TWI750212B - Temperature sensitive adhesive sheet and method for manufacturing wafer using the same - Google Patents

Temperature sensitive adhesive sheet and method for manufacturing wafer using the same Download PDF

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TWI750212B
TWI750212B TW106128433A TW106128433A TWI750212B TW I750212 B TWI750212 B TW I750212B TW 106128433 A TW106128433 A TW 106128433A TW 106128433 A TW106128433 A TW 106128433A TW I750212 B TWI750212 B TW I750212B
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temperature
adhesive layer
crystalline polymer
chain crystalline
side chain
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TW106128433A
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TW201833268A (en
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山下幸志
山田行
河原伸一郎
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日商霓塔股份有限公司
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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a temperature sensitive adhesive sheet which comprises a film-like base material 2, a first adhesive layer 3 laminated on one side of the base material 2 and adhered to a pedestal 100, and a second adhesive layer 4 laminated on the other side of the base material 2 and adhered to a workpiece. The first adhesive layer 3 contains a first side chain crystalline polymer and a foaming agent and exhibits fluidity at a temperature equal to or higher than the melting point of the first side chain crystalline polymer, and the melting point of the first side chain crystalline polymer is lower than the foaming temperature of the foaming agent. The second adhesive layer 4 contains a second side chain crystalline polymer and exhibits fluidity at a temperature equal to or higher than the melting point of the second side chain crystalline polymer.

Description

感溫性黏著片及使用該感溫性黏著片之晶圓的製造方法 Temperature-sensitive adhesive sheet and method for manufacturing wafer using the same

本發明涉及例如在製造附有圖案的晶圓時為了暫時維持晶圓而使用的感溫性黏著片以及使用該感溫性黏著片之晶圓的製造方法。 The present invention relates to, for example, a temperature-sensitive adhesive sheet used for temporarily maintaining the wafer when manufacturing a patterned wafer, and a method of manufacturing a wafer using the temperature-sensitive adhesive sheet.

晶圓(wafer)是半導體元件製造的材料，是將由矽、藍寶石、碳化矽等原材製作的圓柱狀的鑄錠薄薄地切片而成的圓盤狀的板。晶圓的製造中，使用黏著片將晶圓黏接在基座(支撐基板)上，然後進行磨削、研磨而將晶圓調整為預定厚度之後，使晶圓與黏著片一起從基座剝離，然後從晶圓剝離黏著片。 A wafer is a material for manufacturing semiconductor elements, and is a disk-shaped plate formed by thinly slicing a cylindrical ingot made of a raw material such as silicon, sapphire, and silicon carbide. In the manufacture of wafers, the wafer is bonded to a susceptor (support substrate) using an adhesive sheet, and after grinding and polishing to adjust the wafer to a predetermined thickness, the wafer is peeled off from the susceptor together with the adhesive sheet. , then peel the sticker from the wafer.

為了對晶圓進行磨削、研磨，需要將晶圓牢固地維持於基座。若晶圓的維持不充分，則磨削、研磨時晶圓有可能偏移。再者，由於薄膜化後的晶圓脆弱，因此若晶圓未被牢固地維持於基座，則有可能因磨削、研磨時的振動等的影響導致晶圓破裂。 In order to grind and polish the wafer, it is necessary to firmly hold the wafer on the susceptor. If the wafers are not maintained sufficiently, the wafers may shift during grinding and polishing. Furthermore, since the thinned wafer is fragile, if the wafer is not firmly held on the susceptor, the wafer may be broken due to the influence of grinding, vibration during polishing, or the like.

再者，從晶圓剝離黏著片時，要求在晶圓表面沒有附著黏著劑的殘渣。 Furthermore, when peeling the adhesive sheet from the wafer, it is required that no adhesive residue adheres to the wafer surface.

日本專利第5623125號公報中，記載了為了在精密磨削、研磨步驟中使用的黏著片。該黏著片含有側鏈結晶性聚合物、和發泡劑，側鏈結晶性聚合物在未達熔點的溫度下結晶化且在熔點以上的溫度下顯示流動性，使在上述熔點以上且未達發泡劑的發泡溫度的溫度下貼合的被黏物在未達側鏈結晶性聚合物熔點的溫度下固定，並且在前述發泡劑的發泡溫度以上的溫度下移除。 Japanese Patent No. 5623125 describes an adhesive sheet for use in precision grinding and polishing steps. The adhesive sheet contains a side chain crystalline polymer and a foaming agent. The side chain crystalline polymer is crystallized at a temperature below the melting point and exhibits fluidity at a temperature above the melting point. The adherend attached at the temperature of the foaming temperature of the foaming agent is fixed at a temperature less than the melting point of the side chain crystalline polymer, and is removed at a temperature above the foaming temperature of the foaming agent.

再者，日本特開2015-183162號公報中記載了暫時固定用之雙面黏著帶。該暫時固定用雙面黏著帶在基材的單面具有用以貼合於基座的第1黏著層，在另一面具有用以貼合於晶圓的第2黏著層。第1黏著層含有感壓性接著劑、側鏈結晶性聚合物和發泡劑，在側鏈結晶性聚合物的熔點以上的溫度下黏著力降低。第2黏著層含有感壓性接著劑和側鏈結晶性聚合物，在側鏈結晶性聚合物的熔點以上的溫度下黏著力降低。 Furthermore, Japanese Patent Application Laid-Open No. 2015-183162 describes a double-sided adhesive tape for temporary fixation. The double-sided adhesive tape for temporary fixation has a first adhesive layer on one side of the base material for adhering to a base, and a second adhesive layer on the other side for adhering to a wafer. The first adhesive layer contains a pressure-sensitive adhesive, a side-chain crystalline polymer, and a foaming agent, and the adhesive force decreases at a temperature equal to or higher than the melting point of the side-chain crystalline polymer. The second adhesive layer contains a pressure-sensitive adhesive and a side-chain crystalline polymer, and the adhesive force decreases at a temperature equal to or higher than the melting point of the side-chain crystalline polymer.

日本特開2015-183162號公報中記載的雙面黏著帶係在從基座剝離時，將第1黏著層加熱至側鏈結晶性聚合物的熔點以上、且發泡劑膨脹甚至發泡的溫度以上，從而使對基座的黏著力降低者。然後，將晶圓與黏著帶一起從基座剝離後，將第2黏著層加熱至側鏈結晶性聚合物的熔點以上的溫度，使第2黏著層對晶圓的黏著力降低，而從晶圓剝離黏著帶。 In the double-sided adhesive tape described in Japanese Patent Laid-Open No. 2015-183162, when peeling off the base, the first adhesive layer is heated to a temperature above the melting point of the side chain crystalline polymer and the foaming agent expands or even foams above, thereby reducing the adhesion to the base. Then, after peeling off the wafer and the adhesive tape from the susceptor, the second adhesive layer is heated to a temperature higher than the melting point of the side chain crystalline polymer, so that the adhesion of the second adhesive layer to the wafer is reduced, and the wafer is removed from the wafer. Round peel off adhesive tape.

但是，期望提供一種黏著片，其在磨削、研磨的加工時能夠將晶圓牢固地維持於基座，能夠可靠地兼顧沒有偏移或破裂的加工維持性、和在磨削、研磨後剝離了黏著帶的晶圓表面上沒有附著黏著劑殘渣的無殘渣性。 However, it is desired to provide an adhesive sheet that can securely hold a wafer on a susceptor during grinding and polishing, and which can reliably achieve both process retention without misalignment or cracking, and peeling after grinding and polishing. Residue-free without adhesive residues adhering to the wafer surface with the adhesive tape.

特别是對於如外延/晶圓之類在表面具有凹凸狀圖案的晶圓而言，由於經流動化黏著劑浸入圖案內，故以不會殘留黏著劑残渣的方式剝離晶圓是重要的。 In particular, for wafers with concave and convex patterns on the surface such as epitaxial/wafer, it is important to peel off the wafer in such a way that no adhesive residue remains since the fluidized adhesive is immersed in the pattern.

本發明的課題係提供一種即使是在表面具有圖案的晶圓如此之被加工物，也能沒有偏移或破裂地牢固維持，且剝離時殘渣殘留減少的感溫性黏著片以及使用其的晶圓的製造方法。 An object of the present invention is to provide a temperature-sensitive adhesive sheet that can maintain firmness without shifting or cracking even in a workpiece such as a wafer having a pattern on its surface, and that reduces residue residues during peeling, and a wafer using the same. How to make circles.

本發明人等為了解決上述課題而反復深入研究的結果，進而完成本發明。亦即，本發明的感溫性黏著片具備：膜狀基材、積層於前述基材的單面且黏貼於基座的第1黏著層、以及積層於前述基材的另一面且黏貼於被加工物的第2黏著層。第1黏著層含有第1側鏈結晶性聚合物和發泡劑，在第1側鏈結晶性聚合物的熔點以上的溫度下顯示流動性，並且第1側鏈結晶性聚合物的熔點未達發泡劑的發泡溫度。第2黏著層含有第2側鏈結晶性聚合物，並且在前述第2側鏈結晶性聚合物的熔點以上的溫度下顯示流動性。 The inventors of the present invention have completed the present invention as a result of repeated intensive studies in order to solve the above-mentioned problems. That is, the temperature-sensitive adhesive sheet of the present invention includes a film-like base material, a first adhesive layer laminated on one side of the base material and adhered to the base, and laminated on the other side of the base material and adhered to the substrate. The second adhesive layer of the processed product. The first adhesive layer contains the first side chain crystalline polymer and a foaming agent, exhibits fluidity at a temperature equal to or higher than the melting point of the first side chain crystalline polymer, and does not reach the melting point of the first side chain crystalline polymer The foaming temperature of the blowing agent. The second adhesive layer contains the second side chain crystalline polymer, and exhibits fluidity at a temperature equal to or higher than the melting point of the second side chain crystalline polymer.

本發明的附有圖案之晶圓的製造方法包括下述步驟：使用上述感溫性黏著片，將感溫性黏著片的第1黏著層在前述第1側鏈結晶性聚合物的熔點以上且未達發泡起始溫度的溫度下黏貼於基座，並將第2黏著層在前述第2側鏈結晶性聚合物的熔點以上的溫度下黏貼於附有圖案之晶圓的凹凸狀圖案面的步驟；對前述附有圖案之晶圓的與黏貼於前述基座的面為相反側的面進行磨削和/或研磨的步驟；使前述感溫性黏著片的溫度為前述發泡劑的發泡起始溫度以上，並且從前述基座剝離前述感溫性黏著片和前述附有圖案的晶圓的步驟；以及使前述黏著片的溫度為前述第2側鏈結晶性聚合物的熔點以上，並且從前述晶圓剝離黏著片的步驟。 The method for producing a wafer with a pattern of the present invention includes the steps of: using the above-mentioned temperature-sensitive adhesive sheet, forming the first adhesive layer of the temperature-sensitive adhesive sheet to be at or above the melting point of the first side chain crystalline polymer and Adhering to the susceptor at a temperature below the foaming initiation temperature, and adhering the second adhesive layer to the concave-convex pattern surface of the patterned wafer at a temperature higher than the melting point of the second side chain crystalline polymer step of grinding and/or grinding the surface of the wafer with the pattern on the opposite side to the surface attached to the base; making the temperature of the temperature-sensitive adhesive sheet equal to the temperature of the foaming agent Steps of peeling the temperature-sensitive adhesive sheet and the patterned wafer from the base above the foaming initiation temperature; and making the temperature of the adhesive sheet equal to or higher than the melting point of the second side chain crystalline polymer , and the step of peeling the adhesive sheet from the aforementioned wafer.

本發明的感溫性黏著片具有下述效果：即使是表面具有凹凸狀圖案的晶圓如此之被加工物，也能夠沒有偏移或破裂地牢固維持，且剝離時能夠減少黏著片在被加工物表面的殘渣殘留。因此，本發明的感溫性黏著片適宜製造附有凹凸狀圖案的晶圓。 The temperature-sensitive adhesive sheet of the present invention has the following effects: even a processed object such as a wafer having a concavo-convex pattern on the surface can be firmly maintained without displacement or cracking, and the adhesive sheet can be reduced in processing during peeling. residues on the surface of the object. Therefore, the temperature-sensitive adhesive sheet of the present invention is suitable for producing a wafer with a concavo-convex pattern.

1‧‧‧黏著片 1‧‧‧Adhesive Sheet

2‧‧‧基材 2‧‧‧Substrate

3‧‧‧第1黏著層 3‧‧‧First Adhesive Layer

4‧‧‧第2黏著層 4‧‧‧Second Adhesive Layer

5a、5b‧‧‧間隔件 5a, 5b‧‧‧Spacer

100‧‧‧基座 100‧‧‧Pedestal

第1圖為表示本發明的感溫性黏著片的一實施形態的概要說明圖。 Fig. 1 is a schematic explanatory diagram showing an embodiment of the temperature-sensitive adhesive sheet of the present invention.

第2圖(a)至(e)為表示本發明的一實施形態所涉及的附有圖案之晶圓的製造方法的步驟圖。 FIGS. 2( a ) to ( e ) are step diagrams showing a method for manufacturing a patterned wafer according to an embodiment of the present invention.

<感溫性黏著片> <Temperature-sensitive adhesive sheet>

以下，針對本發明一實施形態所述之感溫性黏著片(以下，有僅稱為黏著片之情形)，參照第1圖詳細地說明。 Hereinafter, the temperature-sensitive adhesive sheet according to one embodiment of the present invention (hereinbelow, it may be simply referred to as an adhesive sheet) will be described in detail with reference to FIG. 1 .

如第1圖所示，本實施形態的黏著片1具備基材2、積層於基材2單面的第1黏著層3、和積層於基材2另一面的第2黏著層4。在第1黏著層3和第2黏著層4的表面，分別配置有具有脫模性的間隔件5a、5b。 As shown in FIG. 1 , the adhesive sheet 1 of the present embodiment includes a base material 2 , a first adhesive layer 3 laminated on one side of the base material 2 , and a second adhesive layer 4 laminated on the other side of the base material 2 . On the surfaces of the first adhesive layer 3 and the second adhesive layer 4, spacers 5a and 5b having releasability are arranged, respectively.

(基材2) (Substrate 2)

本實施形態的基材2為膜狀。膜狀不僅限於膜，在不損害本實施形態效果的限度內，亦包括膜甚至片材的概念。 The base material 2 of the present embodiment is in the form of a film. The film shape is not limited to a film, and includes the concept of a film or a sheet as long as the effect of the present embodiment is not impaired.

作為基材2的構成材料，可以舉出例如：聚乙烯、聚對苯二甲酸乙二酯、聚丙烯、聚酯、聚醯胺、聚醯亞胺、聚碳酸酯、乙烯乙酸乙烯酯共聚物、乙烯丙烯酸乙酯共聚物、乙烯聚丙烯共聚物、聚氯乙烯等合成樹脂。 Examples of the constituent material of the base material 2 include polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, and ethylene vinyl acetate copolymer. , ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, polyvinyl chloride and other synthetic resins.

本實施形態的基材2可以是單層體或複層體中的任一種，作為基材2之厚度，較佳為5至250μm，更佳為12至188μm，又更佳為25至100μm。在基材2的單面21和另一面22，在提高相對於第1黏著層3和第2黏著層4的密著性上，可以實施例如電暈放電處理、等離 子體處理、噴磨處理、化學蝕刻處理、底塗處理等表面處理。 The substrate 2 of this embodiment can be either a single layer or a multi-layer, and the thickness of the substrate 2 is preferably 5 to 250 μm , more preferably 12 to 188 μm , and still more preferably 25 to 100 μm . On one side 21 and the other side 22 of the base material 2, in order to improve the adhesion to the first adhesive layer 3 and the second adhesive layer 4, for example, corona discharge treatment, plasma treatment, blasting treatment, Surface treatment such as chemical etching treatment, primer treatment, etc.

(第1黏著層3) (1st adhesive layer 3)

積層於基材2單面的第1黏著層3係黏貼於基座之層，係含有第1側鏈結晶性聚合物和發泡劑。 The first adhesive layer 3 laminated on one side of the base material 2 is a layer adhered to the base, and contains the first side chain crystalline polymer and a foaming agent.

第1側鏈結晶性聚合物是具有熔點的聚合物。熔點是指藉由某個平衡過程，最初整合為有序排列的聚合物的特定部分變成無秩序狀態的溫度，是利用示差熱掃描熱量計(DSC)在10℃/分鐘的測定條件下測定而得到的值。第1側鏈結晶性聚合物的熔點較佳為未達發泡劑的發泡溫度，為30至70℃，較佳為40至60℃。 The first side chain crystalline polymer is a polymer having a melting point. Melting point refers to the temperature at which a specific part of the polymer initially integrated into an ordered arrangement becomes a disordered state by a certain equilibrium process, and is measured by a differential scanning calorimeter (DSC) under the measurement conditions of 10°C/min. value of . The melting point of the first side chain crystalline polymer is preferably 30 to 70°C, preferably 40 to 60°C, below the foaming temperature of the foaming agent.

第1側鏈結晶性聚合物在未達上述熔點的溫度下結晶化，且在熔點以上溫度下相變而顯示流動性。亦即，第1側鏈結晶性聚合物具有對應於溫度變化而可逆地引起結晶狀態和流動狀態的感溫性。 The first side chain crystalline polymer is crystallized at a temperature lower than the above-mentioned melting point, and at a temperature higher than the melting point, it undergoes phase transition and exhibits fluidity. That is, the 1st side chain crystalline polymer has temperature sensitivity which reversibly induces a crystalline state and a fluid state according to a temperature change.

本實施形態中的第1黏著層3含有第1側鏈結晶性聚合物作為主成分，相對於第1側鏈結晶性聚合物100質量份，以10至110質量份，較佳為20至80質量份、更佳為40至60質量份的比例含有發泡劑。藉此，在上述熔點以上且未達發泡劑的發泡溫度的溫度下，藉由顯示流動性的第1側鏈結晶性聚合物，使黏著片表現黏著力，從而能夠貼合於基座。 The first adhesive layer 3 in the present embodiment contains the first side chain crystalline polymer as a main component, and is 10 to 110 parts by mass, preferably 20 to 80 parts by mass relative to 100 parts by mass of the first side chain crystalline polymer The foaming agent is contained in parts by mass, more preferably 40 to 60 parts by mass. Thereby, at a temperature higher than the above-mentioned melting point and less than the foaming temperature of the foaming agent, the first side chain crystalline polymer showing fluidity can make the pressure-sensitive adhesive sheet exhibit adhesive force, so that it can be attached to the base. .

再者，黏著片成為無間隙地侵入存在於基座 表面的微細的凹凸、空隙內。若將該狀態的黏著片冷卻到未達上述熔點的溫度，則側鏈結晶性聚合物結晶化而表現錨定效果，從而可以得到高的固定力。而且，包含經結晶化的側鏈結晶性聚合物的黏著片顯示高的彈性模數，因而能夠使基座的固定狀態穩定，能夠高精度地加工後述被貼附於第2黏著層4的被加工物。 Furthermore, the adhesive sheet penetrates into the fine irregularities and voids existing on the surface of the susceptor without gaps. When the pressure-sensitive adhesive sheet in this state is cooled to a temperature lower than the above-mentioned melting point, the side chain crystalline polymer is crystallized to exhibit an anchoring effect, and a high fixing force can be obtained. Furthermore, since the adhesive sheet containing the crystallized side chain crystalline polymer exhibits a high elastic modulus, the fixed state of the susceptor can be stabilized, and the substrate to be adhered to the second adhesive layer 4, which will be described later, can be processed with high precision. processed product.

進一步，若將黏著片加熱到發泡劑的發泡溫度以上的溫度，則由於第1側鏈結晶性聚合物顯示流動性故黏著片的凝聚力降低，並且由於發泡劑也膨脹甚至發泡，因而能夠充分降低上述固定力，從而能夠簡單地從基座移除黏著片。因此，本實施形態的黏著片可以作為在上述熔點以上且未達發泡劑的發泡溫度的溫度下貼合於基座，在未達上述熔點的溫度下固定，並且在發泡劑的發泡溫度以上的溫度下移除的黏著片來使用。 Further, if the adhesive sheet is heated to a temperature higher than the foaming temperature of the foaming agent, the cohesive force of the adhesive sheet is reduced because the first side chain crystalline polymer exhibits fluidity, and the foaming agent also expands and even foams. Therefore, the above-mentioned fixing force can be sufficiently reduced, so that the adhesive sheet can be easily removed from the base. Therefore, the pressure-sensitive adhesive sheet of the present embodiment can be attached to a base at a temperature equal to or higher than the above-mentioned melting point and less than the foaming temperature of the foaming agent, can be fixed at a temperature less than the above-mentioned melting point, and can be fixed at a temperature less than the above-mentioned melting point. Use the adhesive sheet removed at a temperature above the bubble temperature.

上述的熔點能夠藉由改變第1側鏈結晶性聚合物的組成等來調整。作為第1側鏈結晶性聚合物的組成，可以舉出例如：使具有碳數16以上，較佳為18以上的直鏈狀烷基的(甲基)丙烯酸酯30至70質量份、具有碳數1至6的烷基的(甲基)丙烯酸酯30至70質量份、和極性單體1至10質量份聚合而得到的聚合物等。(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。 The above-mentioned melting point can be adjusted by changing the composition or the like of the first side chain crystalline polymer. Examples of the composition of the first side chain crystalline polymer include 30 to 70 parts by mass of (meth)acrylates having a linear alkyl group having 16 or more carbon atoms, preferably 18 or more carbon atoms, A polymer obtained by polymerizing 30 to 70 parts by mass of (meth)acrylate of an alkyl group of 1 to 6 and 1 to 10 parts by mass of a polar monomer, and the like. (Meth)acrylate means acrylate or methacrylate.

作為具有碳數16以上的直鏈狀烷基的(甲基)丙烯酸酯，可以舉出例如：(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十烷基酯、(甲 基)丙烯酸二十二烷基酯等具有碳數16至22的線狀烷基的(甲基)丙烯酸酯。作為具有碳數1至6的烷基的(甲基)丙烯酸酯，可以舉出例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯等。作為極性單體，可以舉出例如：丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、馬來酸、富馬酸等具有羧基的乙烯不飽和單體；(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥己酯等具有羥基的乙烯不飽和單體等。此等可以使用1種或混合使用2種以上。 Examples of (meth)acrylates having a linear alkyl group having 16 or more carbon atoms include cetyl (meth)acrylate, stearyl (meth)acrylate, and (meth)acrylic acid. (Meth)acrylates having linear alkyl groups having 16 to 22 carbon atoms, such as eicosyl esters and behenyl (meth)acrylates. Examples of (meth)acrylates having an alkyl group having 1 to 6 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate ) Hexyl acrylate, etc. Examples of polar monomers include ethylenically unsaturated monomers having carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; 2-hydroxyethyl (meth)acrylate , 2-hydroxypropyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate and other ethylenically unsaturated monomers having hydroxyl groups, etc. These can be used alone or in combination of two or more.

作為第1側鏈結晶性聚合物的聚合方法，沒有特別限定，可以採用例如溶液聚合法、本體聚合法、懸浮聚合法、乳液聚合法等。例如在採用溶液聚合法的情況下，將上述例示的單體混合於溶劑，在40至90℃左右攪拌2至10小時左右從而使上述單體聚合。 It does not specifically limit as a polymerization method of a 1st side chain crystalline polymer, For example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, etc. can be used. For example, when a solution polymerization method is employed, the monomers exemplified above are mixed in a solvent, and the monomers are polymerized by stirring at about 40 to 90° C. for about 2 to 10 hours.

作為第1側鏈結晶性聚合物的重均分子量，較佳為200,000至1,000,000，更佳為300,000至900,000，又更佳為400,000至800,000。藉此，能夠抑制將黏著片1從基座剝離時產生殘膠。再者，第1側鏈結晶性聚合物在熔點以上的溫度下顯示流動性時，能夠充分地降低第1黏著層3的黏著力。重均分子量是經由凝膠滲透色譜法(GPC)測定第1側鏈結晶性聚合物，對所得到的測定值以聚苯乙烯換算的值。 The weight average molecular weight of the first side chain crystalline polymer is preferably 200,000 to 1,000,000, more preferably 300,000 to 900,000, and still more preferably 400,000 to 800,000. Thereby, it is possible to suppress the generation of adhesive residue when the adhesive sheet 1 is peeled off from the base. Furthermore, when the first side chain crystalline polymer exhibits fluidity at a temperature equal to or higher than the melting point, the adhesive force of the first adhesive layer 3 can be sufficiently reduced. The weight average molecular weight is a value obtained by measuring the first side chain crystalline polymer by gel permeation chromatography (GPC) in terms of polystyrene.

另一方面，作為發泡劑，沒有特別限定，通常的化學發泡劑、物理發泡劑皆可採用。化學發泡劑中， 包含熱分解型和反應型的有機系發泡劑以及無機系發泡劑。 On the other hand, as a foaming agent, it does not specifically limit, A common chemical foaming agent and a physical foaming agent can be used. The chemical foaming agents include thermally decomposable and reactive organic foaming agents and inorganic foaming agents.

作為熱分解型的有機系發泡劑，可以舉出例如：各種偶氮化合物(偶氮二甲醯胺等)、亞硝基化合物(N,N’-二亞硝基五亞甲基四胺等)、肼衍生物[4,4’-氧代雙(苯磺醯肼)等]、胺基脲(聯二脲等)、疊氮化合物、四唑化合物等，作為反應型的有機系發泡劑，可以舉出例如異氰酸酯化合物等。 Examples of the thermally decomposable organic foaming agent include various azo compounds (azodimethylamide, etc.), nitroso compounds (N,N'-dinitrosopentamethylenetetramine, etc.) etc.), hydrazine derivatives [4,4'-oxobis(benzenesulfonylhydrazine) etc.], aminoureas (biureas, etc.), azide compounds, tetrazole compounds, etc., are developed as reactive organic systems. As a foaming agent, an isocyanate compound etc. are mentioned, for example.

作為熱分解型的無機系發泡劑，可以舉出例如：碳酸氫鹽/碳酸鹽(碳酸氫鈉等)、亞硝酸鹽/氫化物等，作為反應型的無機系發泡劑，可以舉出例如：碳酸氫鈉與酸的組合、過氧化氫與酵母菌的組合、鋅粉末與酸的組合等。 Examples of the thermally decomposable inorganic foaming agent include bicarbonate/carbonate (sodium bicarbonate, etc.), nitrite/hydride, and the like, and examples of the reactive inorganic foaming agent include For example: the combination of sodium bicarbonate and acid, the combination of hydrogen peroxide and yeast, the combination of zinc powder and acid, etc.

作為物理發泡劑，可以舉出例如：丁烷、戊烷、己烷等脂肪族烴類、二氯乙烷、二氯甲烷等氯化烴類、氟氯烷等氟化氯化烴類等有機系物理發泡劑、空氣、碳酸氣體、氮氣等無機系物理發泡劑等。 Examples of physical foaming agents include aliphatic hydrocarbons such as butane, pentane, and hexane, chlorinated hydrocarbons such as dichloroethane and dichloromethane, and fluorinated chlorinated hydrocarbons such as fluorochloroalkane. Organic physical foaming agents, inorganic physical foaming agents such as air, carbon dioxide gas, nitrogen, etc.

再者，作為其他發泡劑，可以採用作為微膠囊化後的熱膨脹性微粒，所謂的微球發泡劑。微球發泡劑是在由熱塑性或熱固性樹脂構成的聚合物殼的內部，封入了包含固體、液體或氣體的加熱膨脹性物質的發泡劑。換言之，微球發泡劑具備：具有微米級的平均粒徑的中空狀的聚合物殼、和封入聚合物殼的內部的加熱膨脹性物質。微球發泡劑藉由加熱體積膨脹到40倍以上，得到獨立氣泡 形式的發泡體。因此，微球發泡劑與通常的發泡劑相比，具有發泡倍率變得相當大的特性。如此之微球發泡劑可以使用市售的發泡劑，例如適用EXPANCEL公司製的“461DU20”、“551DU40”等。 In addition, as another foaming agent, what is called a microsphere foaming agent which is heat-expandable microparticles|fine-particles after microencapsulation can be used. The microsphere foaming agent is a foaming agent in which a heat-expandable substance containing a solid, liquid or gas is enclosed in a polymer shell made of thermoplastic or thermosetting resin. In other words, the microsphere foaming agent includes a hollow polymer shell having a micron-order average particle diameter, and a heat-expandable substance enclosed in the polymer shell. The volume of the microsphere foaming agent is expanded to more than 40 times by heating to obtain a foam in the form of independent cells. Therefore, the microsphere foaming agent has a characteristic that the expansion ratio becomes considerably larger than that of a normal foaming agent. As such a microsphere foaming agent, commercially available foaming agents can be used, for example, "461DU20" and "551DU40" manufactured by EXPANCEL Corporation are applicable.

發泡劑發生膨脹甚至發泡的溫度是高於第1側鏈結晶性聚合物的熔點的溫度。作為發泡劑膨脹甚至發泡的溫度，通常較佳為180℃以下，例如，較佳為在90℃開始膨脹甚至發泡，在120℃實質上完全發泡。 The temperature at which the foaming agent expands and even foams is a temperature higher than the melting point of the first side chain crystalline polymer. The temperature at which the blowing agent expands or even foams is usually preferably 180°C or lower, for example, it is preferable to start expanding or even foaming at 90°C, and substantially complete foaming at 120°C.

作為發泡劑的平均粒徑，較佳為5至50μm，更佳為5至20μm。平均粒徑是用粒度分佈測定裝置測定而得到的值。 The average particle diameter of the blowing agent is preferably 5 to 50 μm , more preferably 5 to 20 μm . The average particle diameter is a value measured with a particle size distribution analyzer.

為了將含有如此之發泡劑，並且含有第1側鏈結晶性聚合物的第1黏著層3積層於基材2的單面，例如將在溶劑中加入第1側鏈結晶性聚合物和發泡劑的塗佈液通過塗佈機等塗佈在基材2的單面並使其乾燥即可。作為塗佈機，可以舉出例如：刮刀塗佈機、輥塗機、壓延塗佈機、逗點塗佈機、凹版塗佈機、棒塗機等。 In order to laminate the first adhesive layer 3 containing such a foaming agent and containing the first side chain crystalline polymer on one side of the base material 2, for example, the first side chain crystalline polymer and the foaming agent are added to a solvent. The coating liquid of the foaming agent may be applied to one side of the base material 2 by a coater or the like and dried. As a coater, a knife coater, a roll coater, a calender coater, a comma coater, a gravure coater, a bar coater, etc. are mentioned, for example.

作為第1黏著層3的厚度，較佳為10至50μm，更佳為15至45μm。 The thickness of the first adhesive layer 3 is preferably 10 to 50 μm , more preferably 15 to 45 μm .

第1黏著層3中，可以添加例如交聯劑、增黏劑、塑化劑、抗老化劑、紫外線吸收劑等各種添加劑，例示的添加劑之中較佳為添加交聯劑。作為交聯劑，可以舉出例如異氰酸酯化合物等。以固形份換算，相對於第1側鏈結晶性聚合物100質量份，交聯劑較佳為以0.1至10 質量份的比例添加，更佳為以0.1至5質量份的比例添加，又更佳為以0.3至3質量份的比例添加。 Various additives such as a crosslinking agent, a tackifier, a plasticizer, an antiaging agent, and an ultraviolet absorber can be added to the first adhesive layer 3, and among the exemplified additives, a crosslinking agent is preferably added. As a crosslinking agent, an isocyanate compound etc. are mentioned, for example. In terms of solid content, the crosslinking agent is preferably added in a ratio of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the first side chain crystalline polymer, and still more It is preferable to add in a ratio of 0.3 to 3 parts by mass.

作為上述的第1黏著層3中的第1側鏈結晶性聚合物、發泡劑和交聯劑的較佳調配，可以舉出：以質量比計，第1側鏈結晶性聚合物：發泡劑：交聯劑=100：40至60：0.3至3的比率。 Preferable blending of the first side chain crystalline polymer, the foaming agent, and the crosslinking agent in the above-mentioned first adhesive layer 3 includes, in terms of mass ratio, the first side chain crystalline polymer: hair Foaming agent:crosslinking agent=100:40 to 60:0.3 to 3 ratio.

(第2黏著層) (2nd adhesive layer)

積層於基材2的另一面的第2黏著層4，係被黏物為被加工物，含有第2側鏈結晶性聚合物，並且在第2側鏈結晶性聚合物的熔點以上的溫度下黏著力降低的感溫性黏著層。 The second adhesive layer 4 laminated on the other side of the base material 2 is an adherend that is a workpiece, contains a second side chain crystalline polymer, and is at a temperature higher than the melting point of the second side chain crystalline polymer A temperature-sensitive adhesive layer with reduced adhesion.

第2側鏈結晶性聚合物與上述的第1側鏈結晶性聚合物相同，其熔點為30至70℃，較佳為40至60℃。亦即，本實施形態中，第1側鏈結晶性聚合物的熔點和第2側鏈結晶性聚合物的熔點均為30至70℃，較佳為40至60℃。藉此，例如對被加工物進行研磨時，第1、第2側鏈結晶性聚合物均能夠維持結晶狀態，因而能夠確保第1黏著層3、第2黏著層4的黏著力，結果能夠抑制研磨不良等加工不良的發生。 The second side chain crystalline polymer is the same as the above-mentioned first side chain crystalline polymer, and has a melting point of 30 to 70°C, preferably 40 to 60°C. That is, in this embodiment, the melting point of the first side chain crystalline polymer and the melting point of the second side chain crystalline polymer are both 30 to 70°C, preferably 40 to 60°C. Thereby, for example, when the workpiece is polished, both the first and second side chain crystalline polymers can maintain the crystalline state, so that the adhesive force of the first adhesive layer 3 and the second adhesive layer 4 can be ensured, and as a result, the adhesive force of the first adhesive layer 3 and the second adhesive layer 4 can be suppressed. The occurrence of poor processing such as poor grinding.

第2側鏈結晶性聚合物的重均分子量較佳為200,000至1,000,000，更佳為300,000至900,000，又更佳為400,000至800,000。 The weight average molecular weight of the second side chain crystalline polymer is preferably 200,000 to 1,000,000, more preferably 300,000 to 900,000, and still more preferably 400,000 to 800,000.

第2側鏈結晶性聚合物的熔點、組成、重均 分子量、調配量等可以與上述第1側鏈結晶性聚合物相同，也可以不同。 The melting point, composition, weight average molecular weight, compounding amount, etc. of the second side chain crystalline polymer may be the same as or different from those of the above-mentioned first side chain crystalline polymer.

亦即，第2側鏈結晶性聚合物與第1側鏈結晶性聚合物相同，使具有碳數16以上的直鏈狀烷基的丙烯酸酯或甲基丙烯酸酯30至70質量份、具有碳數1至6的烷基的丙烯酸酯或甲基丙烯酸酯30至70質量份、和極性單體1至10質量份聚合而得到。 That is, the second side chain crystalline polymer is the same as the first side chain crystalline polymer, and 30 to 70 parts by mass of an acrylate or methacrylate having a linear alkyl group having 16 or more carbon atoms, a carbon It is obtained by polymerizing 30 to 70 parts by mass of an acrylate or methacrylate of an alkyl group of 1 to 6 and 1 to 10 parts by mass of a polar monomer.

此時，具有碳數1至6的烷基的丙烯酸酯或甲基丙烯酸酯較佳為相對於該酯的總量而包含具有碳數1或2的烷基的丙烯酸酯或甲基丙烯酸酯2至70質量%。藉此，第2黏著層的黏著力提高，晶圓難以剝落，且硬度提高，因而能夠抑制第2黏著層偏移、或變形，晶圓的加工性提高。其他與上述第1側鏈結晶性聚合物相同。 In this case, the acrylate or methacrylate having an alkyl group having 1 to 6 carbon atoms preferably contains 2 acrylate or methacrylate having an alkyl group having 1 or 2 carbon atoms with respect to the total amount of the ester. to 70% by mass. Thereby, the adhesive force of the second adhesive layer is improved, the wafer is less likely to be peeled off, and the hardness is improved, so that the second adhesive layer can be suppressed from being displaced or deformed, and the workability of the wafer is improved. Others are the same as the above-mentioned first side chain crystalline polymer.

此外，第1側鏈結晶性聚合物與第2側鏈結晶性聚合物相同，可以是相對於總量而包含具有碳數1或2的烷基的丙烯酸酯或甲基丙烯酸酯2至70質量%的組成。 In addition, the 1st side chain crystalline polymer, like the 2nd side chain crystalline polymer, may be 2 to 70 mass of acrylate or methacrylate containing an alkyl group having 1 or 2 carbon atoms with respect to the total amount % composition.

第2黏著層4的厚度與上述第1黏著層3的厚度相同，為5至50μm，較佳為5至20μm為宜。此時，含有第2側鏈結晶性聚合物的第2黏著層4的厚度可以與第1黏著層3的厚度相同，或小於第1黏著層3的厚度，但在使黏著劑追隨晶圓等被加工物表面的凹凸，將被加工物牢固地固定而言，較佳為大於第1黏著層3的厚度。 The thickness of the second adhesive layer 4 is the same as the thickness of the first adhesive layer 3, and is preferably 5 to 50 μm , preferably 5 to 20 μm . At this time, the thickness of the second adhesive layer 4 containing the second side chain crystalline polymer may be the same as the thickness of the first adhesive layer 3 or smaller than the thickness of the first adhesive layer 3, but the thickness of the second adhesive layer 4 can be made to follow the wafer or the like. The unevenness on the surface of the workpiece is preferably larger than the thickness of the first adhesive layer 3 in order to firmly fix the workpiece.

此外，第2黏著層4中，與第1黏著層3相同，較佳為添加交聯劑。以固形份換算，相對於第2側鏈 結晶性聚合物100質量份，交聯劑較佳為以0.1至10質量份的比例添加，更佳為以0.1至5質量份的比例添加，又更佳為以0.3至3質量份的比例添加。 In addition, in the second adhesive layer 4, like the first adhesive layer 3, it is preferable to add a crosslinking agent. In terms of solid content, the crosslinking agent is preferably added in a ratio of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the second side chain crystalline polymer, and still more It is preferable to add in a ratio of 0.3 to 3 parts by mass.

第2黏著層4的其他構成與上述的第1黏著層3相同，因而省略說明。 The other structures of the second adhesive layer 4 are the same as those of the above-described first adhesive layer 3 , so the description is omitted.

(第1黏著層3和第2黏著層4) (1st adhesive layer 3 and 2nd adhesive layer 4)

本實施形態中的第1黏著層3和第2黏著層4在未達上述第1側鏈結晶性聚合物和上述第2側鏈結晶性聚合物的熔點(通常23℃)下，儲存模數均為1×106至1×108Pa。藉此，能夠使被加工物對基座的固定狀態穩定，能夠高精度地加工被加工物。 The storage modulus of the first adhesive layer 3 and the second adhesive layer 4 in this embodiment does not reach the melting point (usually 23° C.) of the first side chain crystalline polymer and the second side chain crystalline polymer. All are 1×10 6 to 1×10 8 Pa. Thereby, the fixed state of the workpiece to the base can be stabilized, and the workpiece can be processed with high precision.

此時，第2黏著層4的儲存模數可以與第1黏著層3的儲存模數相同，或小於第1黏著層3的儲存模數，但較佳為大於第1黏著層3的儲存模數。藉此，能夠使晶圓等被加工物的固定狀態穩定，能夠高精度地加工被加工物。 At this time, the storage modulus of the second adhesive layer 4 may be the same as the storage modulus of the first adhesive layer 3 , or smaller than the storage modulus of the first adhesive layer 3 , but preferably greater than the storage modulus of the first adhesive layer 3 number. Thereby, the fixed state of the workpiece such as the wafer can be stabilized, and the workpiece can be processed with high precision.

未達側鏈結晶性聚合物的熔點的溫度下的儲存模數G’能夠藉由例如改變側鏈結晶性聚合物的組成等而任意地調整。各溫度下的儲存模數G’是利用後述實施例記載的測定方法測定而得到的值。 The storage modulus G' at a temperature below the melting point of the side-chain crystalline polymer can be arbitrarily adjusted by, for example, changing the composition of the side-chain crystalline polymer or the like. The storage modulus G' at each temperature is a value measured by the measurement method described in the examples described later.

另一方面，第1黏著層3在經過熔點以上且未達前述發泡劑溫度的溫度後的未達熔點的狀態下的相對於聚對苯二甲酸乙二酯的剝離強度較佳為0.5至 5.0N/25mm。藉此，可以得到對基座的固定力。未達上述熔點的狀態下的第1黏著層3的剝離強度是依照JIS Z0237測定23℃的環境溫度下的相對於聚對苯二甲酸乙二酯膜的180°剝離強度而得到的值。 On the other hand, the peel strength with respect to polyethylene terephthalate of the first adhesive layer 3 in a state of not reaching the melting point after passing through a temperature equal to or higher than the melting point and not reaching the temperature of the foaming agent is preferably 0.5 to 5.0N/25mm. Thereby, the fixing force to the base can be obtained. The peeling strength of the 1st adhesive layer 3 in the state which did not reach the said melting|fusing point is the value obtained by measuring the 180 degree peeling strength with respect to a polyethylene terephthalate film in the ambient temperature of 23 degreeC in accordance with JIS Z0237.

再者，第2黏著層4在經過熔點以上且未達前述發泡劑溫度的溫度後的未達熔點的狀態下的相對於聚對苯二甲酸乙二酯的剝離強度較佳為0.1至3.0N/25mm。藉此，可以得到對晶圓等被加工物的固定力。第2黏著層4的剝離強度是依照JIS Z0237測定23℃的環境溫度下的相對於聚對苯二甲酸乙二酯膜的180°剝離強度而得到的值。 Furthermore, the peel strength of the second adhesive layer 4 with respect to polyethylene terephthalate is preferably 0.1 to 3.0 in a state where the second adhesive layer 4 has passed through a temperature higher than the melting point and less than the temperature of the foaming agent and has not reached the melting point. N/25mm. Thereby, the fixing force to the workpiece such as a wafer can be obtained. The peel strength of the second adhesive layer 4 is a value obtained by measuring the 180° peel strength with respect to a polyethylene terephthalate film at an ambient temperature of 23° C. in accordance with JIS Z0237.

本實施形態中，較佳為第2黏著層4的180°剝離強度小於第1黏著層3的180°剝離強度。此意指對被加工物的固定力小於對基座的固定力。藉此，能夠降低剝離被加工物時黏著層對被加工物的殘渣附著。具體而言，較佳為第2黏著層4的180°剝離強度低於第1黏著層3的180°剝離強度0.1至3.0N/25mm左右。 In the present embodiment, the 180° peel strength of the second adhesive layer 4 is preferably smaller than the 180° peel strength of the first adhesive layer 3 . This means that the fixing force to the workpiece is smaller than the fixing force to the base. Thereby, it is possible to reduce residue adhesion of the adhesive layer to the workpiece when the workpiece is peeled off. Specifically, the 180° peel strength of the second adhesive layer 4 is preferably lower than the 180° peel strength of the first adhesive layer 3 by about 0.1 to 3.0 N/25 mm.

第1黏著層3和第2黏著層4的各180°剝離強度的調整可以通過改變各側鏈結晶性聚合物的組成來進行。 The adjustment of each 180° peel strength of the first adhesive layer 3 and the second adhesive layer 4 can be performed by changing the composition of each side chain crystalline polymer.

(間隔件) (spacer)

本實施形態的間隔件5a、5b是保護第1黏著層3和第2黏著層4的各表面的間隔件。 The spacers 5 a and 5 b of the present embodiment are spacers for protecting the surfaces of the first adhesive layer 3 and the second adhesive layer 4 .

作為間隔件5a、5b，可以舉出例如在由聚乙烯、聚對苯二甲酸乙二酯等構成的膜的表面上塗佈了有機 矽、氟等脫模劑的間隔件。再者，作為間隔件5a、5b的各自的厚度，較佳為10至110μm。 As spacer 5a, 5b, the spacer which apply|coated mold release agents, such as silicone and fluorine, to the surface of the film which consists of polyethylene, polyethylene terephthalate, etc. is mentioned, for example. Moreover, as the spacers 5a, 5b each have a thickness of preferably 10 to 110 μ m.

間隔件5a、5b彼此的組成、厚度等可以相同，也可以不同。本實施形態中，間隔件5a是在聚乙烯膜的表面塗佈有機矽系脫模劑而形成者，間隔件5b是在聚對苯二甲酸乙二酯膜的表面塗佈有機矽系脫模劑而形成者。 The composition, thickness, etc. of the spacers 5a and 5b may be the same or different. In this embodiment, the spacer 5a is formed by coating the surface of the polyethylene film with a silicone-based mold release agent, and the spacer 5b is formed by coating the surface of the polyethylene terephthalate film with a silicone-based mold release agent formed by the agent.

此外，本實施形態中，使第1黏著層3的第1側鏈結晶性聚合物中含有發泡劑，也可以使第2黏著層4的第2側鏈結晶性聚合物中含有發泡劑。該情況下，第2黏著層4的發泡劑使用與第1黏著層3的發泡劑相比發泡溫度較高的發泡劑，若為相同的發泡劑，則較佳為減少含量。 In addition, in the present embodiment, the first side chain crystalline polymer of the first adhesive layer 3 contains a foaming agent, and the second side chain crystalline polymer of the second adhesive layer 4 may contain a foaming agent . In this case, the foaming agent of the second adhesive layer 4 uses a foaming agent having a higher foaming temperature than the foaming agent of the first adhesive layer 3, and if it is the same foaming agent, it is preferable to reduce the content .

<附有圖案的晶圓的製造方法> <Manufacturing method of patterned wafer>

接著，參照第2圖說明被加工物為附有圖案的晶圓時的該晶圓的製造方法。就附有圖案的晶圓而言，可以舉出例如外延/晶圓、3維堆疊結構的半導體器件、MEMS晶圓等，均在表面具有凹凸狀圖案。作為晶圓的原材，可以舉出矽、藍寶石玻璃、碳化矽(SiC)、氮化鎵(GaN)等。尤其藍寶石玻璃、碳化矽和氮化鎵是難研磨材料。 Next, with reference to FIG. 2, the manufacturing method of the wafer when the to-be-processed object is a wafer with a pattern will be described. The patterned wafer includes, for example, an epitaxial/wafer, a semiconductor device with a three-dimensional stack structure, a MEMS wafer, and the like, all of which have an uneven pattern on the surface. As the raw material of the wafer, silicon, sapphire glass, silicon carbide (SiC), gallium nitride (GaN), and the like can be mentioned. Especially sapphire glass, silicon carbide and gallium nitride are difficult to grind materials.

本實施形態中的晶圓的製造方法是使用上述的黏著片1對晶圓進行磨削和/或研磨的方法，具備下述(i)至(v)的步驟。 The wafer manufacturing method in this embodiment is a method of grinding and/or polishing a wafer using the above-described adhesive sheet 1, and includes the following steps (i) to (v).

(i)如第2圖(a)所示，從黏著片1剝離第1圖所 示的間隔件5a，載置於基座100上，在前述第1側鏈結晶性聚合物的熔點以上且未達發泡起始溫度的溫度下，一邊從上面利用輥6(加壓單元)進行加壓，一邊將黏著片1黏貼在基座100上。作為基座100，可以舉出例如陶瓷製的基座。 (i) As shown in FIG. 2(a), the spacer 5a shown in FIG. 1 is peeled off from the adhesive sheet 1, and placed on the susceptor 100 at a temperature equal to or higher than the melting point of the first side chain crystalline polymer and At a temperature lower than the foaming initiation temperature, the pressure-sensitive adhesive sheet 1 is attached to the base 100 while being pressed from above by the roller 6 (pressing means). As the susceptor 100, for example, a susceptor made of ceramics can be mentioned.

(ii)如第2圖(b)所示，在第2黏著層4的表面、於第2側鏈結晶性聚合物的熔點以上的溫度下黏貼附有圖案的晶圓200的凹凸狀圖案面。 (ii) As shown in FIG. 2(b), the concave-convex patterned surface of the wafer 200 having the pattern is adhered to the surface of the second adhesive layer 4 at a temperature higher than the melting point of the second side chain crystalline polymer .

此外，(i)步驟與(ii)步驟的順序可以顛倒。 Furthermore, the order of steps (i) and (ii) may be reversed.

(iii)如第2圖(c)所示，對附有圖案的晶圓200的表面(亦即，與貼合於基座100的面為相反側的面)進行磨削和/或研磨。第2圖(c)中，用符號201表示磨削片。 (iii) As shown in FIG. 2( c ), grinding and/or polishing is performed on the surface of the patterned wafer 200 (that is, the surface on the opposite side to the surface attached to the susceptor 100 ). In Fig. 2(c), a grinding sheet is indicated by reference numeral 201.

(iv)如第2圖(d)所示，使黏著片1的溫度為第1黏著層3中含有的發泡劑的發泡起始溫度以上，從基座100剝離黏著片1和附有圖案的晶圓200。第2圖(d)中，用符號3’表示剝離後的第1黏著層。 (iv) As shown in FIG. 2(d), the temperature of the adhesive sheet 1 is set to be equal to or higher than the foaming initiation temperature of the foaming agent contained in the first adhesive layer 3, and the adhesive sheet 1 and the adhesive sheet 1 are peeled off from the base 100. Patterned wafer 200 . In Fig. 2(d), the first adhesive layer after peeling is indicated by the symbol 3'.

(v)如第2圖(e)所示，將附有圖案的晶圓200載置於加熱器300上，加熱而使黏著片1的溫度為第2黏著層4的第2側鏈結晶性聚合物的熔點以上，從晶圓200剝離黏著片1。 (v) As shown in FIG. 2(e), the patterned wafer 200 is placed on the heater 300 and heated so that the temperature of the adhesive sheet 1 becomes the second side chain crystallinity of the second adhesive layer 4 Above the melting point of the polymer, the adhesive sheet 1 is peeled off from the wafer 200 .

本實施形態所涉及的晶圓的製造方法使用上述黏著片1，因而在上述(i)的步驟中，能夠將附有圖案的晶圓200穩定且牢固地固定於基座100。因此，上述(ii)的步驟中，能夠將附有圖案的晶圓200沒有偏移或破裂且 高精度地進行微米級的精密研磨。磨削的情況下，也能夠磨削成所期望的形狀。 The wafer manufacturing method according to the present embodiment uses the above-described adhesive sheet 1 , so that the patterned wafer 200 can be stably and firmly fixed to the susceptor 100 in the step (i) above. Therefore, in the step (ii) above, the patterned wafer 200 can be subjected to micron-level precision grinding with high precision without shifting or cracking. In the case of grinding, it can also be ground into a desired shape.

並且，上述(iv)、(v)的步驟中，能夠充分地降低固定力，因而能夠容易地進行附有圖案的晶圓200的移除，能夠減少黏著片1的殘渣附著於晶圓200的表面的情形。 In addition, in the steps (iv) and (v) above, the fixing force can be sufficiently reduced, so that the patterned wafer 200 can be easily removed, and the residues of the adhesive sheet 1 can be reduced to adhere to the wafer 200 . surface situation.

[實施例] [Example]

以下，舉出合成例和實施例詳細地說明本發明，但本發明不僅限於下述合成例和實施例。此外，以下的說明中“份”是指質量份。 Hereinafter, the present invention will be described in detail with reference to synthesis examples and examples, but the present invention is not limited to the following synthesis examples and examples. In addition, in the following description, "part" means a mass part.

(合成例1：第1側鏈結晶性聚合物) (Synthesis example 1: 1st side chain crystalline polymer)

以丙烯酸二十二烷基酯45份、丙烯酸丁酯50份、丙烯酸羥乙酯5份、和作為聚合引發劑的Perbutyl ND(日油公司製)0.5份的比例，分別加入到乙酸乙酯：正庚烷=7：3(質量比)的混合溶劑230份中，在60℃攪拌5小時，使此等單體聚合。所得到的共聚物的重均分子量為550,000、熔點為44℃。 45 parts of behenyl acrylate, 50 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, and 0.5 part of Perbutyl ND (manufactured by NOF Corporation) as a polymerization initiator were added to ethyl acetate respectively: These monomers were polymerized by stirring at 60° C. for 5 hours in 230 parts of a mixed solvent of n-heptane=7:3 (mass ratio). The obtained copolymer had a weight average molecular weight of 550,000 and a melting point of 44°C.

(合成例2：第2側鏈結晶性聚合物) (Synthesis example 2: 2nd side chain crystalline polymer)

以丙烯酸二十二烷基酯45份、丙烯酸丁酯50份、丙烯酸5份、和作為聚合引發劑的Perbutyl ND(日油公司製)0.5份的比例，分別加入到乙酸乙酯：正庚烷=7：3(質量比)的混合溶劑230份中，在60℃攪拌5小時，使此等單 體聚合。所得到的共聚物的重均分子量為580,000、熔點為45℃。 45 parts of behenyl acrylate, 50 parts of butyl acrylate, 5 parts of acrylic acid, and 0.5 part of Perbutyl ND (manufactured by NOF Corporation) as a polymerization initiator were added to ethyl acetate:n-heptane, respectively. In 230 parts of mixed solvents of =7:3 (mass ratio), these monomers were polymerized by stirring at 60° C. for 5 hours. The obtained copolymer had a weight average molecular weight of 580,000 and a melting point of 45°C.

(合成例3：第2側鏈結晶性聚合物) (Synthesis example 3: 2nd side chain crystalline polymer)

以丙烯酸二十二烷基酯45份、甲基丙烯酸酯15份、丙烯酸丁酯35份、丙烯酸5份、和作為聚合引發劑的Perbutyl ND(日油公司製)0.5份的比例，分別加入到乙酸乙酯：正庚烷=7：3(質量比)的混合溶劑230份中，在60℃攪拌5小時，使此等單體聚合。所得到的共聚物的重均分子量為600,000、熔點為45℃。 Add 45 parts of behenyl acrylate, 15 parts of methacrylate, 35 parts of butyl acrylate, 5 parts of acrylic acid, and 0.5 part of Perbutyl ND (manufactured by NOF Corporation) as a polymerization initiator, respectively. These monomers were polymerized by stirring at 60° C. for 5 hours in 230 parts of a mixed solvent of ethyl acetate:n-heptane=7:3 (mass ratio). The obtained copolymer had a weight average molecular weight of 600,000 and a melting point of 45°C.

(比較合成例3：感壓接著劑) (Comparative Synthesis Example 3: Pressure-Sensitive Adhesive)

以丙烯酸2-乙基己酯52份、丙烯酸甲酯40份、丙烯酸2-羥乙酯8份、和作為聚合引發劑的Perbutyl ND(日油公司製)0.3份的比例，分別加入到乙酸乙酯：甲苯=7：3(質量比)的混合溶劑200份中，在60℃攪拌5小時，使此等單體聚合。所得到的共聚物的重均分子量為450,000。 52 parts of 2-ethylhexyl acrylate, 40 parts of methyl acrylate, 8 parts of 2-hydroxyethyl acrylate, and 0.3 parts of Perbutyl ND (manufactured by NOF Corporation) as a polymerization initiator were added to ethyl acetate respectively. These monomers were polymerized by stirring at 60° C. for 5 hours in 200 parts of a mixed solvent of ester:toluene=7:3 (mass ratio). The weight average molecular weight of the obtained copolymer was 450,000.

將合成例1至2、比較合成例3的各共聚物示於表1。此外，熔點是通過將共聚物用DSC在10℃/分鐘的測定條件下測定而得到者。重均分子量是用GPC測定共聚物，並對所得到的測定值以聚苯乙烯換算而得到者。 The copolymers of Synthesis Examples 1 to 2 and Comparative Synthesis Example 3 are shown in Table 1. In addition, the melting point is obtained by measuring the copolymer by DSC under the measurement conditions of 10°C/min. The weight average molecular weight is obtained by measuring the copolymer by GPC, and converting the obtained measured value into polystyrene.

Figure 106128433-A0202-12-0019-1
1)C22A：丙烯酸二十二烷基酯、C4A：丙烯酸丁酯、HEA：丙烯酸2-羥乙酯、AA：丙烯酸、EHA：丙烯酸2-乙基己酯、C1A：丙烯酸甲酯
Figure 106128433-A0202-12-0019-1
 1) C22A: behenyl acrylate, C4A: butyl acrylate, HEA: 2-hydroxyethyl acrylate, AA: acrylic acid, EHA: 2-ethylhexyl acrylate, C1A: methyl acrylate

[實施例1] [Example 1] (感溫性黏著片的製作) (Production of temperature-sensitive adhesive sheet)

使用的發泡劑和交聯劑如下。 The blowing agents and crosslinking agents used are as follows.

‧發泡劑：平均粒徑為6至9μm、發泡起始溫度為90℃以上的EXPANCEL公司製的微球發泡劑“461DU20” ‧Foaming agent: Microsphere foaming agent "461DU20" manufactured by EXPANCEL Co., Ltd. with an average particle diameter of 6 to 9 μm and a foaming initiation temperature of 90°C or higher

‧交聯劑：日本聚胺酯工業公司製的異氰酸酯化合物“Coronate L-45E” ‧Crosslinking agent: Isocyanate compound "Coronate L-45E" manufactured by Japan Polyurethane Industry Co., Ltd.

(第1黏著層的製備) (Preparation of the first adhesive layer)

將合成例1中得到的側鏈結晶性聚合物/發泡劑/交聯劑以100/50/1的比例(質量比)混合於乙酸乙酯中並以使固形份成為30%的方式進行調整，得到塗佈液，將該塗佈液塗佈於由聚對苯二甲酸乙二酯構成的厚度100μm的膜狀的基材並使其乾燥，形成厚度20μm的第1黏著層。 The side chain crystalline polymer/foaming agent/crosslinking agent obtained in Synthesis Example 1 was mixed in ethyl acetate in a ratio (mass ratio) of 100/50/1, and the solid content was 30%. After adjustment, a coating liquid was obtained, and the coating liquid was applied to a film-like base material with a thickness of 100 μm composed of polyethylene terephthalate and dried to form a first adhesive with a thickness of 20 μm. Floor.

(第2黏著層的製備) (Preparation of the second adhesive layer)

將合成例2中得到的側鏈結晶性聚合物/交聯劑以100/3的比例(質量比)混合於乙酸乙酯中並以使固形份成為30%的方式進行調整，得到塗佈液。接著，在單面形成有第1黏著層的前述基材的相反面塗佈塗佈液並使其乾燥，形成厚度40μm的第2黏著層，得到黏著片。 The side chain crystalline polymer/crosslinking agent obtained in Synthesis Example 2 was mixed with ethyl acetate at a ratio of 100/3 (mass ratio) and adjusted so that the solid content was 30% to obtain a coating solution . Next, the coating liquid was applied to the opposite surface of the substrate having the first adhesive layer formed on one side thereof, and was dried to form a second adhesive layer having a thickness of 40 μm , thereby obtaining an adhesive sheet.

[實施例2] [Example 2] (感溫性黏著片的製作) (Production of temperature-sensitive adhesive sheet)

使用的發泡劑和交聯劑如下。 The blowing agents and crosslinking agents used are as follows.

‧發泡劑：平均粒徑為6至9μm、發泡起始溫度為90℃以上的EXPANCEL公司製的微球發泡劑“461DU20” ‧Foaming agent: Microsphere foaming agent "461DU20" manufactured by EXPANCEL Co., Ltd. with an average particle size of 6 to 9 μm and a foaming initiation temperature of 90°C or higher

‧交聯劑：日本聚胺酯工業公司製的異氰酸酯化合物“Coronate L-45E” ‧Crosslinking agent: Isocyanate compound "Coronate L-45E" manufactured by Japan Polyurethane Industry Co., Ltd.

(第1黏著層的製備) (Preparation of the first adhesive layer)

將合成例1中得到的側鏈結晶性聚合物/發泡劑/交聯劑以100/50/1的比例(質量比)混合於乙酸乙酯中並以使固形份成為30%的方式進行調整，得到塗佈液，將該塗佈液塗佈於由聚對苯二甲酸乙二酯構成的厚度100μm的膜狀 的基材並使其乾燥，形成厚度20μm的第1黏著層。 The side chain crystalline polymer/foaming agent/crosslinking agent obtained in Synthesis Example 1 was mixed in ethyl acetate in a ratio (mass ratio) of 100/50/1, and the solid content was 30%. After adjustment, a coating liquid was obtained, and the coating liquid was applied to a film-like base material with a thickness of 100 μm made of polyethylene terephthalate and dried to form a first adhesive layer with a thickness of 20 μm.

(第2黏著層的製備) (Preparation of the second adhesive layer)

將合成例3中得到的側鏈結晶性聚合物/交聯劑以100/3的比例(質量比)混合於乙酸乙酯中並以使固形份成為30%的方式進行調整，得到塗佈液。接著，在單面形成有第1黏著層的上述基材的相反面塗佈塗佈液並使其乾燥，形成厚度40μm的第2黏著層，得到黏著片。 The side chain crystalline polymer/crosslinking agent obtained in Synthesis Example 3 was mixed in ethyl acetate at a ratio of 100/3 (mass ratio) and adjusted so that the solid content was 30% to obtain a coating solution . Next, the coating liquid was applied to the opposite surface of the base material having the first adhesive layer formed on one side thereof, and was dried to form a second adhesive layer having a thickness of 40 μm, thereby obtaining an adhesive sheet.

[比較例1] [Comparative Example 1] (感壓黏著片的製作) (Production of pressure-sensitive adhesive sheet)

(第1黏著層的調整) (Adjustment of the first adhesive layer)

將比較合成例3中得到的感壓接著劑/發泡劑/交聯劑以100/30/0.5的比例(質量比)混合於乙酸乙酯中並以使固形份成為30%的方式進行調整，得到塗佈液，將該塗佈液塗佈在由聚對苯二甲酸乙二酯構成的厚度100μm的脫模膜上並使其乾燥，形成厚度40μm的黏著層。 The pressure-sensitive adhesive/foaming agent/crosslinking agent obtained in Comparative Synthesis Example 3 was mixed with ethyl acetate in a ratio (mass ratio) of 100/30/0.5 and adjusted so that the solid content was 30% , to obtain a coating liquid, which was coated on a release film with a thickness of 100 μm made of polyethylene terephthalate and dried to form an adhesive layer with a thickness of 40 μm.

(第2黏著層的調整) (Adjustment of the second adhesive layer)

將比較合成例3中得到的感壓接著劑/交聯劑以100/1的比例(質量比)混合於乙酸乙酯中並以使固形份成為30%的方式進行調整，得到塗佈液。接著，在單面形成有第1黏著層的上述基材的相反面塗佈塗佈液並使其乾燥，形成厚度40μm的第2黏著層，得到黏著片。 The pressure-sensitive adhesive/crosslinking agent obtained in Comparative Synthesis Example 3 was mixed with ethyl acetate at a ratio (mass ratio) of 100/1, and adjusted so that the solid content might be 30% to obtain a coating liquid. Next, the coating liquid was applied on the opposite side of the base material having the first adhesive layer formed on one side thereof, and was dried to form a second adhesive layer having a thickness of 40 μm , thereby obtaining an adhesive sheet.

[實施例3] [Example 3] (晶圓的製造) (fabrication of wafers)

按照下述步驟進行附有圖案的晶圓的製造。 Fabrication of patterned wafers was performed according to the following procedure.

(i)從實施例1中得到的黏著片1剝離第1圖所示的間隔件5a，載置於陶瓷制的基座100(支撐基板)上，在60℃的溫度下，一邊從上面利用輥6(加壓單元)進行加壓，一邊將黏合帶1黏貼於基座100上(第2圖(a))。 (i) The spacer 5a shown in FIG. 1 was peeled off from the adhesive sheet 1 obtained in Example 1, placed on a ceramic susceptor 100 (support substrate), and used from above at a temperature of 60° C. The adhesive tape 1 is attached to the base 100 while being pressurized by the roller 6 (pressing means) (FIG. 2(a)).

(ii)在第2黏著層4的表面，在60℃的溫度下黏貼附有圖案的晶圓200的凹凸狀圖案面(第2圖(b))。 (ii) On the surface of the second adhesive layer 4, the concave-convex patterned surface of the wafer 200 having the pattern is adhered at a temperature of 60°C (FIG. 2(b)).

(iii)如第2圖(c)所示，對於附有圖案的晶圓200的與貼合於基座100的面相反一側的面進行磨削和研磨，達到規定的厚度(第2圖(c))。 (iii) As shown in FIG. 2( c ), grinding and polishing the surface of the patterned wafer 200 on the opposite side from the surface to which the susceptor 100 is bonded to a predetermined thickness ( FIG. 2 ). (c)).

(iv)使黏著片1的溫度成為120℃，從基座100剝離黏著片1和附有圖案的晶圓200(第2圖(d))。 (iv) The temperature of the adhesive sheet 1 was set to 120° C., and the adhesive sheet 1 and the patterned wafer 200 were peeled off from the susceptor 100 ( FIG. 2 ( d )).

(v)將附有圖案的晶圓200載置在加熱器300上，加熱到60℃，從晶圓200剝離黏著片1(第2圖(e))。 (v) The patterned wafer 200 is placed on the heater 300 and heated to 60° C. to peel the adhesive sheet 1 from the wafer 200 ( FIG. 2( e )).

其結果，藉由使用實施例1中得到的黏著片1，在上述(iii)步驟中，晶圓200未確認到磨削和研磨導致的偏移或破裂的發生。藉此可知黏著片1具有高的加工維持性。 As a result, by using the adhesive sheet 1 obtained in Example 1, in the step (iii) described above, the wafer 200 was not observed to be offset or cracked due to grinding and polishing. From this, it can be seen that the adhesive sheet 1 has high process retention.

再者，上述(v)步驟中，在剝離的晶圓200的圖案面，沒有附著第2黏著層4的殘渣。 In addition, in the above-mentioned step (v), the residue of the second adhesive layer 4 does not adhere to the pattern surface of the wafer 200 that has been peeled off.

[實施例4] [Example 4] (晶圓的製造) (fabrication of wafers)

作為黏著片1，除了使用實施例2中得到的黏著片之 外，其餘以與實施例3相同的步驟製造附有圖案的晶圓。 As the adhesive sheet 1, except that the adhesive sheet obtained in Example 2 was used, a patterned wafer was produced in the same manner as in Example 3.

其結果，藉由使用實施例2中得到的黏著片1，在與實施例3相同的(iii)步驟中，晶圓200未確認到磨削和研磨導致的偏移或破裂的發生。藉此可知，黏著片1具有高的加工維持性。 As a result, by using the adhesive sheet 1 obtained in Example 2, in the same step (iii) as in Example 3, the wafer 200 was not observed to be offset or cracked due to grinding and polishing. From this, it can be seen that the adhesive sheet 1 has high process retention.

再者，在與實施例3相同的(v)步驟中，在剝離的晶圓200的圖案面，沒有附著第2黏著層4的殘渣。 In addition, in the same step (v) as in Example 3, the residue of the second adhesive layer 4 did not adhere to the pattern surface of the wafer 200 that was peeled off.

[比較例2] [Comparative Example 2]

除了代替實施例1中得到的黏著片，使用比較例1中得到的感溫性黏著片以外，其餘以與實施例3相同地製作晶圓，結果晶圓200由於磨削和研磨，晶圓偏移，產生破裂。藉此可知，比較例1中得到的感壓黏著片沒有加工維持性。再者，上述(v)步驟中，在剝離的晶圓200的圖案面，附著有殘渣。 Wafers were produced in the same manner as in Example 3 except that the temperature-sensitive adhesive sheet obtained in Comparative Example 1 was used instead of the adhesive sheet obtained in Example 1. As a result, the wafer 200 was uneven due to grinding and polishing. move, resulting in rupture. From this, it can be seen that the pressure-sensitive adhesive sheet obtained in Comparative Example 1 has no processing maintainability. In addition, in the above-mentioned step (v), residues are attached to the pattern surface of the wafer 200 peeled off.

<評估> <Assessment>

對於實施例1和比較例1中分別所得到的黏著片的第1黏著層和第2黏著層，評估儲存模數G’、180°剝離強度。再者，對於黏著片的磨削、研磨維持性和殘膠性也進行評價。評估方法如下。 The storage modulus G' and the 180° peel strength were evaluated for the first adhesive layer and the second adhesive layer of the adhesive sheets obtained in Example 1 and Comparative Example 1, respectively. In addition, the grinding|polishing retention property and residual adhesive property of the adhesive sheet were also evaluated. The evaluation method is as follows.

(儲存模數G’) (storage modulus G')

使用精工儀器公司(Seiko Instruments Inc.)製的動態黏彈性測定裝置“DMS 6100”，在10Hz、5℃/分鐘、0至 100℃的升溫過程中，測定23℃下的第1黏著層和第2黏著層的儲存模數G’。 Using a dynamic viscoelasticity measuring apparatus "DMS 6100" manufactured by Seiko Instruments Inc., the first adhesive layer and the second adhesive layer at 23°C were measured during a temperature rise at 10 Hz, 5°C/min, and 0 to 100°C. 2 The storage modulus G' of the adhesive layer.

(180°剝離強度) (180° peel strength)

將第1黏著層作為上側，將第2黏著層經由市售雙面膠帶固定於不銹鋼鋼板。接著，使第1黏著層與厚度25μm的聚對苯二甲酸乙二酯膜疊合，經過60℃(熔點以上且未達發泡劑溫度)的溫度後，在23℃(未達熔點)的溫度下貼合兩者。然後，使用測力傳感器以300mm/分鐘的速度將聚對苯二甲酸乙二酯膜從第1黏著層180°剝離。依照JIS Z0237測定此時的180°剝離強度，評估第1黏著層的23℃的環境溫度下的相對於聚對苯二甲酸乙二酯膜的180°剝離強度。 With the first adhesive layer on the upper side, the second adhesive layer was fixed to the stainless steel plate via a commercially available double-sided tape. Next, the first adhesive layer was laminated with a polyethylene terephthalate film with a thickness of 25 μm , and after passing through a temperature of 60° C. (above the melting point and less than the temperature of the foaming agent), at 23° C. (less than the melting point) ) at the temperature to fit both. Then, the polyethylene terephthalate film was peeled 180° from the first adhesive layer at a speed of 300 mm/min using a load cell. The 180° peel strength at this time was measured according to JIS Z0237, and the 180° peel strength with respect to the polyethylene terephthalate film at the ambient temperature of 23° C. of the first adhesive layer was evaluated.

另一方面，與上述相同地，使第2黏著層與聚對苯二甲酸乙二酯膜疊合，經過60℃(熔點以上且未達發泡劑溫度)的溫度後，在23℃(未達熔點)的溫度下貼合兩者。然後，與上述相同地評估相對於聚對苯二甲酸乙二酯膜的180°剝離強度。 On the other hand, in the same manner as above, the second adhesive layer was laminated with the polyethylene terephthalate film, and after passing through a temperature of 60° C. (more than the melting point and less than the foaming agent temperature), at 23° C. (not less than the temperature of the foaming agent). The two are bonded together at a temperature up to the melting point). Then, the 180° peel strength with respect to the polyethylene terephthalate film was evaluated in the same manner as above.

(磨削、研磨維持性) (grinding, grinding maintenance)

首先，將黏著片的第1黏著層在60℃(熔點以上且未達發泡劑溫度)黏貼於基座，並且施加2kg/cm2的壓力使第2黏著層也在上述相同的60℃下對直徑100mm×厚度700μm的由藍寶石玻璃構成的板狀的被加工物壓合5分 鐘。然後，解除壓力後，從60℃降溫至23℃並放置20分鐘。然後，對被加工物按照磨削和研磨的順序進行加工。磨削/研磨條件按照下述方式設定。 First, stick the first adhesive layer of the adhesive sheet to the base at 60°C (above the melting point and less than the temperature of the foaming agent), and apply a pressure of 2kg/cm 2 so that the second adhesive layer is also at the same 60°C above. A plate-shaped workpiece made of sapphire glass having a diameter of 100 mm and a thickness of 700 μm was pressed for 5 minutes. Then, after releasing the pressure, the temperature was lowered from 60°C to 23°C and left to stand for 20 minutes. Then, the workpiece is processed in the order of grinding and grinding. Grinding/grinding conditions were set as follows.

<磨削條件> <Grinding Conditions>

磨削機：單晶圓式磨削盤 Grinder: Single Wafer Grinding Disc

‧粗磨削 ‧Rough grinding

‧‧除去量：400μm ‧‧Removal amount: 400μm

‧‧轉速：1000rpm ‧‧Rotation speed: 1000rpm

‧‧切入：1μm/s以下 ‧‧Incision: 1μm/s or less

‧精磨削 ‧Fine grinding

‧‧除去量：200μm ‧‧Removal amount: 200μm

‧‧轉速：1000rpm ‧‧Rotation speed: 1000rpm

‧‧切入：0.5μm/s以下 ‧‧Incision: 0.5μm/s or less

<研磨條件> <Polishing conditions>

‧‧模座(日文：定盤)：铜 ‧‧Mold base (Japanese: fixed plate): Bronze

‧‧金剛石磨粒：5μm ‧‧Diamond grit: 5μm

‧‧轉速：30rpm ‧‧Rotation speed: 30rpm

‧‧壓力：300g/cm2 ‧‧Pressure: 300g/cm 2

在上述的條件下，將被加工物薄膜化至厚度70μm。此時，通過目視觀察作為被加工物的藍寶石玻璃是否發生破裂來評價磨削、研磨維持性。此外，目視觀察在研磨後進行。再者，評估基準按照下述方式設定。 Under the above conditions, the workpiece was thinned to a thickness of 70 μm . At this time, grinding and polishing retention were evaluated by visually observing whether or not the sapphire glass as the workpiece was cracked. In addition, visual observation was performed after grinding|polishing. In addition, the evaluation criteria were set as follows.

○：研磨後的藍寶石玻璃未發生破裂。 ○: No cracking occurred in the sapphire glass after grinding.

×：研磨後的藍寶石玻璃發生破裂。 ×: Cracks occurred in the polished sapphire glass.

(殘膠性) (residual glue)

施加2kg/cm2的壓力使黏著片的第2黏著層在60℃下對直徑100mm×厚度800μm的有機矽晶圓鏡面側壓合5分鐘。然後，解除壓力後，從60℃降溫至23℃並放置20分鐘。然後，再次升溫至60℃，放置5分鐘後，使用測力傳感器以300mm/分鐘的速度將第2黏著層從有機矽晶圓180°剝離。利用電子顯微鏡(倍率：20倍)觀察剝離後的有機矽晶圓鏡面側，確認殘膠的有無。再者，評估基準按照下述方式設定。 A pressure of 2 kg/cm 2 was applied to press the second adhesive layer of the adhesive sheet to the mirror side of the silicone wafer with a diameter of 100 mm and a thickness of 800 μm at 60° C. for 5 minutes. Then, after releasing the pressure, the temperature was lowered from 60°C to 23°C and left to stand for 20 minutes. Then, the temperature was raised to 60°C again, and after standing for 5 minutes, the second adhesive layer was 180° peeled off from the silicone wafer at a speed of 300 mm/min using a load cell. The mirror surface side of the silicone wafer after peeling was observed with an electron microscope (magnification: 20 times), and the presence or absence of adhesive residue was confirmed. In addition, the evaluation criteria were set as follows.

○：未觀察到殘膠。 ○: Residual glue was not observed.

×：觀察到殘膠。 ×: Residual glue was observed.

將以上的評估結果示於表2。 The above evaluation results are shown in Table 2.

Figure 106128433-A0202-12-0026-2
Figure 106128433-A0202-12-0026-2

1‧‧‧黏著片 1‧‧‧Adhesive Sheet

2‧‧‧基材 2‧‧‧Substrate

3‧‧‧第1黏著層 3‧‧‧First Adhesive Layer

4‧‧‧第2黏著層 4‧‧‧Second Adhesive Layer

5a、5b‧‧‧間隔件 5a, 5b‧‧‧Spacer

Claims (8)

一種感溫性黏著片，其具備：膜狀的基材、積層於前述基材的單面且黏貼於基座的第1黏著層、以及積層於前述基材的另一面且黏貼於被加工物的第2黏著層，其中，前述第1黏著層含有第1側鏈結晶性聚合物及發泡劑，在前述第1側鏈結晶性聚合物的熔點以上的溫度下顯示流動性，並且第1側鏈結晶性聚合物的熔點未達發泡劑的發泡溫度，前述第2黏著層含有第2側鏈結晶性聚合物，並且在前述第2側鏈結晶性聚合物的熔點以上的溫度下顯示流動性；前述第2黏著層的儲存模數大於前述第1黏著層的儲存模數。 A temperature-sensitive adhesive sheet comprising: a film-like base material, a first adhesive layer laminated on one side of the base material and adhered to a base, and laminated on the other side of the base material and adhered to a workpiece the second adhesive layer, wherein the first adhesive layer contains a first side chain crystalline polymer and a foaming agent, exhibits fluidity at a temperature higher than the melting point of the first side chain crystalline polymer, and the first The melting point of the side chain crystalline polymer is lower than the foaming temperature of the foaming agent, the second adhesive layer contains the second side chain crystalline polymer, and the temperature is higher than the melting point of the second side chain crystalline polymer Show fluidity; the storage modulus of the second adhesive layer is greater than the storage modulus of the first adhesive layer. 如申請專利範圍第1項所述之感溫性黏著片，其中，在未達前述第1側鏈結晶性聚合物和前述第2側鏈結晶性聚合物的熔點時，前述第1黏著層和第2黏著層的儲存模數均為1×106至1×108Pa。 The temperature-sensitive adhesive sheet according to claim 1, wherein, when the melting points of the first side chain crystalline polymer and the second side chain crystalline polymer are not reached, the first adhesive layer and the The storage modulus of the second adhesive layer is all 1×10 6 to 1×10 8 Pa. 如申請專利範圍第1項所述之感溫性黏著片，其中，前述第1側鏈結晶性聚合物和前述第2側鏈結晶性聚合物的熔點均未達發泡起始溫度，均為30℃至70℃。 The temperature-sensitive adhesive sheet according to claim 1, wherein the melting points of the first side chain crystalline polymer and the second side chain crystalline polymer do not reach the foaming initiation temperature, and both are 30°C to 70°C. 如申請專利範圍第1項所述之感溫性黏著片，其中，前述第1側鏈結晶性聚合物和前述第2側鏈結晶性聚合物是使具有碳數16以上的直鏈狀烷基的丙烯酸酯或甲基 丙烯酸酯30至70質量份、具有碳數1至6的烷基的丙烯酸酯或甲基丙烯酸酯30至70質量份、和極性單體1至10質量份聚合而得到的聚合物。 The temperature-sensitive adhesive sheet according to claim 1, wherein the first side-chain crystalline polymer and the second side-chain crystalline polymer are a linear alkyl group having 16 or more carbon atoms. acrylate or methyl A polymer obtained by polymerizing 30 to 70 parts by mass of an acrylate, 30 to 70 parts by mass of an acrylate or methacrylate having an alkyl group having 1 to 6 carbon atoms, and 1 to 10 parts by mass of a polar monomer. 如申請專利範圍第4項所述之感溫性黏著片，其中，前述第2側鏈結晶性聚合物是使具有碳數16以上的直鏈狀烷基的丙烯酸酯或甲基丙烯酸酯30至70質量份、具有碳數1至6的烷基的丙烯酸酯或甲基丙烯酸酯30至70質量份、和極性單體1至10質量份聚合而得到的聚合物，前述具有碳數1至6的烷基的丙烯酸酯或甲基丙烯酸酯相對於該酯的總量，包含具有碳數1或2的烷基的丙烯酸酯或甲基丙烯酸酯2至70質量%。 The temperature-sensitive adhesive sheet according to claim 4, wherein the second side-chain crystalline polymer is an acrylate or methacrylate having a linear alkyl group having 16 or more carbon atoms of 30 to 30 70 parts by mass, a polymer obtained by polymerizing 30 to 70 parts by mass of an acrylate or methacrylate having an alkyl group having 1 to 6 carbon atoms, and 1 to 10 parts by mass of a polar monomer, the aforementioned having 1 to 6 carbon atoms The acrylate or methacrylate of the alkyl group contains 2 to 70% by mass of the acrylate or methacrylate having an alkyl group having 1 or 2 carbon atoms with respect to the total amount of the ester. 如申請專利範圍第1項所述之感溫性黏著片，其中，經過熔點以上且未達前述發泡劑溫度的溫度後的未達熔點的前述第1黏著層相對於聚對苯二甲酸乙二酯的剝離強度為0.5至5.0N/25mm，經過熔點以上且未達前述發泡劑溫度的溫度後的未達熔點的前述第2黏著層相對於聚對苯二甲酸乙二酯的剝離強度為0.1至3.0N/25mm。 The temperature-sensitive adhesive sheet according to claim 1, wherein the first adhesive layer that has not reached the melting point after passing through a temperature equal to or higher than the melting point and less than the temperature of the foaming agent is relatively stable to polyethylene terephthalate. The peel strength of the diester is 0.5 to 5.0 N/25mm, and the peel strength of the second adhesive layer that has not reached the melting point after passing a temperature higher than the melting point and less than the temperature of the blowing agent with respect to polyethylene terephthalate 0.1 to 3.0N/25mm. 如申請專利範圍第6項所述之感溫性黏著片，其中，前述第2黏著層的剝離強度小於前述第1黏著層的剝離強度。 The temperature-sensitive adhesive sheet according to claim 6, wherein the peel strength of the second adhesive layer is lower than the peel strength of the first adhesive layer. 一種附有圖案之晶圓的製造方法，其包括下述步驟：使用申請專利範圍第1至7項中任一項所述之感溫性黏著 片，將前述感溫性黏著片的第1黏著層在前述第1側鏈結晶性聚合物的熔點以上且未達發泡起始溫度的溫度下黏貼於基座，並且將第2黏著層在前述第2側鏈結晶性聚合物的熔點以上的溫度下黏貼於附有圖案的晶圓的凹凸狀圖案面的步驟；對前述附有圖案的晶圓的與黏貼於前述基座的面為相反側的面進行磨削和/或研磨的步驟；使前述感溫性黏著片的溫度為前述發泡劑的發泡起始溫度以上，並且從前述基座剝離前述感溫性黏著片和前述附有圖案的晶圓的步驟；以及使前述黏著片的溫度為前述第2側鏈結晶性聚合物的熔點以上，並且從前述晶圓剝離黏著片的步驟。 A method for manufacturing a wafer with a pattern, comprising the steps of: using the temperature-sensitive adhesive described in any one of items 1 to 7 of the patent application scope sheet, the first adhesive layer of the temperature-sensitive adhesive sheet is attached to the base at a temperature higher than the melting point of the first side chain crystalline polymer and less than the foaming initiation temperature, and the second adhesive layer is The step of adhering to the concave-convex pattern surface of the patterned wafer at a temperature higher than the melting point of the second side chain crystalline polymer; the surface of the patterned wafer is opposite to the surface adhered to the base The step of grinding and/or grinding the side surface; the temperature of the temperature-sensitive adhesive sheet is made to be higher than the foaming initiation temperature of the foaming agent, and the temperature-sensitive adhesive sheet and the adhesive sheet are peeled off from the base. A patterned wafer step; and a step of peeling the adhesive sheet from the wafer by making the temperature of the adhesive sheet equal to or higher than the melting point of the second side chain crystalline polymer.
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