TWI808170B - Manufacturing method of semiconductor wafer - Google Patents

Manufacturing method of semiconductor wafer Download PDF

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TWI808170B
TWI808170B TW108115195A TW108115195A TWI808170B TW I808170 B TWI808170 B TW I808170B TW 108115195 A TW108115195 A TW 108115195A TW 108115195 A TW108115195 A TW 108115195A TW I808170 B TWI808170 B TW I808170B
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expandable
adhesive
base material
semiconductor wafer
layer
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TW108115195A
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TW202003771A (en
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山田忠知
也
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日商琳得科股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—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
    • 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
    • C09J7/29—Laminated material
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/206—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer comprising non-adhesive protrusions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

一種半導體晶片之製造方法，其係由使用黏著薄片之半導體晶片之製造方法，該黏著薄片具有：至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之基材(Y)，與分別於基材(Y)的兩面之第1黏著劑層(X1)及第2黏著劑層(X2)；且前述第1黏著劑層(X1)可藉由前述膨脹性粒子的膨脹而於黏著表面產生凹凸，且該半導體晶片之製造方法具有下述步驟(1)~(3)： ･步驟(1)：將第1黏著劑層(X1)貼附於硬質支撐體，並將第2黏著劑層(X2)貼附於半導體晶圓表面之步驟， ･步驟(2)：得到複數個半導體晶片之步驟， ･步驟(3)：使膨脹性粒子膨脹，於前述硬質支撐體與第1黏著劑層(X1)之界面P進行分離之步驟。A method of manufacturing a semiconductor wafer, which is a method of manufacturing a semiconductor wafer using an adhesive sheet comprising: a substrate (Y) having at least an expandable base material layer (Y1) containing expandable particles and a non-expandable base material layer (Y2), and a first adhesive layer (X1) and a second adhesive layer (X2) respectively on both sides of the base material (Y); Convex, and the manufacturing method of the semiconductor wafer has the following steps (1) to (3): ･Step (1): the step of attaching the first adhesive layer (X1) to the hard support, and attaching the second adhesive layer (X2) to the surface of the semiconductor wafer, ･Step (2): The step of obtaining a plurality of semiconductor wafers, ･Step (3): A step of expanding the expandable particles and separating them at the interface P between the hard support and the first adhesive layer (X1).

Description

半導體晶片之製造方法Manufacturing method of semiconductor wafer

本發明有關半導體晶片之製造方法。The present invention relates to a method of manufacturing a semiconductor wafer.

半導體晶片之製造步驟大多於使用黏著薄片將半導體晶圓貼附於支撐體之狀態實施各種加工。 此時使用之黏著薄片要求於加工時可充分固定半導體晶圓且於加工後可容易自支撐體剝離之性質。 作為對應於此等要求之黏著薄片，已知有具有含有熱膨脹性粒子之熱膨脹性黏著劑層之熱剝離性黏著薄片。Most of the manufacturing steps of semiconductor wafers are performed in a state where the semiconductor wafer is attached to a support using an adhesive sheet, and various processes are performed. The adhesive sheet used at this time requires properties that can sufficiently fix the semiconductor wafer during processing and can be easily peeled off from the support after processing. A heat-peelable adhesive sheet having a heat-expandable adhesive layer containing heat-expandable particles is known as an adhesive sheet corresponding to these requirements.

例如，專利文獻1中，揭示使用於基材單面設有包含熱膨脹性微小球之熱膨脹性黏著層，於另一面設有黏著層之熱剝離性雙面黏著薄片，將熱膨脹性黏著層貼附於支撐體，於另一黏著層貼合晶圓等之被黏著體，對被黏著體進行加工之方法。 依據專利文獻1，藉由使用上述熱剝離性雙面黏著薄片，於被黏著體加工時可保持被接著體表面之平滑性，且於加工後，可減小剝離該雙面黏著薄片時之應力，可不損傷被黏著體地容易剝離。 [先前技術文獻] [專利文獻]For example, Patent Document 1 discloses a method of processing the adherend by using a heat-peelable double-sided adhesive sheet provided with a heat-expandable adhesive layer containing heat-expandable microspheres on one side of the base material and an adhesive layer on the other side, attaching the heat-expandable adhesive layer to a support, attaching a wafer or the like to the other adhesive layer. According to Patent Document 1, by using the above-mentioned heat-peelable double-sided adhesive sheet, the smoothness of the surface of the adherend can be maintained during the processing of the adherend, and after processing, the stress when peeling the double-sided adhesive sheet can be reduced, and the adherend can be easily peeled without damaging the adherend. [Prior Art Literature] [Patent Document]

[專利文獻1]日本特開2003-292916號公報[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-292916

[發明欲解決之課題][Problem to be solved by the invention]

專利文獻1中記載之被黏著體之加工方法，係將上述雙面黏著薄片之熱膨脹性黏著層貼附於支撐體上，於另一黏著劑層貼合被黏著體，實施該被接著體之加工。 然而，於專利文獻1之加工方法所用之雙面黏著薄片所具有之熱膨脹性黏著層由於含有熱膨脹性微小球，故與未含有熱膨脹性微小球之黏著層相比，有與支撐體之黏著力降低之顧慮。 與支撐體之黏著力的降低成為產生起因於被黏著體未充分固定於支撐體所致之各種弊端的原因。例如藉由先切割法或隱形切割(stealth dicing)法般之研削晶圓背面分割為晶片之晶片加工方法，無法充分固定於支撐體，可能產生所得晶片之端部缺損等之弊端。The method of processing an adherend described in Patent Document 1 is to attach the heat-expandable adhesive layer of the above-mentioned double-sided adhesive sheet to a support, attach the adherend to another adhesive layer, and implement processing of the adherend. However, since the heat-expandable adhesive layer of the double-sided adhesive sheet used in the processing method of Patent Document 1 contains heat-expandable microspheres, there is a concern that the adhesive force with the support may be lowered compared with an adhesive layer not containing heat-expandable microspheres. The decrease in the adhesive force with the support is a cause of various problems due to insufficient fixation of the adherend to the support. For example, the wafer processing method of dividing the backside of the ground wafer into wafers by dicing first or stealth dicing cannot be sufficiently fixed on the support body, which may cause defects such as end defects of the obtained wafers.

又，專利文獻1中，自支撐體剝離雙面黏著薄片時，藉由加熱處理，使熱膨脹性微小球膨脹，於熱膨脹性黏著層表面形成凹凸，減低與支撐體之接觸面積，而使黏著力降低並剝離。 然而，藉上述剝離方法，自支撐體剝離雙面黏著薄片時，由於多少殘存黏著力，故有難以剝離之情況。又，剝離後，有熱膨脹性黏著層之一部分殘存於支撐體表面之情況，而有必要對支撐體之洗淨步驟，而成為生產性降低之要因。 又，為了防止對支撐體之污染，作為構成熱膨脹性黏著層之黏著性樹脂，雖亦考慮選擇低黏著性之樹脂，但該情況下，如上述，於被黏著體加工時，被黏著體可能產生未充分固定於被黏著體之弊端。Also, in Patent Document 1, when the double-sided adhesive sheet is peeled off from the support, the heat-expandable microspheres are expanded by heat treatment, forming unevenness on the surface of the heat-expandable adhesive layer, reducing the contact area with the support, thereby reducing the adhesive force and peeling off. However, when the double-sided adhesive sheet is peeled from the support by the above-mentioned peeling method, it may be difficult to peel due to some residual adhesive force. Also, after peeling, a part of the heat-expandable adhesive layer may remain on the surface of the support body, and a step of washing the support body is necessary, which causes a decrease in productivity. Also, in order to prevent contamination of the support, it is also considered to select a low-adhesive resin as the adhesive resin constituting the thermally expandable adhesive layer. However, in this case, as described above, the adherend may not be sufficiently fixed to the adherend during processing of the adherend.

本發明之目的在於提供可抑制半導體晶片之端部缺損等且提高良率，同時將支撐體與經貼附之黏著薄片分離時，可容易地一次分離，並且抑制分離後之支撐體污染，可省略支撐體之洗淨步驟之半導體晶片之製造方法。 [用以解決課題之手段]The object of the present invention is to provide a method for manufacturing a semiconductor wafer that can suppress chipping at the end of a semiconductor wafer and improve yield, and can easily separate a support from an attached adhesive sheet at one time, suppress contamination of the support after separation, and omit the step of cleaning the support. [Means to solve the problem]

本發明人等發現於將半導體晶圓分割製造半導體晶片之過程中，藉由使用於至少具備包含膨脹性粒子之膨脹性基材層及非膨脹性基材層之基材的兩面分別具有第1黏著劑層及第2黏著劑層之黏著薄片，可解決上述課題。The inventors of the present invention have found that the above-mentioned problems can be solved by using an adhesive sheet having a first adhesive layer and a second adhesive layer on both sides of a substrate having at least an expandable base material layer containing expandable particles and a non-expandable base material layer in the process of dividing a semiconductor wafer into semiconductor wafers.

亦即，本發明係提供下述[1]~[11]者。 [1] 一種半導體晶片之製造方法，其係使用黏著薄片自半導體晶圓製造半導體晶片之方法，該黏著薄片具有： 至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之基材(Y)，與 分別於基材(Y)的兩面之第1黏著劑層(X1)及第2黏著劑層(X2)； 藉由前述膨脹性粒子的膨脹，可於第1黏著劑層(X1)的黏著表面產生凹凸，且該半導體晶片之製造方法具有下述步驟(1)~(3)： ･步驟(1)：將第1黏著劑層(X1)的黏著表面貼附於硬質支撐體，並將第2黏著劑層(X2)的黏著表面貼附於半導體晶圓表面之步驟， ･步驟(2)：將前述半導體晶圓進行分割而得到複數個半導體晶片之步驟， ･步驟(3)：使前述膨脹性粒子膨脹，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於前述硬質支撐體與第1黏著劑層(X1)之界面P進行分離之步驟。 [2] 如上述[1]之半導體晶片之製造方法，其中前述黏著薄片於前述基材(Y)的前述膨脹性基材層(Y1)側具有第1黏著劑層(X1)，於該基材(Y)的前述非膨脹性基材層(Y2)側具有前述第2黏著劑層(X2)。 [3] 如上述[1]之半導體晶片之製造方法，其中前述基材(Y)具有：前述膨脹性基材層(Y1)，與設置於前述膨脹性基材層(Y1)之前述第1黏著層(X1)側之非膨脹性基材層(Y2-1)，與設置於前述膨脹性基材層(Y1)之前述第2黏著層(X2)側之非膨脹性基材層(Y2-2)； 前述膨脹性粒子進行膨脹時之非膨脹性基材層(Y2-1)的儲存模數E’低於前述膨脹性粒子進行膨脹時之非膨脹性基材層(Y2-2)的儲存模數E’。 [4] 如上述[1]或[2]之半導體晶片之製造方法，其中前述非膨脹性基材層(Y2)係存在於比前述膨脹性基材層(Y1)更遠離前述第1黏著劑層(X1)的位置，且前述膨脹性基材層(Y1)與前述第1黏著劑層(X1)之間不存在前述非膨脹性基材層(Y2)； 前述膨脹性粒子進行膨脹時之前述非膨脹性基材層(Y2)的儲存模數E’大於前述膨脹性粒子進行膨脹時之前述膨脹性基材層(Y1)的儲存模數E’。 [5] 如上述[1]~[4]中任一項之半導體晶片之製造方法，其中於步驟(3)中，當使前述膨脹性粒子膨脹時，構成前述黏著薄片之各層的層間不會分離。 [6] 如上述[1]~[5]中任一項之半導體晶片之製造方法，其中進一步具有下述步驟(4)， ･步驟(4)：於步驟(3)中自前述硬質支撐體分離後，將與複數個半導體晶片的電路面為相反側的背面貼附於具有基材薄膜、黏著劑層及/或接著劑層之轉印膠帶後，將前述黏著薄片自半導體晶片進行去除之步驟。 [7] 如上述[1]~[6]中任一項之半導體晶片之製造方法，其中前述膨脹性粒子為膨脹開始溫度(t)為60~270℃之熱膨脹性粒子。 [8] 如上述[7]之半導體晶片之製造方法，其中藉由於熱膨脹性粒子之「膨脹開始溫度(t)+10℃」~「膨脹開始溫度(t)+60℃」之間的加熱處理進行前述熱膨脹性粒子的膨脹。 [9] 如上述[7]或[8]之半導體晶片之製造方法，其中前述膨脹性基材層(Y1)為含有前述熱膨脹性粒子之熱膨脹性基材層(Y1-1)，且於23℃中的熱膨脹性基材層(Y1-1)的儲存模數E’(23)為1.0×106 Pa以上。 [10] 如上述[1]~[9]中任一項之半導體晶片之製造方法，其中前述非膨脹性基材層(Y2)的體積變化率(%)為未達2體積%。 [11] 如上述[1]~[10]中任一項之半導體晶片之製造方法，其中步驟(2)為：於具有改質領域之半導體晶圓中，將與電路面為相反側之未形成電路的背面進行研磨，分割該半導體晶圓而得到複數個半導體晶片之步驟。 [發明效果]That is, the present invention provides the following [1] to [11]. [1] A method of manufacturing a semiconductor wafer, which is a method of manufacturing a semiconductor wafer from a semiconductor wafer using an adhesive sheet comprising: a substrate (Y) having at least an expandable substrate layer (Y1) containing expandable particles and a non-expandable substrate layer (Y2), and a first adhesive layer (X1) and a second adhesive layer (X2) on both sides of the substrate (Y); The adhesive surface of the semiconductor wafer has unevenness, and the manufacturing method of the semiconductor wafer has the following steps (1) to (3): ･Step (1): a step of attaching the adhesive surface of the first adhesive layer (X1) to a hard support, and attaching the adhesive surface of the second adhesive layer (X2) to the surface of the semiconductor wafer. ･Step (2): The step of dividing the aforementioned semiconductor wafer to obtain a plurality of semiconductor wafers. The plurality of semiconductor wafers on the agent layer (X2) are kept attached, and the step of separation is performed at the interface P between the aforementioned hard support and the first adhesive layer (X1). [2] The method for manufacturing a semiconductor wafer according to [1] above, wherein the adhesive sheet has a first adhesive layer (X1) on the expandable base layer (Y1) side of the base (Y), and has a second adhesive layer (X2) on the non-expandable base layer (Y2) side of the base (Y). [3] The method for manufacturing a semiconductor wafer according to the above [1], wherein the base material (Y) comprises: the expandable base material layer (Y1), a non-expandable base material layer (Y2-1) provided on the first adhesive layer (X1) side of the expandable base material layer (Y1), and a non-expandable base material layer (Y2-2) provided on the second adhesive layer (X2) side of the expandable base material layer (Y1); The storage modulus E' of Y2-1) is lower than the storage modulus E' of the non-expandable base material layer (Y2-2) when the said expandable particle expands. [4] The method for manufacturing a semiconductor wafer according to [1] or [2] above, wherein the non-expandable base material layer (Y2) exists at a position farther from the first adhesive layer (X1) than the expandable base material layer (Y1), and the non-expandable base material layer (Y2) does not exist between the expandable base material layer (Y1) and the first adhesive layer (X1); the storage modulus E' of the non-expandable base material layer (Y2) when the expandable particles are expanded is greater than the aforementioned The storage modulus E' of the said expandable base material layer (Y1) when expandable particle expands. [5] The method for manufacturing a semiconductor wafer according to any one of [1] to [4] above, wherein in the step (3), when the expandable particles are expanded, the layers constituting the adhesive sheet are not separated from each other. [6] The method for manufacturing a semiconductor wafer according to any one of [1] to [5] above, further comprising the following step (4): ·Step (4): after separating from the hard support in step (3), attaching the back surface opposite to the circuit surface of the plurality of semiconductor wafers to a transfer tape having a base film, an adhesive layer, and/or an adhesive layer, and then removing the aforementioned adhesive sheet from the semiconductor wafer. [7] The method for manufacturing a semiconductor wafer according to any one of [1] to [6] above, wherein the expandable particles are thermally expandable particles having an expansion start temperature (t) of 60 to 270°C. [8] The method of manufacturing a semiconductor wafer according to [7] above, wherein the thermally expandable particles are expanded by heat treatment between "expansion start temperature (t) + 10°C" and "expansion start temperature (t)+60°C" of the heat expandable particles. [9] The method for producing a semiconductor wafer according to the above [7] or [8], wherein the expandable base layer (Y1) is a thermally expandable base layer (Y1-1) containing the thermally expandable particles, and the storage modulus E'(23) of the thermally expandable base layer (Y1-1) at 23°C is 1.0×10 6 Pa or more. [10] The method for manufacturing a semiconductor wafer according to any one of [1] to [9] above, wherein the volume change rate (%) of the non-expandable base material layer (Y2) is less than 2% by volume. [11] The method for manufacturing a semiconductor wafer according to any one of [1] to [10] above, wherein step (2) is a step of: grinding the backside of the semiconductor wafer having a reformed region on the side opposite to the circuit surface without forming a circuit, and dividing the semiconductor wafer to obtain a plurality of semiconductor wafers. [Invention effect]

依據本發明之半導體晶片之製造方法，由於可抑制所得半導體晶片之端部缺損等且提高良率，同時將支撐體與經貼附之黏著薄片分離時，可容易地一次分離，並且抑制分離後之支撐體污染，可省略支撐體之洗淨步驟，故可提高生產性。According to the manufacturing method of the semiconductor wafer of the present invention, since the edge defects of the obtained semiconductor wafer, etc. can be suppressed and the yield can be improved. At the same time, when the support body is separated from the attached adhesive sheet, it can be easily separated at one time, and the contamination of the support body after separation can be suppressed. The cleaning step of the support body can be omitted, so the productivity can be improved.

本發明中成為對象之層是「膨脹性層」或「非膨脹性層」之哪一者的判斷係基於進行為使膨脹之處理3分鐘後，自下述式算出該處理前後之體積變化率而判斷。 ・體積變化率(%)={(處理後之前述層的體積-處理前之前述層的體積)/處理前之前述層的體積}×100 亦即，體積電阻率若為5體積%以上，則判斷該層為「膨脹性層」，該體積電阻率若未達5體積%，則判斷該層為「非膨脹性層」。 又，作為「為使膨脹之處理」，例如於膨脹性粒子為熱膨脹性粒子時，只要於該熱膨脹性粒子之膨脹開始溫度(t)進行3分鐘加熱處理即可。In the present invention, the determination of whether the target layer is an "expandable layer" or a "non-expandable layer" is based on calculating the volume change rate before and after the treatment from the following formula after performing the treatment for swelling for 3 minutes. ・Volume change rate (%)={(volume of the aforementioned layer after treatment-volume of the aforementioned layer before treatment)/volume of the aforementioned layer before treatment}×100 That is, if the volume resistivity is 5% by volume or more, the layer is judged to be an "expandable layer", and if the volume resistivity is less than 5% by volume, the layer is judged to be a "non-expandable layer". Also, as "treatment for expanding", for example, when the expandable particles are heat-expandable particles, heat treatment at the expansion start temperature (t) of the heat-expandable particles may be performed for 3 minutes.

本說明書中，所謂「有效成分」係指成為對象的組成物中所含之成分中，稀釋溶劑除外之成分。 又，質量平均分子量(Mw)係以凝膠滲透層析(GPC)法測定之標準聚苯乙烯換算之值，具體而言係基於實施例中記載之方法測定之值。In this specification, the term "active ingredient" refers to a component excluding a diluting solvent among the components contained in the target composition. Moreover, mass average molecular weight (Mw) is the value measured by the standard polystyrene conversion measured by the gel permeation chromatography (GPC) method, Specifically, it is the value measured based on the method as described in an Example.

本說明書中，例如「(甲基)丙烯酸」表示「丙烯酸」與「甲基丙烯酸」兩者，其他類似用語亦相同。 又，關於較佳之數值範圍(例如含量等之範圍)，階段性記載之下限值及上限值可分別獨立組合。例如基於「較好為10~90，更好30~60」之記載，亦可組合「較佳之下限值(10)」與「更佳之上限值(60)」而成為「10~60」。In this specification, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also the same. In addition, regarding a preferable numerical range (for example, a range of content, etc.), the lower limit and upper limit described in stages can be independently combined. For example, based on the description of "preferably 10~90, more preferably 30~60", "10~60" may be obtained by combining "preferably lower limit (10)" and "more preferably upper limit (60)".

(本發明之半導體晶片之製造方法) 本發明之半導體晶片之製造方法(以下亦簡稱為「本發明之製造方法」)係使用黏著薄片自半導體晶圓製造半導體晶片之方法，該黏著薄片具有： 至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之基材(Y)，與分別於基材(Y)的兩面之第1黏著劑層(X1)及第2黏著劑層(X2)；藉由前述膨脹性粒子的膨脹，可於第1黏著劑層(X1)的黏著表面產生凹凸。 而且本發明之製造方法具有下述步驟(1)~(3)。 ･步驟(1)：將第1黏著劑層(X1)的黏著表面貼附於硬質支撐體，並將第2黏著劑層(X2)的黏著表面貼附於半導體晶圓表面之步驟。 ･步驟(2)：將前述半導體晶圓進行分割而得到複數個半導體晶片之步驟。 ･步驟(3)：使前述膨脹性粒子膨脹，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於前述硬質支撐體與第1黏著劑層(X1)之界面P進行分離之步驟。(Method for Manufacturing Semiconductor Wafer of the Present Invention) The method for manufacturing a semiconductor wafer of the present invention (hereinafter also referred to simply as "the manufacturing method of the present invention") is a method for manufacturing a semiconductor wafer from a semiconductor wafer using an adhesive sheet, the adhesive sheet having: A base material (Y) comprising at least an expandable base material layer (Y1) and a non-expandable base material layer (Y2) containing expandable particles, and a first adhesive layer (X1) and a second adhesive layer (X2) respectively on both sides of the base material (Y); through the expansion of the aforementioned expandable particles, unevenness can be produced on the adhesive surface of the first adhesive layer (X1). And the production method of the present invention has the following steps (1) to (3). ･Step (1): A step of attaching the adhesive surface of the first adhesive layer (X1) to a hard support, and attaching the adhesive surface of the second adhesive layer (X2) to the surface of the semiconductor wafer. ･Step (2): The step of dividing the aforementioned semiconductor wafer to obtain a plurality of semiconductor wafers. ･Step (3): Inflate the expandable particles, keep the multiple semiconductor wafers on the second adhesive layer (X2) attached, and separate them at the interface P between the hard support and the first adhesive layer (X1).

[本發明之製造方法所用之黏著薄片之構成] 圖1係顯示本發明之製造方法所用之黏著薄片之構成的一例，係該黏著薄片之剖面示意圖。 本發明之製造方法所用之黏著薄片舉例為如圖1(a)所示，係具有至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之基材(Y)，與分別於基材(Y)的兩面之第1黏著劑層(X1)及第2黏著劑層(X2)之黏著薄片1a。[Constitution of the adhesive sheet used in the production method of the present invention] Fig. 1 shows an example of the structure of the adhesive sheet used in the production method of the present invention, and is a schematic cross-sectional view of the adhesive sheet. The adhesive sheet used in the production method of the present invention is exemplified as shown in Figure 1(a), which is an adhesive sheet 1a having at least a substrate (Y) comprising an expandable substrate layer (Y1) containing expandable particles and a non-expandable substrate layer (Y2), and a first adhesive layer (X1) and a second adhesive layer (X2) respectively on both sides of the substrate (Y).

如圖1(a)所示之黏著薄片1a具有之基材(Y)係具有膨脹性基材層(Y1)及非膨脹性基材層(Y2)直接積層之構成者，但基材(Y)亦可為其以外之構成。 例如，亦可如圖1(b)所示之黏著薄片1b具有之基材(Y)般，於膨脹性基材層(Y1)之兩面設置第1非膨脹性基材層(Y2-1)及第2非膨脹性基材層(Y2-2)之構成。The base material (Y) of the adhesive sheet 1a shown in Figure 1 (a) is a structure in which an expandable base material layer (Y1) and a non-expandable base material layer (Y2) are directly laminated, but the base material (Y) may also have other configurations. For example, like the base material (Y) that the adhesive sheet 1b shown in FIG.

又，本發明之一態樣之黏著薄片，亦可構成為於第1黏著劑層(X1)之黏著表面及第2黏著劑層(X2)之黏著表面進而積層剝離材之構成。 該構成中，亦可構成為將第1黏著劑層(X1)及第2黏著劑層(X2)之一黏著表面積層於兩面經施以剝離處理之剝離材者捲繞成輥狀者。 該等剝離材係用以保護第1黏著劑層(X1)及第2黏著劑層(X2)之黏著表面而設者，為於黏著薄片使用時去除者。In addition, the adhesive sheet according to an aspect of the present invention may be formed by laminating a release material on the adhesive surface of the first adhesive layer (X1) and the adhesive surface of the second adhesive layer (X2). In this configuration, the adhesive surface layer of the first adhesive layer (X1) and the second adhesive layer (X2) may be wound into a roll shape with a peeling material that has been peeled on both sides. These release materials are provided to protect the adhesive surfaces of the first adhesive layer (X1) and the second adhesive layer (X2), and are removed when the adhesive sheet is used.

又，例如圖1(a)所示之黏著薄片1a中，剝離積層於第1黏著劑層(X1)上之剝離材時之剝離力與剝離積層於第2黏著劑層(X2)上之剝離材時之剝離力為相同程度時，若欲將兩者剝離材朝外側拉伸剝下時，有時會產生黏著薄片1a伴隨兩個剝離材而斷裂剝下之弊端。 因此，積層於第1黏著劑層(X1)上之剝離材與積層於第2黏著劑層(X2)上之剝離材較好使用經設計為自相互貼附之黏著劑層之剝離力不同之2種剝離材。Also, for example, in the adhesive sheet 1a shown in FIG. 1(a), if the peeling force when peeling off the release material laminated on the first adhesive layer (X1) is the same as the peeling force when peeling off the release material laminated on the second adhesive layer (X2), if the two release materials are pulled outward and peeled off, the adhesive sheet 1a may be broken and peeled off along with the two release materials. Therefore, the release material laminated on the first adhesive layer (X1) and the release material laminated on the second adhesive layer (X2) are preferably two types of release materials designed to have different peeling forces from the adhesive layers attached to each other.

而且，本發明之製造方法所用之黏著薄片，藉由前述膨脹性粒子之膨脹，而調整為可於第1黏著劑層(X1)之黏著表面產生凹凸。 例如，圖1(a)所示之黏著薄片1a具有於含有膨脹性粒子之膨脹性基材層(Y1)上積層第1黏著劑層(X1)，於非膨脹性基材層(Y2)上積層第2黏著劑層(X2)之構成。 黏著薄片1a中，膨脹性基材層(Y1)中之膨脹性粒子若膨脹，則於膨脹性基材層(Y1)表面產生凹凸，與該表面接觸之第1黏著劑層(X1)因該凹凸而上推，結果亦可於第1黏著劑層(X1)之黏著表面形成凹凸。 本發明之製造方法中，如上述步驟(1)，第1黏著劑層(X1)之黏著表面係貼附於硬質支撐體。 接著，上述步驟(3)中，於膨脹性粒子膨脹時，由於於第1黏著劑層(X1)之黏著表面形成凹凸，減少與硬質支撐體之接觸面積，故於硬質支撐體與第1黏著劑層(X1)之界面P以少許力即可容易地一次分離。 且，亦可調整為於膨脹性粒子膨脹時，於膨脹性基材層(Y1)與非膨脹性基材層(Y2)之界面亦藉少許力即可容易地一次分離。Furthermore, the adhesive sheet used in the production method of the present invention is adjusted so that unevenness can be generated on the adhesive surface of the first adhesive layer (X1) by the expansion of the aforementioned expandable particles. For example, the adhesive sheet 1a shown in FIG. 1(a) has a structure in which a first adhesive layer (X1) is laminated on an expandable base material layer (Y1) containing expandable particles, and a second adhesive layer (X2) is laminated on a non-expandable base material layer (Y2). In the adhesive sheet 1a, if the expandable particles in the expandable base material layer (Y1) expand, unevenness will be generated on the surface of the expandable base material layer (Y1), and the first adhesive layer (X1) in contact with the surface will be pushed up due to the unevenness, resulting in the formation of unevenness on the adhesive surface of the first adhesive layer (X1). In the manufacturing method of the present invention, as in the above step (1), the adhesive surface of the first adhesive layer (X1) is attached to the hard support. Next, in the above-mentioned step (3), when the expandable particles expand, unevenness is formed on the adhesive surface of the first adhesive layer (X1), reducing the contact area with the hard support, so the interface P between the hard support and the first adhesive layer (X1) can be easily separated at one time with a little force. Also, it can be adjusted so that when the expandable particles are expanded, the interface between the expandable base material layer (Y1) and the non-expandable base material layer (Y2) can be easily separated at one time with a little force.

另一方面，如上述步驟(1)，於第2黏著劑層(X2)之黏著表面貼附半導體晶圓之表面，於步驟(2)中，分割半導體晶圓，成為複數個半導體晶片。接著，如上述步驟(3)所規定，於膨脹性粒子膨脹時，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於硬質支撐體與第1黏著劑層(X1)之界面P予以分離。 亦即，自硬質支撐體分離時，複數個半導體晶片必須保持於黏著薄片之第2黏著劑層(X2)上。 因此，第2黏著劑層(X2)之黏著表面亦較好調整為不因前述膨脹性粒子之膨脹而使黏著力減低之方式，抑制凹凸之形成。On the other hand, as in the above step (1), the surface of the semiconductor wafer is pasted on the adhesive surface of the second adhesive layer (X2), and in the step (2), the semiconductor wafer is divided into a plurality of semiconductor wafers. Then, as stipulated in the above step (3), when the expandable particles expand, the plurality of semiconductor wafers on the second adhesive layer (X2) remain attached, and are separated at the interface P between the hard support and the first adhesive layer (X1). That is, when separating from the hard support, a plurality of semiconductor wafers must be held on the second adhesive layer (X2) of the adhesive sheet. Therefore, the adhesive surface of the second adhesive layer (X2) is also preferably adjusted so that the adhesive force does not decrease due to the expansion of the aforementioned expandable particles, and the formation of unevenness is suppressed.

例如，於圖1(a)所示之黏著薄片1a中，構成為於膨脹性基材層(Y1)之與第1黏著劑層(X1)相反之表面，具備非膨脹性基材層(Y2)，並於該非膨脹性基材層(Y2)之表面上積層第2黏著劑層(X2)。 黏著薄片1a中，膨脹性粒子膨脹時，由於存在非膨脹性基材層(Y2)，故因膨脹性粒子膨脹所致之自膨脹性基材層(Y1)側之應力被非膨脹性基材層(Y2)吸收。結果，抑制積層於非膨脹性基材層(Y2)上之第2黏著劑層(X2)之黏著表面的凹凸形成，可保持經貼附於該黏著表面之半導體晶片。For example, in the adhesive sheet 1a shown in FIG. 1(a), the non-expandable base material layer (Y2) is provided on the surface of the expandable base material layer (Y1) opposite to the first adhesive layer (X1), and the second adhesive layer (X2) is laminated on the surface of the non-expandable base material layer (Y2). In the adhesive sheet 1a, when the expandable particles swell, the non-expandable base layer (Y2) is present to absorb the stress from the expandable base layer (Y1) side caused by the expansion of the expandable particles by the non-expandable base layer (Y2). As a result, unevenness formation on the adhesive surface of the second adhesive layer (X2) laminated on the non-expandable base material layer (Y2) is suppressed, and the semiconductor wafer attached to the adhesive surface can be held.

又，較好於圖1(b)所示之黏著薄片1b中，於膨脹性粒子膨脹時，於第1黏著劑層(X1)之黏著表面形成凹凸之方式，將第1非膨脹性基材層(Y2-1)之儲存模數E’調整為較低。 另一方面，較好於膨脹性粒子膨脹時，抑制於第2黏著劑層(X2)之黏著表面形成凹凸之方式，將第2非膨脹性基材層(Y2-2)之儲存模數E’調整為較高。 亦即，較好將膨脹性粒子膨脹時之第1非膨脹性基材層(Y2-1)之儲存模數E’調整為低於膨脹性粒子膨脹時之第2非膨脹性基材層(Y2-2)之儲存模數E’。Also, it is preferable to adjust the storage modulus E' of the first non-expandable base material layer (Y2-1) to be relatively low in the adhesive sheet 1b shown in FIG. On the other hand, it is preferable to adjust the storage modulus E' of the second non-expandable base material layer (Y2-2) to be higher in order to suppress the formation of unevenness on the adhesive surface of the second adhesive layer (X2) when the expandable particles are expanded. That is, it is preferable to adjust the storage modulus E' of the first non-expandable base material layer (Y2-1) when the expandable particles are expanded to be lower than the storage modulus E' of the second non-expandable base material layer (Y2-2) when the expandable particles are expanded.

而且，如專利文獻1所記載，使用具有包含膨脹性粒子之膨脹性黏著劑層之雙面黏著薄片，將該膨脹性黏著劑層貼附於硬質支撐體，於另一黏著劑層上貼附半導體晶圓製造半導體晶片時，與硬質支撐體貼附之膨脹性黏著劑層由於含有膨脹性粒子，故黏著力易變不充分。Moreover, as described in Patent Document 1, when a double-sided adhesive sheet having an expandable adhesive layer containing expandable particles is used, the expandable adhesive layer is attached to a hard support, and a semiconductor wafer is attached to the other adhesive layer to manufacture a semiconductor wafer, the expandable adhesive layer attached to the hard support contains expandable particles, so the adhesive force tends to become insufficient.

因膨脹性黏著劑層對硬質支撐體之黏著力降低，而使半導體晶圓對硬質支撐體未充分固定，於例如分割半導體晶圓獲得複數個半導體晶片時，容易產生所得晶片端部缺損等之弊端。 又，藉由隱形切割(註冊商標，以下同)法製造半導體晶片時，必須於半導體晶圓之內部設置改質領域，但改質領域數越增加，半導體晶圓越容易產生翹曲。此處，半導體晶圓若未充分固定於硬質支撐體，則無法抑制半導體晶圓翹曲，而成為產生晶片龜裂等之要因。Due to the reduction of the adhesive force of the expandable adhesive layer to the hard support, the semiconductor wafer is not sufficiently fixed to the hard support. For example, when the semiconductor wafer is divided to obtain a plurality of semiconductor chips, defects such as chip end defects are likely to occur. In addition, when manufacturing semiconductor wafers by stealth dicing (registered trademark, the same below) method, it is necessary to provide modified regions inside the semiconductor wafer, but the more the number of modified regions increases, the easier it is for the semiconductor wafer to warp. Here, if the semiconductor wafer is not sufficiently fixed to the hard support, warpage of the semiconductor wafer cannot be suppressed, and this becomes a cause of occurrence of wafer cracks and the like.

另一方面，藉由選擇黏著性樹脂，將貼附半導體晶圓之黏著劑層或膨脹性黏著劑層設為高黏著力，認為亦可避免上述弊端。 然而，將貼附半導體晶圓之黏著劑層設為高黏著力時，會有所得複數個半導體晶片難以自該黏著劑層剝離之情況。 又，將膨脹性黏著劑層設為高黏著力時，膨脹性粒子膨脹而自硬質支撐體剝離該雙面黏著薄片時，於硬質支撐體表面會殘存一部分膨脹性黏著劑層，而有必要需要支撐體之洗淨步驟，亦成為生產性降低之要因。且，剝離貼附於硬質支撐體之雙面黏著薄片時，需要某程度之力，亦有容易地一次剝離變困難之情況。On the other hand, it is considered that the above-mentioned disadvantages can also be avoided by selecting an adhesive resin and setting the adhesive layer or the expandable adhesive layer for attaching the semiconductor wafer to a high adhesive force. However, when the adhesive layer for attaching the semiconductor wafer is made to have a high adhesive force, it may be difficult to peel off the obtained plurality of semiconductor wafers from the adhesive layer. Also, when the expansive adhesive layer is set to a high adhesive force, when the expansive particles expand and the double-sided adhesive sheet is peeled off from the hard support, a part of the expansive adhesive layer remains on the surface of the hard support, and a cleaning step of the support is necessary, which also causes a decrease in productivity. In addition, when peeling off the double-sided adhesive sheet attached to the hard support, a certain degree of force is required, and it may become difficult to easily peel off at one time.

另一方面，本發明之製造方法所用之黏著薄片具有至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之基材(Y)，於膨脹性粒子膨脹時，調整為於第1黏著劑層(X1)之黏著表面形成凹凸。 因此，與硬質支撐體貼附之第1黏著劑層(X1)中，由於並無必要包含膨脹性粒子，故可將半導體晶圓充分固定於硬質支撐體，可有效地抑制晶片端部缺損等之弊端，可提高良率。 且，硬質支撐體與貼附之黏著薄片分離時，可容易地一次分離並且可抑制分離後之硬質支撐體之污染，可省略支撐體之洗淨步驟，可提高生產性。 再者，第1黏著劑層(X1)及第2黏著劑層(X2)之形成材料的黏著劑組成物之選擇性自由度亦高。On the other hand, the adhesive sheet used in the production method of the present invention has a substrate (Y) having at least an expandable base material layer (Y1) containing expandable particles and a non-expandable base material layer (Y2), and is adjusted to form irregularities on the adhesive surface of the first adhesive layer (X1) when the expandable particles expand. Therefore, since the first adhesive layer (X1) attached to the hard support does not need to contain expandable particles, the semiconductor wafer can be fully fixed on the hard support, and defects such as chip end defects can be effectively suppressed, and the yield rate can be improved. In addition, when the hard support is separated from the attached adhesive sheet, it can be easily separated at one time, and the contamination of the separated hard support can be suppressed, and the cleaning step of the support can be omitted, thereby improving productivity. Furthermore, the degree of freedom of selection of the adhesive composition of the formation material of the 1st adhesive layer (X1) and the 2nd adhesive layer (X2) is also high.

[黏著薄片之各種物性] 本發明之一態樣所用之黏著薄片，藉由膨脹性粒子之膨脹，於與硬質支撐體貼附之第1黏著劑層(X1)之黏著表面產生凹凸，於硬質支撐體與第1黏著劑層(X1)之界面P，稍施加力即可容易地一次分離。 本發明之一態樣所用之黏著薄片中，作為膨脹性粒子膨脹而於界面P分離時之剝離力(F1 )通常為0~2000mN/25mm，較好為0~1000mN/25mm，更好為0~150mN/25mm，又更好為0~100mN/25mm，再更好為0~50mN/25mm。 又，該剝離力(F1 )為0mN/25mm時，以實施例中記載之方法測定剝離力時，亦包含由於剝離力過小而無法測定之情況。[Physical properties of the adhesive sheet] The adhesive sheet used in one aspect of the present invention generates unevenness on the adhesive surface of the first adhesive layer (X1) attached to the hard support by the expansion of the expandable particles, and can be easily separated at one time by applying a slight force at the interface P between the hard support and the first adhesive layer (X1). In the adhesive sheet used in one aspect of the present invention, the peel force (F 1 ) when the expandable particles are expanded and separated at the interface P is usually 0-2000mN/25mm, preferably 0-1000mN/25mm, more preferably 0-150mN/25mm, more preferably 0-100mN/25mm, and still more preferably 0-50mN/25mm. In addition, when the peeling force (F 1 ) is 0 mN/25 mm, when the peeling force is measured by the method described in the examples, the case where the peeling force is too small and cannot be measured is also included.

另一方面，膨脹性粒子之膨脹前，自半導體晶圓製造複數個半導體晶片時，基於抑制晶片端部缺損等之發生，提高良率之觀點，較好第1黏著劑層(X1)之黏著力越高越好。 基於上述觀點，本發明之一態樣所用之黏著薄片中，作為膨脹性粒子膨脹前之於界面P分離時之剝離力(F0 )，較好為0.05~10.0N/25mm，更好為0.1~8.0N/25mm，又更好為0.15~6.0N/25mm，再更好為0.2~4.0N/25mm。 又，上述剝離力(F0 )亦可視為第1黏著劑層(X1)對於硬質支撐體之黏著力。On the other hand, before the expansion of the expandable particles, when manufacturing a plurality of semiconductor wafers from the semiconductor wafer, from the viewpoint of suppressing the occurrence of chip end defects and improving yield, the higher the adhesive force of the first adhesive layer (X1), the better. Based on the above viewpoint, in the adhesive sheet used in one aspect of the present invention, the peeling force (F 0 ) when the expandable particles separate from the interface P before expansion is preferably 0.05-10.0N/25mm, more preferably 0.1-8.0N/25mm, more preferably 0.15-6.0N/25mm, and still more preferably 0.2-4.0N/25mm. In addition, the above-mentioned peeling force (F 0 ) can also be regarded as the adhesive force of the first adhesive layer (X1) to the hard support.

本發明之一態樣所用之黏著薄片中，剝離力(F1 )與剝離力(F0 )之比[(F1 )/(F0 )]較好為0~0.9，更好為0~0.8，又更好為0~0.5，再更好為0~0.2。In the adhesive sheet used in one aspect of the present invention, the ratio of peel force (F 1 ) to peel force (F 0 ) [(F 1 )/(F 0 )] is preferably from 0 to 0.9, more preferably from 0 to 0.8, more preferably from 0 to 0.5, still more preferably from 0 to 0.2.

又，剝離力(F1 )係於膨脹性粒子膨脹時之環境下測定之值。例如膨脹性粒子為熱膨脹性粒子時，作為測定剝離力(F1 )時之溫度條件，只要為該熱膨脹性粒子之膨脹開始溫度(t)以上即可。 另一方面，作為測定剝離力(F0 )時之溫度條件，只要為不使膨脹粒子膨脹之溫度即可，基本上為室溫(23℃)。 但，剝離力(F1 )與剝離力(F0 )之更具體測定條件及測定方法係基於實施例記載之方法。In addition, the peeling force (F 1 ) is a value measured under the environment when the expandable particle is expanded. For example, when the expandable particles are heat-expandable particles, the temperature condition for measuring the peeling force (F 1 ) may be equal to or higher than the expansion start temperature (t) of the heat-expandable particles. On the other hand, the temperature condition for measuring the peeling force (F 0 ) is basically room temperature (23° C.) as long as the expanded particles are not expanded. However, the more specific measurement conditions and measurement methods of the peeling force (F 1 ) and the peeling force (F 0 ) are based on the methods described in the examples.

本發明之一態樣所用之黏著薄片中，作為室溫(23℃)下之第2黏著劑層(X2)之黏著力，較好為0.1 ~10.0N/25mm，更好為0.2~8.0N/25mm，又更好為0.4~6.0 N/25mm，再更好為0.5~4.0N/25mm。 本說明書中，第2黏著劑層(X2)之黏著力意指藉由實施例記載之方法測定之值。 以下針對構成本發明一態樣所用之黏著薄片之各層加以說明。In the adhesive sheet used in one aspect of the present invention, the adhesive force of the second adhesive layer (X2) at room temperature (23° C.) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm, more preferably 0.4 to 6.0 N/25 mm, and still more preferably 0.5 to 4.0 N/25 mm. In this specification, the adhesive force of a 2nd adhesive agent layer (X2) means the value measured by the method described in an Example. Each layer constituting the adhesive sheet used in one aspect of the present invention will be described below.

＜基材(Y)＞ 本發明一態樣所用之黏著薄片具有之基材(Y)係至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)。 又，作為基材(Y)，可如圖1(a)所示之黏著薄片1a，為膨脹性基材層(Y1)及非膨脹性基材層(Y2)分別逐層積層而成者，亦可如圖1(b)所示之黏著薄片1b，於膨脹性基材層(Y1)之兩面設置第1非膨脹性基材層(Y2-1)及第2非膨脹性基材層(Y2-2)而構成。＜Substrate (Y)＞ The substrate (Y) of the adhesive sheet used in one aspect of the present invention has at least an expandable substrate layer (Y1) containing expandable particles and a non-expandable substrate layer (Y2). Also, as the base material (Y), the adhesive sheet 1a shown in Figure 1(a) can be formed by layering the expandable base material layer (Y1) and the non-expandable base material layer (Y2) layer by layer, or the adhesive sheet 1b shown in Figure 1(b) can be formed by setting the first non-expandable base material layer (Y2-1) and the second non-expandable base material layer (Y2-2) on both sides of the expandable base material layer (Y1).

本發明一態樣所用之黏著薄片具有之基材(Y)亦可構成為於膨脹性基材層(Y1)與非膨脹性基材層(Y2)之間設置接著層。 例如，圖1(b)所示之黏著薄片1b之構成時，可於膨脹性基材層(Y1)與第1非膨脹性基材層(Y2-1)及/或第2非膨脹性基材層(Y2-2)之間設置接著層。 藉由設置接著層，可使膨脹性基材層(Y1)與非膨脹性基材層(Y2)之層間密著性良好。 接著層一般可由接著劑或第1接著劑層(X1)及第2黏著劑層(X2)之形成材料的黏著劑組成物形成。The substrate (Y) included in the adhesive sheet used in one aspect of the present invention may also be configured such that an adhesive layer is provided between the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2). For example, when the composition of the adhesive sheet 1b shown in Fig. 1(b), an adhesive layer can be set between the expandable base material layer (Y1) and the first non-expandable base material layer (Y2-1) and/or the second non-expandable base material layer (Y2-2). By providing the adhesive layer, the interlayer adhesion between the expandable base material layer (Y1) and the non-expandable base material layer (Y2) can be improved. The adhesive layer can generally be formed of an adhesive or an adhesive composition that is a material for forming the first adhesive layer (X1) and the second adhesive layer (X2).

本發明一態樣中，基於設為藉由膨脹性粒子之膨脹而於第1黏著劑層(X1)之黏著表面產生凹凸，另一方面抑制於第2黏著劑層(X2)之黏著表面形成凹凸之黏著薄片之觀點，作為基材(Y)較好為至少於最表面具備膨脹性基材層(Y1)及非膨脹性基材層(Y2)者。 作為該態樣，舉例為具有圖1(a)所示之黏著薄片1a之基材(Y)，或依序積層膨脹性基材層(Y1)、接著劑層及非膨脹性基材層(Y2)而成之基材(Y)等。 作為該接著劑層之形成材料舉例為與後述之轉印膠帶具有之接著劑層之形成材料的接著劑組成物相同者。In one aspect of the present invention, the base material (Y) is preferably one having an expandable base material layer (Y1) and a non-expandable base material layer (Y2) at least on the outermost surface, based on the viewpoint of providing an adhesive sheet that produces irregularities on the adhesive surface of the first adhesive layer (X1) due to expansion of the expandable particles and suppresses the formation of irregularities on the adhesive surface of the second adhesive layer (X2). As this aspect, for example, the base material (Y) having the adhesive sheet 1a shown in FIG. Examples of the forming material of the adhesive layer include the same adhesive composition as that of the forming material of the adhesive layer included in the transfer tape described later.

又，構成基材(Y)之膨脹性基材層(Y1)及非膨脹性基材層(Y2)均為非黏著性之層。 本發明中，是否為非黏著性之層的判斷係對於成為對象之層的表面，依據JIS Z0237:1991測定之探針觸黏值若未達50mN/5mmϕ，則該層判斷為「非黏著性之層」。 本發明一態樣所用之黏著薄片(I)具有之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之表面的探針觸黏值通常分別獨立為未達50mN/5mmϕ，但較好未達30mN/5mmϕ，更好未達10mN/5mmϕ，又更好未達5mN/5mmϕ。 又，本說明書中，熱膨脹基材表面之探針觸黏值之具體測定方法係依據實施例記載之方法。In addition, both the expandable base material layer (Y1) and the non-expandable base material layer (Y2) constituting the base material (Y) are non-adhesive layers. In the present invention, whether it is a non-adhesive layer is judged as a "non-adhesive layer" if the probe-tack value measured according to JIS Z0237:1991 is less than 50mN/5mmϕ on the surface of the target layer. The adhesive sheet (I) used in one aspect of the present invention has the probe-tack values of the surfaces of the intumescent base material layer (Y1) and the non-expandable base material layer (Y2) respectively independently generally being less than 50mN/5mmϕ, but preferably less than 30mN/5mmϕ, more preferably less than 10mN/5mmϕ, and more preferably less than 5mN/5mmϕ. In addition, in this specification, the specific measurement method of the probe contact tack value on the surface of the heat-expandable substrate is based on the method described in the examples.

本發明一態樣所用之黏著薄片中，作為基材(Y)之厚度，較好為15~2000μm，更好為25~1500μm，又更好為30~1000μm，再更好為40~500μm。In the adhesive sheet used in one aspect of the present invention, the thickness of the substrate (Y) is preferably from 15 to 2000 μm, more preferably from 25 to 1500 μm, more preferably from 30 to 1000 μm, still more preferably from 40 to 500 μm.

膨脹性粒子之膨脹前之膨脹性基材(Y1)之厚度，較好為10~1000μm，更好為20~700μm，又更好為25~500μm，再更好為30~300μm。 非膨脹性基材(Y2)之厚度，較好為10~1000μm，更好為20~700μm，又更好為25~500μm，再更好為30~300μm。 又，本說明書中，例如如圖1(b)所示之黏著薄片1b，膨脹性基材(Y1)或非膨脹性基材(Y2)介隔其他層存在複數時，上述膨脹性基材(Y1)或非膨脹性基材(Y2)之厚度意指各每一層之厚度。The thickness of the expandable base material (Y1) before expansion of the expandable particles is preferably from 10 to 1000 μm, more preferably from 20 to 700 μm, more preferably from 25 to 500 μm, still more preferably from 30 to 300 μm. The thickness of the non-expandable base material (Y2) is preferably from 10 to 1000 μm, more preferably from 20 to 700 μm, more preferably from 25 to 500 μm, still more preferably from 30 to 300 μm. Also, in this specification, for example, in the adhesive sheet 1b shown in Figure 1(b), when there are multiple expandable substrates (Y1) or non-expandable substrates (Y2) interposed by other layers, the thickness of the above-mentioned expandable substrate (Y1) or non-expandable substrate (Y2) means the thickness of each layer.

本發明一態樣所用之黏著薄片中，膨脹性粒子之膨脹前之膨脹性基材層(Y1)與非膨脹性基材層(Y2)之厚度比[(Y1)/(Y2)]，較好為0.02~200，更好為0.03~150，更好為0.05~100。In the adhesive sheet used in one aspect of the present invention, the thickness ratio [(Y1)/(Y2)] of the expandable base material layer (Y1) to the non-expandable base material layer (Y2) before expansion of the expandable particles is preferably 0.02-200, more preferably 0.03-150, more preferably 0.05-100.

本發明一態樣所用之黏著薄片中，作為膨脹性粒子之膨脹前之膨脹性基材層(Y1)與和膨脹性基材層(Y1)直接積層之第1黏著劑層(X1)之厚度比[(Y1)/(X1)]，較好為0.2以上，更好為0.5以上，又更好為1.0以上，再更好為5.0以上，且較好為1000以下，更好為200以下，又更好為60以下，再更好為30以下。In the adhesive sheet used in one aspect of the present invention, the thickness ratio [(Y1)/(X1)] of the expandable substrate layer (Y1) before expansion as the expandable particles and the first adhesive layer (X1) directly laminated with the expandable substrate layer (Y1) is preferably at least 0.2, more preferably at least 0.5, more preferably at least 1.0, still more preferably at least 5.0, and is preferably at most 1000, more preferably at most 200, and more preferably at most 60. More preferably below 30.

又，本發明一態樣所用之黏著薄片中，作為非膨脹性基材層(Y2)與和非膨脹性基材層(Y2)直接積層之第2黏著劑層(X2)之厚度比[(Y2)/(X2)]，較好為0.1以上，更好為0.2以上，又更好為0.3以上，且較好為20以下，更好為10以下，又更好為5以下。Also, in the adhesive sheet used in one aspect of the present invention, the thickness ratio [(Y2)/(X2)] of the non-expandable base layer (Y2) and the second adhesive layer (X2) directly laminated with the non-expandable base layer (Y2) is preferably at least 0.1, more preferably at least 0.2, more preferably at least 0.3, and is preferably at most 20, more preferably at most 10, still more preferably at most 5.

以下針對構成基材(Y)之膨脹性基材層(Y1)及非膨脹性基材層(Y2)加以說明。The expandable base material layer (Y1) and the non-expandable base material layer (Y2) which comprise a base material (Y) are demonstrated below.

＜膨脹性基材層(Y1)＞ 構成基材(Y)之膨脹性基材層(Y1)係含有膨脹性粒子，藉由特定之膨脹處理可膨脹之層。 膨脹性基材層(Y1)中之膨脹性粒子含量，相對於膨脹性基材層(Y1)之總質量(100質量%)，較好為1~40質量%，更好為5~35質量%，又更好為10~30質量%，再更好為15~ 25質量%。＜Expandable Base Layer (Y1)＞ The expandable base material layer (Y1) constituting the base material (Y) is a layer that contains expandable particles and is expandable by specific expansion treatment. The content of the expandable particles in the expandable base layer (Y1) is preferably from 1 to 40% by mass, more preferably from 5 to 35% by mass, more preferably from 10 to 30% by mass, and still more preferably from 15 to 25% by mass, relative to the total mass (100% by mass) of the expandable base material layer (Y1).

又，基於提高膨脹性基材層(Y1)與積層之其他層之層間密著性之觀點，亦可對於膨脹性基材層(Y1)表面實施利用氧化法或凹凸化法等之表面處理、易接著處理或底塗處理。 作為氧化法舉例為例如電暈放電處理、電漿放電處理、鉻酸處理(濕式)、熱風處理、臭氧及紫外線照射處理等，作為凹凸化法，舉例為例如噴砂法、溶劑處理法等。In addition, from the viewpoint of improving the interlayer adhesion between the expandable base material layer (Y1) and other laminated layers, the surface of the expandable base material layer (Y1) may be subjected to surface treatment such as an oxidation method or a roughening method, an easy-adhesive treatment, or a primer treatment. Examples of oxidation methods include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet method), hot air treatment, ozone and ultraviolet irradiation treatment, etc., and examples of roughening methods include sand blasting and solvent treatment.

作為膨脹性基材層(Y1)所含之膨脹性粒子若為藉由進行特定處理而膨脹之粒子即可，舉例為例如藉由加熱至特定溫度以上而膨脹之熱膨脹性粒子，或藉由吸收特定量紫外線而於粒子內部產生氣體並膨脹之UV膨脹性粒子等。The expandable particles contained in the expandable substrate layer (Y1) may be particles that are expanded by performing a specific treatment, for example, thermally expandable particles that expand by heating to a specific temperature or higher, or UV expandable particles that generate gas inside the particles and expand by absorbing a specific amount of ultraviolet rays.

膨脹性粒子之體積最大膨脹率較好為1.5~100倍，更好為2~80倍，又更好為2.5~60倍，再更好為3~40倍。The maximum volume expansion ratio of the expandable particles is preferably from 1.5 to 100 times, more preferably from 2 to 80 times, more preferably from 2.5 to 60 times, and still more preferably from 3 to 40 times.

於23℃下之膨脹前之膨脹性粒子的平均粒徑較好為3~100μm，更好為4~70μm，又更好為6~60μm，再更好為10~50μm。 又，所謂膨脹性粒子之平均粒徑係體積中值粒徑(D50 )，意指使用雷射繞射式粒度分佈測定裝置(例如Malvern公司製，製品名「Mastersizer 3000」)測定之膨脹性粒子的粒子分佈中，自膨脹性粒子之粒徑小者起計算的累積體積頻度相當於50%之粒徑。The average particle diameter of the expandable particles before expansion at 23° C. is preferably from 3 to 100 μm, more preferably from 4 to 70 μm, more preferably from 6 to 60 μm, still more preferably from 10 to 50 μm. Also, the average particle diameter of the expandable particles is the volume median particle diameter (D 50 ), which means a particle diameter corresponding to 50% of the cumulative volume frequency calculated from the smaller particle diameter of the expandable particles in the particle distribution of the expandable particles measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name "Mastersizer 3000").

於23℃下之膨脹前的膨脹性粒子的90%粒徑(D90 )較好為10~ 150μm，更好為20~100μm，又更好為25~ 90μm，再更好為30~80μm。 又，膨脹性粒子之90%粒徑(D90 )，意指使用雷射繞射式粒度分佈測定裝置(例如Malvern公司製，製品名「Mastersizer 3000」)測定之膨脹性粒子的粒子分佈中，自膨脹性粒子之粒徑小者起計算的累積體積頻度相當於90%之粒徑。The 90% particle size (D 90 ) of the expandable particles before expansion at 23° C. is preferably from 10 to 150 μm, more preferably from 20 to 100 μm, more preferably from 25 to 90 μm, still more preferably from 30 to 80 μm. Also, the 90% particle diameter (D 90 ) of the expandable particles refers to the particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the expandable particles in the particle distribution of the expandable particles measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name "Mastersizer 3000").

本發明之一態樣中，作為膨脹性粒子較好係膨脹開始溫度(t)為60~270℃之熱膨脹性粒子。 亦即，作為膨脹性基材層(Y1)，較好為包含膨脹開始溫度(t)為60~270℃之熱膨脹性粒子之熱膨脹性基材層(Y1-1)，更好熱膨脹性基材層(Y1-1)滿足下述要件(1)。 ・要件(1)：前述熱膨脹性粒子之膨脹開始溫度(t)下之前述熱膨脹性基材層(Y1-1)之儲存模數E’(t)為1.0×107 Pa以下。 又，本說明書中，特定溫度下之熱膨脹性基材層(Y1-1)之儲存模數E’意指依據實施例記載之方法測定之值。In one aspect of the present invention, the expandable particles are preferably thermally expandable particles having an expansion start temperature (t) of 60 to 270°C. That is, the expandable base material layer (Y1) is preferably a thermally expandable base material layer (Y1-1) containing thermally expandable particles having an expansion start temperature (t) of 60 to 270°C, more preferably the thermally expandable base material layer (Y1-1) satisfies the following requirement (1).・Requirement (1): The storage modulus E'(t) of the thermally expandable base material layer (Y1-1) at the expansion start temperature (t) of the thermally expandable particles is 1.0×10 7 Pa or less. In addition, in this specification, the storage modulus E' of the thermally expandable base material layer (Y1-1) at a specific temperature means the value measured by the method described in an Example.

上述要件(1)可說是熱膨脹性粒子即將膨脹前之熱膨脹性基材層(Y1-1)的剛性之指標。 亦即，熱膨脹性粒子膨脹時，於滿足上述要件(1)之程度內，若熱膨脹性基材層(Y1-1)具有柔軟性，則熱膨脹性基材層(Y1-1)之表面容易形成凹凸，於第1黏著劑層(X1)之黏著表面亦容易產生凹凸。其結果，於硬質支撐體與第1黏著劑層(X1)之界面P稍施加力即可容易地一次分離。The above requirement (1) can be said to be an indicator of the rigidity of the heat-expandable base material layer (Y1-1) immediately before the heat-expandable particles expand. That is to say, when the heat-expandable particles expand, to the extent that the above-mentioned requirement (1) is satisfied, if the heat-expandable base material layer (Y1-1) has flexibility, the surface of the heat-expandable base material layer (Y1-1) is easy to form unevenness, and the adhesive surface of the first adhesive layer (X1) is also likely to produce unevenness. As a result, the interface P between the hard support and the first adhesive layer (X1) can be easily separated at one time by applying a slight force.

熱膨脹性基材層(Y1-1)之要件(1)所規定之儲存模數E’(t)，基於上述觀點，較好為9.0×106 Pa以下，更好為8.0×106 Pa以下，又更好為6.0×106 Pa以下，再更好為4.0×106 Pa以下。 又，基於抑制膨脹之熱膨脹性粒子之流動，提高熱膨脹性基材層(Y1-1)表面產生之凹凸形狀維持性，於第1黏著劑層(X1)之黏著表面亦容易產生凹凸之觀點，熱膨脹性基材層(Y1-1)之要件(1)所規定之儲存模數E’(t)，較好為1.0×103 Pa以上，更好為1.0×104 Pa以上，又更好為1.0× 105 Pa以上。The storage modulus E'(t) specified in the requirement (1) of the heat-expandable base material layer (Y1-1) is preferably at most 9.0×10 6 Pa, more preferably at most 8.0×10 6 Pa, more preferably at most 6.0×10 6 Pa, still more preferably at most 4.0×10 6 Pa, from the above viewpoint. In addition, from the viewpoint of suppressing the flow of the thermally expandable particles that expand, improving the shape retention of the irregularities generated on the surface of the thermally expandable base material layer (Y1-1), and easily producing irregularities on the adhesive surface of the first adhesive layer (X1), the storage modulus E'(t) specified in the requirement (1) of the thermally expandable base material layer (Y1-1) is preferably at least 1.0×10 3 Pa, more preferably at least 1.0×10 4 Pa, still more preferably at least 1.0×1 0 5 Pa or more.

又，熱膨脹性基材層(Y1-1)亦較好滿足下述要件(2)，更好與上述要件(1)一起滿足該要件(2)。 ・要件(2)：23℃下之熱膨脹性基材層(Y1-1)之儲存模數E’(23)為1.0×106 Pa以上。In addition, the heat-expandable base material layer (Y1-1) also preferably satisfies the following requirement (2), more preferably satisfies the requirement (2) together with the above-mentioned requirement (1).・Requirement (2): The storage modulus E'(23) of the thermally expandable base material layer (Y1-1) at 23°C is 1.0×10 6 Pa or more.

藉由設為滿足上述要件(2)之熱膨脹性基材層(Y1-1)，可防止將半導體晶圓貼附於第2黏著劑層(X2)之黏著表面時之位置偏移，且，亦可防止半導體晶圓向第2黏著劑層(X2)之過度沉入。By setting the heat-expandable base material layer (Y1-1) satisfying the above-mentioned requirement (2), it is possible to prevent positional displacement when the semiconductor wafer is attached to the adhesive surface of the second adhesive layer (X2), and it is also possible to prevent excessive sinking of the semiconductor wafer into the second adhesive layer (X2).

基於上述觀點，以上述要件(2)規定之熱膨脹性基材層(Y1-1)之儲存模數E’(23)較好為5.0×106 ~5.0×1012 Pa，更好為1.0×107 ~1.0×1012 Pa，又更好為5.0×107 ~1.0× 1011 Pa，再更好為1.0×108 ~1.0×1010 Pa。Based on the above viewpoint, the storage modulus E'(23) of the thermally expandable substrate layer (Y1-1) specified in the above requirement (2) is preferably 5.0×10 6 ~5.0×10 12 Pa, more preferably 1.0×10 7 ~1.0×10 12 Pa, still more preferably 5.0×10 7 ~1.0×10 11 Pa, still more preferably 1.0×10 8 ~1.0× 10 10 Pa.

作為熱膨脹性基材層(Y1-1)中所含之熱膨脹性粒子較好為膨脹開始溫度(t)為60~270℃之熱膨脹性粒子。 又，本說明書中，熱膨脹性粒子之膨脹開始溫度(t)意指基於以下方法測定之值。 [熱膨脹性粒子之膨脹開始溫度(t)之測定法] 製作於直徑6.0mm(內徑5.65mm)、深4.8mm之鋁盤中，添加成為測定對象之熱膨脹性粒子0.5mg，自其上蓋住鋁蓋(直徑5.6mm，厚0.1mm)之試料。 使用動態黏彈性測定裝置，對該試料自鋁蓋上部藉由加壓子施加0.01N的力之狀態，測定試料高度。接著，以藉由加壓子施加0.01N的力之狀態，以10℃/min之升溫速度自20℃加熱至300℃，測定加壓子於垂直方向之位移量，將朝正方向之位移開始溫度作為膨脹開始溫度(t)。As the heat-expandable particles contained in the heat-expandable base material layer (Y1-1), heat-expandable particles having an expansion start temperature (t) of 60 to 270° C. are preferred. Moreover, in this specification, the expansion start temperature (t) of a heat-expandable particle means the value measured based on the following method. [Measuring method of expansion start temperature (t) of heat-expandable particles] Made in an aluminum pan with a diameter of 6.0mm (inner diameter 5.65mm) and a depth of 4.8mm, adding 0.5mg of thermally expandable particles to be measured, and covering the sample with an aluminum cover (diameter 5.6mm, thickness 0.1mm). Using a dynamic viscoelasticity measuring device, measure the height of the sample in a state where a force of 0.01 N is applied from the upper part of the aluminum cover to the sample by a presser. Then, in the state where the force of 0.01N is applied by the presser, the temperature is heated from 20°C to 300°C at a heating rate of 10°C/min, and the displacement of the presser in the vertical direction is measured, and the displacement start temperature in the positive direction is taken as the expansion start temperature (t).

作為熱膨脹性粒子較好係由熱塑性樹脂所構成之外殼與由該外殼所內包且加熱至特定溫度時會氣化之內包成分所構成之微膠囊化發泡劑。 作為構成微膠囊化發泡劑之外殼的熱塑性樹脂舉例為例如偏氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯縮丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏氯乙烯、聚碸等。The heat-expandable particles are preferably a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and a microencapsulated foaming agent wrapped in the outer shell and vaporized when heated to a specific temperature. Examples of the thermoplastic resin constituting the shell of the microencapsulated blowing agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polyvinyl chloride.

作為內包於外殼之內包成分舉例為例如丙烷、丁烷、戊烷、己烷、庚烷、辛烷、壬烷、癸烷、異丁烷、異戊烷、異己烷、異庚烷、異辛烷、異壬烷、異癸烷、環丙烷、環丁烷、環戊烷、環己烷、環庚烷、環辛烷、新戊烷、十二烷、異十二烷、環十三烷、己基環己烷、十三烷、十四烷、十五烷、十六烷、十七烷、十八烷、十九烷、異十三烷、4-甲基十二烷、異十四烷、異十五烷、異十六烷、2,2,4,4,6,8,8-七甲基壬烷、異十七烷、異十八烷、異十九烷、2,6,10,14-四甲基十七烷、環十三烷、庚基環己烷、正辛基環己烷、環十五烷、壬基環己烷、癸基環己烷、十五烷基環己烷、十六烷基環己烷、十七烷基環己烷、十八烷基環己烷等。 該等內包成分可單獨使用，亦可併用兩種以上。 熱膨脹性粒子之膨脹開始溫度(t)可藉由適當選擇內包成分之種類而調整。Examples of components contained in the shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane , Octadecane, Nonadecane, Isotridecane, 4-Methyldodecane, Isotetradecane, Isopentadecane, Isohexadecane, 2,2,4,4,6,8,8-Heptamethylnonane, Isohexadecane, Isooctadecane, Isnonadecane, 2,6,10,14-Tetramethylheptadecane, Cyclotridecane, Heptylcyclohexane, n-Octylcyclohexane, Cyclopentadecane, Nonylcyclohexane, Decylcyclohexane, Pentadecylcyclohexane, Hexadecylcyclohexane, Heptadecylcyclohexane Hexane, octadecylcyclohexane, etc. These inclusion components may be used alone or in combination of two or more. The expansion start temperature (t) of the heat-expandable particles can be adjusted by appropriately selecting the type of the contained component.

膨脹性基材層(Y1)較好由包含樹脂及膨脹性粒子之樹脂組成物(y)形成。 又，樹脂組成物(y)中，於不損及本發明效果之範圍內，可根據需要含有基材用添加劑。 作為基材用添加劑舉例為例如紫外線吸收劑、光安定劑、抗氧化劑、抗靜電劑、滑劑、抗黏連劑、著色劑等。 又，該等基材用添加劑分別可單獨使用，亦可併用2種以上。 含有該等基材用添加劑時，各基材用添加劑之含量，相對前述樹脂100質量份，較好為0.0001~20質量份，更好為0.001~10質量份。The expandable base material layer (Y1) is preferably formed of a resin composition (y) containing a resin and expandable particles. Moreover, the resin composition (y) can contain the additive for base materials as needed within the range which does not impair the effect of this invention. Examples of additives for substrates include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, colorants, and the like. Moreover, these additives for base materials may be used individually, respectively, and may use 2 or more types together. When these base material additives are contained, the content of each base material additive is preferably from 0.0001 to 20 parts by mass, more preferably from 0.001 to 10 parts by mass, based on 100 parts by mass of the aforementioned resin.

膨脹性基材層(Y1)之形成材料的樹脂組成物(y)所含之膨脹性粒子係如上述較好為熱膨脹性粒子。 膨脹性粒子之含量，相對於樹脂組成物(y)之有效成分總量(100質量%)，較好為1~40質量%，更好為5~35質量%，又更好為10~30質量%，又更好為15~25質量%。The expandable particles contained in the resin composition (y) of the forming material of the expandable base material layer (Y1) are preferably thermally expandable particles as described above. The content of the expandable particles is preferably from 1 to 40% by mass, more preferably from 5 to 35% by mass, more preferably from 10 to 30% by mass, and still more preferably from 15 to 25% by mass, based on the total active ingredient (100% by mass) of the resin composition (y).

作為膨脹性基材層(Y1)之形成材料的樹脂組成物(y)所含之樹脂，可為非黏著性樹脂，亦可為黏著性樹脂。 亦即，樹脂組成物(y)所含之樹脂即使為黏著性樹脂，只要在自樹脂組成物(y)形成膨脹性基材層(Y1)之過程中，該黏著性樹脂與聚合性化合物進行聚合反應，使所得樹脂成為非黏著性樹脂，而使包含該樹脂之膨脹性基材層(Y1)成為非黏著性即可。The resin contained in the resin composition (y) which is the forming material of the expandable base material layer (Y1) may be a non-adhesive resin or an adhesive resin. That is, even if the resin contained in the resin composition (y) is an adhesive resin, the adhesive resin and the polymerizable compound undergo a polymerization reaction during the process of forming the expandable base material layer (Y1) from the resin composition (y), so that the obtained resin becomes a non-adhesive resin, and the expandable base material layer (Y1) containing the resin becomes non-adhesive.

作為樹脂組成物(y)所含之前述樹脂之質量平均分子量(Mw)較好為1000~100萬，更好為1000~70萬，又更好為1000~50萬。 又，該樹脂為具有2種以上構成單位之共聚物時，該共聚物之形態並未特別限定，可為嵌段共聚物、無規共聚物及接枝共聚物之任一者。The mass average molecular weight (Mw) of the aforementioned resin contained in the resin composition (y) is preferably from 10 million to 1 million, more preferably from 10 million to 700 thousand, still more preferably from 10 million to 500 thousand. Also, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.

樹脂之含量，相對於樹脂組成物(y)之有效成分總量(100質量%)，較好為50~99質量%，更好為60~95質量%，又更好為65~90質量%，再更好為70~85質量%。The content of the resin is preferably from 50 to 99% by mass, more preferably from 60 to 95% by mass, more preferably from 65 to 90% by mass, still more preferably from 70 to 85% by mass, relative to the total active ingredient (100% by mass) of the resin composition (y).

本發明之一態樣中，基於膨脹性粒子之膨脹時，成為易於表面形成凹凸之膨脹性基材層(Y1)之觀點，作為樹脂組成物(y)所含之前述樹脂較好包含選自丙烯酸胺基甲酸酯系樹脂及烯烴系樹脂之1種以上。 又，作為上述丙烯酸胺基甲酸酯系樹脂，較好為以下之樹脂(U1)。 ・胺基甲酸酯預聚物(UP)與包含(甲基)丙烯酸酯之乙烯基化合物聚合成之丙烯酸胺基甲酸酯系樹脂(U1)。In one aspect of the present invention, the aforementioned resin contained in the resin composition (y) preferably contains at least one selected from the group consisting of acrylic urethane resins and olefin resins, from the viewpoint that when the expandable particles are expanded, the expandable substrate layer (Y1) tends to form unevenness on the surface. Moreover, as said urethane acrylate resin, the following resin (U1) is preferable. ・Acrylic urethane resin (U1) polymerized from urethane prepolymer (UP) and vinyl compound containing (meth)acrylate.

[丙烯酸胺基甲酸酯系樹脂(U1)] 成為丙烯酸胺基甲酸酯系樹脂(U1)之主鏈的胺基甲酸酯預聚物(UP)舉例為多元醇與多元異氰酸酯之反應物。 又，胺基甲酸酯預聚物(UP)較好使用進而使用鏈延長劑實施鏈延長反應而得者。[Acrylic urethane resin (U1)] The urethane prepolymer (UP) used as the main chain of the urethane acrylate resin (U1) is exemplified by a reaction product of a polyhydric alcohol and a polyvalent isocyanate. Moreover, it is preferable to use the urethane prepolymer (UP) which further performed chain extension reaction using a chain extender.

作為成為胺基甲酸酯預聚物(UP)之原料的多元醇舉例為例如伸烷基型多元醇、醚型多元醇、酯型多元醇、酯醯胺型多元醇、酯・醚型多元醇、碳酸酯型多元醇等。 該等多元醇可單獨使用，亦可併用2種以上。 作為本發明之一態樣所用之多元醇較好為二醇，更好為酯型二醇、伸烷基型二醇及碳酸酯型二醇，又更好為酯型二醇、碳酸酯型二醇。Examples of polyols used as raw materials for the urethane prepolymer (UP) include alkylene polyols, ether polyols, ester polyols, esteramide polyols, ester-ether polyols, and carbonate polyols. These polyols may be used alone or in combination of two or more. The polyol used as an aspect of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and more preferably an ester diol or a carbonate diol.

作為酯型二醇舉例為例如1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇等之烷二醇；乙二醇、丙二醇、二乙二醇、二丙二醇等之烷二醇；等之二醇類選擇之1種或2種以上與鄰苯二甲酸、間苯二甲酸、對苯二甲酸、萘二羧酸、4,4-二苯基二羧酸、二苯基甲烷-4,4’-二羧酸、琥珀酸、己二酸、壬二酸、癸二酸、氯橋酸(Het acid)、馬來酸、富馬酸、依康酸、環己烷-1,3-二羧酸、環己烷-1,4-二羧酸、六氫鄰苯二甲酸、六氫間苯二甲酸、六氫對苯二甲酸、甲基六氫鄰苯二甲酸等之二羧酸及該等之酸酐選擇之1種或2種以上之聚縮合物。 具體而言，舉例為聚己二酸伸乙酯二醇、聚己二酸伸丁酯二醇、聚己二酸六亞甲酯二醇、聚間苯二甲酸六甲亞酯二醇、聚己二酸新戊酯二醇、聚己二酸伸乙基伸丙基酯二醇、聚己二酸伸乙基伸丁基酯二醇、聚己二酸伸丁基六亞甲基酯二醇、聚己二酸二伸乙基酯二醇、聚(聚四亞甲基醚)己二酸酯二醇、聚(3-甲基伸戊基己二酸酯)二醇、聚壬二酸伸乙酯二醇、聚癸二酸伸乙酯二醇、聚癸二酸伸丁酯二醇、聚癸二酸伸丁酯二醇及聚對苯二甲酸新戊酯二醇等。Examples of ester diols include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; alkanediols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; and one or more diols selected from phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenyl Methane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, etc. Two or more polycondensates. Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butyl adipate diol, polybutylene hexamethylene adipate diol, poly(diethylene adipate diol), poly(tetramethylene ether) hexamethylene adipate are exemplified. Diol diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene sebacate diol, polybutylene sebacate diol, polyneopentyl terephthalate diol, etc.

作為伸烷基型二醇舉例為例如1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇等之烷二醇；乙二醇、丙二醇、二乙二醇、二丙二醇等之烷二醇；聚乙二醇、聚丙二醇、聚丁二醇等之聚烷二醇；聚四甲亞基二醇等之聚氧伸烷二醇等。Examples of alkylene glycols include alkanediols such as 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; alkanediols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polyoxyalkylene glycols such as polytetramethylene glycol.

作為碳酸酯型二醇舉例為例如碳酸1,4-四亞甲基酯二醇、碳酸1,5-五亞甲基酯二醇、碳酸1,6-六亞甲基酯二醇、碳酸1,2-伸丙基酯二醇、碳酸1,3-伸丙基酯二醇、碳酸2,2-二甲基伸丙基酯二醇、碳酸1,7-七亞甲基酯二醇、碳酸1,8-八亞甲基酯二醇、碳酸1,4-環己酯二醇等。Examples of carbonate-type diols include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, 1,3-propylene carbonate diol, 2,2-dimethylpropylene carbonate diol, 1,7-hepamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexyl carbonate diol, and the like.

作為成為胺基甲酸酯預聚物(UP)之原料的多元異氰酸酯舉例為芳香族聚異氰酸酯、脂肪族聚異氰酸酯、脂環式聚異氰酸酯等。 該等多元異氰酸酯可單獨使用，亦可併用2種以上。 且，該等多元異氰酸酯亦可為三羥甲基丙烷加成型改質體、與水反應之縮二脲型改質體、含有異氰脲酸酯環之異氰脲酸酯型改質體。As a raw material of a urethane prepolymer (UP), polyvalent isocyanate is exemplified by aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and the like. These polyvalent isocyanates may be used alone or in combination of two or more. Furthermore, these polyisocyanates may also be trimethylolpropane addition-type modifiers, biuret-type modifiers reacting with water, or isocyanurate-type modifiers containing isocyanurate rings.

該等中，作為本發明之一態樣所用之多元異氰酸酯，較好為二異氰酸酯，更好為選自4,4’-二苯基甲烷二異氰酸酯(MDI)、2,4-甲苯二異氰酸酯(2,4-TDI)、2,6-甲苯二異氰酸酯(2,6-TDI)、六亞甲基二異氰酸酯(HMDI)及脂環式二異氰酸酯中之1種以上。Among these, the polyisocyanate used as an aspect of the present invention is preferably a diisocyanate, more preferably one or more selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI) and alicyclic diisocyanate.

作為脂環式二異氰酸酯舉例為例如3-異氰酸酯基甲基-3,5,5-三甲基環己基異氰酸酯(異佛爾酮二異氰酸酯，IPDI)、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2,6-環己烷二異氰酸酯等，較好為異佛爾酮二異氰酸酯(IPDI)。Examples of alicyclic diisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., preferably isophorone diisocyanate (IPDI).

本發明之一態樣中，作為成為丙烯酸胺基甲酸酯系樹脂(U1)之主鏈的胺基甲酸酯預聚物(UP)係二醇與二異氰酸酯之反應物，較好為於兩末端具有乙烯性不飽和基之直鏈胺基甲酸酯預聚物。 作為於該直鏈胺基甲酸酯預聚物之兩末端導入乙烯性不飽和基之方法，舉例為使二醇與二異氰酸酯化合物反應而成之直鏈胺基甲酸酯預聚物之末端的NCO基與(甲基)丙烯酸羥基烷酯反應之方法。In one aspect of the present invention, the reaction product of the urethane prepolymer (UP) diol and diisocyanate forming the main chain of the urethane acrylate resin (U1) is preferably a linear urethane prepolymer having ethylenically unsaturated groups at both terminals. As a method of introducing an ethylenically unsaturated group into both ends of the linear urethane prepolymer, there is, for example, a method of reacting an NCO group at the end of a linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound with a hydroxyalkyl (meth)acrylate.

作為(甲基)丙烯酸羥基烷酯舉例為例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

作為成為丙烯酸胺基甲酸酯系樹脂(U1)之側鏈的乙烯基化合物至少包含(甲基)丙烯酸酯。 作為(甲基)丙烯酸酯，較好為選自(甲基)丙烯酸烷酯及(甲基)丙烯酸羥基烷酯之1種以上，更好併用(甲基)丙烯酸烷酯及(甲基)丙烯酸羥基烷酯。At least (meth)acrylate is contained as a vinyl compound used as a side chain of an urethane acrylate resin (U1). The (meth)acrylate is preferably at least one selected from alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates, and it is more preferable to use alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates in combination.

併用(甲基)丙烯酸烷酯及(甲基)丙烯酸羥基烷酯時，相對於(甲基)丙烯酸烷酯100質量份，作為(甲基)丙烯酸羥基烷酯之調配比例，較好為0.1~100質量份，更好為0.5~30質量份，又更好為1.0~20質量份，再更好為1.5 ~10質量份。When an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate are used together, the blending ratio of the hydroxyalkyl (meth)acrylate is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass, relative to 100 parts by mass of the alkyl (meth)acrylate.

作為該(甲基)丙烯酸烷酯所具有之烷基碳數較好為1~24，更好為1~12，又更好為1~8，再更好為1~3。The carbon number of the alkyl group which this alkyl (meth)acrylate has is preferably 1-24, More preferably, it is 1-12, More preferably, it is 1-8, More preferably, it is 1-3.

又，作為(甲基)丙烯酸羥基烷酯，舉例為與用以於上述直鏈胺基甲酸酯預聚物之兩末端導入乙烯性不飽和基所用之(甲基)丙烯酸羥基烷酯相同者。Moreover, as hydroxyalkyl (meth)acrylate, the thing similar to the hydroxyalkyl (meth)acrylate used for introducing ethylenically unsaturated group into both terminals of the above-mentioned linear urethane prepolymer is mentioned, for example.

作為(甲基)丙烯酸烷酯以外之乙烯基化合物，舉例為例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯等之芳香族烴系乙烯基化合物；甲基乙烯醚、乙基乙烯醚等之乙烯醚類；乙酸乙烯酯、丙酸乙烯酯、(甲基)丙烯腈、N-乙烯基吡咯啶酮、(甲基)丙烯酸、馬來酸、富馬酸、依康酸、甲基(丙烯醯胺)等之含極性基之單體；等。 該等可單獨使用，亦可併用2種以上。Vinyl compounds other than alkyl (meth)acrylates include, for example, aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; polar group-containing monomers such as vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and methyl (acrylamide); These may be used alone or in combination of two or more.

作為乙烯基化合物中之(甲基)丙烯酸酯之含量，相對於該乙烯基化合物之全量(100質量%)，較好為40~100質量%，更好為65~100質量%，又更好為80~100質量%，再更好為90~100質量%。The content of the (meth)acrylate in the vinyl compound is preferably from 40 to 100% by mass, more preferably from 65 to 100% by mass, more preferably from 80 to 100% by mass, still more preferably from 90 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound.

作為乙烯基化合物中之(甲基)丙烯酸烷酯及(甲基)丙烯酸羥基烷酯之合計含量，相對於該乙烯基化合物之總量(100質量%)，較好為40~100質量%，更好為65~100質量%，又更好為80~100質量%，再更好為90~100質量%。The total content of the alkyl (meth)acrylate and the hydroxyalkyl (meth)acrylate in the vinyl compound is preferably from 40 to 100% by mass, more preferably from 65 to 100% by mass, more preferably from 80 to 100% by mass, and still more preferably from 90 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound.

本發明之一態樣所用之丙烯酸胺基甲酸酯系樹脂(U1)中，源自胺基甲酸酯預聚物(UP)之構成單位(u11)與源自乙烯基化合物之構成單位(u12)之含量比[(u11)/(u12)]，以質量比計，較好為10/90~80/20，更好為20/80~70/30，又更好為30/70~60/40，再更好為35/65~ 55/45。In the urethane acrylate resin (U1) used in one aspect of the present invention, the content ratio [(u11)/(u12)] of the constituent unit (u11) derived from the urethane prepolymer (UP) to the constituent unit (u12) derived from the vinyl compound is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and still more preferably 3 in terms of mass ratio. 5/65~55/45.

[烯烴系樹脂] 作為樹脂組成物(y)所含之樹脂，作為較佳之烯烴系樹脂，係至少具有源自烯烴單體之構成單位的聚合物。 作為上述烯烴單體，較好為碳數2~8之α-烯烴，具體而言舉例為乙烯、丙烯、丁烯、異丁烯、1-己烯等。 該等中，較好為乙烯及丙烯。[Olefin resin] As the resin contained in the resin composition (y), a preferable olefin-based resin is a polymer having at least a constituent unit derived from an olefin monomer. The above-mentioned olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, and specifically, ethylene, propylene, butene, isobutylene, 1-hexene, and the like are exemplified. Among these, ethylene and propylene are preferred.

作為具體之烯烴系樹脂舉例為例如超低密度聚乙烯(VLDPE，密度：880kg/m3 以上且未達910kg/m3 )、低密度聚乙烯(LDPE，密度：910kg/m3 以上且未達915 kg/m3 )、中密度聚乙烯(MDPE，密度：915kg/m3 以上且未達942kg/m3 )、高密度聚乙烯(HDPE，密度：942kg/m3 以上)、直鏈狀低密度聚乙烯等之聚乙烯樹脂；聚丙烯樹脂(PP)；聚丁烯樹脂(PB)；乙烯-丙烯共聚物；烯烴系彈性體(TPO)；乙烯-乙酸乙烯酯共聚物(EVA)；乙烯-丙烯-(5-亞乙基-2-降冰片烯)等之烯烴系三元共聚物；等。As a specific olefin resin, for example, ultra-low density polyethylene (VLDPE, density: 880kg/m3 More than but less than 910kg/m3 ), low density polyethylene (LDPE, density: 910kg/m3 More than but less than 915 kg/m3 ), medium density polyethylene (MDPE, density: 915kg/m3 More than but less than 942kg/m3 ), high-density polyethylene (HDPE, density: 942kg/m3 Polyethylene resins such as the above), linear low-density polyethylene, etc.; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin-based elastomer (TPO); ethylene-vinyl acetate copolymer (EVA);

本發明之一態樣中，烯烴系樹脂亦可為進而施以選自酸改質、羥基改質、及丙烯酸改質之1種以上改質之改質烯烴系樹脂。In one aspect of the present invention, the olefin-based resin may be further modified by one or more types of modification selected from acid modification, hydroxyl modification, and acrylic modification.

例如作為對烯烴系樹脂施以酸改質之酸改質烯烴系樹脂，舉例為對上述之無改質烯烴系樹脂接枝聚合不飽和羧酸或其酸酐而成之改質聚合物。 作為上述不飽和羧酸或其酸酐舉例為例如馬來酸、富馬酸、依康酸、檸康酸、戊烯二酸、四氫鄰苯二甲酸、烏頭酸、(甲基)丙烯酸、馬來酸酐、依康酸酐、戊烯二酸酐、檸康酸酐、烏頭酸酐、降冰片烯二羧酸酐、四氫鄰苯二甲酸酐等。 又，不飽和羧酸或其酸酐可單獨使用，亦可併用2種以上。For example, as an acid-modified olefin-based resin that is acid-modified to an olefin-based resin, a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof to the above-mentioned unmodified olefin-based resin is exemplified. Examples of the unsaturated carboxylic acid or its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like. Moreover, unsaturated carboxylic acid or its anhydride may be used individually, and may use 2 or more types together.

作為對烯烴系樹脂施以丙烯酸改質之丙烯酸改質烯烴系樹脂，舉例為對主鏈的上述無改質烯烴系樹脂接枝聚合作為側鏈之(甲基)丙烯酸烷酯之改質聚合物。 作為上述(甲基)丙烯酸烷酯所具有的烷基之碳數較好為1~20，更好為1~16，又更好為1~12。 作為上述(甲基)丙烯酸烷酯舉例為例如與作為後述之單體(a1’)而可選擇之化合物相同者。Examples of the acrylic-modified olefin-based resin in which an olefin-based resin is modified with acrylic acid include a modified polymer in which an alkyl (meth)acrylate is graft-polymerized as a side chain to the above-mentioned unmodified olefin-based resin in the main chain. As carbon number of the alkyl group which the said alkyl (meth)acrylate has, Preferably it is 1-20, More preferably, it is 1-16, More preferably, it is 1-12. Examples of the above-mentioned alkyl (meth)acrylate include, for example, the same compounds that can be selected as the monomer (a1') described later.

作為對烯烴系樹脂施以羥基改質之羥基改質烯烴系樹脂，舉例為對主鏈的上述無改質烯烴系樹脂接枝聚合含羥基之化合物之改質聚合物。 作為上述含羥基之化合物舉例為例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等之(甲基)丙烯酸羥基烷酯類；乙烯醇、烯丙醇等之不飽和醇類等。Examples of the hydroxy-modified olefin-based resin obtained by modifying the olefin-based resin with a hydroxyl group include a modified polymer obtained by graft-polymerizing a hydroxyl-containing compound to the above-mentioned unmodified olefin-based resin in the main chain. Examples of the hydroxyl group-containing compound include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and unsaturated alcohols such as vinyl alcohol and allyl alcohol.

(丙烯酸胺基甲酸酯系樹脂及烯烴系樹脂以外之樹脂) 本發明之一態樣中，樹脂組成物(y)中，在不損及本發明效果之範圍內，可含有丙烯酸胺基甲酸酯系樹脂及烯烴系樹脂以外之樹脂。 作為此等樹脂舉例為例如聚氯乙烯、聚偏氯乙烯、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯醇共聚物等之乙烯系樹脂；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等之聚酯系樹脂；聚苯乙烯；丙烯腈-丁二烯-苯乙烯共聚物；三乙酸纖維素；聚碳酸酯；不相當於丙烯酸胺基甲酸酯系樹脂之聚胺基甲酸酯；聚甲基戊烯；聚碸；聚醚醚酮；聚醚碸；聚苯硫醚；聚醚醯亞胺；聚醯亞胺等之聚醯亞胺系樹脂；聚醯胺系樹脂；丙烯酸樹脂；氟系樹脂等。(Acrylic urethane resins and resins other than olefin resins) In one aspect of the present invention, the resin composition (y) may contain resins other than urethane-acrylic resins and olefin-based resins within the range that does not impair the effects of the present invention. Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; Polyether ether ketone; polyether ketone; polyphenylene sulfide; polyether imide; polyimide resin such as polyimide; polyamide resin; acrylic resin; fluorine resin, etc.

惟，基於膨脹性粒子膨脹時，作成易於表面形成凹凸之膨脹性基材層(Y1)之觀點，樹脂組成物(y)中之丙烯酸胺基甲酸酯系樹脂及烯烴系樹脂以外之樹脂含有比例較少較好。 作為丙烯酸胺基甲酸酯系樹脂及烯烴系樹脂以外之樹脂含有比例，相對於樹脂組成物(y)中所含之樹脂總量100質量份，較好為未達30質量份，更好未達20質量份，又更好未達10質量份，再更好未達5質量份，又再更好未達1質量份。However, from the viewpoint of forming an expandable substrate layer (Y1) that tends to form unevenness on the surface when the expandable particles expand, it is preferable that the resin composition (y) contains less resin than the urethane-acrylic resin and the olefin-based resin. The proportion of resins other than urethane-acrylic resins and olefin-based resins is preferably less than 30 parts by mass, more preferably less than 20 parts by mass, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, still more preferably less than 1 part by mass, based on 100 parts by mass of the total resin contained in the resin composition (y).

[無溶劑型樹脂組成物(y1)] 作為樹脂組成物(y)之一態樣，舉例為調配有質量平均分子量(Mw)為50000以下之具有乙烯性不飽和基之寡聚物與能量線聚合性單體與上述熱膨脹性粒子而成，未調配溶劑之無溶劑型樹脂組成物(y1)。 無溶劑型樹脂組成物(y1)雖未調配溶劑，但係能量線聚合性單體有助於提高前述寡聚物之可塑性者。 藉由對由無溶劑型樹脂組成物(y1)形成之塗膜照射能量線，而於膨脹性粒子膨脹時，容易形成易於表面形成凹凸之膨脹性基材層(Y1)，尤其容易形成滿足上述要件(1)及(2)之熱膨脹性基材層(Y1-1)。[Solvent-free resin composition (y1)] An example of the resin composition (y) is a solvent-free resin composition (y1) in which an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer, and the above-mentioned heat-expandable particles are blended, and no solvent is blended. Although the solvent-free resin composition (y1) does not contain a solvent, the energy ray polymerizable monomer contributes to the improvement of the plasticity of the aforementioned oligomer. By irradiating the coating film formed of the solvent-free resin composition (y1) with energy rays, when the expandable particles expand, it is easy to form an expandable base material layer (Y1) that tends to form unevenness on the surface, and it is particularly easy to form a thermally expandable base material layer (Y1-1) that satisfies the above requirements (1) and (2).

又，針對於無溶劑型樹脂組成物(y1)中調配之膨脹性粒子之種類及形狀、調配量(含量)，與樹脂組成物(y)相同而如前述。Also, the type, shape, and compounding amount (content) of the expandable particles compounded in the solvent-free resin composition (y1) are the same as those for the resin composition (y) and are as described above.

無溶劑型樹脂組成物(y1)中所含之前述寡聚物之質量平均分子量(Mw)為50000以下，但較好為1000~ 50000，更好為2000~40000，又更好為3000~35000，再更好為4000~30000。The mass average molecular weight (Mw) of the aforementioned oligomer contained in the solvent-free resin composition (y1) is 50000 or less, preferably 1000-50000, more preferably 2000-40000, still more preferably 3000-35000, still more preferably 4000-30000.

又，作為前述寡聚物，只要為上述樹脂組成物(y)中所含之樹脂中，質量平均分子量為50000以下之具有乙烯性不飽和基者即可，但較好為上述之胺基甲酸酯預聚物(UP)。 又，作為該寡聚物亦可使用具有乙烯性不飽和基之改質烯烴系樹脂。In addition, the aforementioned oligomer may be any resin contained in the aforementioned resin composition (y) as long as it has an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less, but is preferably the aforementioned urethane prepolymer (UP). Moreover, the modified olefin resin which has an ethylenically unsaturated group can also be used as this oligomer.

無溶劑型樹脂組成物(y1)中前述寡聚物及能量線聚合性單體之合計含量，相對於無溶劑型樹脂組成物(y1)之總量(100質量%)，較好為50~99質量%，更好60~95質量%，又更好65~90質量%，再更好為70~85質量%。The total content of the aforementioned oligomers and energy ray polymerizable monomers in the solvent-free resin composition (y1) is preferably 50-99% by mass, more preferably 60-95% by mass, more preferably 65-90% by mass, still more preferably 70-85% by mass, based on the total amount (100% by mass) of the solvent-free resin composition (y1).

作為能量線聚合性單體舉例為例如(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯氧基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸金剛烷酯、丙烯酸三環癸酯等之脂環式聚合性化合物；丙烯酸苯基羥基丙酯、丙烯酸苄酯、苯氧基環氧乙烷改質丙烯酸酯等之芳香族聚合性化合物；(甲基)丙烯酸四氫糠酯、嗎啉丙烯酸酯、N-乙烯基吡咯啶銅、N-乙烯基己內醯胺等之雜環式聚合性化合物等。 該等能量線聚合性單體可單獨使用，亦可併用2種以上。Examples of energy ray polymerizable monomers include alicyclic polymerizable compounds such as isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, and tricyclodecanyl acrylate; aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate, and phenoxyethylene-modified acrylate; tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, and N-ethylene. Heterocyclic polymeric compounds such as copper pyrrolidine, N-vinylcaprolactam, etc. These energy ray polymerizable monomers may be used alone or in combination of two or more.

前述寡聚物與能量線聚合性單體之調配比(前述寡聚物/能量線聚合性單體)較好為20/80~90/10，更好為30/70~85/15，又更好為35/65~80/20。The blending ratio of the aforementioned oligomer and the energy ray polymerizable monomer (the aforementioned oligomer/energy ray polymerizable monomer) is preferably 20/80-90/10, more preferably 30/70-85/15, still more preferably 35/65-80/20.

本發明之一態樣中，無溶劑型樹脂組成物(y1)較好進而調配光聚合起始劑。 藉由含有光聚合起始劑，即使藉由比較低能量之能量線照射，亦可充分進行硬化反應。In one aspect of the present invention, the solvent-free resin composition (y1) is preferably further formulated with a photopolymerization initiator. By containing a photopolymerization initiator, even when irradiated with relatively low-energy energy rays, the hardening reaction can be sufficiently advanced.

作為光聚合起始劑，舉例為例如1-羥基-環己基-苯基-酮、苯偶因、苯偶因甲醚、苯偶因***、苯偶因丙醚、苄基苯基硫化物、四甲基秋蘭姆單硫化物、偶氮雙異丁腈、聯苯醯、聯乙醯、8-氯蒽醌等。 該等光聚合起始劑可單獨使用，亦可併用2種以上。As the photopolymerization initiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, diphenylamide, diacetyl, 8-chloroanthraquinone, etc. are exemplified. These photopolymerization initiators may be used alone or in combination of two or more.

光聚合起始劑之調配量，相對於前述寡聚物及能量線聚合性單體之總量(100質量份)，較好為0.01~5質量份，更好為0.01~4質量份，又更好為0.02~3質量份。The compounded amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, more preferably 0.02 to 3 parts by mass relative to the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer.

＜非膨脹性基材層(Y2)＞ 作為構成基材(Y)之非膨脹性基材層(Y2)之形成材料，舉例為例如紙材、樹脂、金屬等。 作為紙材舉例為例如薄片紙、中質紙、上等紙、含浸紙、塗層紙、銅版紙、硫酸紙、玻璃紙等。 作為樹脂舉例為例如聚乙烯、聚丙烯等之聚烯烴樹脂；聚氯乙烯、聚偏氯乙烯、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯醇共聚物等之乙烯系樹脂；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等之聚酯系樹脂；聚苯乙烯；丙烯腈-丁二烯-苯乙烯共聚物；三乙酸纖維素；聚碳酸酯；聚胺基甲酸酯、丙烯酸改性聚胺基甲酸酯等之胺基甲酸酯樹脂；聚甲基戊烯；聚碸；聚醚醚酮；聚醚碸；聚苯硫醚；聚醚醯亞胺、聚醯亞胺等之聚醯亞胺系樹脂；聚醯胺系樹脂；丙烯酸樹脂；氟系樹脂等。 作為金屬舉例為例如鋁、錫、鉻、鈦等。＜Non-expandable substrate layer (Y2)＞ As a formation material of the non-expandable base material layer (Y2) which comprises a base material (Y), paper material, resin, metal, etc. are mentioned, for example. Examples of the paper material include thin paper, medium paper, fine paper, impregnated paper, coated paper, coated paper, sulfuric acid paper, cellophane, and the like. Examples of resins include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; Formate resin; polymethylpentene; polyamide; polyether ether ketone; polyether resin; polyphenylene sulfide; polyimide resin such as polyetherimide, polyimide, etc.; polyamide resin; acrylic resin; Examples of the metal include, for example, aluminum, tin, chromium, titanium, and the like.

該等形成材料可由1種構成，亦可併用2種以上。 作為併用2種以上之形成材料之非膨脹性基材層(Y2)，舉例將紙材以聚乙烯等之熱塑性樹脂層合而成者，或於包含樹脂之樹脂薄膜或薄面之表面形成金屬膜者等。 又，作為金屬層之形成方法舉例為例如藉由真空蒸鍍、濺鍍、離子鍍敷等之PVD法蒸鍍上述金屬之方法，或使用一般黏著劑貼附由上述金屬所成之金屬箔之方法等。These formation materials may consist of 1 type, and may use 2 or more types together. Examples of the non-expandable base layer (Y2) using two or more forming materials include paper materials laminated with thermoplastic resins such as polyethylene, or those in which a metal film is formed on the surface of a resin film or thin surface containing resin. Also, examples of the method of forming the metal layer include a method of vapor-depositing the above-mentioned metal by a PVD method such as vacuum deposition, sputtering, and ion plating, or a method of attaching a metal foil made of the above-mentioned metal using a general adhesive.

再者，基於提高非膨脹性基材層(Y2)與積層之其他層之層間密著性之觀點，非膨脹性基材層(Y2)包含樹脂時，亦可對於非膨脹性基材層(Y2)表面，與上述膨脹性基材層(Y1)同樣，施以利用氧化法或凹凸化法等之表面處理、易接著處理或底塗處理。Furthermore, from the viewpoint of improving the interlayer adhesion between the non-expandable base material layer (Y2) and other laminated layers, when the non-expandable base material layer (Y2) contains a resin, the surface of the non-expandable base material layer (Y2) may also be subjected to surface treatment, adhesion-facilitating treatment, or primer treatment by an oxidation method or a concave-convex method, etc., similarly to the above-mentioned expandable base material layer (Y1).

又，非膨脹性基材層(Y2)包含樹脂時，亦可與該樹脂一起含有樹脂組成物(y)中，亦可含有上述之基材用添加劑。Moreover, when the non-expandable base material layer (Y2) contains resin, it may contain in resin composition (y) together with this resin, and may contain the above-mentioned additive for base materials.

較好非膨脹性基材層(Y2)存在於比上述膨脹性基材層(Y1)更遠離上述第1黏著劑層(X1)的位置，且膨脹性基材層(Y1)與第1黏著劑層(X1)之間不存在非膨脹性基材層(Y2)，前述膨脹性粒子膨脹時之前述非膨脹性基材層(Y2)的儲存模數E’大於前述膨脹性粒子膨脹時之前述膨脹性基材層(Y1)的儲存模數E’。由於膨脹性基材層(Y1)與第1黏著劑層(X1)之間不存在非膨脹性基材層(Y2)，故因膨脹性粒子膨脹而於膨脹性基材層(Y1)表面產生之凹凸，並未經由非膨脹性基材層(Y2)而傳遞至第1黏著劑層(X1)，故於第1黏著劑層(X1)之黏著表面亦容易產生凹凸。又，由於膨脹性粒子膨脹時非膨脹性基材層(Y2)的儲存模數E’大於膨脹性基材層(Y1)的儲存模數E’，故膨脹性粒子膨脹時抑制了膨脹性基材層(Y1)中非膨脹性基材層(Y2)側之表面產生凹凸，其結果，膨脹性基材層(Y1)中之第1黏著劑層(X1)側之表面容易產生凹凸，因此於第1黏著劑層(X1)之黏著表面亦容易產生凹凸。 前述膨脹性粒子膨脹時之非膨脹性基材層(Y2)的儲存模數E’，基於如上述於第1黏著劑層(X1)之黏著表面亦容易產生凹凸之觀點，較好為1.0MPa以上，且基於貼附作業及剝離作業之容易性之觀點、於第2黏著劑層(X2)之黏著表面亦容易產生凹凸之觀點、或輥形體之處理容易性之觀點，較好為1.0×103 MPa以下。基於該等觀點，膨脹性粒子膨脹時之非膨脹性基材層(Y2)的儲存模數E’較好為1.0~ 5.0×102 MPa，更好為1.0×101 ~1.0×102 MPa，又更好為5.0× 101 ~1.0×103 MPa。 又基於上述觀點及防止半導體晶圓貼附於第2黏著劑層(X2)之黏著表面時之位置偏移之觀點，於23℃下的非膨脹性基材層(Y2)的儲存模數E’(23)較好為5.0×101 ~5.0× 104 MPa，更好為1.0×102 ~1.0×104 MPa，又更好為5.0×102 ~ 5.0×103 MPa。 非膨脹性基材層(Y2)係基於上述方法判斷之非膨脹性層。 因此，作為自上述式算出之非膨脹性基材層(Y2)的體積變化率(%)，為未達5體積%，但較好未達2體積%，更好未達1體積%，又更好未達0.1體積%，再更好未達0.01體積%。Preferably, the non-expandable base material layer (Y2) exists at a position farther from the above-mentioned first adhesive layer (X1) than the above-mentioned expandable base material layer (Y1), and there is no non-expandable base material layer (Y2) between the expandable base material layer (Y1) and the first adhesive layer (X1). Since there is no non-expandable base material layer (Y2) between the expandable base material layer (Y1) and the first adhesive layer (X1), the unevenness generated on the surface of the expandable base material layer (Y1) due to the expansion of the expandable particles is not transmitted to the first adhesive layer (X1) through the non-expandable base material layer (Y2), so unevenness is also likely to occur on the adhesive surface of the first adhesive layer (X1). Also, since the storage modulus E' of the non-expandable base material layer (Y2) is greater than the storage modulus E' of the expandable base material layer (Y1) when the expandable particles are expanded, the expansion of the expandable particles suppresses the unevenness of the surface on the non-expandable base material layer (Y2) side of the expandable base material layer (Y1). produce bumps. The storage modulus E' of the non-expandable base material layer (Y2) when the expandable particles are expanded is preferably at least 1.0 MPa in view of the fact that unevenness is likely to occur on the adhesive surface of the first adhesive layer (X1) as described above, and is preferably at most 1.0×10 3 MPa in view of the ease of attachment and peeling operations, the ease of unevenness on the adhesive surface of the second adhesive layer (X2), or the ease of handling of the roll-shaped body. Based on these viewpoints, the storage modulus E' of the non-expandable substrate layer (Y2) when the expandable particles are expanded is preferably from 1.0 to 5.0×10 2 MPa, more preferably from 1.0×10 1 to 1.0×10 2 MPa, still more preferably from 5.0×10 1 to 1.0×10 3 MPa. Based on the above viewpoints and the viewpoint of preventing positional displacement when the semiconductor wafer is attached to the adhesive surface of the second adhesive layer (X2), the storage modulus E'(23) of the non-expandable substrate layer (Y2) at 23°C is preferably 5.0×10 1 ~5.0×10 4 MPa, more preferably 1.0×10 2 ~1.0×10 4 MPa, and more preferably 5.0×10 2 ~5. 0×10 3 MPa. The non-expandable base material layer (Y2) is a non-expandable layer judged based on the above method. Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) calculated from the above formula is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume, more preferably less than 0.1% by volume, and still more preferably less than 0.01% by volume.

又，非膨脹性基材層(Y2)只要體積變化率為上述範圍，則亦可含有熱膨脹性粒子。例如藉由選擇非膨脹性基材層(Y2)中所含之樹脂，即使含有熱膨脹性粒子，亦可將體積變化率調整於上述範圍內。 但，非膨脹性基材層(Y2)中之熱膨脹性粒子之含量越少越好。 作為具體之熱膨脹性粒子之含量，相對於非膨脹性基材層(Y2)之總質量(100質量%)，通常未達3質量%，較好未達1質量%，更好未達0.1質量%，又更好未達0.01質量%，再更好未達0.001質量%。Moreover, the non-expandable base material layer (Y2) may contain thermally expandable particle|grains as long as volume change rate is the said range. For example, by selecting the resin contained in the non-expandable base material layer (Y2), even if thermally expandable particles are contained, the volume change rate can be adjusted within the above-mentioned range. However, the less the content of the thermally expandable particles in the non-expandable base material layer (Y2), the better. The content of specific heat-expandable particles is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass, relative to the total mass (100% by mass) of the non-expandable base material layer (Y2).

＜第1黏著劑層(X1)、第2黏著劑層(X2)＞ 本發明之一態樣所用之黏著薄片具有第1黏著劑層(X1)及第2黏著劑層(X2)。 本發明之製造方法中，第1黏著劑層(X1)之黏著表面與硬質支撐體貼附，第2黏著劑層(X2)之黏著表面與半導體晶圓貼附。＜1st adhesive layer (X1), 2nd adhesive layer (X2)＞ The adhesive sheet used in one aspect of the present invention has a first adhesive layer (X1) and a second adhesive layer (X2). In the manufacturing method of the present invention, the adhesive surface of the first adhesive layer (X1) is attached to the hard support, and the adhesive surface of the second adhesive layer (X2) is attached to the semiconductor wafer.

對第1黏著劑層(X1)要求於膨脹性基材層(Y1)中所含之膨脹性粒子膨脹前，與硬質支撐體之密著性高，可將半導體晶圓充分固定於硬質支撐體之性質。 基於該觀點，於23℃下之第1黏著劑層(X1)之儲存剪切模數G’(23)較好為1.0×108 Pa以下，更好為5.0×107 Pa以下，更好為1.0×107 Pa以下。The first adhesive layer (X1) is required to have high adhesion to the hard support before the expandable particles contained in the expandable base material layer (Y1) expand, and to sufficiently fix the semiconductor wafer to the hard support. From this viewpoint, the storage shear modulus G'(23) of the first adhesive layer (X1) at 23°C is preferably at most 1.0×10 8 Pa, more preferably at most 5.0×10 7 Pa, more preferably at most 1.0×10 7 Pa.

其另一方面，亦要求於膨脹性基材層(Y1)中所含之膨脹性粒子膨脹時，於膨脹性基材層(Y1)之表面產生之凹凸亦可形成於第1黏著劑層(X1)之黏著表面之程度的剛性。 基於該觀點，23℃下之第1黏著劑層(X1)之儲存剪切模數G’(23)較好為1.0×104 Pa以上，更好為5.0×104 Pa以上，更好為1.0×105 Pa以上。On the other hand, when the expandable particles contained in the expandable base material layer (Y1) expand, rigidity is required to the extent that unevenness generated on the surface of the expandable base material layer (Y1) can also be formed on the adhesive surface of the first adhesive layer (X1). From this viewpoint, the storage shear modulus G'(23) of the first adhesive layer (X1) at 23°C is preferably at least 1.0×10 4 Pa, more preferably at least 5.0×10 4 Pa, more preferably at least 1.0×10 5 Pa.

又，第2黏著劑層(X2)不僅要求與半導體晶圓之密著性，亦要求與將該半導體晶圓分割所得之半導體晶片之密著性，並且要求亦抑制該半導體晶片過度沉入第2黏著劑層(X2)之現象。 基於該等觀點，23℃下之第2黏著劑層(X2)之儲存剪切模數G’(23)較好為1.0×104 ~1.0×108 Pa，更好為5.0×104 ~ 5.0×107 Pa，更好為1.0×105 ~1.0×107 Pa以上。 本說明書中，第1黏著劑層(X1)及第2黏著劑層(X2)之儲存剪切模數G’(23)意指藉由實施例記載之方法測定之值。In addition, the second adhesive layer (X2) requires not only adhesion to the semiconductor wafer, but also adhesion to the semiconductor wafers obtained by dividing the semiconductor wafer, and it is also required to suppress excessive sinking of the semiconductor wafer into the second adhesive layer (X2). Based on these viewpoints, the storage shear modulus G'(23) of the second adhesive layer (X2) at 23°C is preferably 1.0×10 4 to 1.0×10 8 Pa, more preferably 5.0×10 4 to 5.0×10 7 Pa, more preferably 1.0×10 5 to 1.0×10 7 Pa or more. In this specification, the storage shear modulus G'(23) of the 1st adhesive layer (X1) and the 2nd adhesive layer (X2) means the value measured by the method described in an Example.

第1黏著劑層(X1)之厚度較好為1~60μm，更好為2~50μm，又更好為3~40μm，再更好為5~30μm。The thickness of the first adhesive layer (X1) is preferably from 1 to 60 μm, more preferably from 2 to 50 μm, more preferably from 3 to 40 μm, still more preferably from 5 to 30 μm.

第2黏著劑層(X2)之厚度較好為1~60μm，更好為2~50μm，又更好為3~40μm，再更好為5~30μm。The thickness of the second adhesive layer (X2) is preferably from 1 to 60 μm, more preferably from 2 to 50 μm, more preferably from 3 to 40 μm, still more preferably from 5 to 30 μm.

第1黏著劑層(X1)及第2黏著劑層(X2)可由包含黏著性樹脂之黏著劑組成物(x)形成。 又，黏著劑組成物(x)根據需要亦可含有交聯劑、黏著賦予劑、聚合性化合物、聚合起始劑等之黏著劑用添加劑。 以下針對黏著劑組成物(x)含有之各成分加以說明。The first adhesive layer (X1) and the second adhesive layer (X2) can be formed of an adhesive composition (x) containing an adhesive resin. Moreover, the adhesive agent composition (x) may contain the additive for adhesive agents, such as a crosslinking agent, an adhesive imparting agent, a polymeric compound, and a polymerization initiator, as needed. Each component contained in the adhesive composition (x) will be described below.

(黏著性樹脂) 作為本發明之一態樣所用之黏著性樹脂只要以該樹脂單獨具有黏著性，質量平均分子量(Mw)為1萬以上之聚合物即可。 作為本發明之一態樣所用之黏著性樹脂之質量平均分子量(Mw)，基於提高黏著力之觀點，較好為1萬~200萬，更好為2萬~150萬，又更好為3萬~100萬。(adhesive resin) The adhesive resin used as an aspect of the present invention may be a polymer having adhesiveness alone and a mass average molecular weight (Mw) of 10,000 or more. The mass average molecular weight (Mw) of the adhesive resin used as an aspect of the present invention is preferably from 10,000 to 2 million, more preferably from 20,000 to 1.5 million, and still more preferably from 30,000 to 1 million, from the viewpoint of improving the adhesive force.

作為具體的黏著性樹脂舉例為例如丙烯酸系樹脂、胺基甲酸酯系樹脂、聚異丁烯系樹脂等之橡膠系樹脂、聚酯系樹脂、烯烴系樹脂、矽氧系樹脂、聚乙烯醚系樹脂等。 該等黏著性樹脂可單獨使用，亦可併用2種以上。 且該等黏著性樹脂為具有2種以上之構成單位之共聚物時，該共聚物之形態並未特別限定，可為嵌段共聚物、無規共聚物及接枝共聚物之任一者。Specific adhesive resins include rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based resins. These adhesive resins may be used alone or in combination of two or more. In addition, when the adhesive resin is a copolymer having two or more constituent units, the form of the copolymer is not particularly limited, and may be any of block copolymer, random copolymer, and graft copolymer.

本發明之一態樣所用之黏著性樹脂亦可為於上述黏著性樹脂之側鏈導入聚合性官能基之能量線硬化型之黏著性樹脂。 例如藉由使第2黏著劑層(X2)由包含能量線硬化型之黏著性樹脂之能量線硬化型黏著劑組成物所形成，可藉由照射能量線而使黏著力降低，故所得半導體晶片可容易自第2黏著劑層(X2)拾取。 作為該聚合性官能基舉例為(甲基)丙烯醯基、乙烯基等。 又，作為能量線，舉例為紫外線或電子束，但較好為紫外線。 又，作為照射能量線可使黏著力降低之黏著劑層之形成材料可為含有具有聚合性官能基之單體或寡聚物之能量線硬化型黏著劑組成物。The adhesive resin used in one aspect of the present invention may be an energy ray-curable adhesive resin in which a polymerizable functional group is introduced into a side chain of the aforementioned adhesive resin. For example, by forming the second adhesive layer (X2) from an energy ray-curable adhesive composition containing an energy ray-curable adhesive resin, the adhesive force can be reduced by irradiating energy rays, so that the resulting semiconductor chip can be easily picked up from the second adhesive layer (X2). As this polymerizable functional group, a (meth)acryl group, a vinyl group, etc. are mentioned, for example. Moreover, as an energy ray, an ultraviolet-ray or an electron beam is mentioned, Preferably it is an ultraviolet-ray. Also, the material for forming the adhesive layer whose adhesive force can be lowered by irradiation with energy rays may be an energy-ray-curable adhesive composition containing a monomer or oligomer having a polymerizable functional group.

該等能量線硬化型黏著劑組成物中，較好進而含有光聚合起始劑。 藉由含有光聚合起始劑，即使照射比較低能量之能量線，亦可充分進行硬化反應。 作為光聚合起始劑，舉例為與上述無溶劑型樹脂組成物(y1)中調配者相同者。 光聚合起始劑之含量，相對於能量線硬化型之黏著性樹脂100質量份或具有聚合性官能基之單體或寡聚物100質量份，較好為0.01~10質量份，更好為0.03~5質量份，又更好為0.05~2質量份。In the isoenergy ray-curing adhesive composition, it is preferable to further contain a photopolymerization initiator. By containing a photopolymerization initiator, even if irradiated with relatively low-energy energy rays, the hardening reaction can sufficiently proceed. As a photoinitiator, the same thing as what was prepared in the said non-solvent type resin composition (y1) is mentioned, for example. The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass relative to 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of the monomer or oligomer having a polymerizable functional group.

本發明之一態樣中，基於展現優異黏著力之觀點，黏著性樹脂較好包含丙烯酸系樹脂。尤其藉由第1黏著劑層(X1)由包含丙烯酸系樹脂之黏著劑組成物而形成，可容易於第1黏著劑層表面形成凹凸。In one aspect of the present invention, the adhesive resin preferably includes an acrylic resin from the viewpoint of exhibiting excellent adhesive force. In particular, when the first adhesive layer (X1) is formed of an adhesive composition containing an acrylic resin, unevenness can be easily formed on the surface of the first adhesive layer.

黏著性樹脂中之丙烯酸系樹脂含有比例，相對於黏著劑組成物(x)中所含之黏著性樹脂總量(100質量%)，較好為30~100質量%，更好為50~100質量%，又更好為70~100質量%，再更好為85~100質量%。The content ratio of the acrylic resin in the adhesive resin is preferably from 30 to 100% by mass, more preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass, and still more preferably from 85 to 100% by mass, based on the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x).

作為黏著性樹脂之含量，相對於黏著劑組成物(x)之有效成分總量(100質量%)，較好為35~100質量%，更好為50~100質量%，又更好為60~98質量%，再更好為70 ~95質量%。The content of the adhesive resin is preferably from 35 to 100% by mass, more preferably from 50 to 100% by mass, more preferably from 60 to 98% by mass, still more preferably from 70 to 95% by mass, based on the total active ingredient (100% by mass) of the adhesive composition (x).

(交聯劑) 本發明之一態樣中，黏著劑組成物(x)含有具有官能基之黏著性樹脂時，黏著劑組成物(x)較好進而含有交聯劑。 該交聯劑係與具有官能基之黏著性樹脂反應，以該官能基為交聯起點，使黏著性樹脂彼此交聯者。(crosslinking agent) In one aspect of the present invention, when the adhesive composition (x) contains an adhesive resin having a functional group, the adhesive composition (x) preferably further contains a crosslinking agent. The cross-linking agent reacts with the adhesive resin having a functional group to cross-link the adhesive resins with the functional group as the starting point of cross-linking.

作為交聯劑舉例為例如異氰酸酯系交聯劑、環氧系交聯劑、氮丙啶系交聯劑、金屬螯合物系交聯劑等。 又，該等交聯劑可單獨使用，亦可併用2種以上。 該等交聯劑中，基於提高凝集力，提高黏著力之觀點，及取得容易性等之觀點，較好為異氰酸酯系交聯劑。As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned, for example. Moreover, these crosslinking agents may be used individually, and may use 2 or more types together. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferred from the viewpoints of improving cohesion and adhesion, and ease of acquisition.

交聯劑含量，可藉由黏著性樹脂具有之官能基數而適當調整，但例如相對於具有官能基之黏著性樹脂100質量份，較好為0.01~10質量份，更好為0.03~7質量份，又更好為0.05~5質量份。The content of the crosslinking agent can be appropriately adjusted according to the number of functional groups in the adhesive resin, but for example, it is preferably 0.01-10 parts by mass, more preferably 0.03-7 parts by mass, and more preferably 0.05-5 parts by mass relative to 100 parts by mass of the adhesive resin with functional groups.

(黏著賦予劑) 本發明一態樣中，黏著劑組成物(x)，基於更提高黏著力之觀點，亦可進而含有黏著賦予劑。 本說明書中，所謂「黏著賦予劑」係輔助提高上述黏著性樹脂之黏著力的成分，係指質量平均分子量(Mw)未達1萬之寡聚物，且與上述黏著性樹脂有所區別者。 黏著賦予劑之質量平均分子量(Mw)較好為400~10000，更好為500~8000，又更好為800~5000。(adhesion imparting agent) In one aspect of the present invention, the adhesive composition (x) may further contain an adhesive imparting agent from the viewpoint of further improving the adhesive force. In this specification, "adhesion imparting agent" is a component that assists in improving the adhesive force of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, which is different from the above-mentioned adhesive resin. The mass average molecular weight (Mw) of the adhesion imparting agent is preferably from 400 to 10,000, more preferably from 500 to 8,000, still more preferably from 800 to 5,000.

作為黏著賦予劑舉例為例如松脂系樹脂、萜烯系樹脂、苯乙烯系樹脂、石油腦之熱分解所生成之戊烯、異戊二烯、胡椒鹼、1,3-戊二烯等之C5餾分共聚合所得之C5系石油樹脂、石油腦之熱分解所生成之茚、乙烯基甲苯等之C9餾分共聚合所得之C9系石油樹脂及該等之氫化石油樹脂等。Examples of tackifiers include rosin-based resins, terpene-based resins, styrene-based resins, C5-based petroleum resins obtained by copolymerization of C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene produced by thermal decomposition of naphtha, C9-based petroleum resins obtained by copolymerization of C9 fractions such as indene and vinyltoluene produced by thermal decomposition of naphtha, and hydrogenated petroleum resins.

黏著賦予劑之軟化點較好為60~170℃，更好為65~160℃，又更好為70~150℃。 又，本說明書中，黏著賦予劑之「軟化點」意指依據JIS K2531測定之值。 黏著賦予劑可單獨使用，亦可併用軟化點或構造不同之2種以上。 又，使用2種以上之複數黏著賦予劑時，該等複數黏著賦予劑之軟化點之加權平均較好屬於前述範圍。The softening point of the tackifier is preferably from 60 to 170°C, more preferably from 65 to 160°C, still more preferably from 70 to 150°C. In addition, in this specification, the "softening point" of an adhesive agent means the value measured based on JISK2531. The tackifier may be used alone, or two or more kinds having different softening points or structures may be used in combination. Moreover, when using 2 or more types of plural tackifiers, it is preferable that the weighted average of the softening point of these plural tackifiers falls within the said range.

黏著賦予劑之含量，相對於黏著劑組成物(x)之有效成分總量(100質量%)，較好為0.01~65質量%，更好為0.1~50質量%，又更好為1~40質量%，再更好為2~ 30質量%。The content of the adhesion-imparting agent is preferably from 0.01 to 65% by mass, more preferably from 0.1 to 50% by mass, more preferably from 1 to 40% by mass, still more preferably from 2 to 30% by mass, relative to the total active ingredient (100% by mass) of the adhesive composition (x).

(黏著劑用添加劑) 本發明一態樣中，在不損及本發明效果之範圍內，黏著劑組成物(x)亦可含有上述黏著賦予劑以外之一般黏著劑所使用之黏著劑用添加劑。 作為該等黏著劑用添加劑舉例為例如抗氧化劑、軟化劑(可塑劑)、防鏽劑、顏料、染料、延遲劑、反應促進劑(觸媒)、紫外線吸收劑、抗靜電劑等。 又，該等黏著劑用添加劑各可單獨使用，亦可併用2種以上。(additive for adhesive) In one aspect of the present invention, the adhesive composition (x) may contain adhesive additives used for general adhesives other than the above-mentioned adhesive imparting agent within the range that does not impair the effects of the present invention. Examples of such additives for adhesives include antioxidants, softeners (plasticizers), antirust agents, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, and antistatic agents. In addition, each of these adhesive additives may be used alone, or two or more kinds may be used in combination.

含有該等黏著劑用添加劑時，各黏著劑用添加劑之含量，相對黏著性樹脂100質量份，較好為0.0001 ~20質量份，更好為0.001~10質量份。When these additives for adhesives are contained, the content of each additive for adhesives is preferably 0.0001-20 parts by mass, more preferably 0.001-10 parts by mass, based on 100 parts by mass of the adhesive resin.

又，第1黏著劑層(X1)及第2黏著劑層(X2)較好為非膨脹性黏著劑層。因此，第1黏著劑層(X1)及第2黏著劑層(X2)之形成材料的黏著劑組成物(x)中之膨脹性粒子之含量越極力減少越好。 作為膨脹性粒子之含量，相對於黏著劑組成物(x)之有效成分總量(100質量%)，或相對於第1黏著劑層(X1)及第2黏著劑層(X2)之總質量(100質量%)，較好未達1質量%，更好未達0.1質量%，又更好未達0.01質量%，再更好未達0.001質量%。Also, the first adhesive layer (X1) and the second adhesive layer (X2) are preferably non-expandable adhesive layers. Therefore, the content of the expandable particles in the adhesive composition (x) of the forming material of the first adhesive layer (X1) and the second adhesive layer (X2) should be reduced as much as possible. The content of the expandable particles is preferably less than 1% by mass, more preferably less than 0.1% by mass, more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass relative to the total amount of active ingredients (100% by mass) of the adhesive composition (x), or relative to the total mass (100% by mass) of the first adhesive layer (X1) and the second adhesive layer (X2).

＜剝離材＞ 作為本發明之一態樣所用之黏著薄片亦可於第1黏著劑層(X1)及第2黏著劑層(X2)之黏著表面進而積層剝離材。 作為剝離材舉例為使用兩面經剝離處理之剝離薄片、單面經剝離處理之剝離薄片等，將剝離劑塗佈於剝離材用之基材上者等。＜Releasable material＞ The adhesive sheet used as an aspect of the present invention may be laminated with a release material on the adhesive surfaces of the first adhesive layer (X1) and the second adhesive layer (X2). Examples of the release material include a release sheet with release treatment on both sides, a release sheet with release treatment on one side, etc., and a release agent applied to a base material for the release material.

作為剝離材用基材舉例為例如上等紙、玻璃紙、牛皮紙等之紙類；聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚萘二甲酸乙二酯樹脂等之聚酯樹脂膜，聚丙烯樹脂、聚乙烯樹脂等之烯烴樹脂膜等之塑膠膜；等。Examples of the base material for the release material include paper such as high-quality paper, cellophane, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; plastic films such as olefin resin films such as polypropylene resin and polyethylene resin; and the like.

作為剝離劑舉例為例如矽氧系樹脂、烯烴系樹脂、異戊二烯系樹脂、丁二烯系樹脂等之橡膠系彈性體、長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂等。Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

剝離材厚度並未特別限制，但較好為10~ 200μm，更好為25~170μm，又更好為35~80μm。The thickness of the peeling material is not particularly limited, but is preferably from 10 to 200 μm, more preferably from 25 to 170 μm, and still more preferably from 35 to 80 μm.

[本發明之半導體晶片之製造方法的各步驟] 本發明之製造方法係使用上述黏著薄片之自半導體晶圓製造半導體晶片之方法，具有下述步驟(1)~(3)。 ･步驟(1)：將第1黏著劑層(X1)的黏著表面貼附於硬質支撐體，並將第2黏著劑層(X2)的黏著表面貼附於半導體晶圓的表面之步驟。 ･步驟(2)：將前述半導體晶圓進行分割而得到複數個半導體晶片之步驟。 ･步驟(3)：使前述膨脹性粒子膨脹，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於前述硬質支撐體與第1黏著劑層(X1)之界面P進行分離之步驟。[Each step of the manufacturing method of the semiconductor wafer of the present invention] The manufacturing method of the present invention is a method of manufacturing a semiconductor wafer from a semiconductor wafer using the above-mentioned adhesive sheet, and has the following steps (1) to (3). ･Step (1): A step of attaching the adhesive surface of the first adhesive layer (X1) to the hard support, and attaching the adhesive surface of the second adhesive layer (X2) to the surface of the semiconductor wafer. ･Step (2): The step of dividing the aforementioned semiconductor wafer to obtain a plurality of semiconductor wafers. ･Step (3): Inflate the aforementioned expandable particles, keep the plurality of semiconductor wafers on the second adhesive layer (X2) attached, and separate at the interface P between the aforementioned hard support and the first adhesive layer (X1).

本發明之半導體晶片之製造方法亦可應用於所謂之隱形切割法，亦可應用於先切割法。The manufacturing method of the semiconductor wafer of the present invention can also be applied to the so-called stealth dicing method, and can also be applied to the dicing-first method.

又，本發明一態樣之製造方法較好進而具有下述步驟(4)，更好具有下述步驟(4)~(6)。 ･步驟(4)：於步驟(3)中自前述硬質支撐體分離後，將複數個半導體晶片的與電路面為相反側的背面貼附於具有基材薄膜、黏著劑層及/或接著劑層之轉印膠帶後，將前述黏著薄片自半導體晶片去除之步驟。 ･步驟(5)：將前述轉印膠帶於MD方向拉伸，將複數個半導體晶片彼此之間隔擴展之步驟。 ･步驟(6)：將複數個半導體晶片自前述轉印膠帶分離，獲得半導體晶片之步驟。Moreover, the production method of one aspect of the present invention preferably further has the following step (4), more preferably has the following steps (4) to (6). ･Step (4): After separating from the hard support in step (3), attach the backside of the plurality of semiconductor wafers on the opposite side to the circuit surface to the transfer tape with the base film, adhesive layer and/or adhesive layer, and then remove the aforementioned adhesive sheet from the semiconductor wafer. ･Step (5): The step of stretching the aforementioned transfer tape in the MD direction to expand the distance between a plurality of semiconductor wafers. ･Step (6): A step in which a plurality of semiconductor wafers are separated from the aforementioned transfer tape to obtain semiconductor wafers.

圖2係本發明之半導體晶片之製造方法的步驟(1)~(3)之剖面示意圖，圖3係步驟(4)~(6)之示意剖面圖。 以下，邊適當參考圖2及3，邊針對步驟(1)~(4)予以說明。Fig. 2 is a schematic cross-sectional view of steps (1) to (3) of the manufacturing method of the semiconductor wafer of the present invention, and Fig. 3 is a schematic cross-sectional view of steps (4) to (6). Hereinafter, steps (1) to (4) will be described with appropriate reference to FIGS. 2 and 3 .

＜步驟(1)＞ 圖2(a)係顯示使用圖1(a)所示之黏著薄片1a，於硬質支撐體50上貼附半導體晶圓60之狀態之步驟(1)的剖面示意圖。 步驟(1)中，較好將黏著薄片1a之第1黏著劑層(X1)之黏著表面貼附於硬質支撐體50，將第2黏著劑層(X2)之黏著表面貼附半導體晶圓60之形成電路之電路面61上。 又，圖2中雖顯示使用圖1(a)所示之黏著薄片1a之狀態，但於使用具有其他構成之黏著薄片時，亦同樣，較好依序積層硬質支撐體、黏著薄片及半導體晶圓，將黏著薄片之第1黏著劑層(X1)之黏著表面貼附於硬質支撐體，及將第2黏著劑層(X2)之黏著表面貼附半導體晶圓之電路面。＜Step (1)＞ FIG. 2(a) is a schematic cross-sectional view showing the step (1) of attaching the semiconductor wafer 60 on the hard support 50 using the adhesive sheet 1a shown in FIG. 1(a). In step (1), preferably, the adhesive surface of the first adhesive layer (X1) of the adhesive sheet 1a is attached to the hard support 50, and the adhesive surface of the second adhesive layer (X2) is attached to the circuit surface 61 of the semiconductor wafer 60 where the circuit is formed. Also, although FIG. 2 shows the state of using the adhesive sheet 1a shown in FIG. 1(a), when using an adhesive sheet with other structures, it is also the same. It is better to laminate the hard support, the adhesive sheet, and the semiconductor wafer sequentially. The adhesive surface of the first adhesive layer (X1) of the adhesive sheet is attached to the hard support, and the adhesive surface of the second adhesive layer (X2) is attached to the circuit surface of the semiconductor wafer.

硬質支撐體較好貼附於黏著薄片之第1黏著劑層(X1)之黏著表面全面。因此，硬質支撐體較好為板狀。 又，與第1黏著劑層(X1)貼附之硬質支撐體之表面面積較好如圖2所示，為第1黏著劑層(X1)之黏著表面的面積以上。The hard support is preferably attached to the entire adhesive surface of the first adhesive layer (X1) of the adhesive sheet. Therefore, the hard support is preferably in the form of a plate. In addition, the surface area of the rigid support adhered to the first adhesive layer (X1) is preferably equal to or greater than the area of the adhesive surface of the first adhesive layer (X1) as shown in FIG. 2 .

作為構成硬質支撐體之材質舉例為例如SUS等之金屬材料；玻璃、矽晶圓等之非金屬無機材料；環氧樹脂、ABS樹脂、丙烯酸樹脂、工程塑膠、超級工程塑膠、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂等之樹脂材料；玻璃環氧樹脂等之複合材料等，該等中，較好為SUS、玻璃及矽晶圓。 又，作為工程塑膠舉例為尼龍、聚碳酸酯(PC)及聚對苯二甲酸乙二酯(PET)等。 作為超級工程塑膠舉例為聚苯硫醚(PPS)、聚醚碸(PES)及聚醚醚酮(PEEK)等。Examples of the material constituting the rigid support include metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; resin materials such as epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, polyimide resins, and polyamideimide resins; Moreover, examples of engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like. Examples of super engineering plastics include polyphenylene sulfide (PPS), polyethersulfone (PES), and polyetheretherketone (PEEK).

作為硬質支撐體厚度較好為20μm以上50μm以下，更好為60μm以上20μm以下。The thickness of the hard support is preferably from 20 μm to 50 μm, more preferably from 60 μm to 20 μm.

硬質支撐體之楊氏模數，基於提高晶片龜裂之防止性能之觀點，較好為1.0GPa以上，更好為5.0GPa以上，又更好為10GPa以上，再更好為20GPa以上。 又，本說明書中，硬質支撐體之楊氏模數係依據JIS Z2280：1993之靜態楊氏模數試驗方法，於室溫(25℃)測定之值。The Young's modulus of the hard support is preferably at least 1.0 GPa, more preferably at least 5.0 GPa, still more preferably at least 10 GPa, still more preferably at least 20 GPa, from the viewpoint of improving wafer crack prevention performance. In addition, in this specification, the Young's modulus of a rigid support is the value measured at room temperature (25 degreeC) based on the static Young's modulus test method of JISZ2280:1993.

貼附於第2黏著劑層(X2)之黏著表面的半導體晶圓表面較好為形成有電路之電路面。 另一方面，半導體晶圓之與該電路面相反側之面(以下亦稱為「背面」)於下一步驟進行研磨處理，為了將半導體晶圓分割作成複數個半導體晶片，較好為未形成電路或電極等之平坦面。 藉由將第2黏著劑層(X2)之黏著表面貼附於半導體晶圓之電路面，可保護該電路面。The surface of the semiconductor wafer attached to the adhesive surface of the second adhesive layer (X2) is preferably a circuit surface on which a circuit is formed. On the other hand, the surface of the semiconductor wafer opposite to the circuit surface (hereinafter also referred to as "back surface") is subjected to grinding treatment in the next step. In order to divide the semiconductor wafer into a plurality of semiconductor wafers, it is preferably a flat surface on which no circuits or electrodes are formed. By attaching the adhesive surface of the second adhesive layer (X2) to the circuit surface of the semiconductor wafer, the circuit surface can be protected.

本發明之製造方法所用之半導體晶圓可藉由於由矽、SiC(碳化矽)、鎵、砷等構成之半導體晶圓之一表面，以蝕刻法、剝除法等形成電路而獲得。The semiconductor wafer used in the manufacturing method of the present invention can be obtained by forming a circuit on one surface of a semiconductor wafer made of silicon, SiC (silicon carbide), gallium, arsenic, etc., by etching, lift-off, or the like.

又，半導體晶圓必須進行為了適用於隱形切割法而於半導體晶圓內部形成改質領域之處理，或進行為了適用先切割法而自半導體晶圓表面向厚度方向形成溝槽之處理。 預先進行該等處理之半導體晶圓之電路面亦可貼附於第2黏著劑層(X2)之黏著表面。又，本步驟中，亦可將未進行該等處理之半導體晶圓之電路面貼附於第2黏著劑層(X2)之黏著表面後，自半導體晶圓之背面進行該等處理。In addition, the semiconductor wafer must be processed to form modified regions inside the semiconductor wafer in order to apply the stealth dicing method, or to form grooves from the surface of the semiconductor wafer in the thickness direction in order to apply the dicing-first method. The circuit surface of the pre-processed semiconductor wafer can also be attached to the adhesive surface of the second adhesive layer (X2). In addition, in this step, after the circuit surface of the semiconductor wafer that has not been subjected to such treatment is attached to the adhesive surface of the second adhesive layer (X2), the treatment can be performed from the back surface of the semiconductor wafer.

尤其，針對為了適用於隱形切割法而於半導體晶圓內部形成改質領域之處理，較好將半導體晶圓之電路面貼附於第2黏著劑層(X2)之黏著表面後進行。 藉由將半導體晶圓之電路面貼附於第2黏著劑層(X2)之黏著表面後進行改質領域之形成處理，由於半導體晶圓經由黏著薄片貼附於硬質支撐體，故形成改質領域後可能產生之半導體晶圓之翹曲可有效地抑制。In particular, it is preferable to attach the circuit surface of the semiconductor wafer to the adhesive surface of the second adhesive layer (X2) for the process of forming a modified area inside the semiconductor wafer for the stealth dicing method. By attaching the circuit surface of the semiconductor wafer to the adhesive surface of the second adhesive layer (X2) and then performing the formation of the modified domain, since the semiconductor wafer is attached to the hard support through the adhesive sheet, the warping of the semiconductor wafer that may occur after the modified domain is formed can be effectively suppressed.

藉由隱形切割法製造半導體晶片時，作為於半導體晶圓內部形成改質領域之處理，舉例為將半導體晶圓之背面作為雷射光入射斜面，藉由於工作內部配合聚光點照射雷射光，而利用多光子吸收形成改質領域之方法。改質領域形成時，亦形成自改質領域向半導體晶圓厚度方向延伸之龜裂線。When manufacturing semiconductor wafers by the stealth dicing method, as the process of forming modified areas inside the semiconductor wafer, for example, the back surface of the semiconductor wafer is used as a laser light incident slope, and the laser light is irradiated with the laser light inside the work, and the method of using multiphoton absorption to form modified areas. When the modified domain is formed, crack lines extending from the modified domain to the thickness direction of the semiconductor wafer are also formed.

另一方面，為了適用先切割法而自半導體晶圓表面向厚度方向形成溝槽之處理，可於半導體晶圓對第2黏著劑層(X2)之貼附前進行，亦可於貼附後進行。 藉由先切割法製造半導體晶片時，作為自半導體晶圓表面向厚度方向形成溝槽之處理，舉例為使用習知晶圓切割裝置等藉由切割而進行之方法。On the other hand, the process of forming grooves from the surface of the semiconductor wafer to the thickness direction in order to apply the dicing-first method can be performed before or after the semiconductor wafer is attached to the second adhesive layer (X2). When a semiconductor wafer is manufactured by the dicing-first method, the process of forming grooves from the surface of the semiconductor wafer in the thickness direction is, for example, a method of dicing using a conventional wafer dicing device or the like.

又，步驟(1)較好於膨脹性粒子不膨脹之環境下進行。 例如，作為膨脹性粒子使用熱膨脹性粒子時，步驟(1)只要於未達該熱膨脹性粒子之膨脹開始溫度(t)之溫度條件下進行即可，具體而言，較好於0~80℃之環境下(膨脹開始溫度(t)為60~80℃時，為未達膨脹開始溫度(t)之環境下)。Also, step (1) is preferably carried out in an environment where the expandable particles do not expand. For example, when heat-expandable particles are used as expandable particles, step (1) may be carried out at a temperature lower than the expansion start temperature (t) of the heat-expandable particles.

＜步驟(2)＞ 步驟(2)係將前述半導體晶圓進行分割而得到複數個半導體晶片之步驟。 作為分割半導體晶圓之方法，較好為研磨半導體晶圓背面，將半導體晶圓單片化為複數個半導體晶片之方法。 圖2(b)係研磨半導體晶圓60之背面，單片化為複數個半導體晶片時之示意剖面圖。＜Step (2)＞ Step (2) is a step of dividing the aforementioned semiconductor wafer to obtain a plurality of semiconductor wafers. As a method of dividing the semiconductor wafer, a method of grinding the back surface of the semiconductor wafer and singulating the semiconductor wafer into a plurality of semiconductor wafers is preferable. FIG. 2( b ) is a schematic cross-sectional view when the back surface of the semiconductor wafer 60 is ground and singulated into a plurality of semiconductor wafers.

例如，隱形切割法中，本步驟成為將具有改質領域之半導體晶圓，對與電路面相反側之未形成電路之背面進行研磨，將半導體晶圓分割，獲得複數個半導體晶片之步驟。 於隱形切割法中，改質領域由於係於半導體晶圓中之脆質化部分，故藉由研磨半導體晶圓背面，使厚度變薄，或藉由施加研磨之力，破壞半導體晶圓而成為單片化為半導體晶片的起點之領域。其結果，半導體晶圓沿著改質領域及龜裂現而分割，作為複數個半導體晶片予以單片化。For example, in the stealth dicing method, this step is a step in which the semiconductor wafer having modified regions is polished on the backside of the non-circuited side opposite to the circuit surface, and the semiconductor wafer is divided to obtain a plurality of semiconductor wafers. In the stealth dicing method, the reformed area is the brittle part of the semiconductor wafer, so the back surface of the semiconductor wafer is ground to make the thickness thinner, or the semiconductor wafer is destroyed by applying grinding force to become the starting area of the semiconductor wafer. As a result, the semiconductor wafer is divided along the modified regions and cracks, and is singulated as a plurality of semiconductor wafers.

又，於先切割法中，本步驟成為將具有預先於厚度方向形成之溝槽之半導體晶圓，研磨與電路面相反側之未形成電路之背面，分割半導體晶圓，獲得複數個半導體晶片之步驟。 先切割法中，形成於半導體晶圓之溝槽係比半導體晶圓厚度淺的深度之溝槽。此處，本步驟藉由研磨半導體晶圓薄至至少到達溝槽底部之位置，而此該溝槽成為貫通晶圓之切痕，使半導體晶圓進行分割，單片化成複數個半導體晶片。In addition, in the dicing-first method, this step becomes a step of grinding a semiconductor wafer having grooves previously formed in the thickness direction, grinding the non-circuit-formed back surface opposite to the circuit surface, dividing the semiconductor wafer, and obtaining a plurality of semiconductor wafers. In the dicing-first method, the trench formed in the semiconductor wafer is a trench having a depth shallower than the thickness of the semiconductor wafer. Here, this step divides the semiconductor wafer into a plurality of semiconductor wafers by grinding the semiconductor wafer so thin that it reaches at least the position at the bottom of the groove, and the groove becomes a cut through the wafer.

如上述，本發明之製造方法中，由於與硬質支撐體貼附之第1黏著劑層(X1)中並無必要包含膨脹性粒子，故可於半導體晶圓充分固定於硬質支撐體之狀態下，進行用以分割半導體晶圓之背面研磨。其結果，可有效地抑制所得半導體晶片之端部缺損等之弊端，可提高半導體晶片製造時之良率。As mentioned above, in the production method of the present invention, since the first adhesive layer (X1) attached to the hard support does not necessarily contain expandable particles, the backside grinding for dividing the semiconductor wafer can be performed in a state where the semiconductor wafer is sufficiently fixed on the hard support. As a result, defects such as edge chipping of the obtained semiconductor wafer can be effectively suppressed, and the yield rate at the time of semiconductor wafer manufacturing can be improved.

又，步驟(2)中，較好在膨脹性粒子不膨脹之環境下進行。 例如作為膨脹性粒子使用熱膨脹性粒子時，步驟(2)只要於未達該熱膨脹性粒子之膨脹開始溫度(t)之溫度條件下進行即可，具體而言，較好於0~80℃之環境下(膨脹開始溫度(t)為60~80℃時，為未達膨脹開始溫度(t)之環境下)。In addition, in step (2), it is preferable to carry out in an environment where the expandable particles do not expand. For example, when heat-expandable particles are used as the expandable particles, step (2) may be carried out at a temperature lower than the expansion start temperature (t) of the heat-expandable particles.

＜步驟(3)＞ 步驟(3)係使前述膨脹性粒子膨脹，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於前述硬質支撐體與第1黏著劑層(X1)之界面P進行分離之步驟。 圖2(c)係顯示使膨脹性基材層(Y1)中之膨脹性粒子膨脹，於硬質支撐體50與第1黏著劑層(X1)之界面P分離之狀態。 如圖2(c)所示，本步驟中，於膨脹性粒子膨脹時，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於界面P自硬質支撐體50分離，但較好進而於構成前述黏著薄片之各層之層間不分離。＜Step (3)＞ Step (3) is to expand the aforementioned expandable particles, keep the multiple semiconductor wafers on the second adhesive layer (X2) attached, and separate them at the interface P between the aforementioned hard support and the first adhesive layer (X1). Fig. 2(c) shows the state where the expandable particles in the expandable substrate layer (Y1) are expanded and separated at the interface P between the hard support body 50 and the first adhesive layer (X1). As shown in Figure 2(c), in this step, when the expandable particles expand, the plurality of semiconductor wafers on the second adhesive layer (X2) remain attached and are separated from the hard support 50 at the interface P, but it is better not to separate between the layers that constitute the aforementioned adhesive sheet.

本步驟中，作為使膨脹性粒子膨脹之方法，係對應於膨脹性粒子種類而適當決定。 例如作為膨脹性粒子使用熱膨脹性粒子時，於該熱膨脹性粒子之膨脹開始溫度(t)以上之溫度進行加熱處理，使該熱膨脹性粒子膨脹。 此時，作為上述之「膨脹開始溫度(t)以上之溫度」，較好為「膨脹開始溫度(t)+10℃」以上「膨脹開始溫度(t) +60℃」以下，更好為「膨脹開始溫度(t)+15℃」以上「膨脹開始溫度(t)+40℃」以下。In this step, the method for expanding the expandable particles is appropriately determined according to the type of the expandable particles. For example, when heat-expandable particles are used as the expandable particles, the heat-expandable particles are heated at a temperature not lower than the expansion start temperature (t) to expand the heat-expandable particles. In this case, the above-mentioned "temperature above the expansion start temperature (t)" is preferably at least "expansion start temperature (t) + 10°C" and "expansion start temperature (t) + 60°C", more preferably "expansion start temperature (t) + 15°C" or more and "expansion start temperature (t)+40°C" or less.

本發明之製造方法中，藉由使用具有包含膨脹性粒子之膨脹性基材層(Y1)之黏著薄片，使該膨脹性粒子膨脹，於與硬質支撐體貼附之第1黏著劑層(X1)之黏著表面形成凹凸，而調整為可於硬質支撐體與第1黏著劑層(X1)之界面P分離。 因此，可抑制如分離後於硬質支撐體表面殘存一部分第1黏著劑層(X1)般之硬質支撐體的污染，可省略硬質支撐體之洗淨步驟，可提高生產性。In the production method of the present invention, by using an adhesive sheet having an expandable base material layer (Y1) containing expandable particles, the expandable particles are expanded to form irregularities on the adhesive surface of the first adhesive layer (X1) attached to the hard support, and adjusted to allow separation at the interface P between the hard support and the first adhesive layer (X1). Therefore, contamination of the hard support such as a part of the first adhesive layer (X1) remaining on the surface of the hard support after separation can be suppressed, and the cleaning step of the hard support can be omitted, thereby improving productivity.

＜步驟(4)＞ 步驟(4)係於步驟(3)中自前述硬質支撐體分離後，將複數個半導體晶片的與電路面為相反側的背面貼附於具有基材薄膜、黏著劑層及/或接著劑層之轉印膠帶後，將前述黏著薄片自半導體晶片去除之步驟。 圖3(a)顯示將複數個半導體晶片70之背面72貼附於轉印膠帶80後，將黏著薄片1a自半導體晶片70去除之狀態。＜Step (4)＞ Step (4) is a step of removing the above-mentioned adhesive sheet from the semiconductor wafer after separating from the aforementioned hard support in step (3), after attaching the backs of the plurality of semiconductor wafers on the opposite side to the circuit surface to the transfer tape having a base film, an adhesive layer and/or an adhesive layer. FIG. 3( a ) shows a state in which the adhesive sheet 1 a is removed from the semiconductor wafer 70 after the back surfaces 72 of a plurality of semiconductor wafers 70 are attached to the transfer tape 80 .

本步驟中，黏著薄片1a具有之第2黏著劑層(X2)係由能量線硬化型黏著劑組成物形成之層時，亦可照射能量線，使第2黏著劑層(X2)之黏著力降低，去除黏著薄面1a。 用以使第2黏著劑層(X2)之黏著力降低所照射之能量線較好自黏著薄片側進行照射。 去除黏著薄片1a後，複數個半導體晶片70之電路面71露出，將背面72貼附於轉印膠帶80。In this step, when the second adhesive layer (X2) of the adhesive sheet 1a is a layer formed of an energy ray-curable adhesive composition, energy rays may also be irradiated to reduce the adhesive force of the second adhesive layer (X2) and remove the adhesive thin surface 1a. The energy ray irradiated to reduce the adhesive force of the second adhesive layer (X2) is preferably irradiated from the side of the adhesive sheet. After removing the adhesive sheet 1a, the circuit surfaces 71 of the plurality of semiconductor chips 70 are exposed, and the back surfaces 72 are attached to the transfer tape 80 .

轉印膠帶80係設計為藉由於MD方向伸長而伸展者，係設計為可使複數個半導體晶片70彼此之間隔擴展的黏著膠帶。 本發明一態樣中使用之轉印膠帶係具有基材薄膜、黏著劑層及/或接著劑層者，但作為具體構成，舉例為例如以下之(1)~(3)之態樣。 (1)依序積層基材薄膜及黏著劑層而成之轉印膠帶。 (2)依序積層基材薄膜及接著劑層而成之轉印膠帶。 (3)依序積層基材薄膜、黏著劑層及接著劑層而成之轉印膠帶。The transfer tape 80 is designed to be stretched by elongation in the MD direction, and is designed as an adhesive tape that can expand the distance between a plurality of semiconductor wafers 70 . The transfer tape used in one aspect of the present invention has a base film, an adhesive layer, and/or an adhesive layer, but as specific configurations, for example, the following aspects (1) to (3) are exemplified. (1) A transfer tape made by sequentially laminating the base film and the adhesive layer. (2) A transfer tape made by sequentially laminating the base film and the adhesive layer. (3) A transfer tape made by sequentially laminating a base film, an adhesive layer, and an adhesive layer.

圖3中，顯示使用上述(1)之態樣的轉印膠帶時之情況，係顯示於依序積層基材薄膜81及黏著劑層82而成之轉印膠帶80的黏著劑層82上貼附複數個半導體晶片70之背面72之狀態。In FIG. 3 , when the transfer tape of the above (1) aspect is used, it shows the state where the back surfaces 72 of a plurality of semiconductor chips 70 are attached to the adhesive layer 82 of the transfer tape 80 formed by sequentially laminating the base film 81 and the adhesive layer 82.

(基材薄膜) 作為構成轉印膠帶之基材薄膜，舉例為例如包含選自聚氯乙烯樹脂、聚酯樹脂(聚對苯二甲酸乙二酯等)、丙烯酸樹脂、聚碳酸酯樹脂、聚乙烯樹脂、聚丙烯樹脂、丙烯腈・丁二烯・苯乙烯樹脂、聚醯亞胺樹脂、聚胺基甲酸酯樹脂及聚苯乙烯樹脂等之一種以上樹脂之樹脂薄膜。 又，構成轉印膠帶之基材薄膜較好含有熱塑性彈性體、橡膠系材料，更好含有熱塑性彈性體。 作為熱塑性彈性體舉例為胺基甲酸酯系彈性體、烯烴系彈性體、氯乙烯系彈性體、聚酯系彈性體、苯乙烯系彈性體、丙烯酸系彈性體、醯胺系彈性體等。(substrate film) As the base film constituting the transfer tape, for example, a resin film containing one or more resins selected from polyvinyl chloride resin, polyester resin (polyethylene terephthalate, etc.), acrylic resin, polycarbonate resin, polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene resin, polyimide resin, polyurethane resin, and polystyrene resin. Also, the base film constituting the transfer tape preferably contains a thermoplastic elastomer or a rubber-based material, more preferably contains a thermoplastic elastomer. Examples of thermoplastic elastomers include urethane-based elastomers, olefin-based elastomers, vinyl chloride-based elastomers, polyester-based elastomers, styrene-based elastomers, acrylic-based elastomers, and amide-based elastomers.

基材薄膜可為單層構成，亦可為2層以上積層而成之複層構成。 又，基材薄膜亦可進而含有顏料、染料、難燃劑、可塑劑、抗靜電劑、滑劑、填料等之各種添加劑。 作為構成轉印膠帶之基材薄膜厚度，較好為20~300 μm，更好為30~250μm，又更好為40~200μm。The base film may be composed of a single layer or a multi-layer composed of two or more layers. In addition, the base film may further contain various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, and fillers. The thickness of the base film constituting the transfer tape is preferably from 20 to 300 μm, more preferably from 30 to 250 μm, still more preferably from 40 to 200 μm.

(黏著劑層) 作為構成轉印膠帶之黏著劑層，可為自上述第1黏著劑層(X1)及第2黏著劑層(X2)之形成材料的黏著劑組成物(x)所形成之層，但較好為自適合作為第2黏著劑層(X2)之形成材料的上述能量線硬化型黏著劑組成物所形成之能量線硬化型黏著劑層。(adhesive layer) The adhesive layer constituting the transfer tape may be a layer formed from the adhesive composition (x) which is the forming material of the first adhesive layer (X1) and the second adhesive layer (X2), but is preferably an energy ray-curable adhesive layer formed from the above-mentioned energy ray-curable adhesive composition which is suitable as a forming material for the second adhesive layer (X2).

構成轉印膠帶之黏著劑層若為能量線硬化型黏著劑層，則步驟(6)之拾取步驟作業性變良好。 但，於步驟(4)中去除黏著薄片時照射能量線之情況，較好以使轉印膠帶之能量線硬化型黏著劑層之黏著力不降低之方式，自黏著薄片側照射去除黏著薄片時之能量線。If the adhesive layer constituting the transfer tape is an energy ray-curable adhesive layer, the workability of the pick-up step in step (6) becomes better. However, when irradiating energy rays when removing the adhesive sheet in step (4), it is preferable to irradiate the energy rays when removing the adhesive sheet from the side of the adhesive sheet so that the adhesive force of the energy ray-curable adhesive layer of the transfer tape is not reduced.

作為構成轉印膠帶之黏著劑層之厚度，較好為1~100μm，更好為3~50μm，又更好為5~40μm。The thickness of the adhesive layer constituting the transfer tape is preferably from 1 to 100 μm, more preferably from 3 to 50 μm, still more preferably from 5 to 40 μm.

(接著劑層) 作為構成轉印膠帶之接著劑層，較好為自包含黏合劑樹脂及熱硬化性成分之接著劑組成物形成之層。 作為黏合劑樹脂，舉例為例如丙烯酸系樹脂、聚酯樹脂、胺基甲酸酯樹脂、丙烯酸胺基甲酸酯樹脂、聚矽氧樹脂、橡膠系聚合物、苯氧樹脂等，但較好為丙烯酸系樹脂。 作為熱硬化性成分，較好包含環氧樹脂及熱硬化劑。(adhesive layer) The adhesive layer constituting the transfer tape is preferably a layer formed from an adhesive composition containing an adhesive resin and a thermosetting component. Examples of the binder resin include acrylic resins, polyester resins, urethane resins, acrylic urethane resins, silicone resins, rubber-based polymers, and phenoxy resins, but acrylic resins are preferred. As a thermosetting component, it is preferable to contain an epoxy resin and a thermosetting agent.

作為構成轉印膠帶之接著劑層厚度，較好為1~100μm，更好為5~75μm，又更好為5~50μm。The thickness of the adhesive layer constituting the transfer tape is preferably from 1 to 100 μm, more preferably from 5 to 75 μm, still more preferably from 5 to 50 μm.

＜步驟(5)＞ 步驟(5)係將轉印膠帶於MD方向拉伸，將複數個半導體晶片彼此之間隔擴展之步驟。 如圖3(b)所示，將轉印膠帶80於MD方向拉伸，將複數個半導體晶片70彼此之間隔擴展，而使下一步驟之拾取性良好。＜Step (5)＞ Step (5) is a step of stretching the transfer tape in the MD direction to expand the distance between a plurality of semiconductor wafers. As shown in FIG. 3( b ), the transfer tape 80 is stretched in the MD direction to expand the distance between the plurality of semiconductor wafers 70 , so that the pick-up performance in the next step is improved.

＜步驟(6)＞ 步驟(6)係將複數個半導體晶片自前述轉印膠帶分離，獲得半導體晶片之步驟。 圖3(c)係顯示使用上述(1)之態樣之轉印膠帶，於本步驟中拾取，獲得複數個半導體晶片70之狀態。 此處，所使用之轉印膠帶係具有能量線硬化型黏著劑層者之情況，藉由照射能量線，可使黏著力降低，使拾取性良好。 又，此時能量線較好自基材薄膜側照射。＜Step (6)＞ Step (6) is a step of separating a plurality of semiconductor wafers from the aforementioned transfer tape to obtain semiconductor wafers. FIG. 3( c ) shows the state in which a plurality of semiconductor wafers 70 are obtained by picking up the transfer tape of the above (1) in this step. Here, the transfer tape used has an energy ray-curable adhesive layer, and by irradiating the energy ray, the adhesive force can be reduced and the pick-up property can be improved. Also, at this time, energy rays are preferably irradiated from the base film side.

作為轉印膠帶使用上述(2)及(3)之態樣的轉印膠帶時，本步驟之拾取時，接著劑層固黏殘存於半導體晶片背面，可獲得附接著劑層之半導體晶片，可省略黏合步驟。 [實施例]When the transfer tapes of the above (2) and (3) are used as the transfer tape, when picking up in this step, the adhesive layer remains on the back of the semiconductor wafer, and the semiconductor wafer with the adhesive layer attached can be obtained, and the bonding step can be omitted. [Example]

本發明係藉由以下實施例具體加以說明，但本發明並非限定於以下實施例者。又，以下之製造例及實施例中之物性值係藉由以下方法測定之值。The present invention is specifically described by the following examples, but the present invention is not limited to the following examples. Moreover, the physical property value in the following manufacture example and an Example is the value measured by the following method.

＜質量平均分子量(Mw)＞ 使用凝膠滲透層析裝置(TOSOH股份有限公司製，製品名「HLC-8020」)，於下述條件下測定，使用以標準聚苯乙烯換算所測定之值。 (測定條件) ・管柱：「TSK保護管柱HXL-L」「TSK gel G2500HXL」「TSK gel G2000HXL」「TSK gel G1000HXL」(均為TOSOH股份有限公司製)依序連結者。 ・管柱溫度：40℃ ・展開溶劑：四氫呋喃 ・流速：1.0mL/分鐘＜Mass average molecular weight (Mw)＞ Using a gel permeation chromatography apparatus (manufactured by TOSOH Co., Ltd., product name "HLC-8020"), it measured under the following conditions, and used the value measured in standard polystyrene conversion. (measurement conditions) ・Column: "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", "TSK gel G1000HXL" (all made by TOSOH Co., Ltd.) connected in sequence. ・Column temperature: 40°C ・Developing solvent: Tetrahydrofuran ・Flow rate: 1.0mL/min

＜各層厚度之測定＞ 使用TECLOCK股份有限公司製之定壓厚度測定器(型號「PG-02J」，標準規格：依據JIS K6783、Z1720、Z1709)測定。＜Measurement of thickness of each layer＞ Measured using a constant-pressure thickness measuring device manufactured by TECLOCK Co., Ltd. (model "PG-02J", standard specification: in accordance with JIS K6783, Z1720, Z1709).

＜熱膨脹性基材層(Y1)之儲存模數E’＞ 將形成之熱膨脹性基材層(Y1)作成縱5mm×橫30mm×厚200μm之大小，將去除剝離材者作為試驗樣品。 使用動態黏彈性測定裝置(TA Instrument公司製，製品名「DMAQ800」)，以試驗開始溫度0℃、試驗結束溫度300℃、升溫速度3℃/分鐘，振動數1Hz、振幅20μm之條件，測定特定溫度下之該試驗樣品之儲存模數E’。<Storage modulus E' of thermally expandable substrate layer (Y1)> The formed heat-expandable base material layer (Y1) was made into the size of 5 mm in length x 30 mm in width x 200 micrometers in thickness, and what removed the peeling material was made into the test sample. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), the storage modulus E' of the test sample at a specific temperature was measured under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, a vibration frequency of 1 Hz, and an amplitude of 20 μm.

＜第1黏著劑層(X1)及第2黏著劑層(X2)之儲存剪切模數G’＞ 將形成之第1黏著劑層(X1)及第2黏著劑層(X2)作成直徑8mm之圓形者，去除剝離材，重疊作成厚3mm作為試驗樣品。 使用黏彈性測定裝置(Anton Parr公司製，製品名「MCR300」)，以試驗開始溫度0℃、試驗結束溫度300℃、升溫速度3℃/分鐘，振動數1Hz之條件，藉由扭轉剪切法，測定特定溫度下之試驗樣品之儲存剪切模數G’。<Storage shear modulus G' of the first adhesive layer (X1) and the second adhesive layer (X2)> Make the first adhesive layer (X1) and the second adhesive layer (X2) into a circle with a diameter of 8 mm, remove the peeling material, and overlap to make a thickness of 3 mm as a test sample. Using a viscoelasticity measuring device (manufactured by Anton Parr, product name "MCR300"), the storage shear modulus G' of the test sample at a specific temperature was measured by the torsional shear method under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, and a vibration frequency of 1 Hz.

＜探針觸黏值＞ 將成為測定對象之基材層切斷為一邊10mm之正方形後，於23℃、50%RH(相對濕度)之環境下靜置24小時者作為試驗樣品。 於23℃、50%RH(相對濕度)之環境下，使用TACKING試驗機(日本特殊測器股份有限公司製，製品名「NTS-4800」)，依據JIS Z0237:1991測定試驗樣品表面之探針觸黏值。 具體而言，將直徑5mm之不鏽鋼製之探針以1秒、接觸荷重0.98N/cm2 接觸試驗樣品之表面後，測定該探針以10mm/秒之速度，自試驗樣品表面離開時之必要力，將所得值作為該試驗樣品之探針觸黏值。<Probe Tack Value> Cut the substrate layer to be measured into a square of 10 mm on one side, and then set it aside for 24 hours at 23°C and 50% RH (relative humidity) as a test sample. In an environment of 23°C and 50%RH (relative humidity), use a TACKING testing machine (manufactured by Nippon Special Sekki Co., Ltd., product name "NTS-4800") to measure the probe touch sticking value on the surface of the test sample according to JIS Z0237:1991. Specifically, after touching a stainless steel probe with a diameter of 5 mm to the surface of the test sample for 1 second with a contact load of 0.98 N/ cm2 , measure the necessary force when the probe leaves the surface of the test sample at a speed of 10 mm/s, and use the obtained value as the probe sticking value of the test sample.

＜第2黏著劑層(X2)之黏著力測定＞ 於形成於剝離薄膜上之第2黏著劑層(X2)之黏著表面上，積層厚50μm之PET薄膜(東洋紡股份有限公司製，製品名「Cosmoshine A4100」)，作成附基材之黏著薄片。 接著，去除剝離薄膜，將露出之第2黏著劑層(X2)之黏著表面貼附於被黏著體之不鏽鋼鋼板(SUS 304 360號研磨)，於23℃、50%RH(相對濕度)環境下，靜置24小時後，於相同溫度下，基於JIS Z0237:2000，藉由180˚剝離法，以拉伸速度300mm/分鐘，測定於23℃下之黏著力。＜Adhesive force measurement of the second adhesive layer (X2)＞ On the adhesive surface of the second adhesive layer (X2) formed on the release film, a 50 μm thick PET film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine A4100") was laminated to form an adhesive sheet with a substrate. Next, the release film was removed, and the exposed adhesive surface of the second adhesive layer (X2) was attached to a stainless steel plate (SUS 304 No. 360 grinding) of the adherend. After standing at 23°C and 50%RH (relative humidity) for 24 hours, at the same temperature, based on JIS Z0237:2000, the adhesive force at 23°C was measured by the 180° peeling method at a tensile speed of 300mm/min.

＜硬質支撐體之楊氏模數＞ 依據JIS Z2280:1993之靜態楊氏模數試驗方法，於室溫(25℃)測定。＜Young's modulus of rigid support＞ Measured at room temperature (25°C) according to the static Young's modulus test method of JIS Z2280:1993.

製造例1(丙烯酸胺基甲酸酯系樹脂之合成) (1)胺基甲酸酯預聚物之合成 於氮氣環境下之反應容器內，對於質量平均分子量1,000之聚碳酸酯二醇100質量份(固形分比)，以聚碳酸酯二醇之羥基與異佛爾酮二異氰酸酯之異氰酸酯基的當量比成為1/1之方式調配異佛爾酮二異氰酸酯，進而添加甲苯160質量份，於氮氣環境下，邊攪拌邊於80℃反應6小時以上直至異氰酸酯濃度達到理論量。 其次，添加將甲基丙烯酸2-羥基乙酯(2-HEMA) 1.44質量份(固形分比)以甲苯30質量份稀釋後之溶液，進而於80℃反應6小時直至兩末端之異氰酸酯基消失，獲得質量平均分子量2.9萬之胺基甲酸酯預聚物。Production Example 1 (Synthesis of Acrylic Urethane Resin) (1) Synthesis of urethane prepolymer In a reaction vessel under a nitrogen atmosphere, for 100 parts by mass (solid fraction) of polycarbonate diol with a mass average molecular weight of 1,000, isophorone diisocyanate was prepared so that the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of isophorone diisocyanate was 1/1, and 160 parts by mass of toluene was added, and reacted at 80° C. for more than 6 hours while stirring under nitrogen atmosphere until the isocyanate concentration reached the theoretical amount. Next, add a solution diluted with 1.44 parts by mass (solid fraction) of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by mass of toluene, and then react at 80°C for 6 hours until the isocyanate groups at both ends disappear to obtain a urethane prepolymer with a mass average molecular weight of 29,000.

(2)丙烯酸胺基甲酸酯系樹脂之合成 於氮氣環境下之反應容器內，添加製造例1所得之胺基甲酸酯預聚物100質量份(固形分比)、甲基丙烯酸甲酯(MMA)117質量份(固形分比)、甲基丙烯酸2-羥基乙酯(2-HEMA)5.1質量份(固形分比)、1-硫代甘油1.1質量份(固形分比)及甲苯50質量份，邊攪拌邊升溫至105℃。 接著，於反應容器內，將自由基起始劑(日本精密化學股份有限公司製，製品名「ABN-E」)2.2質量份(固形分比)以甲苯210質量份稀釋後之溶液，以維持於105℃之狀態歷時4小時予以滴加。 滴加結束後，於105℃反應6小時，獲得質量平均分子量10.5萬之丙烯酸胺基甲酸酯系樹脂的溶液。(2) Synthesis of Acrylic Urethane Resin 100 parts by mass (solid content) of the urethane prepolymer obtained in Production Example 1, 117 parts by mass (solid content) of methyl methacrylate (MMA), 5.1 parts by mass (solid content) of 2-hydroxyethyl methacrylate (2-HEMA), 1.1 parts by mass (solid content) of 1-thioglycerol and 50 parts by mass of toluene were added to the reaction vessel under a nitrogen atmosphere, and the temperature was raised to 105° C. while stirring. Next, in the reaction vessel, a solution diluted with 210 parts by mass of toluene of 2.2 parts by mass (solid fraction) of a free radical initiator (manufactured by Nippon Seiko Chemical Co., Ltd., product name "ABN-E") was added dropwise over 4 hours while maintaining the temperature at 105°C. After completion of the dropwise addition, the reaction was carried out at 105° C. for 6 hours to obtain a solution of an acrylic urethane-based resin with a mass average molecular weight of 105,000.

製造例2(黏著薄片之製作) 製作以下黏著薄片時，各層之形成所使用之黏著性樹脂、添加劑、熱膨脹性粒子、基材及剝離材之細節如以下。 ＜黏著性樹脂＞ ・丙烯酸系共聚物(i)：具有源自由丙烯酸2-乙基己酯(2EHA)/丙烯酸2-羥基乙酯(HEA)=80.0/20.0(質量比)所成之原料單體之構成單位的Mw60萬之丙烯酸系共聚物。 ・丙烯酸系共聚物(ii)：具有源自丙烯酸正丁酯(BA)/甲基丙烯酸甲酯(MMA)/丙烯酸2-羥基乙酯(HEA)/丙烯酸=86.0/8.0/5.0/1.0(質量比)所成之原料單體之構成單位的Mw60萬之丙烯酸系共聚物。 ＜添加劑＞ ・異氰酸酯交聯劑(i)：TOSOH股份有限公司製，製品名「Coronate L」，固形分濃度：75質量%。 ＜熱膨脹性粒子＞ ・熱膨脹性粒子(i)：KUREHA股份有限公司製，製品名「S2640」，膨脹開始溫度(t)=208℃，平均粒徑(D50 )= 24μm，90%粒徑(D90 )=49μm。 ＜剝離材＞ ・重剝離薄膜：於LINTEK股份有限公司製，製品名「SP-PET382150」，聚對苯二甲酸乙二酯(PET)薄膜之單面，設置由矽氧系剝離劑所形成之剝離劑層者，厚：38μm。 ・輕剝離薄膜：於LINTEK股份有限公司製，製品名「SP-PET381031」，PET薄膜之單面，設置由矽氧系剝離劑所形成之剝離劑層者，厚：38μm。Production Example 2 (Preparation of Adhesive Sheet) When producing the following adhesive sheet, the details of the adhesive resin, additives, heat-expandable particles, base material, and release material used in the formation of each layer are as follows. <Adhesive resin> ・Acrylic copolymer (i): An acrylic copolymer having a Mw of 600,000 having a constituent unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio).・Acrylic copolymer (ii): an acrylic copolymer having a Mw of 600,000 having a constituent unit derived from a raw material monomer composed of n-butyl acrylate (BA)/methyl methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid=86.0/8.0/5.0/1.0 (mass ratio). <Additives> ・Isocyanate crosslinking agent (i): manufactured by TOSOH Co., Ltd., product name "Coronate L", solid content concentration: 75% by mass. <Heat-expandable particles> ・Heat-expandable particles (i): manufactured by KUREHA Co., Ltd., product name "S2640", expansion start temperature (t) = 208°C, average particle diameter (D 50 ) = 24 μm, 90% particle diameter (D 90 ) = 49 μm. <Release material> ・Heavy release film: Made by Lintek Co., Ltd., product name "SP-PET382150", one side of a polyethylene terephthalate (PET) film, provided with a release agent layer formed by a silicone release agent, thickness: 38 μm.・Light release film: Made by LINTEK Co., Ltd., product name "SP-PET381031", one side of PET film is provided with a release agent layer formed by a silicone release agent, thickness: 38 μm.

(1)第1黏著劑層(X1)之形成 於黏著性樹脂的上述丙烯酸系共聚物(i)之固形分100質量份中，調配上述異氰酸酯系交聯劑(i)5.0質量份(固形分比)，以甲苯稀釋，均一攪拌，調製固形分濃度(有效成分濃度)25質量%之黏著劑組成物。 接著，於上述重剝離薄膜之剝離劑層表面上，塗佈該黏著劑組成物形成塗膜，將該塗膜於100℃乾燥60秒，形成厚5μm之非膨脹性黏著劑層的第1黏著劑層(X1)。 又，23℃下之第1黏著劑層(X1)之儲存剪切模數G’(23)為2.5×105 Pa。(1) In the first adhesive layer (X1), 5.0 parts by mass (solid content) of the above-mentioned isocyanate-based crosslinking agent (i) was prepared in 100 parts by mass of the above-mentioned acrylic copolymer (i) of the adhesive resin, diluted with toluene, and uniformly stirred to prepare an adhesive composition with a solid content concentration (active ingredient concentration) of 25 mass%. Next, on the surface of the release agent layer of the above-mentioned heavy-release film, apply the adhesive composition to form a coating film, and dry the coating film at 100°C for 60 seconds to form the first adhesive layer (X1) of a non-expandable adhesive layer with a thickness of 5 μm. Also, the storage shear modulus G'(23) of the first adhesive layer (X1) at 23°C was 2.5×10 5 Pa.

(2)第2黏著劑層(X2)之形成 於黏著性樹脂的上述丙烯酸系共聚物(ii)之固形分100質量份中，調配上述異氰酸酯系交聯劑(i)0.8質量份(固形分比)，以甲苯稀釋，均一攪拌，調製固形分濃度(有效成分濃度)25質量%之黏著劑組成物。 接著，於上述輕剝離薄膜之剝離劑層表面上，塗佈該黏著劑組成物形成塗膜，將該塗膜於100℃乾燥60秒，形成厚10μm之第2黏著劑層(X2)。 又，23℃下之第2黏著劑層(X2)之儲存剪切模數G’(23)為9.0×103 Pa。 又，基於上述方法測定之第2黏著劑層(X2)之黏著力為1.0N/ 25mm。 且，由於第2黏著劑層(X2)及前述第1黏著劑層(X1)之探針觸黏值明顯為50mN/5mmϕ以上，故省略探針觸黏值之測定。(2) In the second adhesive layer (X2), 0.8 parts by mass (solid content) of the above-mentioned isocyanate-based crosslinking agent (i) was prepared in 100 parts by mass of the above-mentioned acrylic copolymer (ii) of the adhesive resin, diluted with toluene, uniformly stirred, and an adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass was prepared. Next, the adhesive composition was coated on the surface of the release agent layer of the light release film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a second adhesive layer (X2) with a thickness of 10 μm. Also, the storage shear modulus G'(23) of the second adhesive layer (X2) at 23°C was 9.0×10 3 Pa. Moreover, the adhesive force of the 2nd adhesive layer (X2) measured based on the said method was 1.0N/25mm. Moreover, since the probe tack values of the second adhesive layer (X2) and the aforementioned first adhesive layer (X1) are obviously above 50mN/5mmϕ, the measurement of the probe tack values is omitted.

(3)基材(Y)之製作 於製造例1所得之丙烯酸胺基甲酸酯系樹脂之固形分100質量份中，調配上述異氰酸酯系交聯劑(i)6.3質量份(固形分比)、作為觸媒之二辛基錫雙(2-乙基己酸酯)1.4質量份(固形分比)及上述熱膨脹性粒子(i)，以甲苯稀釋，均一攪拌，調製固形分濃度(有效成分濃度)30質量%之樹脂組成物。 又，相對於所得樹脂組成物中之有效成分總量(100質量%)的熱膨脹性粒子(i)之含量為20質量%。 接著，於非膨脹性基材的厚50μm之聚對苯二甲酸乙二酯(PET)薄膜(東洋紡股份有限公司製，製品名「Cosmoshine A4100」，探針觸黏值：0mN/5mmϕ)之表面上，塗佈該樹脂組成物形成塗膜，將該塗膜於100℃乾燥120秒，形成厚50μm之膨脹性基材層(Y1)。 此處，上述PET薄膜相當於非膨脹性基材層(Y2)。(3) Preparation of substrate (Y) In 100 parts by mass of the solid content of the urethane acrylate resin obtained in Production Example 1, 6.3 parts by mass (solid fraction) of the above-mentioned isocyanate-based crosslinking agent (i), 1.4 parts by mass (solid fraction) of dioctyltin bis(2-ethylhexanoate) as a catalyst, and the above-mentioned thermally expandable particles (i) were mixed, diluted with toluene, and uniformly stirred to prepare a resin composition with a solid content concentration (active ingredient concentration) of 30 mass%. Moreover, content of the thermally expandable particle (i) with respect to the active ingredient total amount (100 mass %) in the obtained resin composition was 20 mass %. Next, on the surface of a 50 μm thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “Cosmoshine A4100”, probe contact value: 0 mN/5 mmϕ), the resin composition was coated to form a coating film, and the coating film was dried at 100° C. for 120 seconds to form a 50 μm thick expansion substrate layer (Y1). Here, the said PET film corresponds to a non-expandable base material layer (Y2).

又，作為測定膨脹性基材層(Y1)之物性值的樣品，於上述輕剝離薄膜之剝離劑層表面塗佈該樹脂組成物形成塗膜，將該塗膜於100℃乾燥120秒，同樣形成厚50μm之膨脹性基材層(Y1)。 接著，基於上述測定方法，測定膨脹性基材層(Y1)之各溫度下之儲存模數及探針觸黏值。該測定結果如下述。 ・23℃下之儲存模數E’(23)=2.0×108 Pa ・208℃下之儲存模數E’(208)=5.0×105 Pa ・探針觸黏值=0mN/5mmϕ 又，測定上述PET薄膜亦即非膨脹性基材層(Y2)之各溫度下之儲存模數及探針觸黏值。該測定結果如下述。 ・23℃下之儲存模數E’(23)=1.0×103 MPa ・208℃下之儲存模數E’(208)=0.8×102 MPa ・探針觸黏值=0mN/5mmϕAlso, as a sample for measuring the physical properties of the expansive substrate layer (Y1), the resin composition was coated on the surface of the release agent layer of the above-mentioned light release film to form a coating film, and the coating film was dried at 100° C. for 120 seconds to form an expansive substrate layer (Y1) with a thickness of 50 μm in the same manner. Next, based on the above-mentioned measurement method, the storage modulus and probe tack value at each temperature of the expandable base material layer (Y1) were measured. The measurement results are as follows.・Storage modulus E'(23) at 23°C=2.0×10 8 Pa ・Storage modulus E'(208)=5.0×10 5 Pa at 208°C ・Probe tack value=0mN/5mmϕ Also, measure the storage modulus and probe tack value at each temperature of the above-mentioned PET film, that is, the non-expandable substrate layer (Y2). The measurement results are as follows.・Storage modulus E'(23)=1.0×10 3 MPa at 23°C ・Storage modulus E'(208)=0.8×10 2 MPa at 208°C ・Probe tack value=0mN/5mmϕ

(4)各層之積層 將上述(1-3)製作之基材(Y1)的非膨脹性基材層(Y2)與上述(2)形成之第2黏著劑層(X2)貼合，並且將熱膨脹性基材層(Y1)與上述(1)形成之第1黏著劑層(X1)貼合。 接著，製作依重剝離薄膜/第1黏著劑層(X1)/膨脹性基材層(Y1)/非膨脹性基材層(Y2)/第2黏著劑層(X2)/輕剝離薄膜之順序層合而成之黏著薄片。(4) Lamination of each layer Lay the non-expandable substrate layer (Y2) of the substrate (Y1) prepared in the above (1-3) with the second adhesive layer (X2) formed in the above (2), and bond the thermally expandable substrate layer (Y1) with the first adhesive layer (X1) formed in the above (1). Next, make an adhesive sheet laminated in the order of heavy release film/first adhesive layer (X1)/expandable substrate layer (Y1)/non-expandable substrate layer (Y2)/second adhesive layer (X2)/light release film.

又，針對所製作之黏著薄片，基於上述方法，依據以下方法測定剝離力(F0 )及(F1 )。 其結果，剝離力(F0 )=0.23N/25mm，剝離力(F1 )=0N/25mm，剝離力(F1 )與剝離力(F0 )之比[(F1 )/(F0 )]為0。Moreover, the peeling force (F 0 ) and (F 1 ) of the produced adhesive sheet were measured according to the following method based on the above-mentioned method. As a result, the peeling force (F 0 )=0.23N/25mm, the peeling force (F 1 )=0N/25mm, and the ratio [(F 1 )/(F 0 )] of the peeling force (F 1 ) to the peeling force (F 0 ) was 0.

＜剝離力(F0 )之測定＞ 所製作之黏著薄片於23℃、50%RH(相對濕度)之環境下靜置24小時後，去除該黏著薄片具有之重剝離薄膜，將露出之第1黏著劑層(X1)貼附於矽晶圓上。 其次，將貼附有黏著薄片之矽晶圓端部固定於萬能拉伸試驗機(ORIENTEC公司製，製品名「TENSILON UTM-4-100」)之下部夾具，以上部夾具固定黏著薄片。 接著，於與上述相同環境下，依據JIS Z0237:2000，藉由180˚剝除法，以拉伸速度300mm/分鐘，將矽晶圓與黏著薄片之第1黏著劑層(X1)之界面P剝離時所測定之剝離力設為「剝離力(F0 )」。<Measurement of Peeling Force (F 0 )> After the prepared adhesive sheet was left to stand at 23°C and 50%RH (relative humidity) for 24 hours, the heavy release film of the adhesive sheet was removed, and the exposed first adhesive layer (X1) was attached to the silicon wafer. Next, fix the end of the silicon wafer with the adhesive sheet attached to the lower fixture of a universal tensile testing machine (manufactured by ORIENTEC, product name "TENSILON UTM-4-100"), and fix the adhesive sheet to the upper fixture. Next, under the same environment as above, according to JIS Z0237:2000, the peeling force measured when peeling the interface P between the silicon wafer and the first adhesive layer (X1) of the adhesive sheet by the 180° peeling method at a tensile speed of 300mm/min was set as "peeling force (F 0 )".

＜剝離力(F1 )之測定＞ 去除所製作之黏著薄片具有之重剝離薄膜，將露出之第1黏著劑層(X1)貼附於矽晶圓上，於240℃加熱3分鐘，使膨脹性基材層(Y1)中之熱膨脹性粒子膨脹。 隨後，與上述剝離力(F0 )之測定同樣地，以上述條件，將矽晶圓與黏著薄片之第1黏著劑層(X1)之界面P剝離時所測定之剝離力設為「剝離力(F1 )」。 又，剝離力(F1 )之測定中，以萬能拉伸試驗機之上部夾具固定黏著薄片時，黏著薄片(I)自矽晶圓完全分離而無法固定時，結束測定，將此時之剝離力(F1 )設為「0N/25mm」。<Measurement of Peeling Force (F 1 )> Remove the heavy peeling film of the prepared adhesive sheet, attach the exposed first adhesive layer (X1) to the silicon wafer, and heat at 240°C for 3 minutes to expand the thermally expandable particles in the expandable substrate layer (Y1). Then, similarly to the measurement of the peeling force (F 0 ), under the above conditions, the peeling force measured when the interface P of the silicon wafer and the first adhesive layer (X1) of the adhesive sheet is peeled is referred to as "peeling force (F 1 )". In addition, in the measurement of the peeling force (F 1 ), when the adhesive sheet (I) was completely separated from the silicon wafer and could not be fixed when the adhesive sheet was fixed by the upper jig of the universal tensile testing machine, the measurement was terminated, and the peeling force (F 1 ) at this time was set as "0N/25mm".

製造例3(轉印膠帶之製作) 將丙烯酸丁酯/丙烯酸2-羥基乙酯=85/15(質量比)反應所得之丙烯酸系共聚物與對於丙烯酸2-羥基乙酯反應80莫耳%之甲基丙烯醯氧基乙基異氰酸酯(MOI)而得之質量平均分子量(Mw)60萬之能量線硬化型丙烯酸系共聚物作為黏著性樹脂使用。 對於該能量線硬化型丙烯酸系共聚物之固形分100質量份，於溶劑中混合光聚合起始劑的1-羥基環苯基酮(BASF公司製，製品名「IRGACURE 184」)3質量份與交聯劑之甲苯二異氰酸酯系交聯劑(TOSOH公司製，製品名「CORONATE L」)0.45質量份，獲得黏著性組成物。 其次，於上述輕剝離薄膜(i)之剝離處理面塗佈上述黏著性組成物形成塗膜，使該塗膜乾燥，形成厚10μm之黏著劑層。 接著，於該黏著劑層之露出表面，貼合作為基材薄膜之聚酯系聚胺基甲酸酯彈性體薄片(SHEEDOM公司製，製品名「Higress DUS202」，厚50μm)之單面。 如以上，獲得依序積層基材薄膜、黏著劑層及輕剝離薄膜而成之轉印膠帶。Production example 3 (production of transfer tape) An energy-ray-curable acrylic copolymer with a mass average molecular weight (Mw) of 600,000 obtained by reacting an acrylic copolymer obtained by reacting butyl acrylate/2-hydroxyethyl acrylate=85/15 (mass ratio) with methacryloxyethyl isocyanate (MOI) at 80 mole % to 2-hydroxyethyl acrylate was used as an adhesive resin. With respect to 100 parts by mass of the solid content of the energy ray-curable acrylic copolymer, 3 parts by mass of 1-hydroxycyclophenyl ketone (manufactured by BASF, product name "IRGACURE 184") as a photopolymerization initiator and 0.45 parts by mass of a toluene diisocyanate-based crosslinking agent (manufactured by TOSOH Corporation, product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. Next, the above-mentioned adhesive composition was applied to the release-treated surface of the above-mentioned light release film (i) to form a coating film, and the coating film was dried to form an adhesive layer with a thickness of 10 μm. Next, on the exposed surface of the adhesive layer, one side of a polyester polyurethane elastomer sheet (manufactured by SHEEDOM, product name "Higress DUS202", thickness 50 μm) was attached as a base film. As above, a transfer tape obtained by sequentially laminating the base film, the adhesive layer, and the lightly peeled film.

實施例1 ＜步驟(1)＞ 將製造例2製作之黏著薄片切斷為230mm×230mm之正方形。 使用背面研磨用膠帶層合機(LINTEC公司製，裝置名「RAD-3510F/12」)，剝離裁斷後之黏著薄片之重剝離薄膜，將露出之第1黏著劑層(X1)之黏著表面貼附於硬質支撐體(材質：矽，厚：725μm，楊氏模數：30GPa)。接著，進而亦剝離輕剝離薄膜，於露出之第2黏著劑層(X2)之黏著表面，貼附具有於一表面形成有電路之電路面之半導體晶圓(直徑200mm，厚725μm之圓板狀)之該電路面。 隨後，使用隱型雷射照射裝置(東京精密公司製，裝置名「ML300PlusWH」)，自半導體晶圓之與電路面相反側之背面進行隱形雷射照射，於半導體晶圓的內部形成改質領域。Example 1 ＜Step (1)＞ The adhesive sheet produced in Production Example 2 was cut into a square of 230 mm×230 mm. Using a tape laminator for back grinding (manufactured by LINTEC, device name "RAD-3510F/12"), the weight of the cut adhesive sheet was peeled off, and the exposed adhesive surface of the first adhesive layer (X1) was attached to a hard support (material: silicon, thickness: 725 μm, Young's modulus: 30 GPa). Then, the light release film was peeled off, and on the exposed adhesive surface of the second adhesive layer (X2), the circuit surface of a semiconductor wafer (diameter 200mm, thickness 725μm disc shape) having a circuit surface formed on one surface was attached. Then, using a stealth laser irradiation device (manufactured by Tokyo Seiki Co., Ltd., device name "ML300PlusWH"), stealth laser irradiation was performed from the back surface of the semiconductor wafer opposite to the circuit surface to form a modified region inside the semiconductor wafer.

＜步驟(2)＞ 使用拋光研磨機(東京精密公司製，裝置名「PG3000RM」)，對半導體晶圓之未形成電路之背面邊暴露於超純水中邊進行研磨，分割半導體晶圓，同時進行晶片之單片化，獲得厚20μm之複數個半導體晶片。＜Step (2)＞ Using a polishing machine (manufactured by Tokyo Seiki Co., Ltd., device name "PG3000RM"), the back surface of the semiconductor wafer without the formation of the circuit was polished while being exposed to ultra-pure water, and the semiconductor wafer was divided. At the same time, the wafer was singulated to obtain a plurality of semiconductor wafers with a thickness of 20 μm.

＜步驟(3)＞ 將包含硬質支撐體、黏著薄片及複數個半導體晶片之系內溫度設為熱膨脹性粒子(i)之膨脹開始溫度(208℃)以上的240℃，進行3分鐘之加熱處理。 加熱處理後，於硬質支撐體與第1黏著劑層(X1)之界面可容易地一次分離。此時，以複數個半導體晶片貼附於第2黏著劑層(X2)之狀態，於構成黏著薄片之各層之層間未產生分離。 又，自硬質支撐體分離後，於硬質支撐體表面未確認到第1黏著劑層(X1)之一部分殘存，未見到污染。因此，認為不需要對硬質支撐體表面進行新的洗淨步驟。＜Step (3)＞ Heat treatment was performed for 3 minutes by setting the internal temperature of the system including the hard support, the adhesive sheet, and a plurality of semiconductor chips at 240° C. above the expansion start temperature (208° C.) of the thermally expandable particles (i). After heat treatment, the interface between the hard support and the first adhesive layer (X1) can be easily separated at one time. At this time, in the state where the plurality of semiconductor wafers were attached to the second adhesive layer (X2), separation did not occur between the layers constituting the adhesive sheet. Also, after separation from the hard support, part of the first adhesive layer (X1) was not confirmed to remain on the surface of the hard support, and contamination was not observed. Therefore, a new cleaning step for the hard support surface is not considered necessary.

＜步驟(4)＞ 將製造例3所得之轉印膠帶切斷為210mm×210mm之正方形。此時，係裁斷為使裁斷後之轉印膠帶之各邊與基材薄膜(Y2)之MD方向平行或垂直。 其次，自轉印膠帶剝離輕剝離薄膜，將露出之黏著劑層表面與步驟(3)之與硬質支撐體分離後之複數個半導體晶片之背面貼附。 又，此時，以將複數個半導體晶片之一群位於轉印膠帶之中央部之方式貼附，並且以使自半導體晶圓單片化時之切割線與轉印膠帶之各邊平形或垂直之方式予以貼附。接著，複數個半導體晶片之一群自第2黏著劑層(X2)之黏著表面剝離，去除黏著薄片。＜Step (4)＞ The transfer tape obtained in Production Example 3 was cut into a square of 210 mm×210 mm. At this time, it is cut so that each side of the transfer tape after cutting is parallel to or perpendicular to the MD direction of the base film (Y2). Next, peel off the light peeling film from the transfer tape, and attach the surface of the exposed adhesive layer to the backside of the plurality of semiconductor wafers separated from the hard support in step (3). In addition, at this time, a group of a plurality of semiconductor wafers is attached so that a group of the plurality of semiconductor wafers is positioned at the central portion of the transfer tape, and the dicing lines at the time of singulating the semiconductor wafers are attached so that they are flat or perpendicular to each side of the transfer tape. Next, one group of the plurality of semiconductor wafers is peeled off from the adhesive surface of the second adhesive layer (X2), and the adhesive sheet is removed.

＜步驟(5)＞ 貼附複數個半導體晶片之轉印膠帶設置於可雙軸延伸之擴展裝置上。擴展裝置具有相互正交之X軸方向(正的方向設為+X軸方向，負的方向設為-X軸方向)與Y軸方向(正的方向設為+Y軸方向，負的方向設為-Y軸方向)，具有用以於各方向(亦即+X軸方向、-X軸方向、+Y軸方向、-Y軸方向)延伸之保持手段。 此處，轉印膠帶之MD方向與X軸或Y軸方向一致，設置於擴展裝置，藉由保持手段，把持轉印膠帶之各邊後，以下述條件，拉伸轉印膠帶，將貼附於轉印膠帶上之複數個半導體晶片彼此之間隔擴展。 ・保持手段之個數：一邊周圍5個 ・延伸速度：5mm/sec ・延伸距離：各邊逐次延伸60mm。＜Step (5)＞ The transfer tape for sticking a plurality of semiconductor chips is arranged on the expansion device capable of biaxial extension. The expansion device has mutually orthogonal X-axis directions (the positive direction is defined as the +X-axis direction, and the negative direction is defined as the -X-axis direction) and the Y-axis direction (the positive direction is defined as the +Y-axis direction, and the negative direction is defined as the -Y-axis direction). Here, the MD direction of the transfer tape coincides with the X-axis or the Y-axis direction, and it is installed on the expansion device. After holding each side of the transfer tape by the holding means, the transfer tape is stretched under the following conditions, and the plurality of semiconductor chips attached to the transfer tape are expanded at intervals. ・Number of holding means: 5 around one side ・Extension speed: 5mm/sec ・Extension distance: each side is extended by 60mm successively.

＜步驟(6)＞ 使用紫外線照射裝置(LINTEC股份有限公司製，製品名「RAD-2000」)，自轉印膠帶之基材薄膜側照射紫外線(光量：500mJ/cm2 ，照度：220mW/cm2 ，照射速度：15 mm/sec)，使轉印膠帶具有之黏著劑層之黏著力降低。接著拾取，獲得半導體晶片。 又，所得複數個半導體晶片中未確認到見到端部缺損等者。<Step (6)> Using an ultraviolet irradiation device (manufactured by LINTEC Co., Ltd., product name "RAD-2000"), irradiate ultraviolet rays from the substrate film side of the transfer tape (light intensity: 500mJ/cm 2 , illuminance: 220mW/cm 2 , irradiation speed: 15 mm/sec) to reduce the adhesive force of the adhesive layer of the transfer tape. Then pick up to obtain a semiconductor wafer. In addition, among the obtained plurality of semiconductor wafers, no chipping at the end or the like was observed.

1a、1b‧‧‧黏著薄片 (X1)‧‧‧第1黏著劑層 (X2)‧‧‧第2黏著劑層 (Y)‧‧‧基材 (Y1)‧‧‧膨脹性基材層 (Y2)‧‧‧非膨脹性基材層 (Y2-1)‧‧‧第1非膨脹性基材層 (Y2-2)‧‧‧第2非膨脹性基材層 50‧‧‧硬質支撐體 60‧‧‧半導體晶圓 61‧‧‧電路面 62‧‧‧背面 70‧‧‧半導體晶片 71‧‧‧電路面 72‧‧‧背面 80‧‧‧轉印膠帶 81‧‧‧基材薄膜 82‧‧‧黏著劑層1a, 1b‧‧‧adhesive sheet (X1)‧‧‧1st adhesive layer (X2)‧‧‧The second adhesive layer (Y)‧‧‧Substrate (Y1)‧‧‧expandable substrate layer (Y2)‧‧‧Non-expandable substrate layer (Y2-1)‧‧‧The first non-expandable substrate layer (Y2-2)‧‧‧The second non-expandable substrate layer 50‧‧‧hard support body 60‧‧‧semiconductor wafer 61‧‧‧circuit surface 62‧‧‧back 70‧‧‧semiconductor chip 71‧‧‧circuit surface 72‧‧‧back 80‧‧‧Transfer tape 81‧‧‧Substrate film 82‧‧‧adhesive layer

圖1係顯示本發明之半導體晶片之製造方法所用之黏著薄片之構成的一例，係該黏著薄片之剖面示意圖。 圖2係本發明之半導體晶片之製造方法之步驟(1)~(3)之剖面示意圖。 圖3係本發明之半導體晶片之製造方法之步驟(4)~(6)之剖面示意圖。FIG. 1 shows an example of the structure of an adhesive sheet used in the method of manufacturing a semiconductor wafer of the present invention, and is a schematic cross-sectional view of the adhesive sheet. 2 is a cross-sectional schematic diagram of steps (1) to (3) of the manufacturing method of the semiconductor wafer of the present invention. 3 is a cross-sectional schematic diagram of steps (4) to (6) of the manufacturing method of the semiconductor wafer of the present invention.

Claims (11)

一種半導體晶片之製造方法，其係由使用黏著薄片之半導體晶圓製造半導體晶片之方法，該黏著薄片具有：至少具備包含膨脹性粒子之膨脹性基材層(Y1)及非膨脹性基材層(Y2)之基材(Y)，與分別於基材(Y)的兩面之第1黏著劑層(X1)及第2黏著劑層(X2)；且藉由前述膨脹性粒子的膨脹，可於第1黏著劑層(X1)的黏著表面產生凹凸，且構成前述基材(Y)之膨脹性基材層(Y1)及非膨脹性基材層(Y2)均為非黏著性之層，該半導體晶片之製造方法具有下述步驟(1)~(3)：．步驟(1)：將第1黏著劑層(X1)的黏著表面貼附於硬質支撐體，並將第2黏著劑層(X2)的黏著表面貼附於半導體晶圓的表面之步驟，．步驟(2)：將前述半導體晶圓進行分割而得到複數個半導體晶片之步驟，．步驟(3)：使前述膨脹性粒子膨脹，在第2黏著劑層(X2)上之複數個半導體晶片保持貼附的狀態，於前述硬質支撐體與第1黏著劑層(X1)之界面P進行分離之步驟。 A method of manufacturing a semiconductor wafer, which is a method of manufacturing a semiconductor wafer from a semiconductor wafer using an adhesive sheet comprising: a substrate (Y) having at least an expandable substrate layer (Y1) containing expandable particles and a non-expandable substrate layer (Y2), and a first adhesive layer (X1) and a second adhesive layer (X2) respectively on both sides of the substrate (Y); The surface is uneven, and the expandable base material layer (Y1) and the non-expandable base material layer (Y2) constituting the aforementioned base material (Y) are both non-adhesive layers. The manufacturing method of the semiconductor wafer has the following steps (1) to (3): . Step (1): a step of attaching the adhesive surface of the first adhesive layer (X1) to the hard support, and attaching the adhesive surface of the second adhesive layer (X2) to the surface of the semiconductor wafer,. Step (2): the step of dividing the aforementioned semiconductor wafer to obtain a plurality of semiconductor wafers. Step (3): Inflate the expandable particles, keep the plurality of semiconductor wafers on the second adhesive layer (X2) attached, and separate at the interface P between the aforementioned hard support and the first adhesive layer (X1). 如請求項1之半導體晶片之製造方法，其中，前述黏著薄片於前述基材(Y)的前述膨脹性基材層(Y1)側具有第1 黏著劑層(X1)，於該基材(Y)的前述非膨脹性基材層(Y2)側具有前述第2黏著劑層(X2)。 The method for manufacturing a semiconductor wafer according to claim 1, wherein the adhesive sheet has a first The adhesive layer (X1) has the said 2nd adhesive layer (X2) on the said non-expandable base material layer (Y2) side of this base material (Y). 如請求項1之半導體晶片之製造方法，其中，前述基材(Y)具有：前述膨脹性基材層(Y1)，與設置於前述膨脹性基材層(Y1)之前述第1黏著層(X1)側之非膨脹性基材層(Y2-1)，與設置於前述膨脹性基材層(Y1)之前述第2黏著層(X2)側之非膨脹性基材層(Y2-2)；前述膨脹性粒子進行膨脹時之非膨脹性基材層(Y2-1)的儲存模數E’低於前述膨脹性粒子進行膨脹時之非膨脹性基材層(Y2-2)的儲存模數E’。 The method for manufacturing a semiconductor wafer according to claim 1, wherein the base material (Y) comprises: the expandable base material layer (Y1), a non-expandable base material layer (Y2-1) disposed on the first adhesive layer (X1) side of the expandable base material layer (Y1), a non-expandable base material layer (Y2-2) disposed on the second adhesive layer (X2) side of the expandable base material layer (Y1), and a non-expandable base material layer (Y2-1) when the expandable particles are expanded. ) storage modulus E' is lower than the storage modulus E' of the non-expandable substrate layer (Y2-2) when the aforementioned expandable particles are expanded. 如請求項1或2之半導體晶片之製造方法，其中，前述非膨脹性基材層(Y2)係存在於比前述膨脹性基材層(Y1)更遠離前述第1黏著劑層(X1)的位置，且前述膨脹性基材層(Y1)與前述第1黏著劑層(X1)之間不存在前述非膨脹性基材層(Y2)；前述膨脹性粒子進行膨脹時之前述非膨脹性基材層(Y2)的儲存模數E’大於前述膨脹性粒子進行膨脹時之前述膨脹性基材層(Y1)的儲存模數E’。 The method for manufacturing a semiconductor wafer according to claim 1 or 2, wherein the non-expandable base material layer (Y2) exists at a position farther from the first adhesive layer (X1) than the expandable base material layer (Y1), and the non-expandable base material layer (Y2) does not exist between the expandable base material layer (Y1) and the first adhesive layer (X1); the storage modulus E' of the non-expandable base material layer (Y2) when the expandable particles are expanded is larger than when the expandable particles are expanded. The storage modulus E' of the aforementioned expansive substrate layer (Y1). 如請求項1或2之半導體晶片之製造方法，其中，於步 驟(3)中，當使前述膨脹性粒子膨脹時，構成前述黏著薄片之各層的層間不會分離。 The method for manufacturing a semiconductor wafer as claimed in item 1 or 2, wherein, in step In the step (3), when the expandable particles are expanded, the layers constituting the adhesive sheet are not separated from each other. 如請求項1或2之半導體晶片之製造方法，其中，進一步具有下述步驟(4)，．步驟(4)：於步驟(3)中由前述硬質支撐體分離後，將與複數個半導體晶片的電路面為相反側的背面貼附於具有基材薄膜、黏著劑層及/或接著劑層之轉印膠帶後，將前述黏著薄片由半導體晶片進行去除之步驟。 Such as claim 1 or 2 of the semiconductor wafer manufacturing method, which further has the following step (4),. Step (4): After being separated from the hard support in step (3), the backside opposite to the circuit surface of the plurality of semiconductor chips is attached to the transfer tape having a base film, an adhesive layer and/or an adhesive layer, and then the aforementioned adhesive sheet is removed from the semiconductor chip. 如請求項1之半導體晶片之製造方法，其中，前述膨脹性粒子為膨脹開始溫度(t)為60~270℃之熱膨脹性粒子。 The method of manufacturing a semiconductor wafer according to claim 1, wherein the aforementioned expandable particles are thermally expandable particles with an expansion start temperature (t) of 60 to 270°C. 如請求項7之半導體晶片之製造方法，其中，藉由於熱膨脹性粒子之「膨脹開始溫度(t)+10℃」~「膨脹開始溫度(t)+60℃」之間的加熱處理進行前述熱膨脹性粒子的膨脹。 The method of manufacturing a semiconductor wafer according to Claim 7, wherein the thermally expandable particles are expanded by heat treatment between "expansion start temperature (t) + 10°C" and "expansion start temperature (t)+60°C" of the heat expandable particles. 如請求項7或8之半導體晶片之製造方法，其中，前述膨脹性基材層(Y1)為含有前述熱膨脹性粒子之熱膨脹性基材層(Y1-1)，且於23℃中的熱膨脹性基材層(Y1-1)的儲存模數E’(23)為1.0×106Pa以上。 The method for manufacturing a semiconductor wafer according to claim 7 or 8, wherein the expandable base material layer (Y1) is a thermally expandable base material layer (Y1-1) containing the thermally expandable particles, and the storage modulus E'(23) of the thermally expandable base material layer (Y1-1) at 23°C is 1.0×10 6 Pa or more. 如請求項1或2之半導體晶片之製造方法，其中，前述 非膨脹性基材層(Y2)的體積變化率(%)為未達2體積%。 The method for manufacturing a semiconductor wafer according to claim 1 or 2, wherein the aforementioned The volume change rate (%) of the non-expandable base material layer (Y2) is less than 2 volume%. 如請求項1或2之半導體晶片之製造方法，其中，步驟(2)為：於具有改質領域之半導體晶圓中，將與電路面為相反側之未形成電路的背面進行研磨，分割該半導體晶圓而得到複數個半導體晶片之步驟。 The method for manufacturing a semiconductor wafer as claimed in claim 1 or 2, wherein step (2) is: grinding the backside of the semiconductor wafer having a modified region that is opposite to the circuit surface without forming a circuit, and dividing the semiconductor wafer to obtain a plurality of semiconductor wafers.
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