TW201204800A

TW201204800A - Adhesive sheet for semiconductor wafer processing

Info

Publication number: TW201204800A
Application number: TW100110953A
Authority: TW
Inventors: Akira Yabuki; Shozo Yano; Yuri Tamagawa
Original assignee: Furukawa Electric Co Ltd
Priority date: 2010-03-31
Filing date: 2011-03-30
Publication date: 2012-02-01
Also published as: WO2011125683A1; KR20150001804A; CN102714151A; KR20120092694A; SG184325A1; TWI507502B

Abstract

Even when using a device that bonds a dicing sheet directly to the underside of a wafer, the disclosed adhesive sheet for semiconductor wafer processing can be easily peeled off after a dicing step is finished and can drastically reduce the adherence of contaminants. Said adhesive sheet comprises a radiotransparent resin base film and an adhesive layer formed on top of said resin base film. The adhesive layer may use a radiation-curable resin composition (I) that contains between 0.1 and 10 mass parts of a photopolymerization initiator (b), with a weight-average molecular weight less than 1,000 as measured by gel permeation chromatography calculated with polystyrene as the reference substance, per 100 mass parts of a base resin consisting primarily of a polymer (a) in which a residue, which has a (meth)acryl monomer part with a group containing a radiation-curable carbon-carbon double bond, is bonded to the main-chain repeating unit. Alternatively, the adhesive layer may use a radiation-curable resin composition (II) that contains, per 100 mass parts of a base resin: between 1 and 300 mass parts of a compound that has a weight-average molecular weight of at most 10,000, with each molecule having at least two photopolymerizable carbon-carbon double bonds; and between 0.1 and 10 mass parts of a photopolymerization initiator with a weight-average molecular weight less than 1,000 as measured by gel permeation chromatography calculated with polystyrene as the reference substance.

Description

201204800 六、發明說明：【發明所屬之技術領域】本發明係關於一種加工薄型半導體晶圓時所使用之具有放射線硬化型之黏著劑層的半導體晶圓加工用黏著片。【先前技術】先前以來，藉由以接著劑將在晶片座（Die pad)上形成有特定之電路圖案之半導體晶片加以固定，來製造半導體積體電路。此時使用之半導體晶片例如可藉由以下方法而製造0 (1) 將高純度石夕單晶切片而製成半導體晶圓後，於安晶圓表面形成1C等特定之電路圖案。 (2) 貼合保護半導體晶圓電路面之表面保護膠帶，击保護所形成之電路面後，藉由研磨機研磨該晶圓背面，相 =之厚度變薄至100〜600_左右，其後將表面保制 τρ*自電路面剝離β 貼合以㈣大於半導體晶圓之直徑之 # ^ . 將上述以研磨機研磨之晶厦貪面貼。於露出於該框之中空部分之黏著劑層。 (4 )自貼合有切割片之面 ^ ^ % X ΦΙ 相反側（即，形成有電紹之側）進仃切割而製成丰练使切^ 片’照射紫外線等放射錦使切割片之黏著劑層之黏著割片之基》^ 下降再以針將該晶片自切 W之基材膜側向上頂起而進行拾取。關於該步驟中使用之切割片會剝離之程度之黏著力，另…需有於切割加工中不於切割後之拾取時， 4 201204800 必需能夠以可容易剝離之程度之較低黏著力將半導體晶片自切割片剝離，並於晶片背面不附著以黏著劑為代表之污染物質。另一方面，近年來，由直徑300mm之大口徑之晶圓獲得厚度100//m以下之薄型半導體晶片漸成為主流。因此二如何由該薄型晶圓順利地獲得半導體晶片已成為重要課題。針對此問題之解決方法之 π你逆碩装置内進仃上述（1)〜（3)之步驟的所謂線内製造裝置、或迅速進行⑺及⑴之步驟之製造方法等（例如參考專利文獻1、2八例如於線内製造裝置中，連續地進行之曰圓背面之研磨步驟及（3) <於晶圓背面貼合切割片之：驟。因此，於線内製造裝置内，可減少半導體晶圓或半導 ::片:破損。於該裝置中，在生成晶圓背面之氧化被膜之刚貼合切割片。然而，具有先前之黏著劑層之切割片係於晶圓背面生 =化破臈後進行貼合，故而產生以下問H便於該情 ::可順利㈣，但同樣地用於線内製造利地剝離。 *且』π順於死前之製造步驟中，由於被膜後貼合切料岐在曰曰圓皮面生成氧化枝故而產生以下問題：即便將於哕衿恥時可順利剝離之且古“ 卩便將於騎形線内製造裝置由〃、黏著劑層之切割片同樣地用於 '"罝中亦無法順利剝離。[Technical Field] The present invention relates to an adhesive sheet for processing a semiconductor wafer having a radiation-curable adhesive layer used for processing a thin semiconductor wafer. [Prior Art] Conventionally, a semiconductor integrated circuit has been fabricated by fixing a semiconductor wafer having a specific circuit pattern formed on a die pad with an adhesive. The semiconductor wafer used at this time can be manufactured, for example, by the following method: (1) A high-purity Shi Xi single crystal is sliced to form a semiconductor wafer, and a specific circuit pattern such as 1C is formed on the surface of the wafer. (2) After bonding the surface protection tape of the circuit surface of the semiconductor wafer, after protecting the circuit surface formed by the protection, the back surface of the wafer is polished by a grinder, and the thickness of the phase is reduced to about 100~600_, thereafter The surface protection τρ* is peeled from the circuit surface β to (4) is larger than the diameter of the semiconductor wafer # ^. The above-mentioned crystal grinding machine is ground. Adhesive layer exposed to the hollow portion of the frame. (4) Self-adhesive surface of the cutting piece ^ ^ % X Φ Ι The opposite side (that is, the side on which the electric shovel is formed) is cut into the sputum to make a puncture, and the slab is irradiated with ultraviolet rays and the like. The base of the adhesive sheet of the adhesive layer is lowered, and the wafer is lifted up by the needle from the substrate film side of the cut W to pick up. The adhesion of the dicing sheet used in this step will be peeled off, and the other is required to be picked up after cutting. 4 201204800 It is necessary to be able to transfer the semiconductor wafer with a low adhesion which can be easily peeled off. The self-cut sheet is peeled off, and a contaminant represented by an adhesive is not attached to the back surface of the wafer. On the other hand, in recent years, thin semiconductor wafers having a thickness of 100//m or less have been obtained from a large-diameter wafer having a diameter of 300 mm. Therefore, how to successfully obtain semiconductor wafers from the thin wafer has become an important issue. A solution to the problem is a so-called in-line manufacturing apparatus in which the steps (1) to (3) are carried out, or a manufacturing method in which the steps (7) and (1) are quickly performed (for example, refer to Patent Document 1). For example, in the in-line manufacturing apparatus, the step of polishing the back surface of the wafer is continuously performed, and (3) < the step of bonding the dicing sheet to the back surface of the wafer. Therefore, in the in-line manufacturing apparatus, the reduction can be reduced. Semiconductor wafer or semi-conductor:: piece: damaged. In this device, the oxidized film on the back side of the wafer is just bonded to the dicing sheet. However, the dicing sheet with the previous adhesive layer is attached to the back side of the wafer. After the breakage, the bonding is performed, so that the following question H is generated to facilitate the situation:: It can be smoothly (4), but it is also used for the in-line manufacturing to peel off. *And π is in the manufacturing step before death, due to the film after the film The combination of the cutting material and the oxidized branch on the round leather surface has the following problems: even if it will be smoothly peeled off, it will be manufactured in the riding line. The cutting piece is also used in '" Smooth release.

又’其他解；古、土 A Μ方法之一，提出有將成形為膜狀之下述 5 201204800 接著劑預先積層於切割膠帶之黏著劑層而成的所謂切割黏晶片（dicing die bond sheet)，該接著劑係於將半導體晶片固定於晶片座上時使用。使用該切割黏晶片時，與一般之切割片同樣地貼合於晶圓背面，但亦與黏著劑層一併切割接著劑層。由於該片材貼合有接著劑層，故而膠帶整體之強度增加，片材本身具有加強薄型晶圓之強度之效果。因此可順利進行薄型晶圓之㈣。然巾，於切割結束後接著劑層會殘留於半導體晶片背面’必須將接著劑層與黏著劑層剝離。因A，採用使用特定之放射線硬化型者作為黏著劑層的片材。最近’正提高切割步驟後之放射線照射量來加决半導體晶片之製造步驟。然而，若放射線照射量增多則發熱量增多，從而產生因切割步驟後之放射線照：步驟中所產生之熱而難以剝離接著劑層與黏著劑層之問題。 [專利文獻1]日本特開2002 _ 343756號公報 [專利文獻2]日本特開2004—40114號公報【發明内容】本發明之課題在於提供一種半導體晶圓加工用黏片，其於使切割片緊密貼合於晶圓背面之裝置中，亦可切割步驟結束後容易地剝離，且可減少污染物質之附著 “又，本發明之課題在於提供一種半導體晶圓加工用者片’其藉由在黏著劑層上進—步設置有接著劑層體晶圆加工用黏著片，可於拾取步驟中容易將接黏著劑層剝離，而獲得附有接著劑層之半導體晶片。本發明人等針對上述課題進行潛心研究，結果發現 6 201204800 若使用以下任一種半導體晶圓加工用黏著片，則可分別解決上述課題： (I)使用含有以特定之放射線硬化性之丙烯酸系聚合物作為主成分之基底樹脂、及特定分子量之光聚合起始劑的放射線硬化性樹脂組成物，於基材樹脂膜上形成黏著劑層之半導體晶圓加工用黏著片；或 (Π)形成有於丙烯酸系聚合物中含有放射線聚合性化合物及特定分子量之光聚合起始劑之樹脂組成物的放射線聚合性黏著劑層之半導體晶圓加工用黏著片。本發明係基於该見解而完成者。即，本發明係提供以下半導體晶圓加工用黏著片： < 1 > 一種半導體晶圓加工用黏著片，係由放射線穿透性之基材樹脂膜與該基材樹脂膜上之黏著劑層所形成，該黏著劑層係由使用相對於（i—n基底樹脂100質量份含有 (iii)光聚合起始劑（b) 〇」〜〗〇質量份之放射線硬化性樹脂組成物之層所構成，該（i一 1)基底樹脂，其係以對於主鏈之重複單位鍵結有具有（甲基）丙烯酸系單體部的殘基之丙稀酸系聚合物⑴ 作為主成分’該（甲基）丙稀㈣單體部具有放射線硬化性碳 -碳雙鍵含有基、該（iH )光聚合起始劑（b )，其藉由凝膠渗透層析（以下稱為「GPC」）法，以聚苯乙烯作為標準物質換算之重量平均分子量未達1〇〇〇 ; <2>—種半導體晶圓加工用黏著片，係由放射線穿透性之基材樹脂膜與該基材樹脂膜上之黏著劑層所形成，該 7 201204800 黏著劑層係由使用相對於（i 一 2)丙烯酸系聚合物1 〇〇質量份含有（Π)化合物（c) 1〜300質量份、及（iii)光聚合起始劑（b )0· 1〜10質量份之放射線硬化性樹脂組成物之層所構成，該（ii)化合物（c)’其於分子内具有至少2個光聚合性碳一碳雙鍵之重量平均分子量為10,000以下該（iii )光聚合起始劑（b ) ’其藉由凝膠滲透層析（以下稱為「GPC」）法，以聚苯乙烯作為標準物質換算之重量平均分子量未達1000 ; <3>如<1>或<2>之半導體晶圓加工用黏著片，其中，上述光聚合起始劑（b)係選自由1—經基一環己基苯基一酮、2,2 —二曱氧基一丨’2 —二笨基乙烷一1 一酮、2_曱基一 1 — (4一曱硫基苯基）一 2一味啉基丙烷一1—酮、及下述通式（1)所表示之寡聚物通式（1 )Also, 'other solutions; one of the methods of the ancient and soil A ,, the so-called dicing die bond sheet which is formed by laminating the adhesive layer of the dicing tape to the following 5 201204800. The adhesive is used when the semiconductor wafer is fixed on the wafer holder. When the dicing die is used, it is bonded to the back surface of the wafer in the same manner as a general dicing sheet, but the bonding layer is also cut together with the adhesive layer. Since the sheet is bonded to the adhesive layer, the overall strength of the tape is increased, and the sheet itself has the effect of enhancing the strength of the thin wafer. Therefore, the thin wafer can be smoothly carried out (4). However, the adhesive layer remains on the back side of the semiconductor wafer after the dicing, and the adhesive layer and the adhesive layer must be peeled off. For A, a sheet using a specific radiation curing type as an adhesive layer is used. Recently, the amount of radiation irradiation after the cutting step has been increased to increase the manufacturing steps of the semiconductor wafer. However, if the amount of radiation irradiation is increased, the amount of heat generation is increased, and there is a problem that it is difficult to peel off the adhesive layer and the adhesive layer due to the heat generated in the step after the cutting step. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-40114 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2004-40114. SUMMARY OF THE INVENTION An object of the present invention is to provide a semiconductor wafer processing adhesive sheet which is used for a dicing sheet. The device can be easily adhered to the back surface of the wafer, and can be easily peeled off after the cutting step, and the adhesion of the contaminant can be reduced. Further, the object of the present invention is to provide a semiconductor wafer processing user sheet. The adhesive layer is provided with an adhesive layer for processing an adhesive layer on the adhesive layer, and the adhesive layer can be easily peeled off in the pick-up step to obtain a semiconductor wafer with an adhesive layer. The inventors of the present invention have As a result of the research, it was found that 6 201204800 can solve the above problems by using any of the following adhesive sheets for semiconductor wafer processing: (I) Using a substrate containing a specific radiation curable acrylic polymer as a main component a radiation curable resin composition of a resin and a photopolymerization initiator having a specific molecular weight, forming an adhesive layer on the base resin film An adhesive sheet for processing a conductor wafer; or a semiconductor wafer processing having a radiation polymerizable adhesive layer containing a resin composition containing a radiation polymerizable compound and a photopolymerization initiator of a specific molecular weight in an acrylic polymer; The present invention is based on the above findings. The present invention provides the following adhesive sheet for semiconductor wafer processing: <1> An adhesive sheet for semiconductor wafer processing, which is irradiated by radiation The base resin film is formed with an adhesive layer on the base resin film, and the adhesive layer is used by using (iii) a photopolymerization initiator (b) in relation to (i-n base resin 100 parts by mass). a layer of a radiation curable resin composition of the mass fraction, wherein the (i-1) base resin is bonded to a repeating unit of the main chain with a (meth)acrylic monomer moiety The acrylic polymer (1) as a main component 'the (meth) propylene (tetra) monomer portion has a radiation curable carbon-carbon double bond-containing group, and the (iH) photopolymerization initiator (b) Gel permeation layer (hereinafter referred to as "GPC") method, the weight average molecular weight in terms of polystyrene as a standard substance is less than 1 〇〇〇; <2> - an adhesive sheet for semiconductor wafer processing, which is made of radiation penetrating The base resin film is formed with an adhesive layer on the base resin film, and the adhesive layer of the 201204800 is composed of (Π) compound (c) by using 1 part by mass relative to the (i-2) acrylic polymer. 1 to 300 parts by mass, and (iii) a photopolymerization initiator (b): 0.1 to 10 parts by mass of a layer of a radiation curable resin composition, wherein (ii) the compound (c) is in a molecule The weight average molecular weight of at least two photopolymerizable carbon-carbon double bonds is 10,000 or less. (iii) Photopolymerization initiator (b) 'by gel permeation chromatography (hereinafter referred to as "GPC") method The weight average molecular weight of the semiconductor wafer processing according to <1> or <2>, wherein the photopolymerization initiator (b) is used. ) is selected from the group consisting of 1-hydroxy-cyclohexylphenyl-one, 2,2-dimethoxy ''2-diphenyl ethane-1-one ketone, 2' fluorenyl-1' (4-monothiophenyl)-2- oxalylpropane-1-one, and the following formula (1) The represented oligomer has the general formula (1)

所組成之群中之至少1種； <4>如<3>之半導體晶圓加工用黏著片，其中 8 201204800 述通式（1)所表示之寡聚物之聚合度為n= 2〜4 ; <5>如<1>、<3>或<4>之半導體晶圓加工用黏者片，其中，上述相對於主鏈之重複單位含有具有放射線聚合性碳—碳雙鍵含有丙烯酸系卩ϋ作為才冓成單位的聚合物（a)之碘值為ι〜5〇;及 <6>—種半導體晶圓加工用黏著片，其係在〈丨〉至 < 5 >中任項之半導體晶圓加工用黏著片之黏著劑層上進一步設置接著劑層。藉由本發明之半導體晶圓加工用黏著片，在用於使切割片緊密貼合於晶圓背面之裝置時，可於切割步驟結束後容易地剝離，且可明顯減少污染物質之附著。又’藉由在本發明之黏著劑層上進一步設置有接著劑層之半導體晶圓加工用黏著片，可於拾取步驟中容易將接著劑層與黏著劑層剝離’而獲得附有接著劑層之半導體晶片。本發明之上述及其他特徵及優點可適當參照隨附之圖式’根據下述記載而更為明確。【實施方式】以下’參照圖式’對本發明之較佳之半導體晶圓加工用黏著片加以說明。圖1係表示本發明之半導體晶圓加工用黏著片之較佳之-實施形態的概略剖㈣，其形成有基材樹脂冑卜且於基材樹脂膜1上形成有料劑層2。又，圖2係表示本發明之半導體晶圓加工用黏著片之較佳之另一實施形態的概略 201204800 剖面圖。於圖2中，其形成有基材樹脂膜1，且於基材樹脂膜1上形成有黏著劑層2，進而形成接著劑層3.。本發明中之黏著劑層係由下述放射線硬化性樹脂組成物所構成’該放射線硬化性樹脂組成物係：在基底樹脂中含有特定摻合量之放射線聚合性化合物，且以特定之摻合量含有特定之光聚合起始劑者。使用本發明之半導體晶圓加工用黏著片，於切割加工結束後，自下述放射線穿透性之基材樹脂膜側照射放射線，而降低黏著劑層之黏著力。藉此，可順利地拾取半導體晶片。對於如圖2所示在黏著劑層上形成有接著劑層之半導體晶圓加工用黏著片，亦同樣地自下述放射線穿透性之基材樹脂膜側照射放射線，而降低黏著劑層之黏著力。於該情形時，藉由在接著劑層與黏著劑層之界面進行剝離，可獲得附有接著劑層之半導體晶片’而可直接固定於晶片座上。圖1所示之本發明之半導體晶圓加工用黏著片即便於半導體晶圓之背面研磨結束後迅速貼合於該背面時，亦可於放射線照射後之拾取步驟中順利地剝離。研磨剛結束後之半導體晶圓表面未全面地形成自然氧化膜，成為存在未氧化狀態之活性原子之活性面。即便於該情形時，本發明之半導體晶圓加工用黏著片於放射線照射後，亦可順利地剝離’且可明顯減少由黏著劑成分引起之污染物之附著。又’圖2所示之於黏著劑層上進一步設置有接著劑層之本發明之半導體晶圓加工用黏著片不會因於切割步驟結束後之照射放射線中所產生之熱，而於黏著劑層與接著劑 10 201204800 層之剝離上產生問題。於本發明之半導體晶圓加工用片材中，黏著劑層係於下述基材樹脂獏上形成使用放射線硬化性之樹脂組成物之層本發明之半導體晶圓加工用片材係包括第1態樣及第2 態樣。於各態樣中，包括圖丨所示之態樣、及圖2所示之癌樣之半導體晶圓加工用片材。第1態樣之半導體晶圓加工用片材之黏著劑層之基底樹脂為（i — i )，其係以對於主鏈之重複單位而鍵結有包含具有放射線硬化性碳一碳雙鍵含有基之（甲基）丙烯酸系單體部的殘基之丙烯酸系聚合物 (a )作為主成分者。 (第1態樣之半導體晶圓加工用片材之黏著劑層之基底樹脂）第1態樣之半導體晶圓加工用片材之黏著劑層中所使用的放射線硬化性樹脂組成物之基底樹脂係以對於主鏈之重複單位而鍵結有包含具有放射線硬化性碳—碳雙鍵含有基之（甲基）丙烯酸系單體部的殘基之丙烯酸系聚合物（a) 作為主成分者。於本發明中，所謂以聚合物（a )作為主成分’係指基底樹脂中之含有比例為50〜丨0〇質量％。又，於本發明中’（甲基）丙烯酸系單體係指包括丙烯酸系單體及曱基丙烯酸系單體之兩者。上述5^合物（a )為可以任意方式而製造者。例如，上述聚合物（a)，可列舉使下述丙烯酸系共聚物及/或曱基丙烯酸系共聚物（al )與化合物（a2 )進行反應而獲得，丙稀酸系共聚物及/或曱基丙烯酸系共聚物（al )係：對於主鏈 11 201204800 之重複單位具有放射線硬化性碳—碳雙鍵，且具有官能基者；化合物（a2 )係：具有可與該官能基反應之官能基者。又，亦可以具有官能基之丙烯酸系共聚物及/或甲基丙稀酸系共聚物為（al·)，以具有放射線硬化性碳—碳雙鍵且具有可與（al’）之官能基反應之官能基的化合物為（a2,)，使該等進行反應而形成聚合物（a)。上述對於主鏈之重複單位具有放射線硬化性碳—碳雙鍵’且具有官能基之丙烯酸系共聚物及//或甲基丙烯酸系共聚物（al )例如可使下述（al _ 1 )與（al _ 2 )進行共聚而獲得，（al — 1 )係：具有放射線硬化性碳—碳雙鍵之丙烯酸烷基酯及/或甲基丙烯酸烷基酯等單體（al_ i)，（al_2) 係：具有官能基之單體（al — 2)。單體（al — 1 )例如可列舉：烷基酯之烷基碳數為6〜 12之（甲基）丙烯酸烷基酯（例如丙烯酸己酯、丙稀酸正辛酯、丙烯酸異辛酯、丙烯酸一2 —乙基己酯、丙烯酸十二烷基酯、丙烯酸癸酯）。又，可列舉：烷基酯之烷基碳數為5 以下之（甲基）丙烯酸烧基酯（例如丙稀酸戊酯、丙稀酸正丁酯、丙烯酸異丁酯、丙烯酸乙酯、丙烯酸曱酯、或與該等相同之曱基丙烯酸酯等）。單體（al — 1)，存在使用烷基酯之烷基碳數越大之（曱基）丙烯酸烷基酯，則玻璃轉移點越低之傾向。因此，藉由適§選擇單體（al_l)之烷基酯之烷基碳數，可獲得具有所需之玻璃轉移點之聚合物（a )。又’除玻璃轉移點以外’亦可為提高與其他成分之相 12 201204800 '合丨生或各種性能，而於（a 1 — 1 )添加乙酸乙烯酯、苯乙烯、丙稀猜等具有碳—碳雙鍵之低分子化合物而獲得聚合物 (a )。咸等低分子化合物之摻合量較佳為設為單體（al _ j ) 之5質量％以下。單體（al ~ 2 )所具有之官能基，可列舉：羧基、羥基、胺基、環狀酸酐基、環氧基、異氰酸酯基等。單體（al — 2) 之具體例，例如可列舉：丙烯酸、曱基丙烯酸、桂皮酸、衣康酸、反丁烯二酸'鄰苯二曱酸、丙烯酸2—羥基烷基酯類、甲基丙烯酸2 —羥基烷基酯類、二醇單丙烯酸酯類、二醇單曱基丙烯酸醋類、N—羥甲基丙烯醯胺、N —羥甲基甲基丙烯醯胺、烯丙醇、丙烯酸N_烷基胺基乙酯類、甲基丙烯酸N~烷基胺基乙酯類、丙烯醯胺類'甲基丙烯醯胺類、 J丨員丁烯一g文酐、衣康酸酐、反丁烯二酸酐、鄰苯二曱酸酐、丙稀酸環氧丙基S旨、甲基丙稀酸環氧丙基醋、烯丙基環氧丙基醚、及將聚異氰酸酯化合物之異氰酸酯基之一部分以具有羥基或羧基及放射線硬化性碳一碳雙鍵之單體進行胺 S旨化而成者等。於上述（a2)之官能基為羧基或環狀酸酐基之情形時， (a 1 )所具有之官能基，例如可列舉羥基、環氧基、異氛酸酉曰基等又，於（a2 )之官能基為羥基之情形時，（a丨）所具有之官能基’例如可列舉環狀㈣基、異氰酸醋基等。於（a2 )之官能基為胺基之情形時，（以）所具有之官能基，可列舉環氧基、異氰酸酯基等。於（a2)之官能基為環氧基之隋形時，（al )所具有之官能基，例如可列舉敌基、環狀 13 201204800 酸酐基、胺基等。同者具體例可列舉與單體（al — 2)之具體例中所列舉者相於U1)與U2)之反應中，藉由殘留未反應之官能基，可將酸值或羥基值等適當設定於較佳為如下所内。祀固對於主鏈之重複單位含有具有放身十、線聚合性碳〜碳雙鍵含有基之丙烯酸系單體作為構成單位的聚合物（a)可^ 由在各種溶劑中進行溶液聚合而獲得。進行溶液聚合之時之有機溶劑，可使用酮系、酯系、醇系 '芳香族系者。通常較佳為使用為丙烯酸系聚合物之較佳溶劑，且沸點為〜120°C之溶劑。例如，可使用甲苯、乙酸乙酯、異丙醇、苯、甲赛路蘇、乙赛路蘇、丙酮、甲基乙基酮等。聚合起始劑，可使用α，α ’ 一偶氮雙異丁腈等偶氮雙系、過氧化苯甲醢專有機過氧化物系等自由基產生劑。此時，視需要可併用觸媒、聚合抑制劑，藉由調整聚合溫度及聚合時間，可獲得所需分子量之聚合物（a )。又，關於調整分子量，較佳為使用硫醇、四氣化碳系溶劑。再者，聚合物（a)之合成並非限疋於溶液聚合，亦可使用整體聚合、懸浮聚合等其他方法。於本發明中，對於主鏈之重複單位而鍵結有包含具有放射線硬化性碳一碳雙鍵含有基之（甲基）丙烯酸系單體部的殘基之丙烯酸系聚合物（a)之重量平均分子量較佳為3〇萬〜1〇〇萬左右。當分子量未達30萬時’存在由放射線照 201204800 蒋2凝聚力減小’於切割晶圓時，容易產生元件之偏二圖二識別變得困難之情形。為極力防止該元件之偏移，較佳為分子量為4〇萬以上。又婪又右/刀子量超過1〇〇萬，則有可tb於合成時及塗敷時進行凝牒彳卜方了延仃/疑膠化。本發明中之聚合物 ⑴之重量平均分子量例如可利用以下方法作為以聚苯乙稀換算之重量平均分子量而求出。 (重量平均分子量之測定條件）㈣裝置：HLC — 8 120Gpc (商品名，T〇s〇h公司製造）管柱：TSK gel Super HM-H/H4000/H3000/H2000 (商品名，Tosoh公司製造）流量：〇.6ml/min 濃度：0.3質量％注入量：20 y 1 管柱溫度：40°C 展開溶劑：氣仿於本發明中’相對於主鏈之重複單位含有具有放射線聚合性碳一碳雙鍵含有基之丙烯酸系單體作為構成單位的聚合物（a)之碘值較佳為1〜50。進而較佳為2〜30，若蛾值未達1，則放射線照射後之交聯度較少，剝離力不會完全降低’因此無法充分地拾取晶片。若蛾值超過5 〇，則放射線照射後之交聯度較多，產生硬化收縮，而使晶片之拾取性下降。於上述聚合物（a)之經基值為5〜100之情形時，可藉由減少放射線照射後之黏著力而進一步降低拾取失敗之危 15 201204800 險性，故而較佳》又，聚合物（a)之酸值較佳為成為〇 5 〜3 0 〇此處，羥基值及酸值係指藉由JIS Κ 0070而測定之值。藉由將聚合物（a)之羥基值設於適當之範圍内’可使放射線照射後之黏著劑層之流動性處於適當之範圍内，從而可充分降低放射線照射後之黏著力。藉由將聚合物（a )之酸值設於適當之範圍内，可使放射線照射後之黏著劑層之流動性處於適當之範圍内’從而可滿足膠帶恢復性。使用於構成本發明之黏著劑層之放射線硬化性樹脂組成物的基底樹脂’亦可於不違背本發明之宗旨之範圍内摻合先前之材料。例如可使用天然橡膠、各種合成橡膠等橡膠系聚合物；或聚（曱基）丙烯酸烷基酯、（甲基）丙烯酸烷基酯、及（曱基）丙烯酸烷基酯與可與其共聚之其他不飽和單體之共5^物專丙稀酸系共聚物。 (第2態樣之半導體晶圓加工用片材之黏著劑層之基底樹脂）第2態樣之半導體晶圓加工用片材之黏著劑層中所使用的放射線硬化性樹脂組成物之基底樹脂為丙烯酸系聚合物。丙烯酸系聚合物，可列舉以（甲基）丙烯酸酯成分作為單體主成分（聚合物中之質量％超過50%)，使該（曱基）丙烯酸醋成分與可共聚之單體成分進行共聚而成者。於丙烯酸系聚合物中，單體主成分之（甲基）丙烯酸酯成分例如可列舉：（甲基）丙稀酸甲醋、（曱基）丙稀酸乙酿、（甲 201204800 基）丙烯酸丙酯、（曱基）丙烯酸異丙酯、（曱基）丙烯酸丁酯、 (甲基）丙烯酸異丁酯、（甲基）丙烯酸第二丁酯、（曱基）丙烯酸第三丁酯、（曱基）丙烯酸戊酯 '(曱基）丙烯酸己酯、（曱基）丙烯酸庚酯、（甲基）丙烯酸辛酯、（曱基）丙烯酸異辛酯、（甲基）丙烯酸2 —乙基己酯、（曱基）丙烯酸壬酯、（甲基）丙烯酸異壬酯、（曱基）丙烯酸癸酯、（曱基）丙烯酸異癸酯、（曱基）丙烯酸十一烷酯、（甲基）丙烯酸十二烷酯、（曱基）丙烯酸十三烷酯、（甲基）丙烯酸十四烷酯、（甲基）丙烯酸十五烷酯、（曱基）丙烯酸十六烧酯、（曱基）丙烯酸十七烷酯、（甲基）丙烯酸十八烷酯等（甲基）丙烯酸烷基酯；（甲基）丙烯酸環己酯等（曱基）丙烯酸環烷基酯；（甲基）丙烯酸苯酯等（甲基）丙烯酸芳基酯等。（曱基）丙烯酸酯可單獨使用，或組合2種以上而使用。 (硬化劑）於構成上述第1態樣及第2態樣之半導體晶圓加工用黏著片之黏著劑層的放射線硬化性樹脂組成物中，可含有聚異氰酸酯化合物、烷基醚化三聚氰胺化合物、環氧系化合物、石夕烧偶合劑等先前以來所使用之硬化劑。藉由製成摻合有硬化劑之樹脂組成物，可將初始黏著力設定為任意值。於硬化劑中，較佳為使用異氰酸酯系硬化劑。異氰酸酯系硬化劑，具體可使用多元異氰酸酯化合物，例如2,4一甲苯二異氰酸酯、2,6_甲苯二異氰酸酯、1)3 一伸二甲苯二異氰酸酯（Xylylene(JiiS〇Cyanate)、14_ 二甲苯二異氰酸酯、二苯基甲烷—4,4,一二異氰酸酯、二苯基曱烷 —2,4’一二異氰酸酯、3_曱基二苯基曱烷二異氰酸酯、六 17 201204800 亞甲基二異氰酸酯 4，4 —二異氰酸酯、胺酸異氰酸酯等。、異佛酮二異氰酸酯、二環己基曱烷— 二環己基甲烷~ 2,4, 一二異氰酸酯、離 (刀子内具有至少2個光聚合性碳一碳雙鏈之重量平均勿子量為1 〇,〇〇〇以下之化合物）第2態樣之半導體晶圓加工用片材之黏著劑層中所使用的放射線硬化性樹脂組成物含有分子内具有至少2個光聚。丨生炭碳雙鍵之重量平均分子量為1〇,〇〇〇以下之化合物（c )。亥化合物（c )，只要為藉由放射線之照射進行硬化而進仃二維網狀化者’則可無特別限制地使用。該化合物包括重量平均分子量為1〇,〇〇〇以下之寡聚物，而不包括重量平均分子量超過10,0000之高分子聚合物。為高效地進行由放射線之照射所致之黏著劑層之三維網狀化，較佳為2 子量為5，〇〇〇以下且分子内之放射線聚合性之碳〜碳雙之數量為2〜6個者。建再者’所謂本發明中之於分子内具有至少2個光聚八性碳一碳雙鍵之低分子量化合物之重量平均分子量，係於利用下述條件之GPC (凝膠滲透層析法）所測定之曰冰乂聚笨乙烯換算之重量平均分子量。 (重量平均分子量之測定條件） GPC裝置：HLC— 8120 GPC(商品名’ Tosoh公司製、生管柱：TSK- GEL G2500 HHR (商品名，Tosoh 公司製造）流量：1 ml / min 18 201204800 濃度.0.2mg/ml 注入量：100 y 1 恆溫槽溫度：4 0 °C 流動相：氣仿放射線聚合性化合物（c )，例如可列舉：三羥曱基丙烷三丙烯酸酯、四羥曱基曱烷四丙烯酸酯、新戊四醇三丙烯酸醋、新戊四醇四㈣酸醋、二新戊四料經基五丙稀酸酯、二新戊四醇六丙烯酸酯、L4— 丁二醇二丙烯酸酯、^ —己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、有機聚矽氧組成物、市售之寡酯丙烯酸酯、丙烯酸胺酯等。分子内具有至少2個光聚合性碳—碳雙鍵之重量平均分子量為10 ’ 000以下之化合物可單獨使用i種亦可併用2種以上。摻合量係相對於基底樹月旨【質量份，為^ 300質量伤。較佳為相對於基底樹脂⑽質量份，為〜2則量份’進而較佳為5〇〜15〇質量份。若該量過少，則有黏著劑層之由放射線之昭如艮之‘、.、射所致之三維網狀化變得不充分，難以將半導體晶圓加门，用黏者片自晶圓剝離，而污染晶圓之虞。若該量過多，貝J過度進行利用放射線之聚合反應，產生由放射線之昭鉍 ..a ^ ''射引起之硬化收縮。其結果’黏者劑層隨者被黏著體之矣& .^ ^ θ Μ ^ ^ 面而陷入其中，於拾取切割後之平導體日日片時變侍難以才人 —旦1夕β, 士又’若放射線聚合性化合物之量過夕，則存在難以保持差等問題。 ^黏者劑層之形狀，厚度精度變 (光聚合起始劑） 19 201204800 於構成第1態樣及第2態樣之半導體晶圓加工用黏著片之黏著劑層的放射線硬化性樹脂組成物中，使用藉由凝膠滲透層析（以下稱為「GPC」）法，以聚苯乙烯作為標準物質換算之重量平均分子量未達1〇〇〇之光聚合起始劑。於本發明中’光聚合起始劑之重量平均分子量係指利用下述條件之GPC所測定之值。 (重量平均分子量之測定條件） GPC裝置：島津製作所製造LCVP系列管柱：OligoPore 300x7.5 (商品名）（商品名， PolymerLaboratories 製造）<4> The adhesive sheet for semiconductor wafer processing of <3>, wherein 8201204800 The degree of polymerization of the oligomer represented by the general formula (1) is n=2 The adhesive sheet for semiconductor wafer processing according to <1>, <3> or <4>, wherein the repeating unit with respect to the main chain contains a radiation-polymerizable carbon-carbon The double bond contains an acrylic ruthenium as a unit (a) having an iodine value of ι 〜5 〇; and <6>-a semiconductor wafer processing adhesive sheet, which is in the range of <丨> to < 5 > Further, an adhesive layer is further provided on the adhesive layer of the adhesive sheet for semiconductor wafer processing. According to the adhesive sheet for processing a semiconductor wafer of the present invention, when the cut sheet is closely attached to the back surface of the wafer, the peeling step can be easily peeled off after the cutting step, and the adhesion of the contaminant can be remarkably reduced. Further, by using an adhesive sheet for semiconductor wafer processing in which an adhesive layer is further provided on the adhesive layer of the present invention, the adhesive layer and the adhesive layer can be easily peeled off during the pick-up step to obtain an adhesive layer. Semiconductor wafer. The above and other features and advantages of the present invention will become more apparent from the appended claims appended claims. [Embodiment] Hereinafter, a preferred adhesive sheet for semiconductor wafer processing of the present invention will be described with reference to the drawings. Fig. 1 is a cross-sectional view (four) showing a preferred embodiment of the adhesive sheet for semiconductor wafer processing of the present invention, in which a base resin is formed and a material layer 2 is formed on the base resin film 1. Further, Fig. 2 is a cross-sectional view showing a preferred embodiment of the adhesive sheet for semiconductor wafer processing of the present invention in 201204800. In Fig. 2, a base resin film 1 is formed, and an adhesive layer 2 is formed on the base resin film 1, thereby forming an adhesive layer 3. The adhesive layer in the present invention is composed of the following radiation curable resin composition. The radiation curable resin composition contains a radiation-polymerizable compound having a specific blending amount in the base resin, and is specifically blended. Amounts containing a specific photopolymerization initiator. By using the adhesive sheet for processing a semiconductor wafer of the present invention, after the end of the dicing process, the radiation is irradiated from the side of the substrate of the radiation-permeable substrate to reduce the adhesion of the adhesive layer. Thereby, the semiconductor wafer can be picked up smoothly. In the same manner as the adhesive sheet for semiconductor wafer processing in which the adhesive layer is formed on the adhesive layer as shown in FIG. 2, the radiation is irradiated from the side of the base material resin film to be irradiated, and the adhesive layer is lowered. Adhesion. In this case, by peeling off the interface between the adhesive layer and the adhesive layer, the semiconductor wafer attas with the adhesive layer can be obtained and can be directly fixed to the wafer holder. The adhesive sheet for semiconductor wafer processing of the present invention shown in Fig. 1 can be smoothly peeled off during the pick-up step after radiation irradiation even after the back surface of the semiconductor wafer is polished and adhered to the back surface. The surface of the semiconductor wafer immediately after the polishing is not completely formed with a natural oxide film, and becomes an active surface of an active atom in an unoxidized state. That is, in this case, the adhesive sheet for semiconductor wafer processing of the present invention can be smoothly peeled off after radiation irradiation, and the adhesion of contaminants caused by the adhesive component can be remarkably reduced. Further, the adhesive sheet for semiconductor wafer processing of the present invention in which the adhesive layer is further provided on the adhesive layer as shown in FIG. 2 does not cause heat generated in the irradiation radiation after the end of the dicing step, but is in the adhesive. There is a problem with the peeling of the layer and the adhesive 10 201204800 layer. In the semiconductor wafer processing sheet of the present invention, the adhesive layer is formed on the base resin enamel to form a layer using a radiation curable resin composition. The semiconductor wafer processing sheet of the present invention includes the first sheet. Aspect and second aspect. In each of the aspects, the sheet shown in Fig. 2 and the cancer-like semiconductor wafer processing sheet shown in Fig. 2 are included. The base resin of the adhesive layer of the semiconductor wafer processing sheet of the first aspect is (i - i ), which is bonded to the repeating unit of the main chain and contains a radioluble carbon-carbon double bond. The acrylic polymer (a) which is a residue of the (meth)acrylic monomer portion is used as a main component. (Base resin of the adhesive layer of the semiconductor wafer processing sheet of the first aspect) The base resin of the radiation curable resin composition used in the adhesive layer of the semiconductor wafer processing sheet of the first aspect The acrylic polymer (a) having a residue containing a (meth)acrylic monomer portion having a radiation curable carbon-carbon double bond-containing group as a main component is bonded to a repeating unit of the main chain. In the present invention, the term "polymer (a) as a main component" means that the content of the base resin is 50 to 〇0% by mass. Further, in the present invention, the '(meth)acrylic monosystem refers to both an acrylic monomer and a mercapto acrylic monomer. The above 5-based compound (a) can be produced by any means. For example, the polymer (a) may be obtained by reacting the following acrylic copolymer and/or mercaptoacrylic copolymer (al) with the compound (a2), and an acrylic copolymer and/or an anthracene. Acrylic copolymer (al) system: a compound having a radiation curable carbon-carbon double bond and having a functional group for a repeating unit of the main chain 11 201204800; and a compound (a2) having a functional group reactive with the functional group By. Further, the acrylic copolymer and/or the methyl acrylate copolymer having a functional group may be (al·), having a radiation curable carbon-carbon double bond and having a functional group capable of reacting with (al') The compound of the functional group of the reaction is (a2,), and these are reacted to form a polymer (a). The acrylic copolymer and/or the methacrylic copolymer (al ) having a radiation-curable carbon-carbon double bond in the repeating unit of the main chain and having a functional group can, for example, be as follows (al _ 1 ) (al _ 2 ) obtained by copolymerization, (al-1) is a monomer (al_i) such as an alkyl acrylate and/or an alkyl methacrylate having a radiation-curable carbon-carbon double bond, (al_2) ): a monomer having a functional group (al - 2). The monomer (al-1) may, for example, be an alkyl (meth)acrylate having an alkyl carbon number of 6 to 12 (for example, hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-Ethylhexyl acrylate, dodecyl acrylate, decyl acrylate). Further, examples thereof include a (meth)acrylic acid alkyl ester having an alkyl group having an alkyl group number of 5 or less (e.g., amyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, acrylic acid). An oxime ester, or the same thiol acrylate as described above). The monomer (al-1) has a tendency that the glass transition point is lower as the alkyl (meth) acrylate having a larger alkyl carbon number is used. Therefore, by selecting the alkyl carbon number of the alkyl ester of the monomer (al-1), the polymer (a) having the desired glass transition point can be obtained. In addition to 'except the glass transfer point' can also be used to improve the phase with other ingredients 12 201204800 'synthesis or various properties, and (a 1 - 1) add vinyl acetate, styrene, acryl, etc. with carbon - The polymer (a) is obtained by a low molecular compound of a carbon double bond. The blending amount of the low molecular compound such as salt is preferably 5% by mass or less based on the monomer (al _ j ). Examples of the functional group of the monomer (al ~ 2 ) include a carboxyl group, a hydroxyl group, an amine group, a cyclic acid anhydride group, an epoxy group, and an isocyanate group. Specific examples of the monomer (al-2) include acrylic acid, mercaptoacrylic acid, cinnamic acid, itaconic acid, fumaric acid 'phthalic acid, 2-hydroxyalkyl acrylate, and nails. 2-hydroxyalkyl acrylates, diol monoacrylates, diol monodecyl acrylates, N-methylol acrylamide, N-methylol methacrylamide, allyl alcohol, N-alkylaminoethyl acrylate, N-alkylaminoethyl methacrylate, propylene amide amine methacrylamide, J-butylene butylic acid, itaconic anhydride, Fumaric anhydride, phthalic anhydride, acrylic acid propyl propyl group, methyl propylene oxide propylene propyl acrylate, allyl epoxidized propyl ether, and isocyanate group of polyisocyanate compound A part of the monomer is a monomer having a hydroxyl group or a carboxyl group and a radiation-curable carbon-carbon double bond. In the case where the functional group of the above (a2) is a carboxyl group or a cyclic acid anhydride group, the functional group of (a1) may, for example, be a hydroxyl group, an epoxy group, a thiol group or the like, and (a2) When the functional group is a hydroxyl group, the functional group which the (a) has is, for example, a cyclic (tetra) group or an isocyanato group. When the functional group of (a2) is an amine group, the functional group which the (a) has may be an epoxy group, an isocyanate group or the like. When the functional group of (a2) is a quinone of an epoxy group, the functional group of (al) may, for example, be an ester group or a cyclic group: 201204800 an acid anhydride group or an amine group. Specific examples of the same may be mentioned in the reaction between U1) and U2) in the specific examples of the monomer (al-2), and the acid value or the hydroxyl value may be appropriately determined by leaving an unreacted functional group. It is preferably set as follows. The polymer (a) containing, as a constituent unit, an acrylic monomer having a fluorinated carbon-carbon double bond-containing group as a repeating unit of the main chain can be obtained by solution polymerization in various solvents. . As the organic solvent at the time of solution polymerization, a ketone system, an ester system or an alcohol type "aromatic system" can be used. It is usually preferred to use a solvent which is a preferred solvent for the acrylic polymer and has a boiling point of -120 °C. For example, toluene, ethyl acetate, isopropanol, benzene, methacrylate, cesetil, acetone, methyl ethyl ketone, or the like can be used. As the polymerization initiator, a radical generator such as an azo double system such as α,α '-azobisisobutyronitrile or a benzoyl peroxide-specific organic peroxide system can be used. At this time, a polymer (a) having a desired molecular weight can be obtained by adjusting a polymerization temperature and a polymerization time by using a catalyst or a polymerization inhibitor as needed. Further, in order to adjust the molecular weight, it is preferred to use a mercaptan or a tetra-gasified carbon-based solvent. Further, the synthesis of the polymer (a) is not limited to solution polymerization, and other methods such as bulk polymerization and suspension polymerization may be used. In the present invention, the weight of the acrylic polymer (a) containing a residue having a (meth)acrylic monomer portion having a radiation-curable carbon-carbon double bond-containing monomer group is bonded to a repeating unit of the main chain. The average molecular weight is preferably about 30,000 to 10,000. When the molecular weight is less than 300,000, there is a case where the radiation is reduced by the amount of radiation. When the wafer is cut, it is easy to cause the component to be misaligned. In order to prevent the offset of the element as much as possible, the molecular weight is preferably 40,000 or more. Moreover, the right/knife amount is more than 1 million, and there is a possibility that tb can be condensed during the synthesis and at the time of coating. The weight average molecular weight of the polymer (1) in the present invention can be determined, for example, by the following method as a weight average molecular weight in terms of polystyrene. (Measurement conditions for weight average molecular weight) (4) Device: HLC — 8 120Gpc (trade name, manufactured by T〇s〇h Co., Ltd.) Pipe column: TSK gel Super HM-H/H4000/H3000/H2000 (trade name, manufactured by Tosoh Corporation) Flow rate: 〇.6 ml/min Concentration: 0.3% by mass Injection amount: 20 y 1 Column temperature: 40 ° C Development solvent: Gas-like in the present invention 'The radioactive carbon-carbon is contained in a repeating unit with respect to the main chain The iodine value of the polymer (a) having a double bond-containing acrylic monomer as a constituent unit is preferably from 1 to 50. Further, it is preferably 2 to 30. If the moth value is less than 1, the degree of crosslinking after radiation irradiation is small, and the peeling force is not completely lowered. Therefore, the wafer cannot be sufficiently picked up. If the moth value exceeds 5 〇, the degree of crosslinking after radiation irradiation is large, and hardening shrinkage occurs, and the pick-up property of the wafer is lowered. When the base value of the above polymer (a) is 5 to 100, the risk of picking failure can be further reduced by reducing the adhesion after radiation irradiation. Therefore, the polymer is The acid value of a) is preferably 〇5 to 30. Here, the hydroxyl value and the acid value refer to values measured by JIS Κ 0070. By setting the hydroxyl value of the polymer (a) within an appropriate range, the fluidity of the adhesive layer after the radiation irradiation can be made to be within an appropriate range, so that the adhesion after the radiation irradiation can be sufficiently reduced. By setting the acid value of the polymer (a) within an appropriate range, the fluidity of the adhesive layer after the radiation irradiation can be made within an appropriate range, thereby satisfying the tape recovery property. The base resin ' used in the radiation curable resin composition constituting the adhesive layer of the present invention can also be blended with the prior materials within the scope not departing from the gist of the present invention. For example, a rubber-based polymer such as natural rubber or various synthetic rubbers; or an alkyl (meth) acrylate, an alkyl (meth) acrylate, and an alkyl (meth) acrylate may be used, and other copolymers thereof may be used. A total of 5 monomers of unsaturated monomers are copolymers of acrylic acid. (Base resin of the adhesive layer of the semiconductor wafer processing sheet of the second aspect) The base resin of the radiation curable resin composition used in the adhesive layer of the semiconductor wafer processing sheet of the second aspect It is an acrylic polymer. Examples of the acrylic polymer include a (meth) acrylate component as a monomer main component (% by mass in the polymer), and copolymerization of the (mercapto) acryl vinegar component with a copolymerizable monomer component. Founder. In the acrylic polymer, examples of the (meth) acrylate component of the monomer main component include (meth)acrylic acid methyl vinegar, (mercapto) acrylic acid, and (a 201204800 meth) acrylic acid propylene. Ester, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, (曱Ethyl pentyl acrylate '(mercapto) hexyl acrylate, (decyl) heptyl acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (mercapto) decyl acrylate, isodecyl (meth) acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate, (meth) acrylate Dodecyl ester, tridecyl (mercapto) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, (mercapto) acrylate (heptadecane ester, octadecyl (meth)acrylate, etc. (meth)acrylic acid Ester; (meth) acrylate, cyclohexyl methacrylate (Yue-yl) acrylic acid cycloalkyl esters; (meth) acrylate, phenyl (meth) acrylate, aryl esters and the like. The (fluorenyl) acrylate may be used singly or in combination of two or more. (The curing agent) The radiation curable resin composition constituting the adhesive layer of the adhesive sheet for semiconductor wafer processing of the first aspect and the second aspect may contain a polyisocyanate compound or an alkyl etherified melamine compound. A curing agent previously used, such as an epoxy compound or a sulphur coupling agent. The initial adhesion can be set to an arbitrary value by forming a resin composition blended with a hardener. Among the hardeners, an isocyanate-based hardener is preferably used. As the isocyanate-based hardener, specifically, a polyvalent isocyanate compound such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1) 3 xylene diisocyanate (Xiiylene (JiiS〇Cyanate), 14-xylene diisocyanate) can be used. , diphenylmethane-4,4,diisocyanate, diphenyldecane-2,4'-diisocyanate, 3-decyldiphenyldecane diisocyanate, hexa-17 201204800 methylene diisocyanate 4, 4-diisocyanate, amino acid isocyanate, etc., isophorone diisocyanate, dicyclohexyldecane-dicyclohexylmethane ~ 2,4, diisocyanate, leaving (having at least 2 photopolymerizable carbon-carbon in the knife) The average weight of the double-chain is 1 〇, the following compound) The radiation-curable resin composition used in the adhesive layer of the semiconductor wafer processing sheet of the second aspect contains at least a molecule having at least 2 photopolymerization. The weight average molecular weight of the twin carbon-carbon double bond is 1 〇, the compound (c) below 。. The compound (c), as long as it is hardened by radiation irradiation, enters the two-dimensional network. The present invention can be used without particular limitation. The compound includes an oligomer having a weight average molecular weight of 1 Å or less, and does not include a high molecular weight polymer having a weight average molecular weight of more than 10,000. The three-dimensional network of the adhesive layer by irradiation of radiation is preferably 2 or less in the amount of 2, and the number of carbon-carbon doubles in the molecule is less than 2 to 6. Further, the weight average molecular weight of the low molecular weight compound having at least two photopolymeric octacarbon carbon-carbon double bonds in the molecule in the present invention is based on GPC (gel permeation chromatography) using the following conditions. The weight average molecular weight of the measured hail ice polystyrene. (Measurement conditions of weight average molecular weight) GPC apparatus: HLC-8120 GPC (trade name: Tosoh company, raw pipe column: TSK-GEL G2500 HHR (trade name) , manufactured by Tosoh) Flow rate: 1 ml / min 18 201204800 Concentration: 0.2 mg/ml Injection amount: 100 y 1 Temperature of the bath: 40 °C Mobile phase: gas-like radiation polymerizable compound (c), for example, Trihydroxyl Propane triacrylate, tetrahydroxydecyl decane tetraacrylate, neopentyl alcohol triacrylate vinegar, neopentyl alcohol tetrakis (tetra) acid vinegar, dipentaerythritol, pentane acrylate, dipentane pentoxide Alcohol hexaacrylate, L4-butanediol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate, organic polyoxo composition, commercially available oligoester acrylate, urethane acrylate, etc. The compound having a weight average molecular weight of at least 2 photopolymerizable carbon-carbon double bonds in the molecule of 10' or less may be used alone or in combination of two or more. The blending amount is based on the basis weight of the base tree, which is a mass loss of 300. It is preferably from 2 to 2 parts by mass and further preferably from 5 to 15 parts by mass based on the mass of the base resin (10). If the amount is too small, the three-dimensional network due to the radiation of the adhesive layer is not sufficient, and it is difficult to add the semiconductor wafer to the wafer. Stripped and contaminated wafers. If the amount is too large, the shell J excessively undergoes a polymerization reaction using radiation to cause hardening shrinkage caused by the radiation of the radiation. As a result, the layer of the adhesive layer is immersed in the surface of the adhesive body and the .^ ^ θ Μ ^ ^ surface, and it becomes difficult to be able to pick up the flat conductor after the cutting. In addition, if the amount of the radiation polymerizable compound is on the eve, there is a problem that it is difficult to maintain the difference. The shape of the adhesive layer and the thickness precision (photopolymerization initiator) 19 201204800 The radiation curable resin composition of the adhesive layer of the adhesive sheet for semiconductor wafer processing which constitutes the first aspect and the second aspect In the gel permeation chromatography (hereinafter referred to as "GPC") method, a photopolymerization initiator having a weight average molecular weight of less than 1 Å in terms of polystyrene as a standard material is used. In the present invention, the weight average molecular weight of the photopolymerization initiator refers to a value measured by GPC under the following conditions. (Measurement conditions for weight average molecular weight) GPC device: LCVP series manufactured by Shimadzu Corporation Pipe column: OligoPore 300x7.5 (trade name) (trade name, manufactured by Polymer Laboratories)

流量：1 ml / min 濃度：lmg/ ml 注入量：50 " 1 管柱溫度：4(TC 展開溶劑：氣仿光聚合起始劑藉由照射光或紫外線等放射線而產生自由基。藉此，可促進黏著劑層中所含之對於主鏈之重複單位含有具有放射線聚合性碳一碳雙鍵含有基之丙烯酸系單體作為構成單位的聚合物（a)之硬化反應，或者促進黏著劑層中所含之於分子内具有至少2個光聚合性碳—碳雙鍵之重量平均分子量為10,000以下的化合物之硬化反應。若光聚合起始劑之以聚苯乙烯換算之利用Gpc所得之重量平均分子量過大，則於黏著劑層中之光聚合起始劑之分散產生問題，所產生之自由基之移動難以迅速進行，從而無法 20 201204800 高效地進行硬化反應。於該情形時，必需照射超過需要之高照度之放射線，由於發熱而難以有效地降低黏著劑層與被黏著體之密著性。關於該情形時之現象，若參照圖式加以說明，則如圖【所示，於基材樹脂膜1上形成有黏著劑層2之半導體晶圓加工用黏著片10之情形時，於半導體晶片之拾取方面存在障礙。又，如圖2所示，於基材樹脂膜丨上設置有黏著劑層2，進而形成有接著劑層3之半導體晶圓加工用黏著片 20之情形時，難以順利地將接著劑層3與黏著劑層2剝離。光聚合起始劑之以聚苯乙烯換算之利用Gpc所得的重量平均分子量之上限較佳為800，進而較佳為6〇〇。關於光聚合起始劑之以聚笨乙烯換算之利用Gpc所得的重量平均分子量之下限’並無特別限制，較佳為2〇〇以上。若分子量較小，則變得容易昇華，自黏著劑層向非黏著體層之移動變得顯著而容易污染晶圓。又，黏著劑層之耐熱性變差，於製造時之基材塗敷後之乾燥步驟中變得容易分解。因此，未表現出穩定之硬化反應。光聚合起始劑’例如可列舉：二苯曱酮、4,4 —雙（二乙基胺基）二苯甲酮、2,4,6 —三曱基二苯甲酮、4 —笨基二苯甲酮、第三丁基蒽醌、2 —乙基蒽醌、二乙氧基苯乙酮、2〜羥基一2 —曱基一1—笨基丙烷_丨一酮、2,2 —二曱氧基〜 1，2_二苯基乙烷一1~酮、丨一羥基環己基—苯基酮、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、甲基[4一（曱硫基）苯基]—2 — 口末啦基丙炫—1 _酮、2 21 201204800 —苄基一2 —二甲基胺基一 1-(4- α末啉基笨基）一丁酮— 1、二乙基一9 —氧硫d星、異丙基一9 一氧硫口星、2，4,6 —三甲基本曱酿基二笨基氧化鱗、雙（2，4,6—三甲基笨曱酿基）—笨基氧化膦、2 —羥基一 1 一 {4 一 [4 — (2一羥基一 2 —曱基丙醯基）苄基]苯基}一2—曱基丙炫一1— _、2—(二曱基胺基）一2 — [(4 —甲基苯基）甲基]-1 一 [4-(4- 口末啉基）苯基]—1— 丁酮、及下述通式（1)所表示之寡聚物。通式（1 )Flow rate: 1 ml / min Concentration: lmg/ml Injection volume: 50 " 1 Column temperature: 4 (TC developing solvent: a gas-like photopolymerization initiator generates radicals by irradiation of light such as light or ultraviolet rays. It is possible to promote the hardening reaction of the polymer (a) containing the acrylic polymer having a radiation-polymerizable carbon-carbon double bond-containing group as a constituent unit in the repeating unit of the adhesive layer contained in the adhesive layer, or to promote the adhesive a hardening reaction of a compound having a weight average molecular weight of at least two photopolymerizable carbon-carbon double bonds in the molecule of 10,000 or less contained in the layer. If the photopolymerization initiator is used in a polystyrene conversion using Gpc When the weight average molecular weight is too large, the dispersion of the photopolymerization initiator in the adhesive layer causes a problem, and the movement of the generated radicals is difficult to proceed rapidly, so that the hardening reaction cannot be efficiently performed in 201204800. In this case, irradiation is necessary. It is difficult to effectively reduce the adhesion between the adhesive layer and the adherend due to heat generation, which is higher than the required high-illumination radiation. In the case of the semiconductor wafer processing adhesive sheet 10 in which the adhesive layer 2 is formed on the base resin film 1, as shown in the figure, there is a problem in picking up the semiconductor wafer. As shown in FIG. 2, when the adhesive layer 2 is provided on the base resin film, and the adhesive sheet 20 for semiconductor wafer processing of the adhesive layer 3 is formed, it is difficult to smoothly bond the adhesive layer 3 and adhere thereto. The upper limit of the weight average molecular weight by Gpc of the photopolymerization initiator is preferably 800, and more preferably 6 Å. The photopolymerization initiator is polystyrene. The lower limit of the weight average molecular weight obtained by using Gpc is not particularly limited, and is preferably 2 Å or more. When the molecular weight is small, the sublimation is easy, and the movement from the adhesive layer to the non-adhesive layer becomes remarkable. It is easy to contaminate the wafer. Moreover, the heat resistance of the adhesive layer is deteriorated, and it is easily decomposed in the drying step after the substrate is applied at the time of production. Therefore, a stable hardening reaction is not exhibited. Photopolymerization initiator For example, List: diphenyl fluorenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethyl benzophenone, 4-phenyl benzophenone, third Base, 2-ethyl hydrazine, diethoxy acetophenone, 2~ hydroxy 2- 2 fluorenyl 1 - phenyl propane 丨酮 ketone, 2, 2 曱曱〜〜 1, 2 _Diphenylethane-1-one, oxime-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl [4-(indolylthio)phenyl ]—2 — 口啦基丙 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Base- 9-oxo-sulfur d-star, isopropyl- 9-oxo-sulfur-star, 2,4,6-trimethyl phthalocyanine-based diphenyl oxidized scale, double (2,4,6-trimethyl alum Stuffed base) - stupyl phosphine oxide, 2-hydroxyl - 1 - {4 - [4 - (2 - hydroxy- 2 - fluorenyl propyl benzyl) benzyl] phenyl) - 2 - fluorenyl propyl 1 - _, 2-(didecylamino)- 2 - [(4-methylphenyl)methyl]-1-[4-(4-normanoryl)phenyl]-1-butanone And the following general formula (1) represents the oligomer. General formula (1)

(式中，R表示烷基，η為整數）上述光聚合起始劑中’難以昇華且難以產生污染之殘存物之優異的光聚合起始劑，可列舉：2,2—二甲氧基一1，2 一二苯基乙烧一1—酮（分子量260)、2 —甲基一1 — (4 —甲硫基苯基）一2 — d末·#基丙烧一 (分子量28〇)、卜經基一環己基苯基一酮（分子量205 )。上述通式〇)之寡聚物較佳為聚合度η=2〜4 (分子 η=2〜3 (分子量400 量400〜700 )者，進而較佳為聚人声〜5 0 0 )者。 22 201204800(In the formula, R represents an alkyl group, and η is an integer.) In the photopolymerization initiator, an excellent photopolymerization initiator which is difficult to sublimate and which is less likely to cause contamination is exemplified by 2,2-dimethoxy. 1,2,2-diphenylethene-1-one (molecular weight 260), 2-methyl- 1 - (4-methylthiophenyl)- 2 - d-end · #基丙烧一 (molecular weight 28〇 ), a cyclyl-cyclohexyl phenyl ketone (molecular weight 205). The oligomer of the above formula 〇) is preferably one having a degree of polymerization η = 2 to 4 (molecule η = 2 to 3 (molecular weight: 400: 400 to 700), more preferably polyphonic ~ 50,000). 22 201204800

2,2 —二曱氧基一1，2—二苯基乙烷—} 一酮2,2-dimethoxy-1,2-diphenylethane-}one

2一甲基一 1— (4 -甲硫基笨基）—2 一口末啉基丙烷—1 __ 酮關於光聚合起始劑，相對於構成第丨態樣之半導體晶圓加工用黏著片之黏著劑層的放射線硬化性樹脂組成物中之基底樹脂100質量份，而摻合01〜10質量份。較佳為相對於基底樹脂100質量份，而較佳為摻合丨〜1〇質量份，進而較佳為2〜7質量份。於構成第2態樣之半導體晶圓加工用黏著片之黏著劑層的放射線硬化性樹脂組成物中，相對於丙烯酸系聚合物100質量份而摻合〇1〜1〇質量份。較佳為相對於丙烯酸系聚合物100質量份，而較佳為摻合i 〜10質量份’進而較佳為2〜7質量份。若光聚合起始劑過少，則導致黏著劑層之因放射線之照射所致之三維網狀化變得不充分’而無法順利地应接著劑層剝離，或污染半導體晶片。又，若光聚合起始劍過多， 23 201204800 則不僅無法獲得與此相應之效果，而且有於晶圓上殘留該光聚合起始劑之虞。根據需要’可併用2種以上之上述光聚合起始劑。只要所使用之光聚合起始劑各自之利用GPC所得之重量平均分子量未達1000即可。又’亦可將三乙胺、四乙五胺、二曱基胺基乙醇等胺化合物或9 —氧硫α星系光聚合起始劑作為光聚合促進劑而加以併用。於放射線硬化性樹脂組成物中，視需要亦可為了調整對半導體晶圓之黏著力含有黏著賦予劑、黏著調整劑、界面活性劑、其他改質劑或慣用成分。其中，界面活性劑或表現出界面活性之化合物等會污染半導體晶圓，故較佳為儘量減少使用其之情形。於本發明中，將含有上述基底樹脂 '分子内具有至少2 個光聚合性碳一碳雙鍵之重量平均分子量為1〇,〇〇〇以下之化合物、特定之光聚合起始劑、以及視需要之交聯劑及其他摻合劑成分的放射線聚合性樹脂組成物直接塗佈於基材樹脂膜上並加熱乾燥，或者暫時塗佈於剝離紙上並加以乾燥後再轉印至基材樹脂膜上，藉此可製造黏著劑層係由使用放射線聚合性樹脂組成物之層所構成之半導體晶圓加工用黏著片。黏著劑層之厚度並無特別限制。通常，以將黏著劑層之厚度通常設為5〜1〇〇之方式，形成黏著劑層，而製成片狀、帶狀等之半導體晶圓加工用黏著片。放射線可使用α射線、7射線、電子束、紫外線等， 24 201204800 要為藉由使黏著劑層硬化可降低黏著力者，則並無特別限制。較佳為電子束、紫外線，於使用光聚合起始劑時，進而較佳為紫外線。本發明之半導體晶圓加工用黏著片如圖2所示，亦可於基材樹脂膜！上設置黏著劑層2,進而於其上形成接著劑層3。於基材樹脂膜上形成黏著劑層，繼而形成接著劑層之方法並無特別限制，只要根據先前之方法，於基材樹脂膜上積層黏著劑層，進而於黏著劑層上積層接著劑層即可。於該情形時，將半導體晶圓加工用黏著片貼合於研磨後之半導體晶圓背面，其後自半導體晶圓之電路形成面側以切割加工同時切入黏著劑及接著劑。於是可獲得附有接著劑層之半導體晶片。接著劑層3中所使用之接著劑，可使用以往之接著劑。接著劑層可使用將接著劑預先膜化而成者。例如可使用使用於接著劑之以往之聚醯亞胺樹脂、聚醯胺樹脂、聚醚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚酯樹脂、聚酯醯亞胺树爿a、笨氧樹脂、聚ί風樹脂、聚醚礙樹脂、聚苯硫樹脂、聚醚酮樹脂、氣化聚丙烯樹脂、丙烯酸系樹脂、聚胺酯樹脂、環氧樹脂、聚丙烯醢胺樹脂、三聚氰胺樹脂等或該等之混合物。其中’就硬化後之耐熱性優良之方面而言，尤佳為使用環氧樹脂。環氧樹脂只要為進行硬化而表現接著作用者即可。為提高玻璃轉移溫度（Tg )而確保接著劑層之对熱性’亦可添加多官能環氧樹脂。多官能環氧樹脂可例示： 25 201204800 苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等。環氧樹脂之硬化劑只要為通常用作硬化劑者，則並無特別限制，可列舉胺系化合物、聚醯胺、酸酐、多硫化物j三氟化硼、1分子中具有2個以上酚性羥基之化合物即雙酚 A'雙酚F、及雙酚^等。由於吸濕時之对電腐触性特別優異，故較佳為使用作為酚樹脂之苯酚酚醛清漆樹脂或雙酚酚醛清漆樹脂等。又’就可縮短用以硬化之熱處理之時間而t，較佳為與硬化劑一併使用硬化促進劑。硬化促進劑，可使用2 —曱基咪唑、2-乙基—4—甲基咪唑、卜氰乙基一2一笨基咪唑、丄氘基—2—苯基咪唑鏽偏苯三甲酸鹽（1 —Cyan〇ethyl—2 Phenyl imidazolium trimeUitate)等各種咪唑類等鹼。又，為強化對半導體晶片或導線架之接著力，較理想為將矽烷偶合劑或鈦偶合劑作為添加劑而添加至上述樹脂或其混合物中°又，亦可為提高耐熱性或調節流動性而添加填料。作為該種填料，例如可使用二氧切、氧化銘、及録之氧化物等。該等填料只要為最大粒徑小於接著劑層之厚度者，則可以任意之比例進行摻合而使用。接者劑層之厚度並無特別限制，通常較佳為5〜1〇〇 “爪 =。又，接著劑層可積層於黏著膜之整個黏著劑層。又， :可將預：切割（precut)成與所貼合之半導體晶圓對應之形狀的接著劑層積層於黏著劑層之—部分。於該情形時， 1下述形狀：貼合有半導體晶圓之部分存在接著劑層，。有切割用J裒狀框（ring frame)之部分不存在接著劑層而 26 201204800 僅存在黏著膜之黏著劑層。藉由形成該形狀，於環狀框上貼合有黏㈣層’而未貼合通常難以與被黏著體剝離之接著劑層，目此本發明之半導體晶圓加工用黏著片於使用後可容易地自環狀框剝離。關於本發明之半導體晶圓加工用黏著片，為了於㈣時自基材樹脂膜側照射放射線而使黏著劑層硬化，必需使基材樹月曰膜具有放射線穿透性。χ，於晶圓加工時會因切削刀等而受到衝擊’並受到清洗水等之壓力。因此基材樹脂膜係選擇具有可耐受該等之強度且適合該等之材料及 X為使黏著劑層難以自基材樹脂膜剝離，較佳為預先對基材樹脂膜之黏著劑層形成面實施以電暈處理為代表之各種表面處理。使用於基材樹脂膜之材料，可列舉：聚乙烯、聚丙烯、乙丙烯共聚物、聚氣乙烯、聚對苯二曱酸乙二醋、聚對苯—曱酸丁二酯、乙烯—乙酸乙烯酯共聚物、聚丁烯— 1 、 * —4 —甲基戊烯一丨、乙烯—丙烯酸乙酯共聚物、乙烯丙烯酸甲酯共聚物、乙烯—丙烯酸共聚物、聚胺酯、聚甲基戊烯、聚丁二烯等之膜。基材樹脂膜之厚度為3〇〜5〇〇;iZm，較祛為4〇〜300" 讯，進而較佳為50〜2〇〇//m。若該厚度過薄，則強度減弱，因此有時會產生由半導體晶圓加工中之斷裂等引起之不良2 monomethyl- 1 -(4-methylthiophenyl)- 2 mono-l-phenyl-propanyl- 1 - ketone as a photopolymerization initiator, relative to the semiconductor wafer processing adhesive sheet constituting the second aspect 100 parts by mass of the base resin in the radiation curable resin composition of the adhesive layer, and blended in an amount of from 01 to 10 parts by mass. It is preferably 100 parts by mass relative to the base resin, and more preferably 掺1 to 1 part by mass, more preferably 2 to 7 parts by mass. In the radiation-curable resin composition of the adhesive layer of the adhesive sheet for semiconductor wafer processing of the second aspect, 1 to 1 part by mass of 〇 is blended with respect to 100 parts by mass of the acrylic polymer. It is preferably contained in an amount of from i to 10 parts by mass, more preferably from 2 to 7 parts by mass, based on 100 parts by mass of the acrylic polymer. If the amount of the photopolymerization initiator is too small, the three-dimensional network due to irradiation of the adhesive layer becomes insufficient, and the adhesive layer may not be smoothly peeled off or the semiconductor wafer may be contaminated. Moreover, if there are too many photopolymerization start swords, 23 201204800 will not only have the corresponding effect, but also the photopolymerization initiator remaining on the wafer. Two or more kinds of the above photopolymerization initiators may be used in combination as needed. The weight average molecular weight obtained by GPC of each of the photopolymerization initiators used may be less than 1,000. Further, an amine compound such as triethylamine, tetraethylenepentamine or decylaminoethanol or a 9-oxosulfo alpha star photopolymerization initiator may be used in combination as a photopolymerization accelerator. The radiation curable resin composition may optionally contain an adhesion-imparting agent, an adhesion modifier, an surfactant, another modifier, or a conventional component for adjusting the adhesion to the semiconductor wafer. Among them, a surfactant or a compound exhibiting interface activity may contaminate a semiconductor wafer, so it is preferable to minimize the use thereof. In the present invention, a compound having a weight average molecular weight of at least 2 photopolymerizable carbon-carbon double bonds in the molecule of the above-mentioned base resin' is 1 〇, a compound below 〇〇〇, a specific photopolymerization initiator, and The radiation-polymerizable resin composition of the crosslinking agent and other admixture components required is directly applied onto the base resin film and dried by heating, or temporarily applied onto the release paper, dried, and then transferred onto the base resin film. By this, it is possible to manufacture an adhesive sheet for semiconductor wafer processing which is composed of a layer using a radiation polymerizable resin composition. The thickness of the adhesive layer is not particularly limited. Usually, an adhesive layer is formed so that the thickness of the adhesive layer is usually 5 to 1 Å, and an adhesive sheet for semiconductor wafer processing such as a sheet or a strip is produced. For the radiation, α-rays, 7-rays, electron beams, ultraviolet rays, or the like can be used. 24 201204800 There is no particular limitation on the ability to reduce the adhesion by hardening the adhesive layer. It is preferably an electron beam or an ultraviolet ray, and when a photopolymerization initiator is used, it is preferably ultraviolet ray. The adhesive sheet for semiconductor wafer processing of the present invention is also shown in Fig. 2, and may be a base resin film! An adhesive layer 2 is provided thereon, and an adhesive layer 3 is formed thereon. The method of forming the adhesive layer on the base resin film and then forming the adhesive layer is not particularly limited as long as the adhesive layer is laminated on the base resin film according to the prior method, and the adhesive layer is laminated on the adhesive layer. Just fine. In this case, the semiconductor wafer processing adhesive sheet is bonded to the back surface of the polished semiconductor wafer, and thereafter, the adhesive and the adhesive are cut by cutting from the circuit formation surface side of the semiconductor wafer. Thus, a semiconductor wafer with an adhesive layer can be obtained. In the adhesive layer used in the layer 3, a conventional adhesive can be used. The subsequent layer can be formed by pre-filming an adhesive. For example, a conventional polyimide resin, a polyamide resin, a polyether phthalimide resin, a polyamidimide resin, a polyester resin, a polyester phthalimide tree a, a stupid used for an adhesive can be used. Oxygen resin, polyphenol resin, polyether resin, polyphenylene sulfide resin, polyether ketone resin, vaporized polypropylene resin, acrylic resin, polyurethane resin, epoxy resin, polypropylene amide resin, melamine resin, etc. or a mixture of these. Among them, it is preferable to use an epoxy resin in terms of excellent heat resistance after hardening. The epoxy resin may be used as it is for curing. A multifunctional epoxy resin may also be added to ensure the thermal conductivity of the adhesive layer in order to increase the glass transition temperature (Tg). Examples of the polyfunctional epoxy resin are: 25 201204800 Phenolic novolak type epoxy resin, cresol novolak type epoxy resin, and the like. The curing agent for the epoxy resin is not particularly limited as long as it is generally used as a curing agent, and examples thereof include an amine compound, a polyamine, an acid anhydride, a polysulfide j boron trifluoride, and two or more phenols in one molecule. The compound of a hydroxyl group is bisphenol A'bisphenol F, and bisphenol^. Since it is particularly excellent in electric rot resistance at the time of moisture absorption, it is preferred to use a phenol novolak resin or a bisphenol novolac resin as a phenol resin. Further, the time for heat treatment for hardening can be shortened, and it is preferable to use a hardening accelerator together with the hardener. As the hardening accelerator, 2-nonyl imidazole, 2-ethyl-4-methylimidazole, cyanoethyl-2-phenylimidazole, fluorenyl-2-phenylimidazole rust trimellitate ( 1 - Cyan〇ethyl-2 Phenyl imidazolium trimeUitate) and other bases such as imidazoles. Further, in order to enhance the adhesion to the semiconductor wafer or the lead frame, it is preferable to add a decane coupling agent or a titanium coupling agent as an additive to the above resin or a mixture thereof, or to improve heat resistance or adjust fluidity. Add filler. As such a filler, for example, dioxo, oxidized, and recorded oxides can be used. These fillers may be blended at any ratio as long as the maximum particle diameter is smaller than the thickness of the adhesive layer. The thickness of the adapter layer is not particularly limited, and is usually preferably 5 to 1 〇〇 "claw =. Further, the adhesive layer can be laminated on the entire adhesive layer of the adhesive film. Also, pre-cut: The adhesive in a shape corresponding to the bonded semiconductor wafer is laminated on the portion of the adhesive layer. In this case, the following shape: the adhesive layer is present in the portion to which the semiconductor wafer is bonded. There is no adhesive layer in the portion of the ring frame for cutting. 26 201204800 There is only an adhesive layer of the adhesive film. By forming the shape, a sticky (four) layer is attached to the ring frame. The adhesive layer for semiconductor wafer processing of the present invention can be easily peeled off from the ring frame after use. The adhesive sheet for semiconductor wafer processing of the present invention is In order to cure the adhesive layer by irradiating radiation from the side of the base resin film at the time of (4), it is necessary to make the substrate dendritic film have radiolucent property. Therefore, it is affected by a cutter or the like during wafer processing. Subject to pressure from washing water, etc. The base resin film is selected to have a strength that can withstand such strength and is suitable for the material, and X is such that the adhesive layer is hardly peeled off from the base resin film, and it is preferred to form a surface of the adhesive layer of the base resin film in advance. Various surface treatments represented by corona treatment are carried out. Materials used for the base resin film include polyethylene, polypropylene, ethylene propylene copolymer, polyethylene gas, polyethylene terephthalate, and poly Benzene-butyl phthalate, ethylene-vinyl acetate copolymer, polybutene-1, *4-methylpentene mono-, ethylene-ethyl acrylate copolymer, ethylene methyl acrylate copolymer, ethylene - a film of an acrylic copolymer, a polyurethane, a polymethylpentene, a polybutadiene, etc. The thickness of the base resin film is 3 〇 to 5 〇〇; iZm is more preferably 4 〇 to 300 quot; It is 50 to 2 〇〇//m. If the thickness is too thin, the strength is weakened, so that defects due to breakage or the like in semiconductor wafer processing may occur.

情形D 另一方面’若基材樹脂膜過厚，則於切割步驟結束後之半導體晶片之拾取步驟中，半導體晶圓加工用黏著片過 27 201204800 硬’藉由針向上頂起時發生故障《又，於切割步驟結束後且於拾取步驟前之延伸（expand)步驟中，難以充分延伸半導體晶圓加工用黏著片。因此’半導體晶片之間隙較小，圖像之晶片識別性變得不充分，產生半導體晶片之拾取不良。 [實施例] 以下’基於實施例，對本發明進行更加詳細之說明，但本發明並不限定於該等實施例。 A.放射線硬化性 1.第1態樣之半導體晶圓加工用黏著膠帶之黏著劑層中所使用的放射線硬化性樹脂組成物之製備 (1 )對於主鍵之重複單位而鍵結有具有具放射線硬化性碳一碳雙鍵含有基之（甲基）丙烯酸系單體部的殘基之聚合物之製備使用丙稀酸丁酯（59mol% )、丙稀酸2 —經基乙酯 (25mol% )及丙烯酸（i6m〇i% )製造丙烯酸系共聚物。使該丙烯酸系共聚物之丙烯酸2 —羥基乙酯側鏈末端之〇H 基、與2 —甲基丙烯醯氧基乙基異氰酸酯之nc〇基進行反應’獲得對於主鏈之重複單位而鍵結有包含具有放射線硬化性碳一碳雙鍵含有基之（曱基）丙烯酸系單體部的殘基之聚合物。此時，適當變更甲基丙烯酸2_異氰酸基乙酯之滴加量，獲得雙鍵量不同之聚合物（（al )〜（a4 ))。所得聚合物（（al)〜（a4))之任一者均係重量平均分子量為7〇萬、玻璃轉移溫度為一60 °C者。於表1— 1〜1 — 4中，實施例1 一 1〜1 — 9、1 — 11、及比較例！ _ i〜i _ 4、i 一 7中所 28 201204800 使用之聚合物（al )之碘值為2〇。又，實施例i — ι〇中所使用之聚合物（a2 )之碘值為5〇，實施例i _丨2中所使用之聚合物（a3 )之碘值為〇 5，實施例丨_丨3中所使用之聚合物（a4)之蛾值為55。於以下說明中，α聚合⑯（（al)〜（a4))作為聚合物 (a )加以說明。 (i )重量平均分子量利用下述條件之GPC，對聚合物（a )測定重量平均分子量。 GPC裝置：HLC- 8120GPC(商品名，T〇s〇h公司製造）管柱：TSK gel Super HM— H/H4000/H3000/H2000 (商品名，Tosoh公司製造）流量：0.6ml/ min 濃度：0.3質量％注入量：20 μ 1 管柱溫度：40°C 展開溶劑：氣仿 (ii)玻璃轉移溫度使用熱示差掃描分析儀（DSC ) ( DS.C7020 (商品名）， Seiko Instruments股份有限公司公司製造），以升溫速度5 °C / min進行測定。 (iii )雙鍵量根據JIS K 0070求出硬值。 (2 )放射線硬化性樹脂組成物之製備 29 201204800 於（1)中所得之聚合物（a) 1〇〇質量份中以表ι_ i 表1 4所。己載之份數摻合光起始劑，進而摻合聚異氰酸酿化合物曰（Nippon Polyurethane公司製造，商品名c〇r〇nate L ) 3質量份作為硬化劑，從而製備表i i〜表丄—4之實施例及比較例中δ己載之放射線硬化性樹脂組成物。使用VpE —0201 (商品名，和光純藥工業公司製造）作為比較例】一 1、1 — 7中所使用之光起始劑之含聚乙二醇單位之高分子偶氮聚合起始劑~。光起始劑之重量平均分子量係藉由Gpc法進行測定，以聚笨乙烯作為標準物質而算出重量平均分子量。將其結果一併示於表1一1〜1-4中。使用p〇iymer Laboratories 製造之01 igo P〇re 300x7.5(商品名）作為凝膠滲透層析儀。展開溶劑係使用氣仿，於4〇。(：進行測定。 2.第2態樣之半導體晶圆加工用黏著膠帶之放射線硬化性樹脂組成物之製備 (1 )構成黏著劑層之丙烯酸系聚合物使用丙烯酸正丁酯8 5質量份、丙稀酸乙酯1 〇質量份及丙稀酸5質量份，製備丙稀酸系共聚物作為構成黏著劑層之基底樹脂。其重量平均分子量為60萬。 (2)分子内具有至少2個光聚合性碳_碳雙鍵之重量平均分子量為10,000以下之化合物使用UN — 3320HA (商品名，根上工業製造）、UN — 9000PEP (商品名，根上工業製造）、UN - 6050PTM (商品名，根上工業製造）、UN— 901T(商品名，根上工業製造）、 201204800 UN— 9200A (商品名，根上工業製造）。藉由以下方法測定所使用之化合物之以聚苯乙烯換算之重量平均分子量及雙鍵量。其結果如下。 UN- 3 320HA (商品名，根上工業製造）：1500 (雙鍵量：6) UN— 3320HC (商品名，根上工業製造）：1500 (雙鍵量：6) UN— 9000PEP (商品名，根上工業製造）：5000 (雙鍵量:2) UN— 605 0PTM (商品名，根上工業製造）：6000 (雙鍵量：2) UN — 901T (商品名，根上工業製造）：4000 (雙鍵量： 9) UN — 9200A (商品名，根上工業製造）：1 1500 (雙鍵量：2) (重量平均分子量之測定條件） GPC裝置：HLC— 8120GPC (商品名，Tosoh公司製造）管柱：TSK— GEL G2500HHR (商品名，Tosoh公司製造）流量：1ml/min 濃度：〇.2mg/ ml 注入量：100 // 1 恆溫槽溫度：40°C 流動相：氣仿 31 201204800 (雙鍵量之測定方法）雙鍵量根據JIS K 0070求出碘值，並根據該值算出雙鍵量。 (3 )放射線硬化性樹脂組成物之製備於（1)之基底樹脂1〇〇質量份中，以表2-1〜表2~ 4所記載之份數’摻合（2 )所記載之於分子内具有至少2 個光聚合性碳一碳雙鍵之重量平均分子量為1〇,〇〇〇以下之化合物及光起始劑，進而摻合聚異氰酸酯化合物（Nipp〇n Polyurethane公司製造，商品名c〇r〇nate L) 3質量份作為硬化劑，從而製備表2 ~ 1〜表2 一 4之實施例及比較例中所記載之放射線硬化性樹脂組成物。使用vpE—〇2〇1 (商品名’和光純藥工業公司製造）作為比較例2-1、2_6中所使用之光起始劑之含聚乙二醇單位之高分子偶氮聚合起始劑一。光起始劑之重！平均分子量係藉由凝膠渗透層方 (GPC)法而進行測定，以聚苯乙烯作為標準物質，算出1 量平均分子量。將其結果一 PolymerLaboratories 製造之作為凝膠滲透層析儀。展開行測定。併示於表2— 1〜2—4中。使用 OHgoPore 300x7.5 (商品名）溶劑係使用氣仿，並於4〇t進 D.干守使用EMMA樹脂（住友化學公司製造商品名腳則，MT錢製料度_心之基膜 12 該基材樹脂膜塗敷實施例，- θ m 32 201204800 _1〜2-10、比較例1_1〜1_4、2_1〜2一5中所示之放射線硬化性樹脂組成物並適當加以固化。藉此，獲得具有乾燥後之膜厚A 10“m之黏著劑層的ffi 1所示之構成之半導體晶圓加工用黏著片。 3·半導體晶圓加工用黏著片之製作（π) (1)構成接著層之接著劑組成物之製備於相對於作為環氧樹脂之甲酚酚醛清漆型環氧樹脂5 0 夤里伤、酚樹脂5 〇重量份而由作為矽烷偶合劑之γ _酼丙 ::曱氧基矽⑮3質量份及7 —脲基丙基三乙氧基矽烷5 貝®伤、及作為填料之球狀二氧化珍3G重量份所構成的組成物中添加鳅己酮並攪拌混合，進而使用珠磨機混練9〇分鐘於上述組成物中添加丙烯酸系橡膠（重量平均分子量萬）300質重·份、及作為硬化促進劑之氛乙基—2 一 =基米坐1質罝份，並搜拌混合，進行真空脫氣，從而獲得接著劑組成物。 (2 )半導體晶圓加工用黏著片之製作、將（1)中所得之接著劑組成物塗佈於厚度35"m之經脫模處理之聚對苯二甲酸乙二酷膜（脫模膜）i，以14〇力…乾燥5分鐘，獲彳于於膜厚為“以爪之B階段（b 狀態之脫模膜上形成有接著劑層之接著劑片材。繼而，以與上述2.半導體晶圓加工用黏著片之製作（ι) 中所記載之方法相同之方法，獲得圖丨所示之結構之半導體晶圓加Μ黏著片，該結構係：使絲卜4之實施例i 33 201204800 較例1 7中所δ己載之放射線聚合性樹脂組成物於基材樹脂膜上形成黏著劑層。將該黏著劑層與以上述方法製作之接著劑片材之接著劑層對接而積層，獲得圖2所示 m半導體晶圓加工用黏著片上積層有脫模膜之黏著片（實施例1 一 11及比較例丨—7 )。另外以與上述2 ·半導體晶圓加工用黏著片之製作（工）中所記載之方法相同之方法，獲得圖1所示之結構之半導體晶圓加工用黏著片，該結構係：使用表2一4之實施例2 士 11 2 1 5、比較例2 — ό、2 — 7中所記載之放射線聚合性树月曰·.且成物於基材樹脂膜上形成黏著劑層。將該黏著劑層與以上述方法製作之接著劑片材之接著劑層對接而積層，獲得圖2所示之構成之於半導體晶圓加工用黏著片上積層有脫模膜之黏著片（實施例2_u〜2— 15、比較例2_6、2 於以下試驗中，將脫模膜剝離而貼合於半導體晶圓並進行評價。 4 ·性能試驗按，系以下條件進行切割，其後對拾取性及晶片污染性進行評價。 (切割條件） 10，造之 (1)圖1之構成之半導體晶圓加工用黏著片關於實施例1— 1〜1— 10、卜12、13、2_1〜2_ 比較例1-1〜1-4、2-1〜2一5，使用DISC〇公司製 DFD - 840」，以雙軸將矽晶圓之背面研磨掉3〇 "爪 34 201204800 後，以矽晶圓之最終厚度成為100" m之方式進行研磨。此時之研磨條件如下所述。單轴350磨石（轉速：々goorpm，下降速度：pi為3_〇 "m/Sec、P2 為 2.〇“m/sec) 雙軸.#2000磨石（轉速：5500rpm，下降速度：P1為 0.8/zm/Sec、P2 為〇 6Mm/sec) 於背面研磨I 5分鐘以内，將圖i之構成之半導體晶圓加工用黏著片貼合於8英吋用環狀框上，於該貼合固定之狀態下將100 A m厚之8英吋矽晶圓貼合於半導體晶圓加工用黏著片，並使用DISC〇公司製造之切割裝置 (商口口名）王切切割（fullcut dicing)成5mmx5mm之晶片尺寸。關於此時之自半導體晶圓加工用黏著片面起之刀片之切削深度，於圖1所示之構成之黏著片之情形時設為心 m 0 (2)圖2之構成之半導體晶圓加工用黏著片關於實施例i—U'2— U〜2— 15及比較例1一 7、2一 6、2-7,於赃下，將ffl 2之構成之半導體晶圓加工用黏著片貼合於100// m厚之8英吋矽晶圓2〇秒後，使用Disc〇公司製造之DFD6340，按照以下條件進行切割。切割刀片（薄型旋轉磨石）：帛i次使用Disco公司製邊之27HEEE ’第2次使用Dise〇公司製造之27hedd 刀片轉速：35000rpm 刀片進給速度：50mm/s 晶片尺寸：5mm><5mm 35 201204800 切削深度：第1次向矽晶圓切進5 0 μ m 第2次向半導體晶圓加工用黏著片切進40 y m (基材樹脂膜之厚度為100#m、黏著劑層之厚度為10"m、接著劑層之厚度為20/z m) 4 一 1.拾取試驗關於實施例 1— 1〜1 一 10、1— 12、1— 13、2— 1〜2- 10 '比較例1 — 1〜1 _ 4、2 — 1〜2 — 5、及實施例1 一 11、2 —11〜2 _ 1 5、比較例1 一 7、2 — ό、2 — 7之半導體晶圓加工用黏著片，於上述4. (1)及（2)中所示之條件下分別進行切割後，使用高壓水銀燈之紫外線照射機，自半導體晶Case D On the other hand, if the base resin film is too thick, in the semiconductor wafer picking step after the cutting step, the semiconductor wafer processing adhesive sheet is over 27 201204800 hard 'failed when the needle is lifted up. Further, in the expansion step after the cutting step and before the picking step, it is difficult to sufficiently extend the adhesive sheet for semiconductor wafer processing. Therefore, the gap of the semiconductor wafer is small, and the wafer discriminability of the image is insufficient, resulting in poor pickup of the semiconductor wafer. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. A. Radiation hardenability 1. Preparation of a radiation curable resin composition used in an adhesive layer of an adhesive tape for semiconductor wafer processing according to a first aspect (1) Bonding with a radiation unit for a repeating unit of a primary bond The preparation of a polymer having a residue of a (meth)acrylic monomer portion of a sclerosing carbon-carbon double bond is carried out using butyl acrylate (59 mol%), and 2-ethyl benzoic acid (25 mol%). And acrylic acid (i6m〇i%) to produce an acrylic copolymer. The 〇H group of the 2-hydroxyethyl acrylate side chain of the acrylic copolymer is reacted with the nc thiol group of 2-methylpropenyloxyethyl isocyanate to obtain a repeating unit for the main chain and bond There is a polymer comprising a residue having a radiation-hardening carbon-carbon double bond-containing (fluorenyl) acrylic monomer portion. At this time, the amount of the dropwise addition of 2-Isocyanate ethyl methacrylate was appropriately changed to obtain a polymer ((al) to (a4)) having a different double bond amount. Any of the obtained polymers ((al) to (a4)) had a weight average molecular weight of 70,000 and a glass transition temperature of 60 °C. In Tables 1-1 to 1-4, Embodiments 1 to 1 to 9, 9 to 11, and comparative examples! _ i~i _ 4, i a 7 in the 28 201204800 The polymer used (al) has an iodine value of 2〇. Further, the iodine value of the polymer (a2) used in Example i - ι〇 was 5 〇, and the iodine value of the polymer (a3) used in Example i _ 丨 2 was 〇 5, Example 丨The polymer (a4) used in 丨3 has a moth of 55. In the following description, the α polymerization 16 ((al) to (a4)) will be described as the polymer (a). (i) Weight average molecular weight The weight average molecular weight of the polymer (a) was measured by GPC under the following conditions. GPC device: HLC-8120GPC (trade name, manufactured by T〇s〇h Co., Ltd.) Pipe column: TSK gel Super HM—H/H4000/H3000/H2000 (trade name, manufactured by Tosoh) Flow rate: 0.6 ml/min Concentration: 0.3 Mass % Injection volume: 20 μ 1 Column temperature: 40 ° C Development solvent: gas simulation (ii) Glass transition temperature using a thermal differential scanning analyzer (DSC) (DS.C7020 (trade name), Seiko Instruments Co., Ltd. Manufactured), measured at a temperature increase rate of 5 °C / min. (iii) Double bond amount A hard value was obtained in accordance with JIS K 0070. (2) Preparation of Radiation Curable Resin Composition 29 201204800 The polymer (a) obtained in (1) is in the range of 1 part by mass in Table 1-4. The photo-initiator was blended in a portion, and 3 parts by mass of a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., trade name c〇r〇nate L) was blended as a hardener to prepare Table ii~ In the examples and comparative examples of the crucible 4, the radiation curable resin composition contained in δ was contained. VpE — 0201 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) is used as a comparative example. Polymeric azo polymerization initiator containing polyethylene glycol unit of the photoinitiator used in the first, first, and seventh embodiments~ . The weight average molecular weight of the photoinitiator was measured by the Gpc method, and the weight average molecular weight was calculated using polystyrene as a standard material. The results are shown together in Tables 1 to 1 to 1-4. 01 igo P〇re 300x7.5 (trade name) manufactured by P〇iymer Laboratories was used as a gel permeation chromatograph. The solvent was developed using a gas imitation at 4 Torr. (2) The preparation of the radiation curable resin composition of the adhesive tape for semiconductor wafer processing of the second aspect (1) The acrylic polymer constituting the adhesive layer is used in an amount of 85 parts by mass of n-butyl acrylate. An acrylic acid copolymer is used as a base resin constituting the adhesive layer, and has a weight average molecular weight of 600,000. (2) At least two molecules in the molecule. The compound having a weight average molecular weight of 10,000 or less of the photopolymerizable carbon-carbon double bond is used in UN-3320HA (trade name, manufactured by Kokusai Industrial Co., Ltd.), UN-9000 PEP (trade name, manufactured by Kokusai Industrial Co., Ltd.), and UN-6050PTM (trade name, root). Industrial Manufacturing), UN-901T (trade name, manufactured by SG Tech), 201204800 UN-9200A (trade name, manufactured by SG.). The amount of the bond is as follows. UN- 3 320HA (trade name, manufactured by Ghent Industrial Co., Ltd.): 1500 (double bond amount: 6) UN-3320HC (trade name, manufactured on root): 1500 (double bond) Amount: 6) UN - 9000PEP (trade name, manufactured on root): 5000 (double bond amount: 2) UN - 605 0PTM (trade name, manufactured on root): 6000 (double bond amount: 2) UN - 901T (product Name, root industrial manufacturing): 4000 (double bond amount: 9) UN - 9200A (trade name, manufactured by Root Industries): 1 1500 (double bond amount: 2) (measurement conditions for weight average molecular weight) GPC device: HLC-8120GPC (trade name, manufactured by Tosoh) Column: TSK—GEL G2500HHR (trade name, manufactured by Tosoh) Flow: 1ml/min Concentration: 〇.2mg/ ml Injection volume: 100 // 1 Temperature of the bath: 40°C Flow Phase: gas simulation 31 201204800 (Method for measuring double bond amount) The amount of double bond is determined according to JIS K 0070, and the amount of double bond is calculated based on the value. (3) Preparation of radiation curable resin composition (1) In one part by mass of the base resin, at least two photopolymerizable carbon-carbon double bonds are contained in the molecule, as described in Table 2-1 to Tables 2 to 4, in the case of blending (2). a compound having a weight average molecular weight of 1 〇, 〇〇〇 below and a photoinitiator, and further blending polyisocyanate The compound (manufactured by Nipp〇n Polyurethane Co., Ltd., trade name c〇r〇nate L) was used as a curing agent to prepare a radiation curable resin as described in the examples and comparative examples of Tables 2 to 1 to 2 to 4. Composition. Using vpE-〇2〇1 (trade name 'Wako Pure Chemical Industries Co., Ltd.') as a photoinitiator used in Comparative Examples 2-1 and 2-6, a polyethylene glycol unit-containing polymer azo polymerization initiator One. The weight of the light starter! The average molecular weight was measured by a gel permeation layer (GPC) method, and polystyrene was used as a standard material to calculate a one-dimensional average molecular weight. The result was produced by Polymer Laboratories as a gel permeation chromatograph. Expand the line measurement. And shown in Table 2 - 1 ~ 2 - 4. Use OHgoPore 300x7.5 (trade name) solvent to use gas imitation, and enter 4 at 4 〇t. Use EMMA resin (Sumitomo Chemical Co., Ltd. made the name of the product, MT money production degree _ heart base film 12 The substrate resin film was coated with the radiation curable resin composition shown in Examples - θ m 32 201204800 _1 to 2-10, Comparative Examples 1_1 to 1_4, and 2_1 to 2 to 5, and cured as appropriate. An adhesive sheet for semiconductor wafer processing having a film thickness of 10 μm after drying, which is formed by ffi 1 of a film thickness. 3·Production of an adhesive sheet for semiconductor wafer processing (π) (1) constituting an adhesive layer The composition of the adhesive is prepared by using 5% 酼酼 : 、、、、、、、、、 : : : : : : : : : : : : : : : : : : : : : : : : : : : : Adding hexanone to a composition consisting of 153 parts by mass and 7-ureidopropyltriethoxy decane 5 Å®, and 3 gram parts of spherical bismuth dioxide as a filler, stirring and mixing, and further using Bead mill mixing for 9 minutes to add acrylic rubber to the above composition (weight The average molecular weight is 10,000) 300 parts by weight, and the ethyl group as a hardening accelerator is used as a hardening agent, and the mixture is mixed and vacuum degassed to obtain an adhesive composition. The production of the adhesive sheet for semiconductor wafer processing, and the adhesive composition obtained in (1) is applied to the release-treated polyethylene terephthalate film (release film) of thickness 35 " After drying for 5 minutes, the film thickness was "B-stage of the claw (the adhesive sheet in which the adhesive layer was formed on the release film in the b state. Then, with the above 2. Semiconductor The semiconductor wafer-filled adhesive sheet having the structure shown in the figure is obtained by the same method as described in the production of the adhesive sheet for wafer processing (i), and the structure is the embodiment of the silk fabric 4 i 201204800 The radiation-polymerizable resin composition contained in δ of the above Example 1 forms an adhesive layer on the base resin film, and the adhesive layer is laminated on the adhesive layer of the adhesive sheet produced by the above method, and laminated. Obtaining a release film on the adhesive sheet for processing semiconductor wafers shown in FIG. Adhesive sheets (Examples 1 to 11 and Comparative Examples 7 to 7). The structure shown in Fig. 1 was obtained in the same manner as in the above-described method for producing an adhesive sheet for semiconductor wafer processing. The adhesive sheet for semiconductor wafer processing is a radiation polymerizable tree layer described in Example 2, No. 11 2 1 5, and Comparative Example 2 - ό, 2-7, and The adhesive layer is formed on the base resin film, and the adhesive layer is laminated on the adhesive layer of the adhesive sheet produced by the above method, and the laminate shown in FIG. 2 is obtained for semiconductor wafer processing. Adhesive sheets in which a release film was laminated on the adhesive sheet (Examples 2_u to 2-15, Comparative Examples 2-6 and 2) In the following test, the release film was peeled off and bonded to a semiconductor wafer and evaluated. 4·Performance test According to the following conditions, the cutting was performed, and then the pick-up property and the wafer contamination were evaluated. (Cutting conditions) 10, (1) The adhesive sheet for semiconductor wafer processing of the structure of FIG. 1 about Embodiment 1-1 to 1-10, Bu 12, 13, 2_1~2_ Comparative Example 1-1~1- 4, 2-1~2-5, using DISC〇 company's DFD-840", grinding the back surface of the silicon wafer by two axes with a double axis "claw 34 201204800, after the final thickness of the wafer becomes 100" Grinding is performed in the manner of m. The grinding conditions at this time are as follows. Single-axis 350 grindstone (rotation speed: 々goorpm, descending speed: pi is 3_〇"m/Sec, P2 is 2.〇"m/sec) Dual axis. #2000 grindstone (rotation speed: 5500rpm, descending speed: P1 is 0.8/zm/Sec, and P2 is M6Mm/sec. The back surface is polished for 5 minutes or less, and the semiconductor wafer processing adhesive sheet having the structure of FIG. i is bonded to a ring-shaped frame of 8 inches. A 100-inch-thick 100-inch wafer is bonded to a semiconductor wafer processing adhesive sheet in a fixed state, and a cutting device (Singapore name) manufactured by DISC Corporation is used for fullcut dicing. The wafer size is 5 mm x 5 mm. The cutting depth of the blade from the adhesive sheet surface for semiconductor wafer processing at this time is set to the heart m 0 in the case of the adhesive sheet shown in Fig. 1 (2) The semiconductor wafer processing adhesive sheet is constructed. With respect to the examples i-U'2 - U~2-15 and the comparative examples 1-7, 2-6, 2-7, under the armpit, the semiconductor crystal composed of the ffl 2 is formed. After the round processing adhesive sheet was attached to a 100-inch-thick 8-inch wafer for 2 seconds, the DFD 6340 manufactured by Disc Corporation was used to cut the following conditions. Cutting blade (thin rotary grindstone): 帛i used 27HEEE manufactured by Disco's side 2nd used 27hedd manufactured by Dise〇 Blade speed: 35000 rpm Blade feed speed: 50 mm/s Wafer size: 5 mm><5 mm 35 201204800 Depth of cut: Cut the 50 μm into the wafer for the first time and cut 40 μm into the adhesive sheet for semiconductor wafer processing for the second time (the thickness of the base resin film is 100#m, the thickness of the adhesive layer) 10 " m, thickness of the adhesive layer is 20 / zm) 4 - 1. Pick up test with respect to Examples 1 - 1 to 1 - 10, 1 - 12, 1 - 13, 2 - 1 to 2 - 10 'Comparative Example 1 - 1~1 _ 4, 2 - 1~2 - 5, and Example 1 - 11, 2 - 11~2 _ 1 5, Comparative Example 1 - 7, 2 - ό, 2 - 7 semiconductor wafer processing After the cutting is carried out separately under the conditions shown in the above 4. (1) and (2) with an adhesive sheet, an ultraviolet ray irradiator using a high-pressure mercury lamp, from the semiconductor crystal

圓加工用黏著片之基材樹脂膜面側，以照射量成為200mJThe side of the base resin film of the adhesive sheet for round processing, the irradiation amount is 200 mJ

/ cm2之方式進行紫外線照射，其後使用CAN〇N machinery製造之CPS— 6820 (商品名），以5mm之延伸行程（expand stroke)進行延伸，並於該狀態下進行拾取。才。取係使用頂端徑為R250之頂出銷而進行。評價項目係針對以下項目實施。 (1 )拾取性實際拾取晶片’評價a.順利頂出晶片、b以圓形桶夾吸附晶片、& c.將晶片設置於導線架上之任一者是否均可順利進行。評價係根據自8英忖晶圓中拾取2〇〇個晶片，其中可拾取多少晶片數而評價。將2〇〇個晶片中可拾取個晶片以上之情形設為合格，將拾取成功之晶片〜1〜2— 4 Φ。、 36 201204800 (2 )晶片污染性晶片污染性係針對圖1 著片（實施例1 — 1〜1 — 1 〇、比較例1 — 1〜1 — 4、2 — (2 ) — 1目視試驗之構成之半導體晶圓加工用黏 1 一 12、1— 13、2 — 1 〜2 — 1〇、 2—5)，利用以下方法加以評價。評價上述晶片污染性時’剝離晶片以目視加以確認。將晶圓背面不存在因黏著劑之貼合或污染物之附著而引起之彩虹色光澤之情形設為合格，將合格之情形表示為〇，將產生少許光澤但實際應用上不成問題之水平表示為△，將貼合有黏著劑之情形設為不合格，表示為χ。 (2) —2異物試驗於表面經洗淨之鏡面拋光之矽晶圓（6英吋）貼合半導體晶圓加工用黏著片’放置24小時後，剝離該片材。藉由雷射表面檢測裝置（Surfscan6420(商品名，KLA~~ · Tene()r (股份有限公司）製造）測定貼合過該片材之晶圓表面所殘留之異物數。根據以下所示之評價基準對所得之結果進行判定。其中，◎及〇表示合格，△表示實際應用上不成問題之水平’ χ表示不合格。將該結果示於表中。 ◎:未達20個、〇：20個以上且未達90個、△ : 9() 個以上且未達200個、χ : 200個以上 (3 )黏著劑層與接著劑層之剝離性於加熱至80。(：之加熱板上載置直徑5英吋之妙晶圓，確認該矽晶圓之表面溫度達到8(TC後，於大約1〇秒鐘内貼合圖2之構成之半導體晶圓加工用黏著片（實施例丨—1 ^、 37 201204800 2 — 11〜2 ~ 1 5及比較例1 — 7、熱板，將貼合有半導體晶圓加溫度降至室溫。 2 - 6、2 ~ 7 )。此後，除去加工用黏著片之矽晶圓之表面其後，使用高壓水銀燈之紫外線照射機，自半導體晶圓加^用黏著片之基材樹脂膜面側，以照射量成為層… / Cni之方式進行紫外線照射。此後，依據jis — 0237，測定紫外線照射後之半導體晶圓加工用黏著片對矽晶圓之剝離力。測定條件係以90。剝離，剝離速度為5〇mm/min。將該剝離力為〇.5N/ 25mm以下之情形設為合格，記作〇。 38 201204800 實施例1—υ 2-羥基一2 甲基一1-笨基丙烷一 1-酮〇 180/200 <] <3 實施例1 — 5 1 —經基一環己基苯基一酮 205 〇 I 200/200 〇〇實施例1—4 寡Ρ —羥基_2_甲基一1—[4_ (1—甲基乙烯基)苯基] 丙酿1}η = 2〜3 400〜500 〇 200/200 〇 ◎ 實施例1—3 寡{2—羥基一2—甲基一1 — [4_(1 一甲基乙稀基)苯基] 丙嗣}η = 2〜3 400〜500 〇 200/200 〇 ◎ 實施例1 _2 2—甲基一1 一 (4-甲硫基苯基） —2 —昧嚇基丙炫 -1-酮 * 280 A 〇 200/200 〇〇實施例1 — 1 2,2— 二甲氧基一1，2 — 二苯基乙烧_ 1 —嗣 260 ο 200/200 〇〇種類重量平均分子量 1摻合份數聚合物（a)之摻合份數聚合物（a)之碘值拾取成功之晶片數/總晶片數目視試驗異物試驗光起始劑晶片污染性 201204800 -Ultraviolet irradiation was carried out in the manner of /cm2, and then CPS-6820 (trade name) manufactured by CAN〇N Machinery was used, and extended by an extension stroke of 5 mm, and picked up in this state. only. The take-up is performed using the ejector pin whose tip diameter is R250. The evaluation project is implemented for the following projects. (1) Pick-up Actual pickup of the wafer 'Evaluation a. Smoothly ejecting the wafer, b sucking the wafer with a circular barrel clamp, & c. Whether or not any of the wafers on the lead frame can be smoothly performed. The evaluation was based on picking up 2 wafers from a 8 inch wafer, of which the number of wafers that could be picked up was evaluated. The case where more than one wafer can be picked up in 2 wafers is qualified, and the successfully picked wafers are ~1~2 - 4 Φ. 36 201204800 (2) The contamination level of the wafer is contaminated with respect to Figure 1 (Examples 1-1 1 - 1 - 1 〇, Comparative Example 1 - 1 to 1 - 4, 2 - (2) - 1 visual test The composition of the semiconductor wafer processing adhesive 1-12, 1-13, 2-1~2 - 1〇, 2-5) was evaluated by the following method. When the wafer contamination was evaluated, the peeled wafer was visually confirmed. The case where the iridescent luster caused by the adhesion of the adhesive or the adhesion of the contaminant is not present on the back side of the wafer, and the qualified condition is expressed as 〇, which will produce a little gloss but the level of practical application is not a problem. In the case of Δ, the case where the adhesive is applied is regarded as unacceptable, and it is expressed as χ. (2) - 2 foreign matter test The surface-washed mirror-polished wafer (6 inches) was attached to the semiconductor wafer processing adhesive sheet. After standing for 24 hours, the sheet was peeled off. The number of foreign matter remaining on the surface of the wafer to which the sheet was bonded was measured by a laser surface detecting device (Surfscan 6420 (trade name, manufactured by KLA~~Tene(R) Co., Ltd.). The evaluation results were used to determine the results obtained. Among them, ◎ and 〇 indicate pass, and △ indicates that the level of practical use is not a problem ' χ indicates failure. The results are shown in the table. ◎: less than 20, 〇: 20 More than 90 and less than 90, △: 9 () or less and less than 200, χ: 200 or more (3) The peelability of the adhesive layer and the adhesive layer is heated to 80. (: The heating plate is uploaded A 5 inch diameter wafer is placed, and it is confirmed that the surface temperature of the silicon wafer reaches 8 (TC, and the adhesive sheet for semiconductor wafer processing constructed as shown in FIG. 2 is bonded in about 1 second (Example 丨 - 1 ^, 37 201204800 2 — 11~2 ~ 1 5 and Comparative Example 1 — 7. Hot plate, the temperature of the semiconductor wafer is bonded to room temperature. 2 - 6, 2 ~ 7 ). Thereafter, the processing is removed. After the surface of the wafer is adhered, the ultraviolet ray irradiator of the high-pressure mercury lamp is used, and the semiconductor is used. The surface of the base resin film of the adhesive sheet is applied to the surface of the resin film of the adhesive sheet, and the irradiation is performed in the form of layer / Cni. Thereafter, the adhesive sheet for semiconductor wafer processing after ultraviolet irradiation is measured according to jis - 0237 The peeling force of the circle was 90. The peeling speed was 5 mm/min. The peeling force was 〇5 N / 25 mm or less, and it was designated as 〇. 38 201204800 Example 1 - υ 2-hydroxy-l-methyl-l-phenylpropane-l-ketooxime 180/200 <3>3 Example 1 - 5 1 -trans-cyclohexylphenyl ketone 205 〇I 200/200 〇〇 Example 1-4 oligofluorene-hydroxy-2-methyl-1,4-[4-(1-methylvinyl)phenyl] propyl 1}η = 2~3 400~500 〇200/200 〇◎ Example 1-3 oligo{2-hydroxy-2-methyl- 1 -[4_(1-methylethlyl)phenyl]propene}η = 2~3 400~500 〇200/200 〇◎ Example 1 _2 2-methyl-l-(4-methylthiophenyl)-2-pyrene-thiophenan-1-one* 280 A 〇200/200 〇〇Example 1 — 1 2,2-dimethoxy Base 1,2 - diphenyl bromide _ 1 —嗣260 ο 200/200 〇〇 kind weight average molecular weight 1 blending fraction polymer (a) blending fraction polymer (a) iodine value number of wafers successfully picked up / total number of wafers Initiator wafer contamination 201204800 -

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oo(N\§<N <Ν— Ι< § 比較例1 _4 2,2 —二甲氧基一1,2 — 二苯基乙院一1 —飼 260 ο 200/200 X X 比較例1一3 2,2 —二甲氧基一1,2 — 二苯基乙烧一 1 一網 260 0.05 100 150/200 〇〇比較例1 — 2 2,2 —二甲氧基 _1，2_ 二苯基乙炫一1 _飼 260 0.05 ο [ 50/200 〇〇比較例1 — 1 匀破㈣· <〇鮏鉍 \\ W t〇雄鉍屮 <« Φ 2000 ο 100/200 〇〇種類重量平均分子量份數聚合物（a)之摻合份數聚合物（a)之碘值 $ \ m〇3 目視試驗異物試驗光起始劑 ωΟ W 晶片污染性 0寸 if苯破^ 201204800 寸I 1 比較例1—7 含聚乙二醇單位之高分子偶氮聚合起始劑 2000 〇環氧系 100/200 〇比較例1 — 11 2,2 —二甲氧基一1，2 —二苯基乙烧一1 _闕 260 〇環氧系 200/200 〇種類重量平均分子量份數聚合物（a)之摻合份數聚合物（a)之碘值接著劑層拾取成功之晶片數/總晶片數黏著劑層與接著劑層之剝離性光起始劑黏著劑層 201204800 T(N< 實施例2_6 2—羥基一2—甲基 —1 —苯基丙烧一1 -酮 in ο UN-3320HA 〇 200/200 <1 Ο 實施例2 —5 1 一經基一環己基苯基一明 205 ο UN-3320HA 〇 200/200 〇〇實施例2—4 寡P —羥基一2—甲基一1 —[4-(1-甲基乙烯基)苯基]丙明}11=2〜3 400〜500 ro ο UN-3320HA 〇 ψ-^ 200/200 〇 ◎ 實施例2 — 3 寡P —羥基一2—甲基一1 —[4 —(1-甲基乙烯基)苯基]丙嗣}11=2〜3 400〜500 ο UN-3320HA 〇 200/200 〇 ◎ 實施例2 —2 2_甲基一1一 (4—甲硫基笨基)—2 — 0末基丙烷一 1一酮 280 in ο 1 UN-3320HA 〇 200/200 〇〇實施例2—1 2,2—二甲氧基 —1,2 —二苯基乙烷一1 —酮 260 ο UN-3320HA 100 200/200 〇〇種類重量平均分子量摻合份數丙烯酸系基底樹脂種類摻合份數拾取成功之晶片數/總晶片數目視試驗異物試驗光起始劑叫伞黎4〇枇鉍韌$ 畋采镩屮$ e埂丨Φ % 屮《Ν够牮 Φ 21 w 晶片污染性 201204800 ο ΪΤ < 1 (Ν 砩鉍 (〇 ®硪 S CN ο X s m f〇〇 m 〇 (N 〇〇〇 '丨J 1 yd 1 μ ^ 1 5 On 3丄 1 1 < 實施例2 — 2,2 —二曱氧基 —二笨基乙烧-酮 S (N in ο S ro m 1 § r—^ 200/200 〇〇 00 ^ΐ4 | < 1 o 〇 Ϊ8- ^ \ r-H Μ ι ι S ο ο (N m m 〇 (N \ 〇〇省 1飞鉍 1 〇 π 7 ν3 <Ν ι g 卜 ^i4 ι < X ΓΟ m 〇 δ- »1 ^ il 1 1 § ^Η ο 〇 (N \ 〇〇 π 1 〇 7 <Ν § CN 令 U Μ 戥革》W 傘戬 $4 .<>ml 梁 U〇u| <$0 荽 φΐ i)m ΠΣ；囬 τ〇π 璨 m 械1 >ei VE 内具有至少2個光性碳一碳雙鍵之低分子化合物 \ < ±d it 4? < Φ S4 201204800 比較例2 —5 1 i i气 3 <〇 μ i4 1 1，1 一 (N 1 (N § rs ο UN-3320HA Ο m 150/200 〇〇比較例2 — 4 2,2 —二曱氧基一 1，2 —二苯基乙烧一 1 一飼 § (N ο UN-3320HA d 100/200 〇〇比較例2 —3 2,2_二甲氧基一 1，2 —二苯基乙坑一 1-酮 S CN ο UN-3320HA o 200/200 X X 比較例2 —2 2,2 —二甲氧基 _ 1，2—二苯基乙烷一1 -酮 § (N s d ο UN-3320HA o 50/200 〇〇比較例2 — 1 ^ Φ 4〇 Η呢“茶 <0 V ^ 龄与筚破 4« 2000 ο UN-3320HA o 100/200 〇〇戡總重量平均分子量摻合份數丙烯酸系基底樹脂摻合份數拾取成功之晶片數/總晶片數目視試驗異物試驗光起始劑厚黎 «Ν势(吞 Α替伞 ^ 1 ^ 钾楚屮 »1( ±1 Φ ε伞筚 Φ來晶片污染性 2 1X20 寸 —(N< 比較例2 —7 C 2,2-二甲氧基一1,2 — 二苯基乙炫一1 —酿| 1 w-) Ο UN —9200A Ο 環氧系 100/200 〇比較例2 —6 ^ ^ ^ 2000 ο UN-3320HA Ο 環氧系 100/200 〇實施例2_l5 2,2 —二甲氧基 —1，2 —二苯基乙烧 -1-酮 260 ο UN-901T Ο 環氧系 190/200 〇實施例2_l4 2,2_二甲氧基 — 1,2 — 二苯基乙烷 —1-酮 | 260 IT) ο UN —6050PTM Ο 環氧系 195/200 〇實施例2—13 2,2—二甲氧基 ~ 1,2 — 二苯基乙烷 —1 —明 260 ο UN-3320HC ο 環氧系 200/200 〇實施例2 — 12 2,2—二曱氧基 —1,2 — 二苯基乙烷 -1-酮 260 100 UN-9000PEP ο 環氧系 200/200 〇實施例2—11 2,2 —二曱氧基 -1,2-二苯基乙烷 -1-酮 260 ο UN-3320HA ο 環氧系 200/200 〇種類重量平均分子量摻合份數丙烯酸系基底樹脂種類摻合份數接著劑層拾取成功之晶片數/總晶片數黏著劑層與接著劑層之剝離性光起始劑 CN ♦(蓉镩命叫丨与 ^ Si φ C ·4〇 ^ Η- ^ <7 令采 201204800 5 ·第1態樣之半導體晶圓加工用黏著膠帶根據表1一 1〜1—3可知’於對圖1所示之構成之半導體晶圓加工用黏著片進行評價之實施例中，2〇〇個晶片中可才。取1 80個晶片以上之半導體晶片，晶片污染或異物殘留較少，且可順利地拾取。實施例i — 6中見到少許晶片污染或殘留異物’但為實際應用上不成問題之水平。又，於由使用碘值0.5之聚合物（a)作為基底樹脂之黏著劑層所構成的半導體晶圓加工用黏著片之情形時，2〇〇個晶片中可拾取18〇個半導體晶片，表現出合格水平之特性。相對於此，使用含聚乙二醇單位之高分子偶氮聚合起始劑作為光聚合起始劑（比較例丨—丨），結果光起始劑無法充分均勻地溶解’所產生之自由基之移動無法充分順利地進行，結果2 0 0個晶片中僅可拾取一半。又，於使光聚合起始劑之量少於〇_丨質量份之情形時 (比較例1-2 ' 1-3) ’由於起始劑所致之自由基供給不足，而於拾取性上產生問題，於光聚合起始劑之量多於1〇質量份之情形時（比較例丨—4)，由於未反應物所致之昇華而產生晶片污染。又，根據表卜4可知，於對圖2所示之構成之半導體晶圓加工用黏著片進行評價的實施例卜u中，可於黏著劑層與接著劑層之間順利地進行界面剝離，個晶片中可拾取所有之半導體晶片。 ° 相對於此’於比較例卜7中，無法於黏著劑層與接著 46 201204800 劑層之間順利地進行界面剝離，200個晶片中僅可拾取1 〇〇個半導體晶片。 5.第2態樣之半導體晶圓加工用黏著膠帶根據表2— 1〜2—3可知，於對圖i所示之構成之半導體晶圓加工用黏著片進行評價的實施例中，2〇〇個晶片中可才D取所有之半導體晶片，晶片污染或異物殘留較少，且可順利地拾取。實施例2— 6中可見到少許晶片污染或殘留異物，但為實際應用上不成問題之水平。相對於此，使用含聚乙二醇單位之高分子偶氮聚合起始劑作為光聚合起始劑（比較例2—〇,結果光起始劑無法充分均勻地溶解，所產生之自由基之移動無法充分順利地進行，結果200個晶片中僅可拾取一半。又，於使光聚合起始劑之量少於〇.丨質量份之情形時 (比較例2—2)，由於起始劑所致之自由基供給不足，而於才。取性上產生問題，於光聚合起始劑之量多於1 〇質量份之隋形時（比較例2 ~ 3 )，由於未反應物所致之昇華而產生晶片污染。右使分子内具有至少2個光聚合性碳一碳雙鍵之化合物之摻合份數少於1質量份（比較例2—4)，則拾取性下降。反之於放射線聚合性化合物之摻合份數多於3〇〇質量份 =隋形時（比較例2 ~ 5 )，由於黏著劑層產生硬化收縮，黏著劑密著於晶片背面，從而可見到拾取性下降。曰又，根據表2—4可知，於對圖2所示之構成之半導體曰曰圓加工用黏著片進行評價的實施例2— 11〜2— 15中，可 47 201204800 於黏著劑層與接著劑層之間順利地進行界面剝離，2〇〇個晶片中可拾取所有之半導體晶片。相對於此，於使用重量平均分子量較大之光聚合起始劑之比較例2 — 6中，無法於黏著劑層與接著劑層之間順利地進行界面剝離’ 2〇〇個晶片中僅可拾取1 00個半導體晶片。又，於使用分子内具有至少2個光聚合性碳一碳雙鍵之化合物之重量平均分子量為Π，500者的比較例2 — 7中，與比較例2—6同樣地，200個晶片中僅可拾取1〇〇個半導體晶片。以上，對本發明及其實施態樣一併進行了說明，但本發月人等為，只要無特別指定，則於說明之任一細微處句未限定本發明人等之發明，而應於不違背隨附之申請專範圍所不之發明精神及範圍的情況下作廣義地解釋。本申請案係主張基於2〇1〇年3月31日於日本提出專利申請之曰本特願2〇1〇一 84447及2〇1〇年3月η日於日 , π之曰本特願20 10 — 8453 1之優先權，該等係以參昭太斗、收# ^ '、内容作為本說明書之記載之一部分而併入至本說明書中。【圖式簡單說明】圖 1 得矣—4· 、不本發明之晶圓加工用黏著片之一實施形態面圖。圖2係表示本發货月之曰曰圓加工用黏著片之另一實施形 48 201204800 【主要元件符號說明】 1 基材樹脂膜 2 黏著劑層 3 接著劑層Oo(N\§<N <Ν- Ι< § Comparative Example 1 _4 2,2 -Dimethoxy-1,2-diphenyl phenyl- 1 - feeding 260 ο 200/200 XX Comparative Example 1 a 3 2,2-dimethoxy-1,2-diphenylethene-one-one net 260 0.05 100 150/200 〇〇Comparative Example 1 — 2 2,2-dimethoxy_1,2_ 2 Phenyl Ethene 1 _ Feed 260 0.05 ο [ 50/200 〇〇 Comparative Example 1 - 1 Evening (4) · <〇鮏铋\\ W t〇雄铋屮<« Φ 2000 ο 100/200 〇〇 Kind of weight average molecular weight fraction polymer (a) blending fraction polymer (a) iodine value $ \ m〇3 visual test foreign matter test photoinitiator ωΟ W wafer contamination 0 inch if benzene broken ^ 201204800 inch I 1 Comparative Example 1-7 Polymer azo polymerization initiator containing polyethylene glycol unit 2000 〇 Epoxy 100/200 〇 Comparative Example 1 - 11 2,2 -Dimethoxy-1,2 - 2 Phenyl Ethylene 1- 1 阙 260 〇 Epoxy 200/200 〇 Type Weight Average Molecular Weight Part Number Polymer (a) Blend Part of Polymer (a) Iodine Value Binder Layer Pickup Successful Wafers / Total wafer number adhesive layer and connection Adhesive layer peeling photoinitiator adhesive layer 201204800 T (N<Example 2_6 2-hydroxy-2-methyl-1 phenylpropanone-1-ketone in ο UN-3320HA 〇200/200 < 1 Ο Example 2 - 5 1 mono-cyclohexylphenyl phenyl 205 ο UN-3320HA 〇 200/200 〇〇 Example 2-4 oligo P-hydroxyl 2-methyl- 1 -[4-(1 -Methylvinyl)phenyl]propanol}11=2~3 400~500 ro ο UN-3320HA 〇ψ-^ 200/200 〇◎ Example 2-3 Oligo P-hydroxy-2-methyl-1 —[4 —(1-methylvinyl)phenyl]propene}11=2~3 400~500 ο UN-3320HA 〇200/200 〇◎ Example 2-2 2_Methyl-1 1 (4 -Methylthiophenyl)2- 2 -0-propanyl-propanone 280 in ο 1 UN-3320HA 〇200/200 〇〇Example 2-1 2,2-dimethoxy-1,2- 2 Phenylethane-1-ketone 260 ο UN-3320HA 100 200/200 〇〇 kind weight average molecular weight blending parts acrylic base resin type blending parts number of wafers successfully picked up / total number of wafers The initiator is called Umbrella 4畋镩屮镩屮 $ e埂丨 Φ % 屮 "Ν 牮 Φ 21 w wafer contamination 201204800 ο ΪΤ < 1 (Ν 砩铋 (〇®硪S CN ο X smf〇〇m 〇 (N 〇〇〇'丨J 1 yd 1 μ ^ 1 5 On 3丄1 1 < Example 2 - 2,2 -dimethoxy-di-p-ethylidene-ketone S (N in ο S ro m 1 § r-^ 200 /200 〇〇00 ^ΐ4 | < 1 o 〇Ϊ8- ^ \ rH Μ ι ι S ο ο (N mm 〇(N \ 〇〇省1飞铋1 〇π 7 ν3 <Ν ι g 卜^i4 ι < X ΓΟ m 〇δ- »1 ^ il 1 1 § ^Η ο 〇 (N \ 〇〇π 1 〇7 <Ν § CN 令U Μ 戥》》 W Umbrella 4 $4 .<>ml Beam U〇u| <$0 荽φΐ i)m ΠΣ; Back τ〇π 璨m 械1 >ei VE Low molecular compound with at least 2 photonic carbon-carbon double bonds\ < ±d it 4 < Φ S4 201204800 Comparative Example 2 - 5 1 ii gas 3 < 〇 μ i4 1 1,1 a (N 1 (N § rs ο UN-3320HA Ο m 150/200 〇 Comparative Example 2 - 4 2,2-dimethoxy-1,2-diphenylethene- 1st feed § (N ο UN-3320HA d 100/200 〇〇Comparative Example 2 - 3 2,2_2 Methoxy-1,2-diphenylethylidene-1-ketone S CN ο UN-3320HA o 200/200 XX Comparative Example 2-2 2,2-Dimethoxy_ 1,2-diphenyl Alkanol-1 -ketone § (N sd ο UN-3320HA o 50/200 〇〇Comparative Example 2 - 1 ^ Φ 4〇Η?"Tea<0 V ^ Age and smashed 4« 2000 ο UN-3320HA o 100 /200 〇〇戡 total weight average molecular weight blending parts acrylic base resin blending parts number of wafers successfully picked up / total number of wafers depending on test foreign matter test light initiator thick Li «Ν potential (swallowing umbrella ^ 1 ^ 屮屮屮 1 1 1 1 1 1 1 晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片晶片 1 1 1 1 1 — Stuffing | 1 w-) Ο UN —9200A 环氧 Epoxy 100/200 〇Comparative Example 2 —6 ^ ^ ^ 2000 ο UN-3320HA 环氧 Epoxy 100/200 〇Example 2_l5 2,2 —Dimethyl Oxy-1,2-diphenylethidin-1-one 260 ο UN-901T 环氧 Epoxy 19 0/200 〇Example 2_l4 2,2-Dimethoxy-1,2-diphenylethane-1-one | 260 IT) ο UN —6050PTM Ο Epoxy 195/200 〇Example 2-13 2,2-dimethoxy~ 1,2-diphenylethane-1- Ming 260 ο UN-3320HC ο Epoxy 200/200 〇Example 2 - 12 2,2-dimethoxy--1 , 2 - diphenylethane-1-one 260 100 UN-9000PEP ο epoxy 200/200 〇 Example 2-11 2,2-dimethoxy-1,2-diphenylethane-1 -ketone 260 ο UN-3320HA ο Epoxy 200/200 〇 kind weight average molecular weight blending parts acrylic base resin type blending part number of adhesive layer pick-up wafer number / total number of wafers adhesive layer and adhesive Layer peeling photoinitiator CN ♦(镩镩命叫丨和^ Si φ C ·4〇^ Η- ^ <7 采采201204800 5 · The first aspect of the semiconductor wafer processing adhesive tape according to the table 1 to 1 to 3, it can be seen that in the embodiment in which the adhesive sheet for semiconductor wafer processing shown in Fig. 1 is evaluated, it is possible to use two wafers. Taking more than 180 wafers of semiconductor wafers, wafer contamination or foreign matter remains less and can be picked up smoothly. A few wafer contaminations or residual foreign matter were seen in Examples i-6 but were not problematic in practical use. Further, in the case of an adhesive sheet for semiconductor wafer processing comprising a polymer (a) having an iodine value of 0.5 as a base resin, 18 semiconductor wafers can be picked up in two wafers. The characteristics of the qualified level. On the other hand, a polymer azo polymerization initiator containing polyethylene glycol unit was used as a photopolymerization initiator (Comparative Example 丨-丨), and as a result, the photoinitiator could not sufficiently dissolve the radical generated. The movement cannot be performed smoothly enough, and as a result, only half of the 200 wafers can be picked up. Further, when the amount of the photopolymerization initiator is less than 〇_丨 by mass (Comparative Example 1-2 '1-3) 'The radical supply due to the initiator is insufficient, and on the pick-up property There was a problem that in the case where the amount of the photopolymerization initiator was more than 1 part by mass (Comparative Example 4), wafer contamination occurred due to sublimation due to unreacted materials. Further, according to Table 4, in the embodiment in which the adhesive sheet for semiconductor wafer processing shown in FIG. 2 is evaluated, the interface peeling can be smoothly performed between the adhesive layer and the adhesive layer. All of the semiconductor wafers can be picked up in one wafer. In contrast, in Comparative Example 7, the interface peeling could not be smoothly performed between the adhesive layer and the next layer of the layer of the 201204800, and only one semiconductor wafer could be picked up in the 200 wafers. 5. The second aspect of the adhesive tape for processing a semiconductor wafer, according to Tables 2-1 to 2-3, in the embodiment in which the adhesive sheet for semiconductor wafer processing shown in Fig. i is evaluated, 2〇 Only one semiconductor wafer can be taken in one wafer, and wafer contamination or foreign matter remains less, and can be smoothly picked up. A small amount of wafer contamination or residual foreign matter can be seen in Examples 2-6, but it is not a problem level in practical use. On the other hand, a polymer azo polymerization initiator containing polyethylene glycol unit was used as a photopolymerization initiator (Comparative Example 2 - 〇, the photoinitiator was not sufficiently uniformly dissolved, and the generated radicals were produced. The movement could not be carried out sufficiently smoothly, and as a result, only half of the 200 wafers could be picked up. Further, when the amount of the photopolymerization initiator was less than 〇.丨 by mass (Comparative Example 2-2), the initiator was used. The resulting free radical supply is insufficient, and the problem arises when the amount of photopolymerization initiator is more than 1 〇 mass part (Comparative Example 2 ~ 3) due to unreacted materials. The sublimation causes wafer contamination. When the right portion of the compound having at least two photopolymerizable carbon-carbon double bonds in the molecule is less than 1 part by mass (Comparative Example 2-4), the pick-up property is lowered. When the blending ratio of the radiation polymerizable compound is more than 3 parts by mass = 隋 shape (Comparative Examples 2 to 5), since the adhesive layer is hardened and shrinks, the adhesive is adhered to the back surface of the wafer, so that the pickup property is deteriorated.曰 again, according to Table 2-4, as shown in Figure 2 In Example 2-11 to 2-15, which was evaluated by the adhesive sheet for semiconductor processing, it was possible to smoothly perform interfacial peeling between the adhesive layer and the adhesive layer, and in 2 wafers. In contrast, in Comparative Example 2-6 using a photopolymerization initiator having a large weight average molecular weight, interface peeling between the adhesive layer and the adhesive layer could not be smoothly performed. Only one hundred semiconductor wafers can be picked up in one wafer. Further, in Comparative Example 2-7, in which the weight average molecular weight of a compound having at least two photopolymerizable carbon-carbon double bonds in the molecule is Π, 500, In the same manner as in Comparative Example 2-6, only one semiconductor wafer can be picked up in 200 wafers. The present invention and its embodiments have been described above, but the present invention is as long as it is not specified. The inventors of the present invention are not limited to the inventions of the present invention, and should be interpreted broadly without departing from the spirit and scope of the invention as set forth in the appended claims. Based on the application for a patent application filed in Japan on March 31, 2011, the Japanese special offer 2〇1〇184447 and the 2nd year of March η日日日, π之曰本特愿20 10 — 8453 1 The priority is to incorporate the contents of this specification into the specification as part of the description of this specification. [Simplified illustration] Figure 1 矣矣 -4 · , not Fig. 2 is a view showing another embodiment of the adhesive sheet for wafer processing of the invention. Fig. 2 is a view showing another embodiment of the adhesive sheet for round processing of the present shipping month. 201204800 [Description of main components] 1 Base resin film 2 Adhesive layer 3

Claims

201204800 VII. Patent application scope: i An adhesive sheet for processing semiconductor wafers, which is formed by a substrate of a radiation-permeable substrate and an adhesive layer on the resin film of the substrate, and the adhesive layer is used. It is composed of a layer of a radiation curable resin composition containing (in) a photopolymerization initiator (b) in an amount of 0.1 to 10,000 parts by mass based on 1 part by mass of the (i-丨) base resin. a ruthenium (1 - 1 ) base resin which is obtained by binding an acrylic polymer (a) having a residue having a (fluorenyl) acrylic monomer moiety to a repeating unit of a main chain as a main component. The acrylic monomer portion has a radiation-curable carbon-carbon double bond-containing group, and the ruthenium (111) photopolymerization initiator (b) is formed by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight of polystyrene as a standard substance is less than 1,000. 2. An adhesive sheet for processing a semiconductor wafer, which is formed by a radiation-permeable substrate resin film and an adhesive layer on the substrate resin film, the adhesive layer being used in relation to (i-2) 100 parts by mass of the acrylic acid-containing polymer (Π) compound (〇}~% by mass parts, and (out) photopolymerization initiator (b) 〇. 1 to 10 parts by mass of the radiation curable resin composition And (ii) the compound (C) having at least two photopolymerizable carbon-carbon double bonds in the molecule having a weight average molecular weight of 10,000 or less, and (iii) a photopolymerization initiator (b) By means of gel permeation chromatography (hereinafter referred to as "GPC"), the weight average molecular weight of 4 stupid ethylene as a standard substance is less than 1000 ° 50 201204800, such as the semiconductor wafer of claim 1 or 2 The processing adhesive (b) is selected from the group consisting of 1-hydroxy-cyclohexan-1,2-diphenylethene- 1 ketone, 2 sheets, wherein the photopolymerization initiator (base group - _, 2) , 2 - Dimethoxy-indenylmethyl (4-methylthiophenyl) - 2 - α-mercapto-propyl, and description Formula (1) of oligomer represented by the general formula (1)

At least one of the group consisting of H~9~CH3 I 3 OH (wherein R represents an alkyl group and n is an integer). 4. The adhesive sheet for semiconductor wafer processing of the third paragraph of the patent scope of the patent application, wherein the degree of polymerization of the oligomer represented by the general formula (1) is n=2 5. As claimed in claim 1 An adhesive sheet for processing a semiconductor wafer, wherein the repeating unit with respect to the main chain contains a polymer (a) having a radiation-polymerized ruthenium double bond-containing group as a constituent unit, and has a 峨 value of 1 to 50. . Six kinds of adhesive sheets for processing semiconductor wafers, which are further provided with an adhesive layer on the adhesive layer of the adhesive sheet for semiconductor wafer processing of Patent Application No. 1 or 2. 51