhesion after the β-stage is shown in Table 1. (Observation of the warpage of the tantalum wafer after the B-stage) The B-staged tantalum wafer obtained in the above-mentioned "Measurement of the adhesion of the surface of the photosensitive adhesive layer after the B-stage" was observed. No warpage was observed on the Shihwa wafer on which the photosensitive adhesive layer was obtained in Examples 1 to 4. However, in the tantalum wafer on which the photosensitive adhesive layer was obtained in Comparative Example 1, the click of the germanium wafer with heating was observed, and the height difference between the end portion and the center portion of the Si Xi wafer was about 1.5 cm. . The observation results of the warpage of the tantalum wafer after the B-stage are shown in Table 1. (Pickup property) The enamel wafer side laminated dicing tape of the Shiki wafer in which the photosensitive adhesive layer was formed by the screen printing method was placed on the slice, and then a cutting device (manufactured by Disco Co., Ltd.) was used. DAD-322〇" (trade name)), cut to 10 mmxlO mm square. In the examples 1 to 4, the case of the tantalum wafer after the dicing was confirmed, and as a result, the wafer was not lacking and was cut. Further, 10 stone wafers were picked up from the dicing tape, and as a result, the photosensitive adhesive was not transferred onto the dicing tape, and the pickup property was also good. On the other hand, in Comparative Example 1, the adhesion of the photosensitive interface layer after the B P whitening was too strong, and the cutting was impossible.

S 48 201207960 . ----~Γ 11- (剪切強度測定） 將以與上述相同的方式獲得的附接著劑層的矽晶片（5 mm><5 mm見方），熱壓著（200 gf、120°C、3秒）於另行 準備的石夕晶片（8 mm><8 mm見方）上，於烘箱中進行 180°C、1小時的加熱硬化。使用自動接著力試驗機（Arctec 股份有限公司製造，「DAGESERIES4000」（商品名）），對 所得的樣品測定250°C下的剪切強度。測定結果示於表1。 49 201207960 J'ftCNsr-)S 48 201207960 . ----~Γ 11- (Shear Strength Measurement) A tantalum wafer (5 mm >< 5 mm square) of the adhesive layer obtained in the same manner as above was heat-pressed (200 Gf, 120 ° C, and 3 seconds) were heat-hardened at 180 ° C for 1 hour in an oven on a separately prepared Shi Xi wafer (8 mm >< 8 mm square). The obtained sample was measured for shear strength at 250 ° C using an automatic adhesion tester ("DAGESERIES 4000" (trade name) manufactured by Arctec Co., Ltd.). The measurement results are shown in Table 1. 49 201207960 J'ftCNsr-)

【II 比較例 /—\ Ο O CN m寸 V—/ 1 1 /-~N o卜 d v〇 寸 V—/ 1 1 0.40 (1.0) /—N 〇卜 v〇 d d 加熱 12.8 〇 無法測定％ 無法測定” 〇 實例 寸 1 1 N O d (N m寸 Nw/ /—N 〇卜 O v〇 寸W s·_«>' 1 1 0.40 (1.0) o卜 fS o d Vw/ 曝光 00 (N 15.0 CS CN m 1 /—N o o O rn CS Nw/ 1 /-"N o o Ο '-ό 寸VO Sw^ 1 1 0.40 (1.0) 0.20 I (i.o) 16.0 p 40.0 CS /-N O Wi Ο (N m寸 1 1 1 /-N 〇卜 〇 vd 寸m s_«-， 寸。 〇 ^ Vw^ 1 Ο Γ-(N 〇 d d V) 00 〇 85.0 (Ν rn /~N 〇 m d (N m寸 Sw/ 1 1 /—s 〇卜 O v〇 兮V"J 1 1 0.40 (1.0) /-~N 〇卜 (S v〇 o 〇 Vw/ 12.8 cn 12.0 Ο (Ν 單位 質量1 (mass%*1) 質量t (mass%*1) 質量$ | (mass%*1 ) 質量$ (mass%*1) 質量q (mass%*1 ) 質量q (mass%*2) 質量$ (mass%*2) 質量s (mass%*3) 1 Pas 1 gfitm2 Mpa 1 0□ YDCN700-7 YDF-8170C EP1032H60 Aronix M-140 FA-220M 1-819 1-379 EG 1B2PZ B階段化的方法 25°C下的黏度 觸變指數 表面黏力 剪切強度 B階段化後的矽晶圓的翹曲 熱硬化性樹脂 放射線聚合性化合物 光聚合起始劑 熱硬化起始劑 201207960 JUS6rn 。一U3S.I嫦一^砸忘萊味-e-碟桊锯：9* 。^茛丧难€韶二#这丧媸-难夂镍«^起墊9农-®:^. 。^茛丧碟电维哲-^?婦«麵郐墊03矣«:寸* 。拿驷鉍宕岔^1-鉍001嫦叙桀荜±1-¥哿戚筅：£* 。伞«W鉍忘岔甶# 鉍 001 _該#<0^?1<°龄婼某杉S:(N* 『11 『11201207960 表1中的各個記號為下述含義。 YDCN700-7:東都化成（股），曱酚酚醛型環氧樹脂 YDF-8170C :東都化成（股），雙酚F型環氧樹脂 EP1032H60 : JER (股），三（羥基苯基）曱烷型固態環 氧樹脂[II Comparative Example /—\ Ο O CN m inch V—/ 1 1 /-~N o b dv〇 inch V—/ 1 1 0.40 (1.0) /—N 〇 bu v〇dd Heating 12.8 〇 Unable to measure % Determination" 〇 Example 1 1 NO d (N m inch Nw / / - N 〇 Bu O v 〇 W s · _ « > ' 1 1 0.40 (1.0) o Bu f od Vw / Exposure 00 (N 15.0 CS CN m 1 /—N oo O rn CS Nw/ 1 /-"N oo Ο '-ό 寸 VO Sw^ 1 1 0.40 (1.0) 0.20 I (io) 16.0 p 40.0 CS /-NO Wi Ο (N m Inch 1 1 1 /-N 〇 〇 vd inch m s_«-, inch. 〇^ Vw^ 1 Ο Γ-(N 〇dd V) 00 〇85.0 (Ν rn /~N 〇md (N m inch Sw/ 1 1 /—s 〇 O O v〇兮V"J 1 1 0.40 (1.0) /-~N 〇卜(S v〇o 〇Vw/ 12.8 cn 12.0 Ο (Ν Unit mass 1 (mass%*1) quality t (mass%*1) quality $ | (mass%*1 ) quality $ (mass%*1) quality q (mass%*1) quality q (mass%*2) quality $ (mass%*2) quality s (mass%*3) 1 Pas 1 gfitm2 Mpa 1 0□ YDCN700-7 YDF-8170C EP1032H60 Aronix M-140 FA-220M 1-819 1-379 EG 1B2PZ B-stage method Viscosity thixotropic index at 25 ° C Surface adhesion shear strength B-staged tantalum wafer Warp thermosetting resin Radiation polymerizable compound Photopolymerization initiator Thermal curing initiator 201207960 JUS6rn. One U3S.I嫦一^砸忘莱味-e-disc 桊 saw: 9* 。^茛丧茛二#This 媸 媸 夂 夂 夂 « « « « 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农 农-铋001嫦叙桀荜±1-¥哿戚筅:£* . Umbrella «W铋忘岔甶# 铋001 _The#<0^?1<°年婼某杉 S:(N* 『11 『11201207960 The individual symbols in Table 1 have the following meanings. YDCN700-7: Dongdu Chemical Co., Ltd., phenolic phenolic epoxy resin YDF-8170C: Dongdu Chemical Co., Ltd., bisphenol F epoxy resin EP1032H60 : JER (strand), tris(hydroxyphenyl)decane solid epoxy resin

Aronix M-140 :東亞合成（股），N-丙稀醯基氧基乙基 六氫鄰苯二曱醯亞胺 FA-220M :日立化成工業（股），聚乙二醇#200二曱 基丙烯酸酯 1-819 : Ciba Japan (股），苯基雙(2,4,6-三曱基苯曱醯 基)-氧化膦 I-379EG : Ciba Japan (股），2-(二甲基胺基)-2-(4-曱基 十基)-1-(4-嗎琳基苯基)丁烧-1-酉同 1B2PZ :四國化成工業（股），1-苄基-2-苯基咪唑。 【圖式簡單說明】 圖1是表示半導體裝置的製造方法的一實施形態的示 意圖。 圖2是表示半導體裝置的製造方法的一實施形態的示 意圖。 圖3是表示半導體裝置的製造方法的一實施形態的示 意圖。 圖4是表示半導體裝置的製造方法的一實施形態的示 意圖。 圖5是表示半導體裝置的製造方法的一實施形態的示Aronix M-140 : East Asian Synthetic (Shares), N-Alkyloxyethylhexahydrophthaleneimide FA-220M: Hitachi Chemical Industry Co., Ltd., Polyethylene Glycol #200 Dimercapto Acrylate 1-819 : Ciba Japan (R), Phenyl bis(2,4,6-trimercaptophenyl)-phosphine oxide I-379EG : Ciba Japan (share), 2-(dimethylamine 2-(4-mercaptodecyl)-1-(4-morphinylphenyl)butan-1-one with 1B2PZ: Shikoku Chemical Industry Co., Ltd., 1-benzyl-2-benzene Imidazole. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 2 is a view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 3 is a view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 4 is a view showing an embodiment of a method of manufacturing a semiconductor device. FIG. 5 is a view showing an embodiment of a method of manufacturing a semiconductor device;

S 52 201207960“ 意圖。 圖6是表示半導體裝置的一實施形態的示意剖面圖。 【主要元件符號說明】 I :印刷版外框 2:網眼印刷版内的以樹脂填埋的部分 3:網眼印刷版内的開口部 4 :刮漿板 5:感光性接著劑 6 :半導體晶圓 7:感光性接著劑層 8 :藉由曝光而B階段化的感光性接著劑層 9 ··框架（切片） 10 :切割膜 II :附接著劑層的半導體晶片 12 :切割刀片 13a :第1段的半導體晶片 13b :第2段的半導體晶片 14 :支持構件 15 :密封材 16 :將第1段的半導體晶片與支持構件接合的感光性 接著劑層 17:將第2段的半導體晶片與第1段的半導體晶片接 合的感光性接著劑層 18 :接合線 20 :附接著劑層的半導體晶圓 53S 52 201207960 "Intended. Fig. 6 is a schematic cross-sectional view showing an embodiment of a semiconductor device. [Description of main component symbols] I: Printing frame 2: Resin-filled portion 3: mesh in a mesh printing plate Opening portion 4 in the printing plate of the eye: squeegee 5: photosensitive adhesive 6: semiconductor wafer 7: photosensitive adhesive layer 8: photosensitive adhesive layer 9 which is B-staged by exposure · frame Slicing) 10: dicing film II: semiconductor wafer 12 with adhesive layer: dicing blade 13a: semiconductor wafer 13b of the first stage: semiconductor wafer 14 of the second stage: supporting member 15: sealing material 16: the first paragraph A photosensitive adhesive layer 17 for bonding a semiconductor wafer and a supporting member: a photosensitive adhesive layer 18 for bonding the semiconductor wafer of the second stage to the semiconductor wafer of the first stage: bonding wire 20: semiconductor wafer 53 with an adhesive layer

Claims (1)

201207960 . a'U 七、申請專利範圍： 1· 一種附接著劑層的半導體晶圓的製造方法，包括以 下步驟： =半導體晶圓的一側的表面整體’利用網版印刷 佈感光性接著劑以形成感光性接著劑層；以及 土 藉由曝光將上述感光性接著劑層進行B階段化。 2.如申請專利範m第1項所述之附接著舰的半導體 晶圓的製造方法，其中上述感光性接著劑包含熱硬化性樹 脂、放射線聚合性化合物及光聚合起始劑。 3，如申請專利範圍第1項或第2項所述之附接著劑層 的半導體晶圓的製造方法，其中上述感光性接著劑更包^ 熱硬化起始劑。 4·如申請專利範圍第1項至第3項中任一項所述之附 接著劑層的半導體晶圓的製造方法，其中上述感光性接著 劑的25eC下的黏度為1 pa.s〜l〇〇pa.s，且上述感光性接著 劑的觸變指數為1.0〜3.0。 5. —種感光性接著劑，包含熱硬化性樹脂、放射線聚 合性化合物及光聚合起始劑，且用於如申請專利範圍第i 項所述之附接著劑層的半導體晶圓的製造方法。 6. 如申請專利範圍第5項所述之感光性接著劑，其中 更包含熱硬化起始劑。 7. 如申請專利範圍第5項或第6項所述之感光性接著 劑，其中25°C下的黏度為1 pa.s〜lOOPa.s，且觸變指數為 1.0〜3.0。 54 201207960 得：8.—種半導體裳置，藉由包括々步驟的方法而護 將利用如申請專利範圍第 半導體晶圓的製造方法 及導體阳圓單片化，獲得附接著劑層的半導體晶片；以 的半導體晶片接著於 將上述附接著劑層的半導體晶片 支持構件或者其他的半導體晶片上。 9. 一種網版印刷用感光性接者劑，包含熱硬化性樹 脂、放射線聚合性化合物及光聚合起始劑，並且25°C下的 黏度為1 Pa.s〜lOOPa.s，觸變指數為1.〇〜3.〇。 55201207960 . a'U VII. Patent Application Range: 1. A method for manufacturing a semiconductor wafer with an adhesive layer, comprising the following steps: = the entire surface of one side of the semiconductor wafer 'using a screen printing cloth photosensitive adhesive The photosensitive adhesive layer is formed in a B-stage by exposure to light to form a photosensitive adhesive layer; 2. The method for producing a semiconductor wafer according to the invention of claim 1, wherein the photosensitive adhesive comprises a thermosetting resin, a radiation polymerizable compound, and a photopolymerization initiator. 3. The method of producing a semiconductor wafer with an adhesive layer according to claim 1 or 2, wherein the photosensitive adhesive further comprises a heat curing initiator. The method for producing a semiconductor wafer with an adhesive layer according to any one of claims 1 to 3, wherein the photosensitive adhesive has a viscosity of 1 pa.s to 1 at 25 eC. 〇〇pa.s, and the photosensitive adhesive has a thixotropic index of 1.0 to 3.0. 5. A photosensitive adhesive comprising a thermosetting resin, a radiation polymerizable compound, and a photopolymerization initiator, and a method for producing a semiconductor wafer for an adhesive layer as described in claim ii . 6. The photosensitive adhesive according to claim 5, which further comprises a thermosetting initiator. 7. The photosensitive adhesive according to claim 5 or 6, wherein the viscosity at 25 ° C is 1 pa.s to 100 Pa.s, and the thixotropic index is 1.0 to 3.0. 54 201207960 得:8---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- The semiconductor wafer is then placed on a semiconductor wafer support member or other semiconductor wafer to which the adhesive layer is attached. A photosensitive developer for screen printing comprising a thermosetting resin, a radiation polymerizable compound, and a photopolymerization initiator, and having a viscosity at 25 ° C of 1 Pa.s to 100 Pa.s, a thixotropic index For 1.〇~3.〇. 55
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