TW201203342A - Adhesive sheet for semiconductor wafer processing - Google Patents
Adhesive sheet for semiconductor wafer processing Download PDFInfo
- Publication number
- TW201203342A TW201203342A TW100113775A TW100113775A TW201203342A TW 201203342 A TW201203342 A TW 201203342A TW 100113775 A TW100113775 A TW 100113775A TW 100113775 A TW100113775 A TW 100113775A TW 201203342 A TW201203342 A TW 201203342A
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive
- adhesive sheet
- acrylate
- semiconductor wafer
- meth
- Prior art date
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 118
- 239000000853 adhesive Substances 0.000 title claims abstract description 117
- 239000004065 semiconductor Substances 0.000 title claims abstract description 44
- 238000012545 processing Methods 0.000 title claims abstract description 30
- 239000012790 adhesive layer Substances 0.000 claims abstract description 36
- 239000004014 plasticizer Substances 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 229920005601 base polymer Polymers 0.000 claims abstract description 27
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- 238000003971 tillage Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Dicing (AREA)
Description
201203342 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種半導體晶圓加工用黏著片。 【先前技術】 形成有IC(Intergrated Circuit,積體電路)等電路圖案之 半導體晶圓為了使其儘可能地變薄,而實施背面研磨處理 等加工。於半導體晶圓之加工時,為了防止例如晶圓破 才貝、或電路圖案形成面由於研磨屑等而污染、損傷等,而 經由自動黏接裝f,預先於其電路圖案形&面上點接表面 保護片。並且,於實施晶圓之背面研磨等加工後,將其表 面保護片剝離去除,送至晶圓清洗步驟等。又,於其後之 步驟中將晶圓單片化’為了使其進人⑽的咖#,、包 製造步驟而使用加工用片。 料此種表面保護片或加卫用片,係使用於基材上 黏者劑層之黏者片,—般已知有於黏著劑層中添加有鄰苯 二甲酸二辛酯、鄰苯二 化劑者。 文-丁 S曰專鄰本二甲酸酯作為塑 :而’具有添加有鄰苯二?酸醋之黏著劑層 跡會析出至㈣劑層二Γ’則源自點著劑成分之印 接於晶圓時污染電路圖宰_其存在於將該黏著片黏 崎固茱形成面之情況。 又’於使用上述表面保護片或加 對將其剝離去除後之電路 用片之障形時,必須 親水性有機溶劑等c利用丙"、異丙醇等 β冼,進而水洗。其結果,存在 15567J.doc 201203342 要十對有機〉谷劑之使用的環境衛生對策,並且清洗效率 較差之問題。 對應於此,摇山士人一,„ 死出有含有如聚丙二醇之水溶性聚合物作為 黏者劑成分的點菩_ y f 1 ^ # J御者片(例如日本專利特開平5_335288號公 報)。 然而,由於即便於使用此種黏著片之情形時,水溶性聚 &物亦會滲出至電路圖案形成面等,故而必需水洗步驟, 因此無法從根本上解決問題。 又,自 2007 年 6 月 1 日起施行 REACH(Registrati〇n, uation, Authorization and Restriction of Chemicals,化 干〇〇註冊、δ平價、許可和限制)限製法,鄰苯二甲酸S旨作 為1種遇可候補之高懸念質而舉出,今後有可能使用受到 限制或使用禁止。 【發明内容】 [發明所欲解決之問題] 本發明係鑒於上述問題而完成者,其目的在於提供—種 於各種環境下之保存穩定性優異’且即便於使用後,亦可 防止對於被黏接體之污染的半導體晶圓加工用黏著片。 [解決問題之技術手段] 本發明者等人對半導體晶圓加工用黏著片之保存穩定性 等進行銳意研究,結果發現以下⑴及(ii),從而完成本發 明。(i)於包含基礎聚合物、塑化劑及界面活性劑之黏著劑 中,即便於預料外,滲出之成分亦並非為塑化劑,而僅係 界面活性劑成分;(Π)於所使用之塑化劑與界面活性劑之 155671.doc 201203342 …’藉由將至今為止未考慮之sp(so丨ubiHty Par_ter’溶解度參數)值之關係設為特定之 便保存於亦包括高溫加濕條件之各 τ里衣J兄下,亦可不使印 跡析出至被黏接體側而穩定地保存。 即,本發明之半導體晶圓加工用黏著片之特徵在於:於 基材之至少單面上具有黏著劑層,上述點著劑層包含基礎 聚合物、聚1系之塑化劑及界面活性劑,且上述塑化劑及 界面活性劑之溶解度參數(s p值)滿足如下關係·· 0.9$ [塑化劑之sp值]/[界面活性劑之Sp值]$ I Q。 於此種半導體晶圓加工用黏著片中, 較佳為相對於基礎聚合物1〇〇重量份含有上述塑化劑 10〜50重量份。 又,較佳為相對於基礎聚合物1〇〇重量份添加上述界面 活性劑1~1〇重量份。 進而,較佳為上述基礎聚合物包含丙烯酸系聚合物。 又,較佳為於將滿足0.2客B/AS5.7之關係之具有膜厚 為Α μηι之黏著劑層的半導體晶圓加工用黏著片貼附於具有 Β μηι之階差之晶圓表面上時, 由階差引起之上述黏著片之初始隆起量di與24小時後之 黏著片之隆起量d2滿足如下關係: (d2/dl)xl〇〇^ 110(%) 〇 [發明之效果] 根據本發明,可提供一種於各種環境下具有優異之保存 穩定性’即便於使用後’亦可防止對於被黏接體之污染的 155671.doc 201203342 半導體晶圓加工用黏著片。 【實施方式】 「本發明之半導體晶圓加工用黏著片(以下有時僅記為 「黏著片」)具有基材及配置於基材之至少單面上之黏著 劑層。黏著劑層係藉由至少包含基礎聚合物、聚醋系之塑 化劑、及界面活性劑之黏著劑而形成。 (塑化劑) 本發明所使用t塑化劑係使黏著劑對於被祕體之黏接 力降低者’較佳為聚s旨系之塑化劑。塑化劑之種類可根據 所使用之#著㈣適當選擇,較佳為滿足下㈣解度參數 (sp值)之關係者。 作為塑化劑’例如較佳為A日本油墨股份有限公司製造 ^W_70G等偏苯三f酸系聚酿、股份有限公司製造之 D620等己二酸系聚醋、順丁烯二酸系聚冑、癸二酸系聚 S:.本甲酸系聚酯、環氧系聚酯、聚醚系聚酯冑。該等可 單獨使用,或者亦可組合2種以上而使用。 相對於基礎聚合物議重量份,塑化劑宜以1〇〜5〇重量份 之比例使用,較佳為10〜30重量份。藉由設為該範圍,可 防止由黏著力過強所引起之剝離時之半導體晶圓等被黏接 體之破損。又,可避免黏著劑層表面之渗出,防止被黏接 (界面活性劑) 本發明所使用之界面活性劑係用以調整對於半導體晶圓 之黏著力的成分’可使用非離子系、陽離子系及陰離二 155671.doc 201203342 界面活性劑之任一者,較佳為使用非離子系界面活性劑。 界面活性劑之具體種類可根據所使用之黏著劑而適當選 擇’較佳為滿足下述SP值之關係者。 • 作為界面活性劑,例如可舉出烷基硫酸鹽(第一工業製 藥股份有限公司製造之Neogen尺等)、烷基磷酸鹽(花王股 份有限公司製造之Electro Stripper N等)等陰離子系界面活 性劑;脂肪族四級銨鹽(花王股份有限公司製造之 Quartamin 24P等)、芳香族四級銨鹽(東邦化學股份有限公 司製造之Catinal HC-100等)等陽離子系界面活性劑;去水 山梨醇脂肪酸酯(花王股份有限公司製造之Rhe〇d〇l SP_L10 等)、聚氧乙烯(第一工業製藥股份有限公司製造之N〇igen EP-120A等)、甘油、醚、脂肪酸等非離子系界面活性劑。 該等可單獨使用,或者亦可組合2種以上使用。 相對於基礎聚合物1〇〇重量份,界面活性劑宜以卜丨❶重 里伤之比例使用,較佳為1〜5重量份,更佳為1〜2重量份。 藉由設為該範圍,可避免黏著力之顯著降低,維持半導體 晶圓圖案面之凹凸追隨性。 (SP 值) 構成上述黏著劑層之塑化劑及界面活性劑之81>值較佳為 ' 滿足如下關係: [塑化劑之SP值]/[界面活性劑之”值];丨〇。 此處,塑化劑之SP值δρ係指根據Small公式,即式(1)所 估算之值。又’界面活性劑之8?值5s係指根據界面活性劑 之HLB(Hydrophilic-Lipophilic Balance,親水親油性平衡) 155671.doc 201203342 值所估算之值,例如係指藉由式(2)(引用文獻:SP值之基 礎·應用與計算方法,山本秀樹著,P.54〜56)所求得之值。 5p[(J/cm3)1/2] = IF/V (1) 此處,δρ為溶解度參數,F為關於分子間相互作用之常 數(依賴於表1中所示之Small常數、取代基之種類),V為 莫耳分子體積。 [表1] 基困種類 F(J1/2/mol) 基團種類 F(J1/2/mol) -ch3 438 Η 164-205 -ch2- 272 OH - ch2= 389 〇(醚) 143 CH- 57 CHO 685-767 -ch(ch3)2 933 CO㈣ 563 -CH= 227 COOH 798-839 -C- 190 coo(酯) 634 C= 39 ch3coo 1072 CHC- 583 CN 839 -C=C- 454 Cl(平均) 532 -ch=ch2- 616 Cl(單獨> 552 苯基 1504 Cl(例如於CCI2中) 532 環己基 - Cl(例如於CC13中) 511 伸苯基(鄰、間、對) 1346 Br(單獨) 696 萘基 2345 1(單獨) 870 五元環 215-235 CF2(正烴) 307 六元環 194〜215 CF3(正烴) 552 共軛 4141 S(硫化物) 460 N〇3(硝酸鹽) 900 SH(硫醇) 644 N02(脂肪族硝基) 900 P〇4(有機磷酸鹽) 1023 I5567l.doc 201203342 5s[(cal/cm3)1/2]=(118.8 + 6.〇)/(54-HLB) (2) 此處,HLB值係將非離子性界面活性劑之親水基與疏水 基之均衡數值化的值’表示非離子性界面活性劑之親水性 之程度。HLB值為使用式(3)所求出之值。 HLB-(親水基部分之分子量/界面活性劑之分子量)χ 1術5⑺ (黏著劑層) 本發明所使用之黏著劑層中包含之黏著劑,即,含有上 述塑化劑及界面活性劑而成之黏著劑對於鏡面晶圓之黏接 力較佳為0.1〜1.0 N/20 mm左右。藉由設為該範圍,可確保 半導體晶圓圖案面之凹凸追隨性’並且可有效地防止剝離 時之半導體晶圓之破壞。 又,黏著劑較佳為具有30〜90%左右之凝膠率,較佳為 3 0〜70 /〇左右。藉由具有該範圍之凝膠率,可防止由凝聚 力不足所引起之糊劑殘餘,並可確保與被黏接體之密接 f生從而維持半導體晶圓圖案面之凹凸追隨性。 此處,所謂黏著劑之凝膠率,係指藉由如下方法算出之 值·自膠帶採集黏著劑’測定所採集之黏著劑之重量 (Wl),將其浸潰於乙酸乙酯中1週後,使溶劑成分乾燥, 測疋殘餘之凝膠之重量(W2),藉由式(4)而算出之值。 凝膠率(o/oMMWWOxlOO (4) 構成黏著劑層之黏著劑中之基礎聚合物無特別限制,例 如可自構成橡膠系黏著劑、丙烯酸系黏著劑、聚醯胺系黏 著劑、聚石夕氧黏著劑、聚酯系黏著劑、胺基甲酸酯系黏著 劑等已知之黏著劑的基礎聚合物中適當選擇。其中,作為 155671.doc 201203342 構成丙烯酸系黏著劑之基礎聚合物的丙烯酸系聚合物由於 耐熱性、耐候性等各種特性優異,藉由選擇構成丙烯酸系 聚合物之單體成分之種類等,可表現出所期望之特性,故 可較佳地使用。 作為丙稀酸系黏著劑之基礎聚合物的丙稀酸系聚合物係 以(曱基)丙烯酸烧基酯作為主單體成分而構成。 作為(甲基)丙烯酸烷基酯,例如可舉出(甲基)丙烯酸甲 酯、(曱基)丙烯酸乙酯、(曱基)丙烯酸丙酯、(曱基)丙烯酸 異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基) 丙烯酸第二丁自旨、(甲基)丙烯酸第三丁酿、(甲基)丙烯酸 戊酯、(甲基)丙烯酸己酯、(曱基)丙烯酸庚酯、(甲基)丙烯 酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛 酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯 酸癸酯、(▼基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基 酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基 酯、(甲基)丙烯酸十四烷基冑、(甲基)丙烯酸十五烷基 醋、(甲基)丙稀酸十八烧基醋、(甲幻丙烯酸十九烧基 酿、(甲基)丙烯酸二十烧基醋等(甲基)丙稀酸%烧基醋 (^交佳為(曱基)丙烯酸Gw烷基酯,進而較佳為(甲基)丙烯 酸<^_8烷基酯)等。(曱基)丙烯酸烷基酯可選擇1種或2種以 上而使用。 丙烯酸系聚合物以凝聚力、耐熱性、交聯性等之改質為 目的’根據需要亦可含有與可與(子基)丙稀酸院基醋共聚 合之其他單體成分相對應之單位。 I5567j.doc 201203342 作為此種單體成分,例如可舉出丙烯酸、曱基丙烯酸、 丙稀酸羧乙酯、丙烯酸羧戊酯、衣康酸、順丁烯二酸、反 丁烯二酸、丁烯酸等含有羧基之單體;(曱基)丙烯酸羥丁 酯、(甲基)丙烯酸羥己酯、(甲基)丙烯酸羥辛酯、(甲基)丙 烯酸羥癸酯、(曱基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥 甲基環己基)甲酯等含有羥基之單體;苯乙烯磺酸、烯丙 基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯 胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺 酸等含有磺酸基之單體;丙烯醯基磷酸2-羥乙酯等含有磷 酸基之單體;(曱基)丙烯醯胺、Ν,Ν-二甲基(曱基)丙烯醯 胺、Ν-丁基(甲基)丙稀酿胺、Ν-經曱基(甲基)丙稀醯胺、 Ν-羥曱基丙烷(甲基)丙烯醯胺等(Ν_取代)胺系單體;(曱 基)丙烯酸胺基乙酯、(甲基)丙烯酸Ν,Ν-二曱基胺基乙醋、 (甲基)丙烯酸第三丁基胺基乙酯等(曱基)丙烯酸胺基烷基 酯系單體;(甲基)丙烯酸烷氧基烷基酯系單體;Ν_環己基 順丁烯二醯亞胺、Ν-異丙基順丁稀二醯亞胺、Ν-月桂基順 丁烯二醯亞胺、Ν-苯基順丁烯二醯亞胺等順丁烯二醯亞胺 系單體;Ν-甲基衣康醯亞胺、Ν-乙基衣康醯亞胺、Ν- 丁基 衣康醯亞胺、Ν-辛基衣康醯亞胺、Ν-2-乙基己基衣康醯亞 胺、Ν-環己基衣康酿亞胺、Ν-月桂基衣康醯亞胺等衣康醯 亞胺系單體;Ν-(甲基)丙烯醯氧基亞曱基丁二醯亞胺、Ν_ (甲基)丙烯醯-6-氧基六亞曱基丁二醯亞胺、Ν-(曱基)丙稀 醯-8-氧基八亞曱基丁二醯亞胺等丁二醯亞胺系單體;乙酸 乙烯酯、丙酸乙烯酯、Ν-乙烯基。比咯烷酮、甲基乙烯基0比 155671.doc • 11 · 201203342 咯烷酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶'乙烯 基哌畊、乙烯基。比畊、乙烯基D比咯、乙烯基咪唑、乙烯美 %唑、乙烯基咪啉、:N-乙烯基甲醯胺類、苯乙烯、甲美 苯乙烯、Ν-乙烯基己内醢胺等乙烯系單體;丙烯腈、甲基 丙烯腈等丙烯酸氰酯系單體;(甲基)丙烯酸縮水甘油酯等 含有環氧基之丙烯酸系單體;(甲基)丙烯酸聚丙二醇酯、 (甲基)丙烯酸甲氧基乙二醇酯、(曱基)丙烯酸甲氧基聚丙 二醇酯等二醇系丙烯酸酯單體;(甲基)丙烯酸四氫糠酯、 氟(曱基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等含有雜環、 _素原子、矽原子等之丙烯酸酯系單體;己二醇二(曱基) 丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、聚丙二醇二(曱 基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二 (曱基)丙烯酸酯、三羥^基丙烷三(甲基)丙烯酸酯、季戊 四醇三(甲基)丙烯酸酯、二季戊四醇六(曱基)丙烯酸酯、 環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸胺基甲酸酯、二乙 烯基苯、二(曱基)丙烯酸丁酯、二(曱基)丙烯酸己酯等多 官能單體,異戊二稀、二丁二稀、異丁婦等稀煙系單體; 乙烯醚等乙烯醚系單體等。該等單體成分可使用丨種或之種 以上。 丙烯酸系共聚物可藉由利用公知之適當之方法使上述 (甲基)丙烯酸烷基酯與視需要之其他單體進行聚合而製 造。 丙烯酸系共聚物之分子量等無特別限制,例如,可使用 重量平均分子量為10萬〜200萬,較佳為15萬〜1〇〇萬,進而 155671.doc 201203342 較佳30萬〜ιοο萬之範圍者4量平均分子量例如可利用凝 膠渗透層析儀作為聚笨乙烯換算值而測定。 黏著劑可藉由添加能量線聚合性化合物,或於基礎聚合 物t導入能量線聚合性雙鍵等而製成能量線硬化型黏著 劑。使用能量線硬化型黏著劑之黏著劑層雖於能量線照射 前表現出充分之黏接力,但於能量線照射後黏接力顯著下 降,可不對被黏接體給予應力而容易地剝離。再者,作為 能量線’例如可舉出紫外線、電子束等。 作為能量線聚合性化合物,可使用分子中含有2個以上 之能量線聚合性碳-碳雙鍵的化合物。作為此種化合物, 例如可舉出多官能丙烯酸酯系化合物。 作為多官能丙烯酸酯系化合物,例如可舉出〗,4_ 丁二醇 二(甲基)丙烯酸酯、1,5-戊二醇二(曱基)丙烯酸酯、込^己 一醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯或聚 乙二醇二(甲基)丙稀酸酯、聚丙二醇二(甲基)丙烯酸酯等 直鏈狀脂肪族多元醇之(曱基)丙烯酸酯;環己烷二甲醇二 (甲基)丙烯酸酯、三環癸烷二甲醇二丙烯酸酯等含有脂環 基之脂肪族多元醇之(曱基)丙烯酸酯;三羥甲基丙烷三(甲 基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四 (曱基)丙浠酸酯等支鏈狀脂肪族多元醇之(甲基)丙烯酸酯 或該等之縮合物(二-三羥甲基丙烷四丙烯酸酯、二季戊四 醇六丙烯酸酯等)。該等可單獨使用,或者亦可組合2種以 上使用。 例如亦可使用丙烯酸胺基甲酸酯系募聚物等多官能丙稀 155671.doc 13 201203342 酸酯系寡聚物作為能量線聚合性化合物β 丙烯酸胺基甲酸酯系募聚物可使例如含有羥基之(甲基) 丙烯k院基s旨對藉由二異氰酸醋化合物與多元醇化合物之 反應而獲得之胺基曱酸酯寡聚物進行反應來獲得。 作為二異氰酸醋化合物,例如可舉出曱苯二異氰酸酯、 二苯基曱烷二異氰酸酯、六亞曱基二異氰酸酯、伸笨基二 異氰曰、一環己基甲烧二異氰酸s旨、二曱苯二異氰酸 酯、四甲基二甲苯二異氰酸酯、萘二異氰酸酯、異佛酮二 異氰酸酯等。 作為多元醇化合物’例如可舉出乙二醇、丨,4_ 丁二醇、 1,6-己二醇、二乙二醇、三羥曱基丙烷、二丙二醇、聚乙 二醇、聚丙二醇、季戊四醇、二季戊四醇、甘油等多元醇 類;藉由上述多元醇類與己二酸、癸二酸、壬二酸、順丁 烯二酸等脂肪族二羧酸或對苯二甲酸、間苯二甲酸等芳香 族二緩酸之縮合反應而獲得之聚酯系多元醇化合物;聚伸 乙醚二醇、聚伸丙醚二醇、聚四亞甲基醚二醇、聚六亞曱 基驗二醇等聚醚系多元醇化合物;聚己内酯二醇、聚丙内 醋二醇、聚戊内酯二醇等内酯系多元醇化合物;藉由乙二 醇、丙二醇、丁二醇、戊二醇、辛二醇、壬二醇等多元醇 與碳酸二乙二酯、碳酸二丙二酯等之脫醇反應而獲得之聚 碳酸醋系多元醇化合物,作為含有羥基之(曱基)丙烯酸烷 基醋化合物’例如可舉出(甲基)丙烯酸2_羥基乙酯、(曱 基)丙烯酸2_羥基丙酯、(曱基)丙烯酸心羥基丁酯 '(曱基) 丙烯酸6-經基己酷、(曱基)丙烯酸8-羥基辛酯、(曱基)丙歸 155671.doc •14- 201203342 酸1〇-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯 酸(4-經甲基環己基)甲g旨等。 能量線聚合性化合物相對於基礎聚合物1〇〇重量份,例 如可於5〜200重量份、較佳為1〇〜1〇〇重量份、進而較佳為 10〜45重量份之範圍中使用。 作為將能量線聚合性雙鍵導入基礎聚合物之方法,例如 可舉出於製備作為基礎聚合物之丙烯酸系聚合物時,使具 有缓基、經基、胺基等反應性官能基之共聚性單體共聚合 之方法。藉此,於基礎聚合物中導入成為反應之基點的官 能基,可使具有能量線聚合性碳_碳雙鍵之多官能性單體 或寡聚物經由成為上述反應之基點的官能基而鍵結,可獲 得於支鏈上具有能量線聚合性碳_碳雙鍵之基礎聚合物。 能量線硬化型黏著劑亦可根據需要包含光聚合起始劑。 光聚合起始劑藉由照射能量線而激發、活性化,生成自由 基,促進黏著劑層之有效之聚合硬化反應。 作為光聚合起始劑,例如可舉出安息香曱醚、安息香乙 謎、安息香異丙鍵、安息香異丁醚等安息香烷基醚系起始 劑’二苯甲酮、苯甲醯苯甲酸、3,31_二曱基_4_甲氧基二苯 曱酮、聚乙烯基二苯甲酮等二苯曱酮系起始劑;α羥基環 己基苯基酮、4-(2-羥基乙氧基)苯基(2_羥基_2_丙基)酮、α_ 羥基-α,α1-二甲基苯乙酮 '甲氧基苯乙酮、2,2·二甲氧基-2_ 苯基苯乙酮、2,2-二乙氧基笨乙酮等芳香族酮系起始劑; 苯偶醯二甲基縮酮等芳香族縮_系起始劑;硫雜葱嗣、2_ 氯硫雜蒽_、2_甲基硫雜蒽鲷、2_乙基硫雜蒽酮、2_異丙 155671.doc •15- 201203342 基硫雜蒽嗣、2-十二烷基硫雜蒽酮、2,4_二氯硫雜蒽酮、 2’4-二甲基硫雜蒽酮、2,4·二乙基硫雜蒽酮、2,4_二異丙基 硫雜蒽酮等硫雜蒽酮系起始劑;上苯乙二酮等二苯乙二酮 系起始劑、安息香等安息香系起始劑、α_酮醇系化合物(2_ 甲基-2-羥基苯丙酮等)、芳香族磺醯氯系化合物(2_萘磺醯 氯等)、光活性肟化合物苯酮_〗,〗_丙二酮_2气鄰乙氧羰 基)肟等)、樟腦醌、南化酮、醯基氧化膦、醯基磷酸酯 等。該等可單獨使用者亦可組合2種以上使用。 黏著劑亦可藉由使用含有m基等酸基之聚合物作為基礎 聚合物’添加中和㈣基礎聚合物中之全部或—部分酸基 中和’而製成賦予了親水性之親水性黏著劑。親水性黏著 劑-般而言於被黏接體上之糊劑殘餘較少,又,即便於產 生糊劑殘餘之情形時’亦可藉由以純水清洗而簡易地去 除0 含有酸基之聚合物可藉由在製備基礎聚合物時使上述含 有羧基之單體等含有酸基之單體共聚合而獲得。 作為中和劑,例如可舉出單乙胺、單乙醇胺等一級胺、 二乙胺、二乙醇胺等二級胺、= — —乙胺、二乙醇胺、ν,ν,ν·- 三曱基乙二胺、Ν-甲其-7·胳认 ^ , 甲基一乙醇胺、Ν,Ν_二乙基羥胺等三級 胺等顯不出驗性之有機胺化合物。 黏著劑亦可根據需要含有交聯劑。 作為交聯劑,例如可佶用< — 以了使用%氣系交聯劑、異氰酸醋系交 聯劑、二聚氰胺系交聯劑、過 孔1匕物糸父聯劑、金屬烷氧 化物系交聯劑、金屬替人物备^ 心口物糸父聯劑、金屬鹽系交聯劑、 155671.doc -16 - 201203342 碳二酿亞胺系交聯劑"号㈣系交聯劑、 劑、胺系交聯劑等交聯劑,可較佳地使用環氧系交聯劑: 異氰酸酯系交聯劑等。該等可單獨使用, 種以上使用。 $者亦可組合2
作為環兔系交聯劑,例如可舉出:N „ ,,N,N_四縮水甘 =二?二胺、二縮水甘油基苯胺、 水甘油基胺基曱基)環己院、i,6_己二醇二縮水甘㈣、新
戍一醇一縮水甘油醚、乙二醇-输士 4、丄W 醉一縮水甘油醚'丙二醇二縮 水甘油_、聚乙二醇二縮水甘油越、聚丙二醇二縮水甘油 趟、山梨酵聚縮水甘油醚、丙三醇聚縮水甘油醚、季戊四 醇聚縮水甘油醚、聚丙三醇聚縮水m去水山梨醇聚 縮水甘油醚、三經甲基丙烷聚縮水甘油越、己二酸二縮水 甘油趟、鄰苯二甲酸二縮水甘油喊、三縮水甘:基-三 經乙基)異氰尿酸醋、間苯二紛二縮水甘油喊、雙盼各二 縮水甘㈣、分子内含有2個以上環氧基之環氧樹月匕等 作為異氛酸醋系交聯劑’例如可舉出仏伸乙基曰二異氛 敵酷、伸丁基二異氮酸醋、W六亞甲基二異氛酸醋 等低級脂肪族聚異氰酸酯類;柚掙屮且 展戊基一異氰酸酯、伸環 己基二異氰酸醋、異佛酮二異氰_旨、氫化甲笨二異氰酸 酯、氫化二甲苯二異氰酸酿等脂肪族聚異氰酸醋類;2,心 甲苯二異氰酸醋、2,6·甲笨二異_、4,4,_二苯基甲炫 二異氰酸醋、苯二甲基二異氰酸酉旨等芳香族聚異氛酸醋類 等。 黏著劑層可藉由利用刀式塗佈機、觀塗機、凹版印刷塗 I55671.doc 201203342 佈機、模塗佈機、反向塗佈機等適當之方法將上述黏著劑 塗佈於基材上而形成,又,例如亦可於表面經脫模處理之 膜等適當之澆鑄用步驟片上形成黏著劑層,將該黏著劑層 轉印於基材上。 黏著劑層之厚度無特別限制,較佳為1〇 μηι以上(例如 10〜200 μιη),進而較佳為15 μιη以上(例如15〜1〇〇叫^),尤 佳為18 μηι以上(例如18〜5〇 μιη)。若黏著劑層之厚度為上 述範圍内,則可減輕基材之應力,提高黏著片之應力緩和 率。 黏著劑層之彈性模數較佳為〗〇χ1〇4〜1〇χ1〇7左右之範 圍。若彈性模數為上述範®,則可表玉見出適於作為半導體 晶圓之背面研磨加工用黏著片之用途的黏著特性。 於使用能量線硬化型黏著劑作為黏著劑之情形時,上述 彈性模數為硬化前(能量線照射前)之黏著劑層之彈性模 數。 (基材) 作為本發明之黏著片之基材並無特別限制,例如可使用 樹脂(塑膠)製膜。 作為構成樹脂製膜之樹脂並無特別限定,可為硬化性樹 脂(熱硬化性樹脂、光硬化性樹脂等)及熱塑性樹脂等之任 一者。 具體而言,可舉出低密度聚乙烯、直鏈狀聚乙烯、中密 度聚乙烯、高密度聚乙稀、超低密度聚乙稀、無規共聚聚 丙婦'嵌段共聚聚丙稀、均聚丙嫌、爭姿 灰内婶聚丁烯、聚甲基戊烯 155671.doc 201203342 等聚烯烴’乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、 乙烯-(曱基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、 交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物等聚缔 烴系樹脂;聚胺基曱酸酯、聚對苯二甲酸乙二酯、聚蔡二 甲®^ —乙醋等聚醋系樹脂;(曱基)丙烯酸系聚合物、聚苯 乙烯、聚碳酸酯、聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚 喊酿亞胺、聚砜、聚醚砜、聚氣乙烯、聚偏二氣乙稀、氟 樹脂、纖維素樹脂及該等之交聯體等聚合物。該等材料可 根據需要使用將數種混合而成者。 又,上述樹脂中亦可含有碳酸鈣、二氧化矽、雲母等無 機填料;鐵、鉛等金屬填料;顏料、染料等著色劑等添加 物。 作為構成基材之材料,只要為熱塑性彈性體等應力緩和 特性較大之樹脂,則就黏著片之應力緩和率提高之觀點而 言較佳。基材可為單層膜,亦可為有效利用各樹脂之優勢 之積層體(多層膜)。 作為積層體’可舉出包含中心層'及設置於中心層之至 單面上之表面層的積層膜。表面層較佳為設置於中心層 少 之兩面上’具有表面層/中心層/表面層三層。作為構成十 心層及表面層之材料,較佳為使用例如上述聚烯烴系樹 脂、或對該等照射UOMrad左右之電子束或情線者。 作為分別構成中心層與表面層之材料,較佳為自該等聚 稀烴系樹脂中選擇為:藉由熱收縮率不同,各層相互緩 衝’而抑制基材整體之熱1缩率。料此種組合,例如可 I55671.doc -19- 201203342 性聚乙烯與非晶 丙烯之積層體作 較佳為於與基材 。於積層體為在 ,較佳為2個表 舉出聚乙烯與聚丙烯之組合,尤佳為結晶 性聚丙稀之組合。於❹包含聚乙稀與聚 為基材之情形時’自固著性之方面而言, 之黏著劑層接觸之側設置包含聚乙烯之層 中心層之兩側具有表面層之形態之情形時 面層包含同一種類之材料。 構成積層體之各層之厚度之比無㈣限制,較佳為中心 度大於表面層之厚度。厚度之比例如可舉出一方之 表面層·中心層= 】·〗 、 ㉟[12〜3:5,較佳為1:1G〜3:10左右。於中 心層之兩面上具有表面層之情形時,-方之表面層盥另一 =表面層的厚度可相同,亦可不同…方之表面層之厚 =另^之表面層之厚度之比例如可自1:1〜ι:5之範圍中 、較佳為2個表面層之厚度相同。其中可尤佳地使用 具有表面層:中心厝.主工a „ Λ 層.表面層=2:9:2左右之厚度比的多層 膜。 於中〜層與表面層之間’亦可根據需要設置適當之中間 層。作為中間層,例如可舉出用以提高層間之密著力的黏 接層、底塗層等。 基材之成膜方法無特職制,例如可舉出:使顆粒狀之 樹脂熔融’利用擠出成膜機而膜化之方法;藉由利訂型 莫-員或人塑法之擠出成形或壓延法而製造之方法等。 黏著片《其疋基材之熱收縮率較佳為設為2%左右以 ;基材之熱收縮率很大程度上依賴於成膜步驟中之 溫度條件,&而期望選擇於成膜步驟中不含延伸步驟的基 155671.doc 201203342
W 為提高與㈣劑之密著性,亦可對基材之上表面,即执 2有點著劑層之側之面實施慣用之表面處理,例如利“ :處理、絡酸處理、臭氧暴露、火炮暴露、高 露、離子化放射線處理等化學或物理方法之氧化處理等Γ 基材之厚度可根據所欲獲得之黏著片等之物性而調節, 例如可舉出30〜1000 較 較佳為4〇〜800 μηι,進而較佳為 川〜5〇〇 μηι,尤佳為100〜2〇〇 μιη。 MU加1㈣片如上所述於基材上形 成有黏著劑層,黏著劑層亦 而加以保護。 冑需要藉由適當之隔離片 又,半導體晶圓加工用考纟α 能★ 用黏者片可具有捲繞為輥狀之形 〜、,亦可具有片狀、膠帶狀等形態。 本發明之半導體晶圓加工用 黏著片例如可用作電子零件 寻各種被黏接體之表面保護用 驴曰〜 更用# ’尤其是用以於研磨半導 體日日圓時保護半導體晶圓之雷 電路面的保遵用黏著片(Back
Grind Sheet,背面研磨片、 #研磨片)、切割時之保護及/或加工用 、丰導體晶圓加工之各步驟中之加工用黏著片等。 明=導體晶圓之背面研磨步驟中,首先’將本發 (圖案電路形成面)。該貼 而進行。 ^驟係使用稱為貼合機之裝置 其次’藉由研磨機等將晶圓背面研磨至特定之厚产(例 如50〜200㈣,根據需 子疋之厚度(例 ㈣仃利用蝕刻等之化學研磨。此 155671.doc •21 · 201203342 時’半導體晶圓加工用黏著片擔負起固定半導體晶圓之作 用、及保護半導體晶圓表面(圖案電路形成面)而防止晶圓 表面污染或破損等之作用。 於晶圓背面研磨步驟結束後,將半導體晶圓加工用黏著 片自被黏接體剝離。 本發明之半導體晶圓加工用黏著片在.貼合於例如半㈣ 晶圓之電路圖案形成面上時,對電路圖案所形成之階差之 追隨性良好,可課求經時隆起量之穩定性。其結果,亦可 提高於使用時之便利性。 即,於本發明之黏著片巾,如圖iamb所示,若將黏 著片12之黏著劑層(未圖示)之膜厚設為A叫,將晶圓⑽ 面之階差U設為Β㈣’則於該等膜厚Α與階差Β滿足 〇·2續⑴之關係之情形時,可確認由階差⑴丨起之黏 著片12之初始隆起量dl(圖1Α)與24小時後之黏著片之隆起 量d2(圖1Β)滿足式(5)之關係: (d2/dl)xl〇〇^ Π〇(〇/〇) (5) 0 又,(d2/dl)xl〇〇較佳為1〇9%以下。 先前’雖使黏著劑層含有界面活性劑作為自被黏接體剝 離半導體晶圓加玉用黏著片時之黏著力調整成分,但存在 該成分析出於黏著劑層表面而污染半導體晶圓之圖案面的 情況。又,於半導體晶圓之切割步驟中,係一面將大量之 水加於半導體晶圓上一面進 〇 琨仃1C之早片化,此時亦擔憂有 相同之源自印跡之污染。 然而,於本發明之黏著片中,藉由選擇塑化劑與界面活 155671.doc -22· 201203342 可古,特疋组合’而即便於各種環境下保存及使用時,亦 L效地防止源自黏著劑成分之印跡之析出。因此,可於 面研:等半導體晶圓加工後,剝離貼合於半導體晶圓表 之黏者片時,防止源自印跡之對晶圓表面之污染,可較 佳地用作要求半導體晶圓等之潔淨度之被黏接體之保管、 移送或加工時之表面保護片。又’藉由清洗步驟等之省略 或簡化等,可有效地提高生產性。 匕進而’於本發明之黏著片巾,由於未使用鄰苯二甲酸 酉曰故而可成為考慮到環境方面之黏著片。 [實施例] 以下列舉實施例更詳細地說明本發明,但本發明並不受 S亥等實施例任何制限。 (實施例1) 使丙烯酸丁酯97重量份、曱基丙烯酸甲酯2重量份、丙 烯酸3重量份於曱苯中藉由溶液聚合法共聚合,獲得重量 平均刀子量為55萬之丙稀酸系聚合物。於所獲得之丙烯酸 系聚合物1 〇〇重量份中混合作為塑化劑之己二酸系聚酯(大 日本油墨股份有限公司製造,商品名「w_23〇H」)1〇重量 份、作為黏著力調整成分之非離子系界面活性劑(第一工 業集樂股伤有限公司製造’商品名「Noigen EP-120A」 重1份、環氧系交聯劑(三菱瓦斯化學股份有限公司製 造,商品名「TETRAD C」)0·5重量份、聚異氰酸酯系交 聯劑(曰本1氣目旨工業股份有限公司製造,商品名 「Coronate L」)3重量份,獲得黏著劑組成物a。 155671.doc -23- 201203342 將所獲得之黏著劑組成物A以乾燥後之厚度成為Μ㈣ 之方式,藉由嗔注模(F〇Untain Die)方式塗佈於邊禱用步驟 片(厚度50 μπι之丁 oray公司製造之pET膜)上形成黏著劑 層。 利用擠出機藉由共擠出而製作包含聚乙稀/非晶聚丙稀/ 聚乙烯之3層且厚度為135 μηΐ2積層膜A作為基材。再者, 積層膜A各層之厚度之比為聚乙烯:非晶丙烯:聚乙烯 =2:9:2。 藉由轉印將黏著劑層A積層於積層膜八上,熟化5〇(>Cx48 小時,獲得黏著片A。 (實施例2) 於上述丙烯酸系聚合物1〇〇重量份中混合作為塑化劑之 偏苯一甲酸系聚酯(大日本油墨股份有限公司製造,商品 名W7〇5」)30重量份、作為黏著力調整成分之非離子系 界面活性劑(第一工業製藥股份有限公司製造,商品名
Noigen EP-120A」)1重量份、環氧系交聯劑(三菱瓦斯化 學股份有限公司製造,商品名「TETRAD c」)〇 5重量 份、聚異氰酸酯系交聯劑(日本聚氨酯工業股份有限公司 製造,商品名「C〇ronate L」)3重量份,獲得黏著劑組成 物B。 除使用黏著劑組成物B代替黏著劑組成物A以外,進行 與實施例1相同之操作,獲得黏著片B。 (實施例3) 於上述丙烯酸系聚合物丨〇 〇重量份中混合作為塑化劑之 155671.doc -24- 201203342 苯甲酸系聚酯(大曰本油栗 个曲墨股份有限公司製造, 「W-83」)50重量份、作為 。口名 …、钻者力調整成分之非離子 面活性劑(第一工業劁越饥八 1 1 系製樂股份有限公司製造,商品名 「Noigen EP-120A」)1 重昔傅 & “ 。口 蕙伤、%氧系父聯劑(三菱瓦斯化 學股份有限公司製造,脔0々「 商品名「TETRAD C」)0.5重量 伤、聚異氛酸醋系交聯劑f 士取—& XW (日本聚氨酯工業股份有限公司 製造’商品名「Coronate L 去曰八 L」)3重量份,獲得黏著劑組成 物C。 除使用黏著劑組成物C代替㈣劑組成物歧外,進行 與實施例1相同之操作,獲得黏著片c。 (實施例4) 於上述丙烯酸系聚合物⑽重量份中混合作為塑化劑之 己二酸系聚i旨(大日本油墨股份有限公司製造,商品名 「W-230H」)1〇重量份、作為黏著力調整成分之非離子系 界面活性劑(第一工業製藥股份有限公司製造,商品名 「N〇igen EP_ i20A」)5重量份、環氧系交聯劑(三菱瓦斯化 干肤伤有限公司製造,商品名「TETRAD c」)〇 5重量 份、聚異氰酸If、交聯#U日本^目旨王#股份有限公司 製造’商品名「C〇ronate L」)3重量,獲得黏著劑組成物 D。 除使用黏著劑組成物D代替黏著劑組成物a以外,進行 與實施例1相同之操作,獲得黏著片D。 (實施例5) 於上述丙烯酸系聚合物1〇〇重量份中,混合作為塑化劑 155671.doc -25- 201203342 之己二酸系聚酯(大日本油墨股份有限公司製造,商品名 「W-230H」)1〇重量份、作為黏著力調整成分之非離子系 界面活性劑(第一工業製藥股份有限公司製造,商品名
Noigen EP-120A」)1〇重量份、環氧系交聯劑(三菱瓦斯 化學股份有限公司製造,商品名「TETRAD c」)〇 5重量 份、聚異氰酸酯系交聯劑(日本聚氨酯工業股份有限公司 製造,商品名「Coronate L」)3重量份,獲得黏著劑組成 物E。 除使用黏著劑組成物E代替黏著劑組成物A以外,進行 與實施例1相同之操作,獲得黏著片E。 (比較例1) 示使用鄰笨一曱酸酯(大日本油墨股份有限公司製造, 商品名「DOP」)30重量份作為塑化劑以外,進行與實施 例1相同之操作,獲得黏著片F。 (比較例2) 。除使用聚㈣聚㈣大日本油墨股份有限公司製造,^ AS 200」)1 〇重量份作為塑化劑以外進行與實方 例1相同之操作,獲得黏著片G。 (比較例3) 。除使用㈣系以旨(大日本油墨股份有限公司製造,^ -名「AS-200」)50重量份作為塑化劑以外,進行與實a 例1相同之操作’獲得黏著片Η。 (試驗評價) 以下之試驗評 對實施例及比較例中所獲得之黏著片進行 155671.doc -26 - 201203342 價。將其結果示於表2。 [保存穩定性試驗] 將實施例及比較例中所獲得之黏著片於0°c及4(TC X92% RH環境中放置3〇天。其後,將黏著片切成50x50 mm,製 . 成試驗片。將所獲得之試驗片使用2 kg之橡膠輥以10 cm/ 秒之速度不施加張力而貼附於4英吋鏡面晶圓表面上。貼 附後’以300 mm/min之速度剝離試驗片,以目視觀察鏡面 晶圓表面狀態。作為觀察方法,係將試驗片貼附面分成 5x5 mm之大小,製作計1〇〇個之柵格,以目視觀察附著有 印跡之栅格的數量。 〇 : 100個中1個印跡都未觀察到。 △ : 100個中觀察到未達50個之印跡。 x : 100個中觀察到50個以上之印跡。 [對鏡面晶圓之黏接力] 依照JIS Z-0237,使用鏡面晶圓作為被黏接體進行剩 定。 [黏著劑之凝膠率] 自黏著片上採集黏著劑,測定所採集之黏著劑之重量 (W〗)將於乙酸乙S旨中浸潰1週後,使溶劑成分乾燥,測 定殘餘之凝膠之重量(w2),由下式算出。 凝膠率(o/c^WsXlOO/Wj [階差追隨性試驗] 155671.doc •27· 201203342 將實施例及比較例中所獲得之黏著片使用日東精機股份 有限公司製造之DR3 00011,以貼合壓〇 4 MPa、貼合速度 10 mm/秒貼合於鏡面晶圓上。此時,與黏著片貼合方向垂 直地將5 3 μπι厚之勝帶貼合於鏡面晶圓上,設為模擬階 差。 於黏著片貼合後’使用光學顯微鏡對由模擬階差引起之 膠帶之隆起距離進行評價,設為初始階差隆起量(d 1 ,參 照圖1A)。進而於貼合24小時後進行相同之評價,測定經 時隆起量(d2 ’參照圖1B) ’使用以下公式算出自初始隆起 量起上升之比例。 經時穩定性(%)=(d2/dl)xl00 [表2] 塑化劑 界面活性劑 塑化劑 界面活性劑 σρ/as 種類 重量份 重量份 SP 值 σρ SP 值 as 丄 己二酸系聚酯 10 1 9.2 9.91 0.93 2 偏笨三曱酸系聚酯 30 1 9.0 9.91 0.91 實施例 3 苯曱酸系聚酯 50 1 9.8 9.91 0.99 4 己二酸系聚酯 10 5 9.2 9.91 0.93 5 己二酸系聚酯 10 10 9.2 9.91 0.93 1 鄰苯二甲酸酯 30 1 8.9 9.91 0.89 比較例 2 聚醚系聚酯 10 1 8.4 9.91 0.85 3 聚醚系聚酯 50 1 8.4 9.91 0.85 155671.doc -28 -
201203342 黏接力 (N/20 mm) 凝膠 率 (%) o°c 40°C ' 92% RH 初始階差 隆起量 ㈣ 經時穩 定性 (%) 污染觀 察數 保存 穩定 性 污染觀 察數 保存 穩定 性 實 施 例 1 0.51 38 0/100 〇 0/100 〇 280 100.4 2 0.43 44 0/100 〇 0/100 〇 311 103.5 3 0.36 58 0/100 〇 0/100 〇 425 101.1 4 0.20 36 0/100 〇 0/100 〇 368 101.8 5 0.15 32 0/100 〇 0/100 〇 316 105.8 比 較 例 1 0.41 35 0/100 〇 31/100 Δ 555 110.2 2 0.68 31 56/100 X 91/100 X 648 121.7 3 0.27 69 51/100 X 69/100 X 581 117.0 (試驗例) 除使黏著劑層之厚度於15-65 μηι之間變化以外,製作與 實施例1相同之黏著片。對於所獲得之黏著片,根據上述 階差追隨性試驗,使階差於18〜85 μηι之間變化而進行試 驗。將其結果示於以下之表中。 [表3] 階差 黏著劑 18 μπι 30 μπι 53 μιη 85 μπι 15 μπι 102.4% 105.8% 108.3% 106.5% 45 μηι 100.3% 104.6% 102.9% 107.0% 65 μιη 101.2% 100.4% 100.9% 105.1% 155671.doc •29· 201203342 [產業上之可利用性] 工用Ιέ著#可作為電子零件等各 片、切割時之加工用片等而廣泛 本發明之半導體晶圓加 種被黏接體之表面保護用 地利用》 【圖式簡單說明】 圖1Α係用以說明相對於本發明之勒基μ 2 * a疋黏考片之階差的初始隆 起量d 1之概略剖面圖。 圖1B係用以說明相對於本發明之黏著片之階差所的經時 隆起量d2之概略剖面圖。 【主要元件符號說明】 10 晶圓 11 階差 12 黏著片 B 階差之厚度 dl 黏著片之初始隆起量 d2 24小時後之黏著片之隆起量 155671.doc •30-
Claims (1)
- 201203342 七、申請專利範圍: 1.種半導體晶圓加工用黏著片,其特徵在於: 於基材之至少單面上具有黏著劑層; 上述黏著劑層包含基礎聚合物、聚醋系之塑化劑及界 面活性劑;且 上述塑化劑及界面活性劑之溶解度參數(sp值)滿足如 下關係: 0.9声[塑化劑之sp值]/[界面活性劑之sp值]^工〇。 2·如印求項1之半導體晶圓加工用黏著片,其中相對於基 礎聚合物100重量份添加上述塑化劑1〇〜5〇重量份。 3'如請求項1之半導體晶圓加工用黏著片,其中相對於基 礎聚合物100重量份添加上述界面活性劑丨〜丨〇重量份。 4.如请求項1之半導體晶圓加工用黏著片,其中上述基礎 聚合物包含丙烯酸系聚合物。 5 ·如請求項1之半導體晶圓加工用黏著片,其中於將滿足 〇.2$8/八$5.7之關係之具有膜厚為八0„1之黏著劑層的半 導體晶圓加工用黏著片貼合於具有Β μπι之階差的晶圓表 面上時, 由階差引起之上述黏著片之初始隆起量dl與24小時後 之黏著片之隆起量d2滿足如下關係: (d2/dl)xl00^ 110(%) 〇 155671.doc
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JP6180139B2 (ja) * | 2013-03-11 | 2017-08-16 | リンテック株式会社 | 保護膜形成用複合シートおよび保護膜形成用フィルム付チップの製造方法 |
CN105247661B (zh) * | 2013-05-29 | 2018-09-21 | 三井化学东赛璐株式会社 | 半导体晶片保护用膜及半导体装置的制造方法 |
US20160312076A1 (en) * | 2013-12-26 | 2016-10-27 | Zeon Corporation | Multilayered film and method for manufacturing the same |
WO2018135546A1 (ja) * | 2017-01-20 | 2018-07-26 | 三井化学東セロ株式会社 | 粘着性フィルムおよび電子装置の製造方法 |
JP2023146907A (ja) * | 2022-03-29 | 2023-10-12 | 株式会社レゾナック | 電子部品加工フィルム及び電子部品加工方法 |
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GB8822857D0 (en) * | 1988-09-29 | 1988-11-02 | Patralan Ltd | Pharmaceutical formulations |
JP3208501B2 (ja) | 1992-06-02 | 2001-09-17 | 日東電工株式会社 | 半導体ウエハの保護部材 |
JP3491911B2 (ja) * | 1992-07-29 | 2004-02-03 | リンテック株式会社 | 半導体ウエハ加工用粘着シート |
US5539044A (en) * | 1994-09-02 | 1996-07-23 | Conoco In. | Slurry drag reducer |
MY142246A (en) * | 2003-06-10 | 2010-11-15 | Hitachi Chemical Co Ltd | Adhesive film and process for preparing the same as well as adhesive sheet and semiconductor device |
JP2005179496A (ja) * | 2003-12-19 | 2005-07-07 | Nitto Denko Corp | 加熱剥離型粘着シート |
JP4627149B2 (ja) * | 2004-05-10 | 2011-02-09 | 東洋ゴム工業株式会社 | 研磨パッド及び半導体デバイスの製造方法 |
JP5283838B2 (ja) * | 2006-11-04 | 2013-09-04 | 日東電工株式会社 | 熱剥離性粘着シート及び被着体回収方法 |
-
2010
- 2010-04-20 JP JP2010097273A patent/JP5406110B2/ja active Active
-
2011
- 2011-04-14 US US13/381,760 patent/US20120114938A1/en not_active Abandoned
- 2011-04-14 KR KR1020117025740A patent/KR20120133985A/ko not_active Application Discontinuation
- 2011-04-14 EP EP11771930A patent/EP2562795A1/en not_active Withdrawn
- 2011-04-14 WO PCT/JP2011/059247 patent/WO2011132595A1/ja active Application Filing
- 2011-04-14 CN CN2011800039307A patent/CN102549720A/zh active Pending
- 2011-04-20 TW TW100113775A patent/TW201203342A/zh unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104756235A (zh) * | 2012-10-18 | 2015-07-01 | 古河电气工业株式会社 | 切割胶带 |
TWI506118B (zh) * | 2012-10-18 | 2015-11-01 | Furukawa Electric Co Ltd | 切割膠帶 |
CN104756235B (zh) * | 2012-10-18 | 2017-05-24 | 古河电气工业株式会社 | 切割胶带 |
Also Published As
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US20120114938A1 (en) | 2012-05-10 |
EP2562795A1 (en) | 2013-02-27 |
JP2011228502A (ja) | 2011-11-10 |
JP5406110B2 (ja) | 2014-02-05 |
WO2011132595A1 (ja) | 2011-10-27 |
KR20120133985A (ko) | 2012-12-11 |
CN102549720A (zh) | 2012-07-04 |
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