TWI466976B - Hot peeling double sided adhesive sheet and processed body processing method - Google Patents

Hot peeling double sided adhesive sheet and processed body processing method Download PDF

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TWI466976B
TWI466976B TW96140908A TW96140908A TWI466976B TW I466976 B TWI466976 B TW I466976B TW 96140908 A TW96140908 A TW 96140908A TW 96140908 A TW96140908 A TW 96140908A TW I466976 B TWI466976 B TW I466976B
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heat
peelable
adhesive
adhesive sheet
adhesive layer
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TW96140908A
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TW200844204A (en
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Kazuyuki Kiuchi
Yoshinori Yoshida
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Nitto Denko Corp
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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
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—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
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C09J2400/243—Presence of a foam 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
    • 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
    • H01L2221/68331—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 of passive members, e.g. die mounting 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
    • H01L2221/6834—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 to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • H—ELECTRICITY
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    • H01L2924/01019—Potassium [K]
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    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19041—Component type being a capacitor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Description

熱剝離性雙面黏著片材及被加工體之加工方法
本發明係關於熱剝離性雙面黏著片材及使用其之被加工體之加工方法，更加詳細而言，係關於藉由加熱處理可迅速地降低黏著力、且適用於加工表面凹凸較大之被加工體的熱剝離性雙面黏著片材及使用其之被加工體之加工方法。
先前，眾所周知有於基材上設置含有熱膨脹性微小球之黏著層的加熱剝離型黏著片材(例如，專利文獻1~4等)。其係以加熱黏著層所引起之發泡或膨脹處理而可降低其之黏著力，從而可簡單地自黏附體剝離，例如，用於陶瓷電容器之製造步驟或半導體晶圓之研削步驟之臨時固定等中。尤其已知有：伴隨近年來之半導體晶圓的薄型化，為防止搬送時晶圓破損等，而採用介隔熱剝離性雙面黏著片材貼合與晶圓大致相同尺寸之支持體的台座方式。
專利文獻1：日本專利特公昭51-24534號公報
專利文獻2：日本專利特開昭56-61468號公報
專利文獻3：日本專利特開昭56-61469號公報
專利文獻4：日本專利特開昭60-252681號公報
然而，近年來之高功能半導體晶圓於晶圓圖案面形成以凸塊為代表之較大突起物、或以電晶體為代表之較大凹坑 等。若向上述半導體晶圓貼合黏著片材，則片材與該晶圓表面形狀吻合，其結果於片材背面側轉印該晶圓表面形狀。該情形時，以台座方式貼合支持體時，出現氣泡相互擠壓破裂、或者於晶圓周邊部支持體翹起，故而研削晶圓背面後，出現進水或晶圓龜裂。
因此，本發明之目的在於提供下述熱剝離性雙面黏著片材、及使用該熱剝離性雙面黏著片材之被加工體之加工方法，該熱剝離性雙面黏著片材於向一面貼合被加工體之表面側、將支持體作為台座向另一面貼合，對被加工體之背面側實施加工時，即使於被加工體表面有較大凹凸，亦不會導致支持體翹起、或由此於加工時在被加工體出現龜裂。
本發明者們為解決上述課題而專心研究之結果發現：若於熱剝離性雙面黏著片材中使用特定基材作為基材，則固定表面凹凸較大之被加工體時，可防止用作台座之支持體的翹起、或由此於加工時在被加工體出現龜裂，從而完成本發明。
即，本發明提供一種熱剝離性雙面黏著片材，其特徵在於其係於基材之一側面設置熱剝離性黏著層A、於另一側面設置黏著層B之熱剝離性雙面黏著片材，且上述基材包含多孔質基材。
該熱剝離性雙面黏著片材中，作為多孔質基材，較好的是密度為0.9g/cm3 以下、且拉伸彈性率為20MPa以下者。 基材亦可由多孔質基材與非多孔質基材之積層體構成。作為構成黏著層B之接著劑，例如可使用感壓性接著劑、紫外線硬化型黏著劑、熱剝離型黏著劑、熱可塑型黏著劑、熱硬化型黏著劑等。
本發明又提供一種被加工體之加工方法，其特徵在於包含：向上述之熱剝離性雙面黏著片材之熱剝離性黏著層A及黏著層B中任一者貼合被加工體，向另一者貼合支持體之貼合步驟；加工所貼合之被加工體的加工步驟；及加工被加工體後，藉由加熱處理將被加工體剝離回收之剝離回收步驟。
該被加工體之加工方法中，作為被加工體可列舉：電子零件、半導體晶圓等。該方法尤其適用於將表面最大凹凸差為10μm以上之面向熱剝離性雙面黏著片材之黏著面貼合，加工具有上述面的被加工體。
藉由本發明，使用多孔質基材作為基材，故而凹凸緩和性優良，對於凸塊晶圓等表面凹凸較大之被加工體，亦可以使用支持體之台座方式實施薄型研削等加工。
以下，視需要一面參照圖式一面詳細說明本發明。圖1係表示本發明熱剝離性雙面黏著片材之一例的概略剖面圖。該例中，於基材1之一面設置熱剝離性黏著層2、於另一面設置黏著層3，進而於熱剝離性黏著層2及黏著層3上積層隔離膜4。
基材1係熱剝離性黏著層2及黏著層3之支持母體，且包含多孔質基材。基材1可僅由多孔質基材構成，亦可由多孔質基材與非多孔質基材之積層體構成。本發明中，至少使用多孔質基材作為基材，故而向表面凹凸較大之被加工體貼附加熱剝離型黏著片材時，吸收凹凸部分之體積，故而於黏著片材之背面側未顯現出凹凸形狀。因此，以台座方式向黏著片材背面側貼合支持體時，可防止由於氣泡相互擠壓破裂、或支持體翹起而於研削晶圓背面後出現進水或晶圓龜裂。
作為基材1之材料，可於不損及黏著片材之使用性等之範圍內加以適當選擇，亦可為熱可塑性樹脂、熱硬化性樹脂、彈性體、其他任一者。作為該材料，例如可列舉：聚乙烯、聚丙烯等烯烴系樹脂；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂；聚苯乙烯等聚苯乙烯系樹脂；聚氯乙烯等乙烯系樹脂；聚胺基甲酸酯系樹脂；聚甲基丙烯酸甲酯等丙烯酸系樹脂；丙烯酸-胺基甲酸酯共聚物；纖維素系樹脂；聚碳酸酯系樹脂；聚醯胺系樹脂；聚醯亞胺系樹脂；聚醯胺-醯亞胺系樹脂；聚碸系樹脂；氟系樹脂；橡膠系聚合物等塑膠薄膜或片材等。
作為多孔質基材亦可為由任意方法而形成者，例如亦可使用下述之任一者：將聚合物溶液流延為薄膜狀後，導入至凝固液而獲得之多孔質薄膜；實施延伸處理而獲得之多孔質薄膜；藉由溶析處理等自混入去除用微粒子之薄膜中去除該微粒子而獲得之多孔質薄膜；對薄膜實施壓印加工 而獲得之多孔質薄膜；藉由於加熱下對聚合物之粉末進行熔融處理而獲得之多孔質薄膜；使用化學發泡劑或物理發泡劑而使其發泡之發泡薄膜；使熱膨脹性微小球或中空琉璃珠等中空填充料分散之薄膜等。上述中空琉璃珠之平均粒徑可考慮多孔質基材之厚度等而適宜選擇，一般為3~200μm、較好的是10~100μm。又，上述熱膨脹性微小球之平均粒徑亦可考慮多孔質基材之厚度等而適宜設定，例如，熱膨脹後為3~100μm、較好的是10~100μm。
作為多孔質基材之較好例，可列舉下述所獲得之片材狀物等，即，將包含胺基甲酸酯聚合物、丙烯酸系單體、光聚合起始劑、及中空琉璃珠或熱膨脹性微小球之混合物塗佈於非多孔質基材等上，形成塗膜後，照射紫外線。
多孔質基材之密度並無特別限制，一般為0.9g/cm3 以下(例如，0.2~0.9g/cm3 左右)、較好的是0.25~0.7g/cm3 左右。於室溫23℃、濕度50%之環境下，以鋼尺測定樣品尺寸(縱橫)，藉由1/1000mm度盤規測定厚度，進而，以1/1000g數位重量計測定質量，從而藉由質量/體積求得密度(重量測定法)。若多孔質基材之密度超過0.9g/cm3 ，則存在凹凸吸收性降低，無法保持黏附體之情形。
多孔質基材之拉伸彈性率並無特別限制，一般為20MPa以下(例如，0.1~20MPa)、較好的是0.1~15MPa左右。拉伸彈性率係使用拉伸荷重測定機根據應力-彎曲曲線求得為初期彈性率。多孔質基材之拉伸彈性率超過20MPa時，存在凹凸吸收性降低，無法保持黏附體之情形。
多孔質基材之厚度並無特別限制，但自切斷性或凹凸吸收性等觀點考慮，一般為10~1000μm、較好的是25~500μm、更好的是50~300μm左右。多孔質基材之厚度未滿10μm時，凹凸吸收性易降低，若超過1000μm則切斷性易降低。又，以多孔質基材與非多孔質基材(例如，包含聚對苯二甲酸乙二酯、聚醯亞胺等之非多孔質基材)的積層體構成基材1時，基材之總厚度例如為20~1100μm、較好的是35~550μm、更好的是60~350μm左右。
以多孔質基材與非多孔質基材之積層體構成基材1時，該積層體可藉由塗層法、擠壓法、乾式層壓法等慣用之薄膜積層法進行製造。
熱剝離性黏著層2係由於加熱而例如膨脹或者發泡，而降低對黏附體(被加工體)之接著力，從而顯示剝離性之層。熱剝離性黏著層2一般由熱膨脹性微小球等發泡劑與黏合劑構成。作為黏合劑可使用允許熱膨脹性微小球等發泡劑由於加熱而發泡及/或膨脹之聚合物類或者蠟類等適宜者。其中較好的是使用儘可能地不約束熱膨脹性微小球等發泡劑之發泡及/或膨脹者。自熱膨脹性微小球等發泡劑之加熱膨脹性或對黏附體之接著力等黏著特性的控制性之觀點考慮，尤好的黏合劑是黏著劑。
作為上述黏著劑並無特別限制，例如可使用包含橡膠系聚合物、丙烯酸系聚合物、乙烯基烷基醚系聚合物、聚矽氧系聚合物、聚酯系聚合物、聚醯胺系聚合物、胺基甲酸酯系聚合物、氟系聚合物、苯乙烯-二烯嵌段共聚物系等 聚合物之黏著劑，或於該等中調配入熔點約200℃以下之熱熔融性樹脂而改良潛變特性之黏著劑，放射線硬化型黏著劑，或者於該等中調配入例如交聯劑(例如，聚異氰酸酯、烷基醚化三聚氰胺化合物、環氧化合物等)、增黏劑(例如，松香衍生物樹脂、聚萜烯樹脂、石油樹脂、油溶性酚樹脂等)、塑化劑、軟化劑、填充劑、顏料、著色劑、抗老化劑、界面活性劑等各種添加劑者等(參照日本專利特開昭56-61468號公報、日本專利特開昭61-174857號公報、日本專利特開昭63-17981號公報、日本專利特開昭56-13040號公報等)。該等黏著劑亦可單獨使用，亦可組合2種以上使用。
作為構成熱剝離性黏著層2之黏著劑，自對黏附體加熱前之適度接著力之控制性與由於加熱而導致接著力之降低性之平衡等觀點考慮，較好的是使用以自常溫至150℃之溫度域的動彈性係數為5萬～1000萬dyn/cm2 之聚合物為基質聚合物者。
一般而言，作為上述黏著劑可使用：將天然橡膠或各種合成橡膠作為基質聚合物之橡膠系黏著劑；以將(甲基)丙烯酸烷基酯(例如，甲酯、乙酯、丙酯、異丙酯、丁酯、2-乙基己酯、異辛酯、異壬酯、異癸酯、十二烷基酯、二十烷基酯等C1-20 烷基酯等)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)作為基質聚合物之丙烯酸系黏著劑等。
再者，上述丙烯酸系聚合物以凝集力、耐熱性、交聯性 等之改質為目的，視需要亦可包含對應於可與上述(甲基)丙烯酸烷基酯共聚合之其他單體成分的單元。作為上述單體成分，例如可列舉：丙烯酸、甲基丙烯酸、伊康酸等含有羧基之單體；順丁烯二酸酐等酸酐單體；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯等含有羥基之單體；苯乙烯磺酸、烯丙基磺酸等含有磺酸基之單體；N-羥甲基(甲基)丙烯酸醯胺等含有醯胺基之單體；(甲基)丙烯酸胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體；(甲基)丙烯酸甲氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體；N-環己基馬來醯亞胺等馬來醯亞胺系單體；N-甲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等琥珀醯亞胺系單體；醋酸乙烯酯、丙酸乙烯酯、乙烯基吡啶、苯乙烯等乙烯系單體；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有環氧基之丙烯酸系單體；(甲基)丙烯酸聚乙二醇等二醇系丙烯酸酯單體；(甲基)丙烯酸四氫糠酯、氟代(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；已二醇二(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、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。該等單體成分可使用1種或2種以上。
作為上述熱膨脹性微小球，例如可列舉下述微小球，將 藉由加熱異丁烷、丙烷、戊烷等容易地氣化而膨脹之物質內包於具有彈性之殼(外殼(shell))內者。上述殼多以熱熔融性物質或由於熱膨脹而破壞之物質形成。作為形成上述殼之物質，例如可列舉：偏二氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯醇縮丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏二氯乙烯、聚碸等。熱膨脹性微小球可藉由慣用之方法例如凝聚法、界面聚合法等進行製造。再者，熱膨脹性微小球亦有例如商品名「Matsumoto Microsphere」[松本油脂製藥(股)製造]等市銷品。
藉由使用熱膨脹性微小球，可穩定地控制由於加熱而增大黏附體之污染度。未微膠囊化之發泡劑等會凝集破壞黏著層等，從而導致使上述汚染度增大之抑制效果變缺乏。為了藉由加熱使熱剝離性黏著層之接著力有效且穩定地降低，較好的是具有體積膨脹率為5倍以上、尤其為7倍以上、特別是達到10倍以上時亦不會破裂之適度強度的熱膨脹性微小球。
熱膨脹性微小球之平均粒徑可根據熱剝離性黏著層2之厚度等而適宜選擇，一般為100μm以下(例如1~100μm)、較好的是80μm以下(例如1~80μm)、更好的是1~50μm，然而並不限定於此。
熱膨脹性微小球等發泡劑之調配量亦可根據熱剝離性黏著層2之膨脹倍率或接著力之降低性等而適宜決定。一般而言，上述黏合劑為黏著劑等時，相對於其基質聚合物100重量份，為1~150重量份、較好的是10~130重量份、更 好的是25~100重量份之範圍。
熱剝離性黏著層2之厚度可考慮接著性及加熱剝離時之接著力的降低性等而適當選擇，一般為300μm以下(例如1~300μm)、較好的是2~200μm、更好的是5~150μm。若厚度過小，則由於基於熱膨脹性微小球等發泡劑導致之表面的凹凸化，無法表現出充分之接著力。又，若厚度過大，則由於基於加熱變形不良導致之接著力降低不足，從而無法順利地進行黏附體之剝離。
作為熱剝離性黏著層2之形成方法，例如可藉由下述方法等進行，視需要使用溶劑混合熱膨脹性微小球等發泡劑與黏合劑等調配成分，以塗佈方式等適宜方式展開該混合物，從而形成片材狀之層。亦可將上述混合物於基材1上直接塗佈等；亦可向適當之隔離膜(剝離紙等)上塗佈等，形成熱剝離性黏著層，再將其向基材1上轉印。
作為黏著層3並無特別限制，可藉由橡膠系、丙烯酸系等感壓性接著劑，紫外線硬化型黏著劑，熱剝離型黏著劑，熱可塑型黏著劑，熱硬化型黏著劑等眾所周知之黏著劑構成。作為橡膠系、丙烯酸系感壓接著劑，可使用上述例示為橡膠系黏著劑、丙烯酸系黏著劑者。亦可向黏著劑中添加例如交聯劑(例如，聚異氰酸酯、烷基醚化三聚氰胺化合物、環氧化合物等)、增黏劑(例如，松香衍生物樹脂、聚萜烯樹脂、石油樹脂、油溶性酚樹脂等)、塑化劑、軟化劑、填充劑、顏料、著色劑、抗老化劑、界面活性劑等各種添加劑。
以多孔質基材與非多孔質基材之積層體構成基材1時，亦可將黏著層3設置於多孔質基材側表面、或非多孔質基材側表面之任一者上。
黏著層3之厚度並無特別限制，自加工後之切斷性或剝離性等觀點考慮，通常為0.1~500μm、較好的是1~300μm、更好的是5~250μm之範圍。
本發明之熱剝離性雙面黏著片材可採取片材狀、帶狀、標籤狀等適宜形態。又，此時，亦可臨時黏附隔離膜4，以保護熱剝離性黏著層2及黏著層3。作為隔離膜4，例如可使用於塑膠薄膜或紙上塗層有聚矽氧系、長鏈烷基系、氟系等適宜之脫模劑者。
本發明之加工方法係包含：向上述本發明之熱剝離性雙面黏著片材之熱剝離性黏著層2及黏著層3中任一者貼合被加工體，向另一者貼合支持體之貼合步驟；加工所貼合之被加工體的加工步驟；及加工被加工體後，藉由加熱處理將被加工體剝離回收之剝離回收步驟。
作為被加工體並無特別限制，例如可列舉：陶瓷電容器等電子零件、半導體晶圓等。本發明之方法中，基材包含多孔質基材，故而即使其係於貼合至熱剝離性雙面黏著片材之熱剝離性黏著層2側之表面具有較大凹凸之黏附體時，藉由上述多孔質基材亦可在體積上緩和、吸收該凹凸。因此，於熱剝離性雙面黏著片材之黏著層3貼附剛直之支持體(台)之際，於該黏著層3並未顯現出凹凸，可維持平滑之面，故而可獲得良好之支持體貼附狀態。因此，貼 合支持體(台)後，藉由被加工體之強固支持，從而可不會出現破損或進入水等異常地進行加工。因此，例如，對附凸塊之半導體晶圓或者電晶體等形成凹坑之半導體晶圓等之表面最大凹凸差為10μm以上(例如，10~150μm、尤其是15~50μm左右)之被加工體背面實施加工(例如研削加工等)時，可發揮特別大之效果。
作為加工種類並無特別限制，例如可列舉：研削、切斷、組裝、積層、煅燒等加工。加工後之加熱處理例如可利用加熱板、熱風乾燥機、近紅外線燈、空氣乾燥器等適宜加熱機構而進行。加熱溫度為熱剝離性黏著層2中之熱膨脹性微小球等發泡劑之熱膨脹開始溫度(開始發泡溫度)以上即可，加熱處理條件可根據黏附體之耐熱性、加熱方法等而適宜設定。作為一般之加熱處理條件係：溫度100~250℃、1~90秒(加熱板等)或1~15分鐘(熱風乾燥機等)。
實施例
以下，藉由實施例對本發明加以更詳細之說明，但本發明並不受該等實施例任何限定。
實施例1
向包含50重量份之胺基甲酸酯聚合物、40重量份之丙烯酸丁脂、10重量份之丙烯酸、0.15重量份之光聚合起始劑之UV(紫外線)反應性丙烯酸胺基甲酸酯糖漿A中，相對於100重量份之A而調配入10重量份之中空琉璃珠(平均粒徑67μm)，從而調製UV反應性丙烯酸胺基甲酸酯糖漿B。將 UV反應性丙烯酸胺基甲酸酯糖漿B向厚度25μm之PET (polyethylene terephthalate；聚對苯二甲酸乙二酯)薄膜上塗佈400μm之厚度，乾燥後，藉由UV照射而獲得總厚度325μm之附PET之多孔質薄膜(包含丙烯酸-胺基甲酸酯共聚物之多孔質基材層/PET薄膜)。另外，向包含100重量份之丙烯酸丁脂、5重量份之2-丙烯酸羥乙酯之丙烯酸系聚合物A中，相對於100重量份之A而調配入3重量份之異氰酸酯系交聯劑、25重量份之熱膨脹性微小球「商品名「Matsumoto Microsphere F301SD」、松本油脂製藥(股)製造]，從而調製熱剝離性黏著劑A，將該熱剝離性黏著劑A向PET隔離膜上塗佈、乾燥，將所獲得之厚25μm之熱剝離性黏著層轉印至上述多孔質薄膜之多孔質側。又，向包含50重量份之丙烯酸丁脂、50重量份之丙烯酸乙酯、3.5重量份之丙烯酸之丙烯酸系聚合物B中，相對於100重量份之B而調配入0.5重量份之環氧系交聯劑，調製丙烯酸系黏著劑B，將該丙烯酸系黏著劑B以成為厚度20μm之方式向PET隔離膜上塗佈、乾燥後，將其向上述多孔質基材之PET薄膜側轉印，從而獲得熱剝離性雙面黏著片材A。
實施例2
向包含100重量份之丙烯酸丁脂、4重量份之丙烯酸之丙烯酸系聚合物中，相對於100重量份之該丙烯酸系聚合物而調配入2.5重量份之異氰酸酯系交聯劑[商品名「CORONET L」、日本聚氨酯工業(股)製造]、40重量份之熱膨脹性微小球[商品名「Matsumoto Microsphere F80VSD」、松本油脂製藥(股)製造]，從而調製熱膨脹性黏著劑，將該熱膨脹性黏著劑向厚50μm之PET(聚對苯二甲酸乙二酯)薄膜上塗佈後，藉由160℃之加熱步驟，使熱膨脹性微小球膨脹，獲得厚170μm之附PET之多孔質薄膜(包含丙烯酸系共聚物之多孔質基材層/PET薄膜)。以下，藉由與實施例1相同之操作獲得熱剝離性雙面黏著片材B。
比較例1
除了不調配入中空琉璃珠以外，藉由與實施例1相同之操作獲得熱剝離性雙面黏著片材C。再者，基材之層結構為包含丙烯酸-胺基甲酸酯共聚物之非多孔質基材層/PET薄膜。
比較列2
除了使用厚250μm之PET薄膜作為基材以外，藉由與實施例1相同之操作獲得熱剝離性雙面黏著片材。
評估試驗
向晶片尺寸10mm×10mm、凸塊高度40μm、凸塊間距130μm、晶圓厚度725μm之全陣列凸塊晶圓(表面最大凹凸差：40μm)貼合實施例或比較例中所獲得之熱剝離性雙面黏著片材之熱剝離性黏著層後，向背面之黏著層貼合與凸塊晶圓同徑之玻璃晶圓(支持體)，目視觀察玻璃晶圓之翹起狀態。其後，將凸塊晶圓之背面研削至75μm厚度，目視觀察有無晶圓龜裂。最後，藉由加熱處理(120℃熱風乾燥機中加熱3分鐘)驗證凸塊晶圓之加熱剝離性。再者，熱剝離性雙面黏著片材與凸塊晶圓之貼合使用商品名 「DR3000II-WS」[日東精機(股)製造]、玻璃晶圓之貼合使用商品名「MA-3000II-WS」[日東精機(股)製造]、晶圓研削使用商品名「DFG-8460」[DISCO公司製造]。將結果示於表1。
再者，凸塊高度及晶圓厚度藉由1/1000mm度盤規直接測定，凸塊間距藉由數位顯微鏡測定。多孔質基材(層)[其中，比較例1為包含丙烯酸-胺基甲酸酯共聚物之非多孔質基材(層)]的密度藉由下述而求得，於室溫23℃、濕度50%之環境下，以鋼尺測定樣品尺寸(縱橫)，藉由1/1000mm度盤規測定厚度，進而以1/1000g數位重量計測定質量，從而藉由質量/體積求得密度。關於拉伸彈性率，使用拉伸荷重測定機，根據應力-彎曲曲線求得初期彈性率。
[表1]
產業上之可利用性
本發明係關於熱剝離性雙面黏著片材及使用其之被加工體之加工方法。更加詳細而言係關於藉由加熱處理可迅速降低黏著力、且適用於加工表面凹凸較大之被加工體之熱 剝離性雙面黏著片材，及使用其之被加工體之加工方法。
1‧‧‧基材
2‧‧‧熱剝離性黏著層
3‧‧‧黏著層
4‧‧‧隔離膜
圖1係表示本發明熱剝離性雙面黏著片材之一例的概略剖面圖。
1‧‧‧基材
2‧‧‧熱剝離性黏著層
3‧‧‧黏著層
4‧‧‧隔離膜

Claims (6)

  1. 一種熱剝離性雙面黏著片材，其特徵在於其係於基材之一側面設置熱剝離性黏著層A、於另一側面設置黏著層B之熱剝離性雙面黏著片材，且上述基材包含密度為0.9g/cm3 以下、且拉伸彈性率為20MPa以下之多孔質基材。
  2. 如請求項1之熱剝離性雙面黏著片材，其中基材由多孔質基材與非多孔質基材之積層體構成。
  3. 如請求項1或2之熱剝離性雙面黏著片材，其中黏著層B包含感壓性接著劑、紫外線硬化型黏著劑、熱剝離型黏著劑、熱可塑型黏著劑或熱硬化型黏著劑。
  4. 一種被加工體之加工方法，其特徵在於包含：向請求項1至3中任一項之熱剝離性雙面黏著片材之熱剝離性黏著層A及黏著層B中任一者貼合被加工體，向另一者貼合支持體之貼合步驟；加工所貼合之被加工體的加工步驟；及加工被加工體後，藉由加熱處理將被加工體剝離回收之剝離回收步驟。
  5. 如請求項4之被加工體之加工方法，其中被加工體係電子零件或半導體晶圓。
  6. 如請求項4或5之被加工體之加工方法，其中將具有表面最大凹凸差為10μm以上之面之被加工體，以該面貼合於熱剝離性雙面黏著片材之黏著面並加工者。
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