TW202024263A - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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TW202024263A
TW202024263A TW109108113A TW109108113A TW202024263A TW 202024263 A TW202024263 A TW 202024263A TW 109108113 A TW109108113 A TW 109108113A TW 109108113 A TW109108113 A TW 109108113A TW 202024263 A TW202024263 A TW 202024263A
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adhesive
acrylate
polymer
area
meth
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TW109108113A
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Chinese (zh)
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平山高正
北山和寬
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日商日東電工股份有限公司
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    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • 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
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • 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
    • 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
    • H01L2221/68327—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 used during dicing or grinding
    • 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
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer

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

Abstract

Provided is an adhesive sheet which is able to realize excellent cutting precision and a reduction in cutting debris when cutting microcomponents such as electronic components. This adhesive sheet is provided only on one side with an adhesive surface in which the adhesive strength decreases when heated, with the elastic modulus of the surface on the opposite side of the adhesive surface measured by nanoindentation being at least 1 MPa. In a preferred embodiment, the sheet is provided with an adhesive region having the adhesive surface as one surface thereof and a coating region which abuts the side of the adhesive region opposite the adhesive surface in a cross-sectional view, with the adhesive region including an adhesive and thermally expandable microspheres.

Description

黏著片材及電子零件之製造方法Adhesive sheet and manufacturing method of electronic parts

本發明係關於一種黏著片材。The present invention relates to an adhesive sheet.

於矽晶圓、積層電容器、透明電極等電子零件之製造中，藉由切斷加工而將大面積且一次整合必要功能而獲得之基板微小化為所需大小。切斷加工時，使用用以防止由加工時之應力及振動引起之切斷精度降低的被加工物(基板)固定用之黏著片材。對於該黏著片材，於加工時要求對被加工物之充分之黏著力，於加工後要求可容易地剝離被切斷之被加工物(電子零件)。作為此種黏著片材，已知有於黏著劑中含有熱膨脹性微球之黏著片材(例如，專利文獻1)。含有熱膨脹性微球之黏著片材藉由利用加熱使熱膨脹性微球膨脹、或發泡而使黏著力降低，因此可於上述加工時表現出充分之黏著力，於加工後藉由加熱而容易地使電子零件剝離。 近年，電子零件之輕量、小型化有所發展，要求可實現更高精度之切斷加工的被加工物固定用之黏著片材。又，亦要求減少切斷加工時產生之加工屑(切削屑)。針對該等要求，認為若使構成黏著片材之黏著劑變薄，則可獲得可實現更高切斷精度及切削屑之減少的黏著片材。然而，於含有熱膨脹性微球之黏著片材中，由於含有熱膨脹性微球，故而存在黏著劑之厚度受到限制之問題。更具體而言，於含有熱膨脹性微球之黏著片材中，若使黏著劑變薄，則熱膨脹性微球自黏著劑突出，存在與基材或加工台之密接性變差等實用性明顯降低之問題。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2002-121510號公報In the manufacture of electronic parts such as silicon wafers, multilayer capacitors, and transparent electrodes, a large area and one-time integration of necessary functions are used to miniaturize a substrate obtained by cutting to a desired size. When cutting, use an adhesive sheet for fixing the workpiece (substrate) to prevent the reduction in cutting accuracy caused by stress and vibration during processing. For this adhesive sheet, sufficient adhesion to the processed object is required during processing, and the cut processed object (electronic part) is required to be easily peeled off after processing. As such an adhesive sheet, an adhesive sheet containing heat-expandable microspheres in an adhesive is known (for example, Patent Document 1). Adhesive sheets containing heat-expandable microspheres are heated to expand or foam the heat-expandable microspheres to reduce the adhesive force. Therefore, they can exhibit sufficient adhesive force during the above-mentioned processing and are easily heated by heating after processing. Ground the electronic parts. In recent years, the light weight and miniaturization of electronic parts have progressed, and there is a demand for adhesive sheets for fixing workpieces that can achieve higher precision cutting processing. In addition, it is also required to reduce machining chips (cutting chips) generated during cutting. In response to these requirements, it is thought that if the adhesive constituting the adhesive sheet is thinned, an adhesive sheet that can achieve higher cutting accuracy and reduction of cutting chips can be obtained. However, in the adhesive sheet containing heat-expandable microspheres, since the heat-expandable microspheres are contained, the thickness of the adhesive is limited. More specifically, in an adhesive sheet containing heat-expandable microspheres, if the adhesive is made thinner, the heat-expandable microspheres will protrude from the adhesive, and the adhesiveness with the substrate or the processing table will deteriorate, and the practicality is obvious. The problem of reduction. [Prior Technical Literature] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2002-121510

[發明所欲解決之問題] 本發明係為了解決上述先前之問題而完成者，其目的在於提供一種於電子零件等微小零件之切斷加工時，可實現優異之切斷精度及切削屑之減少的黏著片材。 [解決問題之技術手段] 本發明之黏著片材僅於單面具有黏著力因加熱而降低之黏著面，並且與該黏著面相反之側之面於25℃下藉由奈米壓痕法所測得之彈性模數為1 MPa以上。 於較佳之實施形態中，於剖面觀察下，具有含有上述黏著面作為表面之黏著劑區域、及與該黏著劑區域之與該黏著面相反之側鄰接之被覆材區域，該黏著劑區域含有黏著劑與熱膨脹性微球。 於較佳之實施形態中，上述黏著劑區域之厚度為50 μm以下。 於較佳之實施形態中，將上述黏著面側貼附於聚對苯二甲酸乙二酯膜時之黏著力為0.2 N/20 mm以上。 於較佳之實施形態中，本發明之黏著片材於加熱前之黏著力(a1)與加熱後之黏著力(a2)之比(a2/a1)為0.0001～0.5。 於較佳之實施形態中，加熱後之上述黏著面之表面粗糙度Ra為3 μm以上。 於較佳之實施形態中，於與上述黏著面相反之側進而具備基材。 根據本發明之另一態樣，提供一種電子零件之製造方法。該製造方法包括於上述黏著片材上貼附電子零件材料後，對該電子零件材料進行切斷加工。 [發明之效果] 根據本發明，具有黏著力因加熱而降低之黏著面，相對地提高與該黏著面相反之側之面之彈性模數，藉此於電子零件等微小零件之切斷加工時，可獲得可實現優異之切斷精度之黏著片材。更詳細而言，於本發明中，形成包含黏著劑與熱膨脹性微球且具有作為表面之黏著面的黏著劑區域，於該黏著劑區域之與黏著面相反之側形成彈性相對較高之被覆材區域，而將自該黏著劑區域突出至該被覆材區域之熱膨脹性微球埋入，藉此可於不受自黏著劑區域突出之熱膨脹性微球引起之凹凸影響之情況下使作為低彈性區域之黏著劑區域變薄，其結果為，可獲得可實現優異之切斷精度之黏著片材。又，根據本發明，由於可使黏著劑區域變薄，故而若使用本發明之黏著片材進行電子零件等微小零件之切斷加工，則可抑制切削屑之產生。[The problem to be solved by the invention] The present invention was completed in order to solve the above-mentioned previous problems, and its object is to provide an adhesive sheet that can achieve excellent cutting accuracy and reduction of cutting chips during the cutting process of small parts such as electronic parts. [Technical means to solve the problem] The adhesive sheet of the present invention only has an adhesive surface on one side whose adhesive force is reduced by heating, and the elastic modulus of the surface opposite to the adhesive surface measured by the nanoindentation method at 25°C is 1 Above MPa. In a preferred embodiment, under cross-sectional observation, there is an adhesive region containing the above-mentioned adhesive surface as a surface, and a covering material region adjacent to the side of the adhesive region opposite to the adhesive surface, and the adhesive region contains adhesive Agent and heat-expandable microspheres. In a preferred embodiment, the thickness of the adhesive region is 50 μm or less. In a preferred embodiment, the adhesive force when the adhesive surface side is attached to the polyethylene terephthalate film is 0.2 N/20 mm or more. In a preferred embodiment, the ratio (a2/a1) of the adhesive force (a1) of the adhesive sheet of the present invention before heating to the adhesive force (a2) after heating is 0.0001 to 0.5. In a preferred embodiment, the surface roughness Ra of the adhesive surface after heating is 3 μm or more. In a preferred embodiment, a substrate is further provided on the side opposite to the above-mentioned adhesive surface. According to another aspect of the present invention, a manufacturing method of an electronic component is provided. The manufacturing method includes, after attaching the electronic part material to the adhesive sheet, cutting the electronic part material. [Effects of Invention] According to the present invention, there is an adhesive surface whose adhesive force is reduced by heating, and the elastic modulus of the surface on the opposite side of the adhesive surface is relatively increased, so that it can be realized during the cutting process of small parts such as electronic parts Adhesive sheet with excellent cutting accuracy. In more detail, in the present invention, an adhesive area including an adhesive and heat-expandable microspheres and having an adhesive surface as the surface is formed, and a relatively high elastic coating is formed on the side of the adhesive area opposite to the adhesive surface The heat-expandable microspheres protruding from the adhesive area to the covering material area are embedded, so that it can be made low without being affected by the unevenness caused by the heat-expandable microspheres protruding from the adhesive area. The adhesive area in the elastic area becomes thinner, and as a result, an adhesive sheet with excellent cutting accuracy can be obtained. Furthermore, according to the present invention, since the adhesive area can be made thinner, if the adhesive sheet of the present invention is used for cutting small parts such as electronic parts, the generation of cutting chips can be suppressed.

A.黏著片材之整體構成 圖1係本發明之較佳之實施形態之黏著片材的概略剖面圖。黏著片材100僅於其單面具有黏著面11。又，黏著片材100具有於25℃下藉由奈米壓痕法所測得之彈性模數為1 MPa以上之面21作為與黏著面11相反之側之面21。具有此種彈性模數之面例如可如下所述藉由設置被覆材區域20而形成。黏著片材100較佳為含有藉由加熱可膨脹或發泡之熱膨脹性微球13。 黏著片材100具有含有作為表面之黏著面11之黏著劑區域10、及與黏著劑區域10之與黏著面11相反之側鄰接之被覆材區域20。黏著劑區域10較佳為含有黏著劑12與熱膨脹性微球13。所謂黏著劑區域10係指自黏著面11至構成黏著劑區域10之黏著劑12與構成被覆材區域20之材料之界面1為止之區域。又，所謂被覆材區域20係指自構成黏著劑區域10之黏著劑12與構成被覆材區域20之材料之界面1至與黏著面11相反之側之面21為止之區域。熱膨脹性微球13可自黏著劑區域10向被覆材區域20突出。自黏著劑區域10突出之熱膨脹性微球13可由被覆材區域20被覆，其結果為，可消除由熱膨脹性微球13產生之凹凸之影響。被覆材區域20之外表面(圖示例中為下表面)係藉由奈米壓痕法所測得之彈性模數為1 MPa以上之面21。再者，雖未圖示，但直至將黏著片材供於實用為止之期間，亦可於黏著面11之外側配置剝離紙而保護黏著面11。又，於圖示例中，雖明確圖示有界面1，但界面亦可為藉由目視、顯微鏡等難以辨別之界面。藉由目視、顯微鏡等難以辨別之界面例如可對各區域之組成進行分析而辨別(詳細內容見下文)。 於本發明中，藉由在與黏著面11相反之側形成彈性模數經適當調整之被覆材區域20，可容許熱膨脹性微球13自黏著劑區域10突出，使黏著劑區域10變薄。若使作為低彈性區域之黏著劑區域10變薄，則作為對電子零件等進行切斷加工時之暫時固定用片材，有助於實現優異之切斷精度。更具體而言，若使用黏著劑區域10較薄之黏著片材作為暫時固定用片材對電子零件等進行切斷加工，則由於該黏著片材之變形較少，故而可防止以下情況：切斷後之晶片再附著；切斷面發生傾斜或成為S字狀，變得不穩定；切斷時產生晶片缺損等。又，於使用黏著劑區域10較薄之黏著片材作為對電子零件等進行切斷加工時之暫時固定用片材之情形時，亦可抑制切削屑之產生。本發明之黏著片材不僅於利用切晶步驟中多採用之旋轉刀所進行之切斷中發揮出上述效果，而且於藉由為了降低切削損耗而採用之利用平刀之壓切所進行之切斷中，亦發揮出上述效果，而尤其有用。又，於加溫下(例如，30℃～150℃)進行切斷之情形時，亦可以上述方式精度良好地切斷。 又，本發明之黏著片材由於在黏著面11側(黏著劑區域10)存在熱膨脹性微球13，故而於將被黏著體(例如，切斷加工後之晶片)自黏著片材剝離時，藉由以熱膨脹性微球13可膨脹或發泡程度之溫度進行加熱，於黏著面產生凹凸，而可使該黏著面之黏著力降低或消失。 將本發明之黏著片材之黏著面貼附於聚對苯二甲酸乙二酯膜(例如，厚度25 μm)上時之黏著力較佳為0.2 N/20 mm以上，更佳為0.2 N/20 mm～20 N/20 mm，進而較佳為2 N/20 mm～10 N/20 mm。若為此種範圍，則可獲得作為對電子零件等進行切斷加工時之暫時固定用片材有用之黏著片材。於本說明書中，所謂黏著力係指藉由依據JIS Z 0237：2000之方法(測定溫度：23℃，貼合條件：2 kg輥往返1次，剝離速度：300 mm/min，剝離角度180°)所測得之黏著力。 將本發明之黏著片材之黏著面貼附於聚對苯二甲酸乙二酯膜(例如，厚度25 μm)並加熱後之黏著力較佳為0.2 N/20 mm以下，更佳為0.1 N/20 mm以下。於本說明書中，所謂對黏著片材之加熱係指以熱膨脹性微球膨脹或發泡而使黏著力降低之溫度、時間所進行之加熱。該加熱例如係於70℃～270℃下進行1分鐘～10分鐘之加熱。 將本發明之黏著片材之黏著面貼附於聚對苯二甲酸乙二酯膜(例如，厚度25 μm)上時之黏著力(即加熱前之黏著力(a1))與加熱後之黏著力(a2)之比(a2/a1)較佳為0.5以下，更佳為0.1以下。(a2/a1)之下限較佳為0.0001，更佳為0.0005。 如上所述，本發明之黏著片材藉由以特定之溫度進行加熱，而於黏著面產生凹凸。將本發明之黏著片材加熱後之黏著面之表面粗糙度Ra較佳為3 μm以上，更佳為5 μm以上。若為此種範圍，則加熱後黏著力降低或消失，可獲得可容易地剝離被黏著體之黏著片材。再者，所謂黏著面之表面粗糙度Ra係指於不存在被黏著體之狀態下加熱後之黏著片材之黏著面之表面粗糙度Ra。表面粗糙度Ra可依據JIS B 0601：1994進行測定。 圖2係本發明之另一較佳之實施形態之黏著片材的概略剖面圖。黏著片材200於與黏著面11相反之側進而具備基材30。再者，雖未圖示，但亦可於基材30之與被覆材區域20相反之側設置任意合適之黏著劑層或接著劑層。又，本發明之黏著片材直至供於實用為止之期間，亦可於基材30之外側配置剝離紙。於在基材30之外側配置剝離紙之情形時，該剝離紙可經由任意合適之黏著劑而貼附於基材上。於圖2中，係表示於基材30之單側形成黏著劑區域10及被覆材區域20之形態，亦可採用於基材30之兩側形成黏著劑區域10及被覆材區域20、例如黏著劑區域/被覆材區域/基材/被覆材區域/黏著劑區域之構成。 B.被覆材區域 關於本發明之黏著片材，與黏著面相反之側之面於25℃下藉由奈米壓痕法所測得之彈性模數如上所述為1 MPa以上，較佳為1 MPa～5000 MPa，更佳為1 MPa～3500 MPa，進而較佳為1 MPa～1000 MPa，尤佳為10 MPa～600 MPa。具有顯示出此種彈性模數之面之黏著片材例如可藉由形成以與黏著劑區域不同之材料所形成之被覆材區域而獲得。上述被覆材區域之藉由奈米壓痕法所測得之彈性模數可相當於與黏著面相反之側之面之藉由奈米壓痕法所測得之彈性模數。所謂藉由奈米壓痕法所測得之彈性模數係指將壓頭壓入試樣(例如，黏著面)中時於負載時、卸載時連續測定施加於壓頭上之負載重量與壓入深度，根據所獲得之負載重量-壓入深度曲線而求出之彈性模數。於本說明書中，所謂藉由奈米壓痕法所測得之彈性模數係指將測定條件設為荷重：1 mN、負載、卸載速度：0.1 mN/s、保持時間：1 s，而以上述方式測得之彈性模數。 於本發明中，藉由於與黏著面相反之側具有藉由奈米壓痕法所測得之彈性模數為1 MPa以上之面，即形成顯示該彈性模數之被覆材區域，可提供作為對電子零件等進行切斷加工時之暫時固定用片材而有助於實現優異之切斷精度之黏著片材。進而，藉由將被覆材區域之藉由奈米壓痕法所測得之彈性模數設為5000 MPa以下，該被覆材區域可與自黏著劑區域突出之熱膨脹性微球之凹凸吻合，可以如埋入該熱膨脹性微球之形態，而將該熱膨脹性微球被覆。又，可於無損作為黏著片材整體所需之柔軟性(例如，可與被黏著體吻合之程度之柔軟性)之情況下，提供有助於實現優異之切斷精度的黏著片材。 上述被覆材區域於25℃下之拉伸彈性模數較佳為1 MPa以上，更佳為1 MPa～5000 MPa，進而較佳為1 MPa～1000 MPa。若為此種範圍，則關於藉由奈米壓痕法所測得之彈性模數，可獲得與上述所說明之效果相同之效果。再者，拉伸彈性模數可依據JIS K 7161：2008進行測定。 上述被覆材區域於25℃下之彎曲彈性模數較佳為1 MPa以上，更佳為1 MPa～5000 MPa，進而較佳為1 MPa～1000 MPa。若為此種範圍，則關於藉由奈米壓痕法所測得之彈性模數，可獲得與上述所說明之效果相同之效果。再者，彎曲彈性模數可依據JIS K 7171：2008進行測定。 上述被覆材區域之厚度可根據自黏著劑區域突出之熱膨脹性微球之凹凸量(大小)而設定為任意合適之值。被覆材區域之厚度較佳為可完全被覆自黏著劑區域突出之熱膨脹性微球之厚度，例如為0.1 μm～200 μm，較佳為0.1 μm～100 μm，更佳為0.1 μm～45 μm。再者，於本說明書中，所謂被覆材區域之厚度，如圖1所示係指自構成被覆材區域20之被覆材料與構成黏著劑區域10之黏著劑12之界面1至被覆材區域之與該界面1相反之側之面21為止之距離。即，熱膨脹性微球13自黏著劑區域10突出之部分並非被覆材區域之厚度之評估對象。於截斷黏著片材並目視截斷面時，在上述界面1明確之情形時，被覆材區域之厚度可使用尺、游標卡尺、測微計進行測定。又，亦可使用電子顯微鏡、光學顯微鏡、原子力顯微鏡等顯微鏡測定被覆材區域之厚度。進而，亦可根據被覆材區域與黏著劑區域之組成之差異而辨別界面並測定被覆材區域之厚度。例如，可藉由拉曼光譜分析、紅外線光譜分析、X射線電子光譜分析等光譜分析；基質輔助雷射脫附游離飛行時間質譜儀(MALDI-TOFMS，Matrix-Assisted Laser Desorption Ionization-time of Flight Mass Spectrometer)或飛行時間二次離子質譜儀(TOF-SIMS，Time-of-Flight Secondary Ion Mass Spectrometer)等之質量分析等，對構成被覆材區域之被覆材料及構成黏著劑區域之黏著劑之組成進行分析，根據該組成之差異而辨別界面並測定被覆材區域之厚度。如上所述，藉由光譜分析或質量分析辨別界面之方法對於使用目視或顯微鏡進行觀察時難以辨別界面之情形有用。 作為構成上述被覆材區域之材料，例如可列舉：聚矽氧系聚合物、環氧系聚合物、聚碳酸酯系聚合物、乙烯系聚合物、丙烯酸系聚合物、胺基甲酸酯系聚合物、聚酯系聚合物(例如，聚對苯二甲酸乙二酯)、聚烯烴系聚合物、聚醯胺系聚合物、聚醯亞胺系聚合物、不飽和烴系聚合物等聚合物材料。若使用該等聚合物材料，則可適當選擇單體種類、交聯劑、聚合度等，而容易地形成具有上述彈性模數之被覆材區域。又，上述聚合物材料於與熱膨脹性微球、構成黏著劑區域之黏著劑及基材之親和性方面優異。上述聚合物材料可單獨使用，或可組合使用2種以上。 作為構成上述被覆材區域之材料，可使用可藉由活性能量線之照射而硬化(高彈性模數化)之樹脂材料。若藉由此種材料形成被覆材區域，則可獲得如下黏著片材：於貼附黏著片材時為低彈性，柔軟性較高，操作性優異，於貼附後可藉由照射活性能量線而調整為上述範圍之彈性模數。作為活性能量線，例如可列舉：γ射線、紫外線、可見光、紅外線(熱線)、射頻波、α射線、β射線、電子束、電漿流、游離射線、粒子束等。關於包含可藉由活性能量線之照射而硬化之樹脂材料的被覆材區域，照射活性能量線後之上述藉由奈米壓痕法所測得之彈性模數成為上述範圍。又，包含可藉由活性能量線之照射而硬化之樹脂材料的被覆材區域較佳為照射活性能量線後之上述拉伸彈性模數及/或彎曲彈性模數成為上述範圍。 作為可藉由照射活性能量線而硬化(高彈性模數化)之樹脂材料，例如可列舉：紫外線硬化系統(加藤清視著，綜合技術中心發行，(1989))、光硬化技術(技術資訊協會編(2000))、日本專利特開2003-292916號公報、日本專利4151850號等所記載之樹脂材料。更具體而言，可列舉含有成為母劑之聚合物與活性能量線反應性化合物(單體或低聚物)之樹脂材料(R1)、含有活性能量線反應性聚合物之樹脂材料(R2)等。 作為上述成為母劑之聚合物，例如可列舉：天然橡膠、聚異丁烯橡膠、苯乙烯-丁二烯橡膠、苯乙烯-異戊二烯-苯乙烯嵌段共聚物橡膠、再生橡膠、丁基橡膠、聚異丁烯橡膠、腈橡膠(NBR)等橡膠系聚合物；聚矽氧系聚合物；丙烯酸系聚合物等。該等聚合物可單獨使用，或組合使用2種以上。 作為上述活性能量線反應性化合物，例如可列舉：具有丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有碳-碳多重鍵之官能基的光反應性之單體或低聚物。作為該光反應性之單體或低聚物之具體例，可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯等含(甲基)丙烯醯基之化合物；該含(甲基)丙烯醯基之化合物之二聚物～五聚物等。 又，作為上述活性能量線反應性化合物，亦可使用環氧化丁二烯、甲基丙烯酸縮水甘油酯、丙烯醯胺、乙烯基矽氧烷等單體；或包含該單體之低聚物。含有該等化合物之樹脂材料(R1)可藉由紫外線、電子束等高能量線而硬化。 進而，作為上述活性能量線反應性化合物，亦可使用鎓鹽等有機鹽類與分子內具有複數個雜環之化合物之混合物。該混合物藉由活性能量線(例如，紫外線、電子束)之照射，有機鹽裂解而生成離子，其成為起始種而引起雜環之開環反應，可形成立體網狀結構。作為上述有機鹽類，例如可列舉：錪鹽、鏻鹽、銨鹽、鋶鹽、硼酸鹽等。作為上述分子內具有複數個雜環之化合物中之雜環，可列舉氧雜環丙烷、氧雜環丁烷、氧雜環戊烷、硫雜環丙烷、氮丙啶等。 於上述含有成為母劑之聚合物與活性能量線反應性化合物之樹脂材料(R1)中，活性能量線反應性化合物之含有比率相對於成為母劑之聚合物100重量份，較佳為0.1重量份～500重量份，更佳為1重量份～300重量份，進而較佳為10重量份～200重量份。 上述含有成為母劑之聚合物與活性能量線反應性化合物之樹脂材料(R1)可視需要而含有任意合適之添加劑。作為添加劑，例如可列舉：活性能量線聚合起始劑、活性能量線聚合促進劑、交聯劑、塑化劑、硫化劑等。作為活性能量線聚合起始劑，可根據所使用之活性能量線之種類而使用任意合適之起始劑。活性能量線聚合起始劑可單獨使用，或組合使用2種以上。於含有成為母劑之聚合物與活性能量線反應性化合物之樹脂材料(R1)中，活性能量線聚合起始劑之含有比率相對於成為母劑之聚合物100重量份，較佳為0.1重量份～10重量份，更佳為1重量份～5重量份。 作為上述活性能量線反應性聚合物，例如可列舉：具有丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有碳-碳多重鍵之官能基的聚合物。作為含有活性能量線反應性官能基之聚合物之具體例，可列舉：含有多官能(甲基)丙烯酸酯之聚合物；光致陽離子聚合型聚合物；聚乙烯肉桂酸酯等含肉桂醯基之聚合物；經重氮化之胺基酚醛樹脂；聚丙烯醯胺等。又，作為含有活性能量線反應性聚合物之樹脂材料(R2)，亦可使用含有烯丙基之活性能量線反應性聚合物與含有硫醇基之化合物之混合物。再者，只要於利用活性能量線照射所進行之硬化前(例如，貼附黏著片材時)，可形成具有可實用之硬度(黏度)之被覆材區域前驅物，則除含有活性能量線反應性官能基之聚合物以外，亦可使用含有活性能量線反應性官能基之低聚物。 上述含有活性能量線反應性聚合物之樹脂材料(R2)可進而含有上述活性能量線反應性化合物(單體或低聚物)。又，上述含有活性能量線反應性聚合物之樹脂材料(R2)可視需要而含有任意合適之添加劑。添加劑之具體例與含有成為母劑之聚合物與活性能量線反應性化合物之樹脂材料(R1)可含有之添加劑相同。於含有活性能量線反應性聚合物之樹脂材料(R2)中，活性能量線聚合起始劑之含有比率相對於活性能量線反應性聚合物100重量份，較佳為0.1重量份～10重量份，更佳為1重量份～5重量份。 上述被覆材區域可進而含有珠粒。作為該珠粒，例如可列舉：玻璃珠、樹脂珠等。若於被覆材區域添加此種珠粒，則可獲得可提高被覆材區域之彈性模數、可精度更良好地加工被加工物之黏著片材。珠粒之平均粒徑例如為0.01 μm～50 μm。珠粒之添加量相對於被覆材區域整體100重量份，例如為10重量份～200重量份，較佳為20重量份～100重量份。 C.黏著劑區域 上述黏著劑區域較佳為含有黏著劑與熱膨脹性微球。 上述黏著劑區域之厚度較佳為50 μm以下，更佳為1 μm～50 μm，進而較佳為1 μm～25 μm，尤佳為1 μm～15 μm。於黏著劑區域之厚度厚於50 μm之情形時，在用作對電子零件等進行切斷加工時之暫時固定用片材之情形時，有產生如下異常情況之虞：切斷後之晶片再附著；切斷面變得不穩定；切斷時產生晶片缺損；產生切削屑等。於本發明中，藉由形成彈性模數經適當調整之被覆材區域，可容許熱膨脹性微球自黏著劑區域突出，使黏著劑區域變薄。另一方面，於黏著劑區域之厚度未達1 μm之情形時，有無法獲得充分之黏著力之虞。再者，於本說明書中，所謂黏著劑區域之厚度，如圖1所示係指自構成被覆材區域20之被覆材料與構成黏著劑區域10之黏著劑之界面1至黏著面11為止之距離。即，熱膨脹性微球13自黏著劑區域10突出之部分並非黏著劑區域之厚度之評估對象。再者，作為界面1之辨別方法，如上述B項所述。 關於本發明之黏著片材，貼附該黏著片材時之溫度下的黏著面之藉由奈米壓痕法所測得之彈性模數較佳為未達100 MPa，更佳為0.1 MPa～50 MPa，進而較佳為0.1 MPa～10 MPa。上述黏著劑區域之藉由奈米壓痕法所測得之彈性模數相當於黏著面之藉由奈米壓痕法所測得之彈性模數。黏著面之所謂藉由奈米壓痕法所測得之彈性模數係指選擇不存在熱膨脹性微球之部分，藉由上述B項所說明之測定方法測得之彈性模數、即黏著劑之彈性模數。所謂貼附上述黏著片材時之溫度，例如於使用丙烯酸系黏著劑作為黏著劑之情形時為10℃～80℃，於使用苯乙烯-二烯嵌段共聚物系黏著劑作為黏著劑之情形時為40℃～120℃。 (黏著劑) 作為上述黏著劑，較佳為加熱時不限制熱膨脹性微球之膨脹或發泡者。作為該黏著劑，例如可列舉：丙烯酸系黏著劑、橡膠系黏著劑、乙烯基烷基醚系黏著劑、聚矽氧系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、胺基甲酸酯系黏著劑、苯乙烯-二烯嵌段共聚物系黏著劑、放射線硬化型黏著劑、於該等黏著劑中調配有熔點約為200℃以下之熱熔融性樹脂的蠕變特性改良型黏著劑等(例如，參照日本專利特開昭56-61468號公報、日本專利特開昭63-17981號公報等)。其中較佳為丙烯酸系黏著劑或橡膠系黏著劑。再者，上述黏著劑可單獨使用，或組合使用2種以上。 作為上述丙烯酸系黏著劑，例如可列舉：以將(甲基)丙烯酸烷基酯之1種或2種以上用作單體成分之丙烯酸系聚合物(均聚物或共聚物)作為基礎聚合物之丙烯酸系黏著劑等。作為(甲基)丙烯酸烷基酯之具體例，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-20烷基酯。其中，可較佳地使用具有碳數為4～18之直鏈狀或支鏈狀之烷基的(甲基)丙烯酸烷基酯。 以凝集力、耐熱性、交聯性等之改質為目的，上述丙烯酸系聚合物可視需要而含有可與上述(甲基)丙烯酸烷基酯共聚合之其他單體成分所對應之單元。作為此種單體成分，例如可列舉：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含羧基之單體；順丁烯二酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基己酯、(甲基)丙烯酸羥基辛酯、(甲基)丙烯酸羥基癸酯、(甲基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥基甲基環己基)甲酯等含羥基之單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體；(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體；(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體；(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體；N-環己基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-月桂基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等順丁烯二醯亞胺系單體；N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體；N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體；乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌

Figure 109108113-A0304-12-0000-4
、乙烯基吡
Figure 109108113-A0304-12-0000-4
、乙烯基吡咯、乙烯基咪唑、乙烯基
Figure 109108113-A0304-12-0059-1
唑、乙烯基嗎啉、N-乙烯基羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯單體；(甲基)丙烯酸縮水甘油酯等含環氧基之丙烯酸系單體；聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系丙烯酸酯單體；(甲基)丙烯酸四氫糠酯、含氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等具有雜環、鹵素原子、矽原子等之丙烯酸酯系單體；己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸胺基甲酸酯等多官能單體；異戊二烯、丁二烯、異丁烯等烯烴系單體；乙烯醚等乙烯醚系單體等。該等單體成分可單獨使用，或組合使用2種以上。 作為上述橡膠系黏著劑，例如可列舉以如下者作為基礎聚合物之橡膠系黏著劑：天然橡膠；聚異戊二烯橡膠、苯乙烯-丁二烯(SB)橡膠、苯乙烯-異戊二烯(SI)橡膠、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)橡膠、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)橡膠、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)橡膠、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)橡膠、苯乙烯-乙烯-丙烯嵌段共聚物(SEP)橡膠、再生橡膠、丁基橡膠、聚異丁烯、該等之改性體等合成橡膠等。 上述黏著劑可視需要而含有任意合適之添加劑。作為該添加劑，例如可列舉：交聯劑、黏著賦予劑、塑化劑(例如，偏苯三甲酸酯系塑化劑、均苯四甲酸酯系塑化劑)、顏料、染料、填充劑、抗老化劑、導電材料、抗靜電劑、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。 作為上述黏著賦予劑，可使用任意合適之黏著賦予劑。作為黏著賦予劑，例如可使用黏著賦予樹脂。作為黏著賦予樹脂之具體例，可列舉：松香系黏著賦予樹脂(例如，未改性松香、改性松香、松香酚系樹脂、松香酯系樹脂等)、萜烯系黏著賦予樹脂(例如，萜烯系樹脂、萜烯-酚系樹脂、苯乙烯改性萜烯系樹脂、芳香族改性萜烯系樹脂、氫化萜烯系樹脂)、烴系黏著賦予樹脂(例如，脂肪族系烴樹脂、脂肪族系環狀烴樹脂、芳香族系烴樹脂(例如，苯乙烯系樹脂、二甲苯系樹脂等)、脂肪族-芳香族系石油樹脂、脂肪族-脂環族系石油樹脂、氫化烴樹脂、薰草咔系樹脂、薰草咔茚系樹脂等)、酚系黏著賦予樹脂(例如，烷酚系樹脂、二甲苯甲醛系樹脂、可溶酚醛樹脂、酚醛樹脂等)、酮系黏著賦予樹脂、聚醯胺系黏著賦予樹脂、環氧系黏著賦予樹脂、彈性體系黏著賦予樹脂等。其中較佳為松香系黏著賦予樹脂、萜烯系黏著賦予樹脂或烴系黏著賦予樹脂(苯乙烯系樹脂等)。黏著賦予劑可單獨使用，或組合使用2種以上。 上述黏著賦予劑亦可使用市售品。作為市售品之黏著賦予劑之具體例，可列舉：Yasuhara Chemical公司製造之商品名「YS Polystar S145」、「Mighty Ace K140」、荒川化學公司製造之商品名「Tamanol 901」等萜烯-酚系樹脂；Sumitomo Bakelite公司製造之商品名「Sumilite Resin PR-12603」、荒川化學公司製造之商品名「Tamanol 361」等松香酚系樹脂；荒川化學公司製造之商品名「Tamanol 1010R」、「Tamanol 200N」等烷酚系樹脂；荒川化學公司製造之商品名「Arkon P-140」等脂環族系飽和烴樹脂等。 上述黏著賦予劑之添加量相對於基礎聚合物100重量份，較佳為5重量份～100重量份，更佳為10重量份～50重量份。 作為上述交聯劑，例如，除異氰酸酯系交聯劑、環氧系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑以外，可列舉脲系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、
Figure 109108113-A0304-12-0059-1
唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等。其中較佳為異氰酸酯系交聯劑或環氧系交聯劑。 作為上述異氰酸酯系交聯劑之具體例，可列舉：伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類；伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛酮二異氰酸酯等脂環族異氰酸酯類；2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類；三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(日本聚氨酯工業公司製造、商品名「Coronate L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(日本聚氨酯工業公司製造、商品名「Coronate HL」)、六亞甲基二異氰酸酯之異氰尿酸酯體(日本聚氨酯工業公司製造、商品名「Coronate HX」)等異氰酸酯加成物等。異氰酸酯系交聯劑之含量可根據所需之黏著力而設定為任意合適之量，相對於基礎聚合物100重量份，具代表性之量為0.1重量份～20重量份，更佳為0.5重量份～10重量份。 作為上述環氧系交聯劑，例如可列舉：N,N,N',N'-四縮水甘油基-間苯二甲胺、二縮水甘油基苯胺、1,3-雙(N,N-縮水甘油基胺基甲基)環己烷(Mitsubishi Gas Chemical公司製造、商品名「Tetrad C」)、1,6-己二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 1600」)、新戊二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 1500 NP」)、乙二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 40E」)、丙二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 70P」)、聚乙二醇二縮水甘油醚(日本油脂公司製造、商品名「Epiol E-400」)、聚丙二醇二縮水甘油醚(日本油脂公司製造、商品名「Epiol P-200」)、山梨糖醇聚縮水甘油醚(Nagase chemteX公司製造、商品名「Denacol EX-611」)、甘油聚縮水甘油醚(Nagase chemteX公司製造、商品名「Denacol EX-314」)、季戊四醇聚縮水甘油醚、聚甘油聚縮水甘油醚(Nagase chemteX公司製造、商品名「Denacol EX-512」)、山梨糖醇酐聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、三縮水甘油基-三(2-羥基乙基)異氰尿酸酯、間苯二酚二縮水甘油醚、雙酚S-二縮水甘油醚、分子內具有2個以上環氧基之環氧系樹脂等。環氧系交聯劑之含量可根據所需之黏著力而設定為任意合適之量，相對於基礎聚合物100重量份，具代表性之量為0.01重量份～10重量份，更佳為0.03重量份～5重量份。 (熱膨脹性微球) 作為上述熱膨脹性微球，只要為可藉由加熱而膨脹或發泡之微球，則可使用任意合適之熱膨脹性微球。作為上述熱膨脹性微球，例如可使用使藉由加熱容易膨脹之物質內包於具有彈性之殼內而成之微球。此種熱膨脹性微球可藉由任意合適之方法製造，例如凝聚法、界面聚合法等。 作為藉由加熱而容易膨脹之物質，例如可列舉：丙烷、丙烯、丁烯、正丁烷、異丁烷、異戊烷、新戊烷、正戊烷、正己烷、異己烷、庚烷、辛烷、石油醚、甲烷之鹵化物、四烷基矽烷等低沸點液體；藉由熱分解而氣化之偶氮二甲醯胺等。 作為構成上述殼之物質，例如可列舉包含如下者之聚合物：丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈、反丁烯二腈等腈單體；丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、反丁烯二酸、檸康酸等羧酸單體；偏二氯乙烯；乙酸乙烯酯；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異
Figure 109108113-003-010-1
酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、丙烯酸β-羧基乙酯等(甲基)丙烯酸酯；苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯單體；丙烯醯胺、取代丙烯醯胺、甲基丙烯醯胺、取代甲基丙烯醯胺等醯胺單體等。包含該等單體之聚合物可為均聚物，亦可為共聚物。作為該共聚物，例如可列舉：偏二氯乙烯-甲基丙烯酸甲酯-丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈-甲基丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丙烯腈-甲基丙烯腈-伊康酸共聚物等。 作為上述熱膨脹性微球，亦可使用無機系發泡劑或有機系發泡劑。作為無機系發泡劑，例如可列舉：碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、硼氫化鈉、各種疊氮類等。又，作為有機系發泡劑，例如可列舉：三氯單氟甲烷、二氯單氟甲烷等氯氟烷烴系化合物；偶氮二異丁腈、偶氮二甲醯胺、偶氮二羧酸鋇等偶氮系化合物；對甲苯磺醯肼、二苯碸-3,3'-二磺醯肼、4,4'-氧雙(苯磺醯肼)、烯丙基雙(磺醯肼)等肼系化合物；對甲苯磺醯胺脲、4,4'-氧雙(苯磺醯胺脲)等胺脲系化合物；5-嗎啉基-1,2,3,4-噻三唑等三唑系化合物；N,N'-二亞硝基五亞甲基四胺、N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺等N-亞硝基系化合物等。 上述熱膨脹性微球亦可使用市售品。作為市售品之熱膨脹性微球之具體例，可列舉：松本油脂製藥公司製造之商品名「Matsumoto Microsphere」(等級：F-30、F-30D、F-36D、F-36LV、F-50、F-50D、F-65、F-65D、FN-100SS、FN-100SSD、FN-180SS、FN-180SSD、F-190D、F-260D、F-2800D)、Nippon Fillite公司製造之商品名「Expancel」(等級：053-40、031-40、920-40、909-80、930-120)、吳羽化學工業公司製造「Daifoam」(等級：H750、H850、H1100、S2320D、S2640D、M330、M430、M520)、積水化學工業公司製造「Advancell」(等級：EML101、EMH204、EHM301、EHM302、EHM303、EM304、EHM401、EM403、EM501)等。 上述熱膨脹性微球於加熱前之粒徑較佳為0.5 μm～80 μm，更佳為5 μm～45 μm，進而較佳為10 μm～20 μm，尤佳為10 μm～15 μm。因此，上述熱膨脹性微球於加熱前之粒子尺寸以平均粒徑計較佳為6 μm～45 μm，更佳為15 μm～35 μm。上述粒徑與平均粒徑係藉由雷射散射法中之粒度分佈測定法所求出之值。 上述熱膨脹性微球較佳為具有體積膨脹率達到較佳為5倍以上、更佳為7倍以上、進而較佳為10倍以上而不破裂之適度之強度。於使用此種熱膨脹性微球之情形時，可藉由加熱處理而高效率地降低黏著力。 上述黏著劑區域中之熱膨脹性微球之含有比率可根據所需之黏著力之降低性等而適當設定。熱膨脹性微球之含有比率相對於形成黏著劑區域之基礎聚合物100重量份，例如為1重量份～150重量份，較佳為10重量份～130重量份，進而較佳為25重量份～100重量份。 D.基材 作為上述基材，例如可列舉：樹脂片材、不織布、紙、金屬箔、織布、橡膠片材、發泡片材、該等之積層體(尤其是含有樹脂片材之積層體)等。作為構成樹脂片材之樹脂，例如可列舉：聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)、聚醯胺(尼龍)、全芳香族聚醯胺(芳族聚醯胺)、聚醯亞胺(PI)、聚氯乙烯(PVC)、聚苯硫醚(PPS)、氟系樹脂、聚醚醚酮(PEEK)等。作為不織布，可列舉：含有馬尼拉麻之不織布等具有耐熱性之由天然纖維製成之不織布；聚丙烯樹脂不織布、聚乙烯樹脂不織布、酯系樹脂不織布等合成樹脂不織布等。 上述基材之厚度可根據所需之強度或柔軟性、及使用目的等而設定為任意合適之厚度。基材之厚度較佳為1000 μm以下，更佳為1 μm～1000 μm，進而較佳為1 μm～500 μm，尤佳為3 μm～300 μm，最佳為5 μm～250 μm。 亦可對上述基材實施表面處理。作為表面處理，例如可列舉：電暈處理、鉻酸處理、臭氧曝露、火焰曝露、高壓電擊曝露、離子化放射線處理、利用底塗劑所進行之塗佈處理等。若進行此種表面處理，則可提高被覆材區域與基材之密接性。尤其是利用有機塗佈材料所進行之塗佈處理由於可提高密接性，且於加熱剝離時被覆材區域不易發生抓固破壞，故而較佳。 作為上述有機塗佈材料，例如可列舉塑膠硬塗材料II(CMC出版、(2004))所記載之材料。較佳為使用胺基甲酸酯系聚合物，更佳為使用聚丙烯酸胺基甲酸酯、聚酯胺基甲酸酯或該等之前驅物。其原因在於，於基材上之塗敷、塗佈較為簡便，且工業上可選擇多種物質，可廉價地獲得。該胺基甲酸酯系聚合物例如為包含異氰酸酯單體與含醇性羥基之單體(例如，含羥基之丙烯酸化合物或含羥基之酯化合物)之反應混合物的聚合物。有機塗佈材料可含有聚胺等鏈延長劑、抗老化劑、氧化穩定劑等作為任意添加劑。有機塗佈層之厚度並無特別限定，例如適宜為0.1 μm～10 μm左右，較佳為0.1 μm～5 μm左右，更佳為0.5 μm～5 μm左右。 E.黏著片材之製造方法 作為本發明之黏著片材之製造方法，例如可列舉如下方法：(1)於脫模膜(剝離紙)上塗佈上述黏著劑而形成黏著劑塗佈層後，藉由加壓等將上述熱膨脹性微球埋入該黏著劑塗佈層中而形成黏著劑區域，於該黏著劑區域上形成(積層)被覆材區域；(2)於脫模膜上塗佈包含上述黏著劑與熱膨脹性微球之黏著劑區域形成用組合物而形成黏著劑塗佈層，於該黏著劑塗佈層上形成(積層)被覆材區域；(3)於脫模膜上塗佈上述黏著劑而形成黏著劑塗佈層後，於該黏著劑塗佈層上形成(積層)被覆材區域，繼而將脫模膜剝離，自黏著劑塗佈層之與被覆材區域相反之側之面(黏著面)側藉由加壓等將上述熱膨脹性微球埋入；(4)於脫模膜上形成被覆材區域，於其一面設置熱膨脹性微球，進而於該設置面上塗佈黏著劑等。於上述(1)～(4)之方法中，藉由將塗佈黏著劑所形成之黏著劑塗佈層進行乾燥，可形成黏著劑區域，該乾燥可於任意合適之時機進行。該乾燥可於將熱膨脹性微球埋入之前進行，亦可於埋入之後進行。又，可於形成被覆材區域之前進行，亦可於形成之後進行。於在將熱膨脹性微球埋入後進行乾燥之情形時，較佳為於熱膨脹性微球不易膨脹或發泡之溫度下進行乾燥。可於上述(1)及(2)所示之操作之後將脫模膜剝離，亦可於直至將黏著片材供於實用為止之期間，保留脫模膜而保護黏著面。 於本發明之黏著片材具備基材之情形時，該黏著片材於上述(1)～(4)之操作後，可介隔任意合適之接著劑或黏著劑，於被覆材區域之與黏著劑區域相反之側之面(與黏著面相反之側之面)上貼附基材。又，亦可分別製作基材與被覆材區域之積層體，及脫模膜與黏著劑區域(或黏著劑塗佈層)之積層體，再將該等積層體貼合。 作為形成上述被覆材區域之方法，可列舉如下方法：(i)使上述B項所說明之聚合物材料或樹脂材料熱熔融，藉由擠出成形而以膜狀獲得成形體，將該成形體積層於上述黏著劑區域(或黏著劑塗佈層)或基材上；(ii)將含有上述聚合物材料或樹脂材料之樹脂溶液塗佈於上述黏著劑區域(或黏著劑塗佈層)或基材上，其後使之乾燥；(iii)將含有可形成上述聚合物材料或樹脂材料之單體、低聚物或大分子單體之被覆材區域形成用組合物塗佈於上述黏著劑區域(或黏著劑塗佈層)或基材上，使被覆材區域形成用組合物聚合(例如，藉由加熱、活性能量線照射等進行聚合)等。藉由該(iii)之方法，可減少溶劑、及/或熱能之使用量。再者，於(ii)之方法中，亦可將樹脂溶液塗佈於別的脫模膜上，其後使之乾燥而獲得膜狀之成形體後，將該成形體積層於上述黏著劑區域(或黏著劑塗佈層)或基材上。又，於(iii)之方法中，亦可將被覆材區域形成用組合物塗佈於別的脫模膜上，其後使之乾燥而形成被覆材區域前驅物，將該前驅物積層於上述黏著劑區域(或黏著劑塗佈層)或基材上，其後使之聚合。 例如，於上述(iii)之方法中，於形成包含環氧系聚合物之被覆材區域之情形時，可採用塗佈含有2,2-(4-羥基苯基)丙烷二縮水甘油醚、雙(4-羥基苯基)甲烷等環氧化合物與任意合適之硬化劑之被覆材區域形成用組合物後進行加熱(例如，60℃～120℃)之方法。 例如，於上述(iii)之方法中，於形成包含胺基甲酸酯系聚合物之被覆材區域之情形時，可採用塗佈含有甲苯二異氰酸酯、六亞甲基二異氰酸酯等異氰酸酯化合物與聚醚多元醇、聚酯多元醇等多元醇化合物之被覆材區域形成用組合物後進行加熱(例如，60℃～120℃)之方法。 例如，於上述(iii)之方法中，於形成包含乙烯系聚合物之被覆材區域之情形時，可使用含有氯乙烯、苯乙烯等乙烯化合物與任意合適之起始劑之被覆材區域形成用組合物。 上述被覆材區域形成用組合物可視需要而含有起始劑、觸媒、紫外線吸收劑、抗氧化劑等添加劑。又，亦可含有上述珠粒。 於上述被覆材區域包含可藉由活性能量線之照射而硬化之樹脂材料之情形時，可於任意合適之時機照射活性能量線而獲得黏著片材。活性能量線之照射例如可於貼附被黏著體(被加工物)後進行。活性能量線之照射亦可分階段進行。例如，亦可於貼附被黏著體前使之半硬化，於貼附後使之正式硬化。活性能量線之種類及照射量可根據構成被覆材區域之樹脂材料之種類而設定為任意合適之種類及量。 根據上述之製造方法，黏著劑區域之脫模膜側(與被覆材區域相反之側)之面成為黏著面。由於黏著面係以與脫模膜相接之狀態形成，故而不存在熱膨脹性微球之突出，而為平坦。另一方面，於黏著劑區域之與黏著面相反之側之面，熱膨脹性微球突出。於本發明中，由於藉由上述被覆材區域而被覆該突出之熱膨脹性微球，故而黏著片材兩面較平坦，故而可使黏著劑區域之厚度較薄。此種本發明之黏著片材作為對電子零件等進行切斷加工時之暫時固定用片材而有助於實現優異之切斷精度、及切削屑之減少。 F.黏著片材之使用方法(電子零件之製造方法) 根據本發明之另一態樣，提供一種電子零件之製造方法。本發明之電子零件之製造方法包括於上述黏著片材上貼附以大面積獲得之電子零件材料(基板)，並對該電子零件材料進行切斷加工。 作為上述電子零件，例如可列舉：矽晶圓等半導體裝置用零件；積層電容器；透明電極等。 於上述製造方法中，首先，於加工台上載置上述黏著片材，於該黏著片材上貼附以大面積獲得之電子零件材料。 其後，藉由任意合適之方法切斷上述電子零件材料，可獲得電子零件。作為上述切斷加工之方法，例如可列舉使用旋轉刀、平刀等刀具之方法，使用雷射光之方法等。於藉由使用平刀之壓切而切斷電子零件材料之情形時，切削屑之產生得以抑制，良率提高。於本發明中，由於可使黏著劑區域變薄，故而即便藉由利用平刀之壓切而切斷電子零件材料，亦可防止以下情況：切斷後之晶片再附著；切斷面發生傾斜或成為S字狀，變得不穩定；切斷時產生晶片缺損等。又，於本發明中，即便於使用較薄之刀切斷之情形時，亦可獲得上述效果，且可降低因刀之厚度產生之製造損耗(由切斷後之晶片間產生之間隙引起之損耗)。於更小型化之電子零件之製造中，由於切斷面數量較多，故而如上所述之可降低製造損耗之本發明變得尤其有用。 於上述切斷加工中，亦可於加溫下進行切斷。例如，亦可將上述加工台加溫至30℃～150℃而進行切斷加工。 [實施例] 以下，藉由實施例對本發明進行具體說明，但本發明並不受該等實施例所限定。實施例中之評估方法如以下所述。又，於實施例中，只要未特別說明，則「份」及「%」為重量基準。 (1)藉由拉曼影像之黏著劑區域及被覆材區域之厚度之測定 利用切片機將實施例1～3、5、6及12～15所獲得之黏著片材切片化而準備測定試樣。針對該測定試樣之剖面，使用WITec公司製造之alpha300RSA進行藉由拉曼光譜之光譜分析，基於源自僅添加至被覆材區域中之成分之波峰(例如，於實施例3中為活性能量線反應性低聚物(UV1700B)之1640 cm-1 之波峰)之波峰強度，測定被覆材區域及黏著劑區域之厚度。以實施例3作為代表例，將該測定中之拉曼影像示於圖3。以僅添加至被覆材區域中之成分之存在量明確不同之面作為界面1，以自黏著面11至該界面1之距離作為黏著劑區域之厚度，以自該界面1至與黏著面相反之側之面21之距離作為被覆材區域之厚度。 再者，拉曼影像測定之測定條件如下所述。 ・激發波長：532 nm ・測定波數範圍：300～3600 cm-1 ・光柵(Grating)：600 gr/mm ・物鏡：×100 ・測定時間：0.2 sec/1光譜 ・測定範圍：20×40 μm ・測定數：100×200點 ・檢測器：EMCCD(Electron Multiplying Charge Coupled Device，電子倍增電荷耦合元件) (2)藉由SEM之黏著劑區域及被覆材區域之厚度之測定 利用修邊刀沿厚度方向切斷實施例4、7～11、16、17及比較例1所獲得之黏著片材，實施Pt-Pd濺鍍處理後，使用Hitachi High-Technologies公司製造之S3400N低真空掃描電子顯微鏡(SEM)觀察切斷面而辨別界面1，以自黏著面11至該界面1之距離作為黏著劑區域之厚度，以自該界面1至與黏著面相反之側之面21作為被覆材區域之厚度。以實施例11作為代表例，將黏著片材之剖面之SEM圖像示於圖4。 再者，SEM觀察之測定條件如下所述。 ・觀察影像：ESED(Environmental Secondary Electron Detector，環境二次電子檢測器)影像 ・加速電壓：10 kV ・倍率：600倍 (3)彈性模數測定 利用切片機將實施例及比較例所獲得之黏著片材沿厚度方向切斷，針對該切斷面，利用奈米壓痕儀測定彈性模數。 更詳細而言，針對被覆材區域，以與切斷面大致垂直之被覆材區域之表面(與黏著面相反之側之面)、及距該表面3 μm左右之切斷面表面作為測定對象。藉由測定裝置附帶之軟體(triboscan)對藉由將探針(壓頭)壓抵於測定對象而獲得之移位-荷重遲滯曲線進行數值處理，藉此獲得彈性模數。再者，於表1中表示於距表面3 μm左右之切斷面表面所測得之彈性模數(3次測定之平均值)。 奈米壓痕裝置及測定條件如下所述。 裝置及測定條件 ・裝置：奈米壓痕儀；Hysitron Inc公司製造之Triboindenter ・測定方法：單一壓入法 ・測定溫度：25℃ ・壓入速度：約1000 nm/sec ・壓入深度：約800 nm ・探針：金剛石製、Berkovich型(三角錐型) (4)黏著力測定 (加熱前(使熱膨脹性微球膨脹前)之黏著力) 將實施例及比較例所獲得之黏著片材切斷為寬：20 mm、長：140 mm之尺寸，依據JIS Z 0237：2009，於將作為被黏著體之聚對苯二甲酸乙二酯膜(商品名「Lumirror S-10」Toray股份有限公司製造；厚：25 μm、寬：30 mm)沿寬度方向左右各伸出5 mm之狀態下，使2 kg之輥往返1次而將其貼合於黏著面上，從而準備測定試樣。將該測定試樣設置於附帶恆溫槽之拉力試驗機(商品名「島津Autograph AG-120kN」島津製作所公司製造)上，放置30分鐘。其後，於剝離角度：180°、剝離速度(拉伸速度)：300 mm/min之條件下，測定將被黏著體沿長度方向自黏著片材剝離時之荷重，求出此時之最大荷重(除測定初期之峰頂以外之荷重之最大值)，將以該最大荷重除以膠帶寬度而獲得之值作為黏著力(N/20 mm寬)。再者，上述操作係於溫度：23±3℃及濕度：65±5%RH之環境下進行。 (加熱後(使熱膨脹性微球膨脹或發泡後)之黏著力) 以與上述相同之方式準備測定試樣，將該測定試樣投入熱風乾燥器中。於熱風乾燥器中，在熱膨脹性微球之最大膨脹溫度(下述)下靜置1分鐘後，以與上述相同之方式剝離被黏著體，測定黏著力。再者，投入熱風乾燥器前後之操作係於溫度：23±3℃及濕度：65±5%RH之環境下進行。 (5)表面粗糙度測定 針對實施例及比較例所獲得之黏著片材，使熱膨脹性微球膨脹或發泡後，測定黏著面之表面粗糙度Ra。熱膨脹性微球之膨脹或發泡係於熱風乾燥器中，在熱膨脹性微球之最大膨脹溫度(下述)下靜置1分鐘而進行。再者，表面粗糙度之測定係利用Olympus公司製造之雷射顯微鏡「OLS4000」進行。 (6)切斷後小片分離性評估 於實施例及比較例所獲得之黏著片材上貼合40 mm×50 mm(厚度500 μm)之積層陶瓷片材。利用UHT公司製造之切斷裝置「G-CUT8AA」將黏著片材上之積層陶瓷片材以成為1 mm×0.5 mm之小片之方式切斷為小塊狀。將黏著片材上之積層陶瓷片材沿直徑30 mm之圓柱之側面設置。於設置於圓柱上之狀態下，以特定之溫度(熱膨脹性微球之最大膨脹溫度(下述))進行加熱處理，使熱膨脹性微球膨脹，藉此將小片自黏著片材剝離，對切斷位置之晶片間未分離之晶片個數進行計數。將以未分離之晶片個數除以100%完全分離時之晶片個數而獲得之數作為分離性之指標。指標未達2%之情況設為◎，指標為2%以上且未達5%之情況設為○，指標為5%以上且未達15%之情況設為△，指標為15%以上之情況設為×。 積層陶瓷片材之組成及切斷裝置之切斷條件之詳細內容如下所述。 (積層陶瓷片材) 於甲苯溶劑中加入鈦酸鋇粉末100份、聚乙烯丁醛樹脂15份、鄰苯二甲酸雙(2-乙基己基)酯6份及雙甘油硬脂酸酯2份，利用球磨分散機進行混合及分散，藉此獲得介電體之甲苯溶液。使用敷料器以溶劑揮發後之厚度達到50 μm之方式將該溶液塗佈於附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜(Mitsubishi Polyester Film公司製造、商品名「MRF38」、厚度：38 μm)之矽脫模劑處理面上，加以乾燥而獲得陶瓷片材。以厚度達到500 μm之方式將陶瓷片材積層複數片，而獲得積層陶瓷片材。 (切斷條件) ・切斷溫度：60℃、切斷深度(自台面起之剩餘量)：約20 μm ・切斷刀：UHT公司製造「U-BLADE2」、刀厚：50 μm、刀尖角度：15° (7)切斷面切割性評估 以與上述(6)相同之方式，將積層陶瓷片材以成為1 mm×0.5 mm之小片之方式切斷為小塊狀。自經切斷之小片中任意選出10個，利用50倍率之放大鏡觀察切斷面，確認有無碎片(因切斷加工而產生之積層陶瓷片材之碎片)，將10個小片所產生之碎片總數之平均值作為指標。將指標0～未達10處之情況設為◎，為10以上且未達20處之情況設為○，為20以上且未達40處之情況設為△，為40處以上之情況設為×。 以下記載聚合物製備方法。再者，此處只要未特別說明，則份為重量份。 [製造例1]聚合物1之製備 於甲苯中加入丙烯酸丁酯100份、丙烯酸5份及作為聚合起始劑之過氧化苯甲醯0.2份後，進行加熱而獲得丙烯酸系共聚物(聚合物1)之甲苯溶液。 [製造例2]聚合物2之製備 於甲苯中加入丙烯酸2-乙基己酯30份、丙烯酸乙酯70份、丙烯酸2-羥基乙酯4份、N-苯基順丁烯二醯亞胺5份及作為聚合起始劑之過氧化苯甲醯0.2份後，進行加熱而獲得丙烯酸系共聚物(聚合物2)之甲苯溶液。 [製造例3]聚合物3之製備 於甲苯中加入丙烯酸2-乙基己酯30份、丙烯酸乙酯70份、丙烯酸2-羥基乙酯4份、甲基丙烯酸甲酯5份及作為聚合起始劑之過氧化苯甲醯0.2份後，進行加熱而獲得丙烯酸系共聚物(聚合物3)之甲苯溶液。 [製造例4]聚合物4之製備 於甲苯中加入丙烯酸丁酯50份、丙烯酸乙酯50份、丙烯酸5份、丙烯酸2-羥基乙酯0.1份及作為聚合起始劑之過氧化苯甲醯0.2份後，進行加熱而獲得丙烯酸系共聚物(聚合物4)之甲苯溶液。 [製造例5]聚合物5之製備 於乙酸乙酯中加入丙烯酸甲酯70份、丙烯酸2-乙基己酯30份、丙烯酸10份及作為聚合起始劑之過氧化苯甲醯0.2份後，進行加熱而獲得丙烯酸系共聚物(聚合物5)之乙酸乙酯溶液。 [製造例6]聚合物6之製備 於甲苯中加入丙烯酸丁酯50莫耳、丙烯酸乙酯50莫耳、丙烯酸2-羥基乙酯22莫耳及作為聚合起始劑之過氧化苯甲醯(相對於丙烯酸丁酯、丙烯酸乙酯及丙烯酸2-羥基乙酯之合計100份為0.2份)後，進行加熱而獲得共聚物溶液。於該共聚物溶液中加入相當於該溶液中之源自丙烯酸2-羥基乙酯之羥基之80莫耳%的量之丙烯酸2-異氰酸基乙酯後，進行加熱而對該源自丙烯酸2-羥基乙酯之羥基加成甲基丙烯酸2-異氰酸基乙酯，藉此獲得側鏈具有甲基丙烯酸酯基的丙烯酸系共聚物(聚合物6)之甲苯溶液。 [製造例7]聚合物7之製備 於甲苯中加入丙烯酸丁酯80莫耳、丙烯醯基嗎啉30莫耳、丙烯酸2-羥基乙酯20莫耳及作為聚合起始劑之過氧化苯甲醯(相對於丙烯酸丁酯、丙烯醯基嗎啉及丙烯酸2-羥基乙酯之合計100份為0.2份)後，進行加熱而獲得共聚物溶液。於該共聚物溶液中加入相當於該溶液中之源自丙烯酸2-羥基乙酯之羥基之50莫耳%的量之丙烯酸2-異氰酸基乙酯後，進行加熱而對該源自丙烯酸2-羥基乙酯之羥基加成甲基丙烯酸2-異氰酸基乙酯，藉此獲得側鏈具有甲基丙烯酸酯基的丙烯酸系共聚物(聚合物7)之甲苯溶液。 [實施例1] (黏著劑區域前驅層之形成) 將製造例2所製備之聚合物2之甲苯溶液(聚合物2：100份)、異氰酸酯系交聯劑(日本聚氨酯公司製造、商品名「Coronate L」)1份、作為黏著賦予劑之萜烯-酚系樹脂(Sumitomo Bakelite公司製造、商品名「Sumilite Resin PR12603」)5份及熱膨脹性微球(松本油脂製藥公司製造、商品名「Matsumoto Microsphere F-50D」、發泡(膨脹)起始溫度：95℃～105℃、最大膨脹溫度：125℃～135℃、平均粒徑10 μm～18 μm)40份混合而製備混合液。於該混合液中進而加入與該混合液中之溶劑相同之溶劑(甲苯)，將黏度調整為容易塗佈之黏度。使用敷料器，以溶劑揮發(乾燥)後之厚度達到10 μm之方式，將該混合液塗佈於附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜(Mitsubishi Chemical Polyester Film公司製造、商品名「MRF38」、厚度：38 μm)上，其後加以乾燥而於該聚對苯二甲酸乙二酯膜上形成黏著劑區域前驅層。 (被覆材區域前驅層之形成) 將製造例1所製備之上述聚合物1之甲苯溶液(聚合物1：100份)、作為活性能量線反應性低聚物之二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯之混合物(東亞合成公司製造、商品名「Aronix M404」)20份、異氰酸酯系交聯劑(日本聚氨酯公司製造、商品名「Coronate L」)2份及能量線聚合起始劑(BASF Japan公司製造、商品名「Irgacure 651」)3份混合而製備混合液。於該混合液中進而加入與該混合液中之溶劑相同之溶劑(甲苯)，將黏度調整為容易塗佈之黏度。使用敷料器，以溶劑揮發(乾燥)後之厚度達到25 μm之方式塗佈於附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜(Mitsubishi Chemical Polyester Film公司製造、商品名「MRF38」、厚度：38 μm)上，其後加以乾燥而於該聚對苯二甲酸乙二酯膜上形成被覆材區域前驅層。 (黏著片材1之形成) 將上述黏著劑區域前驅層與被覆材區域前驅層貼合。繼而，使用紫外線照射機「UM810(高壓水銀燈光源)」(日東精機公司製造)，自被覆劑區域之前驅層側照射累積光量300 mJ/cm2 之紫外線。其後，將附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜剝離，獲得黏著片材1(黏著劑區域之厚度：10 μm、被覆材區域之厚度：25 μm)。 [實施例2～15、比較例1] 如表1所示設定形成黏著劑區域前驅層時之聚合物、交聯劑、黏著賦予劑及熱膨脹性微球之種類及調配量，並且如表1所示設定形成被覆材區域前驅層時之聚合物、活性能量線反應性低聚物、交聯劑及能量線聚合起始劑之種類及調配量，除此以外，以與實施例1相同之方式獲得黏著片材。 再者，於實施例2～5、8、10、13～15及比較例1中，在形成被覆材區域前驅層時，將混合液塗佈於PET膜(厚度：100 μm)上而非附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜上，不剝離該PET膜而獲得具有PET膜(基材)之黏著片材。又，於實施例4及比較例1中，不照射紫外線而獲得黏著片材。 表1中所記載之交聯劑、黏著賦予劑、熱膨脹性微球、活性能量線反應性低聚物、能量線聚合起始劑之詳細內容如以下所述。 ＜交聯劑＞ Tetrad C：Mitsubishi Gas Chemical公司製造、商品名「Tetrad C」、環氧系交聯劑 ＜黏著賦予劑＞ PR51732：Sumitomo Bakelite公司製造、商品名「Sumilite Resin PR51732」 S145：Yasuhara Chemical公司製造、商品名「YS Polystar S145」 U130：Yasuhara Chemical公司製造、商品名「YS Polystar U130」 T160：Yasuhara Chemical公司製造、商品名「YS Polystar T160」 ＜熱膨脹性微球＞ F-30D：松本油脂製藥公司製造、商品名「Matsumoto Microsphere F-30D」、發泡(膨脹)起始溫度：70℃～80℃、最大膨脹溫度：110℃～120℃、平均粒徑10 μm～18 μm F-65D：松本油脂製藥公司製造、商品名「Matsumoto Microsphere F-65D」、發泡(膨脹)起始溫度：105℃～115℃、最大膨脹溫度：145℃～155℃、平均粒徑12 μm～18 μm FN-180SSD：松本油脂製藥公司製造、商品名「Matsumoto Microsphere FN-180SSD」、發泡(膨脹)起始溫度：135℃～150℃、最大膨脹溫度：165℃～180℃、平均粒徑15 μm～25 μm F-260D：松本油脂製藥公司製造、商品名「Matsumoto Microsphere F-260D」、發泡(膨脹)起始溫度：190℃～200℃、最大膨脹溫度：250℃～260℃、平均粒徑20 μm～35 μm ＜活性能量線反應性低聚物＞ UV1700B：日本合成化學公司製造、商品名「紫光UV-1700B」、紫外線硬化型丙烯酸胺基甲酸酯 UV7620EA：日本合成化學公司製造、商品名「紫光UV-7620EA」、紫外線硬化型丙烯酸胺基甲酸酯 UV3000B：日本合成化學公司製造、商品名「紫光UV-3000B」、紫外線硬化型丙烯酸胺基甲酸酯 M321：東亞合成公司製造、商品名「Aronix M321」、三羥甲基丙烷PO改性三丙烯酸酯(環氧丙烷(PO)之平均加成莫耳數：2莫耳) UV7630B：日本合成化學公司製造、商品名「紫光UV-7630B」、紫外線硬化型丙烯酸胺基甲酸酯 ＜能量線聚合起始劑＞ I184：BASF公司製造、商品名「Irgacure 184」 I2959：BASF公司製造、商品名「Irgacure 2959」 I651：BASF公司製造、商品名「Irgacure 651」 [實施例16] 將製造例1所製備之聚合物1之甲苯溶液(聚合物1：100份)、環氧系交聯劑(Mitsubishi Gas Chemical公司製造、商品名「Tetrad C」)0.8份、作為黏著賦予劑之萜烯-酚系樹脂(Yasuhara Chemical公司製造、商品名「YS Polystar S145」)30份及熱膨脹性微球(松本油脂製藥公司製造、商品名「Matsumoto Microsphere F-50D」、發泡(膨脹)起始溫度：95℃～105℃、最大膨脹溫度：125℃～135℃、平均粒徑10 μm～18 μm)30份混合而製備混合液。於該混合液中進而加入與該混合液中之溶劑相同之溶劑(甲苯)，將黏度調整為容易塗佈之黏度。使用敷料器，以溶劑揮發(乾燥)後之厚度達到30 μm之方式將該混合液塗佈於附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜(Mitsubishi Chemical Polyester Film公司製造、商品名「MRF38」、厚度：38 μm)上，其後加以乾燥而於該聚對苯二甲酸乙二酯膜上形成黏著劑區域前驅層。 利用手壓輥使上述黏著劑區域前驅層之黏著面貼合於作為被覆材區域之聚對苯二甲酸乙二酯膜(Toray公司製造、商品名「Lumirror Type X42」、厚度：50 μm)之消光處理面上。進行高壓釜處理(40℃、5 Kgf/cm2 、10分鐘)而獲得黏著片材(黏著劑區域(厚度：30 μm)/被覆材區域(聚對苯二甲酸乙二酯、厚度：50 μm))。 [實施例17] 將製造例4所製備之聚合物4之甲苯溶液(聚合物4：100份)、環氧系交聯劑(Mitsubishi Gas Chemical公司製造、商品名「Tetrad C」)0.8份、作為黏著賦予劑之萜烯-酚系樹脂(Yasuhara Chemical公司製造、商品名「YS Polystar S145」)5份及熱膨脹性微球(松本油脂製藥公司製造、商品名「Matsumoto Microsphere F-50D」、發泡(膨脹)起始溫度：95℃～105℃、最大膨脹溫度：125℃～135℃、平均粒徑10 μm～18 μm)30份混合而製備混合液。於該混合液中進而加入與該混合液中之溶劑相同之溶劑(甲苯)，將黏度調整為容易塗佈之黏度。使用敷料器，以溶劑揮發(乾燥)後之厚度達到40 μm之方式，將該混合液塗佈於附帶聚矽氧脫模劑處理面之聚對苯二甲酸乙二酯膜(Mitsubishi Chemical Polyester Film公司製造、商品名「MRF38」、厚度：38 μm)上，其後加以乾燥而於該聚對苯二甲酸乙二酯膜上形成黏著劑區域前驅層。 利用線棒塗佈器(10支)將乙酸乙酯與二甲基甲醯胺之混合溶劑(乙酸乙酯：二甲基甲醯胺＝1：10(體積%))塗佈於作為被覆材區域之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造之Diafix(PG-CHI(FG、厚度200 μm)))之一個面上，利用手壓輥使上述黏著劑區域前驅層之黏著面貼合於該塗佈面上。於80℃下藉由熱風乾燥機乾燥3分鐘，而獲得黏著片材(黏著劑區域(厚度：40 μm)/被覆材區域(聚對苯二甲酸乙二酯、厚度：200 μm))。 [表1]    黏著劑區域 被覆材區域 基材 與黏著面相反之側之面(被覆材區域)之彈性模數 (MPa) 對PET膜之黏著力(加熱前) (N/20 mm) 對PET膜之黏著力(發泡後) (N/20 mm) 加熱前後之黏著力之比 加熱後之黏著面之表面粗糙度Ra (μm) 切斷後小片分離性評估 切斷面切割性評估 聚合物 交聯劑 黏著賦予劑 熱膨脹性微球 乾燥後之厚度 (μm) 聚合物 活性能量線反應性低聚物 交聯劑 紫外線聚合起始劑 乾燥後之厚度 (μm)    調配量 (份)    調配量 (份)    調配量 (份)    調配量 (份)    調配量 (份)    調配量 (份)    調配量 (份)    調配量 (份)    厚度 (μm) 實施例1 聚合物2 100 Coronate L 1 PR12603 5 F-50D 40 10 聚合物1 100 M404 20 Coronate L 2 I651 3 25 - - 34 3.8 0.04 0.01 8.1 ◎ ◎ 實施例2 聚合物4 100 Tetrad C 1 S145 20 F-65D 20 15 聚合物2 100 M321 50 Coronate L 2 I184 5 25 PET 100 19 2.9 0.03 0.01 9.7 ◎ ◎ 實施例3 聚合物3 100 Coronate L 1.5 PR12603 10 F-50D 30 7 聚合物3 100 UV1700B 30 Coronate L 2 I651 3 25 PET 100 80 2.3 0.02 0.01 8.5 ◎ ◎ 實施例4 聚合物3 100 Coronate L 2 PR12603 10 F-50D 30 8 聚合物3 100 - - Coronate L 20 - - 25 PET 100 1.5 2.1 0.08 0.04 9.8 ○ ○ 實施例5 聚合物1 100 Tetrad C 0.8 S145 30 F-50D 40 8 聚合物4 100 UV1700B 50 Coronate L 1 I2959 3 25 PET 100 175 3.4 0.02 0.01 8.2 ◎ ◎ 實施例6 聚合物1 100 Tetrad C 0.6 PR51732 5 F-30D 60 10 聚合物4 100 UV7620EA 20 Tetrad C 1 I184 5 25 - - 57 4.1 0.08 0.02 10.2 ○ ◎ 實施例7 聚合物3 100 Coronate L 1.5 PR12603 10 F-50D 30 5 聚合物5 100 - - Coronate L 0.5 I651 3 25 - - 87 2.7 0.04 0.01 8.2 ◎ ◎ 實施例8 聚合物3 100 Coronate L 2 S145 30 F-260D 20 20 聚合物5 100 - - Coronate L 0.5 I651 3 50 PET 100 87 3.0 0.03 0.01 8.9 ◎ ○ 實施例9 聚合物1 100 Tetrad C 1.2 - - FN-180SSD 50 8 聚合物6 100 - - Coronate L 0.2 I651 3 30 - - 64 0.9 0.07 0.08 7.2 ◎ ◎ 實施例10 聚合物1 100 Tetrad C 0.8 T160 10 F-30D 30 10 聚合物6 100 - - Coronate L 0.5 I184 5 30 PET 100 61 1.2 0.03 0.03 9.2 ◎ ◎ 實施例11 聚合物2 100 Coronate L 1.5 PR51732 10 F-50D 30 5 聚合物6 100 - - Coronate L 0.2 I651 3 25 - - 64 3.3 0.03 0.01 9.9 ◎ ◎ 實施例12 聚合物2 100 Coronate L 1.5 U130 20 F-30D 30 7 聚合物6 100 UV1700B 100 Coronate L 0.5 I651 3 20 - - 562 3.6 0.02 0.01 8.4 ◎ ◎ 實施例13 聚合物2 100 Coronate L 1 PR12603 20 F-50D 40 10 聚合物5 100 UV1700B 20 Tetrad C 0.5 I651 3 30 PET 100 49 4.2 0.03 0.01 8.3 ◎ ◎ 實施例14 聚合物3 100 Coronate L 1.5 T160 20 F-30D 30 8 聚合物5 100 UV7620EA 40 Tetrad C 0.5 I651 3 25 PET 100 89 3.1 0.03 0.01 8.1 ◎ ◎ 實施例15 聚合物3 100 Coronate L 1.5 T160 20 F-30D 30 6 聚合物3 100 UV7630B 50 Coronate L 1 I184 5 35 PET 100 82 2.9 0.02 0.01 7.9 ◎ ◎ 實施例16 聚合物1 100 Tetrad C 0.8 S145 30 F-50D 30 30 PET - - - - - - - 50 - - 3120 5.8 0.05 0.01 12.8 ○ ○ 實施例17 聚合物4 100 Tetrad C 0.8 S145 5 F-50D 30 40 PET - - - - - - - 200 - - 3120 5.3 0.04 0.01 13.4 ○ ○ 比較例1 聚合物3 100 Coronate L 1.5 PR12603 10 F-50D 30 5 聚合物3 100 - - Coronate L 1 - - 25 PET 100 0.9 3.4 0.09 0.03 10.3 × × 根據表1可明瞭，本發明之黏著片材可藉由加熱而降低黏著力，且於對被黏著體進行切斷加工時，可實現優異之切斷精度。 [產業上之可利用性] 本發明之製造方法及黏著片材可適宜地用於半導體晶片等晶片狀電子零件之製造。A. Overall structure of the adhesive sheet Fig. 1 is a schematic cross-sectional view of the adhesive sheet of a preferred embodiment of the present invention. The adhesive sheet 100 has an adhesive surface 11 only on one side thereof. In addition, the adhesive sheet 100 has a surface 21 having an elastic modulus of 1 MPa or more measured by a nanoindentation method at 25° C. as a surface 21 on the side opposite to the adhesive surface 11. The surface having such an elastic modulus can be formed, for example, by providing the covering material region 20 as described below. The adhesive sheet 100 preferably contains heat-expandable microspheres 13 that can be expanded or foamed by heating. The adhesive sheet 100 has an adhesive region 10 containing an adhesive surface 11 as a surface, and a covering material region 20 adjacent to the side of the adhesive region 10 opposite to the adhesive surface 11. The adhesive region 10 preferably contains an adhesive 12 and thermally expandable microspheres 13. The so-called adhesive area 10 refers to the area from the adhesive surface 11 to the interface 1 between the adhesive 12 constituting the adhesive area 10 and the material constituting the covering material area 20. In addition, the covering material area 20 refers to an area from the interface 1 between the adhesive 12 constituting the adhesive area 10 and the material constituting the covering material area 20 to the surface 21 on the side opposite to the adhesive surface 11. The thermally expandable microspheres 13 may protrude from the adhesive region 10 to the coating material region 20. The heat-expandable microspheres 13 protruding from the adhesive region 10 can be covered by the coating material region 20. As a result, the influence of the unevenness caused by the heat-expandable microspheres 13 can be eliminated. The outer surface of the covering material region 20 (the lower surface in the example in the figure) is the surface 21 whose elastic modulus measured by the nanoindentation method is 1 MPa or more. In addition, although not shown, a release paper may be arranged on the outer side of the adhesive surface 11 to protect the adhesive surface 11 until the adhesive sheet is put into practical use. In addition, in the example of the figure, although the interface 1 is clearly shown, the interface may be an interface that is difficult to distinguish by visual inspection, a microscope, or the like. By visual inspection, microscope and other difficult to distinguish interface, for example, the composition of each area can be analyzed and distinguished (see below for details). In the present invention, by forming a covering material region 20 with an appropriately adjusted elastic modulus on the side opposite to the adhesive surface 11, the thermally expandable microspheres 13 can be allowed to protrude from the adhesive region 10, thereby making the adhesive region 10 thinner. If the adhesive region 10, which is a low elasticity region, is thinned, it will be used as a temporary fixing sheet when cutting electronic parts and the like, which contributes to achieving excellent cutting accuracy. More specifically, if an adhesive sheet with a thinner adhesive area 10 is used as a temporary fixing sheet to cut electronic parts, etc., since the deformation of the adhesive sheet is less, the following can be prevented: After the chip is broken, the chip is attached again; the cut surface is inclined or becomes S-shaped, which becomes unstable; the chip is chipped during cutting. In addition, when an adhesive sheet with a thinner adhesive region 10 is used as a temporary fixing sheet when cutting electronic parts and the like, the generation of cutting chips can also be suppressed. The adhesive sheet of the present invention not only exerts the above-mentioned effect in cutting by the rotary knife that is often used in the crystal cutting step, but also in cutting by the pressure cutting with a flat knife used to reduce cutting loss. It also exerts the above-mentioned effects, and it is especially useful. Moreover, when cutting is performed under heating (for example, 30°C to 150°C), the cutting can be performed accurately as described above. In addition, since the adhesive sheet of the present invention has thermally expandable microspheres 13 on the adhesive surface 11 side (adhesive area 10), when the adherend (for example, a chip after cutting processing) is peeled from the adhesive sheet, By heating at a temperature at which the thermally expandable microspheres 13 can expand or foam, unevenness is generated on the adhesive surface, and the adhesive force of the adhesive surface can be reduced or disappeared. When the adhesive surface of the adhesive sheet of the present invention is attached to a polyethylene terephthalate film (for example, a thickness of 25 μm), the adhesive force is preferably 0.2 N/20 mm or more, more preferably 0.2 N/ 20 mm-20 N/20 mm, more preferably 2 N/20 mm-10 N/20 mm. If it is in such a range, an adhesive sheet useful as a sheet for temporary fixing when cutting electronic parts and the like can be obtained. In this manual, the so-called adhesive force refers to the method based on JIS Z 0237: 2000 (measurement temperature: 23°C, bonding conditions: 2 kg roller reciprocating once, peeling speed: 300 mm/min, peeling angle 180° ) Measured adhesion. The adhesive surface of the adhesive sheet of the present invention is attached to a polyethylene terephthalate film (for example, 25 μm in thickness) and heated. The adhesive force is preferably 0.2 N/20 mm or less, more preferably 0.1 N /20 mm or less. In this specification, the so-called heating of the adhesive sheet refers to heating at a temperature and time at which the thermally expandable microspheres expand or foam to reduce the adhesive force. This heating is, for example, heating at 70°C to 270°C for 1 minute to 10 minutes. The adhesive force when the adhesive surface of the adhesive sheet of the present invention is attached to a polyethylene terephthalate film (for example, a thickness of 25 μm) (ie, the adhesive force (a1) before heating) and the adhesive force after heating The ratio (a2/a1) of the force (a2) is preferably 0.5 or less, more preferably 0.1 or less. The lower limit of (a2/a1) is preferably 0.0001, more preferably 0.0005. As described above, the adhesive sheet of the present invention is heated at a specific temperature to produce unevenness on the adhesive surface. The surface roughness Ra of the adhesive surface after heating the adhesive sheet of the present invention is preferably 3 μm or more, more preferably 5 μm or more. If it is in this range, the adhesive force will decrease or disappear after heating, and an adhesive sheet that can easily peel off the adherend can be obtained. Furthermore, the so-called surface roughness Ra of the adhesive surface refers to the surface roughness Ra of the adhesive surface of the adhesive sheet after heating in a state where there is no adherend. The surface roughness Ra can be measured in accordance with JIS B 0601:1994. Fig. 2 is a schematic cross-sectional view of an adhesive sheet according to another preferred embodiment of the present invention. The adhesive sheet 200 further includes a base material 30 on the side opposite to the adhesive surface 11. Furthermore, although not shown in the figure, any suitable adhesive layer or adhesive layer may be provided on the side of the substrate 30 opposite to the covering material region 20. In addition, a release paper may be arranged on the outer side of the base material 30 until the adhesive sheet of the present invention is put into practical use. In the case of disposing release paper on the outer side of the substrate 30, the release paper may be attached to the substrate via any suitable adhesive. In FIG. 2, it is shown that the adhesive area 10 and the covering material area 20 are formed on one side of the substrate 30, and the adhesive area 10 and the covering material area 20 can also be formed on both sides of the substrate 30, such as adhesive Composition of agent area/coating material area/base material/coating material area/adhesive area. B. Covering material area Regarding the adhesive sheet of the present invention, the elastic modulus measured by the nanoindentation method at 25°C on the side opposite to the adhesive surface is 1 MPa or more, preferably 1 MPa～5000 MPa, more preferably 1 MPa～3500 MPa, still more preferably 1 MPa～1000 MPa, particularly preferably 10 MPa～600 MPa. The adhesive sheet having a surface showing such an elastic modulus can be obtained, for example, by forming a covering material area formed of a material different from the adhesive area. The elastic modulus measured by the nanoindentation method in the above-mentioned covering material area may be equivalent to the elastic modulus measured by the nanoindentation method on the side opposite to the adhesive surface. The so-called modulus of elasticity measured by the nanoindentation method refers to the continuous measurement of the load weight and indentation depth applied to the indenter when the indenter is pressed into the sample (for example, the adhesive surface) during load and unloading. The modulus of elasticity is calculated according to the obtained load weight-indentation depth curve. In this manual, the so-called modulus of elasticity measured by the nanoindentation method means that the measurement conditions are set to load: 1 mN, load, unloading speed: 0.1 mN/s, holding time: 1 s, and the above Modulus of elasticity measured by the method. In the present invention, since the side opposite to the adhesive surface has a surface with a modulus of elasticity of 1 MPa or more measured by the nanoindentation method, a coating area showing the modulus of elasticity is formed, which can be provided as a countermeasure Adhesive sheet for temporary fixing of electronic parts, etc., which contributes to achieving excellent cutting accuracy. Furthermore, by setting the elastic modulus measured by the nanoindentation method in the area of the coating material to less than 5000 MPa, the area of the coating material can be matched with the unevenness of the heat-expandable microspheres protruding from the adhesive area. The form of the heat-expandable microspheres is embedded, and the heat-expandable microspheres are covered. In addition, it is possible to provide an adhesive sheet that contributes to the realization of excellent cutting accuracy without impairing the flexibility required as the entire adhesive sheet (for example, the degree of flexibility that can fit the adherend). The tensile modulus of elasticity of the above-mentioned covering material region at 25° C. is preferably 1 MPa or more, more preferably 1 MPa to 5000 MPa, and still more preferably 1 MPa to 1000 MPa. If it is in this range, the same effect as that described above can be obtained with respect to the elastic modulus measured by the nanoindentation method. Furthermore, the tensile elastic modulus can be measured in accordance with JIS K 7161:2008. The flexural modulus of elasticity of the covering material region at 25°C is preferably 1 MPa or more, more preferably 1 MPa to 5000 MPa, and still more preferably 1 MPa to 1000 MPa. If it is in this range, the same effect as that described above can be obtained with respect to the elastic modulus measured by the nanoindentation method. In addition, the bending elastic modulus can be measured in accordance with JIS K 7171:2008. The thickness of the coating material region can be set to any appropriate value according to the amount (size) of the unevenness (size) of the thermally expandable microspheres protruding from the adhesive region. The thickness of the coating material region is preferably a thickness that can completely cover the thermally expandable microspheres protruding from the adhesive region, for example, 0.1 μm to 200 μm, preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 45 μm. Furthermore, in this specification, the so-called thickness of the covering material area, as shown in FIG. 1, refers to the sum from the interface 1 between the covering material constituting the covering material area 20 and the adhesive 12 constituting the adhesive area 10 to the covering material area The distance to the surface 21 on the opposite side of the interface 1. That is, the part of the heat-expandable microsphere 13 protruding from the adhesive region 10 is not an evaluation target of the thickness of the coating material region. When the adhesive sheet is cut and the cut surface is visually observed, the thickness of the covering material area can be measured using a ruler, a vernier caliper, and a micrometer when the above interface 1 is clear. Furthermore, microscopes such as electron microscopes, optical microscopes, and atomic force microscopes may also be used to measure the thickness of the coating area. Furthermore, it is also possible to distinguish the interface and measure the thickness of the covering material area based on the difference in composition between the covering material area and the adhesive area. For example, Raman spectroscopy, infrared spectroscopy, X-ray electronic spectroscopy and other spectral analysis can be used; matrix-assisted laser desorption free time of flight mass spectrometer (MALDI-TOFMS, Matrix-Assisted Laser Desorption Ionization-time of Flight Mass Spectrometer) or time-of-flight secondary ion mass spectrometer (TOF-SIMS, Time-of-Flight Secondary Ion Mass Spectrometer) and other mass analysis, etc., the composition of the coating material constituting the coating area and the adhesive constituting the adhesive area Analyze, identify the interface based on the difference in composition, and measure the thickness of the coating area. As mentioned above, the method of identifying the interface through spectral analysis or mass analysis is useful for situations where it is difficult to identify the interface when using visual observation or microscope observation. As the material constituting the above-mentioned covering material region, for example, polysiloxane polymer, epoxy polymer, polycarbonate polymer, vinyl polymer, acrylic polymer, urethane polymer Polymers, polyester-based polymers (for example, polyethylene terephthalate), polyolefin-based polymers, polyamide-based polymers, polyimide-based polymers, unsaturated hydrocarbon-based polymers, etc. material. If these polymer materials are used, the type of monomer, crosslinking agent, degree of polymerization, etc. can be appropriately selected, and the coating region having the above-mentioned elastic modulus can be easily formed. In addition, the above-mentioned polymer material is excellent in affinity with the thermally expandable microspheres, the adhesive constituting the adhesive region, and the substrate. The above-mentioned polymer materials may be used alone, or two or more kinds may be used in combination. As the material constituting the above-mentioned covering material region, a resin material that can be cured (high elastic modulus) by irradiation of active energy rays can be used. If the covering material area is formed by such a material, the following adhesive sheet can be obtained: low elasticity, high flexibility, and excellent operability when attaching the adhesive sheet, and can be irradiated with active energy rays after attaching And adjusted to the above-mentioned range of elastic modulus. Examples of active energy rays include γ rays, ultraviolet rays, visible light, infrared rays (heat rays), radio frequency waves, α rays, β rays, electron beams, plasma flow, ionizing rays, and particle beams. Regarding the area of the covering material including the resin material that can be cured by the irradiation of the active energy rays, the elastic modulus measured by the nanoindentation method after the irradiation of the active energy rays falls within the above range. In addition, it is preferable that the region of the coating material including a resin material that can be cured by the irradiation of active energy rays has the above-mentioned tensile modulus and/or bending modulus of elasticity within the above-mentioned range after active energy ray irradiation. Examples of resin materials that can be cured (high elastic modulus) by irradiating active energy rays include: ultraviolet curing system (by Kato Kiyoshi, issued by the Comprehensive Technology Center (1989)), light curing technology (technical information) Association ed. (2000)), Japanese Patent Laid-Open No. 2003-292916, Japanese Patent No. 4151850, etc. More specifically, a resin material (R1) containing a polymer that becomes a master agent and an active energy ray reactive compound (monomer or oligomer), and a resin material (R2) containing an active energy ray reactive polymer can be cited Wait. Examples of the polymer used as the master agent include natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, and butyl rubber. , Polyisobutylene rubber, nitrile rubber (NBR) and other rubber polymers; silicone polymers; acrylic polymers, etc. These polymers can be used alone or in combination of two or more kinds. Examples of the above-mentioned active energy ray reactive compound include photoreactive monomers having functional groups such as acryloyl, methacryloyl, vinyl, allyl, and ethynyl groups having carbon-carbon multiple bonds. Or oligomers. As specific examples of the photoreactive monomer or oligomer, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(methyl) ) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate and other (meth)acrylic acid group-containing compounds; among the (meth)acrylic acid group-containing compounds Dimer to pentamer, etc. In addition, as the above-mentioned active energy ray reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinyl silicone; or oligomers containing the monomers may also be used. The resin material (R1) containing these compounds can be cured by high-energy rays such as ultraviolet rays and electron beams. Furthermore, as the active energy ray reactive compound, a mixture of organic salts such as onium salt and a compound having a plurality of heterocyclic rings in the molecule can also be used. The mixture is irradiated with active energy rays (for example, ultraviolet rays, electron beams), and organic salts are cleaved to generate ions, which become the starting species and cause the ring-opening reaction of the heterocyclic ring to form a three-dimensional network structure. Examples of the above-mentioned organic salts include phosphonium salts, phosphonium salts, ammonium salts, sulfonium salts, and borate salts. Examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include oxetane, oxetane, oxolane, thiolane, aziridine, and the like. In the above-mentioned resin material (R1) containing the polymer used as the master agent and the active energy ray reactive compound, the content ratio of the active energy ray reactive compound relative to 100 parts by weight of the polymer used as the master agent is preferably 0.1 weight Parts to 500 parts by weight, more preferably 1 part by weight to 300 parts by weight, and still more preferably 10 parts by weight to 200 parts by weight. The above-mentioned resin material (R1) containing a polymer used as a master agent and an active energy ray reactive compound may contain any suitable additives as needed. Examples of additives include active energy ray polymerization initiators, active energy ray polymerization accelerators, crosslinking agents, plasticizers, vulcanizing agents, and the like. As the active energy ray polymerization initiator, any suitable initiator can be used according to the type of active energy ray used. The active energy ray polymerization initiator can be used alone or in combination of two or more kinds. In the resin material (R1) containing the polymer that becomes the master agent and the active energy ray reactive compound, the content ratio of the active energy ray polymerization initiator relative to 100 parts by weight of the polymer that becomes the master agent is preferably 0.1 weight Parts to 10 parts by weight, more preferably 1 part by weight to 5 parts by weight. Examples of the active energy ray-reactive polymer include polymers having functional groups such as acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, and ethynyl groups that have carbon-carbon multiple bonds. Specific examples of polymers containing active energy ray reactive functional groups include: polyfunctional (meth)acrylate-containing polymers; photocationically polymerizable polymers; polyethylene cinnamate and other cinnamyl group-containing polymers The polymer; diazotized amino phenolic resin; polypropylene amide, etc. In addition, as the resin material (R2) containing an active energy ray reactive polymer, a mixture of an allyl group-containing active energy ray reactive polymer and a thiol group-containing compound can also be used. Furthermore, as long as the precursor of the coating material area with practical hardness (viscosity) can be formed before curing by active energy ray irradiation (for example, when attaching an adhesive sheet), it will contain active energy ray reaction In addition to polymers with functional functional groups, oligomers containing active energy ray reactive functional groups can also be used. The resin material (R2) containing the active energy ray reactive polymer may further contain the active energy ray reactive compound (monomer or oligomer). Furthermore, the above-mentioned resin material (R2) containing the active energy ray reactive polymer may contain any suitable additives as needed. Specific examples of the additives are the same as the additives that can be contained in the resin material (R1) containing a polymer that becomes a master agent and an active energy ray reactive compound. In the resin material (R2) containing the active energy ray reactive polymer, the content ratio of the active energy ray polymerization initiator relative to 100 parts by weight of the active energy ray reactive polymer is preferably 0.1 to 10 parts by weight , More preferably 1 part by weight to 5 parts by weight. The coating material region may further contain beads. Examples of the beads include glass beads and resin beads. If such beads are added to the area of the coating material, an adhesive sheet can be obtained that can increase the elastic modulus of the area of the coating material and can process the workpiece more accurately. The average particle diameter of the beads is, for example, 0.01 μm to 50 μm. The addition amount of the beads is, for example, 10 parts by weight to 200 parts by weight, preferably 20 parts by weight to 100 parts by weight with respect to 100 parts by weight of the entire coating area. C. Adhesive area The above-mentioned adhesive area preferably contains an adhesive and thermally expandable microspheres. The thickness of the adhesive region is preferably 50 μm or less, more preferably 1 μm-50 μm, still more preferably 1 μm-25 μm, and particularly preferably 1 μm-15 μm. When the thickness of the adhesive area is thicker than 50 μm, when it is used as a temporary fixing sheet for cutting electronic parts, etc., the following abnormalities may occur: the chip after cutting is attached again; The cut surface becomes unstable; wafer defects are generated during cutting; cutting chips are generated. In the present invention, by forming a covering material area with an appropriately adjusted elastic modulus, the heat-expandable microspheres can be allowed to protrude from the adhesive area, and the adhesive area can be thinned. On the other hand, when the thickness of the adhesive area is less than 1 μm, there is a possibility that sufficient adhesive force may not be obtained. Furthermore, in this specification, the so-called thickness of the adhesive area, as shown in FIG. 1, refers to the distance from the interface 1 of the covering material constituting the covering material area 20 and the adhesive constituting the adhesive area 10 to the adhesive surface 11 . That is, the part of the heat-expandable microsphere 13 protruding from the adhesive region 10 is not an evaluation target of the thickness of the adhesive region. Furthermore, as the identification method of interface 1, as described in item B above. Regarding the adhesive sheet of the present invention, the elastic modulus measured by the nanoindentation method of the adhesive surface at the temperature when the adhesive sheet is attached is preferably less than 100 MPa, more preferably 0.1 MPa-50 MPa, more preferably 0.1 MPa to 10 MPa. The elastic modulus of the adhesive area measured by the nanoindentation method is equivalent to the elastic modulus of the adhesive surface measured by the nanoindentation method. The so-called elastic modulus of the adhesive surface measured by the nanoindentation method refers to the selected part without thermally expandable microspheres, and the elastic modulus measured by the measurement method described in item B above, that is, the elastic modulus of the adhesive Modulus of elasticity. The so-called temperature when attaching the above-mentioned adhesive sheet is, for example, 10°C to 80°C when using an acrylic adhesive as the adhesive, and when using a styrene-diene block copolymer adhesive as the adhesive At 40℃～120℃. (Adhesive) The above-mentioned adhesive is preferably one that does not restrict the expansion or foaming of thermally expandable microspheres when heated. Examples of the adhesive include: acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, and amine based adhesives. Formate-based adhesives, styrene-diene block copolymer-based adhesives, radiation-curable adhesives, and improved creep characteristics of hot-melt resins with melting points below 200℃ Type adhesives, etc. (for example, refer to Japanese Patent Laid-Open No. 56-61468, Japanese Patent Laid-Open No. 63-17981, etc.). Among them, an acrylic adhesive or a rubber adhesive is preferred. In addition, the above-mentioned adhesives can be used alone or in combination of two or more kinds. As the above-mentioned acrylic adhesive, for example, an acrylic polymer (homopolymer or copolymer) using one or two or more of alkyl (meth)acrylates as a monomer component is used as a base polymer The acrylic adhesive etc. As specific examples of the alkyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Base) butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate , Heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth) Isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, ten (meth)acrylate Trialkyl ester, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, ( C1-20 alkyl (meth)acrylates such as stearyl meth)acrylate, nonadecyl (meth)acrylate, and eicosanyl (meth)acrylate. Among them, alkyl (meth)acrylates having a linear or branched alkyl group having 4 to 18 carbon atoms can be preferably used. For the purpose of modification of cohesive force, heat resistance, crosslinkability, etc., the acrylic polymer may optionally contain units corresponding to other monomer components copolymerizable with the alkyl (meth)acrylate. Examples of such monomer components include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and other carboxyl-containing ones. Monomers; anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyl (meth)acrylate Hydroxy-containing monomers such as hexyl ester, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc. ; Styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, (meth)sulfopropyl acrylate, (Meth)acryloxynaphthalenesulfonic acid and other monomers containing sulfonic acid groups; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(methyl) ) (N-substituted) amide monomers such as acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; (meth)acrylamide (Meth)aminoalkyl acrylate monomers such as ethyl, N,N-dimethylaminoethyl (meth)acrylate, and tertiary butylaminoethyl (meth)acrylate; (methyl) ) Alkoxyalkyl (meth)acrylate monomers such as methoxyethyl acrylate and ethoxyethyl (meth)acrylate; N-cyclohexyl maleimide, N-isopropyl Maleimide-based monomers such as methyl maleimide, N-lauryl maleimide, and N-phenyl maleimide; N-methylikon Ikonimines, N-Ethyl Ikonimines, N-Butyl Ikonimines, N-octyl Ikonimines, N-2-Ethylhexyl Ikonimines, N-ring Ikonimines such as hexyl Ikonimines and N-Lauryl Ikonimines; N-(meth)acryloxymethylene succinimine, N-(methyl) Succinimidyl monomers such as acryloyl-6-oxyhexamethylene succinimidyl and N-(meth)acryloyl-8-oxyoctamethylene succinimidyl; vinyl acetate Ester, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiper
Figure 109108113-A0304-12-0000-4
Vinylpyridine
Figure 109108113-A0304-12-0000-4
, Vinyl pyrrole, vinyl imidazole, vinyl
Figure 109108113-A0304-12-0059-1
Vinyl monomers such as azole, vinylmorpholine, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinylcaprolactam, etc.; cyano groups such as acrylonitrile and methacrylonitrile Acrylic monomers; glycidyl (meth)acrylate and other epoxy-containing acrylic monomers; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy glycol (Meth) acrylate, methoxy polypropylene glycol (meth) acrylate and other glycol-based acrylate monomers; tetrahydrofurfuryl (meth)acrylate, fluorine-containing (meth)acrylate, polysiloxane ( Meth) acrylate and other acrylate monomers having heterocycles, halogen atoms, silicon atoms, etc.; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly) ) Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Multifunctional monomers such as acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, and urethane acrylate; olefin-based monomers such as isoprene, butadiene, and isobutylene ; Vinyl ether monomers such as vinyl ether. These monomer components can be used individually or in combination of 2 or more types. As the above-mentioned rubber-based adhesives, for example, rubber-based adhesives using the following as the base polymer can be cited: natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene Olefin (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butene -Styrenic block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, recycled rubber, butyl Synthetic rubbers such as rubber, polyisobutylene, these modified products, etc. The aforementioned adhesive may contain any suitable additives as needed. Examples of the additives include: crosslinking agents, adhesion-imparting agents, plasticizers (for example, trimellitate-based plasticizers, pyromellitic acid-based plasticizers), pigments, dyes, and fillers , Anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, stripping regulators, softeners, surfactants, flame retardants, antioxidants, etc. As the above-mentioned adhesion-imparting agent, any suitable adhesion-imparting agent can be used. As the adhesion imparting agent, for example, an adhesion imparting resin can be used. Specific examples of adhesion-imparting resins include: rosin-based adhesion-imparting resins (for example, unmodified rosin, modified rosin, rosin-phenol resin, rosin ester resin, etc.), terpene-based adhesion-imparting resins (for example, terpene Olefin resins, terpene-phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins), hydrocarbon-based adhesion imparting resins (for example, aliphatic hydrocarbon resins, Aliphatic cyclic hydrocarbon resin, aromatic hydrocarbon resin (for example, styrene resin, xylene resin, etc.), aliphatic-aromatic petroleum resin, aliphatic-alicyclic petroleum resin, hydrogenated hydrocarbon resin , Lavender resin, lavender indene resin, etc.), phenolic adhesion imparting resin (for example, alkylphenol resin, xylene formaldehyde resin, phenolic resin, phenolic resin, etc.), ketone-based adhesion imparting resin , Polyamide-based adhesion imparting resin, epoxy-based adhesion imparting resin, elastic system adhesion imparting resin, etc. Among them, rosin-based adhesion-imparting resins, terpene-based adhesion-imparting resins, or hydrocarbon-based adhesion-imparting resins (styrene resins, etc.) are preferred. The adhesion-imparting agent can be used alone or in combination of two or more kinds. Commercial products can also be used for the above-mentioned adhesion imparting agent. Specific examples of commercially available adhesive agents include terpene-phenols such as "YS Polystar S145" and "Mighty Ace K140" manufactured by Yasuhara Chemical, and "Tamanol 901" manufactured by Arakawa Chemical Co., Ltd. Resin; product name "Sumilite Resin PR-12603" manufactured by Sumitomo Bakelite, product name "Tamanol 361" manufactured by Arakawa Chemical Company, and other rosin phenol resins; product name manufactured by Arakawa Chemical Company "Tamanol 1010R", "Tamanol 200N" ”And other alkylphenol resins; alicyclic saturated hydrocarbon resins such as “Arkon P-140” manufactured by Arakawa Chemical Company. The added amount of the above-mentioned adhesion imparting agent is preferably 5 parts by weight to 100 parts by weight, and more preferably 10 parts by weight to 50 parts by weight relative to 100 parts by weight of the base polymer. As the above-mentioned crosslinking agent, for example, in addition to isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, Crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents,
Figure 109108113-A0304-12-0059-1
Oxazoline-based cross-linking agents, aziridine-based cross-linking agents, amine-based cross-linking agents, etc. Among them, an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent is preferred. Specific examples of the above-mentioned isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone Alicyclic isocyanates such as diisocyanate; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/toluene diisocyanate Trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., brand name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., brand name "Coronate L") HL"), hexamethylene diisocyanate isocyanurate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HX") and other isocyanate adducts. The content of the isocyanate-based crosslinking agent can be set to any suitable amount according to the required adhesive force, with respect to 100 parts by weight of the base polymer, a representative amount is 0.1 to 20 parts by weight, more preferably 0.5 parts by weight Parts ~ 10 parts by weight. As the epoxy-based crosslinking agent, for example, N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N- Glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical, trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1600") ``), neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., brand name "Epolight 1500 NP"), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., brand name "Epolight 40E") , Propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., brand name "Epolight 70P"), polyethylene glycol diglycidyl ether (manufactured by Nippon Oil & Fat Co., Ltd., brand name "Epiol E-400"), polypropylene glycol diglycidyl ether Glyceryl ether (manufactured by Nippon Oil & Fat Co., Ltd., brand name "Epiol P-200"), sorbitol polyglycidyl ether (manufactured by Nagase chemteX, brand name "Denacol EX-611"), glycerol polyglycidyl ether (Nagase chemteX) Manufacture, brand name "Denacol EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase chemteX, brand name "Denacol EX-512"), sorbitan polyglycidyl ether, tri Hydroxymethyl propane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl-tris(2-hydroxyethyl) isocyanurate, resorcinol diglycidyl Glycidyl ether, bisphenol S-diglycidyl ether, epoxy resin having two or more epoxy groups in the molecule, etc. The content of the epoxy-based crosslinking agent can be set to any suitable amount according to the required adhesive force, with respect to 100 parts by weight of the base polymer, a representative amount is 0.01 to 10 parts by weight, more preferably 0.03 Parts by weight ~ 5 parts by weight. (Heat-expandable microspheres) As the above-mentioned heat-expandable microspheres, any suitable heat-expandable microspheres can be used as long as they can be expanded or foamed by heating. As the above-mentioned heat-expandable microspheres, for example, microspheres obtained by enclosing a material that easily expands by heating in a shell having elasticity. Such thermally expandable microspheres can be manufactured by any suitable method, such as agglomeration method, interfacial polymerization method, and the like. Examples of substances that easily expand by heating include propane, propylene, butene, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, heptane, Low-boiling liquids such as octane, petroleum ether, methane halides, tetraalkylsilane, etc.; azodimethamide, which is vaporized by thermal decomposition, etc. Examples of the material constituting the shell include polymers containing acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, and other nitrile monomers; acrylic acid , Methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid and other carboxylic acid monomers; vinylidene chloride; vinyl acetate; (meth) acrylate, (methyl) ) Ethyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate
Figure 109108113-003-010-1
(Meth)acrylates such as cyclohexyl (meth)acrylate, benzyl (meth)acrylate, β-carboxyethyl acrylate, etc.; styrene, α-methylstyrene, chlorostyrene, etc. Body; acrylamide, substituted acrylamide, methacrylamide, substituted methacrylamide and other amide monomers. The polymer containing these monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, and methyl methacrylate-acrylonitrile copolymer. Compounds, acrylonitrile-methacrylonitrile-itaconic acid copolymer, etc. As the thermally expandable microspheres, an inorganic foaming agent or an organic foaming agent can also be used. Examples of inorganic foaming agents include ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, various azides, and the like. In addition, as the organic blowing agent, for example, chlorofluoroalkane-based compounds such as trichloromonofluoromethane and dichloromonofluoromethane; azobisisobutyronitrile, azodimethamide, and azodicarboxylic acid Azo compounds such as barium; p-toluenesulfonamide, diphenylsulfonium-3,3'-disulfonylhydrazine, 4,4'-oxybis(phenylsulfonylhydrazine), allylbis(sulfonylhydrazine) Hydrazine compounds; semicarbazide compounds such as p-toluene sulphuramide, 4,4'-oxybis(benzene sulphuramide); 5-morpholino-1,2,3,4-thiatriazole etc. Triazole compounds; N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroso-p-xylylenedimethamide and other N-nitroso Base compounds, etc. Commercial products can also be used for the above-mentioned thermally expandable microspheres. As a specific example of commercially available heat-expandable microspheres, one can cite: the trade name "Matsumoto Microsphere" manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd. (Grade: F-30, F-30D, F-36D, F-36LV, F-50 , F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), the product name manufactured by Nippon Fillite Expancel" (Grade: 053-40, 031-40, 920-40, 909-80, 930-120), "Daifoam" manufactured by Kureha Chemical Industry Co., Ltd. (Grade: H750, H850, H1100, S2320D, S2640D, M330, M430, M520), "Advancell" manufactured by Sekisui Chemical Industry Co., Ltd. (grades: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501), etc. The particle size of the thermally expandable microspheres before heating is preferably 0.5 μm to 80 μm, more preferably 5 μm to 45 μm, still more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 15 μm. Therefore, the particle size of the thermally expandable microspheres before heating is preferably 6 μm to 45 μm in terms of average particle diameter, and more preferably 15 μm to 35 μm. The above-mentioned particle size and average particle size are the values obtained by the particle size distribution measurement method in the laser scattering method. The above-mentioned thermally expandable microspheres preferably have a moderate strength such that the volume expansion rate is preferably 5 times or more, more preferably 7 times or more, and still more preferably 10 times or more without breaking. In the case of using such thermally expandable microspheres, the adhesive force can be efficiently reduced by heat treatment. The content ratio of the heat-expandable microspheres in the above-mentioned adhesive area can be appropriately set according to the required reduction of adhesive force. The content ratio of the heat-expandable microspheres relative to 100 parts by weight of the base polymer forming the adhesive region is, for example, 1 part by weight to 150 parts by weight, preferably 10 parts by weight to 130 parts by weight, and more preferably 25 parts by weight to 100 parts by weight. D. Substrate As the aforementioned substrate, for example, resin sheets, non-woven fabrics, paper, metal foils, woven fabrics, rubber sheets, foamed sheets, laminates of these (especially laminates containing resin sheets) Body) and so on. As the resin constituting the resin sheet, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene ( PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), wholly aromatic polyamide (aromatic polyamide), polyamide Amine (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine resin, polyether ether ketone (PEEK), etc. Examples of non-woven fabrics include non-woven fabrics made of natural fibers with heat resistance, such as non-woven fabrics containing manila hemp; synthetic resin non-woven fabrics such as polypropylene resin non-woven fabrics, polyethylene resin non-woven fabrics, and ester-based resin non-woven fabrics. The thickness of the above-mentioned base material can be set to any suitable thickness according to the required strength or flexibility, and the purpose of use. The thickness of the substrate is preferably 1000 μm or less, more preferably 1 μm to 1000 μm, still more preferably 1 μm to 500 μm, particularly preferably 3 μm to 300 μm, most preferably 5 μm to 250 μm. Surface treatment may also be performed on the above-mentioned base material. Examples of surface treatments include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionized radiation treatment, and coating treatment with a primer. If such surface treatment is performed, the adhesion between the region of the coating material and the substrate can be improved. In particular, the coating treatment with an organic coating material is preferable because it can improve the adhesiveness, and the area of the covering material is less likely to be damaged during heat peeling. Examples of the above-mentioned organic coating material include materials described in Plastic Hard Coating Material II (CMC Publishing, (2004)). Preferably, a urethane-based polymer is used, and more preferably, a polyacrylate urethane, polyester urethane, or these precursors are used. The reason is that coating and coating on the substrate are relatively simple, and a variety of materials can be selected industrially, which can be obtained at low cost. The urethane-based polymer is, for example, a polymer containing a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl-containing monomer (for example, a hydroxyl-containing acrylic compound or a hydroxyl-containing ester compound). The organic coating material may contain chain extenders such as polyamines, anti-aging agents, oxidation stabilizers, etc. as optional additives. The thickness of the organic coating layer is not particularly limited. For example, it is preferably about 0.1 μm to 10 μm, preferably about 0.1 μm to 5 μm, and more preferably about 0.5 μm to 5 μm. E. Manufacturing method of adhesive sheet As a manufacturing method of the adhesive sheet of the present invention, for example, the following methods can be cited: (1) After coating the above-mentioned adhesive on a release film (release paper) to form an adhesive coating layer , By applying pressure or the like to embed the heat-expandable microspheres in the adhesive coating layer to form an adhesive area, and form (laminate) a covering material area on the adhesive area; (2) apply on the release film The cloth includes the composition for forming an adhesive region of the adhesive and heat-expandable microspheres to form an adhesive coating layer, and form (laminate) a covering material region on the adhesive coating layer; (3) on the release film After applying the above-mentioned adhesive to form an adhesive coating layer, form (laminate) a coating material area on the adhesive coating layer, and then peel off the release film, from the adhesive coating layer opposite to the coating material area On the side surface (adhesive surface) side, the above-mentioned thermally expandable microspheres are embedded by pressing or the like; (4) A covering material area is formed on the release film, and the thermally expandable microspheres are placed on one side, and then the setting surface Apply adhesive etc. In the methods (1) to (4) above, by drying the adhesive coating layer formed by applying the adhesive, the adhesive area can be formed, and the drying can be performed at any appropriate timing. The drying can be performed before embedding the heat-expandable microspheres, or after embedding. In addition, it may be performed before forming the coating material region, or may be performed after forming. In the case of drying after embedding the heat-expandable microspheres, it is preferable to perform the drying at a temperature at which the heat-expandable microspheres are not easy to expand or foam. The release film can be peeled off after the operations shown in (1) and (2) above, or the release film can be kept to protect the adhesive surface until the adhesive sheet is put into practical use. When the adhesive sheet of the present invention is provided with a substrate, the adhesive sheet may be interposed with any suitable adhesive or adhesive after the operations of (1) to (4) above to bond the area of the covering material The substrate is attached to the surface on the opposite side of the agent area (the surface on the side opposite to the adhesive surface). In addition, a laminate of the base material and the covering material area, and a laminate of the release film and the adhesive area (or the adhesive coating layer) may be separately produced, and then these laminates may be bonded together. As a method of forming the coating material region, the following method can be cited: (i) The polymer material or resin material described in the above item B is heat-melted, and a molded body is obtained in a film shape by extrusion molding, and the molded body Laminate on the adhesive area (or adhesive coating layer) or substrate; (ii) apply a resin solution containing the polymer material or resin material to the adhesive area (or adhesive coating layer) or On the substrate, it is then dried; (iii) The coating material region forming composition containing the monomer, oligomer or macromonomer that can form the above polymer material or resin material is applied to the above adhesive On the region (or the adhesive coating layer) or the substrate, the composition for forming the coating material region is polymerized (for example, polymerized by heating, active energy ray irradiation, etc.). By the method (iii), the amount of solvent and/or heat used can be reduced. Furthermore, in the method of (ii), the resin solution can also be coated on another release film, and then dried to obtain a film-like molded body, and then the molded bulk layer is placed on the adhesive area (Or adhesive coating layer) or on the substrate. In the method of (iii), the composition for forming the coating material region may be applied to another release film, and then dried to form a precursor of the coating material region, and the precursor may be laminated on the above Adhesive area (or adhesive coating layer) or substrate, after which it is polymerized. For example, in the method of (iii) above, in the case of forming a coating material region containing an epoxy-based polymer, coating containing 2,2-(4-hydroxyphenyl)propane diglycidyl ether, double A method of heating (for example, 60°C to 120°C) after forming a composition for forming a coating material region of an epoxy compound such as (4-hydroxyphenyl)methane and any suitable hardener. For example, in the method of (iii) above, when forming a coating material region containing a urethane-based polymer, a coating containing an isocyanate compound such as toluene diisocyanate and hexamethylene diisocyanate and a poly A method of heating (for example, 60°C to 120°C) after forming a composition for forming a coating material region of a polyol compound such as ether polyol and polyester polyol. For example, in the method of (iii) above, in the case of forming a covering material region containing an ethylene-based polymer, a covering material region forming agent containing vinyl compounds such as vinyl chloride and styrene and any suitable initiator can be used combination. The composition for forming a coating material region may contain additives such as an initiator, a catalyst, an ultraviolet absorber, and an antioxidant, if necessary. In addition, the above-mentioned beads may be contained. In the case where the above-mentioned covering material region contains a resin material that can be cured by the irradiation of active energy rays, the active energy rays can be irradiated at any appropriate timing to obtain an adhesive sheet. The active energy ray irradiation can be performed after attaching the adherend (workpiece), for example. The irradiation of active energy rays can also be carried out in stages. For example, it is also possible to semi-harden the adherend before attaching it, and formally harden it after attaching it. The type and amount of active energy rays can be set to any appropriate type and amount according to the type of resin material constituting the coating area. According to the above-mentioned manufacturing method, the surface of the release film side (the side opposite to the covering material region) of the adhesive region becomes the adhesive surface. Since the adhesive surface is formed in contact with the release film, there is no protrusion of thermally expandable microspheres, and it is flat. On the other hand, the heat-expandable microspheres protrude on the side of the adhesive area opposite to the adhesive surface. In the present invention, since the protruding thermally expandable microspheres are covered by the above-mentioned covering material area, the two sides of the adhesive sheet are relatively flat, so that the thickness of the adhesive area can be made thinner. Such an adhesive sheet of the present invention serves as a temporary fixing sheet when cutting electronic parts and the like, and contributes to achieving excellent cutting accuracy and reduction of cutting chips. F. Using method of adhesive sheet (Method of manufacturing electronic component) According to another aspect of the present invention, a method of manufacturing electronic component is provided. The method of manufacturing an electronic component of the present invention includes attaching an electronic component material (substrate) obtained in a large area on the adhesive sheet, and cutting the electronic component material. Examples of the above-mentioned electronic components include semiconductor device components such as silicon wafers; multilayer capacitors; and transparent electrodes. In the above manufacturing method, first, the adhesive sheet is placed on a processing table, and the electronic component material obtained in a large area is attached to the adhesive sheet. Thereafter, by cutting the above-mentioned electronic component materials by any suitable method, electronic components can be obtained. As the method of the above-mentioned cutting processing, for example, a method using a tool such as a rotary knife and a flat knife, a method using a laser light, and the like can be cited. In the case of cutting electronic parts materials by pressing with a flat knife, the generation of cutting chips is suppressed and the yield is improved. In the present invention, since the adhesive area can be thinned, even if the electronic part material is cut by pressing with a flat knife, the following conditions can be prevented: the chip after the cut reattaches; the cut surface is inclined or It becomes S-shaped and becomes unstable; wafer chipping occurs during cutting. In addition, in the present invention, even when a thinner knife is used for cutting, the above-mentioned effects can be obtained, and the manufacturing loss due to the thickness of the knife (loss caused by the gap between the wafers after cutting can be reduced) ). In the manufacture of smaller electronic parts, since the number of cut surfaces is large, the present invention, which can reduce manufacturing loss as described above, becomes particularly useful. In the above-mentioned cutting process, cutting can also be performed under heating. For example, the above-mentioned processing table may be heated to 30°C to 150°C to perform cutting processing. [Examples] Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. The evaluation methods in the examples are as follows. Moreover, in the examples, unless otherwise specified, "parts" and "%" are based on weight. (1) By measuring the thickness of the adhesive area and the coating area of the Raman image, the adhesive sheets obtained in Examples 1 to 3, 5, 6, and 12 to 15 were sliced using a microtome to prepare measurement samples . For the profile of the measurement sample, the alpha300RSA manufactured by WITec was used to perform spectral analysis by Raman spectroscopy, based on the peaks derived from the components added only to the area of the coating material (for example, the active energy line in Example 3) The peak intensity of the reactive oligomer (UV1700B) at 1640 cm -1 ) was used to measure the thickness of the coating area and the adhesive area. Taking Example 3 as a representative example, the Raman image during the measurement is shown in FIG. 3. The surface with clearly different amounts of ingredients added only to the area of the covering material is taken as interface 1, and the distance from the adhesive surface 11 to the interface 1 is taken as the thickness of the adhesive area, and from the interface 1 to the opposite of the adhesive surface The distance of the side surface 21 is taken as the thickness of the covering material area. In addition, the measurement conditions of Raman imaging measurement are as follows.・Excitation wavelength: 532 nm ・Measurement wave number range: 300～3600 cm -1・Grating: 600 gr/mm ・Objective lens: ×100 ・Measurement time: 0.2 sec/1 spectrum ・Measurement range: 20×40 μm・Measurement number: 100×200 points ・Detector: EMCCD (Electron Multiplying Charge Coupled Device) (2) The thickness of the adhesive area and the coating area of the SEM is measured by trimming the edge thickness The adhesive sheets obtained in Examples 4, 7 to 11, 16, 17 and Comparative Example 1 were cut in the direction and subjected to Pt-Pd sputtering treatment. Then, the S3400N low vacuum scanning electron microscope (SEM) manufactured by Hitachi High-Technologies was used. ) Observe the cut surface to identify the interface 1. The distance from the adhesive surface 11 to the interface 1 is used as the thickness of the adhesive area, and the surface 21 from the interface 1 to the opposite side of the adhesive surface is used as the thickness of the coating area. Taking Example 11 as a representative example, the SEM image of the cross-section of the adhesive sheet is shown in FIG. 4. In addition, the measurement conditions of SEM observation are as follows.・Observation image: ESED (Environmental Secondary Electron Detector, Environmental Secondary Electron Detector) image ・Accelerating voltage: 10 kV ・Magnification: 600 times (3) Measurement of elastic modulus using a microtome to adhere the examples and comparative examples The sheet is cut in the thickness direction, and the elastic modulus of the cut surface is measured with a nanoindenter. In more detail, for the covering material area, the surface of the covering material area approximately perpendicular to the cut surface (the surface on the side opposite to the adhesive surface) and the cut surface surface about 3 μm away from the surface are used as the measurement target. The software (triboscan) attached to the measuring device performs numerical processing on the displacement-load hysteresis curve obtained by pressing the probe (indenter) against the measuring object, thereby obtaining the elastic modulus. In addition, Table 1 shows the elastic modulus (average value of 3 measurements) measured on the surface of the cut section about 3 μm from the surface. The nanoindentation device and measurement conditions are as follows. Apparatus and measuring conditions · Apparatus: Nanoindenter; Triboindenter manufactured by Hysitron Inc. ·Measuring method: Single indentation method ·Measuring temperature: 25℃ ·Indentation speed: about 1000 nm/sec ·Indentation depth: about 800 nm ・Probe: Diamond, Berkovich type (triangular pyramid type) (4) Adhesive force measurement (adhesive force before heating (before expansion of thermally expandable microspheres)) Cut the adhesive sheets obtained in the examples and comparative examples The size is 20 mm wide and 140 mm long. According to JIS Z 0237:2009, the polyethylene terephthalate film (trade name "Lumirror S-10") Toray Co., Ltd. will be used as the adherend. Manufacturing; thickness: 25 μm, width: 30 mm) In the state of extending 5 mm left and right in the width direction, a 2 kg roller is reciprocated once and attached to the adhesive surface to prepare a measurement sample. This measurement sample was set on a tensile tester (trade name "Shimadzu Autograph AG-120kN" manufactured by Shimadzu Corporation) with a constant temperature bath and left for 30 minutes. Then, under the conditions of peeling angle: 180°, peeling speed (stretching speed): 300 mm/min, measure the load when the adherend is peeled from the adhesive sheet along the length direction, and find the maximum load at this time (The maximum value of the load other than the peak top in the initial measurement period), the value obtained by dividing the maximum load by the tape width is used as the adhesive force (N/20 mm width). Furthermore, the above operation is performed under an environment of temperature: 23±3°C and humidity: 65±5%RH. (Adhesion after heating (after expanding or foaming heat-expandable microspheres)) Prepare a measurement sample in the same manner as above, and put the measurement sample into a hot air dryer. In a hot air dryer, after standing for 1 minute at the maximum expansion temperature of the heat-expandable microspheres (described below), the adherend was peeled off in the same manner as above, and the adhesive force was measured. Furthermore, the operation before and after putting into the hot air dryer is performed under the environment of temperature: 23±3℃ and humidity: 65±5%RH. (5) Surface roughness measurement For the adhesive sheets obtained in the examples and comparative examples, after expanding or foaming the heat-expandable microspheres, the surface roughness Ra of the adhesive surface was measured. The expansion or foaming of the heat-expandable microspheres is performed in a hot-air dryer and allowed to stand for 1 minute at the maximum expansion temperature of the heat-expandable microspheres (described below). In addition, the measurement of surface roughness was performed using a laser microscope "OLS4000" manufactured by Olympus. (6) Evaluation of the separability of small pieces after cutting A laminated ceramic sheet of 40 mm×50 mm (thickness 500 μm) was pasted on the adhesive sheets obtained in the examples and comparative examples. Using the cutting device "G-CUT8AA" manufactured by UHT Corporation, the laminated ceramic sheet on the adhesive sheet is cut into small pieces in a manner of 1 mm×0.5 mm. Place the laminated ceramic sheet on the adhesive sheet along the side of a cylinder with a diameter of 30 mm. In the state of being set on a cylinder, heat treatment is performed at a specific temperature (the maximum expansion temperature of heat-expandable microspheres (below)) to expand the heat-expandable microspheres, thereby peeling the small piece from the adhesive sheet and cutting it in half The number of unseparated wafers between the wafers at the broken position is counted. The number obtained by dividing the number of unseparated wafers by the number of wafers at 100% complete separation is used as the index of separability. If the index is less than 2%, it is ◎, if the index is 2% or more and less than 5%, it is ○, if the index is 5% or more and less than 15%, it is △, and the index is 15% or more. Set to ×. The details of the composition of the laminated ceramic sheet and the cutting conditions of the cutting device are as follows. (Laminated ceramic sheet) Add 100 parts of barium titanate powder, 15 parts of polyvinyl butyral resin, 6 parts of bis(2-ethylhexyl) phthalate and 2 parts of diglyceryl stearate in toluene solvent , Use a ball mill disperser to mix and disperse to obtain a toluene solution of the dielectric. Use an applicator to apply the solution to a polyethylene terephthalate film (manufactured by Mitsubishi Polyester Film Co., Ltd., trade name ``MRF38'') with a silicone release agent treatment surface in such a way that the thickness after the solvent volatilizes reaches 50 μm. "Thickness: 38 μm) on the surface treated with silicon release agent and dried to obtain a ceramic sheet. A plurality of ceramic sheets are laminated so that the thickness reaches 500 μm to obtain a laminated ceramic sheet. (Cutting conditions) ・Cutting temperature: 60°C, cutting depth (remaining amount from the table): about 20 μm ・Cutting knife: UHT company "U-BLADE2", knife thickness: 50 μm, tip Angle: 15° (7) Evaluation of cut surface cutability In the same manner as in (6) above, the laminated ceramic sheet was cut into small pieces in a size of 1 mm × 0.5 mm. Randomly select 10 pieces from the cut small pieces, observe the cut surface with a magnifying glass of 50 magnification, and confirm whether there are fragments (fragments of the laminated ceramic sheet produced by the cutting process), and the total number of pieces produced by the 10 small pieces The average value is used as an indicator. Set the index 0 to less than 10 places as ◎, if the index is 10 or more and less than 20 places as ○, if it is 20 or more and less than 40 places, as △, and if it is 40 or more places ×. The polymer preparation method is described below. In addition, unless otherwise specified, a part is a part by weight here. [Production Example 1] Preparation of polymer 1 100 parts of butyl acrylate, 5 parts of acrylic acid and 0.2 part of benzoyl peroxide as a polymerization initiator were added to toluene, and then heated to obtain an acrylic copolymer (polymer 1) The toluene solution. [Production Example 2] Preparation of polymer 2 30 parts of 2-ethylhexyl acrylate, 70 parts of ethyl acrylate, 4 parts of 2-hydroxyethyl acrylate, and N-phenylmaleimide were added to toluene After 5 parts and 0.2 part of benzoyl peroxide as a polymerization initiator, heating was performed to obtain a toluene solution of acrylic copolymer (polymer 2). [Manufacturing Example 3] Preparation of polymer 3 30 parts of 2-ethylhexyl acrylate, 70 parts of ethyl acrylate, 4 parts of 2-hydroxyethyl acrylate, 5 parts of methyl methacrylate were added to toluene and used as a polymerization agent After 0.2 parts of benzyl peroxide as the starting agent, heating was performed to obtain a toluene solution of acrylic copolymer (polymer 3). [Manufacturing Example 4] Preparation of Polymer 4 Add 50 parts of butyl acrylate, 50 parts of ethyl acrylate, 5 parts of acrylic acid, 0.1 part of 2-hydroxyethyl acrylate, and benzyl peroxide as a polymerization initiator to toluene After 0.2 part, heating was performed to obtain a toluene solution of acrylic copolymer (polymer 4). [Production Example 5] Preparation of Polymer 5 After adding 70 parts of methyl acrylate, 30 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, and 0.2 part of benzoyl peroxide as a polymerization initiator to ethyl acetate , Heating to obtain an ethyl acetate solution of acrylic copolymer (polymer 5). [Production Example 6] Preparation of polymer 6 In toluene, 50 mol of butyl acrylate, 50 mol of ethyl acrylate, 22 mol of 2-hydroxyethyl acrylate, and benzyl peroxide as a polymerization initiator were added ( 0.2 part with respect to the total of 100 parts of butyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate), and then heated to obtain a copolymer solution. After adding 80 mol% of 2-isocyanatoethyl acrylate to the copolymer solution derived from the hydroxyl group of 2-hydroxyethyl acrylate in the solution, heating was performed to obtain the acrylic acid-derived The hydroxyl group of 2-hydroxyethyl was added to 2-isocyanatoethyl methacrylate, thereby obtaining a toluene solution of an acrylic copolymer (polymer 6) having a methacrylate group in the side chain. [Production Example 7] Preparation of Polymer 7 In toluene, 80 mol of butyl acrylate, 30 mol of acrylomorpholine, 20 mol of 2-hydroxyethyl acrylate, and benzyl peroxide as a polymerization initiator were added After glutamate (0.2 parts with respect to the total of 100 parts of butyl acrylate, acrylomorpholine, and 2-hydroxyethyl acrylate), heating was performed to obtain a copolymer solution. After adding 50 mol% of 2-isocyanatoethyl acrylate to the copolymer solution derived from the hydroxyl group of 2-hydroxyethyl acrylate in the solution, heating was performed to obtain the acrylic acid-derived The hydroxyl group of 2-hydroxyethyl was added to 2-isocyanatoethyl methacrylate, thereby obtaining a toluene solution of an acrylic copolymer (polymer 7) having a methacrylate group in the side chain. [Example 1] (Formation of the precursor layer in the adhesive area) The toluene solution of polymer 2 prepared in Manufacturing Example 2 (Polymer 2: 100 parts) and isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name " Coronate L''), 5 parts of terpene-phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., brand name "Sumilite Resin PR12603") as an adhesive imparting agent, and 5 parts of thermally expandable microspheres (manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., brand name "Matsumoto 40 parts of Microsphere F-50D", foaming (expansion) starting temperature: 95°C to 105°C, maximum expansion temperature: 125°C to 135°C, average particle size 10 μm to 18 μm) were mixed to prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed liquid is further added to the mixed liquid to adjust the viscosity to a viscosity that is easy to coat. Using an applicator, apply the mixture to a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film) with a silicone release agent treatment surface so that the thickness after the solvent volatilizes (drys) reaches 10 μm. It is manufactured by the company, brand name "MRF38", thickness: 38 μm), and then dried to form an adhesive area precursor layer on the polyethylene terephthalate film. (Formation of the precursor layer of the covering material area) The toluene solution of the above-mentioned polymer 1 prepared in Production Example 1 (polymer 1: 100 parts), dipentaerythritol pentaacrylate and dipentaerythritol as active energy ray reactive oligomers 20 parts of a mixture of hexaacrylate (manufactured by Toagosei Co., Ltd., brand name "Aronix M404"), 2 parts of isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Company, brand name "Coronate L"), and energy ray polymerization initiator (BASF 3 parts made by Japan company, brand name "Irgacure 651") were mixed to prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed liquid is further added to the mixed liquid to adjust the viscosity to a viscosity that is easy to coat. Using an applicator, coat the polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., trade name) with a silicone release agent treatment surface in such a way that the thickness after the solvent volatilizes (drying) reaches 25 μm. "MRF38", thickness: 38 μm), and then dried to form a coating material region precursor layer on the polyethylene terephthalate film. (Formation of Adhesive Sheet 1) The adhesive region precursor layer and the coating material region precursor layer are bonded together. Then, an ultraviolet irradiator "UM810 (high-pressure mercury lamp light source)" (manufactured by Nitto Seiki Co., Ltd.) was used to irradiate ultraviolet rays with a cumulative light intensity of 300 mJ/cm 2 from the precursor layer side of the coating area. After that, the polyethylene terephthalate film with the surface treated with the silicone release agent was peeled off to obtain an adhesive sheet 1 (the thickness of the adhesive area: 10 μm, the thickness of the covering material area: 25 μm). [Examples 2-15, Comparative Example 1] As shown in Table 1, the types and blending amounts of polymer, crosslinking agent, adhesive imparting agent and thermally expandable microspheres when forming the precursor layer of the adhesive area were set as shown in Table 1. The types and blending amounts of polymers, active energy ray reactive oligomers, crosslinking agents, and energy ray polymerization initiators when forming the precursor layer of the covering material region are set, except for this, the same as in Example 1 Way to obtain an adhesive sheet. Furthermore, in Examples 2 to 5, 8, 10, 13 to 15 and Comparative Example 1, when forming the coating material region precursor layer, the mixed solution was coated on the PET film (thickness: 100 μm) instead of incidental On the polyethylene terephthalate film on the surface treated with the silicone release agent, an adhesive sheet with a PET film (base material) is obtained without peeling the PET film. In addition, in Example 4 and Comparative Example 1, the adhesive sheet was obtained without irradiating ultraviolet rays. The details of the crosslinking agent, adhesion imparting agent, thermally expandable microsphere, active energy ray reactive oligomer, and energy ray polymerization initiator described in Table 1 are as follows. <Crosslinking agent> Tetrad C: manufactured by Mitsubishi Gas Chemical, trade name "Tetrad C", epoxy-based crosslinking agent <adhesive imparting agent> PR51732: manufactured by Sumitomo Bakelite, trade name "Sumilite Resin PR51732" S145: Yasuhara Chemical Manufactured by the company, brand name "YS Polystar S145" U130: manufactured by Yasuhara Chemical, brand name "YS Polystar U130" T160: manufactured by Yasuhara Chemical company, brand name "YS Polystar T160"<Thermally expandable microspheres> F-30D: Matsumoto Oil Made by a pharmaceutical company, brand name "Matsumoto Microsphere F-30D", foaming (expansion) starting temperature: 70°C to 80°C, maximum expansion temperature: 110°C to 120°C, average particle size 10 μm to 18 μm F-65D : Manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-65D", foaming (expansion) starting temperature: 105°C to 115°C, maximum expansion temperature: 145°C to 155°C, average particle size 12 μm to 18 μm FN-180SSD: manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., brand name "Matsumoto Microsphere FN-180SSD", foaming (expansion) starting temperature: 135°C to 150°C, maximum expansion temperature: 165°C to 180°C, average particle size 15 μm ～25 μm F-260D: manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-260D", foaming (expansion) starting temperature: 190℃～200℃, maximum expansion temperature: 250℃～260℃, average particle size Diameter 20 μm～35 μm <Active energy ray reactive oligomer> UV1700B: manufactured by Nippon Synthetic Chemical Co., Ltd., brand name "Violet UV-1700B", UV curable acrylic urethane UV7620EA: manufactured by Nippon Synthetic Chemical Co., Ltd. Trade name "Violet UV-7620EA", UV-curable urethane acrylate UV3000B: manufactured by Nippon Synthetic Chemical Co., Ltd., brand name "Violet UV-3000B", UV-curable urethane acrylate M321: manufactured by Toagosei , Trade name "Aronix M321", trimethylolpropane PO modified triacrylate (average addition mol of propylene oxide (PO): 2 mol) UV7630B: manufactured by Nippon Synthetic Chemical Corporation, trade name "Using UV-7630B", UV-curing acrylic urethane <Energy ray polymerization initiator> I184: manufactured by BASF Corporation, brand name "Irgacure 184" I2959: manufactured by BASF Corporation, brand name "Irgacure 2959" I651: manufactured by BASF Corporation, brand name "Irgacure 651" [Example 16] The polymer prepared in Manufacturing Example 1 1 toluene solution (polymer 1: 100 parts), epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical, trade name "Tetrad C") 0.8 part, terpene-phenol resin (Yasuhara Chemical Made by the company, brand name "YS Polystar S145") 30 parts and heat-expandable microspheres (manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., brand name "Matsumoto Microsphere F-50D", foaming (expansion) starting temperature: 95℃～105℃, Maximum expansion temperature: 125°C to 135°C, average particle size 10 μm to 18 μm) 30 parts are mixed to prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed liquid is further added to the mixed liquid to adjust the viscosity to a viscosity that is easy to coat. Using an applicator, apply the mixture to a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film Co., Ltd.) with a silicone release agent treatment surface so that the thickness after the solvent volatilizes (drys) reaches 30 μm. It is manufactured, trade name "MRF38", thickness: 38 μm), and then dried to form an adhesive region precursor layer on the polyethylene terephthalate film. Using a hand roller, the adhesive surface of the precursor layer in the adhesive area was attached to the polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror Type X42", thickness: 50 μm) as the covering material area. Matte treatment surface. Carry out autoclave treatment (40°C, 5 Kgf/cm 2 , 10 minutes) to obtain an adhesive sheet (adhesive area (thickness: 30 μm)/covering material area (polyethylene terephthalate, thickness: 50 μm) )). [Example 17] A toluene solution (polymer 4: 100 parts) of polymer 4 prepared in Production Example 4, and 0.8 parts of epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical, trade name "Tetrad C"), 5 parts of terpene-phenol resin (manufactured by Yasuhara Chemical Co., Ltd., trade name "YS Polystar S145") and heat-expandable microspheres (manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-50D", 30 parts of bubble (expansion) starting temperature: 95°C to 105°C, maximum expansion temperature: 125°C to 135°C, average particle size 10 μm to 18 μm) are mixed to prepare a mixed solution. The same solvent (toluene) as the solvent in the mixed liquid is further added to the mixed liquid to adjust the viscosity to a viscosity that is easy to coat. Using an applicator, apply the mixture to a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film) with a silicone release agent treatment surface so that the thickness after the solvent volatilizes (drys) reaches 40 μm. It is manufactured by the company, brand name "MRF38", thickness: 38 μm), and then dried to form an adhesive area precursor layer on the polyethylene terephthalate film. Use a wire rod coater (10 tubes) to apply a mixed solvent of ethyl acetate and dimethylformamide (ethyl acetate: dimethylformamide=1:10 (vol%)) to the coating material On one side of the area polyethylene terephthalate film (Diafix (PG-CHI (FG, thickness 200 μm)) manufactured by Mitsubishi Plastics Corporation), use a hand roller to make the adhesive surface of the precursor layer of the adhesive area Stick to the coated surface. It was dried by a hot air dryer at 80°C for 3 minutes to obtain an adhesive sheet (adhesive area (thickness: 40 μm)/coating material area (polyethylene terephthalate, thickness: 200 μm)). [Table 1] Adhesive area Covering material area Substrate The elastic modulus of the side opposite to the adhesive surface (covering material area) (MPa) Adhesion to PET film (before heating) (N/20 mm) Adhesion to PET film (after foaming) (N/20 mm) Adhesion ratio before and after heating Surface roughness of the adhesive surface after heating Ra (μm) Evaluation of the separation of small pieces after cutting Evaluation of cut surface polymer Crosslinking agent Adhesion imparting agent Thermally expandable microspheres Thickness after drying (μm) polymer Active energy ray reactive oligomer Crosslinking agent UV polymerization initiator Thickness after drying (μm) Deployment amount (parts) Deployment amount (parts) Deployment amount (parts) Deployment amount (parts) Deployment amount (parts) Deployment amount (parts) Deployment amount (parts) Deployment amount (parts) Thickness (μm) Example 1 Polymer 2 100 Coronate L 1 PR12603 5 F-50D 40 10 Polymer 1 100 M404 20 Coronate L 2 I651 3 25 - - 34 3.8 0.04 0.01 8.1 ◎ ◎ Example 2 Polymer 4 100 Tetrad C 1 S145 20 F-65D 20 15 Polymer 2 100 M321 50 Coronate L 2 I184 5 25 PET 100 19 2.9 0.03 0.01 9.7 ◎ ◎ Example 3 Polymer 3 100 Coronate L 1.5 PR12603 10 F-50D 30 7 Polymer 3 100 UV1700B 30 Coronate L 2 I651 3 25 PET 100 80 2.3 0.02 0.01 8.5 ◎ ◎ Example 4 Polymer 3 100 Coronate L 2 PR12603 10 F-50D 30 8 Polymer 3 100 - - Coronate L 20 - - 25 PET 100 1.5 2.1 0.08 0.04 9.8 ○ ○ Example 5 Polymer 1 100 Tetrad C 0.8 S145 30 F-50D 40 8 Polymer 4 100 UV1700B 50 Coronate L 1 I2959 3 25 PET 100 175 3.4 0.02 0.01 8.2 ◎ ◎ Example 6 Polymer 1 100 Tetrad C 0.6 PR51732 5 F-30D 60 10 Polymer 4 100 UV7620EA 20 Tetrad C 1 I184 5 25 - - 57 4.1 0.08 0.02 10.2 ○ ◎ Example 7 Polymer 3 100 Coronate L 1.5 PR12603 10 F-50D 30 5 Polymer 5 100 - - Coronate L 0.5 I651 3 25 - - 87 2.7 0.04 0.01 8.2 ◎ ◎ Example 8 Polymer 3 100 Coronate L 2 S145 30 F-260D 20 20 Polymer 5 100 - - Coronate L 0.5 I651 3 50 PET 100 87 3.0 0.03 0.01 8.9 ◎ ○ Example 9 Polymer 1 100 Tetrad C 1.2 - - FN-180SSD 50 8 Polymer 6 100 - - Coronate L 0.2 I651 3 30 - - 64 0.9 0.07 0.08 7.2 ◎ ◎ Example 10 Polymer 1 100 Tetrad C 0.8 T160 10 F-30D 30 10 Polymer 6 100 - - Coronate L 0.5 I184 5 30 PET 100 61 1.2 0.03 0.03 9.2 ◎ ◎ Example 11 Polymer 2 100 Coronate L 1.5 PR51732 10 F-50D 30 5 Polymer 6 100 - - Coronate L 0.2 I651 3 25 - - 64 3.3 0.03 0.01 9.9 ◎ ◎ Example 12 Polymer 2 100 Coronate L 1.5 U130 20 F-30D 30 7 Polymer 6 100 UV1700B 100 Coronate L 0.5 I651 3 20 - - 562 3.6 0.02 0.01 8.4 ◎ ◎ Example 13 Polymer 2 100 Coronate L 1 PR12603 20 F-50D 40 10 Polymer 5 100 UV1700B 20 Tetrad C 0.5 I651 3 30 PET 100 49 4.2 0.03 0.01 8.3 ◎ ◎ Example 14 Polymer 3 100 Coronate L 1.5 T160 20 F-30D 30 8 Polymer 5 100 UV7620EA 40 Tetrad C 0.5 I651 3 25 PET 100 89 3.1 0.03 0.01 8.1 ◎ ◎ Example 15 Polymer 3 100 Coronate L 1.5 T160 20 F-30D 30 6 Polymer 3 100 UV7630B 50 Coronate L 1 I184 5 35 PET 100 82 2.9 0.02 0.01 7.9 ◎ ◎ Example 16 Polymer 1 100 Tetrad C 0.8 S145 30 F-50D 30 30 PET - - - - - - - 50 - - 3120 5.8 0.05 0.01 12.8 ○ ○ Example 17 Polymer 4 100 Tetrad C 0.8 S145 5 F-50D 30 40 PET - - - - - - - 200 - - 3120 5.3 0.04 0.01 13.4 ○ ○ Comparative example 1 Polymer 3 100 Coronate L 1.5 PR12603 10 F-50D 30 5 Polymer 3 100 - - Coronate L 1 - - 25 PET 100 0.9 3.4 0.09 0.03 10.3 × × According to Table 1, it is clear that the adhesive sheet of the present invention can reduce the adhesive force by heating, and can achieve excellent cutting accuracy when cutting the adherend. [Industrial Applicability] The manufacturing method and adhesive sheet of the present invention can be suitably used for the manufacture of chip-shaped electronic parts such as semiconductor chips.

1:界面 10:黏著劑區域 11:黏著面 12:黏著劑 13:熱膨脹性微球 20:被覆材區域 21:面 30:基材 100、200:黏著片材1: interface 10: Adhesive area 11: Adhesive surface 12: Adhesive 13: Thermally expandable microspheres 20: Covering material area 21: Noodles 30: Substrate 100, 200: Adhesive sheet

圖1係本發明之較佳之實施形態之黏著片材的概略剖面圖。 圖2係本發明之另一較佳之實施形態之黏著片材的概略剖面圖。 圖3係表示藉由實施例3中之厚度之測定而獲得之拉曼影像的圖。 圖4係表示實施例11中之黏著片材之剖面之SEM(Scanning Electron Microscope，掃描式電子顯微鏡)圖像的圖。Fig. 1 is a schematic cross-sectional view of an adhesive sheet according to a preferred embodiment of the present invention. Fig. 2 is a schematic cross-sectional view of an adhesive sheet according to another preferred embodiment of the present invention. FIG. 3 is a diagram showing the Raman image obtained by the thickness measurement in Example 3. FIG. 4 is a diagram showing an SEM (Scanning Electron Microscope) image of a cross-section of the adhesive sheet in Example 11.

1:界面 1: interface

10:黏著劑區域 10: Adhesive area

11:黏著面 11: Adhesive surface

12:黏著劑 12: Adhesive

13:熱膨脹性微球 13: Thermally expandable microspheres

20:被覆材區域 20: Covering material area

21:面 21: Noodles

Claims (8)

一種黏著片材，其僅於單面具有黏著力因加熱而降低之黏著面，並且 與該黏著面相反之側之面於25℃下藉由奈米壓痕法所測得之彈性模數為1 MPa以上。An adhesive sheet that has an adhesive surface whose adhesive strength is reduced by heating only on one side, and The elastic modulus of the surface opposite to the adhesive surface measured by the nanoindentation method at 25°C is 1 MPa or more. 如請求項1之黏著片材，其於剖面觀察下，具有含有上述黏著面作為表面之黏著劑區域、及與該黏著劑區域之與該黏著面相反之側鄰接的被覆材區域，並且 該黏著劑區域含有黏著劑與熱膨脹性微球。Such as the adhesive sheet of claim 1, which, under cross-sectional observation, has an adhesive region containing the above-mentioned adhesive surface as a surface, and a coating material region adjacent to the adhesive region on the side opposite to the adhesive surface, and The adhesive area contains adhesive and heat-expandable microspheres. 如請求項1或2之黏著片材，其中上述黏著劑區域之厚度為50 μm以下。The adhesive sheet of claim 1 or 2, wherein the thickness of the adhesive area is 50 μm or less. 如請求項1至3中任一項之黏著片材，其中於將上述黏著面側貼附於聚對苯二甲酸乙二酯膜上時之黏著力為0.2 N/20 mm以上。The adhesive sheet according to any one of claims 1 to 3, wherein the adhesive force when the adhesive surface side is attached to the polyethylene terephthalate film is 0.2 N/20 mm or more. 如請求項1至4中任一項之黏著片材，其中加熱前之黏著力(a1)與加熱後之黏著力(a2)之比(a2/a1)為0.0001～0.5。The adhesive sheet according to any one of claims 1 to 4, wherein the ratio (a2/a1) of the adhesive force (a1) before heating to the adhesive force (a2) after heating is 0.0001 to 0.5. 如請求項1至5中任一項之黏著片材，其中加熱後之上述黏著面之表面粗糙度Ra為3 μm以上。The adhesive sheet of any one of claims 1 to 5, wherein the surface roughness Ra of the adhesive surface after heating is 3 μm or more. 如請求項1至6中任一項之黏著片材，其於與上述黏著面相反之側進而具備基材。The adhesive sheet of any one of claims 1 to 6, which further includes a base material on the side opposite to the above-mentioned adhesive surface. 一種電子零件之製造方法，其包括： 於如請求項1至7中任一項之黏著片材上貼附電子零件材料後， 對該電子零件材料進行切斷加工。A manufacturing method of electronic parts, which includes: After attaching the electronic component material to the adhesive sheet of any one of claims 1 to 7, This electronic component material is cut and processed.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI815278B (en) * 2021-03-05 2023-09-11 日商日東電工股份有限公司 adhesive sheet

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6901665B2 (en) * 2016-01-22 2021-07-14 東レフィルム加工株式会社 Laminate
JP6783570B2 (en) * 2016-07-11 2020-11-11 日東電工株式会社 Adhesive sheet
DE102017212854A1 (en) * 2017-07-26 2019-01-31 Tesa Se Web-shaped, with microballoons foamed pressure-sensitive adhesive
JP6769460B2 (en) * 2018-07-04 2020-10-14 王子ホールディングス株式会社 Adhesive sheet, adhesive sheet with release sheet, adhesive sheet with transparent film, laminate and method of manufacturing laminate
JP6724946B2 (en) * 2018-07-17 2020-07-15 王子ホールディングス株式会社 Pressure-sensitive adhesive sheet, pressure-sensitive adhesive sheet with release sheet, pressure-sensitive adhesive sheet with transparent film, laminate and method for producing laminate
WO2020136567A1 (en) * 2018-12-27 2020-07-02 3M Innovative Properties Company Retroreflective articles containing adhesive compositions including styrenic block co-polymers
JP7311293B2 (en) * 2019-03-29 2023-07-19 日東電工株式会社 back grind tape
JP2022032291A (en) * 2020-08-11 2022-02-25 王子ホールディングス株式会社 Adhesive sheet, adhesive sheet with release sheet, multilayer body, and method for producing multilayer body
JP7207379B2 (en) * 2020-08-11 2023-01-18 王子ホールディングス株式会社 Adhesive sheet, adhesive sheet with release sheet, laminate, and method for producing laminate

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6317981A (en) * 1986-07-09 1988-01-25 F S K Kk Adhesive sheet
JP4703833B2 (en) 2000-10-18 2011-06-15 日東電工株式会社 Energy ray-curable heat-peelable pressure-sensitive adhesive sheet and method for producing cut pieces using the same
JP4651799B2 (en) * 2000-10-18 2011-03-16 日東電工株式会社 Energy ray-curable heat-peelable pressure-sensitive adhesive sheet and method for producing a cut piece using the same
JP4877689B2 (en) * 2001-08-30 2012-02-15 日東電工株式会社 Energy ray-curable heat-peelable pressure-sensitive adhesive sheet and method for producing a cut piece using the same
JP4428908B2 (en) * 2002-04-08 2010-03-10 日東電工株式会社 Method for processing adherend using adhesive sheet
JP2005255829A (en) * 2004-03-11 2005-09-22 Nitto Denko Corp Heat-releasable adhesive sheet and processing method of adherend
JP4947921B2 (en) * 2005-05-18 2012-06-06 日東電工株式会社 Heat-peelable pressure-sensitive adhesive sheet and method for processing an adherend using the heat-peelable pressure-sensitive adhesive sheet
JP4671815B2 (en) * 2005-09-05 2011-04-20 日東電工株式会社 Heat-peelable pressure-sensitive adhesive sheet separator and heat-peelable pressure-sensitive adhesive sheet with separator
JP4711783B2 (en) * 2005-09-08 2011-06-29 日東電工株式会社 Ultraviolet curable heat-peelable pressure-sensitive adhesive sheet and method for separating and collecting cut pieces
JP5283838B2 (en) * 2006-11-04 2013-09-04 日東電工株式会社 Thermally peelable pressure-sensitive adhesive sheet and adherend recovery method
JP5689336B2 (en) * 2011-03-03 2015-03-25 日東電工株式会社 Heat release type adhesive sheet
JP5933927B2 (en) * 2011-03-08 2016-06-15 帝人株式会社 Adhesive structure
JP2012136717A (en) * 2012-04-23 2012-07-19 Nitto Denko Corp Heat peeling type adhesive sheet and method for producing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI815278B (en) * 2021-03-05 2023-09-11 日商日東電工股份有限公司 adhesive sheet

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