201243902 六、發明說明： •【發明所屬之技術領域】 • 本發明係關於一種晶圓加工用帶。 【先前技術】 於半導體裝置之製造步驟中，係實施如下步驟：將石夕 晶圓切割（dicing )成晶片單元之步驟、拾取經切割之半導 體元件（晶片）之步驟、進而將拾取之晶片接合（安裝） 於導線框架或封裝基板等步驟。上述半導體裝置之製造步 驟所使用之晶圓加工用帶，近年來已知有於支撐基材上依 序形成有黏著劑層與接著劑層之切割黏晶片（例如參照專 利文獻1 )。 於如此在基材上依序形成有黏著劑層與接著劑層之晶 圓加工用帶中，自製造至使用之期間，黏著劑層與接著: 層接觸之時間必然會變長，因此於使用前黏著劑層與接著 劑層會發生融合，而於拾取經單片化之附有接著劑層之半 導體元件的步驟中，存在無法順利地剝離黏著劑層與接 劑層之問題。 ^ 因此，解決此種問題之晶圓加工用帶，已知有藉由在 黏著劑層與接著劑層之間設置剝離層，而可容易地將經單 片化之附有接著劑層的半導體元件自黏著劑層剝離（例如 參照專利文獻2)。又，已知有一種藉由控制硬化前之 劑層的表面自由台t 由此而不僅有助於自黏著劑層之剝離，且 對被接著物之接荖wi田 者丨生亦優異的晶圓加工用帶（參照專利文 201243902 [專利文獻丨]日本特開昭60- 57642號公報 [專利文獻2]日本特開2〇〇5 _ 277383號公報 [專利文獻3]日本特開2008- 244463號公報 【發明内容】 此種晶圓加工用帶被使用於以下所示之步驟。 (1)依序積層支撐基材、黏著劑層及接著劑層，形成 晶圓加工用帶之步驟、 (2 )將曰s圓加工用帶之接著劑層貼合於矽晶圓背面之 步驟、 (3 )在形成於晶圓加工用帶之支撐基材上的黏著劑層 貼附晶圓壞之步驟、 (4)將上述矽晶圓切割成半導體元件（晶片）之切割 步驟、 ()將附有接著劑層之半導體元件 取出之拾取步驟、及 ⑷將半導體元件接著於如導線㈣之附有配㈣ 部連接用配線構件或其他半導體元件之晶粒接合步驟。 因此藉由aa粒接合步驟而與被接著物接觸之接著 層之面成為與黏著劑層貼…次後剝離之面，其表面 由能發生變化，因而存在如 ^ 下問喊.即使控制單獨使用 者劑層時之表面自由能，古 此有時亦無法發揮充分之接著性 因此’本發明之課題在 於知供一種晶圓加工用帶， 日曰圓加工用帶具有即使是盥 疋與黏者劑層貼合過1次後剝離 面’亦具有充分之接著性的接著劑層。201243902 VI. Description of the Invention: • [Technical Field to Which the Invention Is Ascribed] The present invention relates to a tape for wafer processing. [Prior Art] In the manufacturing step of the semiconductor device, the following steps are performed: a step of dicing a wafer unit into a wafer unit, a step of picking up the cut semiconductor element (wafer), and then bonding the picked wafer (Installation) on the lead frame or package substrate. In the wafer processing belt used in the production of the above-described semiconductor device, a dicing adhesive wafer in which an adhesive layer and an adhesive layer are sequentially formed on a support substrate has been known (for example, see Patent Document 1). In the wafer processing belt in which the adhesive layer and the adhesive layer are sequentially formed on the substrate, the time during which the adhesive layer is in contact with the layer is inevitably long during the period from manufacture to use, and thus is used. The front adhesive layer and the adhesive layer are fused, and in the step of picking up the singulated semiconductor element with the adhesive layer, there is a problem that the adhesive layer and the adhesive layer cannot be smoothly peeled off. Therefore, in the wafer processing belt which solves such a problem, it is known that a semiconductor layer which is singulated with an adhesive layer can be easily formed by providing a peeling layer between the adhesive layer and the adhesive layer. The element is peeled off from the adhesive layer (for example, refer to Patent Document 2). Further, there is known a crystal which is excellent in adhesion to the self-adhesive layer by controlling the surface free stage t of the agent layer before curing, and is excellent in the adhesion of the substrate to the substrate. In the case of a circular processing belt (see Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION This wafer processing belt is used in the following steps. (1) A step of laminating a supporting substrate, an adhesive layer, and an adhesive layer to form a wafer processing belt, 2) a step of bonding the adhesive layer of the 曰s round processing tape to the back surface of the ruthenium wafer, and (3) a step of attaching the wafer to the adhesive layer formed on the support substrate of the wafer processing tape (4) a step of cutting the germanium wafer into a semiconductor device (wafer), a step of picking up the semiconductor component with the adhesive layer removed, and (4) attaching the semiconductor component to a wire (four) (4) Die bonding of wiring members or other semiconductor elements for connection Therefore, the surface of the adhesive layer which is in contact with the adherend by the aa particle bonding step becomes the surface which is attached to the adhesive layer, and the surface of the adhesive layer is changed, and the surface thereof is changed, so that there is a problem such as control. The surface free energy in the case of a separate user agent layer may not be able to exhibit sufficient adhesion in the past. Therefore, the subject of the present invention is to provide a tape for processing a wafer, and the tape for processing a corona round has even a flaw. After the adhesive layer is applied one time, the release surface also has a sufficiently adhesive adhesive layer.
S 201243902 上述課題係藉由以下手段解決。 (1)-種晶圓加卫用帶，其特徵在於：依序積層有支 撐基材、黏著劑層及單層之接著劑 , 增上述接者劑層用於 將半導體元件壓接於附有配線之外 、 不、7卜。p連接用配線構件 他半導體元件，上述接著劑層自勒： '、 增目黏者劑層剝離之面與不和 -者劑層接觸之面的表面自由能差值41〇^/以2以下。 η (2)如⑴之晶圓加工用帶，其中，上述接著劑層 不和黏著劑層接觸之面的表面自由能為3〇mW 5〇mJ/m2 以下。 —(3) *⑴或（2)之晶圓加工用帶，其中，上述接 者劑層含有藉由含丙烯腈之懸浮聚合所生成的高分子化合 物。 ° 再者’於本發明中’所謂接著劑係指—種於製造半導 體裝置之晶粒接合步驟中用以將半導體元# (晶片）與配 線構件或其他半導體元件固定的樹脂組成物，而所謂黏著 劑則是指一種設置於支撐基材上，於製造半導體裝置之切 割步驟中通過接著劑層而貼合於矽晶圓背面，藉由其黏著 力而用於將附有接著劑之石夕晶圓暫時固定於環狀框架的樹 脂組成物》 根據本發明’可提供一種晶圓加工用帶，該晶圓加工 用帶具有即使是與黏著劑層貼合過丨次後剝離之面，亦具 有充分之接著性的接著劑層。 參照本案之圖式，並根據下述記載可更加明白本發明 之上述及其他特徵及優點。 201243902 【實施方式】 本發明之晶圓加工用帶依序積層有支撐基材、黏著劑 層及單層之接著劑層《•目1中以剖面圖示意表示本發明之 晶圓加工用帶。晶圓加工用帶10由黏著膜12與接^劑層 13構成。黏著膜12係於支撐基材12a上積層黏著劑層 而成者。於接著劑層13上疊合有離型1^丁膜u，於使θ用時 將其剝離，使矽晶圓接著於接著劑層13而使用。 (表面自由能） 於本發明中，表面自由能係設為測定水及二碘曱烷之 接觸角（液滴容量：水2"L，二碘曱烷3…讀取時：： 滴下30秒後）並根據下式算出之值。 [數1] r s= r ^ + r ' 72.8 ( 1 + cos0 H) =2 ( 21.8T ^ ) 1/2 + 2 ( 51.〇r p ) 1/2 50.8 ( 1 + cos0 *) =2( 48.5 γ ds ) 1/2+ 2 ( 2.3 r p ) >/2 y s:表面自由能 丫 ^ :表面自由能之極性成分 d * τ s :表面自由能之分散成分 0H:水相對於固體表面之接觸角 0 1 :二碘化甲烷相對於固體表面之接觸角 雖不清楚藉由控制表面自由能差值，可製造具有即使 是與黏著劑層貼合過i次後剝離之面，亦具有充分接著性 之接著劑層的晶圓加工用帶之原因，但推測如下。 藉由控制表面自由能差值，可抑制僅其中一面之接著 201243902 =得非f低的情況，而將接㈣之破壞模㈣持為凝聚 破壞。於㈣劑之破壞模式為凝聚破壞之情形時， 著劑本身沒有問題，則半導體^件之固定就不會有問 而於回焊步驟中即使產生熱應力亦具有抗性。但是，若控 制不=分而僅其中-面之接著性變得非常低時，.則接二 之破壞模式會變為界面破壞，即使接著劑之強度充分，亦 會因熱應力而使剝離持續進行，導致可靠,& ( 裂痕性）下降。 才几 關於本發明之晶圓加工用帶’接著劑層自黏著劑層剝 離之2面與不和黏著劑層接觸之面的表面自由能差值為 /m以下’較佳為〇卜5 〇mJ/m2。於表面自由能差值超 過1 OmJ/ m2之情形日夺，有可能發生成分自料劑層向接著 劑層或自接著和層向黏著劑層轉移。於前者之情形時，會 導致回焊步驟中低分子成分揮發。於後者之情形時，則會 使得接著面粗糙，而於接合步驟中因凹凸沒有被填埋，導 致產生空隙，從而造成可靠性（回焊時之抗裂痕性）下降。 接著劑層不和黏著劑層接觸之面的表面自由能較佳為 3〇mJ/m2以上且50mJ/m2以下，接著劑層自黏著劑層剝 離之面的表面自由能較佳為30mJ/m2以上且6〇mJ/m2以 下。接著劑層不和黏著劑層接觸之面的表面自由能更佳為 3〇mJ/m2以上且40mJ/m2以下，接著劑層自黏著劑層剝 離之面的表面自由能更佳為3〇mJ/ m2以上且50mJ/ m2以 下。若表面自由能未達30mJ/ m2，則潤濕性會不足，因而 有時容易形成空隙，導致可#性（回焊時之抗裂痕性）下 201243902 降。 (接著劑層） 接著劑層係預先將接著劑成膜而成者，例如可使用用 於接著劑之公知的聚醢亞胺樹脂、聚酿胺樹脂、聚轉醯亞 胺樹脂、聚醯胺醯亞胺樹脂、聚酯樹脂、聚酯醯亞胺樹脂、 本氧基樹知 '聚礙樹爿a '聚鱗硬樹脂、聚苯硫峻樹脂、聚 醚酮樹脂、氯化聚丙烯樹脂、丙烯酸樹脂、聚胺酷樹脂 (polyurethane resin)、環氧樹脂、聚丙烯醯胺樹脂、三聚氰 胺樹脂等或其混合物，就接著劑層之接著性與可靠性的觀 點而言’較佳為含有丙烯酸系共聚物、環氧樹脂，且丙稀 酸系共聚物之Tg為0°C以上40°C以下，質量平均分子量為 10萬以上100萬以下。更佳之質量平均分子量為6〇萬以上 90萬以下。 再者，質量平均分子量係藉由凝膠滲透層析（Gpc )法 並使用標準聚苯乙烯之校準曲線而測得者。 (GPC法之測定條件） 使用機器：高效液相層析儀LC~2〇AD[島津製作所股 份有限公司製造，商品名] 管柱：Shodex Column GPC KF— 805[島津製作所股份 有限公司製造，商品名]S 201243902 The above problems are solved by the following means. (1) A wafer holding belt characterized in that a support substrate, an adhesive layer and a single layer of an adhesive are sequentially laminated, and the above-mentioned carrier layer is used for crimping a semiconductor element to be attached thereto. Outside the wiring, no, 7 Bu. The p-connecting wiring member is a semiconductor element, and the adhesive layer is self-extracting: ', the surface free energy difference between the surface on which the adhesion-promoting agent layer is peeled off and the surface in contact with the non-agent layer is 41 〇 ^ / 2 or less . η (2) The wafer processing tape according to (1), wherein a surface free energy of a surface of the adhesive layer not in contact with the adhesive layer is 3 〇 mW 5 〇 mJ/m 2 or less. (3) The wafer processing belt of (1) or (2), wherein the connector layer contains a polymer compound produced by suspension polymerization of acrylonitrile. Further, in the present invention, the term "adhesive" refers to a resin composition for fixing a semiconductor element # (wafer) to a wiring member or other semiconductor element in a die bonding step of manufacturing a semiconductor device, and so-called The adhesive means that it is disposed on the supporting substrate and is adhered to the back surface of the germanium wafer through the adhesive layer in the cutting step of manufacturing the semiconductor device, and is used for bonding the adhesive with the adhesive. A resin composition in which a wafer is temporarily fixed to an annular frame. According to the present invention, a tape for processing a wafer having a surface which is peeled off even after being bonded to the adhesive layer is also provided. An adhesive layer with sufficient adhesion. The above and other features and advantages of the present invention will become more apparent from the description of the appended claims. 201243902 [Embodiment] The wafer processing belt of the present invention sequentially laminates a support substrate, an adhesive layer, and a single-layer adhesive layer. . The wafer processing tape 10 is composed of an adhesive film 12 and a bonding layer 13. The adhesive film 12 is formed by laminating an adhesive layer on the support substrate 12a. A release film 1 is laminated on the adhesive layer 13, and when θ is used, it is peeled off, and the ruthenium wafer is used next to the adhesive layer 13. (Surface free energy) In the present invention, the surface free energy is set to measure the contact angle of water and diiododecane (droplet capacity: water 2 " L, diiododecane 3... when read:: 30 seconds drop After) and calculate the value according to the following formula. [Equation 1] rs= r ^ + r ' 72.8 ( 1 + cos0 H) = 2 ( 21.8T ^ ) 1/2 + 2 ( 51.〇rp ) 1/2 50.8 ( 1 + cos0 *) = 2 ( 48.5 γ ds ) 1/2+ 2 ( 2.3 rp ) >/2 ys: surface free energy 丫 ^ : polar component of surface free energy d * τ s : dispersed component of surface free energy 0H: contact of water with respect to solid surface Angle 0 1 : The contact angle of methylene diiodide with respect to the solid surface is not clear. By controlling the difference in surface free energy, it is possible to manufacture a surface having a peeling even after being bonded to the adhesive layer i times. The reason for the wafer processing tape of the adhesive layer is presumed as follows. By controlling the difference in surface free energy, it is possible to suppress the case where only one of the layers is followed by 201243902 = the case where the f is low, and the failure mode (4) of the connection (4) is held as a cohesive failure. When the failure mode of the (four) agent is a cohesive failure, the agent itself has no problem, and the fixing of the semiconductor member is not problematic, and the thermal stress is resistant in the reflow step. However, if the control is not = and only the adhesion of the - surface becomes very low, then the failure mode of the second will become interface damage, and even if the strength of the adhesive is sufficient, the peeling will continue due to thermal stress. Carrying out, leading to reliability, & (cracking) decline. The difference in surface free energy between the two sides of the wafer processing belt with the 'adhesive layer peeled off from the adhesive layer and the surface not in contact with the adhesive layer is less than /m, which is preferably 5 〇. mJ/m2. In the case where the surface free energy difference exceeds 1 OmJ/m2, it is possible to cause the component to be transferred from the agent layer to the adhesive layer or from the adhesive layer to the adhesive layer. In the case of the former, low molecular components are volatilized during the reflow step. In the latter case, the adhesion surface is roughened, and the unevenness is not buried in the bonding step, resulting in voids, resulting in a decrease in reliability (resistance to cracking during reflow). The surface free energy of the surface of the adhesive layer not contacting the adhesive layer is preferably 3 〇 mJ/m 2 or more and 50 mJ/m 2 or less, and the surface free energy of the surface of the adhesive layer peeled off from the adhesive layer is preferably 30 mJ/m 2 . Above and below 6〇mJ/m2. The surface free energy of the surface of the adhesive layer not contacting the adhesive layer is preferably 3 〇 mJ/m 2 or more and 40 mJ/m 2 or less, and the surface free energy of the surface of the adhesive layer peeled off from the adhesive layer is preferably 3 〇 mJ. / m2 or more and 50mJ/ m2 or less. If the surface free energy is less than 30 mJ/m2, the wettability will be insufficient, and thus voids may be formed easily, resulting in a decrease in the resistance (resistance during reflow) of 201243902. (Adhesive layer) The adhesive layer is formed by filming an adhesive in advance, and for example, a known polyimide resin, a polyamine resin, a polyamidimide resin, or a polyamine can be used for the adhesive.醯imine resin, polyester resin, polyester yttrium imide resin, oxy syllium, 'polymerization tree 爿 a 'polysulfonated hard resin, polyphenyl sulphur resin, polyether ketone resin, chlorinated polypropylene resin, acrylic acid A resin, a polyurethane resin, an epoxy resin, a polypropylene decylamine resin, a melamine resin, or the like, or a mixture thereof, preferably contains an acrylic copolymer from the viewpoint of adhesion and reliability of the adhesive layer. The Tg of the material, the epoxy resin, and the acrylic copolymer is 0° C. or higher and 40° C. or lower, and the mass average molecular weight is 100,000 or more and 1,000,000 or less. A more preferable mass average molecular weight is from 60,000 to 900,000. Further, the mass average molecular weight was measured by a gel permeation chromatography (Gpc) method using a calibration curve of standard polystyrene. (Measurement conditions of the GPC method) Equipment: High-performance liquid chromatography LC~2〇AD [manufactured by Shimadzu Corporation, product name] Column: Shodex Column GPC KF-805 [Made and Yasushi Co., Ltd. name]
溶析液：氣仿 測定溫度：45°C 流量：3.0ml / min RI 檢測器：RID — 10A 8 201243902 丙烯酸系共聚物之聚合方法並無特別限定，例如可列 舉：珠狀聚合、溶液聚合、懸浮聚合等’藉由該等方法。 獲得共聚物。懸浮聚合因耐熱性優異，故而較佳， 这匕丙 烯酸系共聚物，例如可列舉Paracron w—i97C (根上工業 股份有限公司製造，商品名）。 丙嫦酸系共聚物較佳為含有丙烯腈。丙烯腈相對於丙 烯酸系共聚物，較佳為Π)〜50質量％，更佳為2〇〜4〇質量 %。藉由使丙烯腈為10質量％以上，可提高接著劑層之丁/ 而使接著性提高，但若為50質量％以上，則存心著：層 之流動性變差，接著性下降之情形。特佳為藉由含丙歸猜 之懸浮聚合所生成的丙烯酸系共聚物。 為了提高接著性’丙烯酸系共聚物亦可具有官能基。 官能基並無特別限定，例如可列舉：胺基、胺醋基（咖匕咖 g_P)、酿亞胺基、經基、幾基、環氧丙基等，其中較佳為 環，丙基。環氧丙基與作為熱硬化樹脂之環氧樹脂的反應 性良好，與赵基等相比，不易與黏著劑層反應，因此不易 引起表面自由能之變化。 接著劑層亦可含有益播措 Η…、钱填枓’但若添加量高，則流動 性下降，且接著性降低， 千 U此較佳為未達40質量％，更佳 為未達20質量％，再更佳為 再更佳為未達15質量％。又，若粒徑大， 則會於接著面之> & # a ^ μ ^ ^ 、 生凹凸，使接著性下降，因而平均 粒位杈佳為未達丨# m，更 n彳，，.^ 馮未達〇·5#«ι,再更佳為未達 0 _ 1 // m。無機填料之如仰μ τ ' 二的下限並無特別限制，彳曰實際為 0.003 /zm以上。 了』丨「利1一貫u馮 201243902 為了控制表面自由能，亦可添加石夕烧偶合劑或者欽偶 合劑或敦系接枝共聚物作為添加劑。該等添加劑較佳為含 有疏基或環氧丙基者。 接著劑層之厚度並無特別限制，通常較佳為3〜⑽从 m’更佳為5〜20"m。 (支撐基材） 支撐基材之材料，可列舉：聚乙烯、聚丙烯、乙烯— 丙烯共聚物、％ 丁烯—1、聚_4 —甲基戊烯—i、乙烯一乙 酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物'乙烯—丙烯 酸曱酯共聚物、乙烯—丙烯酸共聚物、離子聚合物等α — 烯烴之均聚物或共聚物或者該等之混合物，聚胺醋、苯乙 烯一乙烯一丁烯共聚物或戊烯系共聚物、聚醯胺—多元醇 共聚物等熱可塑性彈性體及該等之混合物。又，可為將選 自該等之群中之2種以上材料混.合而成者，亦可為該等之 單層者或將該等多層化而成者。支撐基材之厚度並無特別 限定’可適宜地設定，較佳為5〇〜2〇〇//m。 (黏著劑層） 黏著劑層有放射線硬化型與黏著力不會因放射線照射 而發生變化之非放射線硬化型。前者容易控制黏著力，後 者可用於不允許放射線照射之裝置，因此可根據用途而適 宜選擇。於選擇放射線硬化型之情形時，較佳為適宜摻合 具有光聚合性碳一碳雙鍵之放射線聚合性化合物或光聚合 起始劑而製備。 於黏著劑層為放射線硬化型之情形時，較佳為使用硬 201243902 化後之黏著劑層與接著劑層之剝離力為〇 〇1N/25mm以上 且0.5N/25mm以下者。更佳為〇 〇1N/25mm以上且〇 /25mm以下。若剝離力未達〇 〇1N/25mm，則有自切割裝 置向拾取裝置搬送時附有接著劑層之半導體元件自黏著劑 層脫離之可此性，若超過〇 5N/ 25mm，則接著劑層變得容 易受到黏著劑層之影響，面粗#，或產生表面成分之轉移， 導致表面自由能容易變化。 於黏著劑層為非放射線硬化型之情形時，較佳為使用 黏著劑層與接著劑層之剝離力為〇.〇1N/25mm以上且〇 5n /25mm以下者。更佳為〇 〇1N/25mm以上且〇 以下。若剝離力未達0.〇lN/25mm，則有於切割時發生晶 片飛起或自切割裝置向拾取裝置搬送時附有接著劑層之半 導體元件自黏著劑層脫離之可能性，若超過〇 5N/25mm， 則接著劑層變得容易受到黏著劑層之影響，面粗糙，或發 生表面成分之轉移，導致表面自由能容易變化。 黏著劑層之厚度並無特別限制’通常較佳為5〜5〇/z m’更佳為7〜20ym。 [實施例] 以下，基於實施例進一步詳細地說明本發明，但本發 明並不限定於該等。 x <丙烯酸聚合物之製造> 首先，對各實施例及各比較例之晶圓加工用帶之接著 劑層所含之丙烯酸聚合物之製造法進行說明。 (丙烯酸聚合物（1 )) 11 201243902 於具備攪拌機之玻璃製之四口圓底燒瓶中加入水3〇〇 質1份，溶解聚乙烯醇〇. 7質量份作為分散穩定劑，一面利 用攪拌翼以30〇rpm進行攪拌，一面一併投入由丙烯酸乙酯 6〇質量份、丙烯酸丁酯5質量份、曱基丙烯酸環氧丙基酯 1 5質量份、丙烯腈20質量份所構成之單體混合物與作為聚 合起始劑之Ν，Ν·—偶氮二異丁腈i質量份，而製作懸浮液。 於繼續授拌下將反應體系内升溫至6 8 °C，並固定地保 持4小時而使其反應。其後，冷卻至室溫（約25。〇)。繼而， 將反應物進行固液分離，並用水充分地清洗後，使用乾燥 機於70°C乾燥1 2小時，接著加入2 — 丁酮並以固形物成分 成為1 5%之方式進行調整，而獲得丙烯酸聚合物（1 )。根 據摻合比所計·算出之Tg為3°C。該聚合物之藉由凝膠滲透 層析法（Gel Permeation Chromatography : GPC )測得之質 量平均分子量為95萬，分散度為3.5。 (丙烯酸聚合物（2)) 除設為丙烯酸乙酯60質量份、丙烯酸丁酯5質量份、 甲基丙烯酸環氧丙基酯6質量份、丙烯腈29質量份以外， 藉由與丙烯酸聚合物（1 )相同之製造法製作丙烯酸聚合物 (2 )。根據摻合比所計算出之Tg為7°C。該聚合物之藉由 凝膠滲透層析法測得之質量平均分子量為60萬，分散度為 3·4 〇 (丙烯酸聚合物（3 )) 除設為丙烯酸乙酯34質量份 '丙烯酸丁酯15質量份、 甲基丙烯酸環氧丙基酯2質量份、丙烯腈49質量份以外，Eluent: gas sampling temperature: 45° C. flow rate: 3.0 ml / min RI detector: RID — 10A 8 201243902 The polymerization method of the acrylic copolymer is not particularly limited, and examples thereof include bead polymerization and solution polymerization. Suspension polymerization, etc. 'by these methods. A copolymer was obtained. The suspension polymerization is preferred because it is excellent in heat resistance. For example, Paracron w-i97C (trade name, manufactured by Kokusai Kogyo Co., Ltd.) is used. The propionic acid-based copolymer preferably contains acrylonitrile. The acrylonitrile is preferably Π) to 50% by mass, more preferably 2 Å to 4% by mass, based on the acrylic copolymer. When the amount of the acrylonitrile is 10% by mass or more, the adhesion of the adhesive layer can be improved, and the adhesion can be improved. However, if the content is 50% by mass or more, the fluidity of the layer is deteriorated and the adhesion is lowered. Particularly preferred is an acrylic copolymer produced by suspension polymerization of a polypropylene. In order to improve the adhesion, the acrylic copolymer may have a functional group. The functional group is not particularly limited, and examples thereof include an amine group, an amine acetonate (glycol g_P), a brewed imino group, a trans group, a benzyl group, a glycidyl group and the like. Among them, a ring and a propyl group are preferred. The epoxy propylene has good reactivity with the epoxy resin as a thermosetting resin, and is less likely to react with the adhesive layer than Zhao et al., so that it is difficult to cause a change in surface free energy. Then, the agent layer may also contain a benefiting device... and the money is filled in. However, if the amount of addition is high, the fluidity is lowered, and the adhesion is lowered, and the amount of the UU is preferably less than 40% by mass, more preferably less than 20%. % by mass, and even more preferably less than 15% by mass. Further, when the particle diameter is large, the adhesion is caused by >&# a ^ μ ^ ^ , and the adhesion is lowered, so that the average grain position is preferably less than #m, more n彳, .^ 冯未达〇·5#«ι, and even better is less than 0 _ 1 // m. The lower limit of the inorganic filler such as the elevation μ τ ' is not particularly limited, and the enthalpy is actually 0.003 /zm or more.丨 丨 利 利 一贯 一贯 冯 2012 201243902 In order to control the surface free energy, you can also add Shi Xi siu coupler or Chin coupling agent or Dun-graft copolymer as an additive. These additives preferably contain a base or epoxy The thickness of the subsequent layer is not particularly limited, and is usually preferably from 3 to 10, more preferably from 5' to 20 m. (Supporting substrate) The material of the supporting substrate may, for example, be polyethylene. Polypropylene, ethylene-propylene copolymer, % butene-1, poly-4-methylpentene-i, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer ethylene-acrylic acid acrylate copolymer, a homopolymer or copolymer of an α-olefin such as an ethylene-acrylic acid copolymer or an ionic polymer or a mixture thereof, a polyamine vinegar, a styrene-ethylene-butene copolymer or a pentene copolymer, and a polyamine- a thermoplastic elastomer such as a polyol copolymer, or a mixture thereof, which may be a mixture of two or more materials selected from the group, or may be a single layer or These layers are multi-layered. The thickness of the support substrate is not The thickness of the adhesive layer is preferably 5 〇 to 2 〇〇 / / m. (Adhesive layer) The adhesive layer has a radiation hardening type and a non-radiation-hardening type in which the adhesion does not change due to radiation. The former is easy to control the adhesion, and the latter can be used for a device that does not allow radiation to be irradiated, and therefore can be appropriately selected depending on the application. In the case of selecting a radiation hardening type, it is preferable to suitably mix the radiation having a photopolymerizable carbon-carbon double bond. It is prepared by using a polymerizable compound or a photopolymerization initiator. When the adhesive layer is a radiation-curable type, it is preferable to use a peeling force of 黏1N/25 mm or more between the adhesive layer and the adhesive layer after hard 201243902. And 0.5N/25mm or less, more preferably 〇〇1N/25mm or more and 〇/25mm or less. If the peeling force is less than N1N/25mm, there is an adhesive layer attached to the pick-up device when the self-cutting device is transported to the pick-up device. If the semiconductor element is detached from the adhesive layer, if it exceeds 〇5N/25mm, the adhesive layer becomes susceptible to the influence of the adhesive layer, the surface is rough, or the surface component is transferred, resulting in a surface self-conduction. When the adhesive layer is a non-radiation-hardening type, it is preferable to use a peeling force of the adhesive layer and the adhesive layer to be 〇1N/25 mm or more and 〇5n /25 mm or less. More preferably 〇〇1N/25mm or more and 〇 below. If the peeling force is less than 〇lN/25mm, there is a semiconductor element that adheres to the adhesive layer when the wafer is flying during cutting or when the self-cutting device is transported to the pick-up device. If the possibility of the agent layer being detached exceeds 〇5N/25mm, the adhesive layer becomes susceptible to the influence of the adhesive layer, the surface is rough, or the surface component is transferred, and the surface free energy is easily changed. The thickness of the adhesive layer There is no particular limitation 'usually preferably 5 to 5 Å/z m' is more preferably 7 to 20 ym. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. x <Production of Acrylic Polymer> First, a method for producing an acrylic polymer contained in the adhesive layer of the wafer processing belt of each of the examples and the comparative examples will be described. (Acrylic polymer (1)) 11 201243902 1 part of water was added to a four-neck round bottom flask equipped with a stirrer to dissolve polyvinyl hydrazine. 7 parts by mass was used as a dispersion stabilizer, and a stirring blade was used. The mixture was stirred at 30 rpm, and a monomer composed of 6 parts by mass of ethyl acrylate, 5 parts by mass of butyl acrylate, 15 parts by mass of glycidyl methacrylate, and 20 parts by mass of acrylonitrile was charged. The mixture was mixed with i.times.-azobisisobutyronitrile as a polymerization initiator to prepare a suspension. The temperature inside the reaction system was raised to 6 8 ° C under continuous mixing, and allowed to react for 4 hours. Thereafter, it was cooled to room temperature (about 25 Torr). Then, the reactant was subjected to solid-liquid separation, and sufficiently washed with water, and then dried at 70 ° C for 1 hour using a dryer, followed by the addition of 2-butanone and adjusted so that the solid content became 15%. An acrylic polymer (1) was obtained. The Tg calculated based on the blending ratio was 3 °C. The polymer had a mass average molecular weight of 950,000 and a degree of dispersion of 3.5 by gel permeation chromatography (GPC). (Acrylic polymer (2)) In addition to 60 parts by mass of ethyl acrylate, 5 parts by mass of butyl acrylate, 6 parts by mass of glycidyl methacrylate, and 29 parts by mass of acrylonitrile, by using an acrylic polymer (1) An acrylic polymer (2) was produced by the same production method. The Tg calculated from the blend ratio was 7 °C. The polymer has a mass average molecular weight of 600,000 by gel permeation chromatography and a dispersion of 3·4 〇 (acrylic polymer (3)), except for ethyl acrylate 34 parts by mass of butyl acrylate. 15 parts by mass, 2 parts by mass of glycidyl methacrylate, and 49 parts by mass of acrylonitrile.
S 201243902 藉由與丙烯酸聚合物（丨）相同之製造法製作丙烯酸聚合物 (3 )。根據摻合比所計算出之τ g為21°C。該聚合物之藉由 凝膠滲透層析法測得之質量平均分子量為12萬，分散度為 2.3。 (丙烯酸聚合物（4)) 除設為丙稀酸乙酯43質量份、丙烯酸丁酯15質量份、 甲基丙烯酸環氧丙基酯5質量份、两烯腈37質量份以外， 藉由與丙烯酸聚合物（1)相同之製造法製作丙烯酸聚合物 (4 )。根據摻合比所計算出之Tg為12°C。該聚合物之藉由 凝膠滲透層析法測得之質量平均分子量為70萬，分散度為 3'6 〇 (丙烯酸聚合物（5)) 除設為丙烯酸乙酯65質量份、丙烯酸丁酯23質量份、 甲基丙烯酸環氧丙基酯2質量份、丙烯腈1〇質量份以外， 藉由與丙烯酸聚合物（1)相同之製造法製作丙烯酸聚合物 (5 )。根據摻合比所計算出之Tg為一22°C。該聚合物之藉 由凝膠滲透層析法測得之質量平均分子量為40萬，分散度 為 3 · 8 〇 (丙烯酸聚合物（6)) 於具備混合機及冷卻器之反應器中加入丙烯酸乙酯6 0 質量份、丙烯酸丁酯5質量份、曱基丙烯酸環氧丙基酯i 6 質$份、丙烯腈19質量份’並加熱至85〇c，於其中添加2 —丁酮2質量份、過氧化苯曱酸第三丁酯〇.〇5質量份後保 溫8小時’冷卻後加入甲醇使聚合物沈澱並去除上清液， 201243902 乾燥殘留於聚合物中之甲醇，桩坌 r ^接者加入2 — 丁酮並以固形物 成为成為1 5 %之方式逸；^千烟敕 Λ,) 、琨仃5周整，而製作丙烯酸聚合物（6 )。S 201243902 An acrylic polymer (3) was produced by the same manufacturing method as the acrylic polymer (丨). The τ g calculated from the blend ratio was 21 °C. The polymer had a mass average molecular weight of 120,000 and a degree of dispersion of 2.3 by gel permeation chromatography. (Acrylic polymer (4)): In addition to 43 parts by mass of ethyl acrylate, 15 parts by mass of butyl acrylate, 5 parts by mass of glycidyl methacrylate, and 37 parts by mass of diennitrile, The acrylic polymer (4) was produced by the same method as the acrylic polymer (1). The Tg calculated from the blend ratio was 12 °C. The polymer has a mass average molecular weight of 700,000 as measured by gel permeation chromatography, and a dispersity of 3'6 〇 (acrylic polymer (5)), except for 65 parts by mass of ethyl acrylate, butyl acrylate. An acrylic polymer (5) was produced by the same production method as the acrylic polymer (1), except for 23 parts by mass, 2 parts by mass of glycidyl methacrylate, and 1 part by mass of acrylonitrile. The Tg calculated from the blend ratio was a 22 ° C. The polymer has a mass average molecular weight of 400,000 by gel permeation chromatography and a dispersion of 3 · 8 〇 (acrylic polymer (6)). Acrylic acid is added to a reactor equipped with a mixer and a cooler. 6 parts by mass of ethyl ester, 5 parts by mass of butyl acrylate, 50 parts by weight of glycidyl methacrylate i 6 , 19 parts by mass of acrylonitrile and heated to 85 〇c, to which 2-butanone 2 mass was added Part, 5 parts by weight of benzoic acid benzoate 〇. 保温 5 parts by mass and then kept for 8 hours. After cooling, methanol was added to precipitate the polymer and the supernatant was removed. 201243902 The methanol remaining in the polymer was dried, and the pile 坌r ^ The initiator was added with 2-butanone and the acrylic polymer (6) was prepared by solidification into a form of 15%.
根據摻合比所計算出之為代。該聚合物之藉由凝膠渗 透層析法測得之質量平均分子量為5()萬，分散度為HI 再者，各丙烯酸聚合物（1 )〜（ 量係藉由凝膠滲透層析（GPC)法並使 準曲線而測定。 6)之質量平均分子 用標準聚苯乙烯之校 〈接著劑層之製造> (接著劑層（1 )) 相對於上述丙烯酸聚合物（1) 1〇〇質量份，添加甲酚 ㈣清漆型環氧樹月旨（環氧當* 197,分子4 1200,軟化 點70 C ) 25質量份、二甲苯酚醛清漆樹脂（羥基當量1 ， 軟化點80。〇 6〇質量份、作為填充材之平均粒徑〇崩 之二氧化矽填料20質量份，而獲得熱硬化性接著劑組成 物。將該接著劑組成物塗佈於形成離型膜之ρΕτ膜，於12〇 °C加熱乾燥1〇分鐘，形成乾燥後之厚度為2〇ym2B階段 狀態的塗膜，並獲得PET膜/接著劑層（丨）/ pET膜之積 層體。 再者，PET膜係使用經聚石夕氧離型處理之pET膜（帝 人.Purex S—314 (商品名），厚度 25/zm)。 (接著劑層（2)〜（6)) 除使用丙烯酸聚合物（2)〜（6)中之任一者代替上 述丙烯酸聚合物（i )以外，利用與接著劑層（丨）相同之 方法分別獲得接著劑層（2 )〜（6 ) » 14 201243902 <黏著膜之製造> (黏著劑層組成物（1 )) •使丙烯酸2 —乙基己酯77質量份、丙烯酸2 —羥基丙 醋23質量份聚合’於質量平均分子量為萬之丙烯酸共 聚物中加入作為硬化劑之聚異氰酸酯3質量份並混合，而 製作黏著劑層組成物（1 )。· (黏著劑層組成物（2 )) 使丙烯酸丁酯65質量份、丙烯酸2 _羥基乙酯25質量 份、丙烯酸10質量份自由基聚合，於滴加曱基丙烯酸2 一 異氰酸基乙酯並使其反應而合成之質量平均分子量為8〇萬 之丙烯酸共聚物令加入作為硬化劑之聚異氰酸酯3質量 份、作為光聚合起始劑之1 一羥基環己基_苯基酮1質量份 並混合，而製作黏著劑層組成物（2 )。 (黏著膜（1 )、（ 2 )) 以乾燥膜厚成為1 0 # m之方式將所製作之黏著劑層組 成物中之任一者塗佈於形成離型膜之PET膜，於120°C乾燥 3分鐘。藉由將塗佈於該PET膜之黏著劑層組成物轉印至作 為支撐基材之厚度100/zm的聚丙烯一氫化苯乙烯丁二烯橡 膠(Polypropylene - Hydrogenated Styrene - Butadiene Rubber)彈性體（pP : HSBR= 80 : 20 )樹脂膜上，分別製 作黏著膜（1 )、（ 2 )。Calculated based on the blend ratio. The polymer has a mass average molecular weight of 5 (50,000) by gel permeation chromatography and a dispersion of HI. Further, each of the acrylic polymers (1) to (by volume gel chromatography) The GPC) method is determined by the quasi-curve. 6) The mass average molecule is made of standard polystyrene. <Manufacture of adhesive layer> (Adhesive layer (1)) Relative to the above acrylic polymer (1) 1〇 〇质量份, added cresol (four) varnish type epoxy tree month (epoxy * 197, molecule 4 1200, softening point 70 C) 25 parts by mass, xylenol varnish resin (hydroxy equivalent 1 , softening point 80. 〇 6 parts by mass, 20 parts by mass of the cerium oxide filler which is an average particle diameter of the filler, and a thermosetting adhesive composition is obtained. The adhesive composition is applied to a ρ Ε 膜 film which forms a release film, The film was dried by heating at 12 ° C for 1 minute to form a coating film having a thickness of 2 μm 2 B after drying, and a laminate of a PET film/adhesive layer (丨)/pET film was obtained. Further, a PET film system Use pET film treated by Juxi Xi oxygen release (Teijin. Purex S-314 (trade name), thickness 25/zm) (Binder layer (2) to (6)) In addition to the use of any of the acrylic polymers (2) to (6) in place of the above acrylic polymer (i), the use of an adhesive layer (丨) The same method is used to obtain the adhesive layer (2) to (6) » 14 201243902 <Manufacturing of Adhesive Film> (Adhesive Layer Composition (1)) • Making 77 parts by mass of 2-ethylhexyl acrylate 23 parts by mass of acrylic acid 2-hydroxypropyl vinegar polymerization was added to 3 parts by mass of a polyisocyanate as a curing agent in an acrylic copolymer having a mass average molecular weight of 10,000, and mixed to prepare an adhesive layer composition (1). Agent layer composition (2)) 65 parts by mass of butyl acrylate, 25 parts by mass of 2-hydroxyethyl acrylate, and 10 parts by mass of acrylic acid were radically polymerized, and 2-isocyanatoethyl methacrylate was added dropwise thereto. The acrylic copolymer having a mass average molecular weight of 80,000, which was synthesized by the reaction, was added to 3 parts by mass of a polyisocyanate as a curing agent, and 1 part by mass of 1-hydroxycyclohexyl-phenyl ketone as a photopolymerization initiator. And make the adhesive layer composition (2). Film (1), (2)) The coated adhesive layer composition was applied to a PET film forming a release film so that the dried film thickness became 10 #m, and dried at 120 ° C. 3 minutes by transferring the adhesive layer composition applied to the PET film to a polypropylene-hydrogenated Styrene - Butadiene Rubber having a thickness of 100/zm as a supporting substrate. Adhesive films (1) and (2) were prepared on the elastomer film (pP: HSBR = 80: 20).
再者，聚丙烯（PP)係使用Japan Polychem股份有限 公司製造之Novatec FG4 (商品名），氫化苯乙烯丁二烯橡 膠（HSBR)係使用JSR股份有限公司製造之Dynaron 1320PFurther, polypropylene (PP) is Novatec FG4 (trade name) manufactured by Japan Polychem Co., Ltd., and hydrogenated styrene butadiene rubber (HSBR) is Dynaron 1320P manufactured by JSR Co., Ltd.
15 201243902 (商品名）。又，PET膜係使用經聚矽氧離型處理之pET膜 (帝人：Purex S—314 (商品名），厚度 25/Zm)。 <實施例1 > 以僅單側剝離接著劑層之PET膜且與黏著劑層接觸之 方式貼合藉由上述方式獲得之接著劑層（1 )與黏著膜（i )， 而獲得依序積層有支撐基材、黏著劑層、接著劑層、離型 膜而成的圖1所示之附有離型膜之晶圓加工用帶。將該晶 圓加工用帶作為實施例1之樣品。 <實施例2〉 使用所得之上述接著劑層（2 )與黏著膜（1 )，藉由與 實施例1相同之方法製作實施例2之晶圓加工用帶。 <實施例3 > 使用所得之上述接著劑層（3 )與黏著膜（1 )，藉由與 實施例1相同之方法製作實施例3之晶圓加工用帶。 <實施例4 > 使用所得之上述接著劑層（4 )與黏著膜（1 )，藉由與 實施例1相同之方法製作實施例4之晶圓加工用帶。 <實施例5 > 使用所付之上述接著劑層（1 )與黏著膜（2 )，藉由與 實施例1相同之方法製作實施例5之晶圓加工用帶。 <比較例1 > 使用所得之上述接著劑層（5 )與黏著膜（1 )，藉由與 實施例1相同之方法製作比較例1之晶圓加工用帶。 <比較例2 > 16 201243902 使用所得之上述接著劑層（6 )與黏著膜（1 )，藉由與 實施例1相同之方法製作比較例2之晶圓加工用帶。 對實施例1〜5及比較例1、2之晶圓加工用帶進行以 下之測定、評價。將結果示於表1。 (表面自由能） 於上述實施例、比較例之各樣品之接著劑層中，將不 與黏著劑層接觸之面設為A面，自黏著劑層剝離之面設為B 面。此時’實施例5係於剝離接著劑層前利用空氣冷卻式 向壓水銀燈（80 W/ cm，照射距離i 00mm )對黏著劑層照 射200mJ/ cm之紫外線。測定水及二峨曱炫相對於該等a 面及B面之接觸角（液滴容量：水2/zL·，二碘甲烷3/zL·， 項取時間.滴下後3〇秒），根據測得之水及二碘甲烷之接 觸角’使用幾何平均法，藉由上述計算式算出表面自由能。 (.剝離力） 幻離實施例、比較例之各樣品之接著劑層之離型膜， =用2kg之親將形狀保持帶（積水化學工業公司製造，商 印名· F0rte )貼合於剝離離型膜之接著劑層之表面，並切 成25__寬度之帶狀’而製作依序積層有支樓基材、黏著劑 ^接著蜊層及形狀保持帶而成之試驗片。利用東洋精機 ’作所（股份有限公司）製造之Strograph ( VE10 )抓取所 製作之試驗Η八#「丄 月刀成支撐基材及黏著劑層」及「接著劑層 及形狀保持帶 」之積層體，於線速300mm/min測定黏著 接I與接著劑層之間之制離力。此時，實施例5係於剝離 者州層則利用空氣冷卻式高壓水銀燈（80W/ cm，照射 17 201243902 距離100mm)對黏著劑層照射200mJ/cm2之紫外線。再者， 剝離力之單位*[N/25mmp又，分成「支撐基材及黏著劑 層」及「接著劑層及形狀保持帶」之積層體，自「支撐基 材及黏著劑層」剝離「接著劑層及形狀保持帶」之原因在 於若僅抓住接著劑層而剝離，則接著劑層會伸長。 (拾取性） 於70 C將上述實施例及比較例之各樣品之晶圓加工用 帶加熱貼合至厚度50以m之矽晶圓1〇秒後，切割成 1〇mmXl〇mm之晶片。其後，實施例5係利用空氣冷卻式高 壓水銀燈（80W/ cm，照射距離1〇cm )對黏著劑層照射 2〇〇mJ〆Cm2之紫外線。對矽晶圓中央部之50個晶片進行利 用晶粒接合機裝置（NEC Machinery製造，商品名：cps — 100FM)之拾取試驗，求出拾取晶片個數之拾取成功率。此 夺所払取之元件中，將保持自黏著劑層剝離之接著劑層 者設為拾取成功者，從而計算出拾取成功率。將其計算結 果示於表1。表i中，◎、〇、△、x之基準（拾取性之基 準）如下所述。 「◎」利用項出銷之頂出高度為0 7_、〇 5_、 0.3mm時之拾取成功率為1〇〇%。 「〇」頂出高度為〇.7mm、〇_5mm時之拾取成功率為 100% ’且頂出高度為〇.3rnm時之拾取成功率未達⑽％。 「△」頂出高度為〇.7mm時之拾取成功率為1〇〇%， 且頂出咼度為0.5mm、〇.3mm時之拾取成功率未達1〇〇%。 「X」頂出高度為〇.7mm、〇 5mm ' 〇 3min時之拾取成15 201243902 (trade name). Further, as the PET film, a pET film treated by polyfluorene ionization (People: Purex S-314 (trade name), thickness 25/Zm) was used. <Example 1> The adhesive film (1) obtained by the above-described manner and the adhesive film (i) were bonded to each other by peeling only the PET film of the adhesive layer on one side and contacting the adhesive layer. The sequence layer has a wafer processing tape with a release film as shown in FIG. 1 which supports a substrate, an adhesive layer, an adhesive layer, and a release film. This ribbon for processing a crystal was used as a sample of Example 1. <Example 2> Using the obtained adhesive layer (2) and the adhesive film (1), the wafer processing belt of Example 2 was produced in the same manner as in Example 1. <Example 3> The wafer processing belt of Example 3 was produced in the same manner as in Example 1 using the obtained adhesive layer (3) and the adhesive film (1). <Example 4> A wafer processing belt of Example 4 was produced in the same manner as in Example 1 using the obtained adhesive layer (4) and the pressure-sensitive adhesive film (1). <Example 5> A wafer processing belt of Example 5 was produced by the same method as in Example 1 using the above-mentioned adhesive layer (1) and the adhesive film (2). <Comparative Example 1> A wafer processing belt of Comparative Example 1 was produced in the same manner as in Example 1 using the obtained adhesive layer (5) and the adhesive film (1). <Comparative Example 2 > 16 201243902 A wafer processing belt of Comparative Example 2 was produced in the same manner as in Example 1 using the obtained adhesive layer (6) and the adhesive film (1). The wafer processing belts of Examples 1 to 5 and Comparative Examples 1 and 2 were subjected to the following measurement and evaluation. The results are shown in Table 1. (surface free energy) In the adhesive layer of each of the samples of the above examples and comparative examples, the surface which is not in contact with the adhesive layer is referred to as the A surface, and the surface from which the adhesive layer is peeled off is referred to as the B surface. At this time, in Example 5, ultraviolet rays of 200 mJ/cm were irradiated to the adhesive layer by means of an air-cooled pressure mercury lamp (80 W/cm, irradiation distance i 00 mm) before peeling off the adhesive layer. Measure the contact angle of water and bismuth relative to the a and B faces (droplet capacity: water 2/zL·, diiodomethane 3/zL·, item take time. 3 seconds after dripping), according to The contact angle of the measured water and diiodomethane was calculated using the geometric mean method, and the surface free energy was calculated by the above calculation formula. (. Peeling force) The release film of the adhesive layer of each of the samples of the examples and the comparative examples was bonded to the strip by a shape holding tape (manufactured by Sekisui Chemical Co., Ltd., trade name F0rte) with 2 kg of the prosthesis. The surface of the adhesive layer of the release film was cut into a strip shape of 25 mm width to prepare a test piece in which a substrate substrate, an adhesive agent, a tantalum layer and a shape-retaining tape were sequentially laminated. The test made by Strograph ( VE10 ) manufactured by Toyo Seiki Co., Ltd. ( VE10 ) was used to test the Η # # # 丄 丄 丄 丄 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着The laminate was tested for the separation force between the adhesive I and the adhesive layer at a line speed of 300 mm/min. At this time, in Example 5, the adhesive layer was irradiated with ultraviolet rays of 200 mJ/cm 2 by an air-cooled high-pressure mercury lamp (80 W/cm, irradiation 17 201243902, distance 100 mm) in the peeler state layer. In addition, the unit of the peeling force*[N/25mmp is divided into a laminated body of "support base material and adhesive layer" and "adhesive layer and shape retaining tape", and is peeled off from "support base material and adhesive layer". The reason for the subsequent layer of the agent layer and the shape retaining tape is that if the adhesive layer is peeled off only by the adhesive layer, the adhesive layer is elongated. (Pickup property) The wafer processing tapes of the respective samples of the above examples and comparative examples were heat-bonded to a wafer having a thickness of 50 m at 70 C for 1 second, and then cut into a wafer of 1 mm × 10 × mm. Thereafter, in Example 5, the adhesive layer was irradiated with ultraviolet rays of 2 〇〇mJ 〆 Cm2 by means of an air-cooled high-pressure mercury lamp (80 W/cm, irradiation distance: 1 〇 cm). A pick-up test using a die bonding machine (manufactured by NEC Machinery, trade name: cps - 100 FM) was carried out on 50 wafers at the center of the wafer to determine the picking success rate of the number of picked wafers. Among the components picked up, the adhesive layer which is kept from the adhesive layer is set as a successful pick-up, and the picking success rate is calculated. The calculation results are shown in Table 1. In Table i, the basis of ◎, 〇, △, and x (the basis for pick-up property) is as follows. The pick-up success rate of the "◎" using the item's ejection height is 0 7_, 〇 5_, and 0.3 mm is 1〇〇%. The pick-up success rate of “〇” is 〇.7mm, 〇_5mm, and the pick-up success rate is 100% ’, and the pick-up height is 〇.3rnm. The pick-up success rate is less than (10)%. The pick-up success rate of "△" when the ejection height is 〇.7mm is 1〇〇%, and the pick-up success rate is 0.5mm, and the pick-up success rate of 〇.3mm is less than 1〇〇%. "X" ejector height is 〇.7mm, 〇 5mm ' 〇 3min when picked up
18 S 201243902 功率未達100%。 (可靠性（回焊時之裂痕產生率）） 於厚度200 # m之矽晶圓之背面貼附各實施例及各比較 例之晶圓加工用帶之接著劑層，並切割成7 5mmx7 後，於溫度16(TC、壓力O.iMPa、時間1秒之條件黏著於 經鍍銀處理之導線框架上。進而，利用密封材（ke — 1000SV，Kyocera Chemical (股份有限公司）製造，商品名） 進行成形，製作20個各實施例及各比較例之樣品。 將各實施例及各比較例之密封後樣品於85C>c / 6〇%rh 之恆溫恆濕層中處理196小時後，將樣品通入以樣品表面 之最咼溫度成為260°C並持續20秒之方式設定之ir (紅外 線）回焊爐中，並藉由室溫放置進行冷卻，將上述處理重 複3次。於各實施例及各比較例中，對經過如上所述處理 之20 .個樣品觀察有無裂痕，計算出2〇個樣品中產生裂痕 之樣品的比例，將回焊時之裂痕產生率作為可靠性而示於 表1。 再者’於觀察有無裂痕時，使用超音波探査裝置 (Scanning Acoustic Tomograph : SAT)並藉由透射法觀察 各樣品，將可見剝離者均設為裂痕。 '0 19 20124390218 S 201243902 Power is less than 100%. (Reliability (rift rate at the time of reflow)) The adhesive layer of the wafer processing tape of each of the examples and the comparative examples was attached to the back surface of the wafer having a thickness of 200 #m, and was cut into 7 5 mm×7. It is adhered to the silver-plated wire frame at a temperature of 16 (TC, a pressure of O.iMPa, and a time of 1 second. Further, a sealing material (ke-1000SV, manufactured by Kyocera Chemical Co., Ltd., trade name) is used. The samples of each of the examples and the comparative examples were prepared by molding. The sealed samples of the respective examples and the comparative examples were treated in a constant temperature and humidity layer of 85 C > c / 6 % % rh for 196 hours, and then the sample was taken. The above treatment was repeated three times in an ir (infrared) reflow furnace set at a temperature at which the temperature of the sample surface became 260 ° C for 20 seconds, and was cooled by standing at room temperature. In each of the comparative examples, the presence or absence of cracks in the 20 samples processed as described above was calculated, and the ratio of the crack-producing sample in the two samples was calculated, and the crack generation rate at the time of reflow was shown as a reliability. 1. In addition, 'see if there is crack When using an ultrasonic probe means (Scanning Acoustic Tomograph: SAT) and each sample was observed by the transmission method, will be caught to release visible cracks' 019201243902.
A面：不與黏著劑接觸之面 B面··自黏著劑剝離之面 比較例1、2於拾取性方面有問題，比較例2於可靠性 方面亦較差。 相對於此，實施例1〜5於剝離力、拾取性可靠性方 :均-充分。可知本發明之晶圓加工用帶的接著劑層，即使 是與黏著劑層貼合過1次之面，亦具有充分之接著性。 雖說明本發明與其實施態樣，但只要本發明沒有特別 指定’則即使在說明本發明之任—細部中，皆非用以限定 本發明，且只要在不違反本案申請專利範圍所示之發明精 神與範圍下，應作最大範圍的解釋。 本案主張基於20 11年6月24曰於曰本提出申請之特願 141266之優先權，本發明係參照此申請案並將其内 容加入作為本說明書記載之一部份。 /、 【圖式簡單說明】 圖1，係示意性表示本發明之晶圓加工用帶的剖面圖。 【主要元件符號說明】 20 201243902 ίο 晶圓加工用帶 11 離型PET膜 12 黏著膜 12a 支撐基材 12b 黏著劑層 13 接著劑層 t t Ο 21Side A: Surface which is not in contact with the adhesive B side · Surface which peeled off from the adhesive Comparative Examples 1 and 2 have problems in pick-up property, and Comparative Example 2 is also inferior in reliability. On the other hand, in Examples 1 to 5, the peeling force and the pick-up reliability were both sufficient. It is understood that the adhesive layer of the wafer processing tape of the present invention has sufficient adhesion even when it is bonded to the adhesive layer once. It is to be understood that the invention is not intended to be limited to the details of the invention, and is not intended to limit the invention. Under the spirit and scope, the maximum scope should be explained. The present invention is based on the priority of the Japanese Patent Application No. 141,266, the entire disclosure of which is incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing a wafer processing belt of the present invention. [Main component symbol description] 20 201243902 ίο Wafer processing tape 11 Release PET film 12 Adhesive film 12a Support substrate 12b Adhesive layer 13 Adhesive layer t t Ο 21