201111466 六、發明說明： 【發明所屬之技術領域】 本發明係有關薄片狀黏著劑及晶圓加工用膠帶。 【先前技術】 半導體裝置的製造步驟係實施下述步驟：將半導體晶 圓切斷分離（切割）成半導體晶片單元的步驟：拾取（ pick up)分離後的半導體晶片的步驟；以及將拾取的半導 體晶片黏著於引線框架或封裝基板等的晶粒黏合（裝配） 步驟。 近年來，作爲上述半導體裝置的製造步驟中使用的晶 圓加工用膠帶，提出有例如在基材薄膜上設有黏貼劑層的 晶圓加工用膠帶、具有在黏貼劑層上進一步層合有薄片狀 黏著劑層的結構的晶圓加工用膠帶（切割晶粒黏合薄膜： DDF)，並已實用化。 另外，爲了提高晶粒黏合（裝配）步驟中的半導體晶 片與引線框架或封裝基板之間的黏著力，揭示有添加矽烷 偶合劑作爲晶圓加工用膠帶的薄片狀黏著劑的組成物（參 見專利文獻1)。然而，由於矽烷偶合劑爲低分子量，故 有隨著時間經過，發生存在於薄片狀黏著劑表面的矽烷偶 合劑進入薄片狀黏著劑的內部，使薄片狀黏著劑表面黏著 力降低（以下稱爲滲出）之問題。 爲了解決上述問題，亦揭示有使矽烷偶合劑彼此反應 並添加作爲晶圓加工用膠帶的薄片狀黏著劑的組成物的方 [S] -5- 201111466 法（參見專利文獻2 )。 先前技術文獻 專利文獻 [專利文獻1]日本專利第3620 1 56號公報 [專利文獻2]日本專利第4165065號公報 【發明內容】 [發明欲解決的課題] 然而，即使是專利文獻2所示的使矽烷偶合劑彼此反 應得到的材料，亦由於矽烷偶合劑與水分反應而發生劣化 ’故在製造薄片狀黏著劑前的階段，必須在嚴格條件下保 管作爲材料的矽烷偶合劑，並且有使薄片狀黏著劑或晶圓 加工用膠帶的生產效率降低的問題。 爲此，本發明係爲了解決上述問題而成者，其目的在 於提供材料保管容易且生產效率高、黏著力經時劣化少、 易的薄片狀黏著劑、以及使用該薄片狀黏著劑製作 的晶圓加工用膠帶。 [用以解決課題之手段] 本發明人等對上述課題進行了積極硏究，結果發現藉 由含有螯合劑改性環氧樹脂作爲薄片狀黏著劑組成物，可 以製作材料保管容易且生產效率高、黏著力經時劣化少、 保管容易的薄片狀黏著劑及晶圓加工用膠帶，因而完成本 發明。 -6- 201111466 即，本發明第1樣態之薄片狀黏著劑，其特徵在於作 爲硬化樹脂成分，含有藉熱或高能量射線硬化的硬化樹脂 及使環氧基硬化的環氧硬化劑，前述硬化樹脂的一部分或 全部爲螯合劑改性環氧樹脂，前述硬化樹脂成分中含有10 質量％以上之前述螯合劑改性環氧樹脂。 本發明第2樣態之薄片狀黏著劑，其特徵在於，在前 述本發明第1樣態之薄片狀黏著劑中，相對於1 00質量份前 述硬化樹脂成分，含有130〜270質量份丙烯酸樹脂共聚物 〇 本發明第1方案之晶圓加工用膠帶，其特徵在於，於 基材膜上層合有黏貼劑層的黏貼膜上，使本發明之第1或 第2樣態之薄片狀黏著劑層合於前述黏貼膜的前述黏貼劑 層上。 根據本發明，可以製作材料保管容易且生產效率高、 黏著力的經時劣化少、保管容易的薄片狀黏著劑。另外， 藉由使用該薄片狀黏著劑製作晶圓加工用膠帶，可以製作 材料保管容易且生產效率高、接著力的經時劣化少、保管 容易的晶圓加工用膠帶。 【實施方式】 以下基於附圖詳細說明本發明實施形態。圖1係表示 使用本發明一實施形態的薄片狀黏著劑12的黏著膜20的截 面圖。 如圖1所示，黏著膜20具有在脫模膜11上層合有本發 201111466 明的薄片狀黏著劑12之構成。又，黏著膜2 0亦可爲在與設 置有脫模膜11的面相反的薄片狀黏著劑12的面上進一步層 合與脫模膜11不同的脫模膜之構成之黏著膜，並捲繞成輥 狀者。另外，上述薄片狀黏著劑12亦可根據使用步驟或裝 置而預先切斷（預剪切）成規定的形狀。 接著，對將本發明的薄片狀黏著劑12與在基材膜上層 合有黏貼劑層的黏貼膜的黏貼劑層予以貼合而得到的晶圓 加工用膠帶（切割晶粒黏合薄膜）加以說明。圖2係表示 本發明一實施形態的晶圓加工用膠帶10的截面圖。 如圖2所示，本發明一實施形態的晶圓加工用膠帶1 〇 具有黏貼膜13和層合於該黏貼膜13上的薄片狀黏著劑12， 所述黏貼膜13係由薄膜狀的基材膜13 a及形成於其上的黏 貼劑層13b構成。由此，晶圓加工用膠帶10，係依次形成 基材膜13a、黏貼劑層13b及薄片狀黏著劑12。 又，黏貼劑層1 3b可由一層黏貼劑層所構成，亦可爲 由二層以上的黏貼劑層層合的構成者。另外，圖2顯示進 而在薄片狀黏著劑12上設置脫模膜11的情況的晶圓加工用 膠帶10。 黏貼膜13及薄片狀黏著劑12可以根據使用步驟或裝置 預先切斷（預剪切）成規定形狀。本發明的晶圓加工用膠 帶10包括切斷成一片片半導體晶圓的形態及將形成有複數 半導體晶圓的長條膜捲繞成輥狀的形態。 以下，詳細說明本實施形態的黏著膜2〇及晶圓加工用 膠帶10的各構成要素。 201111466 (脫模膜） 脫模膜1 1係用於改良薄片狀黏著劑1 2的操作性 作爲脫模膜11，例如，可使用聚乙烯膜、聚丙 聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯 乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚萘二甲 酯膜、聚對苯二甲酸丁二酯膜、聚胺基甲酸酯膜、 乙酸乙烯酯共聚物膜、離聚物樹脂膜、乙烯·（甲 烯酸共聚物膜、乙烯·（甲基）丙烯酸酯共聚物膜 乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。 亦可使用該等之交聯膜。進而亦可爲上述膜的層合 脫模膜11的表面張力較好爲4 0mN/m以下， 3 5mN/m以下。上述表面張力低的脫模膜11可適當 質而得，且亦可以對膜表面塗布矽氧樹脂等實施脫 而得。 脫模膜1 1的膜厚通常爲5〜300μιη，較佳爲10〜 ，特佳爲20〜1 50μπι左右。 (薄片狀黏著劑） 薄片狀黏著劑1 2係作爲在貼合半導體晶圓等進 後，拾取半導體晶片時，附著於半導體晶片背面， 晶片固定於基板或引線框架時的黏著劑而使用者。 薄片狀黏著劑12含有藉熱或高能量射線硬化的 脂，該硬化樹脂的一部分或全部由螯合劑改性環氧 烯膜、 膜、氯 酸乙二 乙烯· 基）丙 、聚苯 另外， 漠。 較好爲 選擇材 模處理 2 0 0 μιη 行切割 用以將 硬化樹 樹脂構 -9 - 201111466 成。即，該硬化樹脂可僅爲螯合劑改性環氧樹脂，亦可含 有螯合劑改性環氧樹脂及未經螯合劑改性的環氧樹脂的其 他硬化樹脂。 螯合劑改性環氧樹脂若爲使含有金屬氧化物及/或金 屬氫氧化物的螯合劑成分與分子內具有2個以上環氧基的 環氧成分反應得到者即可。 作爲金屬氧化物及/或金屬氫氧化物，較好使用氧化 鎂、氧化鈣、氧化鋅、氧化鈦、氧化鎘、氧化鉛、氫氧化 鎂、氫氧化鈣、磷酸等。 作爲環氧成分，可較好地使用例如對苯二酚、間苯二 酣、鄰苯—酣、1，3，5 -三經基苯（Fluor 〇 gluco sino 1)等單核 多元酚化合物的聚縮水甘油醚化合物；二羥基萘、雙酚、 伸甲基雙酚（雙酚F)、伸甲基雙（鄰甲酚） '亞乙基雙 酚、異亞丙基雙酚（雙酚A)、異亞丙基雙（鄰甲酚）、 四溴雙酚A、1，3-雙（4-羥基枯基苯）、1，4-雙（4-羥基枯 基苯）、1，1，3-三（4-羥基苯基）丁烷、1，1，2,2-四（4-羥 基苯基）乙烷、硫代雙酚、磺基雙酚、氧基雙酚（ oxybisphenol)、酚醛清漆、鄰甲酚清漆、乙基酚醛清漆 、丁基酚醛清漆、辛基酚醛清漆、間苯二酚清漆、萜烯酚 等多核多元酚化合物的縮水甘油醚化合物；乙二醇、丙二 醇、丁二醇、己二醇、聚乙二醇、硫二乙二醇、甘油、三 羥甲基丙烷、季戊四醇、山梨醇、雙酚A-環氧乙烷加成物 等多元醇類的聚縮水甘油醚，·馬來酸、富馬酸、衣康酸、 琥珀酸、戊二酸、辛二酸、己二酸、壬二酸、癸二酸、二 -10- 201111466 聚酸、三聚酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、 偏苯三酸、苯均三酸、苯均四酸、四氫鄰苯二甲酸、六氫 鄰苯二甲酸、甲橋四氫鄰苯二甲酸（endomethylene tetrahydrophthalic acid)等脂肪族、芳香族或脂環族多元 酸的縮水甘油酯類與甲基丙烯酸縮水甘油酯的均聚物或共 聚物；N，N-二縮水甘油基苯胺、雙（4-(N-甲基-N-縮水 甘油基胺基）苯基）甲烷等具有縮水甘油基胺基的環氧化 合物；乙烯基環己烯二環氧化物、二環戊二烯二環氧化物 、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、3,4-環氧基-6-甲基環己基甲基-6-甲基環己烷羧酸酯、雙（3,4-環氧基-6-甲基環己基甲基）己二酸酯等環狀烯烴化合物的 環氧化物；環氧化聚丁二烯、環氧化苯乙烯-丁二烯共聚 物等環氧化共軛二烯聚合物、異氰脲酸三縮水甘油基酯等 雜環化合物等。 作爲螯合劑改性環氧樹脂以外可以任意使用的硬化樹 脂，可以舉出未經螯合劑改性的環氧樹脂、丙烯酸樹脂、 矽氧樹脂、酚樹脂、熱硬化型聚醯亞胺樹脂、聚胺基甲酸 酯樹脂、三聚氰胺樹脂、脲樹脂等或其混合物或者改性物 ，特別是基於耐熱性、作業性、可靠性優異的觀點來看， 較好使用環氧樹脂。 另外，薄片狀黏著劑12至少含有使螯合劑改性環氧樹 脂硬化的環氧硬化劑。又，作爲螯合劑改性環氧樹脂以外 可以任意使用的硬化樹脂，於含有未經螯合劑改性的環氧 樹脂時，對該環氧樹脂亦較好使用環氧硬化劑。作爲環氧 -11 - 201111466 硬化劑，例如可以使用酚系樹脂。作爲酚系樹脂，可無特 別限定地使用烷基酚、多元酚、萘酚等酚類與醛類的縮合 物等。該等酚系樹脂中所含的酚性羥基與環氧樹脂的環氧 基藉由加熱可容易進行加成反應，形成耐衝擊性高的硬化 物。 酚系樹脂中較好使用酚醛清漆樹脂、鄰甲酚清漆樹脂 、對甲酚清漆樹脂、第三丁基酚醛清漆樹脂、二環戊二烯 甲酚樹脂、聚對乙烯基酚醛樹脂、雙酚A型清漆樹脂或其 等之改性物等。 此外，作爲硬化劑，亦可使用熱活性型潛在性環氧樹 脂硬化劑。該硬化劑係在室溫不與環氧樹脂反應，經某溫 度以上的加熱而活化才與環氧樹脂反應的類型的硬化劑。 作爲活化方法，存在下述方法：利用加熱進行的化学 反應生成活性物種（陰離子、陽離子）的方法；在室溫附 近穩定地分散於環氧樹脂中，在高溫下與環氧樹脂相溶· 溶解，引發硬化反應的方法；利用分子篩封入型硬化劑在 高溫下溶出引發硬化反應的方法；以及利用微膠囊進行的 方法等。 作爲熱活性型潛在性環氧樹脂硬化劑，可以舉出各種 鑰鹽、二元酸二醯肼化合物、二氰基二醯胺、胺加成物硬 化劑、咪唑化合物等高熔點活性氫化合物等。 另外，作爲助劑，亦可使用硬化促進劑等。作爲可用 於本發明的硬化促進劑，沒有特別限定’可以使用例如三 級胺、咪唑類、四級銨鹽等。作爲本發明中較好使用的咪 12- 201111466 唑類，例如可以使用2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-苯基咪唑鑰偏苯三 酸鹽、2-苯基-4,5-二羥基甲基咪唑等，上述促進劑可使用 1種或倂用2種以上。咪唑類例如由四國化成工業（株）以 2MZ ' 2E4MZ' 2PZ-CN、2PZ-CNS、2PHZ 的商品名進行銷 售 ° 本說明書中，將上述螯合劑改性環氧樹脂、任意使用 的硬化樹脂以及環氧硬化劑稱爲硬化樹脂成分，薄片狀黏 著劑1 2中，在該硬化樹脂成分中含有1 〇質量％以上螯合劑 改性環氧樹脂。如果少於1 0質量％時，則黏著力不足，容 易產生封裝裂紋。 另外，薄片狀黏著劑1 2較好含有聚合物，作爲聚合物 ，可使用苯氧基樹脂、丙烯酸共聚物等。從柔軟性優異的 觀點來看，較好使用丙烯酸共聚物，進而較好爲玻璃轉移 溫度（Tg)爲-10 °C以上30 °C以下的丙烯酸共聚物。玻璃轉 移溫度低於-1 0 °C時，難以膜化，超過3 0 °C時，膜的可撓性 降低。 丙烯酸共聚物的聚合方法沒有特別限定，例如可以舉 出微粒聚合、溶液聚合、懸浮聚合等。藉由該等方法得到 共聚物。懸浮聚合因耐熱性優異而較佳，作爲該種丙烯酸 共聚物’例如可列舉SG-708-6 ( Nagase ChemteX股份有限 公司製，商品名）。 丙烯酸系共聚物的重量平均分子量較好爲5萬以上， 最好在20萬〜1〇〇萬的範圍內。分子量過低時，膜的形成 -13- 201111466 不充分’過高時’與其他成分的相溶性變差，結果妨礙膜 形成。 另外’相對於1〇〇質量份上述硬化樹脂成分，較好含 有130〜270質量份丙烯酸樹脂共聚物。丙烯酸樹脂共聚物 少於130質量份時，硬化收縮量增多，故容易產生封裝裂 紋，多於270質量份時，黏著力降低，容易產生封裝裂紋 〇 另外’薄片狀黏著劑12中，作爲其他成分，可以使用 聚醯亞胺樹脂、聚醯胺樹脂、聚醚醯亞胺樹脂、聚醯胺醯 亞胺樹脂、聚酯樹脂、聚酯樹脂、聚酯醯亞胺樹脂、苯氧 基樹脂、聚颯樹脂、聚醚颯樹脂、聚苯硫醚樹脂、聚醚酮 樹脂、氯化聚丙烯樹脂、丙烯酸樹脂、聚胺基甲酸酯樹脂 、環氧樹脂、聚丙烯醯胺樹脂、三聚氰胺樹脂等或其混合 物。 另外，薄片狀黏著劑1 2中亦可調配塡料。作爲塡料， 可以舉出結晶二氧化矽、熔融二氧化矽、合成二氧化矽等 二氧化矽、氧化鋁、玻璃球等無機塡料。藉由在硬化性保 護膜形成層中添加無機塡料，可提高硬化後的黏著劑的硬 度。另外，可以使硬化後的黏著劑的熱膨脹係數接近半導 體晶圓的熱膨脹係數，由此可以降低半導體晶圓的翹曲。 作爲塡料，較好爲二氧化矽，特別是極力除去了導致半導 體裝置錯誤動作的α射線的射線源的類型的二氧化矽最爲 適當。作爲塡料的形狀，可使用球形、針狀、無定形類型 的塡料中的任一種，特佳爲可最緻密塡充的球形塡料。 -14- 201111466 薄片狀黏著劑1 2由於含有螯合劑改性環氧樹脂，所以 具有良好的黏著力，無需使用偶合劑。但是，偶合劑若爲 少量，則對由吸水導致材料劣化或由薄片狀黏著劑1 2的滲 出現象導致經時劣化的影響少，所以爲了在不劣化的情況 下進一步提高黏著力，亦可調配少量偶合劑。此時，相對 於總計100質量份的其他組成物，較好矽烷偶合劑爲0.1質 量份以下。作爲偶合劑，較好爲矽烷偶合劑。作爲矽烷偶 合劑，可列舉出γ-縮水甘油氧基丙基三甲氧基矽烷、γ-毓 基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ_脲基 丙基三乙氧基矽烷、Ν-(3-胺基乙基-γ-胺基丙基三甲氧基矽 烷等。 另外，清漆化的溶劑較好使用沸點較低的甲基乙基酮 、丙酮、甲基異丁基酮、2-乙氧基乙醇、甲苯、丁基溶纖 劑、甲醇、乙醇、2-甲氧基乙醇等。另外，基於提高塗膜 性等的目的，亦可加入高沸點溶劑。作爲高沸點溶劑，可 列舉出二甲基乙醯胺、二甲基甲醯胺、甲基吡咯烷酮、環 己酮等。 薄片狀黏著劑12的厚度可適當設定，但較好爲5〜 1 ΟΟμιη左右。 爲了提高薄片狀黏著劑12的斷裂強度，增加聚合物、 減少塡料、減少環氧樹脂（固態）爲有效。另外，爲了降 低薄片狀黏著劑1 2從脫模膜1. 1剝離的剝離力，減少聚合物 '減少環氧樹脂（液態）爲有效。 -15- 201111466 (黏貼膜） 作爲黏貼膜1 3並無特別限定，若爲於將半導體晶圓進 行切割時，具有使半導體晶圓不剝離般的充分黏貼力，且 顯示切割後拾取半導體晶片時可以容易地從薄片狀黏著劑 1 2剝離般低的黏貼力者即可。例如，可較好地使用在基材 膜13a上設置黏貼劑層13b的黏貼膜。 作爲黏貼膜13的基材膜13a，只要是現有公知者，即 可無特別限定地使用，但使用放射線硬化性的材料作爲下 述的黏貼劑層13b時，較好使用具有放射線透射性的材料 該 爲 作 如 例 物 聚 共 烯 丙 " 烯 物 聚 共 酯 烯 乙 乙酸甲 、 乙酸 烯稀稀 丙乙-M 聚、嫌 、-1乙 烯烯、 乙戊物 聚基聚 舉甲共 列-4-醋 以聚乙 可、酸 ，-1烯 料^β 材丁 聚 烯 乙 該 烯者 乙或 、物 物聚 聚共 共或 酯物 聚 均 的 烴 烯 零 α 等 物 聚 離、 物 聚 共 酸 烯 丙 燦 乙 苯、 酯 酸 甲 基 胺 聚、 物 合 混 之 等 乙烯-丁烯或者戊烯系共聚物' 聚醯胺-多元醇共聚物等熱 塑性彈性體、以及其等之混合物。另外，基材膜13a可爲 混合從上述組群中選擇的2種以上材料的基材，上述材料 可以爲單層或多層化者。 基材膜13a的厚度無特別限定，可以適當設定，較好 爲 50 〜200μπι 〇 作爲於黏貼膜I3的黏貼劑層13b中使用的樹脂並無特 別限定，可使用用於黏貼劑的公知的氯化聚丙烯樹脂、丙 稀酸樹脂、聚酯樹脂、聚胺基甲酸酯樹脂、環氧樹脂等。 201111466 黏貼劑層1 3 b的樹脂較好適當調配丙烯酸系黏貼劑、 放射線聚合性化合物、光聚合引發劑、硬化劑等來調製黏 貼劑。黏貼劑層13b的厚度可以沒有特別限定地適當設定 ，較好爲5〜30μιη。 將放射線聚合性化合物調配於黏貼劑層1 3 b，可以利 用放射線硬化從薄片狀黏著劑12容易地剝離。該放射線聚 合性化合物使用例如利用光照能發生三維網狀化的分子內 至少具有2個以上光聚合性碳-碳雙鍵的低分子量化合物。 具體而言，可使用三羥甲基丙烷三丙烯酸酯、季戊四 醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇單羥基 五丙烯酸酯、二季戊四醇六丙烯酸酯、1，4_ 丁二醇二丙烯 酸醋、1，6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯或寡 酯丙烯酸酯等。 另外’除上述丙烯酸酯系化合物之外，亦可使用聚胺 基甲酸醋丙烯酸酯系寡聚物。聚胺基甲酸酯丙烯酸酯系寡 聚物可如下得到，使聚酯型或聚醚型等多元醇化合物與多 元異氰酸酯化合物（例如，2,4-甲苯二異氰酸酯、2,6-甲 苯二異氰酸酯、1，3·二甲苯二異氰酸酯、I，4·二甲苯二異 氛酸醋、二苯基甲烷4,4二異氰酸酯等）反應得到的末端 異#1酸醋聚胺基甲酸酯聚合物，與具有羥基的丙烯酸酯或 甲基丙燦酸酯（例如，丙烯酸2_羥基乙酯、甲基丙烯酸2_ 經基乙醋、丙烯酸2_羥基丙酯、甲基丙烯酸2羥基丙酯' 聚乙二醇丙烯酸酯、聚乙二醇甲基丙烯酸酯等）反應而得 到。 -17- 201111466 黏貼劑層13b可以混合選自上述樹脂的2種以上者。 使用光聚合引發劑時，例如可以使用異丙基苯偶因醚 、異丁基苯偶因醚 '二苯甲酮、米氏酮（Michler ket〇ne )、氯噻噸酮、十二烷基噻噸酮、二甲基噻噸酮、二乙基 噻噸酮、苄基二甲基縮酮、α-羥基環己基苯基酮、2_羥基 甲基苯基丙院等。該等光聚合引發劑的調配量相對於1〇〇 質量份丙烯酸系聚合物較好爲0.01〜5質量份。 (實施例） 接著’就本發明實施例加以說明，但本發明並不限定 於下述實施例。 (薄片狀黏著劑的製作方法） 在下述表1所示調配的薄片狀黏著劑組成物1Α〜1Η中 加入甲基乙基酮進行攪拌混合，製作黏著劑清漆。將製作 的薄片狀黏著劑組成物1Α〜1Η的黏著劑清漆塗布於脫模 膜11上，使得乾燥後的厚度爲20μιη，在not：乾燥3分鐘， 分別製作薄片狀黏著劑12。然後，將脫模膜u從薄片狀黏 著劑12剝離’製作下述表2所示的實施例1〜5及下述表3所 示的比較例1〜3的薄片狀黏著劑。 18- 201111466 [表1] 黏著材層組成物 1A 1B 1C 1D 1E 1F 1G 1H 環氧樹脂⑴ 50 10 50 50 50 5 50 環氧樹脂(2) 40 50 45 酚樹脂 50 50 50 50 50 50 50 50 硬化促進劑 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 丙烯酸樹脂 200 200 200 270 130 200 200 200 矽院偶合劑 0.1 0.3 又，上述表1中，各成分的調配比例的單位爲質量份 。另外，環氧樹脂（1)爲EP-49-23 (ADEKA(股）製之商 品名，螯合劑改性雙酚F型環氧樹脂，環氧基當量爲 175g/eq )，環氧樹脂（2)爲RE303S (日本化藥（股）製 之商品名，雙酹F型環氧樹脂’環氧基當量爲165g/eq )。 酚樹脂是爲MIREXXLC-LL (三井化學（股）製商品名， 羥基當量爲175g/eq，吸水率爲1.8%，3 50°C下的加熱減重 率爲4%)。硬化促進劑爲CUREZOL 2PZ (四國化成（股 )製商品名，2-苯基咪唑）。丙烯酸樹脂爲SG-7 08-6 ( Nagase ChemteX(股）製之商品名，重量平均分子量爲70萬 ，玻璃轉移溫度爲6°C )。矽烷偶合劑爲Z-6044 (東麗· 道康寧（股）製之商品名，3 -縮水甘油氧基丙基甲基甲氧 基矽烷）^ -19- 201111466 [表2] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 黏著材層組成物 1Α 1Β 1C 1D 1Ε 原材料可靠性 不良封裝個數(個） 0 0 0 0 0 不良封裝比例(％) 0 0 0 0 0 劣化材料可靠性 不良封裝個數(個） 0 0 0 0 0 不良封裝比例(％) 0 0 0 0 0 薄片狀黏著劑劣 化後可靠性 不良封裝個數(個） 0 0 0 0 0 不良封裝比例(％) 0 0 0 0 0 [表3] 比較例1 比較例2 比較例3 黏著材層組成物 1F 1G 1Η 原材料可靠性 不良封裝個數(個） 7 6 0 不良封裝比例(％) 35 30 0 劣化材料可靠性 不良封裝個數(個） 7 5 6 不良封裝比例(％) 35 25 30 薄片狀黏著劑 劣化後可靠性 不良封裝個數(個） 8 6 4 不良封裝體的比例(％) 40 30 20 對於實施例1〜5及比較例1〜3，分別進行原材料可靠 性的評價、劣化材料可靠性評價及薄片狀黏著劑劣化後可 靠性的評價。表2及表3顯示原材料可靠性的評價、劣化材 料可靠性的評價及薄片狀黏著劑劣化後可靠性的評價β <原材料可靠性的評價> 原材料可靠性的評價中，利用根據使用原調配材料的 上述薄片狀黏著劑的製作方法製作的實施例1〜5的薄片狀 -20- 201111466 黏著劑及比較例1〜3的薄片狀黏著劑，將在矽晶片上形成 了鋁配線的模擬元件透過薄片狀黏著劑在經鍵銀的FR4基 板上進行日日粒黏合’在175°C、7〇kgf/cm2、成型時間i2〇秒 的條件下成型20個厚度爲封裝，將在18〇。〇後 硬化4小時得到者作爲評價封裝。原材料可靠性的評價是 將所得的封裝在預先調整至260 t的焊錫浴浸漬1〇秒後， 用超音波檢測裝置（日立建機（股）製Hyper)，以透射 鲁法評價有無封裝裂紋。表2及表3的不良封裝個數表示2〇個 評價封裝中有裂紋的封裝個數，不良封裝的比例表示不良 封裝個數在2 0個評價封裝中的比例（％ )。 <劣化材料可靠性的評價> 劣化材料可靠性的評價是使用預先在3〇°c、85%RH的 條件下處理168小時的調配材料，使用根據上述的薄片狀 黏著劑的製作方法製作的實施例i〜5的薄片狀黏著劑及比 φ 較例1〜3的薄片狀黏著劑，與上述原材料可靠性的評價相 同地進行評價。 <薄片狀黏著劑劣化後可靠性的評價> 薄片狀黏著劑劣化後可靠性的評價是使用將使用原調 配材·料並根據上述薄片狀黏著劑的製作方法製作的實施例 1〜5的薄片狀黏著劑及比較例1〜3的薄片狀黏著劑在3 (TC 、85%RH的條件下處理ι68小時後的薄片狀黏著劑，與上 述原材料可靠性的評價相同地進行評價。 -21 - 201111466 如表2所示，使用實施例1〜5的薄片狀黏著劑的封裝 ，係使用螯合劑改性環氧樹脂，且螯合劑改性環氧樹脂相 對於1〇〇質量％的硬化樹脂成分（環氧樹脂與酚樹脂）的調 配比例爲1 〇質量％以下’所以在原材料可靠性的評價、劣 化材料可靠性的評價及薄片狀黏著劑劣化後可靠性的任一 評價中，均無封裝裂紋，得到良好結果。 使用實施例3的薄片狀黏著劑的封裝，雖然含有矽烷 偶合劑，但矽烷偶合劑相對於1 00質量份其他組成物的配 合比例爲〇. 1質量份，所以在劣化材料可靠性的評價及薄 片狀黏著劑劣化後可靠性的評價中，並無因矽烷偶合劑劣 化帶來的影響，得到良好結果。 如表3所示，使用比較例1的薄片狀黏著劑的封裝，由 於未使用螯合劑改性環氧樹脂，所以薄片狀黏著劑12的黏 著力（密著力）差，在原材料可靠性的評價中，得到3 5 % 的封裝發生裂紋的結果。另外，在劣化材料可靠性的評價 及薄片狀黏著劑劣化後可靠性的評價中，分別得到35%的 封裝及40%的封裝發生裂紋的結果。即，使用比較例丨的薄 片狀黏著劑的封裝由於未使用螯合劑改性環氧樹脂，所以 薄片狀黏著劑12的黏著力（密著力）差，得到原材料可靠 性'劣化材料可靠性及薄片狀黏著劑劣化後可靠性差的結 杲。 使用比較例2的薄片狀黏著劑的封裝，雖然使用螯合 劑改性環氧樹脂，但是硬化樹脂成分中的螯合劑改性環氧 樹脂成分的含量爲5質量％，在上述規定的10質量％以上的 201111466 範圍之外，所以薄片狀黏著劑12的黏著力（密著力）差， 在原材料可靠性的評價中，得到3 0 %的封裝發生裂紋的結 果。另外，在劣化材料可靠性的評價及薄片狀黏著劑劣化 後可靠性的評價中，分別得到25%的封裝及30%的封裝發 生裂紋的結果。即，使用比較例2的薄片狀黏著劑的封裝 ’雖使用螯合劑改性環氧樹脂，但是硬化樹脂成分中的螯 合劑改性環氧樹脂成分的含量爲5重量％，在上述規定的10 質量％以上的範圍之外，所以薄片狀黏著劑1 2的黏著力（ 密著力）差，得到原材料可靠性、劣化材料可靠性及薄片 狀黏著劑劣化後可靠性差的結果。又，由於使用螯合劑改 性環氧樹脂，因此不發生調配材料隨著保管時間經過發生 劣化或製作的薄片狀黏著劑隨著保管時間經過而滲出等導 致的薄片狀黏著劑劣化’所以劣化材料可靠性及薄片狀黏 著劑劣化後可靠性與原材料可靠性相比並未降低。 使用比較例3的薄片狀黏著劑的封裝，雖使用螯合劑 改性環氧樹脂’但是由於矽烷偶合劑的調配比例多，爲 〇·3質量份’所以在原材料可靠性的評價中未發生封裝裂 紋。但是，砂院偶合劑的材料劣化或滲出導致薄片狀黏著 劑1 2的黏著力（密者力）降低，在劣化材料可靠性的評價 及薄片狀黏者劑劣化後可靠性的評價中，分別爲3 〇 %的封 裝及2 0 %的封裝發生裂紋，得到劣化材料可靠性及薄片狀 黏著劑劣化後可靠性差的結果。 又，使實施例1的丙烯酸樹脂聚合物的調配比例分別 爲280重量份、120重量份，並與實施例1相同地製作薄片 -23- 201111466 狀黏著劑，分別進行原材料可靠性的評價、劣化材料可靠 性的評價及薄片狀黏著劑劣化後可靠性的評價。丙烯酸樹 脂聚合物的調配比例爲較多的280重量份時，由於黏著力 降低，所以在原材料可靠性的評價中，不良封裝個數爲1 個。另外，丙烯酸樹脂聚合物的調配比例爲較少的120重 量份時，硬化收縮量增多，所以在原材料可靠性的評價中 ，不良封裝個數爲2個。但是，兩者均使用規定量的螯合 劑改性環氧基來代替矽烷偶合劑，所以未見材料劣化或薄 片狀黏著劑劣化導致的經年的不良封裝增加。 由表2及表3所示的結果可知，藉由在硬化樹脂成分中 含有1 〇質量％以上的螯合劑改性環氧樹脂，可以提高薄片 狀黏著劑12的黏著力。又，即使使用在嚴格環境下保管的 薄片狀黏著劑12的調配材料（薄片狀黏著劑組成物）來製 作黏著膜20，薄片狀黏著劑12的黏著力也不會降低’調配 材料的保管容易。另外’在嚴格環境下保管製成的黏著膜 20後，薄片狀黏著劑12的黏著力亦未降低’所製作的黏著 膜20的保管容易。即，可以製作薄片狀黏著劑12的黏著力 優異且調配材料的保管容易、生產效率高的黏著膜20 ’同 時製成的黏著膜20的保管也容易。另外’晶圓加工用膠帶 1 0使用上述本實施形態的黏著膜2 0予以製作’所以可以製 作薄片狀黏著劑12的黏著力優異且調配材料的保管容易的 生產效率高的晶圓加工用膠帶10，所製成的晶圓加工用膠 帶10的保管也容易。 • 24- 201111466 【圖式簡單說明】 圖1係表示使用本發明一實施形態的薄片狀黏著劑12 的黏著膜的截面圖。 圖2係表示發明一實施形態的晶圓加工用膠帶的截面 圖。 【主要元件符號說明】 1 〇 :晶圓加工用膠帶 1 1 :脫模膜 1 2 :薄片狀黏著劑 1 3 :黏貼膜 13a :基材膜 1 3 b :黏貼劑層 20 :黏著膜201111466 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a sheet-like adhesive and a tape for wafer processing. [Prior Art] The manufacturing step of the semiconductor device is a step of: separating (cutting) the semiconductor wafer into semiconductor wafer units: a step of picking up the separated semiconductor wafer; and picking up the semiconductor The wafer is adhered to a die bonding (assembly) step of a lead frame or a package substrate or the like. In recent years, as a tape for processing a wafer to be used in the manufacturing process of the semiconductor device, for example, a wafer processing tape having an adhesive layer on a base film has been proposed, and a laminate is further laminated on the adhesive layer. A wafer processing tape (cut die bonding film: DDF) having a structure of an adhesive layer has been put into practical use. In addition, in order to improve the adhesion between the semiconductor wafer and the lead frame or the package substrate in the die bonding (assembly) step, a composition in which a decane coupling agent is added as a sheet-like adhesive for wafer processing tape is disclosed (see Patent) Document 1). However, since the decane coupling agent has a low molecular weight, the decane coupling agent which occurs on the surface of the flaky adhesive enters the inside of the flaky adhesive over time, and the surface adhesive force of the flaky adhesive is lowered (hereinafter referred to as The problem of seepage). In order to solve the above problems, a method of reacting a decane coupling agent with each other and adding a sheet-like adhesive as a tape for wafer processing has been disclosed [S] -5 - 201111466 (see Patent Document 2). [Patent Document 1] Japanese Patent No. 3620 1 56 [Patent Document 2] Japanese Patent No. 4,165, 065, SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] However, even Patent Document 2 The material obtained by reacting the decane coupling agents with each other also deteriorates due to the reaction of the decane coupling agent with water. Therefore, in the stage before the production of the flaky adhesive, it is necessary to store the decane coupling agent as a material under strict conditions, and to have a sheet. The problem of reduced productivity of adhesives for adhesives or wafer processing. Therefore, the present invention has been made to solve the above problems, and an object thereof is to provide a sheet-like adhesive which is easy to store materials, has high production efficiency, has little deterioration in adhesion, and is easy to use, and a crystal produced using the sheet-like adhesive. Tape for round processing. [Means for Solving the Problem] The present inventors have actively studied the above problems, and as a result, it has been found that a chelating agent-modified epoxy resin is used as a sheet-like adhesive composition, and material storage can be easily performed and production efficiency is high. The present invention has been completed in that a sheet-like adhesive which is less deteriorated in adhesion and which is easy to store, and a tape for wafer processing. -6-201111466 The flaky adhesive according to the first aspect of the invention is characterized in that the cured resin component contains a curing resin which is cured by heat or high energy ray, and an epoxy curing agent which hardens the epoxy group, A part or all of the cured resin is a chelating agent-modified epoxy resin, and the hardened resin component contains 10% by mass or more of the chelating agent-modified epoxy resin. In the flaky adhesive according to the first aspect of the present invention, the flaky adhesive according to the first aspect of the present invention contains 130 to 270 parts by mass of the acrylic resin per 100 parts by mass of the cured resin component. The adhesive tape for wafer processing according to the first aspect of the present invention, characterized in that the adhesive sheet of the first or second aspect of the present invention is applied to the adhesive film on which the adhesive layer is laminated on the base film. Laminated on the aforementioned adhesive layer of the aforementioned adhesive film. According to the present invention, it is possible to produce a sheet-like adhesive which is easy to store materials, has high production efficiency, has little deterioration with time in adhesion, and is easy to store. In addition, by using the sheet-like adhesive to form a wafer processing tape, it is possible to produce a wafer processing tape which is easy to store materials, has high production efficiency, has little deterioration in adhesion force over time, and is easy to store. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail based on the drawings. Fig. 1 is a cross-sectional view showing an adhesive film 20 using a sheet-like adhesive 12 according to an embodiment of the present invention. As shown in Fig. 1, the adhesive film 20 has a structure in which a sheet-like adhesive 12 of the present invention is laminated on the release film 11. Further, the adhesive film 20 may be an adhesive film which is formed by laminating a release film different from the release film 11 on the surface of the sheet-like adhesive 12 opposite to the surface on which the release film 11 is provided, and is also wound. Wrap it into a roll. Further, the sheet-like adhesive 12 may be previously cut (pre-sheared) into a predetermined shape in accordance with the use procedure or apparatus. Next, a wafer processing tape (cut die adhesion film) obtained by laminating the sheet-like adhesive 12 of the present invention and an adhesive layer of an adhesive film having a pressure-sensitive adhesive layer laminated on a base film will be described. . Fig. 2 is a cross-sectional view showing a tape 10 for wafer processing according to an embodiment of the present invention. As shown in FIG. 2, the wafer processing tape 1 according to the embodiment of the present invention has an adhesive film 13 and a sheet-like adhesive 12 laminated on the adhesive film 13, and the adhesive film 13 is formed of a film-like base. The material film 13a and the adhesive layer 13b formed thereon are comprised. Thereby, the wafer processing tape 10 is formed by sequentially forming the base film 13a, the adhesive layer 13b, and the sheet-like adhesive 12. Further, the adhesive layer 13b may be composed of a layer of an adhesive layer, or may be a laminate of two or more adhesive layers. Further, Fig. 2 shows a wafer processing tape 10 in the case where the release film 11 is provided on the sheet-like adhesive 12. The adhesive film 13 and the sheet-like adhesive 12 can be previously cut (pre-sheared) into a predetermined shape in accordance with the use procedure or apparatus. The wafer processing tape 10 of the present invention includes a form in which a plurality of semiconductor wafers are cut and a long film in which a plurality of semiconductor wafers are formed are wound into a roll shape. Hereinafter, each component of the adhesive film 2A and the wafer processing tape 10 of the present embodiment will be described in detail. 201111466 (release film) The release film 1 1 is used for improving the workability of the sheet-like adhesive 1 2 as the release film 11, and for example, a polyethylene film, a polypropylene polybutene film, a polybutadiene film, or the like can be used. Polymethylpentene film, polyvinyl chloride ethylene copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, Vinyl acetate copolymer film, ionomer resin film, ethylene·(methacrylate copolymer film, ethylene·(meth)acrylate copolymer film vinyl film, polycarbonate film, polyimide film, fluororesin A film or the like may be used. The surface of the laminated release film 11 of the film may preferably have a surface tension of 40 mN/m or less and 35 mN/m or less. The film 11 can be suitably obtained, and the surface of the film can be coated with a silicone resin or the like. The film thickness of the release film 1 1 is usually 5 to 300 μm, preferably 10 to 20, and particularly preferably 20 to 20 1 50μπι or so. (Sheet-like adhesive) The sheet-like adhesive 1 2 is used as a half after picking up a semiconductor wafer. In the case of a bulk wafer, the user adheres to the back surface of the semiconductor wafer, and the wafer is fixed to the substrate or the lead frame. The sheet-like adhesive 12 contains a grease hardened by heat or high-energy rays, and a part or all of the hardened resin is chelated. Mixture modified epoxy olefin film, film, ethylene glycol chloroacetate, polyphenylene, and other. It is better to select the material mold treatment 2 0 0 μιη line cutting to form the hardened resin structure -9 - 201111466. Namely, the hardening resin may be only a chelating agent-modified epoxy resin, and may also contain a chelating agent-modified epoxy resin and other hardening resins of an epoxy resin modified without a chelating agent. The chelating agent-modified epoxy resin may be obtained by reacting a chelating agent component containing a metal oxide and/or a metal hydroxide with an epoxy component having two or more epoxy groups in the molecule. As the metal oxide and/or metal hydroxide, magnesium oxide, calcium oxide, zinc oxide, titanium oxide, cadmium oxide, lead oxide, magnesium hydroxide, calcium hydroxide or phosphoric acid is preferably used. As the epoxy component, a mononuclear polyphenol compound such as hydroquinone, meta-benzoquinone, ortho-quinone-based or 1,3,5-trisylbenzene (Fluor® glucosino 1) can be preferably used. Polyglycidyl ether compound; dihydroxynaphthalene, bisphenol, methyl bisphenol (bisphenol F), methyl bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A) ), isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1 , 3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol , glycidyl ether compounds of polynuclear polyphenol compounds such as novolac, o-cresol varnish, ethyl novolac, butyl novolac, octyl novolac, resorcin varnish, terpene phenol, ethylene glycol, propylene glycol, Polycondensation of polyhydric alcohols such as butanediol, hexanediol, polyethylene glycol, thiodiethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Glycerol ether, Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, azelaic acid, di-10-201111466 polyacid, trimer acid, o-benzene Formic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl bridge tetrahydrophthalic acid ( Endomethylene tetrahydrophthalic acid) homopolymer or copolymer of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids and glycidyl methacrylate; N,N-diglycidylaniline, bis(4- An epoxy compound having a glycidylamine group such as (N-methyl-N-glycidylamino)phenyl)methane; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane Epoxide of a cyclic olefin compound such as a carboxylic acid ester or bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butyl Diene copolymerization a heterocyclic compound such as an epoxidized conjugated diene polymer or an isocyanuric acid triglycidyl ester. Examples of the hardening resin which can be arbitrarily used as the chelating agent-modified epoxy resin include an epoxy resin which is not modified by a chelating agent, an acrylic resin, a oxime resin, a phenol resin, a thermosetting polyimide resin, and a poly A urethane resin, a melamine resin, a urea resin, or the like, or a mixture or a modified product thereof, in particular, an epoxy resin is preferably used from the viewpoint of excellent heat resistance, workability, and reliability. Further, the sheet-like adhesive 12 contains at least an epoxy curing agent which cures the chelating agent-modified epoxy resin. Further, as the curing resin which can be arbitrarily used as the chelating agent-modified epoxy resin, when an epoxy resin which is not modified by a chelating agent is contained, an epoxy curing agent is preferably used as the epoxy resin. As the epoxy-11-1 201111466 hardener, for example, a phenol resin can be used. As the phenol resin, a condensate of a phenol such as an alkylphenol, a polyphenol or a naphthol and an aldehyde can be used without particular limitation. The phenolic hydroxyl group contained in the phenolic resin and the epoxy group of the epoxy resin can be easily subjected to an addition reaction by heating to form a cured product having high impact resistance. A phenolic resin, an o-cresol varnish resin, a p-cresol varnish resin, a third butyl novolac resin, a dicyclopentadiene cresol resin, a poly-p-vinyl phenolic resin, a bisphenol A are preferably used in the phenol resin. A varnish resin or a modified product thereof or the like. Further, as the curing agent, a thermally active latent epoxy resin hardener can also be used. The hardener is a type of hardener which does not react with an epoxy resin at room temperature and is activated by heating at a temperature or higher to react with the epoxy resin. As the activation method, there is a method of generating an active species (anion, a cation) by a chemical reaction by heating; stably dispersing in an epoxy resin at room temperature, and being compatible with an epoxy resin at a high temperature. A method of initiating a hardening reaction; a method of eluting a hardening reaction by a molecular sieve-sealed hardener at a high temperature; and a method using a microcapsule. Examples of the thermally active latent epoxy resin hardener include various high-melting active hydrogen compounds such as various key salts, dibasic acid diterpenoids, dicyanodiamines, amine adduct hardeners, and imidazole compounds. . Further, as the auxiliary agent, a curing accelerator or the like can also be used. The hardening accelerator which can be used in the present invention is not particularly limited. For example, a tertiary amine, an imidazole, a quaternary ammonium salt or the like can be used. As the azole 12-201111466 azole which is preferably used in the present invention, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- The above-mentioned accelerator may be used alone or in combination of two or more kinds of cyanoethyl-2-phenylimidazolium pyromellitate or 2-phenyl-4,5-dihydroxymethylimidazole. The imidazoles are sold, for example, under the trade names of 2MZ ' 2E4MZ' 2PZ-CN, 2PZ-CNS, and 2PHZ by Shikoku Chemicals Co., Ltd. In the present specification, the above-mentioned chelating agent-modified epoxy resin and any hardening resin used are used. The epoxy curing agent is referred to as a curing resin component, and the flaky adhesive 12 contains 1% by mass or more of a chelating agent-modified epoxy resin in the cured resin component. If it is less than 10% by mass, the adhesion is insufficient and the package crack is easily generated. Further, the sheet-like adhesive 1 2 preferably contains a polymer, and as the polymer, a phenoxy resin, an acrylic copolymer or the like can be used. From the viewpoint of excellent flexibility, an acrylic copolymer is preferably used, and further preferably an acrylic copolymer having a glass transition temperature (Tg) of from -10 °C to 30 °C. When the glass transition temperature is lower than -10 °C, film formation is difficult, and when it exceeds 30 °C, the flexibility of the film is lowered. The polymerization method of the acrylic copolymer is not particularly limited, and examples thereof include microparticle polymerization, solution polymerization, suspension polymerization, and the like. The copolymer is obtained by these methods. The suspension polymerization is preferred because it is excellent in heat resistance. For example, SG-708-6 (trade name, manufactured by Nagase ChemteX Co., Ltd.) is used as the acrylic copolymer. The weight average molecular weight of the acrylic copolymer is preferably 50,000 or more, and preferably in the range of 200,000 to 1,000,000. When the molecular weight is too low, the film formation -13 - 201111466 is insufficient. When it is too high, the compatibility with other components is deteriorated, and as a result, film formation is hindered. Further, it is preferable to contain 130 to 270 parts by mass of the acrylic resin copolymer with respect to 1 part by mass of the above-mentioned cured resin component. When the amount of the acrylic resin copolymer is less than 130 parts by mass, the amount of curing shrinkage is increased, so that cracking of the package is likely to occur. When the amount is more than 270 parts by mass, the adhesive force is lowered, and the package crack is likely to occur. In addition, the sheet-like adhesive 12 is used as the other component. , can use polyimide resin, polyamide resin, polyether phthalimide resin, polyamide amide resin, polyester resin, polyester resin, polyester phthalimide resin, phenoxy resin, poly Anthracene resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, chlorinated polypropylene resin, acrylic resin, polyurethane resin, epoxy resin, polypropylene guanamine resin, melamine resin, etc. or Its mixture. Further, the flaky adhesive 12 may be formulated with a mash. Examples of the feedstock include inorganic tantalum such as cerium oxide, cerium oxide, and synthetic cerium oxide such as cerium oxide, alumina, and glass sphere. By adding an inorganic tantalum to the curable protective film forming layer, the hardness of the adhesive after hardening can be improved. Further, the thermal expansion coefficient of the cured adhesive can be made close to the thermal expansion coefficient of the semiconductor wafer, whereby the warpage of the semiconductor wafer can be reduced. As the dip, it is preferably cerium oxide, and in particular, cerium oxide of the type which is a source of ray which removes the alpha ray which causes the erroneous operation of the semiconductor device is most suitable. As the shape of the dip material, any one of a spherical, needle-like, and amorphous type of tanning material can be used, and a spherical material which is the most densely filled is particularly preferable. -14- 201111466 The flaky adhesive 1 2 has a good adhesion because it contains a chelating agent-modified epoxy resin, and it is not necessary to use a coupling agent. However, if the amount of the coupling agent is small, the effect of deterioration of the material due to water absorption or the occurrence of bleeding by the flaky adhesive 12 is small, so that it can be blended in order to further improve the adhesion without deterioration. A small amount of coupling agent. In this case, the decane coupling agent is preferably 0.1 parts by mass or less based on 100 parts by mass of the total of the other components. As the coupling agent, a decane coupling agent is preferred. Examples of the decane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and γ-ureidopropyl group. Triethoxy decane, hydrazine-(3-aminoethyl-γ-aminopropyltrimethoxydecane, etc. Further, the varnished solvent is preferably a methyl ethyl ketone having a lower boiling point, acetone, and A. Isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, etc. Further, a high boiling point solvent may be added for the purpose of improving coating properties and the like. Examples of the high boiling point solvent include dimethylacetamide, dimethylformamide, methylpyrrolidone, cyclohexanone, etc. The thickness of the sheet-like adhesive 12 can be appropriately set, but preferably about 5 to 1 ΟΟμιη In order to improve the breaking strength of the flaky adhesive 12, it is effective to increase the amount of the polymer, reduce the amount of the smear, and reduce the epoxy resin (solid state). In addition, in order to reduce the peeling of the flaky adhesive 12 from the release film 1.1. Force to reduce the polymer 'reducing epoxy resin (liquid) is effective. -15- 201 111466 (Adhesive film) The adhesive film 1 3 is not particularly limited, and when the semiconductor wafer is diced, it has a sufficient adhesive force to prevent the semiconductor wafer from being peeled off, and can easily pick up the semiconductor wafer after dicing. For example, an adhesive film having the adhesive layer 13b provided on the base film 13a can be preferably used. As the base film 13a of the adhesive film 13, as long as the base film 13a of the adhesive film 13, A conventionally known one can be used without particular limitation. However, when a radiation curable material is used as the adhesive layer 13b described below, it is preferable to use a material having radiolucent property as an example of a polyacrylic quotation. ; olefin polyethyl methacrylate A, acetic acid olefinic propylene-M poly, susceptibility, -1 vinylene, ethyl ethene polyglycol group collateral 4- vinegar to polyethyl ketone, acid, - 1 olefins, β-pyrene, butylene, olefins, or agglomerates, or agglomerates, agglomerates, agglomerates, alkene, alkene, etc. Polyamines A thermoplastic elastomer such as an ethylene-butene or a pentene copolymer, a polyamine-polyol copolymer, or a mixture thereof, etc. The base film 13a may be a mixture of two or more selected from the above group. The material of the substrate may be a single layer or a multilayer. The thickness of the substrate film 13a is not particularly limited and may be appropriately set, and is preferably 50 to 200 μm as the adhesive layer 13b for the adhesive film I3. The resin is not particularly limited, and a known chlorinated polypropylene resin, acrylic resin, polyester resin, polyurethane resin, epoxy resin or the like for the adhesive can be used. 201111466 The resin of the adhesive layer 1 3 b is preferably prepared by mixing an acrylic adhesive, a radiation polymerizable compound, a photopolymerization initiator, a curing agent, or the like to prepare an adhesive. The thickness of the adhesive layer 13b can be appropriately set without particular limitation, and is preferably 5 to 30 μm. The radiation polymerizable compound is blended in the adhesive layer 13b, and can be easily peeled off from the sheet-like adhesive 12 by radiation hardening. As the radiation-polymerizable compound, for example, a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule which is three-dimensionally networked by light energy is used. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate vinegar, 1 can be used. , 6-hexanediol diacrylate, polyethylene glycol diacrylate or oligoester acrylate, and the like. Further, in addition to the above acrylate-based compound, a polyaminocarbamic acid acrylate-based oligomer can also be used. The polyurethane acrylate oligomer can be obtained by using a polyol compound such as a polyester type or a polyether type and a polyvalent isocyanate compound (for example, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate). Terminal 1, # vinegar polyurethane polymer obtained by the reaction of 1,3, xylene diisocyanate, I, 4, xylene diisocyanate, diphenylmethane 4,4 diisocyanate, etc. And an acrylate or methacrylic acid ester having a hydroxyl group (for example, 2-hydroxyethyl acrylate, 2-methythyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate) It is obtained by reacting a glycol acrylate, polyethylene glycol methacrylate or the like. -17- 201111466 The adhesive layer 13b may be mixed with two or more types selected from the above resins. When a photopolymerization initiator is used, for example, isopropyl benzoate ether, isobutyl benzoate ether benzophenone, Michler ketne, chlorothioxanthone, dodecyl group can be used. Thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, benzyl dimethyl ketal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl phenyl propyl ketone, and the like. The amount of the photopolymerization initiator to be added is preferably 0.01 to 5 parts by mass based on 1 part by mass of the acrylic polymer. (Embodiment) Next, the embodiment of the present invention will be described, but the present invention is not limited to the following embodiment. (Manufacturing method of the flaky adhesive) Methyl ethyl ketone was added to the flaky adhesive composition 1 to Η1 shown in the following Table 1, and the mixture was stirred and mixed to prepare an adhesive varnish. The adhesive varnish having a sheet-like adhesive composition of 1 to 1 Å was applied onto the release film 11 so that the thickness after drying was 20 μm, and the sheet-like adhesive 12 was produced by not drying for 3 minutes. Then, the release film u was peeled off from the sheet-like adhesive 12, and the sheet-like adhesives of Comparative Examples 1 to 3 shown in the following Table 2 and Comparative Examples 1 to 3 shown in Table 3 below were produced. 18- 201111466 [Table 1] Adhesive layer composition 1A 1B 1C 1D 1E 1F 1G 1H Epoxy resin (1) 50 10 50 50 50 5 50 Epoxy resin (2) 40 50 45 Phenolic resin 50 50 50 50 50 50 50 50 Hardening accelerator 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acrylic resin 200 200 200 270 130 200 200 200 Brothel coupling agent 0.1 0.3 Further, in the above Table 1, the unit of the mixing ratio of each component is part by mass. Further, the epoxy resin (1) is EP-49-23 (trade name manufactured by ADEKA Co., Ltd., chelating agent-modified bisphenol F-type epoxy resin, epoxy equivalent: 175 g/eq), epoxy resin ( 2) It is a trade name of RE303S (manufactured by Nippon Kayaku Co., Ltd., and the epoxy group equivalent of bismuth F-type epoxy resin is 165 g/eq). The phenol resin was MIREXXLC-LL (trade name of Mitsui Chemicals Co., Ltd.), the hydroxyl equivalent was 175 g/eq, the water absorption was 1.8%, and the heating weight loss rate at 3 50 ° C was 4%. The hardening accelerator is CUREZOL 2PZ (trade name of Shikoku Kasei Co., Ltd., 2-phenylimidazole). The acrylic resin was SG-7 08-6 (trade name, manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight: 700,000, glass transition temperature: 6 ° C). The decane coupling agent is Z-6044 (trade name of Toray Dow Corning Co., Ltd., 3 - glycidoxypropyl methyl methoxy decane) ^ -19- 201111466 [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Adhesive layer composition 1Α 1Β 1C 1D 1Ε Unsatisfactory number of raw materials package(s) 0 0 0 0 0 Poor package ratio (%) 0 0 0 0 0 Degraded material reliability Number of packages (a) 0 0 0 0 0 Poor package ratio (%) 0 0 0 0 0 Poor reliability after laminating adhesive deterioration (number of packages) 0 0 0 0 0 Poor package ratio (%) 0 0 0 0 0 [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Adhesive layer composition 1F 1G 1Η Low reliability of raw materials Package number (s) 7 6 0 Poor package ratio (%) 35 30 0 Degraded material reliability Number of defective packages (units) 7 5 6 Poor package ratio (%) 35 25 30 Poor reliability after deterioration of sheet-like adhesives (number of packages) 8 6 4 Proportion of defective packages (%) 40 30 20 For implementation In Examples 1 to 5 and Comparative Examples 1 to 3, evaluation of raw material reliability and deterioration of materials were performed. Evaluation of reliability can be evaluated and after a sheet of adhesive degradation. Table 2 and Table 3 show the evaluation of the reliability of the raw material, the evaluation of the reliability of the deteriorated material, and the evaluation of the reliability after the deterioration of the flaky adhesive. β <Evaluation of the reliability of the raw material> The evaluation of the reliability of the raw material is based on the use of the original The flaky -20-201111466 adhesive of Examples 1 to 5 and the flaky adhesive of Comparative Examples 1 to 3 produced by the above-described method for producing the above-mentioned flaky adhesive, a simulation of forming an aluminum wiring on a ruthenium wafer The component is formed into a 20-thickness package at 175 ° C, 7 〇 kgf / cm 2 , molding time i 2 〇 seconds through a sheet-like adhesive on a silver-bonded FR4 substrate, and will be packaged at 18 〇. . After hardening for 4 hours, the winner was used as an evaluation package. The reliability of the raw material was evaluated by immersing the obtained package in a solder bath adjusted to 260 t for 1 second, and using an ultrasonic detecting device (Hyper manufactured by Hitachi Construction Machinery Co., Ltd.) to evaluate the presence or absence of a package crack by a transmission method. The number of defective packages in Tables 2 and 3 indicates that the number of packages having cracks in the package was evaluated, and the ratio of defective packages indicates the ratio (%) of the number of defective packages in the 20 evaluation packages. <Evaluation of reliability of deteriorated material> The evaluation of the reliability of the deteriorated material was carried out by using a preparation material which was treated under the conditions of 3 ° C and 85% RH for 168 hours, and was produced by the above-described method for producing a sheet-like adhesive. The flaky adhesives of Examples i to 5 and the flaky adhesives of Comparative Examples 1 to 3 were evaluated in the same manner as the evaluation of the reliability of the above-mentioned raw materials. <Evaluation of reliability after deterioration of the flaky adhesive> The evaluation of the reliability after deterioration of the flaky adhesive was carried out using Examples 1 to 5 which were produced by the method for producing the above-mentioned flaky adhesive using the original preparation material and the material. The flaky adhesives of Comparative Examples 1 to 3 and the flaky adhesives of Comparative Examples 1 to 3 were treated under the conditions of 3 (TC, 85% RH for 67 hours), and evaluated in the same manner as the evaluation of the reliability of the above-mentioned materials. 21 - 201111466 As shown in Table 2, the encapsulation of the flaky adhesives of Examples 1 to 5 was carried out using a chelating agent-modified epoxy resin, and the chelating agent-modified epoxy resin was hardened with respect to 1% by mass. In the evaluation of the reliability of the raw material, the evaluation of the reliability of the deteriorated material, and the reliability of the deterioration of the flaky adhesive, the evaluation of the ratio of the resin component (epoxy resin to the phenol resin) is 1% by mass or less. Good results were obtained without encapsulation cracks. The encapsulation ratio of the decane coupling agent to 100 parts by mass of other components was used in the encapsulation of the flaky adhesive of Example 3, although the decane coupling agent was contained. 1. 1 part by mass, in the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the flaky adhesive, there was no effect due to deterioration of the decane coupling agent, and good results were obtained. As shown in Table 3, In the encapsulation of the flaky adhesive of Comparative Example 1, since the epoxy resin was not modified by using a chelating agent, the adhesive force (adhesion) of the flaky adhesive 12 was inferior, and in the evaluation of the reliability of the raw material, 35 % was obtained. As a result of the occurrence of cracks in the package, in the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the flaky adhesive, a result of cracking occurred in 35% of the package and 40% of the package, respectively, that is, a comparative example was used. Since the flaky adhesive is not modified by the chelating agent, the adhesive force (adhesion) of the flaky adhesive 12 is poor, and the reliability of the raw material is deteriorated, and the reliability of the deteriorated material and the deterioration of the flaky adhesive are reliable. Poorness of the crucible. The encapsulation of the flaky adhesive of Comparative Example 2, although the chelating agent was used to modify the epoxy resin, the chelating agent was modified in the hardened resin component. The content of the oxy-resin component is 5% by mass, and the adhesion of the flaky adhesive 12 (adhesion) is inferior to the above-described predetermined range of 10% by mass or more in the range of 201111466. In the evaluation of the reliability of the raw material, 30 is obtained. The results of cracking occurred in % of the package. In addition, in the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the flaky adhesive, the result of cracking in 25% of the package and 30% of the package was obtained. In the encapsulation of the flaky adhesive of Example 2, the chelating agent-modified epoxy resin is used, but the content of the chelating agent-modified epoxy resin component in the cured resin component is 5% by weight, and the above-described predetermined content is 10% by mass or more. Outside the range, the adhesive force (adhesion) of the sheet-like adhesive 12 is inferior, and the reliability of the raw material, the reliability of the deteriorated material, and the reliability of the deterioration of the sheet-like adhesive are poor. In addition, since the epoxy resin is modified by the chelating agent, the flaky adhesive which is deteriorated during the storage time and the flaky adhesive which has been produced is ooze out after the storage time elapses, and the like, is deteriorated. The reliability and reliability of the sheet-like adhesive after deterioration are not lowered as compared with the reliability of the raw material. In the encapsulation of the flaky adhesive of Comparative Example 3, the chelating agent-modified epoxy resin was used, but since the mixing ratio of the decane coupling agent was 〇·3 parts by mass, the encapsulation did not occur in the evaluation of the reliability of the raw material. crack. However, the deterioration or exudation of the material of the sand compound coupling agent causes the adhesion of the flaky adhesive 12 (the dense force) to be lowered, and in the evaluation of the reliability of the deteriorated material and the evaluation of the reliability after deterioration of the flaky adhesive, respectively Cracks occurred in the package of 30% and 20% of the package, and the reliability of the deteriorated material and the reliability after deterioration of the sheet-like adhesive were poor. In addition, the blending ratio of the acrylic resin of Example 1 was 280 parts by weight and 120 parts by weight, respectively, and a sheet of the sheet-23-201111466 adhesive was produced in the same manner as in Example 1, and the reliability and deterioration of the raw material reliability were respectively performed. Evaluation of material reliability and evaluation of reliability after deterioration of flaky adhesive. When the blending ratio of the acrylic resin polymer is 280 parts by weight, the adhesive strength is lowered, so that the number of defective packages is one in the evaluation of the reliability of the raw material. Further, when the proportion of the acrylic resin polymer is less than 120 parts by weight, the amount of curing shrinkage increases. Therefore, in the evaluation of the reliability of the raw material, the number of defective packages is two. However, both of them used a predetermined amount of a chelating agent to modify the epoxy group instead of the decane coupling agent, so that no deterioration in material or deterioration of the sheet-like adhesive caused an increase in poor packaging over the years. As a result of the results shown in Tables 2 and 3, it is understood that the adhesion of the sheet-like adhesive 12 can be improved by containing the chelating agent-modified epoxy resin in an amount of 1% by mass or more in the cured resin component. Further, even if the adhesive film 20 is formed by using a blending material (flaky adhesive composition) of the sheet-like adhesive 12 stored in a strict environment, the adhesive force of the sheet-like adhesive 12 is not lowered, and the storage of the preparation material is easy. Further, after the adhesive film 20 is stored in a strict environment, the adhesive force of the sheet-like adhesive 12 is not lowered. The storage of the adhesive film 20 produced is easy. In other words, it is possible to produce the adhesive film 20 which is excellent in the adhesive force of the sheet-like adhesive 12 and which is easy to store the preparation material and has high production efficiency, and is also easy to store the adhesive film 20. In addition, the "wafer processing tape 10 is produced by using the adhesive film 20 of the above-described embodiment", so that it is possible to produce a wafer processing tape having excellent adhesion of the sheet-like adhesive 12 and easy storage of the preparation material. 10. The storage of the wafer processing tape 10 is also easy. [Brief Description of the Drawings] Fig. 1 is a cross-sectional view showing an adhesive film using the sheet-like adhesive 12 according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a tape for wafer processing according to an embodiment of the invention. [Description of main component symbols] 1 〇 : Tape for wafer processing 1 1 : Release film 1 2 : Flake adhesive 1 3 : Adhesive film 13a : Substrate film 1 3 b : Adhesive layer 20 : Adhesive film
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