TW202225363A - 黏著帶及加工方法 - Google Patents
黏著帶及加工方法 Download PDFInfo
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- TW202225363A TW202225363A TW110141684A TW110141684A TW202225363A TW 202225363 A TW202225363 A TW 202225363A TW 110141684 A TW110141684 A TW 110141684A TW 110141684 A TW110141684 A TW 110141684A TW 202225363 A TW202225363 A TW 202225363A
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- Prior art keywords
- adhesive tape
- adhesive layer
- adhesive
- mentioned
- polymer
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- IKYDDBGYKFPTGF-UHFFFAOYSA-N octyl 3-oxobutanoate Chemical compound CCCCCCCCOC(=O)CC(C)=O IKYDDBGYKFPTGF-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 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
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction 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
- 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
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- 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
- C09J133/06—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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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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
- C08F8/14—Esterification
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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
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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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
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- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6258—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids the acid groups being esterified with polyhydroxy compounds or epoxy compounds during or after polymerization
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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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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J133/06—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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
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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
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- 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
-
- 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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- 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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- 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
- C09J2301/312—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 parameters being the characterizing feature
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- 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
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
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- C09J2433/00—Presence of (meth)acrylic polymer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- 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
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Abstract
一種黏著帶,其具有基材層、及設於該基材層上之黏著劑層,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,紫外線照射後之上述黏著劑層之拉伸彈性模數為400 MPa以下,紫外線照射後之上述黏著劑層之斷裂伸長率為16%以上。
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。
於上述拾取時,藉由頂起銷自未與黏著帶之被黏著體接觸之背面將單片化之被黏著體頂起,進行拾取。此時,就高效率地製造高品質之電子零件之觀點而言,要求減少黏著帶對被黏著體之糊劑殘留,又,即便為較低之銷高度亦可以高產率進行拾取。
然而,若黏著帶貼附於被黏著體時,黏著劑對被黏著體之濡濕性不佳,則糊劑無法完全追隨被黏著體之階差部等且氣泡進入。如此一來,存在如下情況: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,為了彌補黏著劑對被黏著體之濡濕性,而考慮如下方法:增加黏著劑層之厚度,或者調配低分子量成分或黏著賦予劑等提高黏著力,或者降低黏著劑層之彈性模數而提高黏著力。然而於該情形時,存在如下情況: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。又,存在如下情況:若在刮取黏著劑之狀態下藉由紫外線照射使其硬化,則導致單片化之被黏著體固定於黏著帶,低銷高度之拾取變得困難,或者即便於可拾取之情形時,於與被黏著體之界面亦無法剝離而產生黏著劑本身之破壞,黏著劑殘留於被黏著體。
作為解決此種糊劑殘留而提高拾取性之方法,例如,如專利文獻1所示,揭示一種大量調配相對而言低分子量之紫外線硬化性樹脂成分,大幅度降低紫外線照射後之黏著力之方法。
[先前技術文獻]
[專利文獻]
專利文獻1:日本專利特開2008-13692號公報
[發明所欲解決之問題]
然而於該情形時,由於紫外線照射後之黏著劑變得過硬,產生糊劑無法承受拾取時之膠帶變形而破裂為銷之形狀之現象,反而可能成為糊劑殘留之原因。
進而,近年來由於電路設計之高密度化,於作為被黏著體之晶圓表面大多形成有由微細之配線或電路圖案導致之凹凸。因此,黏著帶之黏著劑易於填充於電路表面之凹凸間之微細間隙中,此種由間隙約束之黏著劑於剝離時被切斷而殘留於電路面,易於產生糊劑殘留。
本發明係鑒於上述問題點而成者,其目的在於提供一種於拾取時不易產生對被黏著體之糊劑殘留,且可以較低之銷高度拾取之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。結果發現藉由對紫外線硬化後之黏著劑層之拉伸彈性模數及斷裂伸長率進行調整,可解決上述課題,從而完成本發明。
即,本發明之黏著帶如以下所示。
[1]
一種黏著帶,其具有基材層、及設於該基材層上之黏著劑層,
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,
紫外線照射後之上述黏著劑層之拉伸彈性模數為400 MPa以下,
紫外線照射後之上述黏著劑層之斷裂伸長率為16%以上。
[2]
如[1]所記載之黏著帶,其中
上述黏著劑層之紫外線硬化前後之體積收縮率為0.50~10.0%。
[3]
如[1]或[2]所記載之黏著帶,其中
紫外線硬化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,
且紫外線硬化後之上述黏著劑層相對於矽晶圓之180°剝離強度於23℃下為0.05~1.0 N/20 mm。
[4]
如[1]至[3]中任一項所記載之黏著帶,其中
上述聚合物A之雙鍵當量為500~2500 g/mol。
[5]
如[1]至[4]中任一項所記載之黏著帶,其中
上述聚合物A具有羥基。
[6]
如[1]至[5]中任一項所記載之黏著帶,其中
上述聚合物A之重量平均分子量為1.0×10
5~2.0×10
6。
[7]
如[1]至[6]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℃。
[8]
如[1]至[7]中任一項所記載之黏著帶,其中
上述黏著劑層之聚合物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。
[9]
如[1]至[8]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。
[10]
如[9]所記載之黏著帶,其中
上述硬化劑為異氰酸酯系化合物。
[11]
如[10]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。
[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,對上述被黏著體進行加工;
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,可提供一種於拾取時不易產生對被黏著體之糊劑殘留,且可以較低之銷高度拾取之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,紫外線照射後之黏著劑層之拉伸彈性模數為400 MPa以下,紫外線照射後之黏著劑層之斷裂伸長率為16%以上。
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或聚合物成分有可能殘留於被黏著體表面。
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,可抑制殘留於被黏著體之表面。
又,於本實施方式中,進而規定包含聚合物A之黏著劑層之紫外線照射後之機械特性,即拉伸彈性模數及斷裂伸長率。藉由使用具有此種機械特性之黏著劑層,拾取時可一邊自晶片四周均等地拉長黏著劑層,一邊剝離晶片。其結果,可以較少之力將晶片自黏著劑層剝離,即便銷高度較低亦可容易地剝離晶片。
進而,即便於在晶片表面存在由微細之配線或電路圖案導致之凹凸之情形時,由於黏著劑硬化物可拉長而伸長但不會斷裂,因此可與周圍之黏著劑硬化物一體脫離晶片之凹部之約束,減少糊劑殘留。
(拉伸彈性模數)
紫外線照射後之黏著劑層之拉伸彈性模數為400 MPa以下,較佳為350 MPa,更佳為300 MPa以下,進而較佳為150 MPa以下,進而更佳為100 MPa以下,進一步更佳為50 MPa以下。又,拉伸彈性模數之下限值並無特別限制,較佳為1.0 MPa以上,可為3.0 MPa以上。
藉由紫外線照射後之黏著劑層之拉伸彈性模數為400 MPa以下,可以更低之銷高度進行拾取。進而,若紫外線照射後之黏著劑層之拉伸彈性模數大於400 MPa,則藉由紫外線照射進行硬化反應後之黏著劑層過硬,因此即便於拾取時增高銷高度亦不會自黏著劑層開始晶片之剝離,有可能產生拾取不良。進而,於該情形時若過度增高銷高度,則銷有可能會突破黏著劑層損傷黏著帶,或者接著劑層破裂而糊劑殘留於晶片。
本說明書中所記載之「拉伸彈性模數」係使用切割為寬度1 cm、長度10 cm、厚度60~110 μm之黏著劑,於23℃之溫度條件下,藉由萬能型拉伸試驗機以拉伸速度5 mm/min、夾頭間距離50 mm所測得之楊氏模數。
(斷裂伸長率)
紫外線照射後之黏著劑層之斷裂伸長率為16%以上,較佳為22%以上,更佳為25%以上,進而較佳為35%以上,進而更佳為45%以上,進一步更佳為55%以上。又,拉伸彈性模數之上限值並無特別限制,較佳為200%以下,可為90%以下。
藉由紫外線照射後之黏著劑層之斷裂伸長率為16%以上,可以更低之銷高度進行拾取。進而,若紫外線照射後之黏著劑層之斷裂伸長率小於16%,則藉由紫外線照射進行硬化反應後之黏著劑層過硬,因此即便於拾取時增高銷高度亦不會自黏著劑層開始晶片之剝離,有可能產生拾取不良。進而,於該情形時若過度增高銷高度,則銷有可能會突破黏著劑層損傷黏著帶,或者接著劑層破裂而糊劑殘留於晶片。
本說明書中所記載之「斷裂伸長率」係使用切割為寬度1 cm、長度10 cm、厚度60~110 μm之黏著劑,於23℃之溫度條件下,藉由萬能型拉伸試驗機以拉伸速度5 mm/min、夾頭間距離50 mm進行測定時之斷裂伸長率。
(體積收縮率)
將紫外線照射前之體積設為100%,則紫外線照射後之黏著劑層之體積收縮率較佳為0.50~10.0%,更佳為0.70~8.0%,進而較佳為0.90~5.0%。
藉由紫外線照射後之黏著劑層之體積收縮率為0.50%以上,黏著劑層可利用紫外線照射而充分硬化,減小黏著帶與被黏著體之接觸面積,藉此減小黏著力,有可更容易地進行剝離之傾向。
又,藉由體積收縮率為10.0%以下,有可抑制黏著劑層之硬化物過度硬化之傾向。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。
本說明書中所記載之「體積收縮率」係沿用「固體之密度及比重之測定法(JIS Z 8807)」,藉由液中稱量法(天平法)測定硬化前後之比重,根據比重變化求出硬化收縮率者。將體積收縮率之運算示於以下。
體積收縮率r={(ds-dl)/dl}×100
硬化前之比重:dl,硬化後之比重:ds
(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
0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6.0~14.0 N/20 mm。
藉由180°剝離強度S
0為2.0 N/20 mm以上,有紫外線照射前之黏著力更加優異之傾向。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或晶片之碎片。
又,藉由180°剝離強度S
0為20.0 N/20 mm以下,由於黏性較小,因此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使晶片固定化而導致產生拾取不良,且於固定化之晶片產生碎片。
紫外線照射後之黏著劑層相對於矽晶圓之180°剝離強度S
1於23℃下較佳為0.05~1.0 N/20 mm,更佳為0.08~0.8 N/20 mm,進而較佳為0.10~0.6 N/20 mm。
藉由180°剝離強度S
1為0.05 N/20 mm以上,有進一步抑制由於拾取時之擴展而晶片剝落或者產生位置偏移之傾向。即,有藉由銷頂起之前,進一步抑制晶片剝落或者產生位置偏移之傾向。藉此,由於擴展,單片化之晶片彼此可維持隔著相等間隔之狀態,裝置可準確識別晶片進行拾取。又,藉由180°剝離強度S
1為1.0 N/20 mm以下,有晶片不易自黏著劑層剝離且進一步提高拾取性之傾向。
較佳為均滿足180°剝離強度S
0及180°剝離強度S
1。
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A,亦可視需要包含硬化劑。
(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。
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;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;較佳為(甲基)丙烯酸2-乙基己酯、甲基丙烯酸之共聚物。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)丙烯酸烷基酯及含羧基單體之(甲基)丙烯酸酯系共聚物、或包含(甲基)丙烯酸烷基酯及含羥基單體之(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環氧化合物與含有含羧基單體單元之(甲基)丙烯酸酯系共聚物進行反應,可經由酯鍵將聚合性雙鍵導入至含羧基單體單元。又,作為其他例,藉由使作為改性劑之具有聚合性雙鍵之異氰酸酯系化合物與含有含羧基單體單元之(甲基)丙烯酸酯系共聚物進行反應,可經由醯胺鍵將聚合性雙鍵導入至含羧基單體單元。
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環氧化合物、具有聚合性雙鍵之異氰酸酯系化合物等。
聚合物A之雙鍵當量較佳為500~2500 g/mol,更佳為800~2000 g/mol,進而較佳為1000~1600 g/mol。若聚合物A之雙鍵當量為上述範圍內,則聚合物A之聚合性雙鍵之交聯反應利用紫外線照射而充分進行,利用硬化收縮減少與被黏著體之接觸面積,藉此充分降低黏著力。於是可容易地進行剝離,因此進一步提高拾取性能。又,於聚合物成分合成之時點無法聚合之單體成分亦可能於紫外線照射時與聚合物成分側鏈之雙鍵進行反應,亦關係到糊劑殘留之抑制。
進而,由於藉由聚合物A之雙鍵當量為500 g/mol以上,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。又,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。
藉由聚合物A之雙鍵當量為2500 g/mol以下,有如下傾向:交聯反應充分進行而黏著力降低,於拾取時可容易地剝離晶片。
本說明書中所記載之「雙鍵當量」係沿用「化學製品之酸值、皂化值、酯值、碘值、羥基值及不皂化物之試驗方法」(JIS K 0070)」,測定碘值而求出雙鍵當量。具體而言,於試樣中添加一氯化碘溶液加成為雙鍵,將過量之I用硫代硫酸鈉溶液滴定,按照以下之式求出。
A={(B-C)×f×1.269}/S
A:碘價
B:空白試驗中所使用之硫代硫酸鈉溶液之量(mL)
C:滴定中所使用之硫代硫酸鈉溶液之量(mL)
f:硫代硫酸鈉溶液之因子
S:試樣之質量(g)
1.269:碘之原子量
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40~95莫耳%,更佳為43~90莫耳%,進而較佳為45~80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40莫耳%以上,有於紫外線照射後黏著力充分降低,進一步提高拾取性之傾向。又,藉由聚合性雙鍵之導入量為95莫耳%以下,有可與下述硬化劑反應之官能基殘留於聚合物A中,更加難以產生基材膜與黏著劑層之抓固破壞之傾向。進而,藉由聚合性雙鍵之導入量為95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,該羥基可為源自含羧基單體等者,可為源自改性劑之羥基,亦可為藉由含羧基單體等單體單元與改性劑反應而產生之羥基。作為藉由含羧基單體與改性劑反應而產生之羥基,例如可例舉如使含羧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。
相對於全部單體單元100莫耳%,聚合物A中所包含之單體單元中具有羥基之單體單元之含量較佳為5~40莫耳%,更佳為10~30莫耳%,進而較佳為10~25莫耳%。藉由具有羥基之單體單元之含量為上述範圍內,有進一步抑制黏著劑層之凝聚力之傾向。
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。
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0.10~5.0重量份,更佳為0.15~3.0重量份,進而較佳為0.20~2.0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0.10~2.0質量%,更佳為0.15~1.5質量%,進而較佳為0.20~1.0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添加黏著賦予劑、交聯延遲劑、抗氧化劑等。
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黏著帶之情形時,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總厚度更佳為70~200 μm,進而較佳為70~180 μm。
(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。
[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莫耳甲基丙烯酸單元中為80莫耳(80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)
使甲基丙烯酸縮水甘油酯之導入量為於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%),除此以外,以與實施例1相同之方式製作黏著帶。
(實施例3)
使硬化劑之使用量成為0.3重量份,除此以外,以與實施例1相同之方式製作黏著帶。
(實施例4)
使丙烯酸2-乙基己酯97重量份、丙烯酸3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,除此以外,以與實施例1相同之方式製作黏著帶。
(實施例5)
以甲基丙烯酸縮水甘油酯之導入量為於丙烯酸系聚合物之每100莫耳丙烯酸單元中為70莫耳(70莫耳%)之方式,使硬化劑之使用量成為0.2重量份,除此以外,以與實施例1相同之方式製作黏著帶。
(比較例1)
調整起始劑之量,調整丙烯酸系聚合物之重量平均分子量,除此以外,以與實施例1相同之方式製作黏著帶。
(比較例2)
使甲基丙烯酸縮水甘油酯不與實施例1中製備之丙烯酸系聚合物進行反應,反而另外添加紫外線聚合性胺基甲酸酯丙烯酸酯,同時對硬化劑及起始劑之量進行調整,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,針對拉伸彈性模數、斷裂伸長率、體積收縮率、180°剝離強度,按以下方式進行評價試驗。將所獲得之結果彙總示於下述表1。
<拉伸彈性模數、斷裂伸長率>
藉由高壓水銀燈對黏著帶照射150 mJ/cm
2之紫外線。而且,將黏著劑層切割為寬度1 cm、長度10 cm、厚度60~110 μm,作為樣品使用。紫外線照射後之黏著劑層之拉伸彈性模數及斷裂伸長率係於溫度23℃濕度50%之環境下,藉由萬能型拉伸試驗機(ORIENTEC公司製造之Tensilon 型號:RTG-1210)進行測定。
測定模式:拉伸
拉伸速度:5 mm/min
夾頭間距離:50 mm
<體積收縮率>
體積收縮率係沿用JIS Z 8807之固體之密度及比重之測定法,藉由液中稱量法(天平法)測定硬化前後之比重,根據比重變化求出硬化收縮率者。按照以下之式求出。
體積收縮率r={(ds-dl)/dl}×100
硬化前之比重:dl,硬化後之比重:ds
<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)
<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S
0,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。
又,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,藉由高壓水銀燈對黏著帶照射150 mJ/cm
2之紫外線。其後,以與上述相同之方式對相對於矽晶圓以180°剝下黏著帶時之180°剝離強度S
1進行測定。將測定條件示於以下。
(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
<雙鍵當量>
雙鍵當量係沿用「化學製品之酸值、皂化值、酯值、碘值、羥基值及不皂化物之試驗方法」(JIS K 0070)」,測定碘值而求出雙鍵當量。具體而言,於試樣中添加一氯化碘溶液加成為雙鍵,將過量之I用硫代硫酸鈉溶液滴定,按照以下之式求出。
A={(B-C)×f×1.269}/S
A:碘價
B:空白試驗中所使用之硫代硫酸鈉溶液之量(mL)
C:滴定中所使用之硫代硫酸鈉溶液之量(mL)
f:硫代硫酸鈉溶液之因子
S:試樣之質量(g)
1.269:碘之原子量
<切割步驟>
於寬度100 mm×深度50 mm×厚度0.76 mm之環氧密封樹脂之背面,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,藉由切割刀片將環氧密封樹脂切割為3.2 mm×3.2 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P1A861 SDC240N75 BR597
切割刀片轉速:25,000 rpm
切割刀片進給速度:35 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。拾取之主要設定如以下所示。再者,針銷頂起高度(銷高度)最初設定為0.1 mm,嘗試10個半導體晶片之拾取,於無法拾取全部半導體晶片之情形時,將針銷頂起高度增加0.1 m,重複進行嘗試10個半導體晶片之拾取之操作。
(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:0.1~1.0 mm
擴展量:8 mm
頂起速度:10,000 μm/秒
對表1中之評價進行說明。
<糊劑殘留性>
於切割、拾取步驟後,藉由顯微鏡觀察對被黏著體之糊劑殘留之有無。
◎(優):晶片上不存在糊劑之附著,亦無污染
○(良):晶片上不存在糊劑之附著,但有輕微污染
△(可):晶片上不存在糊劑之附著,但有嚴重污染
×(不可):於晶片上可看到糊劑之附著及污染
此處,「輕微污染」指貼有矽晶圓之膠帶之場所之顏色隱約變化之程度者,「嚴重污染」指明顯看出膠帶痕跡者。
<拾取產率>
關於拾取時之銷高度,自0.1 mm至1.0 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。又,於晶片之拾取產率於銷高度1.0 mm時亦未達到95%以上之情形時,表中記載為「-」。
[表1]
[產業上之可利用性]
實施例 | 比較例 | ||||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | |||
聚合物A | 原料 | 丙烯酸2-乙基己酯[重量份] | 92 | 92 | 92 | 97 | 92 | 92 | 40 |
丙烯酸甲酯[重量份] | - | - | - | - | - | - | 45 | ||
丙烯酸[重量份] | 8 | 8 | 8 | 3 | 8 | 8 | 5 | ||
丙烯酸2-羥基乙酯[重量份] | - | - | - | - | - | - | 10 | ||
改性劑:甲基丙烯酸縮水甘油酯[反應量mol%] | 80 | 60 | 80 | 80 | 70 | 80 | - | ||
物性 | 雙鍵當量[g/mol] | 1200 | 1600 | 1200 | 900 | 1400 | 1200 | - | |
具有OH基之單元比率[莫耳%] | 14 | 11 | 14 | 5 | 13 | 14 | 10 | ||
玻璃轉移點[℃] | -42 | -42 | -42 | -46 | -42 | -42 | -26 | ||
重量平均分子量(Mw) | 3.0×10 5 | 3.0×10 5 | 3.0×10 5 | 3.0×10 5 | 3.0×10 5 | 8.0×10 5 | 2.0×10 5 | ||
樹脂組合物 | 原料 | 聚合物A[重量份] | 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 | 7.00 | ||
硬化劑[重量份] | 0.50 | 0.50 | 0.30 | 0.50 | 0.20 | 0.50 | 15.00 | ||
紫外線硬化性胺基甲酸酯丙烯酸酯[重量份] | - | - | - | - | - | - | 90 | ||
物性 | 紫外線照射後之拉伸彈性模數[MPa] | 10.0 | 9.0 | 5.0 | 16.0 | 2.0 | 180.0 | 470.0 | |
紫外線照射後之斷裂伸長率[%] | 40.0 | 45.0 | 65.0 | 30.0 | 150.0 | 15.0 | 5.0 | ||
體積收縮率[%] | 2.0 | 1.0 | 2.0 | 2.3 | 1.5 | 0.3 | 4.3 | ||
紫外線照射前之180°剝離強度S 0[N/20 mm] | 8.0 | 12.0 | 8.5 | >3.0 | 13.6 | 4.0 | 12.0 | ||
紫外線照射後之180°剝離強度S 1[N/20 mm] | 0.18 | 0.35 | 0.15 | 0.38 | 0.21 | 0.80 | 0.13 | ||
評價 | 糊劑殘留性 | ◎ | ○ | ○ | ○ | ○ | △ | × | |
拾取產率95%以上銷高度[mm] | 0.3 | 0.6 | 0.4 | 0.6 | 0.7 | - | 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,其具有基材層、及設於該基材層上之黏著劑層, 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, 紫外線照射後之上述黏著劑層之拉伸彈性模數為400 MPa以下, 紫外線照射後之上述黏著劑層之斷裂伸長率為16%以上。
- 如請求項1之黏著帶,其中 上述黏著劑層之紫外線硬化前後之體積收縮率為0.50~10.0%。
- 如請求項1或2之黏著帶,其中 紫外線硬化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, 且紫外線硬化後之上述黏著劑層相對於矽晶圓之180°剝離強度於23℃下為0.05~1.0 N/20 mm。
- 如請求項1至3中任一項之黏著帶,其中 上述聚合物A之雙鍵當量為500~2500 g/mol。
- 如請求項1至4中任一項之黏著帶,其中 上述聚合物A具有羥基。
- 如請求項1至5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6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7中任一項之黏著帶,其中 上述黏著劑層之聚合物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8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9之黏著帶,其中 上述硬化劑為異氰酸酯系化合物。
- 如請求項10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1至11中任一項之黏著帶,其 用於半導體晶圓、半導體元件、各種半導體封裝加工。
- 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,對上述被黏著體進行加工; 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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