TW202223024A - 黏著帶及加工方法 - Google Patents
黏著帶及加工方法 Download PDFInfo
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- TW202223024A TW202223024A TW110141682A TW110141682A TW202223024A TW 202223024 A TW202223024 A TW 202223024A TW 110141682 A TW110141682 A TW 110141682A TW 110141682 A TW110141682 A TW 110141682A TW 202223024 A TW202223024 A TW 202223024A
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- adhesive tape
- polymer
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- adhesive layer
- adhesive
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
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- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
-
- 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
-
- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support
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- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
- H01L2221/68336—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding involving stretching of the auxiliary support post dicing
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- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
一種黏著帶,其係具有基材層、及設於該基材層上之黏著劑層者,且上述黏著劑層包含光自由基起始劑、及具有聚合性碳雙鍵之聚合物A,矽晶圓表面相對於水之接觸角R
0、與將上述黏著劑層貼附於上述矽晶圓放置24小時後對上述黏著劑層照射紫外線而剝離上述黏著劑層後的矽晶圓表面相對於水之接觸角R
1之差|R
0-R
1|為20°以下。
Description
本發明係關於一種黏著帶及加工方法。
於將半導體封裝或半導體晶圓(以下,亦稱為「被黏著體」)等單片化時,將半導體晶圓加工用膠帶貼附於被黏著體,於切割時將被黏著體暫時固定。藉此,可於單片化時防止晶片飛濺。又,於切割後,擴展半導體晶圓加工用膠帶,自半導體晶圓加工用膠帶拾取(剝離)單片化之被黏著體。
作為此種半導體晶圓加工用膠帶,主要使用在對紫外線具有透過性之膜基材上塗佈有藉由紫外線照射進行硬化反應之黏著劑層的黏著帶。於該紫外線硬化型加工用膠帶中,由於藉由在切割後對黏著劑層照射紫外線,使其進行硬化反應而可降低黏著劑層之黏著力,因此可容易地拾取單片化之被黏著體。
於此種半導體晶圓加工用膠帶中,要求於拾取時減少對被黏著體之糊劑殘留,可製造高品質之電子零件之技術。
於該方面,於上述紫外線照射型之加工用膠帶中存在如下情況:將黏著帶貼附於被黏著體時,若氣泡等進入黏著帶與被黏著體之間,則於紫外線照射時會引起由氧抑制等導致之黏著劑之硬化不良,黏著劑以未硬化之狀態殘留於被黏著體。又,若對被黏著體之黏著力不足,則於切割時切削水浸入至被黏著體與黏著帶之間而污染被黏著體,或者進而導致單片化之被黏著體飛散。
對此,為了彌補黏著力,考慮增加黏著劑層之厚度,或者降低黏著劑層之彈性模數而提高黏著力之方法。然而於該情形時,產生如下問題:黏著劑由於因切割時刀片之旋轉而產生之摩擦熱而熔解,由於刮取而造成黏著劑屑附著於被黏著體,或者單片化之被黏著體固定於黏著帶,因此拾取時無法於與被黏著體之界面剝離而產生黏著劑本身之破壞,黏著劑屑殘留於被黏著體。
與此相對,例如於專利文獻1中,揭示藉由使用具有5~6個丙烯醯基之輻射聚合性化合物,將紫外線照射及/或電子束照射後之凝膠分率設為90 wt%以上等,抑制糊劑殘留。
[先前技術文獻]
[專利文獻]
專利文獻1:日本專利特開2000-281993號公報
[發明所欲解決之問題]
然而,於專利文獻1所記載之方法中,雖然多少可抑制糊劑殘留,但反而有黏著力降低之傾向,有切割時切削水浸入被黏著體與黏著帶之間,產生背面污染,或者單片化之被黏著體飛散之可能性。
進而,由於近年來半導體晶圓或元件之高密度化或高性能化之要求,即便為看起來不存在黏著劑之糊劑殘留的半導體晶圓或元件表面,有時亦被起因於黏著劑之有機物污染,此種污染亦成為一個問題。再者,於本說明書中,於簡稱為「污染」時,指此種無法目視之污染,關於可目視者則稱為「糊劑殘留」。
本發明係鑒於上述問題而成者,其目的在於提供一種能夠降低源自黏著劑層之污染的黏著帶及使用其之加工方法。
[解決問題之技術手段]
本發明人等為了解決上述課題,對黏著帶之黏著劑設計進行了銳意研究。結果發現藉由在紫外線硬化前後,使用以表示特定之接觸角特性之方式構成之接著劑層,可解決上述課題,從而完成本發明。
即,本發明如以下所示。
[1]
一種黏著帶,
其係具有基材層、及設於該基材層上之黏著劑層者,且
上述黏著劑層包含光自由基起始劑、及具有聚合性碳雙鍵之聚合物A,
矽晶圓表面相對於水之接觸角R
0、與將上述黏著劑層貼附於上述矽晶圓放置24小時後對上述黏著劑層照射紫外線而剝離上述黏著劑層後的上述矽晶圓表面相對於水之接觸角R
1之差|R
0-R
1|為20°以下。
[2]
如技術方案1所記載之黏著帶,其中
相對於凝膠滲透層析圖之總面積,上述聚合物A中所包含之重量平均分子量20000以下之成分A1之含量為15面積%以下。
[3]
如[1]或[2]所記載之黏著帶,其中
紫外線照射前之上述黏著劑層相對於矽晶圓之180°剝離強度於23℃下為2.0~20.0 N/20 mm。
[4]
如[1]至[3]中任一項所記載之黏著帶,其中
聚合物A具有羥基。
[5]
如[1]至[4]中任一項所記載之黏著帶,其中
上述聚合物A之重量平均分子量為1.0×10
5~2.0×10
6。
[6]
如[1]至[5]中任一項所記載之黏著帶,其中
上述聚合物A之玻璃轉移點為-80~23℃。
[7]
如[1]至[6]中任一項所記載之黏著帶,其中
上述聚合物A包含(甲基)丙烯酸酯系共聚物,
該(甲基)丙烯酸酯系共聚物具有直鏈形狀、支鏈形狀、或交聯形狀。
[8]
如[1]至[7]中任一項所記載之黏著帶,其中
上述黏著劑層進而包含硬化劑。
[9]
如[8]所記載之黏著帶,其中
上述硬化劑包含異氰酸酯系化合物。
[10]
如[9]所記載之黏著帶,其中
上述異氰酸酯系化合物包含2官能以上之多官能異氰酸酯系化合物。
[11]
如[8]至[10]中任一項所記載之黏著帶,其中
相對於聚合物A 100重量份,上述硬化劑之含量為0.1~5.0重量份。
[12]
如[1]至[11]中任一項所記載之黏著帶,其
用於半導體晶圓、半導體元件、各種半導體封裝加工。
[13]
一種加工方法,其具有:
貼合步驟,其將如[1]至[12]中任一項所記載之黏著帶與被黏著體貼合;及
切割步驟,其於上述黏著帶與上述被黏著體貼合之狀態下,將上述被黏著體單片化;
上述被黏著體為半導體晶圓、半導體元件、或各種半導體封裝。
[發明之效果]
根據本發明,可提供一種能夠降低源自黏著劑層之污染的黏著帶及使用其之加工方法。
以下,對本發明之實施方式(以下稱為「本實施方式」)詳細地進行說明,但本發明並不限定於此,於不脫離其主旨之範圍內可進行各種變化。
[黏著帶]
本實施方式之黏著帶具有基材層、及設於該基材層上之黏著劑層,黏著劑層包含光自由基起始劑、及具有聚合性碳雙鍵之聚合物A,矽晶圓表面相對於水之接觸角R
0、與將黏著劑層貼附於矽晶圓放置24小時後對黏著劑層照射紫外線而剝離黏著劑層後的矽晶圓表面相對於水之接觸角R
1之差|R
0-R
1|為20°以下。
先前之黏著劑層例如包含不具有紫外線硬化性之基礎聚合物、及具有紫外線硬化性之低分子量成分。因此,於紫外線照射後以未反應之狀態殘留之低分子量成分有可能污染被黏著體表面。
與此相對,於本實施方式中,藉由使用具有聚合性碳雙鍵之聚合物A,聚合物A彼此進而藉由紫外線照射而聚合,相互交聯。因此,可避免低分子量成分污染被黏著體表面之問題,又,假設即便聚合物A之聚合性碳雙鍵之一部分未反應,與低分子量成分相比,亦可避免被黏著體表面之污染。進而,即便於使用具有聚合性碳雙鍵之低分子量成分之情形時,由於低分子量成分亦可與聚合物A鍵結,因此易於留在黏著劑中,可抑制污染被黏著體之表面。
又,於本實施方式中,包含聚合物A之黏著劑層之利用紫外線照射而得之硬化特性進而由接觸角R
0與接觸角R
1之差|R
0-R
1|所表示之接觸角特性規定。藉由使用具有此種接觸角特性之黏著劑層,可進一步降低源自黏著劑層之污染。以下,對本發明進行詳細說明。
(接觸角)
於本實施方式中,使用矽晶圓表面相對於水之接觸角R
0、與將黏著劑層貼附於矽晶圓放置24小時後對黏著劑層照射紫外線而剝離黏著劑層後的矽晶圓表面相對於水之接觸角R
1之差|R
0-R
1|,規定紫外線照射後之黏著劑層對矽晶圓之低污染性。
更具體而言,差|R
0-R
1|為20°以下,較佳為0~17.5°,更佳為0~15°,進而較佳為0~12.5°。差|R
0-R
1|越少,則被黏著體之污染更加變少。
尤其藉由|R
0-R
1|為20°以下,更顯著地降低污染性,亦提高被黏著體之其後之製造步驟或安裝時之良率。另一方面,若差|R
0-R
1|大於20°,則被黏著體表面易於被污染,進而可能產生對被黏著體之糊劑殘留。
再者,矽晶圓表面由於被空氣中之氧氣氧化而羥基暴露於最表面,因此通常親水性較高。因此,相對於水之接觸角R
1較小意指接近貼附黏著帶前之潔淨之矽晶圓表面之狀態。又,與此相反,若矽晶圓被黏著劑層中所包含之有機成分污染,則矽晶圓表面之親水性降低且相對於水之接觸角變大。
又,接觸角R
1較佳為5~25°,更佳為5~28°,進而較佳為5~32°。藉由接觸角R
1為上述範圍內,進一步抑制紫外線照射後之黏著劑層對矽晶圓之污染。
作為使差|R
0-R
1|及接觸角R
1為上述範圍之方法,並無特別限制,例如可例舉:減少黏著劑層中所包含之低分子量成分、減少聚合物A之低分子量成分、提高紫外線照射時之交聯密度等。作為低分子量成分之減少方法,並無特別限制,例如可例舉:於基材層上形成黏著劑層後,於加溫下進行老化之方法;或使用低分子量成分之含量較少之聚合物A。又,作為提高交聯密度之方法,並無特別限制,例如可例舉對聚合性碳雙鍵之數量、或光自由基起始劑之含量進行調整之方法。
本說明書中所記載之「接觸角」係將黏著帶貼附於矽晶圓,於23℃之條件下放置24小時後,利用高壓水銀燈照射150 mJ/cm
2之紫外線而剝離,利用液滴法測定相對於水之接觸角而得之接觸角。
(180°剝離強度)
紫外線照射前之黏著劑層相對於矽晶圓之180°剝離強度S於23℃下,較佳為2.0~20.0 N/20 mm,更佳為4.0~16.0 N/20 mm,進而較佳為6.0~12.0 N/20 mm。
藉由180°剝離強度S為2.0 N/20 mm以上,紫外線照射前之黏著力有更加優異之傾向。因此,黏著帶不易自環狀框剝落,於切割步驟中亦不易產生晶片飛濺。
又,藉由180°剝離強度S為20 N/20 mm以下,有黏著劑不易被切割步驟之刀片刮掉,被刮掉之黏著劑不易附著於被黏著體之側面等之傾向。因此,有進一步抑制如下情況之傾向:被刮掉之黏著劑以糊劑殘留之形式殘留於被黏著體上,或者由於直接進行紫外線硬化而使晶片固定化,或者產生拾取不良,且於固定化之晶片產生碎片。
本說明書中所記載之「相對於矽晶圓之180°剝離強度」可依據JIS Z0237(2009)之黏著力之測定方法進行測定。具體而言,使用壓接裝置(輥之質量2 kg)使黏著劑層壓接於洗淨表面之被黏著體(矽晶圓),於溫度23℃濕度50%之環境下,藉由萬能型拉伸試驗機對相對於被黏著體以180°剝離時之黏著力進行測定。
(黏著劑層)
黏著劑層包含光自由基起始劑、及具有聚合性碳雙鍵之聚合物A,亦可視需要包含硬化劑或其他成分。
(聚合物A)
聚合物A為具有聚合性碳雙鍵之聚合物,為構成黏著劑層之主成分之成分。若對黏著劑層照射紫外線,則光自由基起始劑產生自由基,藉此聚合物A之聚合性碳雙鍵分別聚合。藉此,於紫外線照射後,聚合物A成為相互交聯之狀態。
就污染降低之觀點而言,較佳為聚合物A中所包含之低分子量成分較少。更具體而言,聚合物A中所包含之重量平均分子量20000以下之成分A1之含量相對於凝膠滲透層析圖之總面積,較佳為15面積%以下,更佳為10面積%以下,進而較佳為8面積%以下,進而更佳為5面積%以下。成分A1之含量之下限並無特別限制,為0面積%。藉由成分A1之含量為15面積%以下,有於紫外線照射後,殘存於被黏著體表面之低分子量成分變少,進一步降低污染之傾向。
又,聚合物A之重量平均分子量較佳為1.0×10
5~2.0×10
6,更佳為2.0×10
5~1.0×10
6,進而較佳為2.5×10
5~8.0×10
5。藉由聚合物A之重量平均分子量為1.0×10
5以上,除高分子量成分變多以外,分子量越高,則1個聚合物A與其他聚合物A藉由聚合性雙鍵進行聚合之機會越多,因此有進一步降低污染之傾向。藉由聚合物A之重量平均分子量為2.0×10
6以下,聚合物A易於移動,1個聚合物A與其他聚合物A進行聚合之機會變多,因此有進一步降低污染之傾向。又,由於分子量越小,則黏著劑之彈性模數越不會變得過高,因此有進一步提高常態下之黏著力之傾向。又,由於對被黏著體之追隨性變得良好且亦可追隨被黏著體之階差,因此可避免由氧抑制導致之UV(Ultraviolet,紫外線)硬化不良所引起之污染。進而,由於柔軟之黏著劑易於因UV照射而充分硬化收縮,因此可充分降低硬化後之黏著力。
本說明書中所記載之「重量平均分子量」係使用凝膠滲透層析分析裝置對將聚合物A溶解於四氫呋喃之樣品進行測定而得之分子量。關於成分A1之含量,可藉由將聚合物A之層析圖之面積設為100面積%,根據標準聚苯乙烯換算之分子量之校準曲線算出重量平均分子量為20000以下之保持時間內之層析圖之面積之比率而求出。
又,聚合物A之玻璃轉移點較佳為-80~23℃,更佳為-70~10℃,進而較佳為-60~0℃。藉由聚合物A之玻璃轉移點為-80℃以上,有進一步降低污染之傾向。又,藉由聚合物A之玻璃轉移點為23℃以下,有進一步提高對被黏著體之接著性之傾向。
作為聚合物A,並無特別限制,例如可例舉具有聚合性雙鍵之(甲基)丙烯酸酯系共聚物。(甲基)丙烯酸酯系共聚物之形狀並無特別限制,例如可例舉直鏈形狀、支鏈形狀、或交聯形狀。其中,較佳為具有交聯形狀。藉由使用此種聚合物A,有提高黏著劑層之凝聚力且進一步提高對被黏著體之接著性,並且進一步降低污染之傾向。具有交聯形狀或支鏈形狀之聚合物A可為具有直鏈形狀之聚合物A之聚合性雙鍵之一部分藉由老化等鍵結而成者。
作為構成(甲基)丙烯酸酯系共聚物之(甲基)丙烯酸酯之單體,並無特別限制,例如可例舉具有甲基、乙基、正丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、十二烷基等直鏈或支鏈烷基之(甲基)丙烯酸烷基酯。該等(甲基)丙烯酸烷基酯可單獨使用1種,或可併用2種以上。
又,作為除上述(甲基)丙烯酸烷基酯以外之單體成分,並無特別限制,例如可例舉:丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、及丁烯酸等含羧基單體;順丁烯二酸酐或伊康酸酐等酸酐單體;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸1-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、及(甲基)丙烯酸(4-羥基甲基環己基)甲酯等含羥基單體;(甲基)丙烯酸乙氧基乙氧基乙酯等含伸烷氧基單體;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、及(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。該等其他單體可單獨使用1種,或可併用2種以上。
其中,較佳為包含(甲基)丙烯酸烷基酯及含羥基單體之(甲基)丙烯酸酯系共聚物、或包含(甲基)丙烯酸烷基酯及含羧基單體之(甲基)丙烯酸酯系共聚物。
聚合性雙鍵導入至(甲基)丙烯酸酯系共聚物之方法並無特別限制,例如可例舉如下方法:使具有聚合性雙鍵之改性劑與含羧基單體之羧基、酸酐單體之酸酐基、或含羥基單體之羥基進行反應。
例如,藉由使作為改性劑之具有聚合性雙鍵之異氰酸酯系化合物與含有含羥基單體單元之(甲基)丙烯酸酯系共聚物進行反應,可經由胺基甲酸酯鍵將聚合性雙鍵導入至含羥基單體單元。又,作為其他例,藉由使作為改性劑之具有聚合性雙鍵之環氧化合物與含有含羥基單體單元之(甲基)丙烯酸酯系共聚物進行反應,可經由醚鍵將聚合性雙鍵導入至含羥基單體單元。
再者,作為改性劑,只要為具有與(甲基)丙烯酸酯系共聚物所具有之官能基進行反應之官能基且具有聚合性雙鍵者,則並無特別限制,例如可例舉具有聚合性雙鍵之異氰酸酯系化合物、具有聚合性雙鍵之環氧化合物等。
又,相對於構成聚合物A之反應性單體單元100莫耳%,聚合性雙鍵之導入量較佳為20~80莫耳%,更佳為30~75莫耳%,進而較佳為40~70莫耳%。再者,此處,「反應性單體單元」指含羧基單體、酸酐單體、及含羥基單體。藉由聚合性雙鍵之導入量為20莫耳%以上,有紫外線照射時未反應之聚合物A不易殘留,污染得到進一步抑制之傾向。又,由於藉由聚合性雙鍵之導入量為80莫耳%以下,可抑制過度交聯,因此有抑制如下情況之傾向:黏著劑層無法承受由拾取時銷之頂起所引起之黏著帶變形而破裂為銷之形狀且因此產生糊劑殘留。進而,藉由聚合性雙鍵之導入量為80莫耳%以下,有未反應之羧基等極性基易於殘存,進一步提高對紫外線照射前之被黏著體之黏著力之傾向。
聚合物A較佳為具有羥基。再者,該羥基可為源自含羥基單體等者,可為源自改性劑之羥基,亦可為藉由含羥基單體與改性劑反應而產生之羥基。作為藉由含羥基單體等單體單元與改性劑反應而產生之羥基,例如可例舉如使含羥基單體與具有聚合性雙鍵之環氧化合物進行反應之例。
藉由聚合物A具有羥基,於調配下述硬化劑之情形時,可經由羥基使多個聚合物間進一步交聯,有進一步提高黏著劑層之凝聚力之傾向。又,有如下傾向:亦進一步提高基材膜與黏著劑層之抓固性,抑制凝聚破壞或抓固破壞,可獲得更加穩定之黏著特性。
相對於黏著劑層之總量,聚合物A之含量較佳為80~99.5質量%,更佳為85~99.5質量%,進而較佳為90~99.5質量%。藉由聚合物A之含量為上述範圍內,有進一步抑制污染之傾向。
(光自由基起始劑)
作為光自由基起始劑,並無特別限定,例如可例舉:苯烷酮系光聚合起始劑、醯基氧化膦系光聚合起始劑、9-氧硫𠮿系光聚合起始劑、芳香族酮類、芳香族鎓鹽化合物、有機過氧化物、硫代化合物(含有苯硫基之化合物等)、α-胺基苯烷酮化合物、六芳基聯咪唑化合物、酮肟酯化合物、硼酸鹽化合物、吖𠯤化合物、茂金屬化合物、活性酯化合物、具有碳鹵鍵之化合物、及烷基胺化合物。
其中,較佳為苯烷酮系光聚合起始劑。
相對於黏著劑層之總量,光自由基起始劑之含量較佳為0.1~5.0質量%,更佳為0.2~4.0質量%,進而較佳為0.3~3.0質量%。藉由光自由基起始劑之含量為上述範圍內,有進一步抑制污染之傾向。
(硬化劑)
作為硬化劑,並無特別限制,例如可例舉異氰酸酯系化合物、環氧系化合物、胺系化合物等。其中,較佳為異氰酸酯系化合物。藉由使用此種硬化劑,有進一步提高黏著劑層之凝聚力之傾向。該等硬化劑可單獨使用1種,亦可併用2種以上。
作為異氰酸酯系化合物,並無特別限制,例如可例舉:甲苯二異氰酸酯、4,4-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族二異氰酸酯;異佛爾酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)等脂環族二異氰酸酯;六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯等脂肪族二異氰酸酯。該等可單獨使用1種,亦可併用2種以上。
其中,硬化劑較佳為2官能以上之多官能異氰酸酯系化合物。由於藉由使用此種硬化劑,亦可利用硬化劑使多個聚合物A間交聯,因此有進一步提高黏著劑層之凝聚力之傾向。又,有亦提高基材層與黏著劑層之抓固性,可獲得更加穩定之黏著特性之傾向。
相對於聚合物A 100重量份,硬化劑之含量較佳為0.1~5.0重量份,更佳為0.3~4.0重量份,進而較佳為0.3~3.0重量份。藉由硬化劑之含量為0.1重量份以上,有如下傾向:進一步提高黏著劑層之交聯密度,進一步抑制剝離時產生之凝聚破壞,進一步抑制起因於凝聚破壞之污染。又,由於藉由硬化劑之含量為5.0重量份以下,交聯密度進一步降低,彈性模數變低,因此有進一步提高黏著力之傾向。
又,相對於黏著劑層之總量,硬化劑之含量較佳為0.1~2.0質量%,更佳為0.2~1.5質量%,進而較佳為0.3~1.0質量%。藉由硬化劑之含量為上述範圍內,有進一步抑制污染之傾向。
(其他添加劑)
本實施方式之黏著劑層可視需要包含黏著賦予劑、交聯延遲劑、抗氧化劑等其他添加劑。
作為黏著賦予劑,並無特別限制,例如可例舉:石油系樹脂、萜烯樹脂、萜烯酚樹脂、芳香族改性萜烯樹脂、苯并呋喃茚樹脂、天然樹脂松香、改性松香、甘油酯松香、季戊四醇酯松香、酚樹脂、二甲苯樹脂、脂環族系石油樹脂、苯乙烯系樹脂、二環戊二烯樹脂等。
作為交聯延遲劑,並無特別限制,例如於含有異氰酸酯系硬化劑之黏著劑組合物中,可藉由將硬化劑所具有之異氰酸基封端,而抑制黏著劑組合物之過度之黏度上升的化合物。作為此種交聯延遲劑,並無特別限制,例如可例舉:乙醯丙酮、己烷-2,4-二酮、庚烷-2,4-二酮、辛烷-2,4-二酮等β-二酮類;乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸丙酯、乙醯乙酸丁酯、乙醯乙酸辛酯、乙醯乙酸油脂、乙醯乙酸月桂酯、乙醯乙酸硬脂酯等β-酮酯類;苯甲醯基丙酮等。
作為抗氧化劑,並無特別限制,例如可例舉:甲基氫醌、對苯二酚、2,2-亞甲基-雙(4-甲基-6-第三丁基苯酚)、兒茶酚、對苯二酚單甲醚、單-第三丁基對苯二酚、2,5-二-第三丁基對苯二酚、對苯醌、2,5-二苯基-對苯醌、2,5-二-第三丁基-對苯醌、苦味酸、檸檬酸、啡噻𠯤、第三丁基兒茶酚、2-丁基-4-羥基甲氧苯、2,6-二-第三丁基-對甲酚及4-[[4,6-雙(辛硫基)-1,3,5-三𠯤-2-基]胺基]-2,6-二-第三丁基苯酚。
(厚度)
黏著劑層之厚度通常為1.0~250 μm,較佳為2.0~50 μm,進而較佳為5.0~40 μm。由於藉由使黏著劑層之厚度為1.0 μm以上,可確保充分之黏著力,因此容易地抑制藉由擴展而分割之半導體晶片之飛散。又,藉由黏著劑層之厚度為250 μm以下,有進一步抑制成本之傾向。
於用作半導體晶圓加工用膠帶之情形時,較佳為以膠帶之總厚度較佳地成為60~250 μm之範圍之方式,於上述範圍內調整基材層及黏著劑層之厚度。半導體晶圓加工用膠帶之厚度更佳為70~200 μm,進而較佳為80~180 μm之範圍。
(基材層)
作為構成基材層之材料,並無特別限制,例如可例舉藉由金屬離子使聚氯乙烯、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸-丙烯酸酯膜、乙烯-丙烯酸乙酯共聚物、聚乙烯、聚丙烯、丙烯系共聚物、乙烯-丙烯酸共聚物、及乙烯-(甲基)丙烯酸共聚物或乙烯-(甲基)丙烯酸-(甲基)丙烯酸酯系共聚物等交聯而成之離子聚合物樹脂。構成基材層之基材膜可為該等樹脂之單個、2種以上之混合物、共聚物、或該等之積層物。
基材層之厚度可於不損害作業性之範圍內適當選擇。基材層之厚度通常為10~500 μm,較佳為50~200 μm,進而較佳為70~150 μm。藉由將基材層之厚度調整為上述範圍內,實用上沒有問題,經濟上亦有效。於由多個基材膜構成基材層之情形時,較佳為以基材層整體之厚度成為上述範圍內之方式進行調整。
基材層為了提高與黏著劑層之密接性,視需要可化學性或物理性實施表面處理。作為上述表面處理,例如可例舉:電暈處理、鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、及離子化輻射處理等。
(保護膜)
本實施方式之黏著帶為了保護黏著劑層,可具有貼合於黏著劑層之保護膜。保護膜在黏著帶之使用時剝離,因此較佳為剝離性優異者。作為保護膜,並無特別限制,例如可例舉包含氟樹脂之表面能較低之膜、以矽酮系剝離劑將聚對苯二甲酸乙二酯之表面進行處理之膜等。
(用途)
本實施方式之黏著帶適宜用於半導體晶圓、半導體元件、或各種半導體封裝之加工用途。半導體晶圓可為形成有電子線路等之單片化前者。又,半導體元件指單片化後之各種半導體晶片或者包含其之元件,半導體封裝指於半導體晶片帶有用於保護其之樹脂及將半導體晶片與外部連接之連接端子者。
[黏著帶之製造方法]
作為黏著帶之製造方法,並無特別限制,可例舉於基材層上形成黏著劑層之方法。
本實施方式之黏著帶之基材層可沿用周知之技術製造。使基材層成形之方法並無特別限定,使用慣用之熔融混練等或各種混合裝置(單軸或雙軸擠出機、輥、班布里混合機、各種捏合機等)將上述各種材料以各成分均勻分散之方式進行混合,藉由T模法、壓光法、吹脹法使該混合物成形為基材。較佳為使用利用厚度精度良好之擠出機之T模法進行製膜之方法。
本實施方式之黏著帶之黏著劑層可沿用周知之技術製造。使黏著劑層成形之方法並無特別限定,藉由使上述各種材料溶解於有機溶劑等溶劑而清漆化,利用刮塗法、輥塗法、噴塗法、凹版塗佈法、棒式塗佈法、或淋幕式塗佈法等將其塗佈於保護膜上,去除溶劑而形成黏著劑層。藉由將其貼合於基材層上,製作黏著帶。
於本實施方式中,於形成黏著劑層後,可進行老化處理。於老化處理中,將形成之黏著劑層於特定之溫度下保管。溫度條件並無特別限制,較佳為30~50℃,更佳為35~45℃。又,保管時間並無特別限制,較佳為24~150小時,更佳為48~100小時。藉由進行該老化處理,黏著劑層之黏著力、或硬化特性發生變化。又,關於紫外線照射後之拉伸彈性模數或斷裂伸長率,亦可控制為上述較佳之範圍。
[加工方法]
本實施方式之加工方法係如下方法:具有將上述黏著帶與被黏著體貼合之貼合步驟、及於黏著帶與被黏著體貼合之狀態下對被黏著體進行加工之切割步驟,且加工半導體晶圓、半導體元件、或各種半導體封裝作為被黏著體。又,本實施方式之加工方法可視需要具有對切割步驟後之黏著帶照射紫外線之紫外線照射步驟、或自紫外線照射後之黏著帶拾取單片化之晶片之拾取步驟。
利用切割步驟之單片化方法並無特別限制,可使用先前公知之方法。例如,藉由使用切割裝置使含有金剛石研磨粒之切割刀片高速旋轉,可將矽晶圓切割為半導體晶片。
紫外線照射方法並無特別限制,可使用先前公知之方法。例如,使用紫外線照射裝置對切割步驟之黏著帶照射紫外線。
其後,拾取方法並無特別限制,可使用先前公知之方法。例如,可使用擴展裝置,將紫外線照射後之黏著帶沿面方向拉長,於將各晶片分離之狀態下利用拾取裝置拾取晶片。
實施例
以下,使用實施例及比較例對本發明更加具體地進行說明,但本發明並不限定於該等。
(實施例1)
使丙烯酸2-乙基己酯63重量份、丙烯酸2-羥基乙酯15重量份、丙烯酸乙氧基乙氧基乙酯22重量份、及起始劑(偶氮二異丁腈)0.03重量份於乙酸乙酯中、65℃下進行24小時之共聚,獲得包含丙烯酸系聚合物之溶液。
使該丙烯酸系聚合物中之丙烯酸2-羥基乙酯單元之羥基與2-甲基丙烯醯氧基乙基異氰酸酯進行反應,獲得於側鏈導入有雙鍵之側鏈雙鍵導入型丙烯酸系聚合物。此時,以2-甲基丙烯醯氧基乙基異氰酸酯之導入量為於上述丙烯酸系聚合物之每100莫耳丙烯酸2-羥基乙酯單元中為50莫耳(50莫耳%)之方式,使兩者進行反應。
繼而,於包含側鏈雙鍵導入型丙烯酸系聚合物100重量份之溶液中,添加作為聚異氰酸酯系化合物之三羥甲基丙烷改性甲苯二異氰酸酯硬化劑(日本聚胺酯股份有限公司:Coronate L-45E)0.5重量份、及作為光自由基起始劑之2,2-二甲氧基-2-苯基苯乙酮(BASF公司製造:Omnirad 651)2.1重量份,製備作為紫外線硬化型黏著劑之樹脂組合物。
將該樹脂組合物以乾燥後之黏著劑層之厚度成為20 μm之方式塗佈於預先實施脫模處理之聚對苯二甲酸乙二酯保護膜之脫模處理面上,於100℃下乾燥1分鐘後,與對預先貼合有黏著劑層之表面實施電暈處理之乙烯-甲基丙烯酸-丙烯酸酯系共聚物之離子聚合物膜(基材樹脂膜)之電暈處理面貼合而將黏著劑轉印至基材樹脂膜。將其於40℃之氛圍下進行72小時之老化,獲得黏著帶。
(實施例2)
使丙烯酸丁酯67重量份、丙烯酸甲酯28重量份、丙烯酸2-羥基乙酯5重量份、及起始劑(偶氮二異丁腈)0.03重量份於甲苯中、65℃下進行24小時之共聚,獲得包含丙烯酸系聚合物之溶液。使該丙烯酸系聚合物中之丙烯酸2-羥基乙酯單元之羥基與2-甲基丙烯醯氧基乙基異氰酸酯進行反應,獲得於側鏈導入有雙鍵之側鏈雙鍵導入型丙烯酸系聚合物。此時,以2-甲基丙烯醯氧基乙基異氰酸酯之導入量為於上述丙烯酸系聚合物之每100莫耳丙烯酸2-羥基乙酯單元中為70莫耳(70莫耳%)之方式,使兩者進行反應。藉由將上述丙烯酸系聚合物於乙酸乙酯:甲醇=1:20之溶液中以固形物成分濃度20%進行洗淨,去除低分子量成分。此後以與實施例1相同之方式獲得黏著帶。
(實施例3)
除省略丙烯酸系聚合物之洗淨步驟以外,以與實施例2相同之方式,獲得黏著帶。
(實施例4)
以2-甲基丙烯醯氧基乙基異氰酸酯之導入量為於丙烯酸系聚合物之每100莫耳丙烯酸2-羥基乙酯單元中為30莫耳(30莫耳%)之方式,使兩者進行反應,除此以外,以與實施例1相同之方式獲得黏著帶。
(實施例5)
調整起始劑之量,使側鏈雙鍵導入型丙烯酸系聚合物之重量平均分子量為80萬,除此以外,以與實施例1相同之方式獲得黏著帶。
(實施例6)
使丙烯酸2-乙基己酯92重量份、丙烯酸8重量份、及起始劑(偶氮二異丁腈)0.05重量份於乙酸乙酯中、65℃下進行24小時之共聚,獲得包含丙烯酸系聚合物之溶液。
使該丙烯酸系聚合物中之丙烯酸單元之羧基與甲基丙烯酸縮水甘油酯進行反應,獲得於側鏈導入有雙鍵之側鏈雙鍵導入型丙烯酸系聚合物。此時,以甲基丙烯酸縮水甘油酯之導入量為於上述丙烯酸系聚合物之每100莫耳丙烯酸單元中為80莫耳(80莫耳%)之方式,使兩者進行反應。藉由將上述丙烯酸系聚合物於乙酸乙酯:甲醇=1:20之溶液中以固形物成分濃度20%進行洗淨,去除低分子量成分。
繼而,於包含側鏈雙鍵導入型丙烯酸系聚合物100重量份之溶液中添加作為聚異氰酸酯系化合物之三羥甲基丙烷改性甲苯二異氰酸酯硬化劑(日本聚胺酯股份有限公司:Coronate L-45E)0.1重量份、及作為光自由基起始劑之2,2-二甲氧基-2-苯基苯乙酮(BASF公司製造:Omnirad 651)2.1重量份,製備作為紫外線硬化型黏著劑之樹脂組合物。此後,以與實施例1相同之方式獲得黏著帶。
(實施例7)
使丙烯酸系聚合物中之丙烯酸單元之羧基與甲基丙烯酸縮水甘油酯進行反應,獲得於側鏈導入有雙鍵之側鏈雙鍵導入型丙烯酸系聚合物時,以甲基丙烯酸縮水甘油酯之導入量為於上述丙烯酸系聚合物之每100莫耳丙烯酸單元中為60莫耳(60莫耳%)之方式,使兩者進行反應,且將作為聚異氰酸酯系化合物之三羥甲基丙烷改性甲苯二異氰酸酯硬化劑(日本聚胺酯股份有限公司:Coronate L-45E)設為0.5重量份,除此以外,以與實施例6相同之方式獲得黏著帶。
(比較例1)
省略丙烯酸系聚合物之洗淨步驟,且將作為聚異氰酸酯系化合物之三羥甲基丙烷改性甲苯二異氰酸酯硬化劑(日本聚胺酯股份有限公司:Coronate L-45E)設為0.5重量份,除此以外,以與實施例6相同之方式獲得黏著帶。
(比較例2)
使丙烯酸2-乙基己酯45重量份、丙烯酸2-羥基乙酯10重量份、丙烯酸甲酯40重量份、丙烯酸5.0重量份、及起始劑(偶氮二異丁腈)0.03重量份於乙酸乙酯中、65℃下進行24小時之共聚,獲得包含丙烯酸系聚合物之溶液。
對該丙烯酸系聚合物,另外添加紫外線聚合性胺基甲酸酯丙烯酸酯,同時調整硬化劑及起始劑之量,除此以外,以與實施例1相同之方式製作黏著帶。
關於以上述方式製備之各樣品,針對有機物污染、接觸角、分子量、180°剝離對矽晶圓黏著力、切割、拾取,按如下方式進行評價試驗。將所獲得之結果彙總示於下述表1。
<有機物污染>
於正規晶圓(Prime wafer)貼附以上述方式製作之黏著帶並放置24小時後,藉由高壓水銀燈照射150 mJ/cm
2之紫外線將其剝離。其後,藉由TD-GC/MS(Thermal desorption-gas chromatography-mass spectrometry,熱脫附-氣相層析/質譜儀)測定正規晶圓表面之揮發有機物成分。將TD-GC/MS之測定條件示於以下。
(測定條件)
試樣預處理:藉由下述裝置將晶圓上之有機吸附物質回收至TENAX管。
・裝置:「WA2560M」(GL Science公司製造)
・加熱條件:室溫→約25℃/min升溫→400℃(保持15 min)
・吸附條件:Tenax管(室溫)
TD-GC/MS
・測定裝置:「TD2530」(GL Science公司製造)
・Agilent Technologies 7890B GC System
・Agilent Technologies 5977A MSD
・TENAX管解吸溫度:270℃
・GC導入法:於-130℃下冷阱後,於270℃下進行加熱
・管柱:InertCap 1MS(長度:60 m,直徑:0.25 mm,膜:0.25 μm)
・載氣:He
・離子化法:EI(Electron Ionization)法
・GC升溫條件:40℃(保持5 min)→10℃/min升溫→280℃(保持11 min)
所使用之正規晶圓:6英吋,微粒:0.3 μm≦15個
<接觸角>
將以上述方式製作之黏著帶貼附於矽晶圓,於23℃之條件下放置24小時後,藉由高壓水銀燈照射150 mJ/cm
2之紫外線將其剝離。其後,藉由液滴法對矽晶圓表面相對於蒸留水之接觸角R
1進行測定。關於黏著帶貼附前之開封時之矽晶圓相對於蒸留水之接觸角R
0,亦以相同之方式進行測定,算出差|R
0-R
1|。將液滴法之測定條件示於以下。
(測定條件)
・水滴:3 mL
・30次/1測定(1次/1秒),採用第30次之值×n3
<重量平均分子量>
將以上述方式合成之側鏈雙鍵導入型丙烯酸系聚合物10 mg溶解於四氫呋喃(THF,不含穩定劑,和光製藥工業股份有限公司製造)10 mL,將藉由膜濾器(PTFE(Polytetrafluoroethylene,聚四氟乙烯)製造,0.50 μm)過濾而得者供於分析。將重量平均分子量之測定條件示於以下。
(分析裝置)
凝膠滲透層析分析裝置(DGU-20AC等,島津製作所股份有限公司製造)
(測定條件)
標準物質:Shodex STANDARD(Type:SM-105,昭和電工股份有限公司製造)
試樣導入量:20 μL
移動相:THF
流量:1 mL/min
管柱:Shim-pack GPC-80M(300 mm×8.0 mmI.D.)
管柱溫度:40℃
檢測器:示差折射率檢測器(RID)
再者,重量平均分子量20000以下之成分A1之含量係藉由將側鏈雙鍵導入型丙烯酸系聚合物之層析圖之面積設為100面積%,根據標準聚苯乙烯換算之分子量之校準曲線算出重量平均分子量為20000以下之保持時間內之層析圖之面積之比率而求出。
<玻璃轉移點>
聚合物A之玻璃轉移點之測定係基於JIS K7121,藉由示差掃描熱量測定法(DSC法)進行測定。
<180°剝離強度>
黏著帶之黏著力係依據JIS Z0237(2009)之黏著力之測定方法(方法1:將膠帶及片材相對於不鏽鋼試驗板拉伸為180°之試驗方法)進行測定。具體而言,使用壓接裝置(輥之質量2 kg)將黏著帶壓接於洗淨表面之矽晶圓,關於相對於矽晶圓以180°剝下黏著帶時之180°剝離強度,藉由萬能型拉伸試驗機(ORIENTEC公司製造之Tensilon 型號:RTG-1210)於溫度23℃濕度50%之環境下進行測定。
(測定條件)
測定模式:拉伸
拉伸速度:300 mm/min
夾頭間距離:50 mm
測定樣品寬度:20 mm
<切割步驟>
於直徑8英吋×厚度0.1 mm之矽晶圓之背面,使用具備輥之膠帶貼裝裝置,貼合以上述方式製作之黏著帶。接著,藉由切割刀片將矽晶圓切割為0.49 mm×0.3 mm之半導體晶片。切割之主要設定條件如以下所示。
(設定條件)
切割裝置:DISCO公司製造之DAD341
切割刀片:DISCO公司製造之NBC-ZH205O-27HEEE
切割刀片轉速:40,000 rpm
切割刀片進給速度:50 mm/秒
切削水溫度:25℃
切削水量:1.0升/分鐘
<拾取步驟>
於切割步驟後,照射150 mJ/cm
2之紫外線使黏著劑層硬化。其後,自黏著帶拾取半導體晶片而剝離。拾取之主要設定條件如以下所示。
(設定條件)
拾取裝置:Canon Machinery公司製造之CAP-300II
針銷形狀:250 μmR
針銷頂起高度:0.5 mm
擴展量:8 mm
頂起速度:10,000 μm/秒
<拾取產率>
關於拾取時之銷高度,自0.1 mm至1.5 mm以每0.1 mm進行拾取試驗。更具體而言,以各銷高度嘗試100個晶片之拾取,針對每一銷高度確認可拾取之晶片之比率(拾取產率)。而且,將晶片之拾取產率為95%以上之銷高度之最小值記載於表中。
[表1]
※R
0為5.0。
[產業上之可利用性]
實施例 | 比較例 | ||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | |||
聚合物A | 原料 | 丙烯酸2-乙基己酯[重量份] | 63 | - | - | 63 | 63 | 92 | 92 | 92 | 40 |
丙烯酸2-羥基乙酯[重量份] | 15 | 5 | 5 | 15 | 15 | - | - | - | 10 | ||
丙烯酸乙氧基乙氧基乙酯[重量份] | 22 | - | - | 22 | 22 | - | - | - | - | ||
丙烯酸丁酯[重量份] | - | 67 | 67 | - | - | - | - | - | - | ||
丙烯酸甲酯[重量份] | - | 28 | 28 | - | - | - | - | - | 45 | ||
丙烯酸[重量份] | - | - | - | - | - | 8 | 8 | 8 | 5 | ||
改性劑:2-甲基丙烯醯氧基乙基異氰酸酯[反應量mol%(對反應性單體單元)] | 50 | 70 | 70 | 30 | 50 | - | - | - | - | ||
改性劑:甲基丙烯酸縮水甘油酯[反應量mol%(對反應性單體單元)] | - | - | - | - | - | 80 | 60 | 80 | - | ||
物性 | 具有OH基之單元比率[莫耳%] | 11.0 | 2.0 | 2.0 | 15.0 | 11.0 | 14.0 | 11.0 | 14.0 | 10.0 | |
玻璃轉移點[℃] | -62 | -32 | -32 | -62 | -62 | -42 | -42 | -42 | -26 | ||
重量平均分子量(Mw) | 4.0×10 5 | 6.0×10 5 | 5.0×10 5 | 4.0×10 5 | 8.0×10 5 | 4.0×10 5 | 4.0×10 5 | 3.5×10 5 | 2.0×10 5 | ||
Mw20,000以下之成分1之含量[面積%] | 4.0 | 3.5 | 8.0 | 5.0 | 6.0 | 15.0 | 13.0 | 20.0 | 55.0 | ||
樹脂組合物 | 組成 | 聚合物A[重量份] | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
光自由基起始劑[重量份] | 2.10 | 2.10 | 2.10 | 2.10 | 2.10 | 2.10 | 2.10 | 2.10 | 7.00 | ||
硬化劑[重量份] | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.10 | 0.50 | 0.50 | 15.00 | ||
紫外線硬化性胺基甲酸酯丙烯酸酯[重量份] | - | - | - | - | - | - | - | - | 90.00 | ||
物性 | 接觸角|R 0-R 1|[°] | 10.5 | 10.0 | 11.5 | 12.5 | 20.0 | 19.0 | 15.0 | 26.0 | 30.0 | |
紫外線照射前之180°剝離強度S[N/20 mm] | 5.4 | 8.0 | 7.5 | 7.0 | 1.8 | 10.8(凝聚) | 12.0 | 8.0 | 12.0 | ||
評價 | 有機物污染揮發有機物成分之總有機物量[pg/ cm 2] | 400 | 300 | 650 | 850 | 8000 | 12000 | 11000 | 17000 | 19500 | |
拾取產率95%以上銷高度[mm] | 0.5 | 0.7 | 0.7 | 0.5 | 1.0 | 1.2 | 0.9 | 1.0 | 0.7 |
本發明之黏著帶作為半導體晶圓加工用膠帶、尤其是切割步驟中所使用之黏著帶,具有產業上之可利用性。
Claims (13)
- 一種黏著帶, 其係具有基材層、及設於該基材層上之黏著劑層者,且 上述黏著劑層包含光自由基起始劑、及具有聚合性碳雙鍵之聚合物A, 矽晶圓表面相對於水之接觸角R 0、與將上述黏著劑層貼附於上述矽晶圓放置24小時後對上述黏著劑層照射紫外線而剝離上述黏著劑層後的上述矽晶圓表面相對於水之接觸角R 1之差|R 0-R 1|為20°以下。
- 如請求項1之黏著帶,其中 相對於凝膠滲透層析圖之總面積,上述聚合物A中所包含之重量平均分子量20000以下之成分A1之含量為15面積%以下。
- 如請求項1或2之黏著帶,其中 紫外線照射前之上述黏著劑層相對於矽晶圓之180°剝離強度於23℃下為2.0~20.0 N/20 mm。
- 如請求項1至3中任一項之黏著帶,其中 聚合物A具有羥基。
- 如請求項1至4中任一項之黏著帶,其中 上述聚合物A之重量平均分子量為1.0×10 5~2.0×10 6。
- 如請求項1至5中任一項之黏著帶,其中 上述聚合物A之玻璃轉移點為-80~23℃。
- 如請求項1至6中任一項之黏著帶,其中 上述聚合物A包含(甲基)丙烯酸酯系共聚物, 該(甲基)丙烯酸酯系共聚物具有直鏈形狀、支鏈形狀、或交聯形狀。
- 如請求項1至7中任一項之黏著帶,其中 上述黏著劑層進而包含硬化劑。
- 如請求項8之黏著帶,其中 上述硬化劑包含異氰酸酯系化合物。
- 如請求項9之黏著帶,其中 上述異氰酸酯系化合物包含2官能以上之多官能異氰酸酯系化合物。
- 如請求項8至10中任一項之黏著帶,其中 相對於聚合物A 100重量份,上述硬化劑之含量為0.1~5.0重量份。
- 如請求項1至11中任一項之黏著帶,其 用於半導體晶圓、半導體元件、或各種半導體封裝之加工。
- 一種加工方法,其具有: 貼合步驟,其將如請求項1至12中任一項之黏著帶與被黏著體貼合;及 切割步驟,其於上述黏著帶與上述被黏著體貼合之狀態下,將上述被黏著體單片化; 上述被黏著體為半導體晶圓、半導體元件、或各種半導體封裝。
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JP5537789B2 (ja) * | 2008-10-01 | 2014-07-02 | 日東電工株式会社 | レーザー加工用粘着シート及びレーザー加工方法 |
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