201241132 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種於不使用金屬製引線框架之無基板半 導體封裝體之製造方法中使用的晶片暫時固定用之半導體 裝置製造用耐熱性黏著帶、及使用其之半導體裝置製造方 法。 【先前技術】 近年來’於LSI(large scale integration，大型積體電路） 之封裝技術中，CSP(Chip Size/Scale Package，晶片尺寸 封裝）技術受到關注。於該技術中，以WLP(Wafer Level Package，晶圓級封裝）為代表的不使用基板而僅為晶片之 形態的封裝係於小型化及高集成方面尤其受到關注的封裝 形態之一種。於WLP之製造方法中，係將不使用基板而整 齊排列之複數個半導體Si晶圓晶片利用樹脂密封一併密封 後，切斷而切分成個別之結構體，藉此，可高效率地生產 較使用基板之先前之封裝體小型之封裝體。 於此種WLP之製造方法中，需要將先前固定於基板上之 晶片固定至其他支持體上。進而經由樹脂密封且成型為個 別之封褒體後，需要解除固定，因此需要該支持體並非永 久接著而可再剝離。因此，使用黏著帶作為此種晶片之暫 時固定用支持體之方法廣為人知。 、生例如，於專利文獻i中記載有_種晶片狀電子零件之製 ，，其包括如下步驟：於基板上，貼附處理前具有黏 者力但處理後黏著力降低的丙烯酸系樹脂系之黏著機構； 162235.doc 201241132 ;該點著機構上’將複數個或複數種半導體晶片以其電極 、、 ％而固疋；將保護物質被覆於包括上述複數個 f複數種半導體晶片間之部分在内的整個面上；對上述黏 “機構實施特之處理而使上述黏著機構之黏著力降低， _ 彔〗離固叱有上述半導體晶片之虛設晶圓；及於上述複數個 * f複數種半導體晶片間切斷上述㈣物質而分離各半導體 晶片或晶片狀電子零件。 又’於專利文獻2中記載有一種晶片狀電子零件之製造 方法其包括如下步驟：於基板上，貼附處理前具有黏著 幻一處理後黏著力降低之丙烯酸系樹脂系之黏著機構；於 6亥黏著機構上’將複數個或複數種半導體晶片以使其電極 朝下之方式而gj定；將保護物質被覆於包括上述複數個 或複數種半導體晶片間之部分在内的整個面上；自與上述 電極面之相反侧去除上述保護物質直至半導體晶片之上述 相反側之表面為止；對上述黏著機構實施特定之處理而使 上述黏著機構之黏著力降低，剝離固定有上述半導體晶片 之虛設晶圓；及於上述複數個或複數種半導體晶片間切斷 上述保護物質而分離各半導體晶片或^曰日片狀電子零件。 ’ 根據該等方法，晶片可得到保護，因此即便於分離後之 . 封裝操作中亦可使晶片得到保護’可獲得使封裝密度提高 等效果。 於專利文獻3中雖為切晶.黏晶帶，但其記載於黏著劑層 中含有環氧樹脂及丙烯酸系橡膠，以及將藉由切晶而獲得 之半導體元件接著於支持構件上之方法，該方法顯然並非 162235.doc 201241132 無基板半導體裝置之方法，而係亦考慮對基板之接著性等 而選擇黏著劑層。 先前技術文獻 專利文獻 專利文獻1 :日本專利特開2001-308116號公報 專利文獻2:日本專利特開2001-3 13350號公報 專利文獻3:曰本專利特開2008·101183號公報 【發明内容】 發明所欲解決之問題 一面於圖1中表示無基板半導體封裝體之製造方法，一 面將問題敍述如下。 將複數個晶片1貼附於兩面具有黏著劑層之半導體裝置 製造用耐熱性黏著帶2上，進而使半導體裝置製造用耐熱 性黏著帶2固定至基板3上，獲得所示之結構。或者，於 基板3上貼附半導體裝置製造用耐熱性黏著帶2,進而固定 晶片1 ’獲得（a)所示之結構。 其人自該（a)所不之結構的晶片1之上方，藉由密封樹[Technical Field] The present invention relates to a heat-resistant adhesive tape for manufacturing a semiconductor device for temporarily fixing a wafer used in a method for manufacturing a substrate-less semiconductor package in which a metal lead frame is not used. And a semiconductor device manufacturing method using the same. [Prior Art] In recent years, CSP (Chip Size/Scale Package) technology has attracted attention in packaging technology of LSI (large scale integration). In this technology, a package which is represented by a WLP (Wafer Level Package) and which does not use a substrate but is only a wafer is one of the package types which are particularly concerned with miniaturization and high integration. In the manufacturing method of the WLP, a plurality of semiconductor Si wafer wafers which are aligned without using a substrate are sealed with a resin, sealed, and cut into individual structures, whereby the production can be efficiently performed. A small package of the previous package of the substrate is used. In the manufacturing method of such a WLP, it is necessary to fix a wafer previously fixed on a substrate to another support. Further, after sealing with a resin and molding into a separate sealing body, it is necessary to release the fixing. Therefore, the support is required to be peeled off without being permanently attached. Therefore, a method of using an adhesive tape as a temporary fixing support for such a wafer is widely known. For example, Patent Document i describes a method for manufacturing a wafer-shaped electronic component, which comprises the steps of: attaching an acrylic resin having a sticky force before the treatment but having a reduced adhesive force after the treatment on the substrate. Adhesive mechanism; 162235.doc 201241132; the point of the mechanism 'will be a plurality of or a plurality of semiconductor wafers with their electrodes, % solid; the protective material is covered between the plurality of semiconductor wafers including the plurality of f The entire surface of the inner surface; the adhesion treatment mechanism is applied to reduce the adhesion of the adhesive mechanism, and the dummy wafer having the semiconductor wafer is fixed; and the plurality of semiconductors of the plurality of semiconductors The semiconductor wafer or the wafer-shaped electronic component is separated by cutting the above-mentioned (4) material between the wafers. Further, Patent Document 2 discloses a method for manufacturing a wafer-shaped electronic component, which comprises the steps of: adhering to the substrate before attaching the treatment Acrylic resin-based adhesive mechanism with reduced adhesion after treatment; 'multiple or plural semiconductor wafers on 6-gear bonding mechanism The protective material is coated on the entire surface including the portion between the plurality of semiconductor wafers; and the protective material is removed from the opposite side of the electrode surface to the semiconductor. a surface of the opposite side of the wafer; performing a specific treatment on the adhesive mechanism to reduce the adhesion of the adhesive mechanism, peeling off and fixing the dummy wafer of the semiconductor wafer; and cutting between the plurality of semiconductor wafers The above-mentioned protective material separates each semiconductor wafer or a chip-shaped electronic component. ' According to these methods, the wafer can be protected, so that even after separation, the wafer can be protected in the packaging operation. Patent Document 3 discloses a dicing layer and a viscous ribbon, but it is described that an epoxy resin and an acryl rubber are contained in an adhesive layer, and a semiconductor element obtained by dicing is attached to a supporting member. In the above method, the method is obviously not the method of the 162235.doc 201241132 substrateless semiconductor device, but The adhesive layer is selected in consideration of the adhesion of the substrate, etc.. PRIOR ART DOCUMENT Patent Document Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-308116. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION A method for manufacturing a substrateless semiconductor package is shown in Fig. 1, and the problem will be described as follows. A plurality of wafers 1 are attached to both sides. In the heat-resistant adhesive tape 2 for manufacturing a semiconductor device having an adhesive layer, the heat-resistant adhesive tape 2 for semiconductor device manufacturing is further fixed to the substrate 3 to obtain the structure shown. Alternatively, the semiconductor device is attached to the substrate 3. The heat-resistant adhesive tape 2 is used to fix the wafer 1' to obtain the structure shown in (a). The person is from above the wafer 1 of the structure (a), by sealing the tree
示者。 片成為一體之方式進行密封，獲得（b)所Shower. The film is sealed in one way to obtain (b)
著帶2者剝離，然後僅將半 162235.doc 201241132 導體裝置製造用耐熱性黏著帶2剝離。 ，於該由密封樹脂4密封之複數個晶片〖的設置半導體裝置 製用耐熱性黏著帶2之側，即露出晶片丨之表面之側，在 曰曰片表面之所需位置形成電極5，獲得（d)所示之結構。 對該結構，於冑封樹脂側視需要接著言免置有切晶環7之 切晶帶8，將由密封樹脂4密封之複數個晶片！固定以進行 切晶步驟。對其如（e)所示般，藉由切晶刀片6進行切晶， 最後如（f)所示’獲得複數個晶片由樹脂密封而成之複數個 無基板封裝體。 於該利用樹脂進行密封之步驟中，半導體裝置製造用耐 熱性黏著帶2必需於樹脂密封時之溫度下亦具有較高之黏 著丨生以使得帶上之晶片1之位置不會因樹脂密封之壓力 而移動。 相對於此，樹脂密封、樹脂硬化後的自晶片剝離半導體 裝置製造用耐熱性黏著帶2之步驟中必需為輕剝離，故而 若為於高溫下具有較高黏著性的通常之感壓型黏著劑，則 存在剝離時無法進行輕剝離而導致剝離變得困難，或產生 如圖2所示之糊劑殘餘，或者發生剝離帶電等問題。 又，若剝離變得困難則相應地需要較長之時間，因此生 產性降低，若產生糊劑殘餘9，則無法實施其後之電極形 成等步驟，另外，若產生剝離帶電，則存在因灰塵等附著 而導致其後之步驟中產生故障的情況。 解決問題之技術手段 為解決上述問題，本發明係採用使用如下之半導體裝置 162235.doc 201241132 製造用耐熱性黏著帶，而製造不使用金屬製引線框架之無 基板半導體晶片的方法，該半導體裝置製造用耐熱性黏著 帶之特徵在於：其係於對無基板半導體晶片進行樹脂密封 時黏貼而使用之晶片暫時固定用黏著帶，其於含有胺基甲 酸醋聚合物成分及乙烯系聚合物之樹脂層之一面，具有含 有熱膨脹性微球體之熱膨脹性黏著層。 發明之效果 本發明係關於一種於不使用金屬製引線框架之無基板半 導體封裝體之製造方法（例如WLP之製造方法等）中使用的 Ba片暫時固定用黏著帶，且發揮如下效果，即可提供一種 晶片不會因樹脂密封時之壓力而自指定位置偏移，且密封 後可於特定溫度以下之溫度下，不產生密封樹脂之糊劑殘 餘地輕剝離的半導體裝置製造用耐熱性黏著帶。 【實施方式】 本發明者等人為解決上述問題而對半導體裝置製造用耐 熱性黏著帶之材料、構成等進行銳意研究。結果發現藉由 使用如下之半導體裝置製造用耐熱性黏著帶可解決上述問 題’從而完成本發明，該半導體裝置製造用耐熱性黏著帶 之特徵在於：於含有胺基曱酸酯聚合物成分及乙烯系聚合 物之樹脂層之一面，具有含有熱膨脹性微球體之熱膨脹性 黏著層。 以下’說明本發明之半導體裝置製造用耐熱性黏著帶。 圖3中例示本發明所使用之半導體裝置製造用耐熱性黏 著帶2。 !62235^〇ς 201241132 為平/月之到離片’ 1!為樹脂層，i 2為橡膠狀有機彈性 層’ 1 3為熱膨脹性黏著劑層。 此處，該樹脂層及該橡膠狀有機彈性層亦可分別包含複 數層。 (樹脂層） 樹月曰層11係包含含有胺基甲酸酯聚合物成分及乙烯系聚 合物之樹脂的層。 (胺基曱酸酯聚合物） 樹脂層所使用U基曱酸酿聚合物係使多A醇與二異氛 酸酯反應而獲得。於多元醇之羥基與異氰酸酯之反應中， 亦可使用例如二丁基二月桂酸錫、辛酸錫、i，4-二氮雜雙 環（2’2’2)辛料胺I曱酸醋反應中it常所使用之觸媒。 作為多元醇，可列舉：使環氧乙烷、環氧丙烷、四氫呋 喃等加成聚合而獲得的聚醚多元醇，或者包含上述二元醇 與己二酸、壬二酸、癸二酸等二元酸之縮聚物的聚酯多元 醇，或丙烯酸多元醇、碳酸酯多元醇、環氧多元醇、己内 醋多元醇等》於該等中，可較佳地使用例如聚氧丁二醇 (PTMG)、聚氧丙二醇（PPG)等聚醚多元醇，非晶質之聚酿 多元醇，非晶質之聚碳酸酯多元醇等。該等多元醇類可單 獨或併用而使用。 作為二異氰酸酯’可列舉芳香族、脂肪族、脂環族之二 異氰酸酯等。作為芳香族、脂肪族、脂環族之二異氰酸 酯’可列舉：曱笨二異氰酸酯、二苯基曱烷二異氰酸酯、 六亞甲基二異氰酸酯、苯二亞甲基二異氰酸酯、氫化苯二 162235.doc 201241132 亞甲基一異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯基曱 烷一異氰馱酯' 1，5_萘二異氰酸酯、丨,3-苯二異氰酸酯、 M·笨二異氛酸醋、丁烷]，4·二異氰酸酯、2,2,4_三曱基六 亞甲基一異氰酸酯、2,4,4•三甲基六亞曱基二異氰酸酯、 環己烷-1，4·二異氰酸酯、二環己甲烷_4,4·二異氰酸酯、 I3雙（異氛酸醋基曱基）環己烷、甲基環己烷二異氰酸 :曰間四甲基苯二亞曱基二異氰酸酯等。該等二異氰酸酯 可單獨或併用而使用。可考慮胺基甲酸醋反應性、與丙炼 S义之相容性等觀點而適當選擇聚異氰酸酯之種類、組合 等。 用以形成胺基甲酸酯聚合物之上述多元醇成分與上述二 異氰酸西旨成分之使用量並無特別限定，例如多元醇成分之 使用量較佳為相對於二異氰酸酯成分nc〇/〇h(當量比）為 L〇以上，進而較佳為2·0以下。若NCO/OH為1.0以上，則 胺基甲酸酿分子键之末端官能基為經基，可防止暫時固定 層之強度降低。又，若NC〇/〇H為2〇以下，則可確保適度 之伸長及強度。 又，較理想為胺纟f酸醋聚合物之至少一部分為丙稀醯 基末端胺基甲酸酯聚合物，藉由具有此種丙烯醯基，可與 乙烯系聚合物交聯而調整凝聚力。 本發明之胺基甲酸酯聚合物成分之分子量可由所使用之 多元醇或一異氰酸3旨之種類、NCO/OH比而適當決定。 其分子量並無特別限定’較佳為數量平均分子量（Mw) 為5000以上，進而較佳為10000以上。 I62235.doc •10- 201241132 較理想為於上述胺基曱酸酯聚合物中，添加與本發明中 之乙稀系聚合物不同之含羥基之丙烯酸系單體。藉由添加 含羥基之丙烯酸系單體，可於胺基曱酸酯聚合物之分子内 導入丙烯酿基，可使其具有與丙烯酸系單體之共聚合性。 作為含羥基之丙烯酸系單體，可使用（曱基）丙烯酸羥基乙 酯、（甲基）丙烯酸羥基丙酯、（曱基）丙烯酸羥基己酯等。 含羥基之丙烯酸系單體之使用量較理想為相對於胺基曱酸 酯聚合物100重量份為O.hiO重量份，更理想為〇」〜5重量 份0 (乙稀系聚合物） 本發明之樹脂層中所使用之乙烯系聚合物，亦可藉由僅 使構成乙烯單體之乙烯化合物聚合而得到，此時，可藉由 使單-之單體或2種以上單體之混合物聚合而得到。聚合 可利用溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等任— 種方式而進行。就防止半導體晶圓等之污染等觀點而言， 黏著劑層較佳為低分子量物質之含量較小。就該點而言， 丙稀酸系聚合物之重量平均分子量較佳為％萬以上，進而 較佳為40萬〜3〇〇萬之程度。 樹脂層可藉由將上述胺基f酸酯聚合物與下述Μ" 合物摻混而獲得，X，亦可藉由製備胺基甲_合物與 乙稀系单體之混合物繼而使乙稀系聚合物聚合而獲得。 其中’就可使用之單體之種類或片材化之 而言，較佳為以下述方式形成：於乙 寻銳點 或2種以上之混合物中，使多成元氰， K夕70醇與異氰酸酯&應而形成 162235.doc -11 _ 201241132 胺基甲酸酯聚合物，將所獲得之含有胺基曱酸酯聚合物及 乙烯系單體之混合物塗佈於基材上，照射放射線使其硬 化。又，作為乙稀系單體，較佳為（曱基）丙烯酸系單體。 另外，如上所述，亦可藉由使用含羥基之丙烯酸系單體 而向胺基曱酸酯聚合物導入丙烯醯基後，使乙烯系單體聚 合，藉此，該丙烯醯基與乙烯基聚合，從而製成該胺基甲 酸酯聚合物與該乙晞系聚合物結合而成之樹脂。 本發明中之乙烯系聚合物係使乙烯系單體聚合而成之聚 合物，作為該乙烯系單體，可較佳地使用如上述之（甲基） 丙稀酸系單體，該（甲基）丙烯酸系單體例如可列舉：（甲 基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙 酯、（曱基）丙稀酸正丁酯、（甲基）丙稀酸第二丁酯、（曱基） 丙烯酸第三丁酯、（甲基）丙烯酸正辛酯、（曱基）丙烯酸異 辛酯、（甲基）丙烯酸-2-乙基己酯、（甲基）丙浠酸異壬酯、 (甲基）丙烯酸十二烷基酯、（甲基）丙烯酸正十八烷基酯、 丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊 酯、衣康酸、順丁烯二酸、丁烯酸等含羧基之單體；（甲 基）丙烯酸-2-羥基乙酯、（曱基）丙烯酸_2_羥基丙酯、（甲 基）丙烯酸-4-羥基丁酯、（甲基）丙烯酸_6_羥基己酯、（甲 基）丙烯酸-8-羥基辛酯' (f基）丙烯酸_1〇_羥基癸酯、（甲 基）丙烯酸-12_羥基月桂基酯、丙烯酸（4_羥曱基環己基）甲 酯等含羥基之單體；（曱基）丙烯酸環己酯、丙烯酸異葙酯 等具有脂環式結構之單體；順丁烯二酸酐、衣康酸酐等酸 酐單體；2-丙烯醯胺-2-甲基丙磺酸、丙烯酸磺丙酯等含磺 16223S.doc 201241132 酸基之單體；磷酸-2-羥乙基丙烯醯酯等含磷酸之單體等。 又，可使用下述者中之1種或2種以上：（甲基）丙烯醯胺、 N-羥曱基丙烯醯胺等N_取代（曱基）丙烯醯胺等醯胺系單 體；N-(曱基）丙烯醯氧基亞曱基琥珀醯亞胺、N_(曱基）丙 烯醯-6-氧基六亞曱基琥珀醯亞胺、N_(甲基）丙烯醯_8•氧基 八亞甲基琥始醯亞胺等琥珀醯亞胺系單體；乙酸乙烯酯、 N-乙烯基吼咯烷酮、N-乙烯基羧醯胺類、N_乙烯基己内醯 胺等乙烯系單體；丙烯腈、曱基丙烯腈等氰基丙烯酸酯系 單體；（曱基）丙烯酸縮水甘油酯、（曱基）丙烯酸四氫糠 Sa、聚乙二醇（甲基）丙烯酸酯、聚丙二醇（甲基）丙烯酸 酯、氟（甲基）丙烯酸酯、聚矽氧（曱基）丙烯酸酯、丙烯酸_ 2-甲氧基乙酯等丙烯酸酯系單體；（甲基）丙烯酸曱酯或（曱 基）丙烯酸十八烷基酯等單體。該等（甲基）丙烯酸系單體可 考慮與胺基f酸酯之相容性、利用放射線等進行光硬化時 之聚合性或所獲得之高分子量體之特性而適當決定種類、 組合、使用量等。 尤其是考慮到加溫時與剝離時之黏著力，較理想為使用 具有羧基之單體’以可使乙烯系聚合物含有羧基，進而， 若使用（曱基）丙烯酸等具有極性基之單體，則加溫時與冷 卻剝離時之黏著力之平衡較好。 作為（甲基）丙烯酸之添加量，較佳為於將胺基甲酸醋聚 合物與乙烯系聚合物之總量設為1〇〇重量份時，為5重量份 以上且未達80重量份，進而較佳為1〇重量份以上且未達7〇 重量份。藉由設為5重量份以上，可易於獲得加溫時斑冷 I62235.doc 201241132 部剝離時之黏著力之平衡，χ，若未達8〇重量份，則具有 柔軟性因而加溫時之黏著力提高。 本發明中，亦可於不損及特性之範圍内添加其他多官能 單體。作為多官能單體，可列舉己二醇二丙稀酸醋、三^ 甲基丙烷三丙烯酸酯、二季戊四醇六丙烯酸酯等。 (胺基甲酸酯聚合物與乙烯系聚合物之含有比率） 本發明中之樹脂層含有胺基甲酸酯聚合物與乙烯系聚合 物作為有效成分。胺基甲酸酯聚合物與乙烯系聚合物之比 率並無特別限定，相對於胺基曱酸酯聚合物與乙烯系聚合 物之合計量’胺基曱酸酯聚合物所占之重量較佳為1〇%以 上且90%以下，進而較佳為2〇%以上且未達8〇%。若胺基 甲酸酯聚合物之比率為10%以上，則高溫時之彈性模數不 會變低而可獲得充分之加工精度。又，若為9〇%以下則 製作片材時之操作性及生產性良好。 (樹脂層形成方法） 本發明之樹脂層可藉由如下方法而獲得：於藉由聚合而 構成乙烯系聚合物之乙烯系單體的單獨丨種或2種以上之混 5物中，使多元醇與異氰酸酯反應而形成胺基甲酸酯聚合 物’將含有胺基甲酸酯聚合物與該乙烯系單體之混合物塗 佈於支持基材上，根據光聚合起始劑之種類等照射α射 線、β射線、γ射線、中子射線、電子束等電離放射線或紫 外線等放射線、可見光等，藉此使其硬化。 又’亦可藉由將胺基曱酸酯聚合物與乙烯系聚合物摻 混’將其塗佈於支持基材上加以乾燥而形成樹脂層。 162235.doc 201241132 又，於使用上述含羥基之丙烯酸系單體之情形時，可藉 由下述方法而獲得樹脂層：於藉由聚合而構成乙烯系聚合 物之乙烯系單體的單獨1種或2種以上之混合物中，使多元 醇與異氰酸酯反應而形成胺基甲酸酯聚合物之後，添加含 經基之丙烯酸系單體，使其與胺基甲酸酯聚合物反應，將 所獲得之混合物塗佈於支持基材上，根據光聚合起始劑之 種類等照射α射線、β射線、γ射線、中子射線、電子束等 電離放射線或紫外線等放射線、可見光等，藉此使其硬 化。 具體而S ，亦可藉由使多元醇溶解於乙烯系單體中之 後，添加二異氰酸酯等與多元醇反應而調整黏度，將所得 者塗佈於支持基材等上之後，使用低壓水銀燈等進行硬 化’而獲得暫時固定片材。該方法中，可於合成胺基甲酸 醋之過程中-次性地添加乙烯系單體，亦可分成幾次添 加。又，亦可於使二異氰酸酉旨溶解於乙歸系單體中之後， 使多元醇反應。根據該方法，分子量不會受到限定，亦可 生成高分子量之聚胺基甲酸酿’因此可將最終獲得之胺基 曱酸酯之分子量設計成任意之大小。 ’可在塗佈於支持基材上 體之混合物上，進而載置 可將剝離襯墊放入至充有 此時’為避免氧對聚合之抑制 之胺基曱酸酯聚合物與乙稀系單 經剝離處理之基材而阻斷氧，亦 惰性氣體之容器内而降低氧遭度 又，為調整㈣之黏度，亦可添力 劑，可自通常使用之溶劑中適當 ’合 選擇，例如可列舉乙酸乙 I62235.doc •15· 201241132 酯、曱苯、氣仿、二曱基甲醯胺等β 於本發明中，放射料之種類或照射所使用之燈之種類 等可適當選擇，可使㈣光化學燈、黑光燈、^燈等低 壓燈，或金屬函素燈、高壓水銀燈等高壓燈等。 束外線等之照射量可根據所要求之暫時固定層之特性而 任意地設定。一般而言，紫外線之照射量為5〇〜〇 ’車交佳為1〇〇〜4〇〇〇 mJ/cm2，進而較佳為⑽〜删 mJ/cm2。若紫外線之照射量在5〇〜5_⑽/⑽2之範圍内， 則 不會劣化且可獲得充分之聚合率。 於以胺基甲酸S旨聚合物及乙烯系單體為主成分之混合物 含有光聚合起始劑。作為光聚合起始劑，可列舉：安息 中 甲謎 安息香異丙醚、2,2-二甲氧基]，2_二苯基乙烷」 香 酮等安息香醚；苯曱醚甲醚等取代安息香醚；2,2_二乙氧 基本乙酮、2,2-二甲氧基_2_苯基苯乙酮、卜羥基-環己基· 苯基酮等取代苯乙酮；2-甲基_2_經基苯丙酮等取代心酮 醇；2-萘磺醯氣等芳香族磺醯氣；丨_苯基-Μ·丙二酮_2_ (〇-乙氧基羰基)-肟等光活性肟；（2,4,6_三甲基苯甲酿基) 二苯基氧化膦、雙（2,4,6_三甲基苯甲酿基）苯基氧化麟等酿 基氧化膦等。 本發明中之樹脂層之厚度可視目的等而適當選擇，一般 而言為5〜500 μηι，較佳為10〜100 μηΐ2程度。 本發明之樹脂層於175t下對矽晶片之剪切接著力為ι〇〇 g/H) “以上，較佳為15〇 g/1〇 _2以上，進而較佳為· g/10 mm2以上，進而更佳為3〇〇 g/1〇 mm2以上，且於它 I62235.doc -16- 201241132 加熱後對密封樹脂之9〇。剝離黏著力為0 50 n/20 mm以 下’較佳為0.40 N/20 mm以下，進而較佳為0.30 N/20 mm 以下’進而更佳為0.20 N/20 mm以下。 通常’樹脂之密封、硬化步驟多於約175〇c左右之溫度 . 下進行，於如上所述的剪切接著力為1〇〇 g/1〇 mm2以上且 剝離黏著力為0.50 n/20 mm以下之情形時，可擔載半導體 晶片且將其固定成於樹脂密封、硬化時該半導體晶片確實 地不偏移。 進而於其後冷卻至特定溫度，並自經分離之封裝體剝離 樹脂層時，對密封樹脂之9〇。膜剝離黏著力越小，則剝離 所需之力可更小，因此不會產生損壞該封裝體等情況。 於本發明中，半導體裝置製造用接著片材之樹脂層較佳 為具有於40 C以上之特定溫度下表現黏著力，且於該特定 溫度以下失去黏著力之性質。進而較佳為於7(rc以上之特 定溫度下具有黏著力，特佳為於1〇〇〇c以上之特定溫度下 具有黏著力。 所謂於40°C以上之特定溫度下表現黏著力，係指於4〇。〇 以上之某溫度下首次表現黏著力，若未達到該溫度則不表 • 現黏著力，結果意味著於至少未達4〇t之溫度下不表現黏 • 著力。利用如此之黏著力根據溫度而變化之特性，可於使 含有熱膨脹性微球體之熱膨脹性黏著層發泡時’將半導體 晶片確實地固定於半f體裝置製造用之無基板耐熱性黏著 帶上，並且於加熱製品時以外之時間可容易地自樹脂層取 出。 162235.doc -17· 201241132 本發明中之樹脂層於l75t下之儲存彈性模數G，為 1.0X105 Pa以上，較佳為2.〇xl〇5 Pa以上，進而較佳為 3.〇xl05 Pa以上，進而更佳為4.〇xl〇5 pa以上。 若儲存彈性模數GH.0x1〇5 Pa以上，則將晶片埋入至 樹脂層中之離板間隙（stand_〇ff)較小，於其後之步驟中不 會產生良率降低之情況。 (橡膠狀有機彈性層） 橡膠狀有機彈性層12亦包含發揮如下功能者：於將半導 體裝置製造用耐熱性黏著帶接著於被黏著體上時，其表面 良好地追隨被黏著體之表面形狀，從而提供較大之接著面 積，及於為自半導體裝置製造用耐熱性黏著帶剝離被黏著 體而對熱膨脹性黏著劑層13加熱，使其發泡及/或膨脹 時，減少半導體裝置製造用耐熱性黏著帶之面方向上的發 泡及/或膨脹之約束，從而對藉由熱膨脹性黏著劑層13產 生立體結構變化而形成起伏結構予以促進。 橡膠狀有機彈性層12可視需要而設置，於設置該橡膠狀 有機彈性層12之情形時’為使其特性充分地發揮，較佳為 將其厚度設為5〜50 μπι。 橡膠狀有機彈性層12可使用基於ASTM D-2240之D型蕭 氏D型硬度為50以下，較佳為40以下之天然橡膠或合成橡 膠、或者具有橡膠彈性之合成樹脂而形成。 作為上述合成橡膠或合成樹脂，例如可列舉：腈系、二 炼系、丙稀酸系等之合成橡膠；如聚稀烴系或聚酯系之熱 塑性彈性體、乙烯-乙酸乙烯酯共聚物、聚胺基曱酸酯' 162235.doc -18 - 201241132 聚丁一烯軟質聚氣乙烯等具有橡膠彈性之合成樹脂。再 者，如聚氣乙烯般雖本質上為硬質系之聚合物但藉由與 塑化劑或柔軟料複合劑組合而具有橡膠彈性者在本發明 中亦可使用。 又’橡膠狀有機彈性層12亦可藉由橡膠系或樹脂等通常 已知之感壓接著劑而形成。 作為感壓接著劑，可使用橡料錢接著劑、丙稀酸系 感壓接著劑、苯乙烯-共軛二烯嵌段共聚物系感壓接著劑 等之適當者。又’亦可使用含有熔點約200。(：以下等之熱 熔融性樹脂而使潛變性得到改善者等。 再者，感壓接著劑中亦可調配有抗靜電劑、交聯劑、黏 著賦予劑、塑化劑、填充劑、防老化劑等適當之添加劑。 更具體而言’例如可列舉將天然橡膠或合成橡膠作為基 底聚合物的橡膠系感壓接著劑、以及將以如下者為主成分 之丙烯酸系聚合物作為基底聚合物的丙烯酸系感壓接著劑 等：具有如甲基、乙基、丙基、丁基、2_乙基己基、異辛 基、異壬基、異癸基、十二烷基、月桂基、十三烷基、十 五烧基、十六烧基、十七烧基、十八烧基、十九烧基、二 十烷基等常例之碳數20以下之烷基的丙烯酸或曱基丙烯酸 等之丙烯酸系烷基酯，丙烯酸、曱基丙烯酸、衣康酸、丙 烯酸羥基乙酯、曱基丙烯酸羥基乙酯、丙烯酸羥基丙酯、 甲基丙烯酸羥基丙酯、N-羥曱基丙烯醯胺、丙烯腈、曱基 丙烯腈、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、乙 酸乙烯酯、苯乙烯、異戊二烯、丁二烯、異丁烯、乙烯醚 162235.doc -19- 201241132 等。 (熱膨脹性黏著劑層） 形成熱膨脹性黏著劑層13之感壓接著劑需要容許加熱時 熱膨脹性微球體之發泡及/或膨脹，可使用上述橡夥狀有 機彈性層中可使用之以橡膠系材料或（甲基）丙烯酸系樹脂 等作為基底的公知之感壓接著劑，較佳為具有儘量不約束 熱膨脹性微球體之發泡及/或膨脹之程度之彈性者。 熱發泡型黏著劑係於上述通常之感壓性黏著劑中調配熱 膨脹性微粒子而成者。藉由因熱所引起之熱膨脹性微粒子 之發泡，熱發泡型黏著劑之接著面積減少從而變得容易剝 離，熱膨脹性微粒子之平均粒徑較佳為丨μιη〜25 之程 度。更佳為5 μηι〜15 μηι，特佳為10 μηι左右。又，於上述 熱膨脹性黏著劑層中適當調配公知之樹脂等之黏著賦予 劑、塑化劑、顏料、填充劑、導電劑、抗靜電劑等，並藉 由多官能性環氧化合物、或異氰酸酯化合物、氮丙啶化合 物、二聚氰胺樹脂、脲樹脂、無水化合物、多胺、含羧基 之聚合物等交聯劑進行交聯。 略服f生黏著劑層i 3可藉由於黏著劑中調配熱膨服性微 球體而形成。作為熱膨脹性微球體，例如可使用將如異丁 燒 '丙院、戊燒等可容易地氣化而表現熱膨服性的適當之 物質’藉由凝集法或界面聚合法等而内包於殼形成物質内 所得的熱膨脹性微球體。所使用之熱膨脹性微球體較理想 為熱膨脹性微球體之體積膨脹倍率為5倍以上，較佳為⑺ 倍以上》 162235.doc •20- 201241132 再者，作為形成熱膨脹性微球體之殼形成物質，例如通 常為偏二氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯丁 酿、聚曱基丙埽酸甲酿、聚丙稀腈、聚偏二氣乙稀、聚艰 等，於本發明中，只要包含熱溶融性物質或可由熱膨脹破 壞之物f等即可。#膨脹性微!求體亦具有與上述黏著劑之 分散混合性優異等優點。作為熱膨脹性微球體之市售品， 例如可列舉MICROSPHERE(商品名；松本油脂製藥（股）製 造）等。 熱膨脹性微球體之調配量可根據使熱膨脹性黏著劑層η 膨脹（發泡）之程度或使其接著力降低之程度而適當地決 定。一般而言，相對於每100重量份之基底聚合物調配 1〜150重量份，較佳為調配25〜丨00重量份。熱膨脹性黏著 劑層之厚度使用5〜1 〇〇 μπι，較佳為使用1 5〜50 μιη。 用以使本發明之半導體裝置製造用耐熱性黏著帶2可自 被黏著體容易地剝離之加熱處理條件，係根據被黏著體之 表面狀態或由熱膨脹性微球體之種類等所決定的接著面積 之減少性、基材或被黏蓍體之耐熱性或者加熱方法等條件 而決定，通常之條件為100〜25(TC、i〜90秒（加熱板等）或 5〜15刀鐘（熱風乾燥器等），於本用途中，由於樹脂密封溫 度為約175度左右，因此較理想為2〇〇〜25〇。〇、1〜9〇秒（加 熱板等）或1〜15分鐘（熱風乾燥器等 (平滑之剝離片） 平滑之剝離片10係於基材膜之單面形成剝離劑層而成之 片材，係於使用本發明之半導體裝置製造用耐熱性黏著帶 162235.doc -21- 201241132 2之前剝離，以使各面之黏著劑層露出之片材。 剝離劑層可根據所接觸之黏著劑而自長鏈烷基系、氟樹 脂系、聚矽氧樹脂系等公知之剝離劑層中適當選擇獲得。 該剝離片可用作形成樹脂層或熱膨脹性黏著劑層時的基 層’另外亦可將其積層於所形成之樹脂層或熱膨脹性黏著 劑層表面而使用。 作為基材膜，可使用公知者，例如可自下述者中選擇： 聚醚醚酮、聚醚醯亞胺、聚芳酯、聚萘二曱酸乙二酯、聚 乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊稀 膜、聚氣乙烯膜、氣乙烯共聚物膜、聚對苯二甲酸乙二酷 膜、聚對苯二曱酸丁二酯膜、聚胺基曱酸酯膜、乙烯·乙 酸乙烯酯共聚物膜、離子聚合物樹脂膜、乙烯甲基）丙烯 酸共聚物膜 '乙稀-(甲基）丙烤酸酯共聚物膜、聚苯乙稀 膜、及聚碳酸酯膜等塑膠膜等。 可使用之剝離劑層係根據黏著劑層之樹脂而選擇含有下 述公知之剝離劑而成之層：經氟化之聚矽氧樹脂系剝離 劑、氟樹脂系剝離劑、聚矽氧樹脂系剝離劑、聚乙稀醇系 樹脂、聚丙烯系樹脂、長鏈烷基化合物等。 (半導體裝置製造用耐熱性黏著帶之製造方法） 本發明之半導體裝置製造用耐熱性黏著帶2可藉由通常 之製造方法而製造。例如依序進行以下步驟：使構成樹脂 層、橡膠狀有機彈性層12、熱膨脹性黏著劑層13各者之組 合物溶解於特疋之溶劑而製備塗佈液，將該等塗佈液，以 獲得目標之半導體裝置製造用耐熱性黏著帶2之層構成的 162235.doc -22· 201241132 於特 橡膠 然後 考慮 可較佳地使用曱基乙基 j塗佈於具有剝離性之分離膜等樹脂層上，其後 疋條件下加熱、乾燥該塗佈層。 亦可藉由流延於剝離性膜等上而製作樹脂層 .有機彈ϋ層12、熱膨脹性點著劑層13之單獨之膜 X等膜依序積層。此處，作為溶劑並無特別限定 到構成材料之溶解性良好之方面 酮等_系溶劑。 (半導體裝置製造用耐熱性黏著帶之使用方法） 半導體裝置製造用耐熱性黏著帶2係用於上述中根據圖i 而說明之步驟中。 I7半導體裝置製造用耐熱性黏著帶2係於以下所示之 半導體4之接著步驟、密封步驟、義步驟巾作為固定 日日片之機構而使用者。 (半導體晶片之接著步驟） 將包含脂層及熱膨脹性黏著劑層之半導體裝置製造用 ^ ’、’、ϋ黏f帶2的去除該熱膨脹性黏著劑層的熱膨服性黏 著層上之⑻離片後之熱膨服性點著劑層U側接著於基板 上，使其相反之樹脂層面側露出為上表面。 於八上將欲藉由樹脂密封之特定之半導體晶片1以成 為才η* -置之方式載置、接著，排列於半導體裝置製造用 耐熱性黏著帶2之樹脂層上。此時之半導體晶片!之結構、 形狀、大小等並無特別限定。 (密封步驟） 使用本發明之半導體裝 置製造用耐熱性黏著帶2的密封 162235.doc -23· 201241132 步驟中所使用之樹脂可根據用途而任意變更，為環氧樹脂 等公知之密封樹脂即可。粉末狀樹脂之熔融溫度或硬化溫 度、液狀樹脂之硬化溫度係考慮半導體裝置製造用耐熱性 黏著帶2之耐熱性而選擇，但本發明之半導體裝置製造用 耐熱性黏著帶2於通常之密封樹脂之熔融溫度或硬化溫度 下均具有对熱性。 密封步驟係為保護晶片而藉由上述樹脂於模具内進行， 例如於170〜180°C下進行。 其後’將半導體裝置製造用耐熱性黏著帶2剝離之後， 進行封膠後烘烤（post mold cure)。 (剝離步驟） 藉由樹脂將固定於基板上之半導體裝置製造用耐熱性黏 著帶2上的晶片密封之後，於200〜250。(：、1〜90秒（加熱板 等）或1〜15分鐘（熱風乾燥器等）之條件下進行加熱，使半導 體跋置製造用耐熱性黏著帶2之熱膨脹性黏著劑層13膨 服’藉此使半導體裝置製造用耐熱性黏著帶2之熱膨脹性 黏著劑層13與基板3之接著力降低，將半導體裝置製造用 耐熱性黏著帶2與基板3剝離。 繼而’冷卻至特定溫度以下後，自藉由樹脂密封晶片而 成之層制離半導體裝置製造用耐熱性黏著帶2。 又’亦可採用如下方法：不將半導體裝置製造用耐熱性 黏著帶2與基板3分離而將其等作為一體，自半導體裝置製 造用耐熱性黏著帶2之樹脂層分離由密封樹脂4密封之複數 個晶片1。 162235.doc • 24· 201241132 (電極形成步驟） 其次，於藉由密封樹脂4密封晶片1 露出於表面之側，即積層半 之晶片1之一面 2之側，藉由網版印刷等 ：1造用耐熱性黏著帶 極5。作為電極材料二==^^ (切晶步驟） 於密封樹則密封晶片1而成之層，較佳為在固定 中：Γ 7之切晶带8上之後，使用通常之切晶步称 中所用之切晶刀片6而分離成各封裝體。 此時’若各晶片1未存在於特 不準確，並且各封裝體二置，則電極之形成 T衣體之日日片1之位置不準確，或者於靡 重之情形時，有切晶時切晶刀片6接觸晶片i之可能性。、 若使用本發明之半導體裝置製造用耐熱性黏著帶2,則 於藉由密封樹脂4所進行之密封步驟中可防止晶片1之位置 產生偏移，因此不存在此種故障，可順利地實施切晶步 驟，結果獲得晶片1準確地定位於密封樹脂内之封裝體。 又，半導體裝置製造用耐熱性黏著帶2可藉由輕剝離而 自由费封樹脂密封之晶片剝離，並且不會產生糊劑殘餘， 故而可一面維持較高良率一面製造。 以下’基於實施例更詳細地說明本發明，但本發明並不 限定於該等實施例。 實施例 實施例1 於包含冷卻管、溫度計及攪拌裝置之反應容器中，投入 162235.doc • 25· 201241132 作為（曱基）丙烯酸系單體的丙烯酸異指酯（IBxa)50重量 份’作為多元醇的數量平均分子量650之聚丁二醇 (PTMG，三菱化學（股）製造）72.8重量份，一面攪拌，一面 滴加氫化苯二亞甲基二異氰酸酯（HXDI，三井化學聚胺酯 (股）製造）27.2重量份’於65°C下反應10小時，獲得胺基曱 酸醋聚合物-丙烯酸系單體混合物《其後，滴加丙烯酸_2_ 經基乙酯（HEA)6.5重量份進而反應3小時之後，添加丙烯 酸（AA)50重量份、及作為光聚合起始劑的2,2·二甲氧基_ 1，2·二苯基乙烷-1-酮（IRGACURE 651，Ciba Japan(股）製 造）0.3重量份。再者，聚異氰酸酯成分與多元醇成分之使 用量為]^(：0/011(當量比）=1.25。 將胺基曱酸酯聚合物與丙烯酸系單體混合物，以硬化後 之厚度達到10 0 μιη之方式塗佈於厚度38 μηι的.經剝離處理 之 PET(polyethylene terephthalate，聚對苯二甲酸乙二酯） 上。於其上重疊被覆經剝離處理之PET膜後，對該被覆之 PET膜表面，使用黑光燈照射紫外線（照度5 mW/cm2，光 量1000 mJ/cm2)而進行硬化，於pET膜上形成樹脂層丨（胺基 甲酸酯-丙烯酸複合膜）。 又，於包含丙烯酸乙酯_丙烯酸丁酯·丙烯酸（2〇份_8〇份一 1 〇份）之共聚聚合物1 〇〇份中，均勻地混合、溶解環氧系交 聯劑1 ·0份、松脂系黏著賦予劑5份、2〇〇t>c發泡膨脹型之 熱膨脹性微球體50份及甲苯而製作塗佈液，將該塗佈液塗 佈於樹脂層上且乾燥，獲得具有作為熱膨脹性黏著劑層之 厚度約40 μηι之黏著劑層的半導體裝置製造用耐熱性黏著 162235.doc -26· 201241132 帶1。 將該半導體裝置製造用耐熱性黏著帶之熱膨脹黏著劑面 壓接固定於平滑之台上後，於相反面之樹脂層上配置尺寸 為5 mmx5 mm之Si晶圓晶片，流入液狀之環氧系密封樹 脂’於175°C x2 min之條件下封膠。其後，藉由150°C X6〇 min之加熱促進樹脂之硬化（封膠後烘烤），製作封裝體。 實施例2 於包含冷卻管、溫度計及攪拌裝置之反應容器中，投入 作為（曱基）丙烯酸系單體的丙烯酸異莅酯（IBXA)80重量 份、丙烯酸丁酯（BA)20重量份，作為多元醇的數量平均分 子量650之聚丁二醇（PTMG，三菱化學（股）製造）72.8重量 份’一面攪拌，一面滴加HXDI 27.2重量份，於65°C下反 應10小時，獲得胺基甲酸酯聚合物-丙烯酸系單體混合 物。其後，滴加丙烯酸-2-羥基乙酯（HEA)6.5重量份進而反 應3小時後，添加丙烯酸（AA)3〇重量份、及作為光聚合起 始劑的IRGACURE 651 0.3重量份。再者，聚異氰酸酯成 分與多元醇成分之使用量為NCO/〇H(當量比）=1.25。 將胺基甲酸酯聚合物與丙烯酸系單體混合物，以硬化後 之厚度達到1〇〇 μιη之方式塗佈於厚度38 μηι的經剝離處理 之PET上。於其上重疊被覆經剝離處理之pet膜後，對該 被覆之PET臈表面，使用黑光燈照射紫外線（照度5 mW/cm2，光量1〇〇〇 mj/cm2)進行硬化，於pet膜上形成樹 脂層2(胺基曱酸酯_丙烯酸複合膜2)，除此以外以與實施例 1同樣之方法製作封裝體。 162235. doc • 27· 201241132 實施例3 於包含冷卻管、溫度計及攪拌裝置之反應容器中，投入 作為（甲基）丙烯酸系單體的丙烯酸異格酯（IBXA) 100重量 份，作為多元醇的數量平均分子量650之聚丁二醇 (PTMG ’三菱化學（股）製造）72.8重量份，一面攪拌，一面 滴加HXDI 27.2重量份，於65°C下反應10小時，獲得胺基 甲酸酯聚合物-丙烯酸系單體混合物。其後，滴加丙烯酸_ 2-羥基乙酯（ΗΕΑ)6·5重量份進而反應3小時後，添加作為 光聚合起始劑的IRGACURE 651 0.3重量份。再者，聚異 氰酸酯成分與多元醇成分之使用量為NCO/OH(當量 比）=1.25 » 將胺基甲酸酯聚合物與丙烯酸系單體混合物，以硬化後 之厚度達到1 00 μιη之方式塗佈於厚度38 μιη的經剝離處理 之PET上。於其上重疊被覆經剝離處理之PET膜後，對該 被覆之PET膜表面，使用黑光燈照射紫外線（照度5 mW/cm2 ’光量1000 mJ/cm2)進行硬化，於PET膜上形成樹 脂層3 (胺基曱酸酯-丙烯酸複合膜3 )，除此以外以與實施例 1同樣之方法製作封裝體。 比較例1 將丙烯酸系共聚物（丙烯酸-2-乙基己酯：丙烯酸乙酯： 丙烯酸-2-羥基乙酯=70重量份：30重量份：5重量份）100重 量份、異氰酸酯系交聯劑（Coronate L，曰本聚胺酯（股）製 造）3重量份溶解於甲苯中，以乾燥後之厚度成為1〇 μΐη2 方式塗佈於厚度1 〇〇 μιη之聚酯膜上而進行製作，除此以外 162235.doc -28- 201241132 以與實施例1同樣之方法製作封裝體。 比較例2 將丙烯酸硬脂基酯100重量份、2,2-二曱氧基_1，2_二苯基 乙烷-1-酮0.3重量份投入至四口燒瓶中，於氮氣環境下曝 露於紫外線中而使其部分地光聚合，藉此獲得部分聚合物 (單體糖漿）。於該部分聚合物40重量份中，添加丙烯酸異 辛酯54份、丙烯酸6重量份、及作為交聯劑的己二醇二丙 烯酸酯0· 1重量份之後，將該等混合均勻而製備光聚合性 組合物。於厚度1 〇 〇 μη!之聚對苯二甲酸乙二自旨膜上，以厚 度達到100 μηι之方式塗佈上述光聚合性組合物，進而於其 上被覆厚度3 8 μπι的單面經剝離處理之聚對苯二甲酸乙二 醋膜’形成塗佈層。對該片材使用黑光燈（丨5 w/cm2)照射 光照度5 mW/cm2(利用波峰感度最大波長35〇 nm之 TOPCON UVR-T1測定）之紫外線1〇0〇 mJ/cm2，獲得含側鏈 可結晶聚合物之暫時固定片材。於該含側鏈可結晶聚合物 之暫時固定片材的基材表面’與實施例1同樣地進行熱膨 脹性黏著層塗佈等’以與實施例1同樣之方法製作封裝 體。 <評價> 對於以如上方式製作之耐熱性熱剝離型黏著片材及封裝 體，評價於175°C下對矽晶片之剪切接著力、自封裝體實 際剝離耐熱性熱剝離型黏著帶時的9〇。剝離黏著力、儲存 彈性模數G’、晶片自初期位置之偏移距離之值、使用顯微 鏡目視觀察的耐熱性熱剝離型黏著片材剝離後糊劑殘餘之 162235.doc -29- 201241132 有無、以及晶片自密封面露出之程度（離板間隙量）。結果 示於表1。 <於175它下對矽晶片之剪切接著> 將實施例及比較例中製作之片材切斷成2〇 mm見方，於 樹脂層（熱膨脹性黏著層之相反側）上放置1〇 mm見方之矽 曰曰片後，设置於附有1751之平台之剪切接著力試驗機中 放置3分鐘，之後如圖4所示般，測定以〇5 mm/sec之速度 沿水平方向推擠矽晶片時之荷重。 <175°C加熱後自封裝體之9〇。剝離黏著力> 經過175 C x2 min之密封步驟後，冷卻至常溫，測定以 剝離速度300 mm/min、牽拉角度90。剝離帶時之荷重。 <储存彈性模數G'之測定方法> 儲存彈性模數（G，）係利用「ARES」（TA Instruments(股） 製造）進行測定《再者’測定係於_60°c〜200〇c之溫度區域 内，於升溫速度5。(：/min、頻率1 Hz之條件下進行。 [表1] 單位 實施例1 實施例2 實施例3 比較例1 比較例2 ^夕晶片之剪切接著 g/10mm2 220 350 130 55 300 對封裝體之剝離力 N/20 mm 0.12 0.30 0.10 0.60 0.25 儲存彈性模數 Pa 4.3χ105 2.5x10s 5.0χ105 l.lxlO5 1.3xl04 ____晶片偏移距離 mm 0.02 0.02 0.03 】.50 0.05 糊劑殘餘 - 無 無 無 有 無 離板間隙 μπι 5 6 5 6 12 於實施例1〜3中，藉由具有充分之封膠時之黏著力，可 抑制晶片偏移，且由於冷卻後對密封樹脂之黏著力較小之 ^2235^00 -30- 201241132 特性，可獲得封裝體輕剝離且剝離後無糊劑殘餘之良好封 裝體，又，離板間隙亦為較小值。 相對於此，於比較例1中，由於樹脂層不含胺基曱酸酯 聚合物成分，因此無法抑制封膠時之晶片偏移，又，於比 較例2中，由於不含乙烯系聚合物，因此丨75它下之彈性模 數較低’ &而⑦晶片埋人至樹脂層中，離板間隙成為較大 值。 根據以上結果，可提供一種於樹脂密封步驟中可保持晶 片’其後藉由冷卻至特定溫度，可無糊劑殘餘地將帶剝 離，並且可達成較小之離板間隙的無基板半導體封裝體製 造時之晶片暫時固定用耐熱性熱剝離型黏著帶。 【圖式簡單說明】 圊1⑷-⑴係無基材封裝體製造方法之示意圖。 圖2係於剝離半導體裝置製造用耐熱性黏著帶時產生帶 電及糊劑殘餘之圖。 圖3係本發明之半導體裝置製造用耐熱性黏著帶之剖面 圖。 圖4係利用剪切接著力試驗機進行試驗之圖。 【主要元件符號說明】 1 晶片 2 半導體裝置製造用耐熱性黏著帶 3 基板 4 密封樹脂 5 電極 162235.doc 201241132 6 切晶刀片 7 切晶環 8 切晶帶 9 糊劑殘餘 10 平滑之剝離片 11 樹脂層 12 橡膠狀有機彈性層 13 熱膨脹性黏著劑層 162235.doc -32-Strip 2 strips, then only half 162235. Doc 201241132 The heat-resistant adhesive tape 2 for conductor device manufacturing is peeled off. The electrode 5 is formed at a desired position on the surface of the wafer, on the side of the heat-resistant adhesive tape 2 for mounting the semiconductor device, which is sealed by the sealing resin 4, on the side where the surface of the wafer is exposed. (d) The structure shown. For this structure, it is necessary to further remove the dicing tape 8 in which the dicing ring 7 is placed on the side of the enamel sealing resin, and to seal the plurality of wafers sealed by the sealing resin 4! Fixed to perform the dicing step. As shown in (e), the dicing blade 6 performs dicing, and finally, as shown in (f), a plurality of substrateless packages in which a plurality of wafers are sealed by a resin are obtained. In the step of sealing with a resin, the heat-resistant adhesive tape 2 for manufacturing a semiconductor device must have a high adhesion at the temperature at which the resin is sealed so that the position of the wafer 1 on the tape is not sealed by the resin. Move with pressure. On the other hand, in the step of peeling off the heat-resistant adhesive tape 2 for producing a semiconductor device from the wafer after the resin sealing and the resin curing, it is necessary to be lightly peeled off, so that it is a general pressure-sensitive adhesive having high adhesiveness at a high temperature. In the case where peeling is impossible, peeling may not be performed, and peeling may become difficult, or a residue of the paste as shown in FIG. 2 may occur, or peeling electrification may occur. Further, if the peeling becomes difficult, a correspondingly long time is required, so that the productivity is lowered. If the paste residue 9 is generated, the subsequent steps of electrode formation and the like cannot be performed, and if peeling electrification occurs, dust is present. The case where the attachment causes a failure in the subsequent steps. Means for Solving the Problems In order to solve the above problems, the present invention employs a semiconductor device 162235 which is as follows. Doc 201241132 A method for manufacturing a substrate-free semiconductor wafer without using a metal lead frame, which is characterized in that it is used for resin-sealing a substrate-free semiconductor wafer when manufacturing a heat-resistant adhesive tape An adhesive tape for temporarily fixing a wafer to be used for adhesion, which has a heat-expandable adhesive layer containing heat-expandable microspheres on one surface of a resin layer containing a urethane polymer component and a vinyl polymer. Advantageous Effects of the Invention The present invention relates to a Ba sheet temporary fixing adhesive tape used in a method for producing a substrateless semiconductor package (for example, a method for manufacturing a WLP) which does not use a metal lead frame, and which has the following effects. Provided is a heat-resistant adhesive tape for manufacturing a semiconductor device in which a wafer is not displaced from a predetermined position by a pressure at the time of resin sealing, and can be lightly peeled off without leaving a paste of a sealing resin at a temperature lower than a specific temperature after sealing. . [Embodiment] The present inventors have made intensive studies on the materials and structures of the heat-resistant adhesive tape for semiconductor device manufacturing in order to solve the above problems. As a result, it has been found that the above problem can be solved by using a heat-resistant adhesive tape for manufacturing a semiconductor device which is characterized in that it contains an amino phthalate polymer component and ethylene. One side of the resin layer of the polymer has a heat-expandable adhesive layer containing heat-expandable microspheres. Hereinafter, the heat-resistant adhesive tape for manufacturing a semiconductor device of the present invention will be described. Fig. 3 illustrates a heat-resistant adhesive tape 2 for manufacturing a semiconductor device used in the present invention. !62235^〇ς 201241132 is a heat-expandable adhesive layer from the flat/month to the release sheet '1! is a resin layer, and i 2 is a rubber-like organic elastic layer'. Here, the resin layer and the rubbery organic elastic layer may each contain a plurality of layers. (Resin layer) The tree layer 11 includes a layer containing a urethane polymer component and a resin of a vinyl polymer. (Amino phthalate polymer) The U-based citric acid-dyeing polymer used in the resin layer is obtained by reacting a polyA alcohol with a diisocyanate. In the reaction of the hydroxyl group of the polyol with the isocyanate, for example, dibutyltin dilaurate, tin octylate, i,4-diazabicyclo(2'2'2) citric acid I citrate may also be used in the reaction. It is often used as a catalyst. Examples of the polyhydric alcohol include a polyether polyol obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or the like, or a dimer acid, adipic acid, sebacic acid, sebacic acid or the like. A polyester polyol of a polycondensate of a monobasic acid, or an acrylic polyol, a carbonate polyol, an epoxy polyol, a caprolactone polyol, or the like. In these, for example, polyoxybutylene glycol (for example, polyoxybutylene glycol) can be preferably used. PTMG), polyether polyols such as polyoxypropylene glycol (PPG), amorphous polyphenols, amorphous polycarbonate polyols, and the like. These polyols can be used singly or in combination. Examples of the diisocyanate include aromatic, aliphatic, and alicyclic diisocyanates. Examples of the aromatic, aliphatic or alicyclic diisocyanate include: stilbene diisocyanate, diphenyl decane diisocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, and hydrogenated benzene 162235. Doc 201241132 Methylene monoisocyanate, isophorone diisocyanate, hydrogenated diphenyl decane monoisocyanate ' 1,5-naphthalene diisocyanate, hydrazine, 3-phenyl diisocyanate, M · stupid acid Vinegar, butane], 4· diisocyanate, 2,2,4-tridecylhexamethylene monoisocyanate, 2,4,4•trimethylhexamethylene diisocyanate, cyclohexane-1,4 Diisocyanate, dicyclohexylmethane-4,4·diisocyanate, I3 bis(isoacetophenoxy)cyclohexane, methylcyclohexane diisocyanate: diammonium tetramethylbenzodiazepine Diisocyanate and the like. These diisocyanates may be used singly or in combination. The type, combination, and the like of the polyisocyanate can be appropriately selected in view of the reactivity of the urethane carboxylic acid, the compatibility with the acrylonitrile, and the like. The amount of the polyol component used to form the urethane polymer and the above-mentioned diisocyanate component is not particularly limited. For example, the amount of the polyol component used is preferably relative to the diisocyanate component nc〇/ 〇h (equivalent ratio) is L〇 or more, and more preferably 2·0 or less. If NCO/OH is 1. When it is 0 or more, the terminal functional group of the amino acid-branched molecular bond is a warp group, and the strength of the temporary fixing layer can be prevented from being lowered. Further, if NC〇/〇H is 2〇 or less, moderate elongation and strength can be ensured. Further, it is preferable that at least a part of the amine oxime vinegar polymer is an acrylonitrile-terminated urethane polymer, and by having such an acrylonitrile group, the ethylene-based polymer can be crosslinked to adjust the cohesive force. The molecular weight of the urethane polymer component of the present invention can be appropriately determined depending on the type of the polyol or monoisocyanate to be used and the NCO/OH ratio. The molecular weight is not particularly limited. The number average molecular weight (Mw) is preferably 5,000 or more, and more preferably 10,000 or more. I62235. Doc • 10 to 201241132 It is preferred to add a hydroxyl group-containing acrylic monomer different from the ethylene polymer of the present invention to the above amino phthalate polymer. By adding a hydroxyl group-containing acrylic monomer, a propylene styrene can be introduced into the molecule of the amino phthalate polymer, and the copolymerizable property with the acrylic monomer can be obtained. As the hydroxyl group-containing acrylic monomer, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, (mercapto)acrylic acid hydroxyhexyl ester or the like can be used. The amount of the hydroxyl group-containing acrylic monomer is preferably from 0 parts by weight relative to 100 parts by weight of the amine phthalate polymer. HiO parts by weight, more preferably 〇5 parts by weight 0 (Ethylene-based polymer) The vinyl-based polymer used in the resin layer of the present invention may be polymerized by merely polymerizing a vinyl compound constituting the ethylene monomer. In this case, it can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can be carried out by any one of solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like. The adhesive layer is preferably a small amount of a low molecular weight substance from the viewpoint of preventing contamination of a semiconductor wafer or the like. In this regard, the weight average molecular weight of the acrylic polymer is preferably 10,000 or more, and more preferably 400,000 to 30,000. The resin layer can be obtained by blending the above-mentioned amino-based acid ester polymer with the following oxime compound, and X can also be prepared by preparing a mixture of an amine-based compound and an ethylene-based monomer. Obtained by polymerization of a rare polymer. Among them, in terms of the type or sheet of the monomer which can be used, it is preferably formed in the following manner: in a mixture of two or more kinds, a multi-component cyanogen, K-70 alcohol and Isocyanate & should form 162235. Doc -11 _ 201241132 A urethane polymer, which is obtained by applying a mixture of the obtained amino phthalate polymer and a vinyl monomer to a substrate, and irradiating the radiation to harden it. Further, as the ethylenic monomer, a (fluorenyl) acrylic monomer is preferred. Further, as described above, by introducing an acrylonitrile group into the amino phthalate polymer by using a hydroxyl group-containing acrylic monomer, the vinyl monomer may be polymerized, whereby the propylene group and the vinyl group may be polymerized. Polymerization is carried out to prepare a resin obtained by combining the urethane polymer with the acetonitrile polymer. The vinyl polymer in the present invention is a polymer obtained by polymerizing a vinyl monomer, and as the vinyl monomer, a (meth)acrylic acid monomer as described above can be preferably used. Examples of the acrylic monomer include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (methyl) Dibutyl acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) isodecyl propionate, dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, a carboxyl group-containing monomer such as itaconic acid, maleic acid or crotonic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid- 4-hydroxybutyl ester, (6) hydroxyhexyl (meth) acrylate, -8-hydroxyoctyl (meth) acrylate (f-) a hydroxyl group-containing monomer such as acid 〇 癸 hydroxy hydroxy ester, (meth) acrylate 12-hydroxylauryl ester, (4-hydroxylcyclohexyl) methyl acrylate; (cyclohexyl) acrylate cyclohexyl ester, a monomer having an alicyclic structure such as isodecyl acrylate; an acid anhydride monomer such as maleic anhydride or itaconic anhydride; 2-sulfonamide-2-methylpropanesulfonic acid, sulfopropyl acrylate or the like containing sulfone 16223S . Doc 201241132 Acid-based monomer; phosphoric acid-containing monomer such as 2-hydroxyethyl propylene phthalate. Further, one or two or more of the following may be used: a guanamine-based monomer such as N-substituted (fluorenyl) acrylamide such as (meth)acrylamide or N-hydroxydecyl acrylamide; N-(indenyl) propylene fluorenyl sulfenyl succinimide, N_(fluorenyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N_(methyl) propylene hydrazine _8 • oxygen Amber quinone imine monomer such as octamethyl succinimide; vinyl acetate, N-vinyl pyrrolidone, N-vinyl carbamide, N-vinyl caprolactam, etc. Vinyl monomer; cyanoacrylate monomer such as acrylonitrile or mercapto acrylonitrile; glycidyl (mercapto) acrylate, tetrahydroanthracene (S), polyethylene glycol (meth) acrylate , acrylate monomer such as polypropylene glycol (meth) acrylate, fluorine (meth) acrylate, poly fluorenyl (meth) acrylate, acrylonitrile 2-methoxyethyl ester; bismuth (meth) acrylate Monomer such as ester or octadecyl (decyl) acrylate. The (meth)acrylic monomer can be appropriately determined in type, combination, and use in consideration of the compatibility with the amino group f-ester, the polymerizability when photocuring by radiation or the like, or the properties of the obtained high molecular weight body. Quantity and so on. In particular, in consideration of the adhesion at the time of heating and peeling, it is preferred to use a monomer having a carboxyl group so that the vinyl polymer may have a carboxyl group, and further, a monomer having a polar group such as (fluorenyl)acrylic acid may be used. , the balance of adhesion between the heating and the cooling and peeling is better. The amount of (meth)acrylic acid added is preferably 5 parts by weight or more and less than 80 parts by weight, based on the total amount of the urethane carboxylic acid polymer and the ethylene-based polymer being 1 part by weight. Further, it is preferably 1 part by weight or more and less than 7 parts by weight. By setting it to 5 parts by weight or more, it is easy to obtain spot cold when heating. I62235. Doc 201241132 The balance of adhesion at the time of peeling, χ, if it is less than 8 parts by weight, it is soft and the adhesion is improved when heating. In the present invention, other polyfunctional monomers may be added within a range not impairing the properties. Examples of the polyfunctional monomer include hexanediol diacrylic acid vinegar, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate. (Content ratio of urethane polymer to vinyl polymer) The resin layer in the present invention contains a urethane polymer and an ethylene polymer as an active ingredient. The ratio of the urethane polymer to the vinyl polymer is not particularly limited, and the weight of the amine phthalate polymer is preferably based on the total amount of the amino phthalate polymer and the ethylene polymer. It is 1%% or more and 90% or less, and more preferably 2%% or more and less than 8〇%. When the ratio of the urethane polymer is 10% or more, the modulus of elasticity at a high temperature does not become low, and sufficient processing precision can be obtained. In addition, when it is 9 % by weight or less, workability and productivity in producing a sheet are good. (Resin Layer Forming Method) The resin layer of the present invention can be obtained by a method in which a vinyl monomer of a vinyl polymer is polymerized by polymerization or a mixture of two or more kinds thereof. The alcohol reacts with the isocyanate to form a urethane polymer. The mixture containing the urethane polymer and the vinyl monomer is coated on a support substrate, and is irradiated according to the type of the photopolymerization initiator. Radiation, visible light, or the like, such as radiation, β-rays, γ-rays, neutron rays, and electron beams, or the like, such as radiation or visible light, is hardened. Further, it may be applied by coating an amine phthalate polymer with a vinyl polymer and applying it to a support substrate to dry it to form a resin layer. 162235. Doc 201241132 Further, when the above-mentioned hydroxyl group-containing acrylic monomer is used, a resin layer can be obtained by the following method: a single type or a 2 type of a vinyl monomer which constitutes a vinyl polymer by polymerization. In the above mixture, after reacting the polyol with the isocyanate to form a urethane polymer, the acrylic monomer containing the radical is added to react with the urethane polymer, and the obtained mixture is obtained. It is applied to a support substrate, and is irradiated with radiation such as ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron beams, or ultraviolet rays, visible light, or the like, depending on the type of the photopolymerization initiator. Specifically, S may be obtained by dissolving a polyhydric alcohol in a vinyl monomer, and then adding a diisocyanate or the like to react with a polyhydric alcohol to adjust the viscosity, and applying the resultant to a support substrate or the like, followed by using a low-pressure mercury lamp or the like. Hardening' to obtain a temporary fixing sheet. In this method, the vinyl monomer may be added in the course of synthesizing the amino carboxylic acid vinegar, or may be added in several portions. Further, the polyol may be reacted after dissolving the diisocyanate in the ethylidene monomer. According to this method, the molecular weight is not limited, and a high molecular weight polyurethane can be produced. Therefore, the molecular weight of the finally obtained amino phthalate can be designed to an arbitrary size. 'On the mixture coated on the support substrate, and then placed on the release liner to the amine phthalate polymer and the ethylene system at this time to avoid the inhibition of polymerization by oxygen The substrate is peeled off and the oxygen is blocked, and the oxygen is also reduced in the container of the inert gas. To adjust the viscosity of (4), it is also possible to add a force agent, which can be appropriately selected from the commonly used solvents, for example, Can be cited ethyl acetate I62235. Doc •15· 201241132 β, such as ester, toluene, gas, and dimercaptocaramine. In the present invention, the type of the radiation material or the type of the lamp used for the irradiation may be appropriately selected, and (4) a photochemical lamp may be used. Low-voltage lamps such as black light lamps and ^ lamps, or high-voltage lamps such as metal element lamps and high-pressure mercury lamps. The amount of irradiation of the beam outer line or the like can be arbitrarily set according to the characteristics of the required temporary fixing layer. In general, the irradiation amount of ultraviolet rays is 5 〇 〇 ’ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 When the irradiation amount of the ultraviolet rays is in the range of 5 Torr to 5 - (10) / (10) 2, the polymerization rate is not deteriorated and a sufficient polymerization ratio can be obtained. A mixture of a carboxylic acid S-based polymer and a vinyl monomer as a main component contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin ether such as benzoin benzoate, 2,2-dimethoxy], 2-diphenylethane, and benzoin ether. Benzoin ether; 2,2-diethoxybenthanone, 2,2-dimethoxy-2-phenylacetophenone, hydroxy-cyclohexyl phenyl ketone, etc. substituted acetophenone; 2-methyl _2_Substituting a ketone alcohol with a phenyl ketone or the like; an aromatic sulfonium gas such as 2-naphthalene sulfonium gas; 丨-phenyl-fluorene-propanedione-2_(〇-ethoxycarbonyl)-fluorene Active hydrazine; (2,4,6-trimethylbenzyl ketone) diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl aryl) phenyl oxidized lining, etc. . The thickness of the resin layer in the present invention is appropriately selected depending on the purpose and the like, and is generally 5 to 500 μηι, preferably 10 to 100 μηΐ2. The resin layer of the present invention has a shearing force on the tantalum wafer at 175t of ι〇〇g/H) "above, preferably 15〇g/1〇_2 or more, and more preferably g/10 mm2 or more. , and more preferably 3〇〇g/1〇mm2 or more, and it is I62235. Doc -16- 201241132 9 密封 for sealing resin after heating. The peel adhesion is 0 50 n/20 mm or less, preferably 0. 40 N/20 mm or less, and further preferably 0. 30 N/20 mm or less' and further preferably 0. 20 N/20 mm or less. Generally, the sealing and hardening steps of the resin are more than about 175 ° C. Under the above, the shearing force is as above 1 〇〇 g / 1 〇 mm 2 and the peeling adhesion is 0. In the case of 50 n/20 mm or less, the semiconductor wafer can be loaded and fixed so that the semiconductor wafer does not shift when the resin is sealed and hardened. Further, after cooling to a specific temperature and peeling off the resin layer from the separated package, the sealing resin was 9 Å. The smaller the film peeling adhesion, the smaller the force required for peeling, and thus the damage to the package or the like is not caused. In the present invention, the resin layer of the succeeding sheet for semiconductor device manufacturing preferably has an adhesive property at a specific temperature of 40 C or more and a property of losing adhesive force below the specific temperature. Further preferably, it has an adhesive force at a specific temperature of 7 or more, and particularly preferably has an adhesive force at a specific temperature of 1 〇〇〇c or more. The so-called adhesive force at a specific temperature of 40 ° C or higher is used. Refers to 4〇. The first time the adhesion is expressed at a temperature above one, if it does not reach the temperature, it will not show the adhesion. The result means that it does not show stickiness at a temperature of at least 4〇t. When the adhesive force changes depending on the temperature, when the heat-expandable pressure-sensitive adhesive layer containing the heat-expandable microspheres is foamed, the semiconductor wafer can be reliably fixed to the substrate-free heat-resistant adhesive tape for manufacturing a semi-fin device, and It can be easily taken out from the resin layer at a time other than when the article is heated. 162235. Doc -17· 201241132 The storage elastic modulus G of the resin layer in the present invention at 175t is 1. 0X105 Pa or more, preferably 2. 〇xl 〇 5 Pa or more, and further preferably 3. 〇xl05 Pa or more, and more preferably 4. 〇xl〇5 pa or more. If the elastic modulus GH is stored. When 0x1 〇 5 Pa or more, the wafer gap (stand_〇ff) in which the wafer is buried in the resin layer is small, and the yield reduction is not caused in the subsequent steps. (Rubber-like organic elastic layer) The rubber-like organic elastic layer 12 also has a function of following the surface shape of the adherend when the heat-resistant adhesive tape for manufacturing a semiconductor device is attached to the adherend. Therefore, it is possible to reduce the heat resistance of the semiconductor device when the heat-expandable pressure-sensitive adhesive layer 13 is heated and foamed and/or expanded by peeling off the adherend from the heat-resistant adhesive tape for manufacturing a semiconductor device. The foaming and/or expansion constraint in the direction of the adhesive tape promotes the formation of the undulating structure by the three-dimensional structural change of the heat-expandable adhesive layer 13. The rubber-like organic elastic layer 12 may be provided as needed. When the rubber-like organic elastic layer 12 is provided, the thickness is preferably 5 to 50 μm. The rubber-like organic elastic layer 12 can be formed using a natural rubber or synthetic rubber having a D-type D-type hardness of 50 or less, preferably 40 or less, or a synthetic resin having rubber elasticity, based on ASTM D-2240. Examples of the synthetic rubber or the synthetic resin include a synthetic rubber such as a nitrile-based, a secondary-based or an acrylic-based resin; a thermoplastic elastomer such as a polyolefin-based or polyester-based thermoplastic copolymer, and an ethylene-vinyl acetate copolymer; Polyamino phthalate '162235. Doc -18 - 201241132 A rubber-elastic synthetic resin such as polybutylene-based soft gas-polymerized ethylene. Further, a polymer which is hard-like in nature like polyethylene gas, but which has rubber elasticity by being combined with a plasticizer or a softener compounding agent can also be used in the present invention. Further, the rubbery organic elastic layer 12 may be formed by a pressure-sensitive adhesive which is generally known as a rubber or a resin. As the pressure-sensitive adhesive, a rubber-based adhesive, an acrylic-based pressure-sensitive adhesive, a styrene-conjugated diene block copolymer-based pressure-sensitive adhesive, or the like can be used. Also, a melting point of about 200 may be used. (: The following is a heat-melting resin to improve the latent denaturation, etc. Further, the pressure-sensitive adhesive may be formulated with an antistatic agent, a crosslinking agent, an adhesion-imparting agent, a plasticizer, a filler, and an anti-static agent. More specifically, the rubber-based pressure-sensitive adhesive having a natural rubber or a synthetic rubber as a base polymer and an acrylic polymer having a main component as a base polymer are exemplified. Acrylic pressure-sensitive adhesive or the like: having, for example, methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isodecyl, isodecyl, dodecyl, lauryl, ten Acrylic acid or mercaptoacrylic acid having a basic alkyl group having a carbon number of 20 or less, such as a trialkyl group, a fifteen alkyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a decyl group or an eicosyl group. Acrylic alkyl ester, acrylic acid, mercaptoacrylic acid, itaconic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-hydroxydecyl acrylamide, Acrylonitrile, mercapto acrylonitrile, acrylic acid shrinkage Ester, glycidyl methacrylate, vinyl acetate, styrene, isoprene, butadiene, isobutylene, vinyl ethers 162,235. Doc -19- 201241132 and so on. (The heat-expandable pressure-sensitive adhesive layer) The pressure-sensitive adhesive forming the heat-expandable pressure-sensitive adhesive layer 13 is required to allow foaming and/or expansion of the heat-expandable microspheres during heating, and rubber which can be used in the above-mentioned rubber-like organic elastic layer can be used. A known pressure-sensitive adhesive which is a base material or a (meth)acrylic resin or the like as a base preferably has an elasticity which does not restrict the degree of foaming and/or expansion of the heat-expandable microspheres as much as possible. The heat-expandable adhesive is one in which the heat-expandable fine particles are blended in the above-mentioned usual pressure-sensitive adhesive. By the foaming of the heat-expandable fine particles due to heat, the area of the heat-expandable pressure-sensitive adhesive is reduced to be easily peeled off, and the average particle diameter of the heat-expandable fine particles is preferably 丨μηη to 25. More preferably, it is 5 μηι to 15 μηι, and particularly preferably about 10 μηι. Further, an adhesive agent, a plasticizer, a pigment, a filler, a conductive agent, an antistatic agent, and the like of a known resin or the like are appropriately blended in the above-mentioned heat-expandable pressure-sensitive adhesive layer, and a polyfunctional epoxy compound or an isocyanate is used. A crosslinking agent such as a compound, an aziridine compound, a melamine resin, a urea resin, an anhydrous compound, a polyamine, or a carboxyl group-containing polymer is crosslinked. Slightly taking the adhesive layer i 3 can be formed by blending the heat-expandable microspheres in the adhesive. As the heat-expandable microspheres, for example, an appropriate substance which can be easily vaporized and the like, and which exhibits thermal expansion, such as isobutylene, can be used, and is encapsulated in a shell by an agglutination method or an interfacial polymerization method. The heat-expandable microspheres obtained in the substance are formed. The heat-expandable microspheres to be used preferably have a volume expansion ratio of the heat-expandable microspheres of 5 times or more, preferably (7) times or more. 162235. Doc •20- 201241132 Further, as a shell-forming substance for forming heat-expandable microspheres, for example, a vinylidene chloride-acrylonitrile copolymer, a polyvinyl alcohol, a polyvinyl butyric acid, a polyacrylonitrile butyric acid, In the present invention, the polyacrylonitrile, the polyvinylidene oxide, the condensate, and the like may be contained as long as it contains a hot meltable substance or a substance f which can be destroyed by thermal expansion. #Expansibility micro! The body also has an advantage of excellent dispersion and mixing property with the above-mentioned adhesive. As a commercial item of the heat-expandable microspheres, for example, MICROSPHERE (trade name; Matsumoto Oil & Fat Pharmaceutical Co., Ltd.) can be cited. The blending amount of the heat-expandable microspheres can be appropriately determined depending on the degree to which the heat-expandable pressure-sensitive adhesive layer η is expanded (foamed) or the extent to which the adhesive force is lowered. In general, it is preferably 1 to 150 parts by weight per 100 parts by weight of the base polymer, preferably 25 to 00 parts by weight. The thickness of the heat-expandable adhesive layer is 5 to 1 〇〇 μπι, preferably 1 5 to 50 μm. The heat treatment conditions for allowing the heat-resistant pressure-sensitive adhesive tape 2 for producing a semiconductor device of the present invention to be easily peeled off from the adherend are based on the surface state of the adherend or the type of the heat-expandable microspheres. It is determined by the reduction, the heat resistance of the substrate or the adherend, or the heating method. The usual conditions are 100 to 25 (TC, i to 90 seconds (heating plate, etc.) or 5 to 15 knives (hot air drying). For this application, since the resin sealing temperature is about 175 degrees, it is preferably 2 〇〇 25 〇 〇, 1 to 9 〇 seconds (heating plate, etc.) or 1 to 15 minutes (hot air drying) Or a smooth release sheet 10 is a sheet obtained by forming a release agent layer on one surface of a base film, and is a heat-resistant adhesive tape 162235 for manufacturing a semiconductor device of the present invention. Doc -21- 201241132 2 Stripped before the adhesive layer of each side is exposed. The release agent layer can be suitably selected from known release agent layers such as a long-chain alkyl type, a fluororesin type, and a polyoxymethylene resin type depending on the adhesive to be contacted. The release sheet can be used as a base layer when forming a resin layer or a heat-expandable pressure-sensitive adhesive layer, or it can be used by laminating it on the surface of the formed resin layer or the heat-expandable pressure-sensitive adhesive layer. As the substrate film, a known one can be used, and for example, it can be selected from the group consisting of polyetheretherketone, polyetherimide, polyarylate, polyethylene naphthalate, polyethylene film, polypropylene film. , polybutene film, polybutadiene film, polymethyl pentylene film, polyethylene film, gas ethylene copolymer film, polyethylene terephthalate film, polybutylene terephthalate film , polyamino phthalate film, ethylene vinyl acetate copolymer film, ionic polymer resin film, vinyl methyl acrylate copolymer film 'ethylene-(meth) acrylate copolymer film, poly benzene Plastic film such as vinyl film and polycarbonate film. The release agent layer which can be used is a layer obtained by selecting a known release agent according to the resin of the adhesive layer: a fluorinated polyoxymethylene resin release agent, a fluororesin release agent, and a polyoxyxene resin system. A release agent, a polyvinyl alcohol resin, a polypropylene resin, a long-chain alkyl compound, or the like. (Manufacturing Method of Heat-Sensitive Adhesive Tape for Semiconductor Device Manufacturing) The heat-resistant adhesive tape 2 for producing a semiconductor device of the present invention can be produced by a usual production method. For example, a coating liquid is prepared by dissolving a composition of each of the resin layer, the rubber-like organic elastic layer 12, and the heat-expandable pressure-sensitive adhesive layer 13 in a solvent, and the coating liquid is prepared by 162235 which is composed of a layer of a heat-resistant adhesive tape 2 for manufacturing a target semiconductor device. Doc -22·201241132 The rubber is then coated on a resin layer such as a release film having a releasability by using mercaptoethyl j, and then the coating layer is heated and dried under the conditions of ruthenium. The resin layer can also be produced by casting on a release film or the like. The organic film layer 12 and the film of the heat-expandable dot-grain layer 13 alone are laminated in this order. Here, the solvent is not particularly limited to a solvent having a good solubility in a constituent material, such as a ketone or the like. (Method of Using Heat-Resistant Adhesive Tape for Semiconductor Device Manufacturing) The heat-resistant adhesive tape 2 for semiconductor device manufacturing is used in the above-described steps described with reference to FIG. The heat-resistant adhesive tape 2 for manufacturing an I7 semiconductor device is used in the following steps of the semiconductor 4 shown below, a sealing step, and a step-by-step process as a mechanism for fixing the day sheet. (Subsequent Step of Semiconductor Wafer) A semiconductor device comprising a grease layer and a heat-expandable adhesive layer is formed on the heat-expandable adhesive layer of the heat-expandable adhesive layer by using a '2' The U-side of the heat-expandable dot-donor layer after the film is placed on the substrate such that the opposite resin layer side is exposed as the upper surface. The semiconductor wafer 1 to be sealed by the resin is placed on the resin layer of the heat-resistant adhesive tape 2 for semiconductor device manufacturing. The structure, shape, size, and the like of the semiconductor wafer! at this time are not particularly limited. (Sealing step) The sealing of the heat-resistant adhesive tape 2 for manufacturing the semiconductor device of the present invention is used 162235. Doc -23·201241132 The resin used in the step may be arbitrarily changed depending on the application, and may be a known sealing resin such as an epoxy resin. The melting temperature or the curing temperature of the powdery resin and the curing temperature of the liquid resin are selected in consideration of the heat resistance of the heat-resistant adhesive tape 2 for semiconductor device manufacturing. However, the heat-resistant adhesive tape 2 for manufacturing a semiconductor device of the present invention is normally sealed. Both the melting temperature and the hardening temperature of the resin have thermal properties. The sealing step is performed by protecting the wafer by the above resin in a mold, for example, at 170 to 180 °C. Thereafter, the heat-resistant adhesive tape 2 for semiconductor device manufacturing is peeled off, and then post-make curing is performed. (Peeling step) The wafer on the heat-resistant adhesive tape 2 for semiconductor device manufacturing fixed on the substrate is sealed with a resin at 200 to 250. (:, 1 to 90 seconds (heating plate, etc.) or 1 to 15 minutes (hot air dryer, etc.) is heated to expand the heat-expandable pressure-sensitive adhesive layer 13 of the heat-resistant adhesive tape 2 for semiconductor device manufacturing. Thereby, the adhesion between the heat-expandable pressure-sensitive adhesive layer 13 of the heat-resistant adhesive tape 2 for semiconductor device manufacturing and the substrate 3 is lowered, and the heat-resistant adhesive tape 2 for semiconductor device manufacturing is peeled off from the substrate 3. Then, after cooling to a specific temperature or lower The heat-resistant adhesive tape 2 for manufacturing a semiconductor device is manufactured by a resin-sealed wafer. The method may be such that the heat-resistant adhesive tape 2 for manufacturing a semiconductor device is not separated from the substrate 3, and the like. As a whole, a plurality of wafers 1 sealed by the sealing resin 4 are separated from the resin layer of the heat-resistant adhesive tape 2 for semiconductor device manufacturing. Doc • 24· 201241132 (electrode forming step) Next, the wafer 1 is sealed by the sealing resin 4 to be exposed on the side of the surface, that is, on the side of one side 2 of the wafer 1 of the laminated half, by screen printing or the like: 1 Sexual adhesion with a pole 5. As the electrode material, two ==^^ (cutting step), the layer formed by sealing the wafer 1 in the sealing tree, preferably in the middle of fixing: the dicing tape 8 of Γ 7, using the usual dicing step The dicing blade 6 used is separated into individual packages. At this time, if each wafer 1 is not present in the inaccuracy, and each package is placed in two, the position of the electrode 1 on which the T-body is formed is inaccurate, or when the wafer is heavy, there is a dicing time. The possibility of the dicing blade 6 contacting the wafer i. When the heat-resistant adhesive tape 2 for semiconductor device manufacturing of the present invention is used, the position of the wafer 1 can be prevented from shifting during the sealing step by the sealing resin 4, so that such a failure does not occur and can be smoothly performed. The dicing step results in a package in which the wafer 1 is accurately positioned in the sealing resin. Further, since the heat-resistant adhesive tape 2 for semiconductor device manufacturing can be peeled off by the resin which is freely sealed by the light-sealing resin, and the paste residue does not occur, it can be manufactured while maintaining a high yield. The present invention will be described in more detail below based on the examples, but the invention is not limited to the examples. EXAMPLES Example 1 In a reaction vessel containing a cooling tube, a thermometer and a stirring device, 162235 was placed. Doc • 25· 201241132 50 parts by weight of acrylic acid isomeric ester (IBxa) as a (fluorenyl) acrylic monomer'. Polytetramethylene glycol (PTMG, manufactured by Mitsubishi Chemical Corporation) 72 as a number average molecular weight of polyol of 650 . 8 parts by weight, while stirring, one side of hydrogenated benzene dimethylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.). 2 parts by weight of the reaction was carried out at 65 ° C for 10 hours to obtain an amino phthalic acid acrylate polymer-acrylic monomer mixture. Thereafter, 0.02 _ ethyl ethyl amide (HEA) was added dropwise. After 5 parts by weight and further reacted for 3 hours, 50 parts by weight of acrylic acid (AA) and 2,2·dimethoxy-1,2·diphenylethane-1-one as a photopolymerization initiator (IRGACURE) were added. 651, manufactured by Ciba Japan Co., Ltd.) 3 parts by weight. Further, the amount of the polyisocyanate component and the polyol component used is ^(:0/011 (equivalent ratio) = 1. 25. The amino phthalate polymer and the acrylic monomer mixture are applied to a thickness of 38 μm by a thickness of 10 0 μm after hardening. Peeled PET (polyethylene terephthalate, polyethylene terephthalate). After coating the peeled PET film thereon, the surface of the coated PET film was cured by ultraviolet light (illuminance 5 mW/cm 2 , light quantity: 1000 mJ/cm 2 ) using a black light lamp to form a resin layer on the pET film.丨 (urethane-acrylic composite film). Further, in the copolymer of 1 part of copolymerized polymer containing ethyl acrylate-butyl acrylate-acrylic acid (2 parts by weight to 1 part by weight), the epoxy crosslinking agent 1 0 was uniformly mixed and dissolved. 5 parts of a rosin-based adhesion-imparting agent, 50 parts of a heat-expandable microsphere of a foam expansion type, and toluene were prepared to prepare a coating liquid, and the coating liquid was applied onto a resin layer and dried to obtain a coating liquid. A heat-resistant adhesive for the manufacture of a semiconductor device having a thickness of about 40 μm as a layer of a heat-expandable adhesive layer. Doc -26· 201241132 with 1. After the thermal expansion adhesive surface of the heat-resistant adhesive tape for semiconductor device manufacturing is pressure-bonded and fixed on a smooth stage, a Si wafer wafer having a size of 5 mm×5 mm is placed on the opposite resin layer, and a liquid epoxy is introduced. Sealing resin 'sealed at 175 ° C x 2 min. Thereafter, curing of the resin (baking after sealing) was promoted by heating at 150 ° C for 6 Torr to prepare a package. Example 2 80 parts by weight of isopropyl acrylate (IBXA) and 20 parts by weight of butyl acrylate (BA) as a (fluorenyl) acrylic monomer were placed in a reaction vessel containing a cooling tube, a thermometer, and a stirring device. Polybutanol (PTMG, manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 650. 8 parts by weight, while stirring, add HXDI 27. 2 parts by weight, which was reacted at 65 ° C for 10 hours, gave a urethane polymer-acrylic monomer mixture. Thereafter, 2-hydroxyethyl acrylate (HEA) was added dropwise. After 5 parts by weight and further reacted for 3 hours, 3 parts by weight of acrylic acid (AA) and IRGACURE 651 as a photopolymerization initiator were added. 3 parts by weight. Further, the polyisocyanate component and the polyol component are used in an amount of NCO / 〇 H (equivalent ratio) = 1. 25. The urethane polymer and the acrylic monomer mixture were applied to the stripped PET having a thickness of 38 μm to a thickness of 1 μm after hardening. After the peeling-treated pet film was overlaid thereon, the coated PET crucible surface was cured by ultraviolet light (illuminance 5 mW/cm 2 , light amount 1 〇〇〇 mj/cm 2 ) using a black light lamp to form a PET film. A package was produced in the same manner as in Example 1 except that the resin layer 2 (amino phthalate-acrylic composite film 2) was used. 162235. Doc • 27· 201241132 Example 3 100 parts by weight of isomeric acrylate (IBXA) as a (meth)acrylic monomer was placed in a reaction vessel containing a cooling tube, a thermometer and a stirring device as the average number of polyols Polybutanediol having a molecular weight of 650 (PTMG 'Mitsubishi Chemical Co., Ltd.) 72. 8 parts by weight, while stirring, add HXDI on one side. 2 parts by weight of the reaction was carried out at 65 ° C for 10 hours to obtain a urethane polymer-acrylic monomer mixture. Thereafter, after dropwise addition of 6.5 parts by weight of 2-hydroxyethyl acrylate (ΗΕΑ) to react for 3 hours, IRGACURE 651 0. as a photopolymerization initiator was added. 3 parts by weight. Further, the amount of the polyisocyanate component and the polyol component used was NCO/OH (equivalent ratio) = 1. 25 » A mixture of a urethane polymer and an acrylic monomer was applied to a stripped PET having a thickness of 38 μm so as to have a thickness of 100 μm after hardening. After the peeling-treated PET film was overlaid thereon, the surface of the coated PET film was cured by irradiation with ultraviolet light (illuminance: 5 mW/cm 2 'light quantity: 1000 mJ/cm 2 ) to form a resin layer 3 on the PET film. A package was produced in the same manner as in Example 1 except that the amine phthalate-acrylic composite film 3 was used. Comparative Example 1 100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: ethyl acrylate: 2-hydroxyethyl acrylate = 70 parts by weight: 30 parts by weight: 5 parts by weight), isocyanate-based crosslinked 3 parts by weight of a solution (manufactured by Coronate L, a glutinous polyester) was dissolved in toluene and applied to a polyester film having a thickness of 1 〇μηη after drying to a thickness of 1 〇μΐη2, and was prepared. Outside 162235. Doc -28-201241132 A package was produced in the same manner as in Example 1. Comparative Example 2 100 parts by weight of stearyl acrylate, 2,2-dimethoxyoxy-1,2-diphenylethane-1-one 0. 3 parts by weight was placed in a four-necked flask, and exposed to ultraviolet rays under a nitrogen atmosphere to partially photopolymerize, thereby obtaining a partial polymer (monomer syrup). After adding 54 parts of isooctyl acrylate, 6 parts by weight of acrylic acid, and 0.1 part by weight of hexanediol diacrylate as a crosslinking agent to 40 parts by weight of the partial polymer, the mixture was uniformly mixed to prepare light. Polymeric composition. The photopolymerizable composition was applied to a polyethylene terephthalate film having a thickness of 1 μm to a thickness of 100 μm, and then coated on one side of a thickness of 3 8 μm. The treated polyethylene terephthalate film 'forms a coating layer. The sheet was subjected to a black light (丨 5 w/cm 2 ) and an ultraviolet ray of 1 m0/cm 2 (measured by TOPCON UVR-T1 having a peak sensitivity of 35 〇 nm) to obtain a side chain. A temporarily fixed sheet of crystallizable polymer. The surface of the substrate of the temporarily fixed sheet containing the side chain crystallizable polymer was subjected to heat-expandable pressure-sensitive adhesive layer coating or the like in the same manner as in Example 1 to prepare a package in the same manner as in Example 1. <Evaluation> For the heat-resistant heat-peelable adhesive sheet and package produced as described above, the shear adhesion force to the tantalum wafer at 175 ° C and the actual peeling of the heat-resistant heat-peelable adhesive tape from the package were evaluated. 9 时. Peeling adhesive force, storage elastic modulus G', value of the offset distance of the wafer from the initial position, and the residue of the paste after peeling off the heat-resistant heat-peelable adhesive sheet visually observed by a microscope 162235.doc -29-201241132 And the extent to which the wafer is exposed from the sealing surface (the amount of gap from the plate). The results are shown in Table 1. <Shearing of the tantalum wafer under 175. Next, the sheets produced in the examples and the comparative examples were cut into 2 mm squares, and placed on the resin layer (opposite side of the heat-expandable adhesive layer). After mm, the square piece was placed in a shearing force tester attached to the platform of 1751 for 3 minutes, and then as shown in Fig. 4, it was measured to push horizontally at a speed of mm5 mm/sec. The load when the wafer is smashed. < 175 ° C after heating from the package 9 〇. Peeling adhesion > After a sealing step of 175 C x 2 min, the film was cooled to room temperature, and the peeling speed was measured at 300 mm/min and the pulling angle was 90. The load when peeling off the belt. <Measurement method of storage elastic modulus G'> Storage elastic modulus (G,) is measured by "ARES" (manufactured by TA Instruments) "There is a measurement" at _60 ° c to 200 〇 In the temperature region of c, the temperature rise rate is 5. (:/min, frequency 1 Hz. [Table 1] Unit Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 The etching of the wafer was followed by g/10 mm 2 220 350 130 55 300 Peeling force of the body N/20 mm 0.12 0.30 0.10 0.60 0.25 Storage elastic modulus Pa 4.3χ105 2.5x10s 5.0χ105 l.lxlO5 1.3xl04 ____ Wafer offset distance mm 0.02 0.02 0.03 】.50 0.05 Paste residue - No or none With or without the interlamellar gap μπι 5 6 5 6 12 In Examples 1 to 3, by having sufficient adhesion at the time of sealing, the wafer shift can be suppressed, and the adhesion to the sealing resin after cooling is small. 2235^00 -30- 201241132 characteristics, a good package with light peeling of the package and no residue after peeling can be obtained, and the gap between the plates is also small. In contrast, in Comparative Example 1, due to the resin Since the layer does not contain the amino phthalate polymer component, the wafer shift at the time of sealing can not be suppressed, and in Comparative Example 2, since the ethylene-based polymer is not contained, the elastic modulus of the crucible 75 is low. ' & and 7 wafers buried in the resin layer, from the gap between the plates According to the above results, it is possible to provide a method in which the wafer can be held in the resin sealing step, and then cooled to a specific temperature, the strip can be peeled off without a paste residue, and a small gap between the plates can be achieved. A heat-resistant heat-peelable adhesive tape for temporarily fixing a wafer at the time of manufacture of a substrate semiconductor package. [Simplified description of the drawings] 圊1(4)-(1) is a schematic view showing a method of manufacturing a substrate-free package. Fig. 3 is a cross-sectional view showing a heat-resistant adhesive tape for manufacturing a semiconductor device of the present invention. Fig. 4 is a view showing a test using a shear adhesion tester. Description] 1 wafer 2 heat-resistant adhesive tape for semiconductor device manufacturing 3 substrate 4 sealing resin 5 electrode 162235.doc 201241132 6 dicing blade 7 dicing ring 8 dicing tape 9 paste residue 10 smooth release sheet 11 resin layer 12 rubber Shaped organic elastic layer 13 heat-expandable adhesive layer 162235.doc -32-