TWI591701B - Tapes for semiconductor processing and semiconductor devices manufactured using the same - Google Patents

Tapes for semiconductor processing and semiconductor devices manufactured using the same Download PDF

Info

Publication number
TWI591701B
TWI591701B TW104129372A TW104129372A TWI591701B TW I591701 B TWI591701 B TW I591701B TW 104129372 A TW104129372 A TW 104129372A TW 104129372 A TW104129372 A TW 104129372A TW I591701 B TWI591701 B TW I591701B
Authority
TW
Taiwan
Prior art keywords
adhesive layer
wafer
tape
resin
semiconductor processing
Prior art date
Application number
TW104129372A
Other languages
Chinese (zh)
Other versions
TW201616560A (en
Inventor
Toshimitsu Nakamura
Jirou Sugiyama
Original Assignee
Furukawa Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Electric Co Ltd filed Critical Furukawa Electric Co Ltd
Publication of TW201616560A publication Critical patent/TW201616560A/en
Application granted granted Critical
Publication of TWI591701B publication Critical patent/TWI591701B/en

Links

Classifications

    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/50—Working by transmitting the laser beam through or within the workpiece
    • B23K26/53—Working by transmitting the laser beam through or within the workpiece for modifying or reforming the material inside the workpiece, e.g. for producing break initiation cracks
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Laser Beam Processing (AREA)

Description

半導體加工用膠帶及使用此所製造之半導體裝置 Tape for semiconductor processing and semiconductor device manufactured using the same

本發明係關於一種能擴展之半導體加工用膠帶，及使用此半導體加工用膠帶所製造之半導體裝置；該半導體加工用膠帶係在將半導體晶圓分離成晶片狀元件之切割(dicing)步驟中，能利用於固定半導體晶圓，並且在接著切割後之晶片與晶片之間或晶片與基板之間之晶粒結合(die bonding)步驟或安裝(rmounting)步驟中亦能利用者，且同時係能利用在藉由擴展(expanding)而沿著晶片分離接著劑層之步驟中者。 The present invention relates to an expandable semiconductor processing tape and a semiconductor device manufactured using the semiconductor processing tape; the semiconductor processing tape is in a dicing step of separating a semiconductor wafer into wafer-like elements, Can be utilized for fixing a semiconductor wafer, and can also be utilized in a die bonding step or a rmounting step between the wafer after the dicing and the wafer or the substrate, and at the same time The step of separating the adhesive layer along the wafer by expansion is utilized.

過往，在積體電路(IC：Integrated Circuit)等之半導體裝置之製造步驟中，實施為了薄膜化電路圖型形成後之晶圓而研削晶圓背面之背面研磨(back grinding)步驟；在晶圓背面貼上具有黏著性及伸縮性之半導體加工用膠帶後，將晶圓分離成晶片單位之切割步驟；擴張(擴展)半導體加工用膠帶之擴展(expanding)步驟、拾取經分離之晶片之拾取步驟；再將經拾取之晶片接著於引線框架或封裝基板等(或在堆疊 封裝(stacked package)中係將晶片彼此層合、接著)之晶片結合(安裝)步驟。 In the past, in the manufacturing process of a semiconductor device such as an integrated circuit (IC: Integrated Circuit), a back grinding step of grinding the back surface of the wafer for forming a wafer after forming a thin film pattern is performed; a step of separating a wafer into wafer units after attaching a tape for semiconductor processing having adhesiveness and stretchability; expanding (expanding) an expanding step of the tape for semiconductor processing, and picking up a step of picking up the separated wafer; The picked wafer is then attached to a lead frame or package substrate, etc. (or stacked In a stacked package, a wafer bonding (mounting) step of laminating wafers to each other is performed.

在上述背面研磨步驟中，為了保護晶圓之電路圖型形成面(晶圓表面)免於汚染，而會使用表面保護膠帶。晶圓之背面研削結束後，從晶圓表面將此表面保護膠帶予以剝離之際，將以下所述之半導體加工用膠帶(切割‧晶片結合膠帶)貼合於晶圓背面後，將半導體加工用膠帶側固定在吸引桌(suction table)上，對表面保護膠帶施以對晶圓之接著力降低之處理後，剝離表面保護膠帶。表面保護膠帶受到剝離之晶圓，其後在背面貼合有晶圓之狀態下，從吸引桌取起而提供至其後之切割步驟。尚且，上述之使接著力降低之處理係指當表面保護膠帶係由紫外線等之能量線硬化性成分所構成時，則為能量線照射處理，而當表面保護膠帶係由熱硬化性成分所構成時，則為加熱處理。 In the above-described back grinding step, in order to protect the circuit pattern forming surface (wafer surface) of the wafer from contamination, a surface protective tape is used. After the surface of the wafer is peeled off from the surface of the wafer, the semiconductor processing tape (cut ‧ wafer bonding tape) described below is bonded to the back surface of the wafer, and the semiconductor processing is performed. The tape side is fixed on a suction table, and after the surface protective tape is subjected to a treatment for lowering the adhesion of the wafer, the surface protective tape is peeled off. The surface protection tape is subjected to the peeling of the wafer, and then the wafer is attached to the back surface, and is taken from the suction table to be supplied to the subsequent cutting step. Further, the above-described treatment for lowering the adhesion force means that when the surface protective tape is composed of an energy ray-curable component such as ultraviolet rays, it is an energy ray irradiation treatment, and when the surface protection tape is composed of a thermosetting component. At the time, it is heat treatment.

上述背面研磨步驟之後之切割步驟至安裝步驟中，使用在基材膜上依黏著劑層與接著劑層之順序層合而成之半導體加工用膠帶。一般而言，在使用此種半導體加工用膠帶時，首先，在晶圓之背面貼合半導體加工用膠帶之接著劑層而固定晶圓，使用切割刀將晶圓及接著劑層切割成晶片單位。其後，實施使膠帶向晶圓之徑方向進行擴張，而拉開晶片彼此間隔之擴展步驟。此擴展步驟係為了在其後之拾取步驟中提高藉由CCD照相機等之對於晶片之認識性，並且在拾取晶片時防止鄰接之晶片因彼此接 觸而產生之晶片破損所實施者。其後，晶片係在拾取步驟中與接著劑層一同地從黏著劑層剝離後被拾取，在安裝步驟中，直接地接著於引線框架或封裝基板等上。因此，藉由使用半導體加工用膠帶，由於變得能將附接著劑層之晶片直接地接著於引線框架或封裝基板等上，故能省略接著劑之塗佈步驟或另外之將各晶片接著於晶片結合膜上之步驟。 In the dicing step to the mounting step after the back surface polishing step, a tape for semiconductor processing in which the adhesive film layer and the adhesive layer are laminated in the order of the adhesive layer are used. In general, when such a tape for semiconductor processing is used, first, an adhesive layer of a semiconductor processing tape is bonded to the back surface of the wafer to fix the wafer, and the wafer and the adhesive layer are cut into wafer units using a dicing blade. . Thereafter, an expansion step of expanding the tape in the radial direction of the wafer and pulling apart the wafers is performed. This expansion step is to improve the visibility of the wafer by the CCD camera or the like in the subsequent pickup step, and prevent the adjacent wafers from being connected to each other when picking up the wafer. The person who is exposed to the damaged wafer is implemented. Thereafter, the wafer is picked up from the adhesive layer together with the adhesive layer in the pickup step, and is directly attached to the lead frame or the package substrate or the like in the mounting step. Therefore, by using the tape for semiconductor processing, since the wafer of the adhesive layer can be directly attached to the lead frame or the package substrate or the like, the application step of the adhesive can be omitted or the respective wafers can be subsequently attached. The step of bonding the wafer to the film.

然而，在上述切割步驟中，如上述般，由於係使用切割刀將晶圓與接著劑層一同地進行切割，故不僅產生晶圓之切削屑，亦會產生接著劑層之切削屑。並且，尚有接著劑層之切削屑堵塞在晶圓切割溝時，晶片彼此黏附而導致產生拾取不良等，半導體裝置之製造產生降低之問題。 However, in the above-described dicing step, as described above, since the wafer is cut together with the adhesive layer using the dicing blade, not only the chips of the wafer but also the chips of the adhesive layer are generated. Further, when the chips of the adhesive layer are clogged in the wafer dicing groove, the wafers adhere to each other to cause pick-up defects and the like, and the manufacturing of the semiconductor device is lowered.

為了解決此種問題，已提出在切割步驟中藉由刀僅切割晶圓，且在擴展步驟中藉由擴張半導體加工用膠帶，而接著劑層分離成個別晶片之方法(例如，專利文獻1)。根據此種利用擴張時之張力而分離接著劑層之分離方法，不會產生接著劑之切削屑，在拾取步驟中亦不會有不良影響。 In order to solve such a problem, a method of cutting only a wafer by a knives in a dicing step and expanding the semiconductor processing tape in the expanding step and separating the adhesive layer into individual wafers has been proposed (for example, Patent Document 1) . According to such a separation method for separating the adhesive layer by the tension at the time of expansion, the chips of the adhesive are not generated, and there is no adverse effect in the pickup step.

又，近年來，作為晶圓之切割方法，已提出有使用雷射加工裝置，以非接觸之形式切割晶圓，即所謂之隱形切割法。例如，專利文獻2中，作為隱形切割法，揭示一種半導體基板之切割方法，其係具備：藉由於使接著劑層(晶粒結合樹脂層)介存並貼附有薄片之半導體基 板之內部聚集焦點光且照射雷射光，而在導體基板之內部形成因多光子吸收所成之改質區域，並將此改質區域作成切割預定部之步驟；藉由使薄片擴張，而沿著切割預定部切割半導體基板及接著劑層之步驟。 Further, in recent years, as a method of cutting a wafer, it has been proposed to use a laser processing apparatus to cut a wafer in a non-contact manner, that is, a so-called stealth cutting method. For example, Patent Document 2 discloses, as a stealth dicing method, a method of dicing a semiconductor substrate, comprising: a semiconductor group in which a thin layer is deposited by attaching an adhesive layer (a die-bonding resin layer) The inside of the panel collects the focus light and illuminates the laser light, and a modified region formed by multiphoton absorption is formed inside the conductor substrate, and the modified region is formed as a step of cutting the predetermined portion; The step of cutting the predetermined portion to cut the semiconductor substrate and the adhesive layer.

又，作為使用雷射加工裝置之其他晶圓切割方法，例如，專利文獻3提出一種晶圓之分割方法，其係包括：在晶圓背面裝上晶片結合用之接著劑層(接著膜)之步驟；在已貼合該接著劑層之晶圓接著劑層側上貼合能伸長之保護黏著片之步驟；從已貼合保護黏著片之晶圓表面，沿著切線照射雷射光線而分割成個別晶片之步驟；擴張保護黏著片而賦予接著劑層拉伸力，將接著劑層切斷成各晶片之步驟；使已切斷之接著劑層上所貼合之晶片從保護黏著片分離之步驟。 Further, as another wafer dicing method using a laser processing apparatus, for example, Patent Document 3 proposes a method of dividing a wafer by attaching an adhesive layer (attachment film) for bonding a wafer to the back surface of the wafer. a step of laminating the stretchable protective adhesive sheet on the side of the wafer adhesive layer to which the adhesive layer has been attached; separating from the surface of the wafer to which the protective adhesive sheet has been attached, illuminating the laser beam along the tangential line a step of forming individual wafers; expanding the protective sheet to impart a tensile force to the adhesive layer, and cutting the adhesive layer into individual wafers; separating the wafer bonded on the cut-off adhesive layer from the protective adhesive sheet The steps.

此等專利文獻2及專利文獻3記載之晶圓切割方法，由於係藉由照射雷射光及擴張膠帶，以非接觸之形式切割晶圓，故對晶圓之物理性負荷小，不會產生在實施現在主流之刀切割時之晶圓切削屑(chipping)，即能切割晶圓。又，由於係藉由擴張而分離接著劑層，故亦不會產生接著劑層之切削屑。因此，該技術係飽受矚目作為能取代刀切割之優異技術。 In the wafer dicing method described in Patent Document 2 and Patent Document 3, since the wafer is cut in a non-contact manner by irradiating the laser light and the expansion tape, the physical load on the wafer is small and does not occur. By performing chipping on the current mainstream knife cutting, the wafer can be cut. Further, since the adhesive layer is separated by expansion, the chips of the adhesive layer are not generated. Therefore, this technology is attracting attention as an excellent technology that can replace knife cutting.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Document]

〔專利文獻1〕日本特開2007-5530號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-5530

〔專利文獻2〕日本特開2003-338467號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-338467

〔專利文獻3〕日本特開2004-273895號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-273895

如上述專利文獻1~3所記載，藉由擴展進行擴張而分離接著劑層之方法中，為了提升接著劑層之分離性，則會有在如0℃或-15℃般之低溫下進行擴張步驟，且其後之拾取步驟、安裝步驟則係在常溫下進行作業的情況。然而，若試圖提升低溫下接著劑層之分離性時，常溫下之分離性亦提上升促使導致變脆。因此，在受到運搬時等之衝撃下，則變得容易出現切痕或破裂，又即使無切痕或破裂，在將接著劑層加工成規定大小之預切(precut)步驟之際若進行拉伸時，則有導致接著劑層會簡單地破裂的問題。 As described in the above Patent Documents 1 to 3, in the method of separating the adhesive layer by expanding the expansion, in order to improve the separation property of the adhesive layer, expansion is performed at a low temperature such as 0 ° C or -15 ° C. The step, and the subsequent picking step and mounting step are the cases where the work is performed at normal temperature. However, when attempting to improve the separation property of the adhesive layer at a low temperature, the separation at room temperature is also increased to cause brittleness. Therefore, when it is subjected to transportation or the like, it becomes easy to be cut or broken, and even if there is no cut or crack, the pull layer is processed to a predetermined size precut step. When stretched, there is a problem that the adhesive layer is simply broken.

因此，本發明之課題在於提供一種半導體加工用膠帶，其係受到運搬時等之衝撃仍不會產生切痕或破裂，又，在將接著劑層加工成規定大小之預切步驟中，即使拉升仍不會破裂之加工性優異者。 Accordingly, an object of the present invention is to provide a tape for semiconductor processing which is not subjected to cutting or cracking during handling, and the like, and in the pre-cutting step of processing the adhesive layer into a predetermined size, even if it is pulled Those who are still not ruptured and have excellent workability.

為了解決以上之課題，本發明之半導體加工用膠帶，其特徵係接著劑層與黏著片受到層合，且前述接著劑層根據JIS K7128-3所規定之直角形試驗法下之撕裂 強度(A)為0.8MPa以上。 In order to solve the above problems, the tape for semiconductor processing of the present invention is characterized in that the adhesive layer and the adhesive sheet are laminated, and the adhesive layer is torn according to the right angle test method prescribed in JIS K7128-3. The strength (A) is 0.8 MPa or more.

上述半導體加工用膠帶之前述接著劑層在前述直角形試驗法下，前述接著劑層在通過試驗片之直角部之前端之中央線上，從前述直角部之前端切入長度1mm之切割部分時之撕裂強度(B)係以0.5MPa以上為佳。 In the above-described adhesive layer of the above-mentioned semiconductor processing tape, in the above-described right angle test method, the adhesive layer is peeled off from the front end of the straight portion of the test piece by cutting the cut portion having a length of 1 mm from the front end of the right angle portion. The crack strength (B) is preferably 0.5 MPa or more.

又，上述半導體加工用膠帶之前述黏著片之延伸率係以200%以上為佳。 Further, the adhesive sheet of the semiconductor processing tape preferably has an elongation of 200% or more.

又，上述半導體加工用膠帶中，將前述黏著片延伸至延伸率200%後，藉由加熱至120℃會變成120%以下為佳。 Further, in the above-mentioned tape for semiconductor processing, it is preferable that the adhesive sheet is stretched to an elongation of 200% and then heated to 120 ° C to be 120% or less.

又，上述半導體加工用膠帶之前述接著劑層在-15℃中JIS K7128-3所規定之直角形試驗法下之撕裂強度(C)係以0.8MPa以下為佳。 Further, the above-mentioned adhesive layer of the above-mentioned semiconductor processing tape preferably has a tear strength (C) of 0.8 MPa or less in a right angle test method prescribed by JIS K7128-3 at -15 °C.

又，上述半導體加工用膠帶係以在藉由擴展前述黏著片，而將貼合於前述接著劑層上之晶圓及前述接著劑層，或單僅前述接著劑層分離成對應於個別晶片上之用途上所使用者為佳。 Further, in the above-mentioned semiconductor processing tape, the wafer and the adhesive layer bonded to the adhesive layer or the adhesive layer alone are separated into individual wafers by expanding the adhesive sheet The user of the application is preferred.

又，為了解決以上之課題，本發明之半導體裝置，其特徵為使用上述半導體加工用膠帶所製造者。 Moreover, in order to solve the above problems, the semiconductor device of the present invention is characterized in that the above-described semiconductor processing tape is used.

根據本發明，由於接著劑層在JIS K7128-3所示之直角形型試驗片之試驗方法下無切入之撕裂強度(A)在0.8MPa以上，故能提供受到運搬時等之衝撃仍 不會產生切痕或破裂，又，在將接著劑層加工成規定大小之預切步驟中，即使拉升仍不會破裂之加工性優異之半導體加工用膠帶。 According to the present invention, since the adhesive layer has a tear strength (A) of not less than 0.8 MPa in the test method of the right-angle type test piece shown in JIS K7128-3, it can provide the rinsing after being transported and the like. In the pre-cutting step of processing the adhesive layer to a predetermined size, the tape for semiconductor processing which is excellent in workability which does not break even if it is pulled up is not produced.

10‧‧‧半導體加工用膠帶 10‧‧‧Semiconductor processing tape

11‧‧‧基材膜 11‧‧‧Base film

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

13‧‧‧接著劑層 13‧‧‧ adhesive layer

14‧‧‧表面保護膠帶 14‧‧‧Surface protection tape

15‧‧‧黏著片 15‧‧‧Adhesive film

20‧‧‧環形框架 20‧‧‧ ring frame

21‧‧‧台階 21 ‧ ‧ steps

22‧‧‧上推構件 22‧‧‧ Push-up components

25‧‧‧加熱桌 25‧‧‧heating table

26‧‧‧吸引桌 26‧‧‧Attraction table

27‧‧‧能量線光源 27‧‧‧Energy line source

28‧‧‧加熱收縮區域 28‧‧‧heat shrinkage area

29‧‧‧溫風噴嘴 29‧‧‧Warm air nozzle

32‧‧‧改質區域 32‧‧‧Modified area

34‧‧‧晶片 34‧‧‧ wafer

100‧‧‧試驗片 100‧‧‧ test piece

110‧‧‧試驗片 110‧‧‧ test piece

115‧‧‧切割部分 115‧‧‧cutting section

A‧‧‧直角部 A‧‧‧right corner

W‧‧‧晶圓 W‧‧‧ wafer

〔圖1〕示意性地展示本發明之實施形態之半導體加工用膠帶構造之剖面圖。 Fig. 1 is a cross-sectional view schematically showing the structure of a tape for semiconductor processing according to an embodiment of the present invention.

〔圖2〕展示在晶圓上貼合表面保護膠帶之狀態之剖面圖。 [Fig. 2] A cross-sectional view showing a state in which a surface protective tape is attached to a wafer.

〔圖3〕用以說明在本發明之實施形態之半導體加工用膠帶上貼合晶圓與環形框架之步驟之剖面圖。 Fig. 3 is a cross-sectional view showing a step of laminating a wafer and an annular frame on a tape for semiconductor processing according to an embodiment of the present invention.

〔圖4〕說明從晶圓表面剝離表面保護膠帶之步驟之剖面圖。 Fig. 4 is a cross-sectional view showing the step of peeling off the surface protective tape from the surface of the wafer.

〔圖5〕展示藉由雷射加工而在晶圓上形成改質區域之狀態之剖面圖。 FIG. 5 is a cross-sectional view showing a state in which a modified region is formed on a wafer by laser processing.

〔圖6〕(a)展示本發明之實施形態之半導體加工用膠帶搭載於擴展裝置上之狀態之剖面圖。(b)展示藉由擴張半導體加工用膠帶而將晶圓分離城晶片之過程之剖面圖。(c)展示擴張後之半導體加工用膠帶、接著劑層、及晶片之剖面圖。 [ Fig. 6] (a) is a cross-sectional view showing a state in which a tape for semiconductor processing according to an embodiment of the present invention is mounted on an extension device. (b) A cross-sectional view showing a process of separating a wafer by expanding a semiconductor processing tape. (c) A cross-sectional view showing the expanded semiconductor processing tape, the adhesive layer, and the wafer.

〔圖7〕用以說明熱收縮步驟之剖面圖。 Fig. 7 is a cross-sectional view for explaining a heat shrinking step.

〔圖8〕(a)為使用直角形試驗法之試驗片之平面圖，(b)切入有切割部分之試驗片之平面圖。 [Fig. 8] (a) is a plan view of a test piece using a right angle test method, and (b) a plan view of a test piece cut into a cut portion.

以下，詳細說明關於本發明之實施形態。 Hereinafter, embodiments of the present invention will be described in detail.

圖1為展示本發明之實施形態之半導體加工用膠帶10之剖面圖。本發明之半導體加工用膠帶10在藉由擴展而將晶圓分離成晶片之際，接著劑層13係沿著晶片而被分離者。此半導體加工用膠帶10具有由基材膜11與設置於基材膜11上之黏著劑層12所構成之黏著片15，與設置在黏著劑層12上之接著劑層13，且在接著劑層13上貼合晶圓之背面者。尚且，個別之層亦可配合使用步驟或裝置而預先切割(預切)成規定形狀。並且，本發明之半導體加工用膠帶10可為切割成每一枚晶圓分之形態，亦可為將複數之切割成每一枚晶圓分者所形成之長條之薄片捲曲成輥狀之形態。以下，說明關於各層之構成。 Fig. 1 is a cross-sectional view showing a tape 10 for semiconductor processing according to an embodiment of the present invention. When the semiconductor processing tape 10 of the present invention separates the wafer into wafers by expansion, the adhesive layer 13 is separated along the wafer. The semiconductor processing tape 10 has an adhesive sheet 15 composed of a base film 11 and an adhesive layer 12 provided on the base film 11, and an adhesive layer 13 provided on the adhesive layer 12, and an adhesive The back side of the wafer is bonded to layer 13. Furthermore, the individual layers may be pre-cut (pre-cut) into a prescribed shape in accordance with the use of the steps or devices. Moreover, the semiconductor processing tape 10 of the present invention may be in the form of being cut into individual wafers, or may be formed by rolling a plurality of thin sheets formed by cutting each of the wafers into rolls. form. Hereinafter, the configuration of each layer will be described.

<基材膜> <Substrate film>

基材膜11若具有均勻且等向性擴張性時，在擴展步驟中由於晶圓能在全方向上能不偏移地切割，故為佳，且其材質亦未受到特別限定。一般而言，交聯樹脂在與非交聯樹脂比較，其對於拉伸之復原力為大，且對擴展步驟後之被拉伸之狀態施加熱時之收縮應力為大。因此，在擴展步驟後藉由加熱收縮去除膠帶所產生之鬆弛，使膠帶繃緊而穩定地保持個別晶片之間隔之熱收縮步驟之面上為優 異。交聯樹脂當中，較佳係使用熱可塑***聯樹脂。另一方面，非交聯樹脂在交聯樹脂與比較，其對於拉伸之復原力為小。因此，在如-15℃~0℃之低溫區域下之擴展步驟後，由於會再度弛緩並回到常溫，送至拾取步驟、安裝步驟時之膠帶不易收縮，故在能防止附著於晶片之接著劑層彼此接觸之面上優異。非交聯樹脂當中，較佳係使用烯烴系之非交聯樹脂。 When the base film 11 has uniform and isotropic expandability, it is preferable that the wafer can be cut in all directions without offset in the expanding step, and the material thereof is not particularly limited. In general, the crosslinked resin has a large restoring force for stretching as compared with the non-crosslinked resin, and has a large shrinkage stress when heat is applied to the stretched state after the expanding step. Therefore, after the expansion step, the slack generated by the tape is removed by heat shrinkage, and the tape is stretched to stably maintain the interval of the individual wafers. different. Among the crosslinked resins, a thermoplastic crosslinked resin is preferably used. On the other hand, the non-crosslinked resin has a small restoring force for stretching as compared with the crosslinked resin. Therefore, after the expansion step in a low temperature region such as -15 ° C to 0 ° C, since the tape is again relaxed and returned to normal temperature, the tape which is sent to the pickup step and the mounting step is not easily shrunk, so that adhesion to the wafer can be prevented. The layers of the agent layer are excellent in contact with each other. Among the non-crosslinked resins, an olefin-based non-crosslinked resin is preferably used.

作為此種熱可塑***聯樹脂，可例示例如，以金屬離子使乙烯-(甲基)丙烯酸2元共聚物或將乙烯-(甲基)丙烯酸-(甲基)丙烯酸烷基酯作為主要聚合物構成成分之3元共聚物進行交聯而成之離子聚合物樹脂。此等在均勻擴張性之面上適宜於擴展步驟，且在藉由交聯而在加熱時產生強大復原力之面上特別適宜。上述離子聚合物樹脂所包含之金屬離子並未受到特別限定，可舉出如鋅、鈉等，鋅離子之溶出性為低，故在低汚染性之面上為佳。上述3元共聚物之(甲基)丙烯酸烷基酯中，由於碳數1~4之烷基之彈性率高而能對晶圓傳播較強力道，故為佳。作為此種(甲基)丙烯酸烷基酯，可舉出如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯等。 As such a thermoplastic crosslinked resin, for example, an ethylene-(meth)acrylic acid 2-ary copolymer or an ethylene-(meth)acrylic acid-alkyl (meth)acrylate as a main polymer can be exemplified by a metal ion. An ionic polymer resin obtained by crosslinking a ternary copolymer of a constituent component. These are suitable for the expansion step on the surface of uniform expansion, and are particularly suitable on the surface which generates a strong restoring force upon heating by crosslinking. The metal ion contained in the ionic polymer resin is not particularly limited, and examples thereof include zinc and sodium, and the elution property of zinc ions is low, so that it is preferably on a surface having low contamination. Among the alkyl (meth)acrylates of the above-mentioned ternary copolymer, it is preferred that the alkyl group having a carbon number of 1 to 4 has a high modulus of elasticity and can propagate a strong force to the wafer. Examples of such (meth)acrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, and acrylic acid acrylate. Ester, butyl acrylate, and the like.

又，作為上述熱可塑***聯樹脂，除上述離子聚合物樹脂之外，對比重0.910以上未滿0.930之低密度聚乙烯，或比重未滿0.910之超低密度聚乙烯，及其他 選自乙烯-乙酸乙烯酯共聚物之樹脂照射電子線等之能量線而使交聯者亦為適宜。此種熱可塑***聯樹脂由於係在樹脂中共存有交聯部位與非交聯部位，故具有固定之均勻擴張性。又，由於加熱時在作用出強力復原力，故在去除擴展步驟所產生之膠帶鬆弛上亦為適宜，且由於分子鏈之構成中幾乎不包含氯，故即使燃燒處分使用後不需要之膠帶，亦不會產生戴奧辛或其類似物之氯化芳香族烴，故對環境負荷亦小。藉由適宜調整對上述聚乙烯或乙烯-乙酸乙烯酯共聚物照射之能量線之量，即能取得具有充分均勻擴張性之樹脂。 Further, as the thermoplastic crosslinked resin, in addition to the above ionic polymer resin, a low density polyethylene having a specific gravity of 0.910 or more and less than 0.930, or an ultra low density polyethylene having a specific gravity of less than 0.910, and the like A resin selected from the group consisting of ethylene-vinyl acetate copolymers illuminates an energy line such as an electron beam to make a crosslinker suitable. Since such a thermoplastic crosslinked resin has a crosslinked portion and a non-crosslinked portion in the resin, it has a uniform uniform expansion property. Further, since a strong restoring force is exerted during heating, it is also suitable for removing the tape slack generated by the expansion step, and since the molecular chain is composed of almost no chlorine, even if the burning is not required after use, It also does not produce chlorinated aromatic hydrocarbons of dioxin or its analogues, so the environmental load is also small. By appropriately adjusting the amount of the energy ray irradiated to the polyethylene or the ethylene-vinyl acetate copolymer, a resin having a sufficiently uniform expansion property can be obtained.

又，作為非交聯樹脂，可例示例如聚丙烯與苯乙烯-丁二烯共聚物之混合樹脂組成物。 Further, as the non-crosslinking resin, a mixed resin composition such as a polypropylene and a styrene-butadiene copolymer can be exemplified.

作為聚丙烯，例如能使用丙烯之均聚物，或，嵌段型或無規型丙烯-乙烯共聚物。無規型之丙烯-乙烯共聚物因剛性小而為佳。丙烯-乙烯共聚物中之乙烯構成單位之含有率若在0.1重量%以上，則在膠帶之剛性與混合樹脂組成物中之樹脂彼此之相溶性為高之面上為優異。膠帶之剛性若為適當者，則晶圓之切割性提升，且在樹脂彼此之相溶性之情況，擠壓吐出量容易安定化。較佳為1重量%以上。又，丙烯-乙烯共聚物中之乙烯構成單位之含有率若在7重量%以下，則在聚丙烯穩定而容易聚合之面上為優異。較佳為5重量%以下。 As the polypropylene, for example, a homopolymer of propylene or a block type or a random type propylene-ethylene copolymer can be used. The random propylene-ethylene copolymer is preferred because of its low rigidity. When the content of the ethylene constituent unit in the propylene-ethylene copolymer is 0.1% by weight or more, the rigidity of the tape and the resin in the mixed resin composition are excellent in compatibility with each other. When the rigidity of the tape is appropriate, the cutting property of the wafer is improved, and when the resins are compatible with each other, the amount of extrusion and discharge is easily stabilized. It is preferably 1% by weight or more. In addition, when the content of the ethylene constituent unit in the propylene-ethylene copolymer is 7% by weight or less, it is excellent in the surface where the polypropylene is stable and easily polymerized. It is preferably 5% by weight or less.

苯乙烯-丁二烯共聚物亦可使用經氫化者。苯乙烯-丁二烯共聚物若受到氫化，與丙烯之相溶性良好且 能防止因丁二烯中之雙鍵造成之氧化劣化所導致之脆化、變色。又，苯乙烯-丁二烯共聚物中之苯乙烯構成單位之含有率如在5重量%以上，則在苯乙烯-丁二烯共聚物穩定而容易聚合之面上為佳。又，在40重量%以下時，因柔軟而在擴張性之面上優異。較佳為25重量%以下，更佳為15重量%以下。作為苯乙烯-丁二烯共聚物，能使用嵌段型共聚物或無規型共聚物之任意者。無規型共聚物由於係苯乙烯相均勻地分散且能抑制剛性變得過大，而使擴張性提升，故為佳。 The styrene-butadiene copolymer can also be used in the hydrogenation. When the styrene-butadiene copolymer is hydrogenated, it has good compatibility with propylene and It can prevent embrittlement and discoloration caused by oxidative degradation caused by double bonds in butadiene. Further, when the content of the styrene constituent unit in the styrene-butadiene copolymer is 5% by weight or more, it is preferable that the styrene-butadiene copolymer is stable and easily polymerized. Moreover, when it is 40% by weight or less, it is excellent in flexibility on the surface of expandability. It is preferably 25% by weight or less, more preferably 15% by weight or less. As the styrene-butadiene copolymer, any of a block type copolymer or a random type copolymer can be used. The random copolymer is preferable because the styrene phase is uniformly dispersed and the rigidity is suppressed from being excessively increased to improve the expandability.

混合樹脂組成物中之聚丙烯之含有率若在30重量%以上，則在能抑制基材膜之厚度不均之面上優異。若厚度均勻，則擴張性容易等向化，又，容易防止基材膜之應力緩和性變得過大，晶片間距離經時性變小，接著劑層彼此接觸而再融著。較佳為50重量%以上。又，聚丙烯之含有率若在90重量%以下，則容易適當地調整基材膜之剛性。基材膜之剛性變得過大時，則有擴張基材膜所需之力亦會變大，對裝置之負荷變大，而無法充分擴展使晶圓或接著劑層分離的情況，故適度進行調整極為重要。混合樹脂組成物中之苯乙烯-丁二烯共聚物之含有率下限係以10重量%以上為佳，容易調整成適合裝置之基材膜之剛性。上限在70重量%以下時，在能抑制厚度不均之面上優異，以50重量%以下為較佳。 When the content of the polypropylene in the mixed resin composition is 30% by weight or more, it is excellent in the surface which can suppress the thickness unevenness of the base film. When the thickness is uniform, the expandability is easily equalized, and the stress relaxation property of the base film is prevented from becoming excessively large, and the distance between wafers is reduced with time, and the adhesive layers are brought into contact with each other to be remelted. It is preferably 50% by weight or more. Further, when the content of the polypropylene is 90% by weight or less, the rigidity of the base film can be easily adjusted. When the rigidity of the base film is too large, the force required to expand the base film is also increased, and the load on the apparatus is increased, and the wafer or the adhesive layer cannot be sufficiently expanded, so that it is appropriately performed. Adjustment is extremely important. The lower limit of the content ratio of the styrene-butadiene copolymer in the mixed resin composition is preferably 10% by weight or more, and it is easy to adjust the rigidity of the substrate film suitable for the apparatus. When the upper limit is 70% by weight or less, it is excellent in a surface capable of suppressing thickness unevenness, and is preferably 50% by weight or less.

尚且，圖1展示之例中，基材膜11雖為單層，但不受限於此，可為使2種以上之樹脂層合而成之複 數層構造，亦可為將1種類之樹脂層合2層以上。2種以上之樹脂若係統一成交聯性或非交聯性，則在發現各別之特性受到更加增強之面上為佳，在組合交聯性及非交聯性進行層合之情況，在各別之缺點受到互補之面上為佳。基材膜11之厚度並無特別規定，只要係在半導體加工用膠帶10之擴展步驟具有容易拉升且不會斷裂之充分強度即可。例如，50~300μm程度為宜，80μm~200μm為較佳。 Further, in the example shown in FIG. 1, the base film 11 is a single layer, but is not limited thereto, and may be formed by laminating two or more kinds of resins. The number of layers may be two or more layers of one type of resin. If two or more kinds of resins are cross-linked or non-crosslinkable, it is better to find that the respective characteristics are more enhanced. When the combination of cross-linking and non-crosslinking is carried out, The disadvantages of each other are better on the complementary side. The thickness of the base film 11 is not particularly limited as long as it is sufficient for the expansion step of the semiconductor processing tape 10 to be easily pulled up without breaking. For example, it is preferably 50 to 300 μm, and preferably 80 μm to 200 μm.

作為複數層之基材膜11之製造方法，能使用過往公知之擠壓法、層合法等。在使用層合法時，於層間亦可介存有接著劑。接著劑係能使用過往公知之接著劑。 As a method of producing the base film 11 of the plurality of layers, a conventionally known extrusion method, lamination method, or the like can be used. When lamination is used, an adhesive may also be interposed between the layers. The subsequent agent can use a conventionally known adhesive.

<黏著劑層> <Adhesive layer>

黏著劑層12係在基材膜11上塗佈黏著劑組成物而能形成。本發明之構成半導體加工用膠帶10之黏著劑層12只要係具有在切割時不會產生與接著劑層13之剝離、晶片飛出等之不良之程度之保持性，或在拾取時容易與接著劑層13剝離之特性者即可。 The adhesive layer 12 can be formed by applying an adhesive composition to the base film 11. The adhesive layer 12 constituting the tape 10 for semiconductor processing of the present invention has a degree of retention which does not cause peeling of the adhesive layer 13 or wafer flying out during dicing, or is easy to follow at the time of picking up. The characteristics of the peeling of the agent layer 13 may be sufficient.

本發明之半導體加工用膠帶10中，構成黏著劑層12之黏著劑組成物之構成並無特別限定，為了提升切割後之拾取性，以能量線硬化性者為佳，以硬化後與接著劑層13之剝離變得容易之材料為佳。作為其一之態樣，黏著劑組成物中，作為基質樹脂，可例示如包含60莫耳%以上之具有碳數6~12之烷基鏈之(甲基)丙烯酸酯，且具有碘價5~30之能量線硬化性碳-碳雙鍵之聚合物 (A)者。尚且，在此能量線係指如紫外線之光線、或電子線等之電離性放射線。 In the adhesive tape 10 for semiconductor processing of the present invention, the composition of the adhesive composition constituting the adhesive layer 12 is not particularly limited, and in order to improve the pick-up property after cutting, it is preferable to use an energy ray hardening property, and to harden the adhesive and the adhesive. A material in which the peeling of the layer 13 becomes easy is preferable. In the adhesive composition, as the matrix resin, a (meth) acrylate having an alkyl chain having 6 to 12 carbon atoms and containing 60 mol% or more, and having an iodine value of 5, may be exemplified. ~30 energy line hardening carbon-carbon double bond polymer (A). Furthermore, the energy line here refers to ionizing radiation such as ultraviolet light or electron lines.

在此種聚合物(A)中，能量線硬化性碳-碳雙鍵之導入量若在碘價5以上，則在能量線照射後之黏著力之減低效果變高之面上優異。較佳為10以上。又，碘價在30以下時，則在能量線照射後到拾取為止之晶片保持力為高，在拾取步驟當前之擴張時容易擴大晶片之間隙之面上為優異。拾取步驟前若能充分擴大晶片之間隙，則因拾取時之各晶片之圖像認識變得容易，或變得容易拾取而為佳。又，碳-碳雙鍵之導入量在碘價5以上30以下時，則由於聚合物(A)自身具有穩定性，且變得容易製造，故為佳。 In the polymer (A), when the amount of introduction of the energy ray-curable carbon-carbon double bond is 5 or more, the effect of reducing the adhesion after the energy ray irradiation is excellent. It is preferably 10 or more. Further, when the iodine value is 30 or less, the wafer holding power until the pickup after the irradiation of the energy ray is high, and it is excellent in the surface which easily enlarges the gap of the wafer at the time of the current expansion of the pickup step. If the gap between the wafers can be sufficiently enlarged before the pickup step, it is preferable to recognize the image of each wafer at the time of picking up, or to make it easy to pick up. Further, when the amount of introduction of the carbon-carbon double bond is 5 or more and 30 or less, the polymer (A) itself is stable and easy to manufacture, which is preferable.

並且，聚合物(A)之玻璃轉移溫度若在-70℃以上，則在對於伴隨能量線照射之熱之耐熱性面上為優異，較佳為-66℃以上。又，若在15℃以下，則在表面狀態為粗之晶圓中防止切割後晶片飛散之效果的面上為優異，較佳為0℃以下，更佳為-28℃以下。 Further, when the glass transition temperature of the polymer (A) is at least -70 ° C, it is excellent in heat resistance on the heat accompanying the energy ray irradiation, and is preferably -66 ° C or higher. Moreover, when it is 15 ° C or less, it is excellent in the surface which has the effect of preventing the wafer from scattering after dicing in the surface of the rough state, and is preferably 0 ° C or less, more preferably -28 ° C or less.

上述之聚合物(A)可為藉由任何方法所製造者，例如，使用使混合丙烯酸系共聚物與具有能量線硬化性碳-碳雙鍵之合物而得者，或具有官能基之丙烯酸系共聚物或具有官能基之甲基丙烯酸系共聚物(A1)，與具有能與該官能基反應之官能基且具有能量線硬化性碳-碳雙鍵之化合物(A2)進行反應而得者。 The above polymer (A) may be produced by any method, for example, using a mixture of a mixed acrylic copolymer and an energy ray-curable carbon-carbon double bond, or an acrylic having a functional group. a copolymer or a methacrylic copolymer (A1) having a functional group, which is reacted with a compound (A2) having a functional group capable of reacting with the functional group and having an energy ray-curable carbon-carbon double bond .

其中，作為上述之具有官能基之甲基丙烯酸 系共聚物(A1)，可例示如使丙烯酸烷基酯或甲基丙烯酸烷基酯等之具有碳-碳雙鍵之單體(A1-1)，與具有碳-碳雙鍵且具有官能基之單體(A1-2)共聚合而得者。作為單體(A1-1)，可例舉如具有碳數6~12之烷基鏈之丙烯酸己基酯、丙烯酸n-辛基酯、丙烯酸異辛基酯、丙烯酸2-乙基己基酯、丙烯酸十二基酯、丙烯酸癸基酯、丙烯酸月桂基酯，或烷基鏈之碳數為5以下之單體即丙烯酸戊基酯、丙烯酸n-丁基酯、丙烯酸異丁基酯、丙烯酸乙基酯、丙烯酸甲基酯，或與此等相同之甲基丙烯酸酯等。 Among them, as the above-mentioned methacrylic acid having a functional group The copolymer (A1) is exemplified by a monomer (A1-1) having a carbon-carbon double bond such as an alkyl acrylate or an alkyl methacrylate, and having a carbon-carbon double bond and having a functional group. The monomer (A1-2) is obtained by copolymerization. The monomer (A1-1) may, for example, be hexyl acrylate having an alkyl chain having 6 to 12 carbon atoms, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate or acrylic acid. Dodecyl ester, decyl acrylate, lauryl acrylate, or a monomer having an alkyl chain of 5 or less, ie, pentyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate An ester, a methyl acrylate, or the like methacrylate or the like.

尚且，單體(A1-1)中，烷基鏈之碳數為6以上之成分由於能縮小黏著劑層與接著劑層之剝離力，故在拾取性之面上為優異。又，12以下之成分則係在室溫下之彈性率為低，黏著劑層與接著劑層之界面接著力之面上為優異。黏著劑層與接著劑層之界面接著力若高，則在擴張膠帶而切割晶圓之際，由於能抑制黏著劑層與接著劑層之界面偏移，而提高切割性，故為佳。 Further, in the monomer (A1-1), since the component having 6 or more carbon atoms in the alkyl chain can reduce the peeling force of the adhesive layer and the adhesive layer, it is excellent in the surface on the pick-up property. Further, the component of 12 or less is excellent in the modulus of elasticity at room temperature, and the surface of the adhesive layer and the adhesive layer is excellent in adhesion. When the adhesive force between the adhesive layer and the adhesive layer is high, it is preferable to reduce the interfacial deviation between the adhesive layer and the adhesive layer while cutting the wafer by expanding the tape.

並且，作為單體(A1-1)，由於若使用烷基鏈之碳數越大之單體，則玻璃轉移溫度變得越低，故藉由適宜選擇，即能調製具有所欲玻璃轉移溫度之黏著劑組成物。又，玻璃轉移溫度之外，在提升相溶性等之各種性能為目的，亦能配合乙酸乙烯酯、苯乙烯、丙烯腈等之具有碳-碳雙鍵之低分子化合物。於此情況，此等低分子化合物係作成在單體(A1-1)總質量之5質量%以下之範圍內所配合者。 Further, as the monomer (A1-1), if a monomer having a larger carbon number of the alkyl chain is used, the glass transition temperature becomes lower, so that it is possible to prepare a desired glass transition temperature by an appropriate selection. Adhesive composition. In addition to the glass transition temperature, it is also possible to blend a low molecular compound having a carbon-carbon double bond such as vinyl acetate, styrene or acrylonitrile for the purpose of improving various properties such as compatibility. In this case, these low molecular weight compounds are formulated so as to be in the range of 5% by mass or less based on the total mass of the monomer (A1-1).

另一方面，作為單體(A1-2)所具有之官能基，可例舉出羧基、羥基、胺基、環狀酸酐基、環氧基、異氰酸酯基等，作為單體(A1-2)之具體例，可舉出如丙烯酸、甲基丙烯酸、肉桂酸、伊康酸、富馬酸、酞酸、2-羥基烷基丙烯酸酯類、2-羥基烷基甲基丙烯酸酯類、二醇單丙烯酸酯類、二醇單甲基丙烯酸酯類、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、烯丙基醇、N-烷基胺基乙基丙烯酸酯類、N-烷基胺基乙基甲基丙烯酸酯類、丙烯醯胺類、甲基丙烯醯胺類、無水馬來酸、無水伊康酸、無水富馬酸、無水酞酸、環氧丙基丙烯酸酯、環氧丙基甲基丙烯酸酯、烯丙基環氧丙基醚等。 On the other hand, the functional group of the monomer (A1-2) may, for example, be a carboxyl group, a hydroxyl group, an amine group, a cyclic acid anhydride group, an epoxy group or an isocyanate group, as a monomer (A1-2). Specific examples thereof include acrylic acid, methacrylic acid, cinnamic acid, itaconic acid, fumaric acid, citric acid, 2-hydroxyalkyl acrylate, 2-hydroxyalkyl methacrylate, and diol. Monoacrylates, diol monomethacrylates, N-methylol acrylamide, N-methylol methacrylamide, allyl alcohol, N-alkylaminoethyl acrylate , N-alkylaminoethyl methacrylates, acrylamides, methacrylamides, anhydrous maleic acid, anhydrous itaconic acid, anhydrous fumaric acid, anhydrous citric acid, epoxy propyl Acrylate, epoxypropyl methacrylate, allyl epoxypropyl ether, and the like.

並且，在化合物(A2)中，作為能使用之官能基，在化合物(A1)具有之官能基為羧基或環狀酸酐基時，可舉出如羥基、環氧基、異氰酸酯基等，在為羥基時，可舉出如環狀酸酐基、異氰酸酯基等，在為胺基時，可舉出如環氧基、異氰酸酯基等，在為環氧基時，可舉出如羧基、環狀酸酐基、胺基等；作為其具體例，可例舉出在單體(A1-2)之具體例中所例示者為相同者。又，作為化合物(A2)，亦能使用聚異氰酸酯化合物之異氰酸酯基之一部分受到具有羥基或羧基及能量線硬化性碳-碳雙鍵之單體而被胺基甲酸酯化者。 Further, in the compound (A2), when the functional group of the compound (A1) is a carboxyl group or a cyclic acid anhydride group, the functional group which can be used is, for example, a hydroxyl group, an epoxy group or an isocyanate group. In the case of a hydroxyl group, for example, a cyclic acid anhydride group or an isocyanate group may be mentioned, and when it is an amine group, an epoxy group or an isocyanate group may, for example, and when it is an epoxy group, a carboxyl group or a cyclic acid anhydride may be mentioned. The base, the amine group, etc., as a specific example, the same as exemplified in the specific example of the monomer (A1-2). Further, as the compound (A2), one of the isocyanate groups of the polyisocyanate compound may be subjected to urethane by a monomer having a hydroxyl group, a carboxyl group and an energy ray-curable carbon-carbon double bond.

尚且，在化合物(A1)與化合物(A2)之反應中，藉由使未反應之官能基殘留，在關於酸價或羥基價等之特性上，即能製造所欲者。若使OH基殘留成聚合物 (A)之羥基價為5~100，則藉由減少能量線照射後之黏著力，而能更加降低拾取失誤之危險性。又，若使COOH殘留成聚合物(A)之酸價為0.5~30，則能取得擴張本發明之半導體加工用膠帶後之黏著劑層之復原後之改善效果而為佳。聚合物(A)之羥基價若為5以上，則在能量線照射後之黏著力之減低效果之面上優異，若為100以下，則在能量線照射後之黏著劑之流動性之面上優異。又，酸價若為0.5以上時，在膠帶復原性之面上優異，在30以下時，在黏著劑之流動性之面上優異。 Further, in the reaction between the compound (A1) and the compound (A2), by leaving the unreacted functional group, it is possible to produce a desired property with respect to properties such as an acid value or a hydroxyl value. If the OH group remains as a polymer (A) The valence of the hydroxyl group is 5 to 100, and the risk of picking up errors can be further reduced by reducing the adhesion after the energy ray is irradiated. In addition, when the acid value of the polymer (A) remaining in the COOH is from 0.5 to 30, the effect of improving the adhesion of the adhesive layer after expanding the tape for semiconductor processing of the present invention can be obtained. When the hydroxyl value of the polymer (A) is 5 or more, it is excellent on the surface of the effect of reducing the adhesion after the energy ray irradiation, and if it is 100 or less, the fluidity of the adhesive after the energy ray irradiation is on the surface. Excellent. In addition, when the acid value is 0.5 or more, it is excellent on the surface of the tape restorability, and when it is 30 or less, it is excellent in the fluidity of the adhesive.

上述聚合物(A)之合成中，作為反應系在溶液聚合下進行時之有機溶劑，可使用酮系、酯系、醇系、芳香族系者，但其中係以甲苯、乙酸乙酯、異丙基醇、苯甲基賽珞蘇、乙基賽珞蘇、丙酮、甲基乙基酮等之一般為丙烯酸系聚合物之良溶劑且沸點60~120℃之溶劑為佳，又作為聚合起始劑，通常係使用、α,α’-偶氮雙異丁腈等之偶氮雙系、過氧化苄醯基等之有機過氧化物系等之自由基發生劑。此時，因應必要，亦能併用觸媒、聚合禁止劑，且藉由調節聚合溫度及聚合時間，即能取得所欲分子量之聚合物(A)。又，關於調節分子量，以使用硫醇、四氯化碳系之溶劑為佳。尚且，此反應並非係受限於溶液聚合者，亦可為塊狀聚合、懸濁聚合等其他方法。 In the synthesis of the polymer (A), as the organic solvent when the reaction system is carried out under solution polymerization, a ketone system, an ester system, an alcohol system or an aromatic group may be used, but in the case of toluene, ethyl acetate or the like, Propyl alcohol, benzyl acesulfame, ethyl cyproterone, acetone, methyl ethyl ketone, etc. are generally good solvents for acrylic polymers and solvents with a boiling point of 60-120 ° C are preferred, as well as polymerization. The initiator is usually a radical generator such as an azobis system such as α,α'-azobisisobutyronitrile or an organic peroxide such as benzamidine peroxide. In this case, if necessary, a catalyst or a polymerization inhibiting agent can be used in combination, and by adjusting the polymerization temperature and the polymerization time, the polymer (A) having a desired molecular weight can be obtained. Further, in order to adjust the molecular weight, it is preferred to use a solvent such as a mercaptan or a carbon tetrachloride. Further, the reaction is not limited to solution polymerization, and may be other methods such as bulk polymerization or suspension polymerization.

藉由如以上之實施，即能取得聚合物(A)，且本發明中，若將聚合物(A)之分子量作成30萬以上，則在提高凝聚力之面上優異。凝聚力若高，則在擴展時具 有抑制在與接著劑層之界面下偏移之效果，變得容易對接著劑層傳播拉伸力，接著劑層之分割性提升之面上為佳。聚合物(A)之分子量若做成200萬以下，則在合成時及塗工時之抑制膠化之面上優異。尚且，本發明之分子量係指由聚苯乙烯換算之質量平均分子量。 By the above, the polymer (A) can be obtained, and in the present invention, when the molecular weight of the polymer (A) is 300,000 or more, it is excellent in the surface which improves the cohesive force. If the cohesion is high, then when expanding It is preferable to suppress the effect of shifting at the interface with the adhesive layer, and it is easy to propagate the tensile force to the adhesive layer, and the surface of the adhesive layer is preferably improved. When the molecular weight of the polymer (A) is 2,000,000 or less, it is excellent in the surface which suppresses gelation at the time of a synthesis and a coating. Further, the molecular weight of the present invention means a mass average molecular weight in terms of polystyrene.

又，本發明之半導體加工用膠帶10中，構成黏著劑層12之樹脂組成物除具有聚合物(A)外，、尚亦可更具有作用作為交聯劑之化合物(B)。例如，可舉出聚異氰酸酯類、三聚氰胺‧甲醛樹脂、及環氧樹脂，此能係能單獨使用或將2種類以上組合使用。此化合物(B)係與聚合物(A)或基材膜進行反應，藉由其結果之交聯構造，在塗佈黏著劑組成物後能提升將聚合物(A)及(B)作為主成分之黏著劑之凝聚力。 Further, in the tape 10 for semiconductor processing of the present invention, the resin composition constituting the adhesive layer 12 may further have a compound (B) which acts as a crosslinking agent in addition to the polymer (A). For example, polyisocyanate, melamine, formaldehyde resin, and epoxy resin can be used, and these can be used individually or in combination of 2 or more types. This compound (B) is reacted with the polymer (A) or the substrate film, and as a result of the crosslinked structure, the polymer (A) and (B) can be promoted after the application of the adhesive composition. The cohesive force of the adhesive of the ingredients.

作為聚異氰酸酯類，並無特別限制，可舉出例如，4,4’-二苯基甲烷二異氰酸酯、甲伸苯基二異氰酸酯、伸茬基二異氰酸酯、4,4’-二苯基醚二異氰酸酯、4,4’-〔2,2-雙(4-苯氧基苯基)丙烷〕二異氰酸酯等之芳香族異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基-六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、2,4’-二環己基甲烷二異氰酸酯、賴胺酸二異氰酸酯、賴胺酸三異氰酸酯等，具體而言，可使用如Coronate L(日本聚胺基甲酸酯股份有限公司製、商品名)等。做為三聚氰胺‧甲醛樹脂，具體地可使用如NikalacMX-45(三和化學股份有限公司製、商品名)、 Melan(日立化成工業股份有限公司製、商品名)等。作為環氧樹脂，可使用如TETRAD-X(三菱化學股份有限公司製、商品名)等。本發明中，尤其係以使用聚異氰酸酯類為佳。 The polyisocyanate is not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate, methylphenyl diisocyanate, decyl diisocyanate, and 4,4'-diphenyl ether. Aromatic isocyanate such as isocyanate or 4,4'-[2,2-bis(4-phenoxyphenyl)propane]diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-six Methylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, lysine diisocyanate, lysine triisocyanate, etc. Specifically, for example, Coronate L (manufactured by Nippon Polyamide Co., Ltd., trade name) or the like can be used. As a melamine ‧ formaldehyde resin, specifically, for example, Nikalac MX-45 (manufactured by Sanwa Chemical Co., Ltd., trade name), Melan (manufactured by Hitachi Chemical Co., Ltd., trade name). As the epoxy resin, for example, TETRAD-X (manufactured by Mitsubishi Chemical Corporation, trade name) or the like can be used. In the present invention, it is particularly preferred to use a polyisocyanate.

相對於聚合物(A)100質量份，將化合物(B)之添加量作成0.1質量份以上之黏著劑層在凝聚力之面上優異。較佳為0.5質量份以上。又，作成10質量份以下之黏著劑層在抑制塗佈時之急劇膠化之面上優異，且黏著劑之配合或塗佈等之作業性變得良好。更佳為5質量份以下。 The adhesive layer in which the amount of the compound (B) is 0.1 parts by mass or more is excellent in the cohesive force with respect to 100 parts by mass of the polymer (A). It is preferably 0.5 parts by mass or more. In addition, the adhesive layer having a thickness of 10 parts by mass or less is excellent in the surface which suppresses the sharp gelation at the time of application, and the workability of the adhesive agent, coating, etc. is favorable. More preferably, it is 5 mass parts or less.

又，本發明中，黏著劑層12亦可包含光聚合起始劑(C)。黏著劑層12所包含之光聚合起始劑(C)並無特別限制，能使用過往周知者。例如，可舉出二苯甲酮、4,4’-二甲基胺基二苯甲酮、4,4’-二乙基胺基二苯甲酮、4,4’-二氯二苯甲酮等之二苯甲酮類、苯乙酮、二乙氧基苯乙酮等之苯乙酮類、2-乙基蒽醌、t-丁基蒽醌等之蒽醌類、2-氯噻噸酮、安息香乙基醚、安息香異丙基醚、苄基、2,4,5-三芳基咪唑二聚物(咯吩二聚物)、吖啶系化合物等，此等係能單獨使用或將2種以上組合使用。作為光聚合起始劑(C)之添加量，相對於聚合物(A)100質量份，係以配合0.1質量份以上為佳，以0.5質量份以上為較佳。又，其上限係以10質量份以下為佳，5質量份以下。 Further, in the present invention, the adhesive layer 12 may further contain a photopolymerization initiator (C). The photopolymerization initiator (C) contained in the adhesive layer 12 is not particularly limited, and those known in the past can be used. For example, benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobiphenyl An acetophenone such as a ketone or the like, an acetophenone such as acetophenone or diethoxyacetophenone, an anthraquinone such as 2-ethylhydrazine or t-butylhydrazine, or a 2-chlorothiazide. Tonsone, benzoin ethyl ether, benzoin isopropyl ether, benzyl, 2,4,5-triarylimidazole dimer (octyl dimer), acridine compound, etc., which can be used alone or Two or more types are used in combination. The amount of the photopolymerization initiator (C) to be added is preferably 0.1 part by mass or more, and preferably 0.5 part by mass or more based on 100 parts by mass of the polymer (A). Further, the upper limit is preferably 10 parts by mass or less, and 5 parts by mass or less.

並且，本發明使用之能量線硬化性之黏著劑 中，因應必要尚能配合黏著賦予劑、黏著調製劑、界面活性劑等，或其他改質劑等。又，亦可適宜添加無機化合物填料。 Moreover, the energy ray hardenable adhesive used in the present invention In the meantime, it is possible to mix an adhesion-imparting agent, an adhesive preparation agent, a surfactant, or the like, or other modifiers. Further, an inorganic compound filler may be suitably added.

黏著劑層12係能利用過往之黏著劑層之形成方法進行形成。例如，將上述黏著劑組成物塗佈於基材膜11之規定面上而形成之方法，或藉由將上述黏著劑組成物塗佈於分隔器(例如，塗佈有離型劑之塑料製薄膜或薄片等)上形成黏著劑層12後，藉由將該黏著劑層12轉印至基材之規定面上之方法，而能在基材膜11上形成黏著劑層12。尚且，黏著劑層12係可具有單層之形態，亦可具有經層合之形態。 The adhesive layer 12 can be formed by a method of forming a past adhesive layer. For example, a method of applying the above-described adhesive composition onto a predetermined surface of the base film 11 or applying the above-described adhesive composition to a separator (for example, a plastic coated with a release agent) After the adhesive layer 12 is formed on a film or a sheet, the adhesive layer 12 can be formed on the base film 11 by transferring the adhesive layer 12 onto a predetermined surface of the substrate. Further, the adhesive layer 12 may have a single layer form or a laminated form.

作為黏著劑層12之厚度，並無特別限制，厚度若在2μm以上，則在黏性力之面上優異，以5μm以上為較佳。若在15μm以下，則拾取性優異，較佳為10μm以下。 The thickness of the adhesive layer 12 is not particularly limited, and if the thickness is 2 μm or more, it is excellent on the surface of the adhesive force, and preferably 5 μm or more. When it is 15 μm or less, the pickup property is excellent, and preferably 10 μm or less.

黏著片15之延伸率係以200%以上為佳。又，以延伸至延伸率200%後，藉由加熱至120℃而延伸率會變成120%以下為佳。藉由作成加熱至120℃時延伸率變成120%以下，藉由擴展而使接著劑層12沿著晶片分離後，在藉由加熱使因擴展而伸長之半導體加工用膠帶之晶片外周部收縮之步驟中，即能使其確實收縮。其結果係能保持晶片間隔，且能防止晶片彼此之衝突所造成之破裂等。為了作成延伸率為200%以上，延伸至延伸率200%後，藉由加熱至120℃而延伸率變成120%以下，則係以 使用具有此種特性之基材膜11為佳。 The elongation of the adhesive sheet 15 is preferably 200% or more. Further, after extending to an elongation of 200%, the elongation is preferably 120% or less by heating to 120 °C. When the elongation is 120% or less when heated to 120° C., the adhesive layer 12 is separated along the wafer by expansion, and the outer peripheral portion of the wafer for the semiconductor processing tape which is elongated by heating is shrunk by heating. In the step, it can make it shrink. As a result, the wafer interval can be maintained, and cracking or the like caused by collision of the wafers with each other can be prevented. In order to produce an elongation of 200% or more and extend to an elongation of 200%, the elongation is 120% or less by heating to 120 ° C. It is preferred to use the substrate film 11 having such characteristics.

<接著劑層> <Binder layer>

本發明之半導體加工用膠帶10中，接著劑層13係貼合於晶圓，在受到切割後，拾取晶片之際，從黏著劑層12剝離而附著於晶片上者。且，使用將晶片固定在基板或引線框架上時之接著劑。 In the semiconductor processing tape 10 of the present invention, the adhesive layer 13 is bonded to the wafer, and after being diced, the wafer is peeled off from the adhesive layer 12 and attached to the wafer. Also, an adhesive when the wafer is fixed on a substrate or a lead frame is used.

接著劑層13並非係受到特別限定者，只要係一般使用於晶圓上之膜狀接著劑即可，例如可舉出含有熱可塑性樹脂及熱聚合性成分而成者。本發明之接著劑層13所使用之上述熱可塑性樹脂係以具有熱可塑性之樹脂，或在未硬化狀態下具有熱可塑性，加熱後形成交聯構造脂樹脂為佳，並特別限制，作為其一之態樣，可舉出如重量平均分子量5000~200,000且玻璃轉移溫度為0~150℃之熱可塑性樹脂。又，作為另一態樣，可舉出如重量平均分子量100,000~1,000,000且玻璃轉移溫度為-50~20℃之熱可塑性樹脂。 The adhesive layer 13 is not particularly limited as long as it is generally used as a film-like adhesive on a wafer, and examples thereof include a thermoplastic resin and a thermally polymerizable component. The above-mentioned thermoplastic resin used in the adhesive layer 13 of the present invention is preferably a thermoplastic resin or a thermoplastic in an uncured state, and is preferably formed into a crosslinked structural aliphatic resin after heating, and is particularly limited as one of them. The thermoplastic resin such as a weight average molecular weight of 5,000 to 200,000 and a glass transition temperature of 0 to 150 ° C can be mentioned. Further, as another aspect, a thermoplastic resin such as a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of -50 to 20 ° C may be mentioned.

作為前者之熱可塑性樹脂，可舉出例如聚醯亞胺樹脂、聚醯胺樹脂、聚醚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚酯樹脂、聚酯醯亞胺樹脂、苯氧基樹脂、聚碸樹脂、聚醚碸樹脂、聚苯硫醚樹脂、聚醚酮樹脂等，其中亦以使用聚醯亞胺樹脂、苯氧基樹脂為佳，作為後者之熱可塑性樹脂，以使用包含官能基之聚合物為佳。 The thermoplastic resin as the former may, for example, be a polyimide resin, a polyamide resin, a polyether quinone resin, a polyamide amide resin, a polyester resin, a polyester phthalimide resin, or a phenoxy group. Base resin, polyfluorene resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, etc., among which polypyrmine resin and phenoxy resin are preferably used, and the latter is used as a thermoplastic resin. A polymer containing a functional group is preferred.

聚醯亞胺樹脂係能使用公知方法使四羧酸二 酐與二胺進行縮合反應而得。即，在有機溶劑中，使用等莫耳或幾乎等莫耳之四羧酸二酐與二胺(各成分之添加順序為任意)，在反應溫度80℃以下，較佳在0~60℃下進行加成反應。伴隨反應進行而反應液之黏度徐徐上昇，而生成聚醯亞胺之前驅物即聚醯胺酸。藉由在50~80℃之溫度下加熱此聚醯胺酸使其解聚合，亦能調整其分子量。聚醯亞胺樹脂係能使上述反應物(聚醯胺酸)進行脫水閉環而得。脫水閉環係能在加熱處理之熱閉環法，與使用脫水劑之化學閉環法下進行。 Polyimine resin can be used to make tetracarboxylic acid II by a known method. The anhydride is obtained by a condensation reaction with a diamine. That is, in the organic solvent, an equimolar or almost equimolar tetracarboxylic dianhydride and a diamine (the order of addition of each component is arbitrary) is used, and the reaction temperature is 80 ° C or lower, preferably 0 to 60 ° C. The addition reaction is carried out. As the reaction progresses, the viscosity of the reaction liquid gradually rises, and the precursor of the polyimine is polyamine. The molecular weight can also be adjusted by heating the polyamic acid at a temperature of 50 to 80 ° C to depolymerize it. The polyimine resin is obtained by subjecting the above reactant (polyglycine) to dehydration ring closure. The dehydration closed loop system can be carried out in a thermal closed loop process using heat treatment and a chemical ring closure method using a dehydrating agent.

作為聚醯亞胺樹脂之原料所使用之四羧酸二酐並無特別限制，可使用例如，1,2-(乙烯)雙(偏苯三甲酸酯無水物)、1,3-(三亞甲基)雙(偏苯三甲酸酯無水物)、1,4-(四亞甲基)雙(偏苯三甲酸酯無水物)、1,5-(五亞甲基)雙(偏苯三甲酸酯無水物)、1,6-(六亞甲基)雙(偏苯三甲酸酯無水物)、1,7-(七亞甲基)雙(偏苯三甲酸酯無水物)、1,8-(八亞甲基)雙(偏苯三甲酸酯無水物)、1,9-(九亞甲基)雙(偏苯三甲酸酯無水物)、1,10-(十亞甲基)雙(偏苯三甲酸酯無水物)、1,12-(十二亞甲基)雙(偏苯三甲酸酯無水物)、1,16-(十六亞甲基)雙(偏苯三甲酸酯無水物)、1,18-(十八亞甲基)雙(偏苯三甲酸酯無水物)、苯均四酸二酐、3,3’、4,4’-聯苯基四羧酸二酐、2,2’、3,3’-聯苯基四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(2,3-二羧基苯基) 乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)碸二酐、3,4,9,10-苝四羧酸二酐、雙(3,4-二羧基苯基)醚二酐、苯-1,2,3,4-四羧酸二酐、3,4,3’,4’-二苯甲酮四羧酸二酐、2,3,2’,3’-二苯甲酮四羧酸二酐、3,3,3’,4’-二苯甲酮四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐、2,7-二氯藥-1,4,5,8-四羧酸二酐、2,3,6,7-四氯萘-1,4,5,8-四羧酸二酐、菲-1,8,9,10-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、噻吩-2,3,5,6-四羧酸二酐、2,3,3’,4’-聯苯基四羧酸二酐、3,4,3’,4’-聯苯基四羧酸二酐、2,3,2’,3’-聯苯基四羧酸二酐、雙(3,4-二羧基苯基)二甲基矽烷二酐、雙(3,4-二羧基苯基)甲基苯基矽烷二酐、雙(3,4-二羧基苯基)二苯基矽烷二酐、1,4-雙(3,4-二羧基苯基二甲基矽基)苯二酐、1,3-雙(3,4-二羧基苯基)-1,1,3,3-四甲基二環己烷二酐、p-伸苯基雙(偏苯三甲酸酯無水物)、乙烯四羧酸二酐、1,2,3,4-丁烷四羧酸二酐、十氫萘-1,4,5,8-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-1,2,5,6-四羧酸二酐、環戊烷-1,2,3,4-四羧酸二酐、吡咯啶-2,3,4,5-四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、雙(外-雙環〔2,2,1〕庚烷-2,3-二羧酸二酐、雙環-〔2,2,2〕-辛-7-烯-2,3,5,6-四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙〔4-(3,4-二羧基苯基)苯基〕六 氟丙烷二酐、4,4’-雙(3,4-二羧基苯氧基)二苯基硫醚二酐、1,4-雙(2-羥基六氟異丙基)苯雙(偏苯三甲酸酐)、1,3-雙(2-羥基六氟異丙基)苯雙(偏苯三甲酸酐)、5-(2,5-二氧代四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸二酐、四氫呋喃-2,3,4,5-四羧酸二酐等，此等係能使用一種或亦能併用2種以上。 The tetracarboxylic dianhydride used as a raw material of the polyimide resin is not particularly limited, and, for example, 1,2-(ethylene) bis(trimellitic anhydride anhydrate), 1,3-(trimethylene) can be used. Bis(p-trimelliate anhydrate), 1,4-(tetramethylene)bis (p-trimelliate anhydrate), 1,5-(pentamethylene) bis(trimellitic acid) Ester anhydrate), 1,6-(hexamethylene)bis(p-trimelliate anhydrate), 1,7-(heptamethylene)bis (p-trimelliate anhydrate), 1,8 - (octamethylene) bis (p-trimelliate anhydrate), 1,9-(nonamethylene) bis (p-trimelliate anhydrate), 1,10-(decamethylene) double (p-trimelliate anhydrate), 1,12-(dodecyl)bis (p-trimelliate anhydrate), 1,16-(hexamethylene) bis(trimelliticate) Anhydrous), 1,18-(octadecyl)bis (p-trimelliate anhydrate), pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid Anhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3- Dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl) Ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) Methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, Benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3'-benzophenone Tetracarboxylic dianhydride, 3,3,3',4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5, 8-tetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetra Carboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethyl phthalane dianhydride, bis(3,4-dicarboxyphenyl)methylphenyl decane dianhydride, double (3,4-dicarboxyphenyl)diphenylnonane Anhydride, 1,4-bis(3,4-dicarboxyphenyldimethylmercapto)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3- Tetramethyldicyclohexane dianhydride, p-phenylene bis(p-benzoate anhydrate), ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, ten Hydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetra Carboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, bis(exo-bicyclo[2,2,1]heptane-2,3-dicarboxylic dianhydride, bicyclo-[2,2,2]-oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl) Phenyl] Fluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzene bis(phenylene) Triic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-ring Hexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, etc., may be used alone or in combination of two or more.

又，作為聚醯亞胺之原料所使用之二胺並無特別限制，可使用例如，o-伸苯基二胺、m-伸苯基二胺、p-伸苯基二胺、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚甲烷、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’-二胺基二苯基二氟甲烷、4,4’-二胺基二苯基二氟甲烷、3,3’-二胺基二苯基碸、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基硫醚、3,4’-二胺基二苯基硫醚、4,4’-二胺基二苯基硫醚、3,3’-二胺基二苯基酮、3,4’-二胺基二苯基酮、4,4’-二胺基二苯基酮、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)六氟丙烷、2,2-(3,4’-二胺基二苯基)六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、1,3-雙(3-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、3,3’-(1,4-伸苯基雙(1-甲基亞乙基))二苯胺、3,4’-(1,4-伸苯基雙(1-甲基亞 乙基))二苯胺、4,4’-(1,4-伸苯基雙(1-甲基亞乙基))二苯胺、2,2-雙(4-(3-胺基苯氧基)苯基)丙烷、2,2-雙(4-(4-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、2,2-雙(4-(4-胺基苯氧基)苯基)六氟丙烷、雙(4-(3-胺基苯氧基)苯基)硫醚、雙(4-(4-胺基苯氧基)苯基)硫醚、雙(4-(3-胺基苯氧基)苯基)碸、雙(4-(4-胺基苯氧基)苯基)碸、3,5-二胺基安息香酸等之芳香族二胺、1,2-二胺基乙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷、1,2-二胺基環己烷、下述一般式(1)所表示之二胺基聚矽氧烷、1,3-雙(胺基甲基)環己烷、Sunechno Chemical股份有限公司製Jeffamine D-230、D-400、D-2000、D-4000、ED-600、ED-900、ED-2001、EDR-148等之聚氧伸烷基二胺等之脂肪族二胺等，此等能使用1種或亦能併用2種以上。上述聚醯亞胺樹脂之玻璃轉移溫度係以0~200℃為佳，重量平均分子量係以1萬~20萬為佳。 Further, the diamine used as a raw material of the polyimine is not particularly limited, and for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3 can be used. '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amine 3-,5-diisopropylphenyl)methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'- Diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3 , 3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodi Phenyl 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)hexafluoropropane, 2,2 -(3,4'- Diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,4-double ( 3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-phenylphenylbis(1-methylethylidene)) Diphenylamine, 3,4'-(1,4-phenylene bis(1-methyl amide) Ethyl))diphenylamine, 4,4'-(1,4-phenylenebis(1-methylethylidene))diphenylamine, 2,2-bis(4-(3-aminophenoxy) Phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoro Propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, bis(4-(3-aminophenoxy)phenyl) sulfide, bis(4-( 4-aminophenoxy)phenyl) sulfide, bis(4-(3-aminophenoxy)phenyl)anthracene, bis(4-(4-aminophenoxy)phenyl)anthracene, An aromatic diamine such as 3,5-diaminobenzoic acid, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-di Aminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-di Amino decane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, diamine represented by the following general formula (1) Polyoxyalkylene, 1,3-bis(aminomethyl)cyclohexane, Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED- by Sunechno Chemical Co., Ltd. 900, ED-2001, EDR-148, etc. Polyoxyalkylene diamine, etc. For the amine or the like, one type of these may be used or two or more types may be used in combination. The glass transition temperature of the above polyimine resin is preferably from 0 to 200 ° C, and the weight average molecular weight is preferably from 10,000 to 200,000.

(式中，R1及R2表示碳原子數1~30之二價烴基，各自可 為相同亦可為相異，R3及R4表示一價烴基，各自可為相同亦可為相異，m為1以上之整數) (wherein R 1 and R 2 represent a divalent hydrocarbon group having 1 to 30 carbon atoms, each of which may be the same or different, and R 3 and R 4 each represent a monovalent hydrocarbon group, each of which may be the same or different , m is an integer greater than 1)

上述其他較佳之熱可塑性樹脂之一之苯氧基樹脂係以藉由使各種之雙酚與環氧氯丙烷反應之方法，或，使液狀環氧樹脂與雙酚反應之方法而得知樹脂為佳，作為雙酚，可舉出如雙酚A、雙酚雙酚AF、雙酚AD、雙酚F、雙酚S。苯氧基樹脂由於係與環氧樹脂之構造類似，故與環氧樹脂之相溶性良好，適宜對接著膜賦予良好之接著性。 The phenoxy resin of one of the other preferred thermoplastic resins described above is known by a method of reacting various bisphenols with epichlorohydrin or by reacting a liquid epoxy resin with bisphenol. Preferably, examples of the bisphenol include bisphenol A, bisphenol bisphenol AF, bisphenol AD, bisphenol F, and bisphenol S. Since the phenoxy resin is similar in structure to the epoxy resin, it has good compatibility with the epoxy resin, and it is suitable to impart good adhesion to the adhesive film.

作為本發明中使用之苯氧基樹脂，可舉出例如具有下述一般式(2)所表示之重複單位之樹脂。 The phenoxy resin used in the present invention may, for example, be a resin having a repeating unit represented by the following general formula (2).

上述一般式(2)中，X表示單鍵或2價之連結基。作為2價之連結基，可舉出如伸烷基、伸苯基、-O-、-S-、-SO-或-SO2-。在此，伸烷基係以碳數1~10之伸烷基為佳，以-C(R1)(R2)-為較佳。R1、R2表示氫原子或烷基，該烷基係以碳數1~8之直鏈或分枝之烷基為佳，可舉出例如，甲基、乙基、n-丙基、異丙基、異辛基、2-乙基己基、1,3,3-三甲基丁基等。又，該烷基亦可經鹵素原子取代，可舉出例如三氟甲基。X係以伸烷基、-O-、-S-、茀基或-SO2-為佳，以伸烷基、-SO2-為較佳。其中亦以-C(CH3)2-、-CH(CH3)-、-CH2-、-SO2-為佳，以-C(CH3)2-、 -CH(CH3)-、-CH2-為較佳，以-C(CH3)2-為特佳。 In the above general formula (2), X represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkyl group, a phenyl group, -O-, -S-, -SO- or -SO 2 -. Here, the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably -C(R1)(R2)-. R1 and R2 represent a hydrogen atom or an alkyl group, and the alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Base, isooctyl, 2-ethylhexyl, 1,3,3-trimethylbutyl and the like. Further, the alkyl group may be substituted by a halogen atom, and examples thereof include a trifluoromethyl group. X is preferably an alkyl group, -O-, -S-, fluorenyl or -SO 2 -, and an alkyl group or -SO 2 - is preferred. Among them, -C(CH 3 ) 2 -, -CH(CH 3 )-, -CH 2 -, -SO 2 - is preferred, and -C(CH 3 ) 2 -, -CH(CH 3 )-, -CH 2 - is preferred, and -C(CH 3 ) 2 - is particularly preferred.

上述一般式(2)所表之苯氧基樹脂只要係具有重複單位，可為具有複數上述一般式(2)之X為相異之重複單位的樹脂，亦可為僅由X為相同重複單位所構成者。本發明中，以僅由X為相同重複單位所構成之樹脂為佳。 The phenoxy resin represented by the above general formula (2) may be a resin having a plurality of repeating units in which X of the above general formula (2) is different, as long as X is the same repeating unit. The constituents. In the present invention, a resin composed only of X and the same repeating unit is preferred.

又，使上述一般式(2)所表示之苯氧基樹脂中含有羥基、羧基等之極性取代基時，與熱聚合性成分之相溶性提升，而能賦予均勻外觀或特性。 In addition, when the phenoxy resin represented by the above formula (2) contains a polar substituent such as a hydroxyl group or a carboxyl group, the compatibility with the thermopolymerizable component is improved, and a uniform appearance or characteristics can be imparted.

苯氧基樹脂之質量平均分子量若為5000以上，則在膜形成性之面上優異。較佳為10,000以上，更佳為30,000以上。又，質量平均分子量若為150,000以下，則在加熱壓著時之流動性或與其他樹脂之相溶性之面上為佳。較佳在100,000以下。又，玻璃轉移溫度若為-50℃以上，則在膜形成性之面上優異，較佳為0℃以上，更佳為50℃以上。玻璃轉移溫度若為150℃，則晶片結合時之接著劑層13之接著力優異，較佳為120℃以下，更佳為110℃以下。 When the mass average molecular weight of the phenoxy resin is 5,000 or more, it is excellent in the film formability. It is preferably 10,000 or more, more preferably 30,000 or more. Further, when the mass average molecular weight is 150,000 or less, it is preferred that the fluidity at the time of heating and pressing or the compatibility with other resins is good. It is preferably 100,000 or less. Further, when the glass transition temperature is -50 ° C or more, it is excellent in film formability, and is preferably 0 ° C or higher, more preferably 50 ° C or higher. When the glass transition temperature is 150 ° C, the adhesion of the adhesive layer 13 at the time of wafer bonding is excellent, and is preferably 120 ° C or lower, more preferably 110 ° C or lower.

另一方面，作為上述包含官能基之聚合物中之官能基，可舉出例如，環氧丙基、丙烯醯基、甲基丙烯醯基、羥基、羧基、異三聚氰酸酯基、胺基、醯胺基等，其中亦以環氧丙基為佳。 On the other hand, examples of the functional group in the polymer containing a functional group include a glycidyl group, an acryloyl group, a methacryl group, a hydroxyl group, a carboxyl group, an isomeric cyanate group, and an amine. The base, the guanamine group and the like, and the epoxy propyl group is also preferred.

作為上述包含官能基之高分子量成分，可舉出例如，含有環氧丙基、羥基、羧基等之官能基之(甲 基)丙烯酸共聚物等。 The high molecular weight component containing the functional group may, for example, be a functional group containing a glycidyl group, a hydroxyl group or a carboxyl group. Base) acrylic copolymer and the like.

作為上述(甲基)丙烯酸共聚物，可使用例如(甲基)丙烯酸酯共聚物、丙烯酸橡膠等，以丙烯酸橡膠為佳。丙烯酸橡膠係將丙烯酸酯作為主成分，且主要係由丁基丙烯酸酯與丙烯腈等之共聚物，或乙基丙烯酸酯與丙烯腈等之共聚物等所構成之橡膠。 As the (meth)acrylic copolymer, for example, a (meth) acrylate copolymer, an acryl rubber or the like can be used, and an acryl rubber is preferred. The acrylic rubber has an acrylate as a main component, and is mainly a rubber composed of a copolymer of butyl acrylate and acrylonitrile, or a copolymer of acrylate or acrylonitrile.

在含有環氧丙基作為官能基時，含有環氧丙基之反復單位之量係以0.5~6.0重量%為佳，以0.5~5.0重量%為較佳，以0.8~5.0重量%為特佳。含有環氧丙基之反復單位係指含有環氧丙基之(甲基)丙烯酸共聚物之構成單體，具體而言為環氧丙基丙烯酸酯或環氧丙基甲基丙烯酸酯。含有環氧丙基之反復單位之量若在範圍，不僅能確保接著力，還能防止膠化。 When the epoxy propyl group is used as the functional group, the amount of the repeating unit containing the epoxy propyl group is preferably 0.5 to 6.0% by weight, preferably 0.5 to 5.0% by weight, more preferably 0.8 to 5.0% by weight. . The repeating unit containing a glycidyl group means a constituent monomer of a (meth)acrylic acid copolymer containing a glycidyl group, specifically, an epoxypropyl acrylate or a propylene methacrylate. If the amount of the repeating unit containing the epoxy propyl group is in the range, not only the adhesion but also the gelation can be prevented.

作為環氧丙基丙烯酸酯、環氧丙基甲基丙烯酸酯以外之上述(甲基)丙烯酸共聚物之構成單體，可舉出例如，乙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯等，此等係能單獨使用或將2種類以上組合使用。尚且，本發明中，乙基(甲基)丙烯酸酯係指乙基丙烯酸酯及/或乙基甲基丙烯酸酯。在組合使用官能性單體時之混合比率係在考量到(甲基)丙烯酸共聚物之玻璃轉移溫度後決定即可。玻璃轉移溫度藉由作成-50℃以上，則在膜形成性優異，能抑制在常溫下之過剩黏性之面上為佳。常溫下之黏性力若過剩，則接著劑層變得難以操作。較佳為-20℃以上，更佳為0℃以上。又，玻璃轉移溫度藉由作成30 ℃以下，則在晶片結合時之接著劑層接著力之面上優異，較佳為20℃以下。 Examples of the constituent monomer of the above (meth)acrylic copolymer other than the epoxy propyl acrylate and the epoxidized methacrylic acid ester include ethyl (meth) acrylate and butyl (methyl). ) Acrylate or the like, these may be used singly or in combination of two or more types. Further, in the present invention, the ethyl (meth) acrylate means ethyl acrylate and/or ethyl methacrylate. The mixing ratio in the case where the functional monomer is used in combination is determined after considering the glass transition temperature of the (meth)acrylic copolymer. When the glass transition temperature is made to be -50 ° C or higher, the film formability is excellent, and it is preferable to suppress the excessive viscosity at normal temperature. If the viscous force at normal temperature is excessive, the adhesive layer becomes difficult to handle. It is preferably -20 ° C or higher, more preferably 0 ° C or higher. Also, the glass transition temperature is created by 30 Below °C, it is excellent in the adhesion layer of the adhesive layer at the time of wafer bonding, and is preferably 20 ° C or less.

在使上述單體聚合而製造包含官能性單體之高分子量成分時，其聚合方法並無特別限制，能使用例如珠狀聚合、溶液聚合等之方法，其中亦以珠狀聚合為佳。 When the monomer is polymerized to produce a high molecular weight component containing a functional monomer, the polymerization method is not particularly limited, and a method such as bead polymerization or solution polymerization can be used. Among them, bead polymerization is preferred.

本發明中，包含官能性單體之高分子量成分之重量平均分子量若為100,000以上，則在膜形成性之面上優異，較佳為200,000以上，更佳為500,000以上。又，重量平均分子量若調整在2,000,000以下，則在晶片結合時之接著劑層之加熱流動性提升之面上優異。若晶片結合時之接著劑層之加熱流動性提升，則接著劑層與被接著物之密著變良好且能使接著力提升，又掩埋被接著物之凹凸而變得容易抑制空隙。較佳為1,000,000以下，更佳為800,000以下，若在500,000以下，則能取得更大之效果。 In the present invention, when the weight average molecular weight of the high molecular weight component containing a functional monomer is 100,000 or more, it is excellent in film formability, and is preferably 200,000 or more, and more preferably 500,000 or more. Further, when the weight average molecular weight is adjusted to 2,000,000 or less, it is excellent in the surface where the heating fluidity of the adhesive layer is improved at the time of wafer bonding. When the thermal fluidity of the adhesive layer is increased when the wafer is bonded, the adhesion between the adhesive layer and the adherend becomes good, and the adhesion can be improved, and the unevenness of the adherend can be buried to easily suppress the void. It is preferably 1,000,000 or less, more preferably 800,000 or less, and if it is 500,000 or less, a larger effect can be obtained.

又，作為熱聚合性成分，只要因熱而聚合者即無特別限制，可舉出例如，具有環氧丙基、丙烯醯基、甲基丙烯醯基、羥基、羧基、異三聚氰酸酯基、胺基、醯胺基等之官能基之化合物與觸發材料(triggering material)，此等此能單獨使用或能將2種類以上組合使用，但在考量到作為接著劑層之耐熱性時，與硬化劑、促進劑一同地含有因熱而硬化產生接著作用之熱硬化性樹脂為佳。作為熱硬化性樹脂，可舉出例如，環氧樹脂、丙烯酸樹脂、聚矽氧樹脂、苯酚樹脂、熱硬化型聚醯亞胺樹 脂、聚胺基甲酸酯樹脂、三聚氰胺樹脂、脲樹脂等，尤其在取得耐熱性、作業性、信賴性優異之接著劑層之面上，以使用環氧樹脂為最佳。 In addition, the thermal polymerization component is not particularly limited as long as it is polymerized by heat, and examples thereof include a glycidyl group, an acryloyl group, a methacryl group, a hydroxyl group, a carboxyl group, and an isocyanurate. a compound of a functional group such as a group, an amine group, a guanamine group, or the like, and a triggering material, which may be used alone or in combination of two or more kinds, but when heat resistance as an adhesive layer is considered, It is preferable to contain a thermosetting resin which is cured by heat and which is used together with a curing agent or a promoter. Examples of the thermosetting resin include an epoxy resin, an acrylic resin, a polyoxyn resin, a phenol resin, and a thermosetting polyimide tree. In particular, it is preferable to use an epoxy resin on the surface of the adhesive layer which is excellent in heat resistance, workability, and reliability, such as a grease, a urethane resin, a melamine resin, or a urea resin.

上述之環氧樹脂只要係硬化而具有接著作用者，即無特別限制，能使用如雙酚A型環氧樹脂等之二官能環氧樹脂、苯酚酚醛型環氧樹脂或甲酚酚醛型環氧樹脂等之酚醛型環氧樹脂等。又，能適用多官能環氧樹脂、環氧丙基胺型環氧樹脂、含雜環之環氧樹脂或脂環式環氧樹脂等一般所周知者。 The epoxy resin described above is not particularly limited as long as it is cured, and a difunctional epoxy resin such as a bisphenol A epoxy resin, a phenol novolac epoxy resin or a cresol novolac epoxy resin can be used. A phenolic epoxy resin or the like such as a resin. Further, a general-purpose one of a polyfunctional epoxy resin, a glycidylamine epoxy resin, a heterocyclic epoxy resin, or an alicyclic epoxy resin can be used.

作為上述雙酚A型環氧樹脂，可舉出如三菱化學股份有限公司製Epikote系列(Epikote 807、Epikote 815、Epikote 825、Epikote 827、Epikote 828、Epikote 834、Epikote 1001、Epikote 1004、Epikote 1007、Epikote 1009)、陶氏化學公司製、DER-330、DER-301、DER-361、及新日鐵住金化學股份有限公司製、YD8125、YDF8170等。作為上述苯酚酚醛型環氧樹脂，可舉出如三菱化學股份有限公司製之Epikote 152、Epikote 154、日本化藥股份有限公司製之EPPN-201、陶氏化學公司製之DEN-438等，又做為上述o-甲酚酚醛型環氧樹脂，可舉出如日本化藥股份有限公司製之EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027，及新日鐵住金化學股份有限公司製、YDCN701、YDCN702、YDCN703、YDCN704等。作為上述多官能環氧樹脂，可舉出如三菱化學股份有限公司製之 Epon1031S、汽巴精化公司製之Araldite 0163、Nagase ChemteX股份有限公司製之Denacol EX-611、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-421、EX-411、EX-321等。作為上述胺型環氧樹脂，可舉出如三菱化學股份有限公司製之Epikote 604、東都化成股份有限公司製之YH-434、三菱氣體化學股份有限公司製之TETRAD-X及TETRAD-C、住友化學工業股份有限公司製之ELM-120等。作為上述含雜環之環氧樹脂，可舉出如汽巴精化公司製之Araldite PT810、UCC公司製之ERL4234、ERL4299、ERL4221、ERL4206等。此等環氧樹脂係能單獨使用或亦能將2種類以上組合使用。 Examples of the bisphenol A type epoxy resin include Epikote series (Epikote 807, Epikote 815, Epikote 825, Epikote 827, Epikote 828, Epikote 834, Epikote 1001, Epikote 1004, Epikote 1007, manufactured by Mitsubishi Chemical Corporation). Epikote 1009), manufactured by The Dow Chemical Company, DER-330, DER-301, DER-361, and Nippon Steel & Sumitomo Chemical Co., Ltd., YD8125, YDF8170, etc. Examples of the phenol novolak type epoxy resin include Epikote 152, Epikote 154 manufactured by Mitsubishi Chemical Corporation, EPPN-20 manufactured by Nippon Kayaku Co., Ltd., and DEN-438 manufactured by Dow Chemical Co., Ltd., and the like. The above-mentioned o-cresol novolac type epoxy resin may, for example, be EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 manufactured by Nippon Kayaku Co., Ltd., and Nippon Steel & Sumitomo Metal Chemical Co., Ltd., YDCN701, YDCN702, YDCN703, YDCN704, etc. The polyfunctional epoxy resin is exemplified by Mitsubishi Chemical Corporation. Epon1031S, Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-421, EX- manufactured by Nagase ChemteX Co., Ltd. 411, EX-321, etc. Examples of the above-mentioned amine-type epoxy resin include Epikote 604 manufactured by Mitsubishi Chemical Corporation, YH-434 manufactured by Tohto Kasei Co., Ltd., TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., Sumitomo ELM-120 manufactured by Chemical Industry Co., Ltd., etc. Examples of the epoxy resin containing a hetero ring include Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., ERL 4234, ERL4299, ERL4221, and ERL4206 manufactured by UCC Corporation. These epoxy resins can be used singly or in combination of two or more types.

為了使上述熱硬化性樹脂硬化，亦能適宜加入添加劑。作為此種添加劑，可舉出例如，硬化劑、硬化促進劑、觸媒等，在添加觸媒時，因應必要能使用助觸媒。 In order to cure the above thermosetting resin, an additive may be appropriately added. Examples of such an additive include a curing agent, a curing accelerator, and a catalyst. When a catalyst is added, a catalyst can be used as necessary.

上述熱硬化性樹脂係使用環氧樹脂時，以使用環氧樹脂硬化劑或硬化促進劑為佳，以併用此等為較佳。作為硬化劑，可舉出例如、苯酚樹脂、二氰二胺、三氟化硼錯化合物、有機醯肼化合物、胺類、聚醯胺樹脂、咪唑化合物、脲或硫脲化合物、聚硫醇化合物、於末端具有巰基之聚硫醚樹脂、酸酐、光‧紫外線硬化劑。此等係能單獨使用或能併用2種以上使用。 When an epoxy resin is used as the thermosetting resin, it is preferred to use an epoxy resin curing agent or a curing accelerator, and it is preferred to use them in combination. Examples of the curing agent include a phenol resin, a dicyandiamide, a boron trifluoride compound, an organic phosphonium compound, an amine, a polyamide resin, an imidazole compound, a urea or a thiourea compound, and a polythiol compound. A polythioether resin having a mercapto group at the terminal, an acid anhydride, and a light ultraviolet curing agent. These systems can be used alone or in combination of two or more.

其中，作為三氟化硼錯化合物，可舉出如與各種胺化合物(較佳為1級胺化合物)之三氟化硼-胺錯合物，作 為有機醯肼化合物，可舉出如異酞酸二醯肼。 Here, examples of the boron trifluoride-discriminating compound include a boron trifluoride-amine complex compound with various amine compounds (preferably, a first-order amine compound). The organic ruthenium compound may, for example, be guanidinium isophthalate.

作為苯酚樹脂，可舉出例如，苯酚酚醛樹脂、酚芳烷基樹脂、甲酚酚醛樹脂、tert-丁基苯酚酚醛樹脂、壬基苯酚酚醛樹脂等之酚醛型苯酚樹脂、甲階酚醛型苯酚樹脂、聚對氧苯乙烯等之聚氧苯乙烯等。其中，以於分子中具有至少2個酚性羥基之苯酚系化合物為佳。 Examples of the phenol resin include a phenolic phenol resin such as a phenol novolac resin, a phenol aralkyl resin, a cresol novolac resin, a tert-butylphenol phenol resin, a nonylphenol phenol resin, and a resol type phenol resin. Polyoxystyrene such as polyoxystyrene. Among them, a phenol compound having at least two phenolic hydroxyl groups in the molecule is preferred.

作為上述於分子中具有至少2個酚性羥基之苯酚系化合物，可舉出例如，苯酚酚醛樹脂、甲酚酚醛樹脂、t-丁基苯酚酚醛樹脂、二環戊二烯甲酚酚醛樹脂、二環戊二烯苯酚酚醛樹脂、伸茬基變性苯酚酚醛樹脂、萘酚酚醛樹脂、參苯酚酚醛樹脂、肆苯酚酚醛樹脂、雙酚A酚醛樹脂、聚-p-乙烯苯酚樹脂、酚芳烷基樹脂等。並且此等苯酚樹脂當中，以苯酚酚醛樹脂、酚芳烷基樹脂為特佳，且能使連接信賴性提升。 Examples of the phenol-based compound having at least two phenolic hydroxyl groups in the molecule include a phenol novolac resin, a cresol novolak resin, a t-butylphenol novolac resin, a dicyclopentadiene cresol novolac resin, and the like. Cyclopentadiene phenol phenolic resin, decyl phenolic phenolic resin, naphthol phenolic resin, phenolic phenolic resin, phenol phenolic phenolic resin, bisphenol A phenolic resin, poly-p-vinyl phenol resin, phenol aralkyl resin Wait. Among these phenol resins, phenol phenol resin and phenol aralkyl resin are particularly preferable, and connection reliability can be improved.

作為胺類，可例示如鏈狀脂肪族胺(二伸乙三胺、三伸乙四胺、六亞甲基二胺、N,N-二甲基丙基胺、苄基二甲基胺、2-(二甲基胺基)酚、2,4,6-參(二甲基胺基甲基)酚、m-茬二胺等)、環狀脂肪族胺(N-胺基乙基哌嗪、雙(3-甲基-4-胺基環己基)甲烷、雙(4-胺基環己基)甲烷、薄荷烯二胺、異佛爾酮二胺、1,3-雙(胺基甲基)環己烷等)、雜環胺(哌嗪、N,N-二甲基哌嗪、三乙二胺、三聚氰胺、胍胺等)、芳香族胺(間亞苯基二胺、4,4’-二胺基二苯基甲烷、二胺基、4,4’-二胺基二苯基碸等)、聚醯胺樹脂(以聚醯胺胺為佳，二聚物酸與聚胺 之縮合物)、咪唑化合物(2-苯基-4,5-二羥基甲基咪唑、2-甲基咪唑、2,4-二甲基咪唑、2-n-十五基咪唑、1-氰基乙基-2-十一基咪唑鎓‧偏苯三甲酸酯、環氧‧咪唑加成物等)、脲或硫脲化合物(N,N-二烷基脲化合物、N,N-二烷基硫脲化合物等)、聚硫醇化合物、於末端具有巰基之聚硫醚樹脂、酸酐(四氫無水酞酸等)、光‧紫外線硬化劑(二苯基錪六氟磷酸酯、三苯基鋶六氟磷酸酯等)。 The amines may, for example, be a chain aliphatic amine (diethylenetriamine, triethylenetetramine, hexamethylenediamine, N,N-dimethylpropylamine, benzyldimethylamine, 2-(Dimethylamino)phenol, 2,4,6-gin (dimethylaminomethyl)phenol, m-nonanediamine, etc.), cyclic aliphatic amine (N-aminoethylpiperine) Pyrazine, bis(3-methyl-4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)methane, menthene diamine, isophorone diamine, 1,3-bis (amino group) Base) cyclohexane, etc.), heterocyclic amines (piperazine, N,N-dimethylpiperazine, triethylenediamine, melamine, decylamine, etc.), aromatic amines (m-phenylenediamine, 4, 4'-diaminodiphenylmethane, diamine, 4,4'-diaminodiphenylphosphonium, etc.), polyamidamine resin (preferably polyamidoamine, dimer acid and polyamine) Condensate), imidazole compound (2-phenyl-4,5-dihydroxymethylimidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-n-pentadecylimidazole, 1-cyano Base ethyl-2-undecylimidazole ‧ trimellitate, epoxy ‧ imidazole adduct, etc., urea or thiourea compound (N, N-dialkyl urea compound, N, N-dioxane a thiourea compound, etc., a polythiol compound, a polythioether resin having a mercapto group at the terminal, an acid anhydride (tetrahydroanhydrous citric acid, etc.), a light ‧ ultraviolet hardener (diphenylphosphonium hexafluorophosphate, triphenyl Hexafluorophosphate, etc.).

作為上述硬化促進劑，只要係使熱硬化性樹脂硬化者即無特別限制，可舉出例如、咪唑類、二氰二胺衍生物、二羧酸二醯肼、三苯基膦、四苯基鏻四苯基硼酸酯、2-乙基-4-甲基咪唑-四苯基硼酸酯、1,8-二吖雙環〔5.4.0〕十一烯-7-四苯基硼酸酯等。 The hardening accelerator is not particularly limited as long as it cures the thermosetting resin, and examples thereof include an imidazole, a dicyandiamide derivative, a dicarboxylic acid diterpene, a triphenylphosphine, and a tetraphenyl group.鏻tetraphenyl borate, 2-ethyl-4-methylimidazolium-tetraphenylborate, 1,8-dioxinbicyclo[5.4.0]undecene-7-tetraphenylborate Wait.

作為咪唑類，可舉出如咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-乙基咪唑、1-苄基-2-乙基-5-甲基咪唑、2-苯基-4-甲基-5-羥基二甲基咪唑、2-苯基-4,5-二羥基甲基咪唑等。 Examples of the imidazoles include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-phenyl-4-methyl-5- Hydroxydimethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like.

環氧樹脂用硬化劑或硬化促進劑在接著劑層中之含量並無特別限定，最佳之含量係根據硬化劑或硬化促進劑之種類而不同。 The content of the curing agent for the epoxy resin or the curing accelerator in the adhesive layer is not particularly limited, and the optimum content varies depending on the type of the curing agent or the curing accelerator.

前述環氧樹脂與苯酚樹脂之配合比例係以例如配合成前述環氧樹脂成分中之環氧基每1當量而苯酚樹脂中之羥基成為0.5~2.0當量為佳。較佳為0.8~1.2當量。即，兩者之配合比例若在前述範圍外，則導致不會進 行充分硬化反應，且接著劑層之特性變得容易劣化。其他熱硬化性樹脂與硬化劑在其一之實施態樣中，相對於熱硬化性樹脂100質量份而言，硬化劑為0.5~20質量份，在其他之實施態樣中，硬化劑為1~10質量份。硬化促進劑之含量係以少於硬化劑之含量為佳，相對於熱硬化性樹脂100質量份，硬化促進劑係以0.001~1.5質量份為佳，以0.01~0.95質量份為更佳。藉由調整在前述範圍內，即能輔助進行充分之硬化反應。觸媒之含量係相對於熱硬化性樹脂100質量份而言，以0.001~1.5質量份為佳，以0.01~1.0質量份為更佳。 The blending ratio of the epoxy resin to the phenol resin is preferably, for example, 1 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component and 0.5 to 2.0 equivalents in the phenol resin. It is preferably from 0.8 to 1.2 equivalents. That is, if the ratio of the two is outside the above range, it will not advance. The hardening reaction is sufficiently performed, and the characteristics of the adhesive layer become easily deteriorated. In another embodiment of the thermosetting resin and the curing agent, the curing agent is 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermosetting resin, and in other embodiments, the curing agent is 1 ~10 parts by mass. The content of the curing accelerator is preferably less than the content of the curing agent, and the curing accelerator is preferably 0.001 to 1.5 parts by mass, more preferably 0.01 to 0.95 parts by mass, per 100 parts by mass of the thermosetting resin. By adjusting within the above range, it is possible to assist in performing a sufficient hardening reaction. The content of the catalyst is preferably 0.001 to 1.5 parts by mass, more preferably 0.01 to 1.0 part by mass, per 100 parts by mass of the thermosetting resin.

又，本發明之接著劑層13在因應其之用途，亦能適宜配合填料。藉此，變得能謀求在未硬化狀態下提升接著劑層之切割性，提升操作性，調整熔融黏度，賦予觸變性，以及在硬化狀態下之接著劑層中賦予導熱性，提升接著力。 Further, the adhesive layer 13 of the present invention can be suitably blended with a filler in accordance with the use thereof. As a result, it is possible to improve the cutting property of the adhesive layer in an uncured state, improve workability, adjust the melt viscosity, impart thixotropic properties, and impart thermal conductivity to the adhesive layer in the cured state, thereby improving the adhesion.

作為本發明使用之填料，以無機填料為佳。無機填料並無特別限制，能使用例如、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶性二氧化矽、非晶性二氧化矽、銻氧化物等。又，此等係能單獨使用或亦能將2種類以上混合使用。 As the filler used in the present invention, an inorganic filler is preferred. The inorganic filler is not particularly limited, and for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, or aluminum borate whisker can be used. , boron nitride, crystalline cerium oxide, amorphous cerium oxide, cerium oxide, and the like. Further, these types can be used alone or in combination of two or more types.

又，上述無機填料當中，從提升導熱性向上之觀點，以使用氧化鋁、氮化鋁、氮化硼、結晶性二氧化矽、非晶性二氧化矽等為佳。又，從調整熔融黏度或賦予 觸變性之觀點，以使用氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、結晶性二氧化矽、非晶性二氧化矽等為佳。又，從提升切割性之觀點，以使用氧化鋁、二氧化矽為佳。 Further, among the above inorganic fillers, alumina, aluminum nitride, boron nitride, crystalline cerium oxide, amorphous cerium oxide, or the like is preferably used from the viewpoint of improving thermal conductivity. Also, from adjusting the melt viscosity or giving Thixotropy, using aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, crystalline cerium oxide, amorphous cerium oxide It is better. Further, from the viewpoint of improving the cutting property, it is preferred to use alumina or cerium oxide.

填料之含有比例若在30質量%以上，則在引線接合性之面上優異。於引線接合時，打線接著晶片之接著劑層之硬化後之儲藏彈性率係以調整成在170℃下20~1000MPa之範圍為佳，填料之含有比例若在30質量%以上，則接著劑層之硬化後之儲藏彈性率容易調整在此範圍內。又，填料之含有比例若在75質量%以下，則膜形成性、晶片結合時之接著劑層之加熱流動性優異。晶片結合時之接著劑層之加熱流動性若提升，則接著劑層與被接著物之密著變得良好且能使接著力提升，又掩埋被接著物之凹凸而變得容易抑制空隙。較佳為70質量%以下，更佳為60質量%以下。 When the content ratio of the filler is 30% by mass or more, it is excellent in the surface of the wire bonding property. In the case of wire bonding, the storage elastic modulus after hardening of the adhesive layer of the wafer is preferably adjusted to a range of 20 to 1000 MPa at 170 ° C, and if the content of the filler is 30% by mass or more, the adhesive layer is used. The storage elastic modulus after hardening is easily adjusted within this range. In addition, when the content ratio of the filler is 75% by mass or less, the film formability and the heating fluidity of the adhesive layer at the time of wafer bonding are excellent. When the heating fluidity of the adhesive layer is increased when the wafer is bonded, the adhesive layer and the adherend are adhered to each other, and the adhesion can be improved, and the unevenness of the adherend can be buried to easily suppress the void. It is preferably 70% by mass or less, more preferably 60% by mass or less.

本發明之接著劑層係能包含平均粒徑相異之2種以上填料作為上述填料。於此情況，在與使用單一之填料之情況相比，在膜化前之原料混合物中，變得容易防止在填料之含有比例較高時之黏度上昇或在填料之含有比例較低時之黏度降低，而變得容易取得良好膜形成性，且能將未硬化之接著劑層之流動性控制成最佳者，又同時在接著劑層之硬化後變得容易取得優異接著力。 The adhesive layer of the present invention can contain two or more kinds of fillers having different average particle diameters as the above filler. In this case, in the raw material mixture before the film formation, it is easy to prevent the viscosity from increasing when the filler content is high or the viscosity when the filler content is low, as compared with the case of using a single filler. When it is lowered, it is easy to obtain good film formability, and it is possible to control the fluidity of the uncured adhesive layer to be optimal, and at the same time, it is easy to obtain excellent adhesion after hardening of the adhesive layer.

又，本發明之接著劑層中，填料之平均粒徑係以2.0μm以下為佳，以1.0μm為較佳。填料之平均粒徑 若在2.0μm以下，則膜之薄膜化變得容易。在此，薄膜係指20μm以下之厚度。又，若為0.01μm以上，則分散性良好。 Further, in the adhesive layer of the present invention, the average particle diameter of the filler is preferably 2.0 μm or less, and more preferably 1.0 μm. Average particle size of the filler When it is 2.0 μm or less, film formation becomes easy. Here, the film means a thickness of 20 μm or less. Moreover, when it is 0.01 micrometer or more, dispersibility is favorable.

並且，從防制膜化前之原料混合物之黏度上昇或降低，將未硬化之接著劑層之流動性控制成最佳，提升接著劑層之硬化後之接著力之觀點，則係以包含平均粒徑在0.1~1.0μm範圍內之第1填料，及一次粒徑之平均粒徑在0.005~0.03μm範圍內之第2填料為佳。以平均粒徑在0.1~1.0μm之範圍內且且99%以上之粒子係分佈在粒徑0.1~1.0μm之範圍內之第1填料，及，一次粒徑之平均粒徑在0.005~0.03μm之範圍內且99%以上之粒子係分佈在粒徑0.005~0.1μm之範圍內之第2填料為佳。 Further, from the viewpoint of increasing or decreasing the viscosity of the raw material mixture before the film formation, controlling the fluidity of the uncured adhesive layer to be optimal, and improving the adhesion of the adhesive layer after hardening, the average is included. The first filler having a particle diameter in the range of 0.1 to 1.0 μm and the second filler having an average particle diameter of the primary particle diameter in the range of 0.005 to 0.03 μm are preferred. The first filler having an average particle diameter in the range of 0.1 to 1.0 μm and 99% or more is distributed in a particle diameter of 0.1 to 1.0 μm, and the average particle diameter of the primary particle diameter is 0.005 to 0.03 μm. Within the range, 99% or more of the particles are preferably distributed in the second filler having a particle diameter of 0.005 to 0.1 μm.

本發明中之平均粒徑係意旨50體積%之粒子具有小於此值之直徑之累積體積分布曲線之D50值。本發明中，平均粒徑或D50值係藉由雷射繞射法，使用例如Malvern Instruments公司製之Malvern Mastersizer 2000而測量。此技術中，分散液中之粒子大小係依據夫朗和斐(Fraunhofer)或米氏(Mie)理論之任一者之應用，使用雷射光線之繞射所測量者。本發明中，則係關於利用米氏理論或針對非球狀粒子修正後之米氏理論，平均粒徑或D50值係相對於入射之雷射光線在0.02~135°下之散射計算測量者。 The average particle diameter in the present invention means that 50% by volume of the particles have a D50 value of a cumulative volume distribution curve of a diameter smaller than this value. In the present invention, the average particle diameter or D50 value is measured by a laser diffraction method using, for example, a Malvern Mastersizer 2000 manufactured by Malvern Instruments. In this technique, the particle size in the dispersion is measured by the diffraction of the laser light according to the application of either Fraunhofer or Mie theory. In the present invention, the Mie theory after correction using the Mie theory or the non-spherical particles, the average particle diameter or the D50 value is measured with respect to the scattering of the incident laser light at 0.02 to 135°.

本發明中，其一之態樣中，相對於構成接著劑層13之接著劑組成物全體，亦可包含10~40質量%之 重量平均分子量5000~200,000之熱可塑性樹脂、10~40質量%之熱聚合性成分，及30~75質量%之填料。此實施形態中，填料之含量可為30~60質量%，亦可為40~60質量%。又，熱可塑性樹脂之質量平均分子量可為5000~150,000，亦可為10,000~100,000。 In the present invention, in one aspect, the total amount of the adhesive composition constituting the adhesive layer 13 may be 10 to 40% by mass. A thermoplastic resin having a weight average molecular weight of 5,000 to 200,000, a thermal polymerizable component of 10 to 40% by mass, and a filler of 30 to 75% by mass. In this embodiment, the content of the filler may be 30 to 60% by mass, or may be 40 to 60% by mass. Further, the thermoplastic resin may have a mass average molecular weight of 5,000 to 150,000 or 10,000 to 100,000.

於另一態樣中，相對於構成接著劑層13之接著劑組成物全體，亦可包含10~20質量%之重量平均分子量200,000~2,000,000之熱可塑性樹脂、20~50質量%之熱聚合性成分，及30~75質量%之填料。此實施形態中，填料之含量可為30~60質量%，亦可為30~50質量%。又，熱可塑性樹脂之質量平均分子量可為200,000~1,000,000，亦可為200,000~800,000。 In another aspect, the thermal polymerizable resin having a weight average molecular weight of 200,000 to 2,000,000 and a thermal polymerization property of 20 to 50% by mass may be contained in an amount of 10 to 20% by mass based on the total of the adhesive composition constituting the adhesive layer 13. Ingredients, and 30 to 75% by mass of filler. In this embodiment, the content of the filler may be 30 to 60% by mass, or may be 30 to 50% by mass. Further, the thermoplastic resin may have a mass average molecular weight of 200,000 to 1,000,000 or 200,000 to 800,000.

藉由調整配合比率，能最佳化接著劑層13之硬化後之儲藏彈性率及流動性，且亦有能充分取得在高溫下之耐熱性之傾向。並且，亦能進行撕裂強度之控制。 By adjusting the blending ratio, the storage elastic modulus and fluidity of the adhesive layer 13 after curing can be optimized, and the heat resistance at high temperatures can be sufficiently obtained. Moreover, the control of the tear strength can also be performed.

接著劑層13在依據JIS K7128-3所規定之直角形試驗法下撕裂強度(A)為0.8MPa以上。撕裂強度(A)若在0.8MPa以上，則受到運搬時等之衝撃不易產生切痕或破裂，在將接著劑層13加工成規定大小之預切步驟中，在拉伸後時能減低接著劑層13上產生破裂。 The subsequent layer 13 has a tear strength (A) of 0.8 MPa or more in the right angle test method according to JIS K7128-3. When the tear strength (A) is 0.8 MPa or more, it is less likely to cause cuts or cracks when being transported, and the like, in the pre-cutting step of processing the adhesive layer 13 to a predetermined size, it can be reduced after stretching. Cracking occurs on the agent layer 13.

又，接著劑層13在直角形試驗法下，在通過試驗片直角部前端之中央線上，從直角部之前端切入長度1mm之切割部分時之撕裂強度(B)係以0.5MPa以上為佳。撕裂強度(B)若在0.5MPa以上，則縱使受到運搬 時等之衝撃而切入有切痕，仍能抑制成最低限度之切入，而若為此程度之切入，在預切步驟中即使延伸後仍能減低接著劑層13產生破裂。 Further, in the right-angle test method, the tear strength (B) when the cut portion having a length of 1 mm is cut from the front end of the right-angle portion at the center line passing through the front end of the straight portion of the test piece is preferably 0.5 MPa or more. . If the tear strength (B) is 0.5 MPa or more, even if it is transported When the punch is cut and the cut is cut, the minimum cut can be suppressed, and if it is cut to this extent, the adhesive layer 13 can be broken even if it is extended in the pre-cutting step.

更進一步，接著劑層13在-15℃中JIS K7128-3所規定之直角形試驗法下之撕裂強度(C)係以0.8MPa以下為佳，以0.67MPa以下為更佳。撕裂強度(C)若在0.8MPa以下，則在低溫區域(-15~0℃)下藉由擴展而擴張半導體加工用膠帶10，將接著劑層13予以分離時，可使接著劑層13良好分離。 Further, the tear strength (C) of the adhesive layer 13 at a right angle test method prescribed by JIS K7128-3 at -15 ° C is preferably 0.8 MPa or less, more preferably 0.67 MPa or less. When the tear strength (C) is 0.8 MPa or less, the semiconductor processing tape 10 is expanded by expanding in a low temperature region (-15 to 0 ° C), and when the adhesive layer 13 is separated, the adhesive layer 13 can be formed. Good separation.

為了將撕裂強度(A)、(B)分別作成上述範圍內，例如藉由使填料之含量在70質量%以下，或包含熱可塑性樹脂5%以上，即能增強撕裂強度。並且，若包含矽烷耦合劑，或使用形狀係實質為真圓形之填料，則填料與樹脂之相溶性、密著性變得良好，故能增強撕裂強度。又，為了將撕裂強度(C)作成上述範圍內，則以將熱可塑性樹脂之玻璃轉移溫度作成15℃以上，將熱可塑性樹脂之分子量作成26萬以下為佳。 In order to set the tear strengths (A) and (B) in the above range, for example, by setting the content of the filler to 70% by mass or less, or by containing 5% or more of the thermoplastic resin, the tear strength can be enhanced. Further, when a decane coupling agent is contained or a filler having a substantially circular shape is used, the compatibility and adhesion of the filler to the resin are improved, so that the tear strength can be enhanced. In addition, in order to set the tear strength (C) within the above range, the glass transition temperature of the thermoplastic resin is set to 15 ° C or higher, and the molecular weight of the thermoplastic resin is preferably 260,000 or less.

本發明之半導體加工用膠帶10中，接著劑層13係亦可將預先已膜化者(以下，稱為接著膜)直接或間接地層合於基材膜11上而形成者。層合時之溫度係以設在10~100℃之範圍，且施加0.01~10N/m之線壓為佳。尚且，此種接著膜可為在剝離膜上形成接著劑層13者，於此情況，於層合後亦可剝離剝離膜，或直接使用當作半導體加工用膠帶10之覆蓋膜，且在貼合於晶圓時剝 離亦可。 In the tape 10 for semiconductor processing of the present invention, the adhesive layer 13 may be formed by directly or indirectly laminating a film (hereinafter referred to as an adhesive film) on the base film 11. The temperature at the time of lamination is preferably in the range of 10 to 100 ° C, and a linear pressure of 0.01 to 10 N/m is preferably applied. Further, such an adhesive film may be formed by forming an adhesive layer 13 on the release film. In this case, the release film may be peeled off after lamination, or a cover film for the semiconductor processing tape 10 may be directly used, and Stripping when wafer Can also be.

前述接著膜亦層合在黏著劑層12之全表面上，但諸多係將切割成因應所預先貼合之晶圓形狀之(經預切)接著膜層合於黏著劑層12。因此，在層合因應晶圓之接著膜時，如圖3所示，在貼合晶圓W之部分上有接著劑層13，在貼合環形框架20之部分上無接著劑層13而僅存在有黏著劑層12。一般而言，接著劑層13由於難以從被接著物剝離，藉由使用經預切之接著膜，環形框架20能與黏著劑層12貼合，且在使用後之膠帶剝離時，可取得在環形框架20上不易產生膠糊殘留之效果。 The foregoing film is also laminated on the entire surface of the adhesive layer 12, but a plurality of layers are cut into (adapted) the film shape in advance to be adhered to the adhesive layer 12. Therefore, when laminating the film corresponding to the wafer, as shown in FIG. 3, the adhesive layer 13 is provided on the portion to which the wafer W is bonded, and the adhesive layer 13 is not provided on the portion to which the annular frame 20 is bonded. There is an adhesive layer 12. In general, since the adhesive layer 13 is difficult to peel off from the adherend, the annular frame 20 can be bonded to the adhesive layer 12 by using the pre-cut adhesive film, and can be obtained when the tape is peeled off after use. The effect of adhesive residue is less likely to occur on the annular frame 20.

<用途> <Use>

本發明之半導體加工用膠帶10係使用於至少包括藉由擴張而分離接著劑層13之擴展步驟之半導體裝置之製造方法者。因此，其他步驟或步驟之順序等並無特別限定。例如，能適宜使用於以下之半導體裝置之製造方法(A)~(E)中。 The semiconductor processing tape 10 of the present invention is used in a method of manufacturing a semiconductor device including at least an expansion step of separating the adhesive layer 13 by expansion. Therefore, the order of other steps or steps and the like are not particularly limited. For example, it can be suitably used in the manufacturing methods (A) to (E) of the following semiconductor devices.

半導體裝置之製造方法(A) Semiconductor device manufacturing method (A)

一種半導體裝置之製造方法，其係包含(a)在已形成電路圖型之晶圓表面上貼合表面保護膠帶之步驟、(b)研削前述晶圓背面之背面研磨步驟、(c)將前述晶圓加熱至70~80℃之狀態下，於前述 晶圓背面貼合前述半導體加工用膠帶之接著劑層之步驟、(d)從前述晶圓表面剝離前述表面保護膠帶之步驟、(e)對前述晶圓之分割預定部分照射雷射光，而在前述晶圓內部形成多光子吸收所成之改質區域之步驟、(f)藉由擴張前述半導體加工用膠帶，沿著分隔線分離前述晶圓與前述半導體加工用膠帶之前述接著劑層，而取得附有前述接著劑層之複數晶片之擴展步驟、(g)在擴張後之前述半導體加工用膠帶中，藉由使與前述晶片不重疊之部分加熱收縮，而去除在前述擴展步驟中產生之鬆弛，進而保持前述晶片間隔之步驟、及(h)從前述半導體加工用膠帶之黏著劑層拾取附有前述接著劑層之前述晶片之步驟。 A method of manufacturing a semiconductor device, comprising: (a) a step of bonding a surface protective tape on a surface of a wafer on which a circuit pattern has been formed, (b) a step of grinding a back surface of the wafer, and (c) the crystal The circle is heated to 70~80 °C, in the foregoing a step of bonding the adhesive layer of the semiconductor processing tape to the back surface of the wafer, (d) removing the surface protective tape from the surface of the wafer, and (e) irradiating the predetermined portion of the wafer with laser light, and a step of forming a modified region formed by multiphoton absorption inside the wafer, and (f) separating the wafer and the adhesive layer of the semiconductor processing tape along a dividing line by expanding the semiconductor processing tape; Obtaining a step of expanding a plurality of wafers with the adhesive layer, and (g) removing the portion of the semiconductor processing tape after expansion by heat-shrinking a portion that does not overlap the wafer, thereby removing the occurrence of the expansion step And a step of (h) picking up the wafer having the adhesive layer from the adhesive layer of the semiconductor processing tape.

半導體裝置之製造方法(B) Semiconductor device manufacturing method (B)

半導體裝置之製造方法，其係包含(a)在已形成電路圖型之晶圓表面上貼合表面保護膠帶之步驟、(b)研削前述晶圓背面之背面研磨步驟、(c)將前述晶圓加熱至70~80℃之狀態下，於前述晶圓背面貼合前述半導體加工用膠帶之接著劑層之步驟、(d)從前述晶圓表面剝離前述表面保護膠帶之步驟、(e)沿著前述晶圓表面之分隔線照射雷射光，將前 述晶圓分離成晶片之步驟、(f)藉由擴張前述半導體加工用膠帶，將前述接著劑層分離成各個前述晶片，而取得附有前述接著劑層之複數晶片之擴展步驟、(g)在擴張後之前述半導體加工用膠帶中，藉由使與前述晶片不重疊之部分加熱收縮，而去除在前述擴展步驟中產生之鬆弛，進而保持前述晶片間隔之步驟、及(h)從前述半導體加工用膠帶之黏著劑層拾取附有前述接著劑層之前述晶片之步驟。 A method of manufacturing a semiconductor device, comprising: (a) a step of bonding a surface protective tape on a surface of a wafer on which a circuit pattern has been formed, (b) a step of grinding a back surface of the wafer, and (c) the wafer a step of bonding the adhesive layer of the semiconductor processing tape to the back surface of the wafer while heating to 70 to 80 ° C, (d) removing the surface protective tape from the surface of the wafer, and (e) The separation line of the aforementioned wafer surface illuminates the laser light, and the front a step of separating the wafer into wafers, and (f) expanding the adhesive layer into the respective wafers by expanding the adhesive tape for semiconductor processing, and obtaining an expansion step of the plurality of wafers with the adhesive layer, (g) In the expanded semiconductor processing tape, the portion which does not overlap with the wafer is heated and shrunk to remove the slack generated in the expanding step, thereby maintaining the wafer spacing step, and (h) from the semiconductor The step of processing the adhesive layer of the adhesive tape to pick up the aforementioned wafer with the aforementioned adhesive layer.

半導體裝置之製造方法(C) Semiconductor device manufacturing method (C)

一種半導體裝置之製造方法，其係包含(a)在已形成電路圖型之晶圓表面上貼合表面保護膠帶之步驟、(b)研削前述晶圓背面之背面研磨步驟、(c)將前述晶圓加熱至70~80℃之狀態下，於前述晶圓背面貼合前述半導體加工用膠帶之接著劑層之步驟、(d)從前述晶圓表面剝離前述表面保護膠帶之步驟、(e)使用切割刀沿著分隔線切削前述晶圓，而分離成晶片之步驟、(f)藉由擴張前述半導體加工用膠帶，將前述接著劑層分離成各前述晶片，而取得附有前述接著劑層之複數晶片之擴展步驟、 (g)在擴張後之前述半導體加工用膠帶中，藉由使與前述晶片不重疊之部分加熱收縮，而去除在前述擴展步驟中產生之鬆弛，進而保持前述晶片間隔之步驟、及(h)從前述半導體加工用膠帶之黏著劑層拾取附有前述接著劑層之前述晶片之步驟。 A method of manufacturing a semiconductor device, comprising: (a) a step of bonding a surface protective tape on a surface of a wafer on which a circuit pattern has been formed, (b) a step of grinding a back surface of the wafer, and (c) the crystal a step of bonding the adhesive layer of the semiconductor processing tape to the back surface of the wafer in a state where the circle is heated to 70 to 80 ° C, (d) a step of peeling off the surface protective tape from the surface of the wafer, and (e) using The cutting blade is formed by cutting the wafer along the dividing line to separate the wafer, and (f) separating the adhesive layer into the respective wafers by expanding the semiconductor processing tape to obtain the adhesive layer Expansion steps of multiple chips, (g) in the above-mentioned semiconductor processing tape after expansion, by heating and shrinking a portion that does not overlap with the wafer, removing the slack generated in the expanding step, and further maintaining the step of the wafer, and (h) The step of picking up the aforementioned wafer with the aforementioned adhesive layer from the adhesive layer of the above-mentioned semiconductor processing tape.

半導體裝置之製造方法(D) Semiconductor device manufacturing method (D)

一種半導體裝置之製造方法，其係包含(a)在已形成電路圖型之晶圓背面上貼合切割膠帶，使用切割刀沿著分離預定線切削至未滿前述晶圓厚度之深度的步驟、(b)於前述晶圓表面上貼合表面保護膠帶之步驟、(c)剝離前述切割膠帶，研削前述晶圓背面而分離成晶片之背面研磨步驟、(d)將前述晶圓加熱至70~80℃之狀態下，在分離成前述晶片之前述晶圓背面貼合前述半導體加工用膠帶之接著劑層之步驟、(e)從分離成前述晶片之前述晶圓表面剝離表面保護膠帶之步驟、(f)藉由擴張前述半導體加工用膠帶，將前述接著劑層分離成各前述晶片，而取得附有前述接著劑層之複數晶片之擴展步驟、(g)在擴張後之前述半導體加工用膠帶中，藉由使不與前述晶片重疊之部分加熱收縮，而去除在前述擴展步 驟中產生之鬆弛，進而保持前述晶片間隔之步驟、及(h)從前述半導體加工用膠帶之黏著劑層拾取附有接著劑層之前述晶片之步驟。 A method of manufacturing a semiconductor device, comprising: (a) a step of bonding a dicing tape on a back surface of a wafer on which a circuit pattern has been formed, and cutting a depth along the separation line to a depth less than the thickness of the wafer using a dicing blade ( b) a step of bonding the surface protective tape to the surface of the wafer, (c) peeling off the dicing tape, grinding the back surface of the wafer to separate the wafer into a back grinding step, and (d) heating the wafer to 70-80 a step of bonding the adhesive layer of the semiconductor processing tape to the back surface of the wafer separated from the wafer, and (e) a step of peeling off the surface protective tape from the surface of the wafer separated into the wafer, in the state of °C, f) by expanding the above-mentioned semiconductor processing tape, separating the adhesive layer into the respective wafers, and obtaining an expansion step of the plurality of wafers with the adhesive layer, and (g) expanding the semiconductor processing tape Removing the expansion step by heating and shrinking a portion that does not overlap with the wafer The step of slackening, thereby maintaining the interval between the wafers, and (h) the step of picking up the wafer with the adhesive layer from the adhesive layer of the semiconductor processing tape.

半導體裝置之製造方法(E) Semiconductor device manufacturing method (E)

一種半導體裝置之製造方法，其係包含(a)在已形成電路圖型之晶圓表面上貼合表面保護膠帶之步驟、(b)對前述晶圓之分割預定部分照射雷射光，而在前述晶圓內部形成多光子吸收所成之改質區域之步驟、(c)研削前述晶圓背面之背面研磨步驟、(d)將前述晶圓加熱至70~80℃之狀態下，於前述晶圓背面貼合前述半導體加工用膠帶之接著劑層之步驟、(e)從前述晶圓表面剝離前述表面保護膠帶之步驟、(f)藉由擴張前述半導體加工用膠帶，沿著分隔線分離前述晶圓與前述半導體加工用膠帶之前述接著劑層，而取得附有前述接著劑層之複數晶片之擴展步驟、(g)在擴張後之前述半導體加工用膠帶中，藉由使與前述晶片不重疊之部分加熱收縮，而去除在前述擴展步驟中產生之鬆弛，進而保持前述晶片間隔之步驟、及(h)從前述半導體加工用膠帶之黏著劑層拾取附有前述接著劑層之前述晶片之步驟。 A method of manufacturing a semiconductor device, comprising: (a) a step of bonding a surface protection tape on a surface of a wafer on which a circuit pattern has been formed, and (b) irradiating a predetermined portion of the wafer to irradiate laser light, and the crystal is a step of forming a modified region formed by multiphoton absorption inside the circle, (c) grinding the back surface polishing step of the wafer back surface, and (d) heating the wafer to 70 to 80 ° C, on the back surface of the wafer a step of bonding the adhesive layer of the semiconductor processing tape, (e) removing the surface protective tape from the surface of the wafer, and (f) separating the wafer along the separation line by expanding the semiconductor processing tape And an expansion step of obtaining the plurality of wafers with the adhesive layer in the adhesive layer of the semiconductor processing tape, and (g) expanding the semiconductor processing tape after the expansion by not overlapping the wafer Partially heating and shrinking, removing the slack generated in the expanding step, thereby maintaining the step of the wafer, and (h) picking up the adhesive layer from the semiconductor processing tape The step of the layer of the wafer.

<使用方法> <How to use>

參照圖2~圖5並同時說明關於將本發明之半導體加工用膠帶10適用於上述半導體裝置之製造方法(A)時之膠帶之使用方法。首先，如圖2所示，在已形成電路圖型之晶圓W之表面上貼合於黏著劑中包含紫外線硬化性成分之電路圖型保護用之表面保護膠帶14，並實施研削晶圓W背面之背面研磨步驟。 A method of using the tape when the semiconductor processing tape 10 of the present invention is applied to the above-described semiconductor device manufacturing method (A) will be described with reference to Figs. 2 to 5 . First, as shown in FIG. 2, a surface protective tape 14 for protecting a circuit pattern including an ultraviolet curable component is adhered to the surface of a wafer W on which a circuit pattern has been formed, and the back surface of the wafer W is ground. Back grinding step.

背面研磨步驟結束後，如圖3所示，在晶圓安裝機之加熱桌25上，使表面側朝下載置晶圓W後，於晶圓W背面貼合半導體加工用膠帶10。在此所使用之半導體加工用膠帶10係層合有預先切割(預切)成因應所貼合之晶圓W形狀之接著膜者，在與晶圓W貼合之面上，在接著劑層13露出之區域周圍上使黏著劑層12露出。貼合此半導體加工用膠帶10之接著劑層13所露出之部分與晶圓W之背面，並同時貼合接著劑層13周圍之黏著劑層12所露出之部分與環形框架20。此時，加熱桌25係設定成70~80℃，藉此而實施加熱貼合。 After the back surface polishing step is completed, as shown in FIG. 3, on the heating table 25 of the wafer mounting machine, the wafer W is attached to the surface side, and then the semiconductor processing tape 10 is bonded to the back surface of the wafer W. The semiconductor processing tape 10 used here is laminated with a film which is pre-cut (pre-cut) in accordance with the shape of the wafer W to be bonded, and is bonded to the wafer W on the adhesive layer. The adhesive layer 12 is exposed around the exposed area. The exposed portion of the adhesive layer 13 of the semiconductor processing tape 10 is bonded to the back surface of the wafer W, and the exposed portion of the adhesive layer 12 around the adhesive layer 13 is bonded to the annular frame 20. At this time, the heating table 25 is set to 70 to 80 ° C, whereby heating bonding is performed.

其次，從加熱桌25上搬出經貼合半導體加工用膠帶10之晶圓W，如圖4所示，半導體加工用膠帶10側朝下而載置於吸引桌26上。且，從吸附固定於吸引桌26上之晶圓W上方，使用能量線光源27，將例如1000mJ/cm2之紫外線照射在表面保護膠帶14之基材面側，而使表面保護膠帶14對晶圓W之接著力降低，並從晶圓W表面剝離表面保護膠帶14。 Next, the wafer W bonded to the semiconductor processing tape 10 is carried out from the heating table 25, and as shown in FIG. 4, the semiconductor processing tape 10 is placed on the suction table 26 with the side facing downward. Further, from the wafer W adsorbed and fixed on the suction table 26, ultraviolet rays of, for example, 1000 mJ/cm 2 are irradiated onto the substrate surface side of the surface protective tape 14 using the energy ray source 27, and the surface protective tape 14 is crystallized. The bonding force of the circle W is lowered, and the surface protective tape 14 is peeled off from the surface of the wafer W.

其次，如圖5所示，對晶圓W之分割預定部分照射雷射光，於晶圓W之內部形成因多光子吸收所成之改質區域32。 Next, as shown in FIG. 5, the predetermined portion of the wafer W is irradiated with the laser light, and the modified region 32 formed by the multiphoton absorption is formed inside the wafer W.

其次，如圖6(a)所示，將已貼合晶圓W及環形框架20之半導體加工用膠帶10，以使基材膜11側朝下之方式載置於擴展裝置之台階21上。 Next, as shown in FIG. 6(a), the semiconductor processing tape 10 to which the wafer W and the ring frame 20 are bonded is placed on the step 21 of the expansion device so that the base film 11 side faces downward.

其次，如圖6(b)所示，在已固定環形框架20之狀態下，使擴展裝置之中空圓柱形狀之上推構件22上昇，而擴張(擴展)半導體加工用膠帶10。作為擴張條件，擴展速度係例如5~500mm/sec，擴展量(上推量)係例如5~25mm。因此，藉由半導體加工用膠帶10被拉伸至晶圓W之徑方向，晶圓W以前述改質區域32為起點而分離成晶片34單位。此時，接著劑層13在與晶圓W背面接著之部分中，雖然因擴張所造成之伸長(變形)受到抑制而未引起破裂，但在晶片34間之位置下，因膠帶之擴張而張力集中導致破裂。因此，如圖6(c)所示，與晶圓W一同地，接著劑層13亦受到分離。藉此，能取得附有接著劑層13之複數之晶片34。 Next, as shown in FIG. 6(b), in the state in which the annular frame 20 is fixed, the hollow cylindrical shape pushing member 22 of the expanding device is raised, and the semiconductor processing tape 10 is expanded (expanded). As the expansion condition, the expansion speed is, for example, 5 to 500 mm/sec, and the expansion amount (upward amount) is, for example, 5 to 25 mm. Therefore, the semiconductor processing tape 10 is stretched to the radial direction of the wafer W, and the wafer W is separated into the wafer 34 unit from the modified region 32 as a starting point. At this time, in the portion of the adhesive layer 13 which is adjacent to the back surface of the wafer W, although the elongation (deformation) due to expansion is suppressed without causing cracking, at the position between the wafers 34, the tension is caused by the expansion of the tape. Concentration leads to rupture. Therefore, as shown in FIG. 6(c), the adhesive layer 13 is also separated together with the wafer W. Thereby, a plurality of wafers 34 with the adhesive layer 13 attached thereto can be obtained.

其次，如圖7所示，實施將上推構件22返回原先之位置，去除先前之擴展步驟中所產生之半導體加工用膠帶10之鬆弛，而穩定保持晶片34之間隔用之步驟。於此步驟中，例如，使用溫風噴嘴29，將90~120℃之溫風吹向半導體加工用膠帶10中晶片34存在之區域與環形框架20之間之圓環狀之加熱收縮區域28而使基材膜11 加熱收縮，而使半導體加工用膠帶10成為緊繃之狀態。其後，對黏著劑層12施予能量線硬化處理或熱硬化處理等，而減弱黏著劑層12對接著劑層13之黏著力後，拾取晶片34。 Next, as shown in Fig. 7, the step of returning the push-up member 22 to the original position and removing the slack of the semiconductor processing tape 10 generated in the previous expansion step to stably maintain the interval between the wafers 34 is carried out. In this step, for example, the warm air nozzle 29 is used to blow a warm air of 90 to 120 ° C to the annular heat-shrinkable region 28 between the region where the wafer 34 exists in the semiconductor processing tape 10 and the annular frame 20. Substrate film 11 The heat shrinkage causes the semiconductor processing tape 10 to be in a tight state. Thereafter, the adhesive layer 12 is subjected to an energy ray hardening treatment or a heat hardening treatment or the like to weaken the adhesion of the adhesive layer 12 to the adhesive layer 13, and then the wafer 34 is picked up.

<實施例> <Example>

其次，為了使本發明之效果更加明確，詳細地說明實施例及比較例，但本發明並非係受到此等實施例所限定者。 Next, the examples and comparative examples will be described in detail in order to clarify the effects of the present invention, but the present invention is not limited by the embodiments.

〔半導體加工用膠帶之製作〕 [Production of Tape for Semiconductor Processing] (1)基材膜之製作 (1) Fabrication of substrate film

<基材膜1> <Substrate film 1>

將藉由自由基聚合法所合成之乙烯-甲基丙烯酸共聚物之鋅離子聚合物(甲基丙烯酸含量13%、軟化點72℃、融點90℃)之樹脂珠粒在140℃下進行熔融，使用擠壓機成形成厚度100μm之長條膜狀而製成基材膜1。 The resin beads of the ethylene-methacrylic acid copolymer zinc ion polymer (methacrylic acid content 13%, softening point 72 ° C, melting point 90 ° C) synthesized by the radical polymerization method were melted at 140 ° C The base film 1 was formed by forming an elongated film having a thickness of 100 μm using an extruder.

<基材膜2> <Substrate film 2>

將低密度聚乙烯(LDPE、密度0.92g/cm3、融點110℃)之樹脂片粒在230℃進行熔融，使用擠壓機成形成厚度100μm之長條膜狀。對取得之膜照射100kGy之電子線而製成基材膜2。 The resin pellets of low-density polyethylene (LDPE, density: 0.92 g/cm 3 , melting point: 110 ° C) were melted at 230 ° C, and formed into a long film having a thickness of 100 μm using an extruder. The obtained film was irradiated with an electron beam of 100 kGy to form a base film 2.

<基材膜3> <Substrate film 3>

將苯乙烯‧丁二烯共聚物(JSR製Dynaron 1320P、 苯乙烯含量：10%、密度：0.89、MFR3.5)與聚丙烯(無規聚丙烯、乙烯含量1.4%、Mw400,000、融點154℃、密度：0.91)之樹脂片粒以35：65之比率乾式摻合後，在200℃下進行熔融，使用擠壓機成形成厚度100μm之長條膜狀而製成基材膜3。 Styrene ‧ butadiene copolymer (Dynaron 1320P made by JSR, Styrene content: 10%, density: 0.89, MFR 3.5) and polypropylene (atactic polypropylene, ethylene content 1.4%, Mw400,000, melting point 154 ° C, density: 0.91) resin pellets at 35:65 After the ratio of the dry blending, the film was melted at 200 ° C, and a base film 3 was formed by forming an elongated film having a thickness of 100 μm using an extruder.

(2)丙烯酸系共聚物之調製 (2) Modulation of acrylic copolymer (a-1) (a-1)

作為具有官能基之丙烯酸系共聚物(A1)，調製出由2-乙基己基丙烯酸酯、2-羥基乙基丙烯酸酯及甲基丙烯酸所構成，且2-乙基己基丙烯酸酯之比率為60莫耳%、質量平均分子量70萬之共聚物。其次，添加2-異氰酸根乙基甲基丙烯酸酯使碘價成為20，而調製成玻璃轉移溫度-50℃、羥基價10mgKOH/g、酸價5mgKOH/g之丙烯酸系共聚物(a-1)。 As the acrylic copolymer (A1) having a functional group, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and methacrylic acid were prepared, and the ratio of 2-ethylhexyl acrylate was 60. a copolymer of mol% and a mass average molecular weight of 700,000. Next, 2-isocyanatoethyl methacrylate was added to have an iodine value of 20, and an acrylic copolymer (a-1) having a glass transition temperature of -50 ° C, a hydroxyl group of 10 mgKOH/g, and an acid value of 5 mgKOH/g was prepared. ).

(a-2) (a-2)

作為具有官能基之丙烯酸系共聚物(A1)，調製出由月桂基丙烯酸酯、2-羥基乙基丙烯酸酯及甲基丙烯酸所構成，且月桂基丙烯酸酯之比率為60莫耳%、質量平均分子量80萬之共聚物。其次，添加2-異氰酸根乙基甲基丙烯酸酯使碘價成為20，而調製成玻璃轉移溫度-5℃、羥基價50mgKOH/g、酸價5mgKOH/g之丙烯酸系共聚物(a-2)。 The acrylic copolymer (A1) having a functional group is composed of lauryl acrylate, 2-hydroxyethyl acrylate, and methacrylic acid, and the ratio of lauryl acrylate is 60 mol%, and the mass average is A copolymer having a molecular weight of 800,000. Next, 2-isocyanatoethyl methacrylate was added to have an iodine value of 20, and an acrylic copolymer (a-2) having a glass transition temperature of -5 ° C, a hydroxyl group of 50 mgKOH/g, and an acid value of 5 mgKOH/g was prepared. ).

作為具有官能基之丙烯酸系共聚物(A1)，調製出由丁基丙烯酸酯、2-羥基乙基丙烯酸酯及甲基丙烯酸所構成，且丁基丙烯酸酯之比率為60莫耳%、質量平均分子量80萬之共聚物。其次，添加2-異氰酸根乙基甲基丙烯酸酯使碘價成為20，而調製成玻璃轉移溫度-40℃、羥基價30mgKOH/g、酸價5mgKOH/g之丙烯酸系共聚物(a-3)。 The acrylic copolymer (A1) having a functional group was prepared by using butyl acrylate, 2-hydroxyethyl acrylate, and methacrylic acid, and the ratio of butyl acrylate was 60 mol%, and the mass average was obtained. A copolymer having a molecular weight of 800,000. Next, 2-isocyanatoethyl methacrylate was added to have an iodine value of 20, and an acrylic copolymer (a-3) having a glass transition temperature of -40 ° C, a hydroxyl group of 30 mgKOH/g, and an acid value of 5 mgKOH/g was prepared. ).

(3)接著劑組成物之調製 (3) Modulation of the composition of the adhesive (b-1) (b-1)

對由環氧樹脂「1002」(三菱化學股份有限公司製、固形雙酚A型環氧樹脂、環氧當量600)6.2質量份、苯酚樹脂「MEH-7851SS」(明和化成股份有限公司製商品名、聯苯酚醛苯酚樹脂、羥基當量201)51.8質量份、環氧樹脂「806」(三菱化學股份有限公司製商品名、雙酚F型環氧樹脂、環氧當量160、比重1.20)41.9質量份、二氧化矽填料「SO-C2」(Admafine股份有限公司製商品名、平均粒徑0.5μm)81.5質量份，及二氧化矽填料之「-Aerosil R972」(Nippon Aerosil股份有限公司製商品名、一次粒徑之平均粒徑0.016μm)2.9質量份所構成之組成物添加MEK，進行攪拌混合而作成均勻組成物。 6.2 parts by mass of epoxy resin "1002" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A epoxy resin, epoxy equivalent 600), and phenol resin "MEH-7851SS" (Minghe Chemical Co., Ltd. product name) , biphenol phenol resin, hydroxyl equivalent 201) 51.8 parts by mass, epoxy resin "806" (trade name of Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy equivalent 160, specific gravity 1.20) 41.9 parts by mass And the cerium oxide filler "SO-C2" (trade name, average particle diameter: 0.5 μm, manufactured by Admafine Co., Ltd.), 81.5 parts by mass, and "-Aerosil R972" (manufactured by Nippon Aerosil Co., Ltd.) MEK was added to the composition of 2.9 parts by mass of the primary particle diameter of 0.016 μm), and the mixture was stirred and mixed to prepare a uniform composition.

對此添加，包含源自環氧丙基丙烯酸酯或環氧丙基甲基丙烯酸酯之單體單位3質量%之丙烯酸共聚物(重量平均分子量26萬)23.0質量份作為含有官能基之聚合物， 作為耦合劑之「KBM-802」(信越聚矽氧股份有限公司製商品名、巰基丙基三甲氧基矽烷)0.6質量份，以及作為硬化促進劑之「Curezol 2PHZ-PW」(四國化成股份有限公司製商品名、2-苯基-4,5-二羥基甲基咪唑、分解溫度230℃)0.1質量份，攪拌混合直到均勻為止。藉由再使用100篩目之過濾器將此予以過濾並進行真空脫泡，而取得接著劑組成物b-1之塗漆。 In this case, 23.0 parts by mass of an acrylic copolymer (weight average molecular weight: 260,000) derived from a monomer unit derived from epoxy acrylate or glycidyl methacrylate is used as a functional group-containing polymer. , "KBM-802" (trade name, decylpropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, 0.6 parts by mass, and "Curezol 2PHZ-PW" as a hardening accelerator (Four Nations Chemicals Co., Ltd.) The product name of the company, 2-phenyl-4,5-dihydroxymethylimidazole, decomposition temperature 230 ° C) 0.1 parts by mass, stirred and mixed until uniform. This was filtered by vacuum filtration using a 100 mesh filter and vacuum defoaming was carried out to obtain a paint of the adhesive composition b-1.

(b-2) (b-2)

對由環氧樹脂「1002」(三菱化學股份有限公司製、固形雙酚A型環氧樹脂、環氧當量600)40質量份、環氧樹脂「806」(三菱化學股份有限公司製商品名、雙酚F型環氧樹脂、環氧當量160、比重1.20)100質量份、硬化劑「Dyhard100SF」(Degusa製商品名、二氰二胺)5質量份、二氧化矽填料「SO-C2」(Admafine股份有限公司製商品名、平均粒徑0.5μm)200質量份，及二氧化矽填料之「Aerosil R972」(Nippon Aerosil股份有限公司製商品名、一次粒徑之平均粒徑0.016μm)3質量份所構成之組成物添加MEK，進行攪拌混合而作成均勻組成物。 For the epoxy resin "1002" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A epoxy resin, epoxy equivalent 600) 40 parts by mass, epoxy resin "806" (Mitsubishi Chemical Co., Ltd. product name, Bisphenol F type epoxy resin, epoxy equivalent 160, specific gravity 1.20) 100 parts by mass, hardener "Dyhard 100SF" (trade name of Degusa, dicyandiamide) 5 parts by mass, cerium oxide filler "SO-C2" ( "Aerosil R972" (trade name of Nippon Aerosil Co., Ltd., average particle diameter of primary particle diameter 0.014 μm) of 3 masses of a product name, an average particle diameter of 0.5 μm, and a cerium oxide filler, manufactured by Admafine Co., Ltd. MEK was added to the composition of the fraction, and the mixture was stirred and mixed to prepare a uniform composition.

對此添加苯氧基樹脂「PKHH」(INCHEM製商品名、質量平均分子量52,000、玻璃轉移溫度92℃)100質量份、作為耦合劑之「KBM-802」(信越聚矽氧股份有限公司製商品名、巰基丙基三甲氧基矽烷)0.6質量份、以及作為硬化促進劑之「Curezol 2PHZ-PW」(四國化成股 份有限公司製商品名、2-苯基-4,5-二羥基甲基咪唑、分解溫度230℃)0.5質量份，攪拌混合直到均勻為止。藉由再使用100篩目之過濾器將此予以過濾並進行真空脫泡，而取得接著劑組成物b-2之塗漆。 In this case, 100 parts by mass of phenoxy resin "PKHH" (trade name, manufactured by INCHEM, mass average molecular weight: 52,000, glass transition temperature: 92 °C) was added, and "KBM-802" (a product manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a coupling agent. Name, mercaptopropyltrimethoxydecane) 0.6 parts by mass, and "Curezol 2PHZ-PW" as a hardening accelerator (Four countries into stocks) The product name of the company, 2-phenyl-4,5-dihydroxymethylimidazole, decomposition temperature 230 ° C) 0.5 parts by mass, stirred and mixed until uniform. This was filtered by vacuum filtration using a 100 mesh filter and vacuum defoaming was carried out to obtain a paint of the adhesive composition b-2.

(b-3) (b-3)

對由環氧樹脂「1002」(三菱化學股份有限公司製、固形雙酚A型環氧樹脂、環氧當量600)40質量份、環氧樹脂「Epikote 828」(三菱化學股份有限公司製商品名、雙酚A型環氧樹脂、環氧當量190)30質量份、硬化劑「Dyhard100SF」(Degusa製商品名、二氰二胺)10質量份、二氧化矽填料「SO-C2」(Admafine股份有限公司製商品名、平均粒徑0.5μm)180質量份所構成之組成物添加MEK，進行攪拌混合而作成均勻組成物。 40 parts by mass of epoxy resin "1002" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A epoxy resin, epoxy equivalent 600), and epoxy resin "Epikote 828" (trade name of Mitsubishi Chemical Corporation) , bisphenol A type epoxy resin, epoxy equivalent 190) 30 parts by mass, hardener "Dyhard 100SF" (trade name of Degusa, dicyandiamide) 10 parts by mass, cerium oxide filler "SO-C2" (Admafine shares) MEK was added to the composition of the product name, the average particle diameter of 0.5 μm, and 180 parts by mass of the product, and the mixture was stirred and mixed to prepare a uniform composition.

對此添加苯氧基樹脂「PKHH」(INCHEM製商品名、質量平均分子量52,000、玻璃轉移溫度92℃)30質量份、作為耦合劑之「KBM-802」(信越聚矽氧股份有限公司製商品名、巰基丙基三甲氧基矽烷)0.6質量份，以及作為硬化促進劑之「Curezol 2PHZ-PW」(四國化成股份有限公司製商品名、2-苯基-4,5-二羥基甲基咪唑、分解溫度230℃)0.5質量份，攪拌混合直到均勻為止。藉由再使用100篩目之過濾器將此予以過濾並進行真空脫泡，而取得接著劑組成物b-3之塗漆。 In this case, 30 parts by mass of phenoxy resin "PKHH" (trade name, manufactured by INCHEM, mass average molecular weight: 52,000, glass transition temperature: 92 °C) was added, and "KBM-802" (a product manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a coupling agent. 0.6 parts by mass of mercaptopropyltrimethoxydecane, and "Curezol 2PHZ-PW" as a hardening accelerator (trade name of Shikoku Kasei Co., Ltd., 2-phenyl-4,5-dihydroxymethyl) Imidazole, decomposition temperature 230 ° C) 0.5 parts by mass, stirred and mixed until homogeneous. This was filtered by vacuum filtration using a 100 mesh filter and vacuum defoaming was carried out to obtain a paint of the adhesive composition b-3.

(b-4) (b-4)

對由環氧樹脂「YX4000」(三菱化學股份有限公司製、聯苯酚醛型環氧樹脂、環氧當量185)15.0質量份、苯酚樹脂「LF-6161」(DIC股份有限公司製商品名、酚醛苯酚樹脂、羥基當量118)40.0質量份、環氧樹脂「Epikote 828」(三菱化學股份有限公司製商品名、雙酚A型環氧樹脂、環氧當量190)45.0重量份、二氧化矽填料之「Aerosil R972」(Nippon Aerosil股份有限公司製商品名、一次粒徑之平均粒徑0.016μm)5質量份所構成之組成物添加MEK，進行攪拌混合而作成均勻組成物。 15.0 parts by mass of epoxy resin "YX4000" (manufactured by Mitsubishi Chemical Corporation, biphenyl aldehyde type epoxy resin, epoxy equivalent 185), and phenol resin "LF-6161" (trade name, phenolic product, manufactured by DIC Corporation) 40.0 parts by mass of phenol resin, hydroxyl equivalent 118), epoxy resin "Epikote 828" (trade name of Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 190) 45.0 parts by weight, cerium oxide filler MEK was added to the composition of 5 parts by mass of "Aerosil R972" (trade name of Nippon Aerosil Co., Ltd., average particle diameter of primary particle diameter: 0.016 μm), and the mixture was stirred and mixed to prepare a uniform composition.

對此添加，包含源自環氧丙基丙烯酸酯或環氧丙基甲基丙烯酸酯之單體單位之丙烯酸共聚物(重量平均分子量85萬、Tg12℃)66.7質量份作為含有官能基之聚合物、作為耦合劑之「KBM-802」(信越聚矽氧股份有限公司製商品名、巰基丙基三甲氧基矽烷)0.6質量份，以及作為硬化促進劑之「Curezol 2PHZ-PW」(四國化成股份有限公司製商品名、2-苯基-4,5-二羥基甲基咪唑、分解溫度230℃)0.1質量份，攪拌混合直到均勻為止。藉由再使用100篩目之過濾器將此予以過濾並進行真空脫泡，而取得接著劑組成物b-4之塗漆。 To this, an acrylic copolymer (weight average molecular weight: 850,000, Tg 12 ° C) containing 60.01 parts by mass of a monomer unit derived from epoxypropyl acrylate or glycidyl methacrylate is added as a functional group-containing polymer. "KBM-802" (trade name, decylpropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, 0.6 parts by mass, and "Curezol 2PHZ-PW" as a curing accelerator (Four Nations) The product name of the company, 2-phenyl-4,5-dihydroxymethylimidazole, decomposition temperature 230 ° C) 0.1 parts by mass, stirred and mixed until uniform. This was filtered by vacuum filtration using a 100 mesh filter and vacuum defoaming was carried out to obtain a paint of the adhesive composition b-4.

(b-5) (b-5)

對由環氧樹脂「1002」(三菱化學股份有限公司製、固形雙酚A型環氧樹脂、環氧當量600)50質量份、環氧 樹脂「Epikote 828」(三菱化學股份有限公司製商品名、雙酚A型環氧樹脂、環氧當量190)20質量份、硬化劑「Dyhard100SF」(Degusa製商品名、二氰二胺)10質量份、二氧化矽填料「SO-C2」(Admafine股份有限公司製商品名、平均粒徑0.5μm)250質量份所構成之組成物添加MEK，進行攪拌混合而作成均勻組成物。 50 parts by mass of epoxy resin "1002" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A epoxy resin, epoxy equivalent 600), epoxy 20 parts by mass of resin "Epikote 828" (trade name of Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 190), and curing agent "Dyhard 100SF" (trade name of Degusa, dicyandiamide) 10 mass MEK was added to the composition of 250 parts by mass of the cerium oxide filler "SO-C2" (trade name, average particle diameter: 0.5 μm, manufactured by Admafine Co., Ltd.), and the mixture was stirred and mixed to prepare a uniform composition.

對此添加苯氧基樹脂「PKHH」(INCHEM製商品名、質量平均分子量52,000、玻璃轉移溫度92℃)20質量份、作為耦合劑之「KBM-802」(信越聚矽氧股份有限公司製商品名、巰基丙基三甲氧基矽烷)0.6質量份，以及作為硬化促進劑之「Curezol 2PHZ-PW」(四國化成股份有限公司製商品名、2-苯基-4,5-二羥基甲基咪唑、分解溫度230℃)0.5質量份，攪拌混合直到均勻為止。藉由再使用100篩目之過濾器將此予以過濾並進行真空脫泡，而取得接著劑組成物b-5之塗漆。 In this case, 20 parts by mass of phenoxy resin "PKHH" (trade name, manufactured by INCHEM, mass average molecular weight: 52,000, and glass transition temperature: 92 °C) was added, and "KBM-802" (a product manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a coupling agent. 0.6 parts by mass of mercaptopropyltrimethoxydecane, and "Curezol 2PHZ-PW" as a hardening accelerator (trade name of Shikoku Kasei Co., Ltd., 2-phenyl-4,5-dihydroxymethyl) Imidazole, decomposition temperature 230 ° C) 0.5 parts by mass, stirred and mixed until homogeneous. This was filtered by vacuum filtration using a 100 mesh filter and vacuum defoaming was carried out to obtain a paint of the adhesive composition b-5.

(b-6) (b-6)

對由環氧樹脂「1002」(三菱化學股份有限公司製、固形雙酚A型環氧樹脂、環氧當量600)20質量份、環氧樹脂「Epikote 828」(三菱化學股份有限公司製商品名、雙酚A型環氧樹脂、環氧當量190)20質量份、硬化劑「Dyhard100SF」(Degusa製商品名、二氰二胺)10質量份、二氧化矽填料「SO-C2」(Admafine股份有限公司製商品名、平均粒徑0.5μm)250質量份所構成之組成物添 加MEK，進行攪拌混合而作成均勻組成物。 Epoxy resin "1002" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A epoxy resin, epoxy equivalent 600) 20 parts by mass, epoxy resin "Epikote 828" (Mitsubishi Chemical Co., Ltd. product name , bisphenol A type epoxy resin, epoxy equivalent 190) 20 parts by mass, hardener "Dyhard 100SF" (trade name of Degusa, dicyandiamide) 10 parts by mass, cerium oxide filler "SO-C2" (Admafine shares) The product name, the average particle size of 0.5 μm, and 250 parts by mass of the product made by the company MEK was added and stirred to form a homogeneous composition.

對此添加，包含源自環氧丙基丙烯酸酯或環氧丙基甲基丙烯酸酯之單體單位之丙烯酸共聚物(重量平均分子量15萬)30質量份作為含有官能基之聚合物、作為耦合劑之「KBM-802」(信越聚矽氧股份有限公司製商品名、巰基丙基三甲氧基矽烷)0.6質量份，以及作為硬化促進劑之「Curezol 2PHZ-PW」(四國化成股份有限公司製商品名、2-苯基-4,5-二羥基甲基咪唑、分解溫度230℃)0.5質量份，攪拌混合直到均勻為止。藉由再使用100篩目之過濾器將此予以過濾並進行真空脫泡，而取得接著劑組成物b-6之塗漆。 To this, 30 parts by mass of an acrylic copolymer (weight average molecular weight: 150,000) containing monomer units derived from epoxypropyl acrylate or glycidyl methacrylate is used as a functional group-containing polymer as a coupling. "KBM-802" (trade name, decyl propyl trimethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.6 parts by mass, and "Curezol 2PHZ-PW" as a hardening accelerator (Shikoku Kasei Co., Ltd.) The product name, 2-phenyl-4,5-dihydroxymethylimidazole, decomposition temperature 230 ° C) 0.5 parts by mass, stirred and mixed until uniform. This was filtered by vacuum filtration using a 100 mesh filter and vacuum defoaming was carried out to obtain a paint of the adhesive composition b-6.

<實施例1> <Example 1>

使對丙烯酸系共聚物(a-1)100質量份添加聚異氰酸酯之Coronate L(日本聚胺基甲酸酯製)5質量份，光聚合起始劑之Esacure KIP 150(Lamberti公司製)3質量份而成之混合物溶解於乙酸乙酯，進行攪拌而調製成黏著劑組成物。 5 parts by mass of Coronate L (manufactured by Nippon Polycarbonate) containing 100 parts by mass of the acrylic copolymer (a-1), Esacure KIP 150 (manufactured by Lamberti Co., Ltd.) 3 mass of a photopolymerization initiator The resulting mixture was dissolved in ethyl acetate and stirred to prepare an adhesive composition.

其次，在經離型處理之聚對酞酸乙烯酯膜所構成之釋離襯墊上，將此黏著劑組成物塗佈成乾燥後之厚度為10μm，在110℃下乾燥3分鐘後，予基材膜1貼合，而製成在基材膜上形成有黏著劑層之黏著片。 Next, on the release liner composed of the release-treated polyethylene terephthalate film, the adhesive composition was applied to a thickness of 10 μm after drying, and dried at 110 ° C for 3 minutes. The base film 1 is bonded to each other to form an adhesive sheet in which an adhesive layer is formed on the base film.

其次，在經離型處理之聚對酞酸乙烯酯膜所構成之釋離襯墊上，將接著劑組成物(b-1)塗佈於乾燥 後之厚度為20μm，在110℃下乾燥5分鐘，而製成在釋離襯墊上形成有接著劑層之接著膜。 Next, the adhesive composition (b-1) is applied to the release liner on the release liner composed of the release-treated polyethylene terephthalate film. Thereafter, the thickness was 20 μm, and it was dried at 110 ° C for 5 minutes to form an adhesive film in which an adhesive layer was formed on the release liner.

將黏著片裁切成能覆蓋開口部之方式對環形框架貼合般之圖3等所示之形狀。又，將接著膜裁切成能覆蓋晶圓背面般之如圖3等所示之形狀。且，如圖3等所示般地，將前述黏著片之黏著劑層側與前述接著膜之接著劑層側貼合在接著膜之周圍上使黏著劑層12露出部分形成，而製成半導體加工用膠帶。 The adhesive sheet is cut into a shape as shown in Fig. 3 and the like which can be attached to the annular frame in such a manner as to cover the opening. Further, the film is cut into a shape as shown in FIG. 3 and the like which can cover the back surface of the wafer. Further, as shown in FIG. 3 and the like, the adhesive layer side of the adhesive sheet is bonded to the adhesive layer side of the adhesive film on the periphery of the adhesive film to expose the adhesive layer 12 to form a semiconductor. Processing tape.

<實施例2~6、比較例1> <Examples 2 to 6 and Comparative Example 1>

除了將丙烯酸系共聚物、黏著劑組成物、接著劑組成物之組合作成表1、2記載之組合以外，其他藉由與實施例1相同之手法，製成半導體加工用膠帶。 A tape for semiconductor processing was produced by the same method as in Example 1 except that the combination of the acrylic copolymer, the adhesive composition, and the adhesive composition was combined as shown in Tables 1 and 2.

如下述般地進行測量、評價關於實施例‧比較例之半導體加工用膠帶之撕裂強度(A)~(C)、預切加工性、接著劑層之分離性。其結果係如表1、2所示。 The tear strength (A) to (C), the pre-cut workability, and the separability of the adhesive layer of the tape for semiconductor processing of Example ‧ Comparative Example were measured and evaluated as follows. The results are shown in Tables 1 and 2.

(1)撕裂強度(A)~(C)之測量 (1) Measurement of tear strength (A) ~ (C)

從實施例‧比較例之半導體加工用膠帶所使用之接著膜之已剝離釋離襯墊之接著劑層，使其疊合成厚度100μm，依據JIS K 7128-3，採取如圖8(a)所示之試驗片100，使用具備能調節溫度之恒溫槽之拉伸試驗機(TCL-NL形、股份有限公司島津製作所製)，進行拉伸試驗，並分別測量23℃下之撕裂強度(A)與-15℃下之 撕裂強度(C)。又，同樣對如圖8(b)所示之在通過直角部A前端之中央線上，從直角部A之前端切入長度1mm之切割部分115之試驗片110測量在23℃下之撕裂強度(B)。 The adhesive layer of the release-release liner of the adhesive film used in the tape for semiconductor processing of the Example ‧ comparative example was laminated to a thickness of 100 μm, and according to JIS K 7128-3, it was taken as shown in Fig. 8(a). The test piece 100 shown was subjected to a tensile test using a tensile tester (TCL-NL-shaped, manufactured by Shimadzu Corporation) having a thermostatic chamber capable of adjusting the temperature, and the tear strength at 23 ° C was measured, respectively. ) with -15 ° C Tear strength (C). Further, also as shown in Fig. 8(b), the test piece 110 cut into the cut portion 115 having a length of 1 mm from the front end of the right angle portion A on the center line passing through the front end of the right angle portion A was measured for tear strength at 23 ° C ( B).

(2)預切加工性之評價 (2) Evaluation of pre-cutting workability

預切加工性之評價係對於實施例1~7之各半導體加工用膠帶所使用之接著膜，及，比較例1之各半導體加工用膠帶所使用之接著膜，將其捲曲於50m輥狀而作成圓筒形狀者，當作成輸送時等之衝撃，從50cm之高度使圓筒形狀之一方之圓形面著地並掉落3次。以目視確認藉由掉落在接著劑層上是否產生切痕後，當作12吋晶圓所使用者，以58.5mm間隔切入直徑320mm之圓之切痕，加工速度設成10m/min下100m，從釋離襯墊剝離切痕之外側之接著劑層並捲曲，進行預切加工。將於捲曲時未引起任何破裂之情況評價為良品「○」，將僅在接著劑層上有造成有切痕之情況下才引起破裂之情況評為可容許品「△」，將產生破裂之情況評為不良品「×」。 The pre-cutting property evaluation was performed by adhering the adhesive film used for each of the semiconductor processing tapes of Examples 1 to 7 and the adhesive film used for each of the semiconductor processing tapes of Comparative Example 1 to a roll of 50 m. In the case of a cylindrical shape, the circular surface of one of the cylindrical shapes was grounded and dropped three times from a height of 50 cm. Visually confirm whether the cut is made by dropping on the adhesive layer, and as a user of the 12-inch wafer, the cut of a circle having a diameter of 320 mm is cut at intervals of 58.5 mm, and the processing speed is set to 100 m at 10 m/min. The adhesive layer on the outer side of the cut is peeled off from the release liner and curled, and pre-cut processing is performed. A condition that does not cause any cracking at the time of curling is evaluated as a good product "○", and the case where the crack is caused only when the adhesive layer is caused to have a crack is evaluated as an allowable product "△", which will cause cracking. The situation was rated as defective product "X".

(3)延伸率之測量 (3) Measurement of elongation

使用拉伸試驗裝置(JIS B 7721)，藉由如以下之拉伸試驗測量半導體加工用膠帶之延伸率及加熱至120℃後之延伸率。將實施例、比較例之半導體加工用膠帶打穿成1號啞鈴形狀(JIS K 6301)而作成試驗片，測量標線間 距離40mm、拉伸速度1000mm/min下之標線間距離，並求取延伸率。又，將藉由前述方法而延伸至200%之實施例、比較例之半導體加工用膠帶放置在已加熱至120℃之加熱板上15秒後，測量其標線間距離，並求取加熱至120℃後之延伸率。 The elongation of the tape for semiconductor processing and the elongation after heating to 120 ° C were measured by a tensile tester (JIS B 7721) by the following tensile test. The tape for semiconductor processing of the examples and the comparative examples was punched into a dumbbell shape No. 1 (JIS K 6301) to prepare a test piece, and the measurement line was measured. The distance between the marking lines at a distance of 40 mm and a tensile speed of 1000 mm/min was obtained and the elongation was determined. Further, the semiconductor processing tape of the examples and the comparative examples which were extended to 200% by the above method was placed on a hot plate heated to 120 ° C for 15 seconds, and the distance between the lines was measured, and the heating was performed until Elongation after 120 °C.

(4)分離性之評價 (4) Evaluation of separation

藉由以下所示之方法，對於前述實施例及前述比較例之各半導體加工用膠帶實施下述半導體加工步驟之適合性試驗。 The following semiconductor processing tapes were subjected to the following suitability tests for the semiconductor processing steps of the above-described examples and the comparative examples by the method described below.

(a)在已形成電路圖型之晶圓表面貼合表面保護膠帶。 (a) Apply a surface protection tape to the surface of the wafer on which the circuit pattern has been formed.

(b)施行研削前述晶圓背面之背面研磨步驟。 (b) performing a back grinding step of grinding the back surface of the wafer.

(c)在將晶圓加熱至70℃之狀態下，在前述晶圓之背面貼合前述半導體加工用膠帶之接著劑層，同時將半導體加工用環形框架貼合在前述半導體加工用膠帶之黏著劑層不與接著劑層重疊而露出之部分。 (c) bonding the adhesive layer of the semiconductor processing tape to the back surface of the wafer while heating the wafer to 70 ° C, and bonding the semiconductor processing annular frame to the adhesion of the semiconductor processing tape The portion of the agent layer that is not overlapped with the adhesive layer.

(d)從前述晶圓表面剝離表面保護膠帶。 (d) peeling off the surface protection tape from the aforementioned wafer surface.

(e)對前述晶圓之分割預定部分照射雷射光，而在該晶圓內部形成因多光子吸收所成之改質區域。 (e) irradiating the predetermined portion of the wafer with the laser beam, and forming a modified region due to multiphoton absorption inside the wafer.

(f)藉由將前述半導體加工用膠帶擴展10%，沿著分隔線分離前述晶圓與前述接著劑層，而取得附有前述接著劑層之複數之晶片。 (f) By spreading the above-mentioned semiconductor processing tape by 10%, the wafer and the adhesive layer are separated along the dividing line to obtain a plurality of wafers with the above-mentioned adhesive layer.

(g)將前述半導體加工用膠帶之不與前述晶片重疊之部分(存在有晶片之區域與環形框架之間之圓環狀區域)加熱至120℃使其收縮，而去除(f)之擴展步驟中所產生之鬆弛，保持該晶片之間隔。 (g) an extension step of removing (f) the portion of the tape for semiconductor processing that does not overlap the wafer (the annular region between the region where the wafer exists and the annular frame) is heated to 120 ° C to shrink The slack generated in the film maintains the spacing of the wafers.

(h)從導體加工用膠帶之黏著劑層拾取附有接著劑層之前述晶片。 (h) Picking up the aforementioned wafer with an adhesive layer from the adhesive layer of the tape for conductor processing.

尚且，(f)步驟係藉由股份有限公司Disco公司製DDS-2300之擴展環(expanding ring)，將貼合於半導體加工用膠帶上之股份有限公司Disco公司製DDS-2300切割用環形框架壓下，並將半導體加工用膠帶之晶圓貼合部位外周之不與晶圓重疊之部分壓向圓形之上推構件來實施擴展。又，(f)及(g)步驟之條件係設成擴展速度300mm/sec、擴展量(上推量)20mm。在此，擴展量係指壓下前與壓下後之環形框架與上推構件之相對位置之變化量。 In addition, the step (f) is a ring frame for cutting DDS-2300 manufactured by Disco Co., Ltd., which is attached to a tape for semiconductor processing, by an expansion ring of DDS-2300 manufactured by Disco Co., Ltd. Then, the portion of the periphery of the wafer bonding portion of the semiconductor processing tape that is not overlapped with the wafer is pressed against the circular push-up member to expand. Further, the conditions of the steps (f) and (g) are set to an expansion speed of 300 mm/sec and an expansion amount (upward pushing amount) of 20 mm. Here, the amount of expansion refers to the amount of change in the relative position of the annular frame and the push-up member before and after the pressing.

對於實施例1~6及比較例1之半導體加工用膠帶，在(g)步驟後以目視觀察任意100個晶片是否成功分離，並算出上述(f)步驟中之接著劑層之分離率。 With respect to the tapes for semiconductor processing of Examples 1 to 6 and Comparative Example 1, after the step (g), it was visually observed whether or not any of the 100 wafers was successfully separated, and the separation ratio of the adhesive layer in the above step (f) was calculated.

如表1所示，實施例1~6之半導體加工用膠帶由於接著劑層在JIS K7128-3所規定之直角形試驗法下撕裂強度(A)為1.11以上，即請求項中界定之0.8MPa以上，故其預切加工性良好。尤其，實施例1~4、6之半導體加工用膠帶由於在接著劑層之直角形試驗法中在通過試驗片直角部之前端之中央線上，從直角部之前端切入長度1mm之切割部分時之撕裂強度(B)為0.5MPa以上，故取得預切加工性非常優異之結果。 As shown in Table 1, the tape for semiconductor processing of Examples 1 to 6 had a tear strength (A) of 1.11 or more, that is, 0.8 as defined in the claim, because the adhesive layer had a right angle test method as specified in JIS K7128-3. Since it is MPa or more, the pre-cut workability is good. In particular, in the semiconductor processing tapes of Examples 1 to 4 and 6, in the rectangular test method of the adhesive layer, when the cut portion having a length of 1 mm was cut from the front end of the right corner portion on the center line passing through the front end of the straight portion of the test piece. Since the tear strength (B) is 0.5 MPa or more, the result of excellent precut workability is obtained.

相對於此，比較例1之半導體加工用膠帶係 如表2所示，由於接著劑層之撕裂強度(A)未滿0.8MPa，故造成預切加工性拙劣之結果。 On the other hand, the tape for semiconductor processing of Comparative Example 1 is As shown in Table 2, since the tear strength (A) of the adhesive layer was less than 0.8 MPa, the result of poor pre-cut workability was caused.

10‧‧‧半導體加工用膠帶 10‧‧‧Semiconductor processing tape

11‧‧‧基材膜 11‧‧‧Base film

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

13‧‧‧接著劑層 13‧‧‧ adhesive layer

15‧‧‧黏著片 15‧‧‧Adhesive film

Claims (5)

一種半導體加工用膠帶，其特徵為：接著劑層與黏著片受到層合，且前述接著劑層根據JIS K7128-3所規定之直角形試驗法下之撕裂強度(A)為0.8MPa以上，在-15℃中JIS K7128-3所規定之直角形試驗法下之撕裂強度(C)為0.8MPa以下。 An adhesive tape for semiconductor processing, characterized in that the adhesive layer and the adhesive sheet are laminated, and the tear strength (A) of the adhesive layer according to the right angle test method specified in JIS K7128-3 is 0.8 MPa or more. The tear strength (C) at a right angle test method prescribed in JIS K7128-3 at -15 ° C was 0.8 MPa or less. 如請求項1之半導體加工用膠帶，其中在前述直角形試驗法下，前述接著劑層在通過試驗片之直角部之前端之中央線上，從前述直角部之前端切入長度1mm之切割部分時之撕裂強度(B)為0.5MPa以上。 The tape for semiconductor processing according to claim 1, wherein in the above-described right-angle test method, the adhesive layer is cut into a cut portion having a length of 1 mm from a front end of the right-angle portion at a front end of a straight portion passing through the straight portion of the test piece. The tear strength (B) is 0.5 MPa or more. 如請求項1或請求項2之半導體加工用膠帶，其中前述黏著片之延伸率為200%以上。 The tape for semiconductor processing according to claim 1 or claim 2, wherein the adhesive sheet has an elongation of 200% or more. 如請求項1或請求項2之半導體加工用膠帶，其中將前述黏著片延伸至延伸率200%後，藉由加熱至120℃，延伸率成為120%以下。 The tape for semiconductor processing according to claim 1 or claim 2, wherein the adhesive sheet is extended to an elongation of 200%, and then the elongation is 120% or less by heating to 120 °C. 如請求項1或請求項2之半導體加工用膠帶，其係藉由擴展前述黏著片，而將貼合於前述接著劑層上之晶圓及前述接著劑層，或單僅前述接著劑層分離成對應於個別晶片所使用者。 The tape for semiconductor processing according to claim 1 or claim 2, wherein the wafer adhered to the adhesive layer and the adhesive layer or the adhesive layer alone is separated by expanding the adhesive sheet The corresponding corresponds to the user of the individual wafer.
TW104129372A 2014-09-05 2015-09-04 Tapes for semiconductor processing and semiconductor devices manufactured using the same TWI591701B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2014181752A JP5863914B1 (en) 2014-09-05 2014-09-05 Semiconductor processing tape and manufacturing method of semiconductor device manufactured using the same

Publications (2)

Publication Number Publication Date
TW201616560A TW201616560A (en) 2016-05-01
TWI591701B true TWI591701B (en) 2017-07-11

Family

ID=55346911

Family Applications (1)

Application Number Title Priority Date Filing Date
TW104129372A TWI591701B (en) 2014-09-05 2015-09-04 Tapes for semiconductor processing and semiconductor devices manufactured using the same

Country Status (8)

Country Link
JP (1) JP5863914B1 (en)
KR (1) KR101828226B1 (en)
CN (1) CN106663617B (en)
MY (1) MY168988A (en)
PH (1) PH12017500394A1 (en)
SG (1) SG11201701479TA (en)
TW (1) TWI591701B (en)
WO (1) WO2016035687A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7471879B2 (en) * 2020-03-18 2024-04-22 リンテック株式会社 Film-like adhesive and dicing die bonding sheet
CN114615835A (en) * 2022-04-26 2022-06-10 生益电子股份有限公司 Stepped circuit board, manufacturing method thereof and double-layer adhesive tape
CN116544151B (en) * 2023-07-05 2023-09-19 砺铸智能设备(天津)有限公司 Detection and packaging equipment for chip

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4358502B2 (en) 2002-03-12 2009-11-04 浜松ホトニクス株式会社 Semiconductor substrate cutting method
JP2004273895A (en) 2003-03-11 2004-09-30 Disco Abrasive Syst Ltd Dividing method of semiconductor wafer
JP4770126B2 (en) * 2003-06-06 2011-09-14 日立化成工業株式会社 Adhesive sheet
CN101471240B (en) * 2003-06-06 2011-07-20 日立化成工业株式会社 Adhesive sheet, dicing tape intergrated type adhesive sheet, and semiconductor device producing method
JP4754278B2 (en) 2005-06-23 2011-08-24 リンテック株式会社 Chip body manufacturing method
JP4979063B2 (en) * 2006-06-15 2012-07-18 日東電工株式会社 Manufacturing method of semiconductor device
JP2009164556A (en) * 2007-12-11 2009-07-23 Furukawa Electric Co Ltd:The Tape for processing wafer
JP4785095B2 (en) * 2009-08-25 2011-10-05 古河電気工業株式会社 Wafer processing tape
JP5323779B2 (en) * 2010-07-26 2013-10-23 古河電気工業株式会社 Wafer processing tape
CN102373017A (en) * 2010-08-19 2012-03-14 古河电气工业株式会社 Wafer processing adhesive tape
WO2014017537A1 (en) * 2012-07-26 2014-01-30 古河電気工業株式会社 Method for manufacturing semiconductor-wafer-processing tape and semiconductor-wafer-processing tape

Also Published As

Publication number Publication date
PH12017500394B1 (en) 2017-07-17
SG11201701479TA (en) 2017-03-30
KR101828226B1 (en) 2018-02-09
PH12017500394A1 (en) 2017-07-17
CN106663617A (en) 2017-05-10
KR20170030645A (en) 2017-03-17
JP5863914B1 (en) 2016-02-17
CN106663617B (en) 2018-05-29
TW201616560A (en) 2016-05-01
WO2016035687A1 (en) 2016-03-10
JP2016058458A (en) 2016-04-21
MY168988A (en) 2019-01-29

Similar Documents

Publication Publication Date Title
JP6230730B2 (en) Semiconductor processing tape
JP6097893B2 (en) Semiconductor processing tape
KR102112789B1 (en) Semiconductor processing tape
TWI591701B (en) Tapes for semiconductor processing and semiconductor devices manufactured using the same
JP6989563B2 (en) Semiconductor processing tape
WO2020240963A1 (en) Tape for glass processing
JP7129375B2 (en) Semiconductor processing tape
TWI735802B (en) Tape for semiconductor processing
JP6535138B1 (en) Semiconductor processing tape
TWI743810B (en) Tape for glass processing
JP6989561B2 (en) Semiconductor processing tape
TWI735803B (en) Tape for semiconductor processing
JP6989562B2 (en) Semiconductor processing tape
JP7060547B2 (en) Glass processing tape