TWI761467B - Adhesive tape for dicing, method for producing adhesive tape for dicing, and method for producing semiconductor chip - Google Patents

Adhesive tape for dicing, method for producing adhesive tape for dicing, and method for producing semiconductor chip Download PDF

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TWI761467B
TWI761467B TW107108427A TW107108427A TWI761467B TW I761467 B TWI761467 B TW I761467B TW 107108427 A TW107108427 A TW 107108427A TW 107108427 A TW107108427 A TW 107108427A TW I761467 B TWI761467 B TW I761467B
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adhesive tape
radiation
dicing
adhesive layer
acrylate
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TW201840412A (en
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田中理恵
酒井貴広
増田晃良
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日商麥克賽爾股份有限公司
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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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • 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
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J133/06—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
    • 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
    • C09J175/14—Polyurethanes having 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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
    • 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
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • 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
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
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  • Medicinal Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)

Abstract

本發明之課題係能提供一種即使對半導體元件用基板的活性面黏貼之場合，也容易將半導體晶片剝離之切割用黏著膠帶等。 　　本發明之解決手段係一種切割用黏著膠帶(1)，其特徵係具有基材(2)、與設置在基材(2)的至少一方的表面側之黏著劑層(3)；黏著劑層(3)係至少具備：作為官能基而具有羥基、羧基中的任一種之丙烯酸酯系共聚物，重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物，與與該丙烯酸酯系共聚物具有的官能基反應之架橋劑。The subject of this invention is to provide the adhesive tape for dicing etc. which can peel off a semiconductor wafer easily even when sticking to the active surface of the board|substrate for semiconductor elements. The solution of the present invention is an adhesive tape (1) for dicing, which is characterized by having a substrate (2) and an adhesive layer (3) provided on at least one surface side of the substrate (2); the adhesive layer (3) An acrylate-based copolymer having at least one of a hydroxyl group and a carboxyl group as a functional group, a weight-average molecular weight Mw of 500 or more and 6000 or less, and having 3 or more radiation polymerizable carbon-carbon bipolymers in the molecule A radiation-curable oligomer having a bond and a hydroxyl value of 3 mgKOH/g or less, and a bridging agent that reacts with the functional group possessed by the acrylate-based copolymer.

Description

切割用黏著膠帶、切割用黏著膠帶之製造方法及半導體晶片之製造方法Adhesive tape for dicing, method for producing adhesive tape for dicing, and method for producing semiconductor chip

本發明係有關可用於元件用基板的切割之切割用黏著膠帶、切割用黏著膠帶之製造方法及半導體晶片之製造方法。The present invention relates to an adhesive tape for dicing, a method for producing the adhesive tape for dicing, and a method for producing a semiconductor wafer which can be used for dicing of substrates for devices.

半導體封裝等半導體關連材料或半導體晶圓等半導體元件用基板，係例如用旋轉刀片而被切斷，被分離成小片的半導體元件或IC零件。 　　例如，以矽、鍺、鎵-砷等作為材料之半導體晶圓，於大徑長的狀態被製造後，將背面研削(背面研磨處理)直到成為預先決定的厚度為止，再者，因應需要而實施背面處理(蝕刻處理、拋光處理等)。 　　接著，進行在半導體晶圓的研削面黏貼切割用黏著膠帶之黏片製程、於將黏著膠帶黏貼在半導體晶圓之狀態下將半導體晶圓切割成個個半導體晶片之切割製程、洗淨半導體晶圓之洗淨製程、為了容易作成之後進行的半導體晶片拾取而將黏著膠帶拉長之擴展製程、將半導體晶片自黏著膠帶揭下之拾取製程等。 　　然後，在上述拾取製程，係採用形成切割用黏著膠帶某種程度伸長之狀態，使用1或複數個上推用插針(針)，對於切割用黏著膠帶從基材位置之側將半導體晶片抬起，於助長半導體晶片與切割用黏著膠帶的剝離之狀態下，使用筒夾並利用真空吸附等將半導體晶片拿起之方式。A semiconductor-related material such as a semiconductor package or a substrate for a semiconductor element such as a semiconductor wafer is a semiconductor element or IC component that is cut with a rotary blade, for example, and separated into small pieces. For example, after a semiconductor wafer made of silicon, germanium, gallium-arsenic, etc., is manufactured in a state with a large diameter, the back surface is ground (back grinding treatment) until it reaches a predetermined thickness, and further, according to needs A backside treatment (etching treatment, polishing treatment, etc.) is performed. Next, a dicing process of sticking an adhesive tape for dicing on the grinding surface of the semiconductor wafer, a dicing process of dicing the semiconductor wafer into individual semiconductor chips in a state where the adhesive tape is attached to the semiconductor wafer, and cleaning the semiconductor wafer The cleaning process of the circle, the extension process of stretching the adhesive tape for easy pick-up of the semiconductor wafer after fabrication, the pick-up process of peeling off the semiconductor wafer from the adhesive tape, etc. Then, in the above-mentioned pick-up process, the adhesive tape for dicing is formed to be stretched to some extent, and one or more pins (pins) for push-up are used to lift the semiconductor wafer from the side of the substrate position for the adhesive tape for dicing. Since then, in a state that promotes the peeling of the semiconductor wafer and the dicing adhesive tape, the semiconductor wafer is picked up by using a collet and vacuum suction.

從前，作成為了製作半導體晶片而使用的切割用黏著膠帶，已知具有放射線硬化性的黏著劑層之黏著膠帶。例如，已知包含具有直鏈烷基的碳數14～18之(甲基)丙烯酸系聚合物之放射線硬化性的黏著劑層之黏著膠帶(參照專利文獻1)。 　　此外，作為切割用黏著膠帶，已知包含具有羥基價15～60mgKOH/g的丙烯酸聚合物之放射線硬化性的黏著劑層之黏著膠帶(參照專利文獻2)。 [先前技術文獻] [專利文獻]Conventionally, as an adhesive tape for dicing used for producing a semiconductor wafer, an adhesive tape having a radiation-curable adhesive layer is known. For example, an adhesive tape including a radiation-curable adhesive layer of a (meth)acrylic polymer having a linear alkyl group having 14 to 18 carbon atoms is known (refer to Patent Document 1). In addition, as an adhesive tape for dicing, an adhesive tape comprising a radiation-curable adhesive layer having an acrylic polymer having a hydroxyl value of 15 to 60 mgKOH/g is known (refer to Patent Document 2). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2010-232629號公報 　　[專利文獻2]日本特開2012-216842號公報[Patent Document 1] Japanese Patent Laid-Open No. 2010-232629 [Patent Document 2] Japanese Patent Laid-Open No. 2012-216842

[發明所欲解決之課題][The problem to be solved by the invention]

可是，近年，在半導體製造製程，有為了半導體晶片生產效率的提升、或防止由於半導體晶圓薄膜化(例如，100μm以下)造成的破損，而在研削半導體晶圓的背面之後，或在背面研削及背面處理之後，在短時間之間對於半導體晶圓的研削面黏貼切割用黏著膠帶之場合。 　　亦即，為了提升切斷半導體晶圓而製作之半導體晶片的生產性，在半導體晶片之製作過程，在進行背面研磨處理後，立刻於線上進行半導體晶圓的切割之情形是愈來愈多。這場合，在研削半導體晶圓的背面而將半導體晶圓薄膜化後，在短期間之間，對於該半導體晶圓的研削面黏貼切割用黏著膠帶。However, in recent years, in the semiconductor manufacturing process, in order to improve the production efficiency of semiconductor wafers or prevent breakage due to thinning of semiconductor wafers (for example, 100 μm or less), after grinding the backside of the semiconductor wafer, or grinding the backside When the adhesive tape for dicing is applied to the ground surface of the semiconductor wafer in a short period of time after the backside treatment. That is, in order to improve the productivity of semiconductor wafers produced by cutting semiconductor wafers, in the production process of semiconductor wafers, there are more and more cases where semiconductor wafers are diced on-line immediately after back grinding treatment. In this case, after grinding the back surface of the semiconductor wafer and thinning the semiconductor wafer, the dicing adhesive tape is affixed to the ground surface of the semiconductor wafer for a short period of time.

此外，伴隨上述的半導體晶圓的薄膜化，出現半導體晶圓本身變得容易翹曲，在處理時或搬送用外殼內之保管時容易破損之問題變多。從改善該不良情況、使作業性提升之觀點而言，在研削半導體晶圓的背面之後，立即於線上進行切割的方法之採用情形也愈來愈多。黏貼在半導體晶圓的研削面之切割用黏著膠帶，由於具有半導體晶圓支撐體的功能，所以，黏貼切割用黏著膠帶的半導體晶圓，並不會被保管在搬送用外殼，而是直接於線上被切割。藉此，可抑制上述的薄膜化的半導體晶圓之破損。In addition, with the thinning of the semiconductor wafers described above, the semiconductor wafers themselves tend to be warped and easily damaged during handling or storage in the transport housing. From the viewpoint of improving this problem and improving the workability, the method of dicing on the line immediately after grinding the back surface of the semiconductor wafer has been increasingly adopted. The adhesive tape for dicing attached to the grinding surface of the semiconductor wafer has the function of supporting the semiconductor wafer. Therefore, the semiconductor wafer to which the adhesive tape for dicing is attached is not stored in the transfer case, but is directly stored in the carrier. The line is cut. Thereby, the above-mentioned breakage of the thinned semiconductor wafer can be suppressed.

如此，在研削半導體晶圓後立即在研削面黏貼黏著膠帶的情形愈來愈多，但在從前的切割用黏著膠帶係有以下之類的問題。亦即，半導體晶圓等半導體元件用基板剛研削後的表面係成為活性的原子存在之活性面，在該活性面黏貼從前的切割用黏著膠帶時，黏著膠帶對半導體元件用基板之黏著力變得過大，結果，出現即使對黏著膠帶照射放射線使黏著劑層硬化，也不易將半導體晶片自黏著膠帶剝離之問題。As described above, there are more and more cases where an adhesive tape is attached to the grinding surface immediately after grinding a semiconductor wafer, but the conventional adhesive tape for dicing has the following problems. That is, the surface of the substrate for semiconductor elements such as semiconductor wafers immediately after grinding becomes an active surface where active atoms exist. If it is too large, as a result, even if the adhesive layer is hardened by irradiating the adhesive tape with radiation, there is a problem that the semiconductor wafer is not easily peeled off from the adhesive tape.

本發明之目的係提供一種即使對半導體元件用基板的活性面黏貼之場合，也容易將得到的半導體晶片剝離之切割用黏著膠帶。 [供解決課題之手段]An object of the present invention is to provide an adhesive tape for dicing which can easily peel the obtained semiconductor wafer even when it is attached to the active surface of the semiconductor element substrate. [Means for solving problems]

為了解決上述課題，本發明人等銳意檢討之結果發現，如使用具備以具有特定範圍的重量平均分子量及羥基價、且具有3個以上放射線聚合性碳-碳雙鍵之放射線硬化性低聚物、與丙烯酸酯系共聚合物作為主成分並併用的黏著劑層之黏著膠帶的話，可抑制黏著劑層與剛研削後的半導體元件用基板表面的活性面之間過度的相互作用，利用切割被形成的個個半導體晶片加上因對黏著膠帶的放射線照射形成的黏著劑層有效的硬化･收縮而變得容易自黏著劑層剝離，達成完成本發明。In order to solve the above-mentioned problems, the inventors of the present invention, as a result of earnest examinations, found that if a radiation-curable oligomer having three or more radiation-polymerizable carbon-carbon double bonds having a weight-average molecular weight and a hydroxyl valence within a specific range is used , If the adhesive tape of the adhesive layer is used together with the acrylate copolymer as the main component, it can suppress the excessive interaction between the adhesive layer and the active surface of the surface of the substrate for semiconductor elements just after grinding. The formed semiconductor wafers are further easily peeled from the adhesive layer due to the effective hardening and shrinkage of the adhesive layer formed by irradiation of the adhesive tape with radiation, and the present invention has been completed.

亦即，本發明之切割用黏著膠帶，其特徵係具有基材、與設置在前述基材的至少一方的表面側之黏著劑層；前述黏著劑層係至少具備：作為官能基而具有羥基、羧基中的任一種之丙烯酸酯系共聚物，與該丙烯酸酯系共聚物具有的該官能基反應之架橋劑，與重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物。That is, the adhesive tape for dicing of the present invention is characterized by having a substrate and an adhesive layer provided on at least one surface side of the substrate; the adhesive layer is characterized by at least having a hydroxyl group as a functional group, a An acrylate-based copolymer of any of the carboxyl groups, a bridging agent that reacts with the functional group possessed by the acrylate-based copolymer, and a weight-average molecular weight Mw of 500 or more and 6000 or less, and has 3 or more radiation polymerizability in the molecule A radiation curable oligomer having a carbon-carbon double bond and a hydroxyl valence of 3 mgKOH/g or less.

在此，前述黏著劑層，其被照射放射線且硬化之後的貯藏彈性係數最好是1.0×106 Pa以上7.0×108 Pa以下。 　　此外，前述黏著劑層，在將前述丙烯酸酯系共聚物設為100質量部時，最好是包含前述放射線硬化性低聚物80質量部以上180質量部以下。Here, the storage elastic modulus of the adhesive layer after being irradiated with radiation and hardened is preferably 1.0×10 6 Pa or more and 7.0×10 8 Pa or less. Moreover, it is preferable that the said adhesive layer contains 80 mass parts or more of the said radiation curable oligomer and 180 mass parts or less when the said acrylate type copolymer is made into 100 mass parts.

此外，本發明之切割用黏著膠帶之製造方法，其特徵係包含：準備基材之基材準備製程；製作供形成黏著劑層用之塗布溶液且至少包含作為官能基而具有羥基、羧基中的任一種之丙烯酸酯系共聚物，與該丙烯酸酯系共聚物具有的該官能基反應之架橋劑，與重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物之塗布溶液之塗布溶液製作製程；使用前述塗布溶液，在前述基材的至少一方的表面側形成前述黏著劑層之黏著劑層形成製程；與包含使前述丙烯酸酯系共聚物與前述架橋劑交聯的處理、使形成的前述黏著劑層熱硬化之熱硬化製程。In addition, the method for producing an adhesive tape for dicing of the present invention is characterized by comprising: a substrate preparation process for preparing a substrate; preparing a coating solution for forming an adhesive layer and comprising at least a functional group having hydroxyl and carboxyl groups as functional groups. Any of the acrylate-based copolymers, a bridging agent reacting with the functional group possessed by the acrylate-based copolymer, and a weight-average molecular weight Mw of 500 to 6000 and having 3 or more radiation polymerizable carbon-carbon in the molecule Process for preparing a coating solution for a coating solution of a radiation-curable oligomer with double bonds and a hydroxyl value of 3 mgKOH/g or less; using the coating solution to form the adhesive layer of the adhesive layer on at least one surface side of the substrate A forming process; and a thermal curing process including a process of crosslinking the acrylate copolymer and the bridging agent, and thermally curing the formed adhesive layer.

此外，本發明之半導體晶片之製造方法，其特徵係包含對於複數半導體元件被形成在基板上的元件用基板、黏貼切割用黏著膠帶之黏貼製程，將黏貼前述切割用黏著膠帶的前述元件用基板、切斷成複數半導體晶片之切斷製程，對於黏貼在前述半導體晶片的前述切割用黏著膠帶照射放射線、使該切割用黏著膠帶的黏著力降低之照射製程，與將前述半導體晶片、自黏著力降低的前述切割用黏著膠帶剝離之剝離製程；前述切割用黏著膠帶係具有基材、與設置在前述基材的至少一方的表面側之黏著劑層；前述黏著劑層係至少具備：作為官能基而具有羥基、羧基中的任一種之丙烯酸酯系共聚物，與該丙烯酸酯系共聚物具有的該官能基反應之架橋劑，與重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物。 [發明之效果]In addition, the method for manufacturing a semiconductor wafer of the present invention is characterized by comprising a step of attaching a device substrate on which a plurality of semiconductor devices are formed on a substrate, and attaching an adhesive tape for dicing, wherein the device substrate to which the adhesive tape for dicing is adhered is attached. , The cutting process of cutting into a plurality of semiconductor wafers, the irradiation process of irradiating the above-mentioned dicing adhesive tape pasted on the above-mentioned semiconductor wafer with radiation to reduce the adhesive force of the dicing adhesive tape, and the above-mentioned semiconductor wafer, self-adhesive force Reduced peeling process of the aforementioned adhesive tape for dicing; the aforementioned adhesive tape for dicing has a substrate and an adhesive layer disposed on at least one surface side of the substrate; the adhesive layer at least has: as a functional group The acrylate-based copolymer having either a hydroxyl group or a carboxyl group, a bridging agent reacting with the functional group of the acrylate-based copolymer, and the weight average molecular weight Mw of 500 or more and 6000 or less and having 3 in the molecule The above radiation-polymerizable carbon-carbon double bond and a radiation-curable oligomer having a hydroxyl valence of 3 mgKOH/g or less. [Effect of invention]

根據本發明，係能提供一種即使對半導體元件用基板的活性面黏貼之場合，也容易將半導體晶片剝離之切割用黏著膠帶等。According to the present invention, it is possible to provide an adhesive tape for dicing, etc., which can easily peel off a semiconductor wafer even when it is attached to an active surface of a substrate for a semiconductor element.

以下，詳細說明供實施本發明之形態。又，本發明並非限定於以下實施形態。此外，在不逸脫於其要旨的範圍，可以實施種種的變形。再者，所使用之圖式係供說明本實施形態用，並非表示實際的大小。Hereinafter, the form for implementing this invention is demonstrated in detail. In addition, this invention is not limited to the following embodiment. In addition, various deformation|transformation can be implemented in the range which does not deviate from the summary. In addition, the drawings used are for describing the present embodiment and do not represent actual sizes.

＜黏著膠帶之構成＞ 　　圖1係圖示適用本實施形態之黏著膠帶1之構成一例。本實施形態之黏著膠帶1，被使用於作為元件用基板之一例之半導體晶圓切割之用途。<Configuration of the adhesive tape> FIG. 1 shows an example of the configuration of the adhesive tape 1 to which the present embodiment is applied. The adhesive tape 1 of the present embodiment is used for semiconductor wafer dicing as an example of a substrate for devices.

如圖1所示，本實施形態之黏著膠帶1，係具有層積基材2與黏著劑層3之構造。 　　又，圖示雖省略，黏著膠帶1，亦可在基材2與黏著劑層3之間因應必要而具備底膠層。此外，亦可在黏著劑層3之與基材2相反之表面側(一方的表面側)，具備剝離襯墊。As shown in FIG. 1 , the adhesive tape 1 of the present embodiment has a structure in which a base material 2 and an adhesive layer 3 are laminated. In addition, although the illustration is omitted, the adhesive tape 1 may be provided with a primer layer between the base material 2 and the adhesive layer 3 as necessary. In addition, a release liner may be provided on the surface side (one surface side) opposite to the base material 2 of the adhesive layer 3 .

＜基材＞ 　　基材2，係成為黏著劑層3的支撐體之物。此外，基材2，係需要具有放射線透過性。 　　作為被使用於此類的基材2之材料，可以使用塑膠製、金屬製、紙製等材料，而於本實施形態，從放射性透過容易之觀點而言，可適宜使用塑膠製材料。作為塑膠製基材2之材料，例如，可以使用：聚烯烴系樹脂(低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等)、乙烯-乙酸乙烯酯共聚物、離子聚合物系樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物(無規共聚物、交替共聚物等)、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨基甲酸酯系樹脂、聚酯系樹脂(聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二酸丁醇酯等)、聚醯亞胺系樹脂、聚醯胺系樹脂、聚醚酮系樹脂、聚醚系樹脂、聚醚碸系樹脂、聚苯乙烯系樹脂(聚苯乙烯等)、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚乙烯醇系樹脂、聚乙酸乙烯酯系樹脂、氯乙烯-乙酸乙烯酯共聚物、聚碳酸酯系樹脂、氟系樹脂、聚矽氧系樹脂、纖維素系樹脂，或該等樹脂的架橋物等。這些可以單獨使用，亦可組合2種以上使用。此外，這些材料也可以具有官能基。此外，在這些材料，也可以接枝(graft)功能性單體或改質性單體。再者，為了提升基材2的表面與鄰接在該基材2的層之密貼性，也可以對基材2的表面實施表面處理。作為此類的表面處理，例如，可列舉電暈放電處理、臭氧暴露處理、高壓電擊暴露處理、離子化放射線處理等。此外，也可以對基材2實施利用底漆劑之塗布處理、底塗處理、毛面處理、交聯處理等。<Substrate> The substrate 2 serves as a support for the adhesive layer 3 . In addition, the base material 2 needs to have radiation permeability. As a material used for such a base material 2, a material made of plastic, metal, paper, etc. can be used, and in this embodiment, a material made of plastic can be suitably used from the viewpoint of easy transmission of radioactivity. As the material of the plastic base material 2, for example, polyolefin resins (low-density polyethylene, linear polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymers) can be used. Propylene, block copolymerized polypropylene, homopolypropylene, polybutene, polymethylpentene, etc.), ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene -(meth)acrylate copolymers (random copolymers, alternating copolymers, etc.), ethylene-butene copolymers, ethylene-hexene copolymers, polyurethane-based resins, polyester-based resins (polypara ethylene phthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.), polyimide resin, polyamide resin, Polyetherketone-based resins, polyether-based resins, polyether-based resins, polystyrene-based resins (polystyrene, etc.), polyvinyl chloride-based resins, polyvinylidene chloride-based resins, polyvinyl alcohol-based resins, polyvinylidene chloride-based resins Vinyl acetate-based resins, vinyl chloride-vinyl acetate copolymers, polycarbonate-based resins, fluorine-based resins, polysiloxane-based resins, cellulose-based resins, or bridges of these resins, etc. These may be used alone or in combination of two or more. In addition, these materials may also have functional groups. In addition, functional monomers or modified monomers may be grafted to these materials. Furthermore, in order to improve the adhesion between the surface of the base material 2 and the layer adjacent to the base material 2 , the surface of the base material 2 may be subjected to surface treatment. As such surface treatment, for example, corona discharge treatment, ozone exposure treatment, high voltage electric shock exposure treatment, ionizing radiation treatment, etc. are mentioned. In addition, a coating treatment with a primer agent, a primer treatment, a matte treatment, a crosslinking treatment, etc. may be performed on the base material 2 .

作為基材2，任何單層構造或層積構造都可使用。此外，在基材2，因應必要，也可以包含充填劑、難燃劑、老化防止劑、帶電防止劑、軟化劑、紫外線吸收劑、氧化防止劑、可塑劑、界面活性劑等添加劑。基材的厚度沒有特別限定，以10～300μm為佳，30～200μm更佳。As the base material 2, any single-layer structure or laminate structure can be used. In addition, the base material 2 may contain additives such as fillers, flame retardants, anti-aging agents, anti-charge agents, softeners, ultraviolet absorbers, anti-oxidants, plasticizers, and surfactants as necessary. The thickness of the base material is not particularly limited, but is preferably 10 to 300 μm, more preferably 30 to 200 μm.

＜黏著劑層＞ 　　黏著劑層3係具有黏著性，於黏著膠帶1與被黏接體之間發揮黏著力之功能層。此外，本實施形態之黏著劑層3，係具有被照射放射線時會硬化･收縮且黏著力降低之性質。 　　藉此，在將黏著膠帶1用於半導體晶圓切割之場合，黏著膠帶1對半導體晶圓具有良好的黏著性。此外，利用切割將半導體晶圓每一等間隔切斷時形成個個半導體晶片，而藉由對黏著膠帶1照射放射線，使該半導體晶片自黏著膠帶1剝離變得容易。作為放射線，例如，可列舉X光、電子線、紫外線等。其中，於本實施形態，可更適宜使用紫外線。<Adhesive layer> The adhesive layer 3 is a functional layer that has adhesiveness and exerts an adhesive force between the adhesive tape 1 and the adherend. In addition, the adhesive layer 3 of the present embodiment has a property of hardening and shrinking when it is irradiated with radiation, and the adhesive force is lowered. Thereby, when the adhesive tape 1 is used for dicing a semiconductor wafer, the adhesive tape 1 has good adhesion to the semiconductor wafer. In addition, each semiconductor wafer is formed by cutting the semiconductor wafer at equal intervals by dicing, and by irradiating the adhesive tape 1 with radiation, the semiconductor wafer can be easily peeled off from the adhesive tape 1 . As radiation, for example, X-rays, electron beams, ultraviolet rays, etc. are mentioned. Among these, in this embodiment, an ultraviolet-ray can be used more suitably.

本實施形態之黏著劑層3，係包含作為黏著劑之丙烯酸酯系共聚物、與放射線硬化性低聚物。此外，黏著劑層3，係包含與丙烯酸酯系共聚物具有的官能基反應之架橋劑、與光聚合開始劑。此外，黏著劑層3，因應必要而包含著色劑等亦可。The adhesive layer 3 of the present embodiment includes an acrylate-based copolymer as an adhesive and a radiation curable oligomer. In addition, the adhesive layer 3 contains a bridging agent and a photopolymerization initiator reacted with the functional group of the acrylate-based copolymer. In addition, the adhesive layer 3 may contain a colorant etc. as needed.

前述黏著劑層3，最好是使用被照射放射線且硬化之後的貯藏彈性係數1.0×106 Pa以上7.0×108 Pa以下者。 　　貯藏彈性係數未滿1.0×106 Pa時，即使對黏著膠帶1照射放射線，黏著力也不易降低。結果，使利用切割被形成的個個半導體晶片變得不易自黏著膠帶1剝離。 　　此外，貯藏彈性係數比7.0×108 Pa還大時，由於黏著劑層3變硬、彎曲彈性係數變得過高，所以在介著黏著膠帶1將半導體晶片上推並將半導體晶片自黏著膠帶1剝離時，半導體晶片薄之場合，有破裂之虞。The aforementioned adhesive layer 3 preferably has a storage elastic modulus of 1.0×10 6 Pa or more and 7.0×10 8 Pa or less after being irradiated with radiation and cured. When the storage elastic modulus is less than 1.0×10 6 Pa, even if the adhesive tape 1 is irradiated with radiation, the adhesive force is not easily reduced. As a result, the individual semiconductor wafers formed by dicing are less likely to be peeled off from the adhesive tape 1 . In addition, when the storage elastic coefficient is larger than 7.0×10 8 Pa, since the adhesive layer 3 becomes hard and the bending elastic coefficient becomes too high, the semiconductor wafer is pushed up through the adhesive tape 1 and the semiconductor wafer is self-adhesive tape. 1 When peeling off, when the semiconductor wafer is thin, there is a possibility of cracking.

此外，黏著劑層3的厚度，為3μm～50μm之範圍佳，5μm～20μm之範圍更佳。 　　在黏著劑層3的厚度未滿3μm之場合，有黏著膠帶1的黏著力過度低下之疑慮。該場合，在半導體晶圓切割時，會有黏著膠帶1不能充分保持半導體晶片、使半導體晶片飛散之疑慮。 　　另一方面，在黏著劑層3的厚度比50μm還厚之場合，切割時的震動容易傳到黏著劑層3，震動幅增加，則有在半導體晶圓切割中該半導體晶圓偏離基準位置之疑慮。該場合，有或在半導體晶片產生破片(碎屑)、或每個半導體晶片發生大小偏差之疑慮。In addition, the thickness of the adhesive layer 3 is preferably in the range of 3 μm to 50 μm, more preferably in the range of 5 μm to 20 μm. When the thickness of the adhesive layer 3 is less than 3 μm, there is a possibility that the adhesive force of the adhesive tape 1 is excessively lowered. In this case, when the semiconductor wafer is diced, the adhesive tape 1 cannot sufficiently hold the semiconductor wafer, and there is a possibility that the semiconductor wafer may be scattered. On the other hand, when the thickness of the adhesive layer 3 is thicker than 50 μm, the vibration during dicing is easily transmitted to the adhesive layer 3, and the vibration amplitude increases, which may cause the semiconductor wafer to deviate from the reference position during the dicing of the semiconductor wafer. doubt. In this case, there is a possibility that a chip (chip) may be generated in the semiconductor wafer, or that the size of each semiconductor wafer may vary.

(丙烯酸酯系共聚物) 　　丙烯酸酯系共聚物，並未特別限定，例如，以(甲基)丙烯酸系聚合物作為主劑之黏著劑。(甲基)丙烯酸系聚合物，例如，可藉由共聚合含有直鏈及/或分歧烷基之(甲基)丙烯酸系聚合物、具有官能基之(甲基)丙烯酸系聚合物、與因應必要其他的單體而得到。 　　作為丙烯酸酯系共聚物，可以適當使用作為官能基而具有羥基、羧基中任一種。(Acrylate-based copolymer) The acrylate-based copolymer is not particularly limited, for example, an adhesive with a (meth)acrylic polymer as the main agent. (Meth)acrylic polymers, for example, can be obtained by copolymerizing (meth)acrylic polymers containing linear and/or branched alkyl groups, (meth)acrylic polymers having functional groups, and corresponding Obtained if other monomers are necessary. As the acrylate-based copolymer, either a hydroxyl group or a carboxyl group can be appropriately used as a functional group.

作為含有直鏈或分歧烷基之(甲基)丙烯酸系單體，例如，可列舉(甲基)丙烯酸甲基、(甲基)丙烯酸乙基、(甲基)丙烯酸丙基、(甲基)丙烯酸異丙基、(甲基)丙烯酸丁基、(甲基)丙烯酸異丁基、(甲基)丙烯酸s-丁基、(甲基)丙烯酸t-丁基、(甲基)丙烯酸戊烷基、(甲基)丙烯酸己基、(甲基)丙烯酸庚基、(甲基)丙烯酸辛基、(甲基)丙烯酸異辛基、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬基、(甲基)丙烯酸異壬基、(甲基)丙烯酸癸基、(甲基)丙烯酸異癸基、(甲基)丙烯酸十一基、(甲基)丙烯酸十二基、(甲基)丙烯酸十三基、(甲基)丙烯酸十四基、(甲基)丙烯酸肉豆蔻基、(甲基)丙烯酸十五基、(甲基)丙烯酸十六基、(甲基)丙烯酸十七基、(甲基)丙烯酸十八基等。這些可以單獨使用也可以併用2種以上。其中於本實施形態，可以適當使用含有碳數4以上12以下的烷基之(甲基)丙烯酸系單體，可以進而適當使用含有碳數8的烷基之(甲基)丙烯酸2-乙基己酯。Examples of the (meth)acrylic monomer containing a straight-chain or branched alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl) Isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate , (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid Nonyl, Isononyl (Meth)acrylate, Decyl (Meth)acrylate, Isodecyl (Meth)acrylate, Undecyl (Meth)acrylate, Dodecyl (Meth)acrylate, (Meth) ) Tridecyl acrylate, tetradecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate , (meth)acrylic acid octadecyl, etc. These may be used alone or in combination of two or more. Among them, in this embodiment, a (meth)acrylic-based monomer containing an alkyl group having 4 to 12 carbon atoms can be appropriately used, and 2-ethyl (meth)acrylate containing an alkyl group having 8 carbon atoms can be appropriately used. hexyl ester.

作為含有羥基之(甲基)丙烯酸系單體，例如，可列舉(甲基)丙烯酸2-羥乙基、(甲基)丙烯酸2-羥丙基、(甲基)丙烯酸4-羥丁基、(甲基)丙烯酸6-羥己基等。這些可以單獨使用，亦可組合2種以上使用。Examples of hydroxyl-containing (meth)acrylic monomers include (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 4-hydroxybutyl, (Meth)acrylic acid 6-hydroxyhexyl and the like. These may be used alone or in combination of two or more.

作為含有羧基之(甲基)丙烯酸系單體，例如，可列舉(甲基)丙烯酸、亞甲基丁二酸、肉桂酸、反丁烯二酸、鄰苯二甲酸等。這些可以單獨使用，亦可組合2種以上使用。As a (meth)acrylic-type monomer containing a carboxyl group, (meth)acrylic acid, methylenesuccinic acid, cinnamic acid, fumaric acid, phthalic acid, etc. are mentioned, for example. These may be used alone or in combination of two or more.

在本實施形態，丙烯酸酯系共聚物，只要在不妨礙本發明之效果，也可以因應必要而含有其他共聚合單體成分。作為此類之其他的共聚合單體成分，具體而言，例如，可列舉順丁烯二酸酐、衣康酸酐等含有酸酐基之單體，(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺等醯胺系單體，(甲基)丙烯酸胺基乙基、(甲基)丙烯酸N,N-二甲基胺基乙基等含有胺基單體，(甲基)丙烯腈等含有氰基單體，乙烯、丙烯、異戊二烯、丁二烯等烯烴系單體，苯乙烯、α-甲基苯乙烯、乙烯基甲苯等苯乙烯系單體，乙酸乙烯酯、丙酸乙烯基等乙烯基酯系單體，甲基乙烯基醚、乙基乙烯基醚等乙烯基醚系單體，氯乙烯、二氯亞乙烯等含有鹵素原子單體，(甲基)丙烯酸甲氧基乙基、(甲基)丙烯酸乙氧基乙基等含有烷氧基單體，或具有N-乙烯基-2-咯烷酮、N-甲基乙烯基咯烷酮等含有氮原子之環之單體等。In the present embodiment, the acrylate-based copolymer may contain other comonomer components as necessary as long as the effects of the present invention are not hindered. Specific examples of such other comonomer components include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, (meth)acrylamide, N,N-di Amide-based monomers such as methyl (meth)acrylamide, (meth)acrylic acid aminoethyl, (meth)acrylic acid N,N-dimethylaminoethyl and other amino group-containing monomers, ( Meth)acrylonitrile containing cyano monomers, ethylene, propylene, isoprene, butadiene and other olefin monomers, styrene, α-methylstyrene, vinyltoluene and other styrene monomers, Vinyl ester monomers such as vinyl acetate and vinyl propionate, vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether, and halogen atom-containing monomers such as vinyl chloride and vinylidene chloride, ( Meth)acrylic acid methoxyethyl, (meth)acrylic acid ethoxyethyl, etc. contain alkoxy monomers, or have N-vinyl-2-rolidone, N-methylvinylrolidone Monomers such as rings containing nitrogen atoms, etc.

此外，在本實施形態，丙烯酸酯系共聚物，也可以使用在側鎖導入放射線聚合性碳-碳雙鍵。例如，可列舉合成具有羥基之丙烯酸酯系共聚物，之後，使合成之丙烯酸酯系共聚物的羥基與2-甲基丙烯醯氧基乙基異氰酸酯反應，在側鎖導入作用成為放射線聚合性碳-碳雙鍵之甲基丙烯醯基之丙烯酸酯系共聚物等。In addition, in the present embodiment, the acrylate-based copolymer can also be used to introduce a radiation polymerizable carbon-carbon double bond into the side lock. For example, it is possible to synthesize an acrylate-based copolymer having a hydroxyl group, and then react the hydroxyl group of the synthesized acrylate-based copolymer with 2-methacryloyloxyethyl isocyanate to form a radiation polymerizable carbon by the side-lock introduction. -Acrylate copolymer of methacryloyl group of carbon double bond, etc.

(放射線硬化性低聚物) 　　放射線硬化性低聚物，係具有在被照射放射線時會硬化之性質。作為放射線硬化性低聚物，並未特別限定，而可以使用環氧丙烯酸酯系低聚物、聚氨酯丙烯酸酯系低聚物、聚酯丙烯酸酯系低聚物等。環氧丙烯酸酯，係利用環氧化合物與羧酸之附加反應而被合成。聚氨酯丙烯酸酯，例如，在多元醇與聚異氰酸酯之附加反應物，使末端殘留的異氰酸酯基與含有羥基的丙烯酸酯反應並將丙烯酸基導入分子末端而被合成。聚酯丙烯酸酯，係利用聚酯多元醇與丙烯酸之反應而被合成。(Radiation curable oligomers) Radiation curable oligomers have the property of hardening when irradiated with radiation. It does not specifically limit as a radiation curable oligomer, An epoxy acrylate type oligomer, a urethane acrylate type oligomer, a polyester acrylate type oligomer, etc. can be used. Epoxy acrylate is synthesized by the additional reaction of epoxy compound and carboxylic acid. The urethane acrylate, for example, is synthesized by reacting the isocyanate group remaining at the terminal with an acrylate group containing a hydroxyl group and introducing the acrylic group into the terminal of the molecule as an additional reactant of a polyol and a polyisocyanate. Polyester acrylate is synthesized by the reaction of polyester polyol and acrylic acid.

在本實施形態，可適宜使用聚氨酯丙烯酸酯系低聚物。利用這放射線硬化性低聚物的硬化，讓黏著劑層3的黏著力降低。 　　黏著劑層3，在將丙烯酸酯系共聚物設為100質量部時，最好是包含放射線硬化性低聚物80質量部以上180質量部以下。In the present embodiment, a urethane acrylate-based oligomer can be suitably used. The hardening of the radiation-curable oligomer reduces the adhesive force of the adhesive layer 3 . The adhesive layer 3 preferably contains 80 parts by mass or more and 180 parts by mass or less of the radiation-curable oligomer when the acrylate-based copolymer is set at 100 parts by mass.

放射線硬化性低聚物的含有量未滿80質量部時，即使對黏著膠帶1照射放射線，黏著劑層3仍不能充分硬化･收縮，黏著力不易變低。結果，變得不易將利用半導體晶圓切割而被形成的個個半導體晶片自黏著膠帶1剝離，而且在該剝離時，有半導體晶片一部分缺損之疑慮。 　　此外，放射線硬化性低聚物的含有量超過180質量部時，由於在對黏著膠帶1照射放射線時，因硬化的低聚物量增大的影響使黏著劑層3變硬、彎曲彈性係數變得過高，所以在介著黏著膠帶1將半導體晶片上推並將半導體晶片自黏著膠帶1剝離時，半導體晶片薄之場合，有破裂之虞。When the content of the radiation-curable oligomer is less than 80 parts by mass, even if the adhesive tape 1 is irradiated with radiation, the adhesive layer 3 is not sufficiently hardened and shrunk, and the adhesive force is unlikely to decrease. As a result, it becomes difficult to peel off the individual semiconductor wafers formed by the dicing of the semiconductor wafers from the adhesive tape 1, and there is a possibility that a part of the semiconductor chips may be damaged during the peeling. In addition, when the content of the radiation-curable oligomer exceeds 180 parts by mass, when the adhesive tape 1 is irradiated with radiation, the adhesive layer 3 becomes hard due to the influence of an increase in the amount of the hardened oligomer, and the flexural modulus of elasticity becomes If the semiconductor wafer is too high, when the semiconductor wafer is pushed up through the adhesive tape 1 and the semiconductor wafer is peeled off from the adhesive tape 1, the semiconductor wafer may be broken if the semiconductor wafer is thin.

在本實施形態，作為放射線硬化性低聚物，最好是使用羥基價3mgKOH/g以下者。在此，羥基價，係為了將對象物1g中所含的OH基乙醯基化所必需之氫氧化鉀之量(mg)。 　　在此，放射線硬化性低聚物的羥基價比3mgKOH/g還大時，特別是在剛研削後的半導體晶圓黏貼黏著膠帶1之場合，黏著劑層3對半導體晶圓之黏著力會變得過大。結果，即使對黏著膠帶1照射放射線，也有變得不易將利用切割而被形成的個個半導體晶片自黏著膠帶1剝離的疑慮，或有半導體晶片缺損之疑慮。In the present embodiment, as the radiation curable oligomer, one having a hydroxyl value of 3 mgKOH/g or less is preferably used. Here, the hydroxyl value is the amount (mg) of potassium hydroxide necessary for acetylation of OH groups contained in 1 g of the object. Here, when the hydroxyl valence of the radiation-curable oligomer is larger than 3 mgKOH/g, especially when the adhesive tape 1 is attached to a semiconductor wafer just after grinding, the adhesive force of the adhesive layer 3 to the semiconductor wafer will change. too big. As a result, even if the adhesive tape 1 is irradiated with radiation, it may become difficult to peel off the individual semiconductor wafers formed by dicing from the adhesive tape 1 or the semiconductor wafer may be damaged.

亦即，在半導體晶片的製作過程，利用研削而薄膜化半導體晶圓時，在該半導體晶圓的表面，會經時地形成自然氧化膜。在此，為了提升半導體晶片的生產性，在研削半導體晶圓而薄膜化之後立即進行朝研削面黏貼黏著膠帶1之製程之場合，被研削的半導體晶圓的表面，係未氧化狀態，而且成為活性原子(例如矽原子等)存在的活性面。當這活性面的活性原子、與放射線硬化性低聚物的羥基結合時，黏著劑層3的黏著力會變得過大。 　　結果，即使照射放射線後，也變得不易將利用切割而被形成的個個半導體晶片自黏著膠帶1剝離，而且在此時，有半導體晶片一部分缺損之疑慮。That is, in the production process of the semiconductor wafer, when the semiconductor wafer is thinned by grinding, a natural oxide film is formed over time on the surface of the semiconductor wafer. Here, in order to improve the productivity of the semiconductor wafer, when the process of attaching the adhesive tape 1 to the ground surface is performed immediately after grinding the semiconductor wafer and thinning it, the surface of the ground semiconductor wafer is in an unoxidized state and becomes Active surface where active atoms (such as silicon atoms, etc.) exist. When the active atoms of the active surface are bonded to the hydroxyl groups of the radiation-curable oligomer, the adhesive force of the adhesive layer 3 becomes excessively large. As a result, even after irradiation with radiation, it becomes difficult to peel off the individual semiconductor wafers formed by dicing from the adhesive tape 1, and at this time, there is a possibility that a part of the semiconductor wafer is damaged.

對此，使用放射線硬化性低聚物的羥基價3mgKOH/g以下之場合，與半導體晶圓的活性面的活性原子結合之羥基(放射線硬化性低聚物的羥基)少，可抑制放射線照射後的黏著劑層3黏著力過大之情形。結果，使半導體晶片變得容易自黏著膠帶1剝離。放射線硬化性低聚物的羥基價最好是0mgKOH/g。On the other hand, when the hydroxyl value of the radiation-curable oligomer is 3 mgKOH/g or less, the number of hydroxyl groups (hydroxyl groups of the radiation-curable oligomer) bound to the active atoms of the active surface of the semiconductor wafer is small, and the post-irradiation can be suppressed. The case where the adhesive force of the adhesive layer 3 is too large. As a result, the semiconductor wafer becomes easy to peel from the adhesive tape 1 . The hydroxyl value of the radiation curable oligomer is preferably 0 mgKOH/g.

此外，作為防射線硬化性低聚物，最好是使用在分子中有3個以上放射線聚合性碳-碳雙鍵者。 　　放射線硬化性低聚物在分子中沒有3個以上放射線聚合性碳-碳雙鍵之場合，即使對黏著膠帶1照射放射線，黏著劑層3仍不能充分硬化･收縮，黏著力不易變低。結果，使利用切割被形成的個個半導體晶片變得不易自黏著膠帶1剝離。 　　又，使用在分子中有3個以上放射線聚合性碳-碳雙鍵的放射性硬化性低聚物之場合，除此之外，在只要不妨礙本案發明之效果，也可以併用分子中有2個放射線聚合性碳-碳雙鍵的放射線硬化性低聚物。在這場合，也最好是使用放射線硬化性低聚物的羥基價3mgKOH/g以下者。In addition, as the radiation-resistant curable oligomer, one having three or more radiation-polymerizable carbon-carbon double bonds in the molecule is preferably used. In the case where the radiation-curable oligomer does not have three or more radiation-polymerizable carbon-carbon double bonds in the molecule, even if the adhesive tape 1 is irradiated with radiation, the adhesive layer 3 cannot be sufficiently hardened and shrunk, and the adhesive force is unlikely to decrease. As a result, the individual semiconductor wafers formed by dicing are less likely to be peeled off from the adhesive tape 1 . In addition, when a radiocurable oligomer having three or more radiation-polymerizable carbon-carbon double bonds in the molecule is used, as long as the effect of the present invention is not hindered, two or more molecules may be used in combination. A radiation-curable oligomer of radiation-polymerizable carbon-carbon double bonds. Also in this case, it is preferable to use a radiation curable oligomer having a hydroxyl value of 3 mgKOH/g or less.

此外，作為放射線硬化性低聚物，最好是使用重量平均分子量Mw為500以上6000以下者。 　　使用重量平均分子量Mw未滿500的放射線硬化性低聚物之場合，由於在對黏著膠帶1照射放射線時，因低聚物彼此的交聯密度增加的影響使黏著劑層3變硬、彎曲彈性係數變高，所以在介著黏著膠帶1將半導體晶片上推並將半導體晶片自黏著膠帶1剝離時，半導體晶片薄之場合，有破裂之虞。Moreover, as a radiation curable oligomer, it is preferable to use the thing whose weight average molecular weight Mw is 500 or more and 6000 or less. When a radiation-curable oligomer having a weight average molecular weight Mw of less than 500 is used, the adhesive layer 3 becomes hard and has a bending elasticity due to the influence of an increase in the crosslinking density of the oligomers when the adhesive tape 1 is irradiated with radiation. Since the coefficient becomes high, when the semiconductor wafer is pushed up through the adhesive tape 1 and the semiconductor wafer is peeled off from the adhesive tape 1, when the semiconductor wafer is thin, there is a possibility of cracking.

此外，使用重量平均分子量Mw比6000還大的放射線硬化性低聚物之場合，對黏著膠帶1照射放射線後黏著劑層3硬化･收縮的程度小，黏著劑層3的黏著力不易變低。結果，使利用切割半導體晶圓被形成的個個半導體晶片變得不易自黏著膠帶1剝離。In addition, when a radiation curable oligomer having a weight average molecular weight Mw larger than 6000 is used, the degree of hardening and shrinkage of the adhesive layer 3 after irradiation of the adhesive tape 1 with radiation is small, and the adhesive force of the adhesive layer 3 is unlikely to decrease. As a result, the individual semiconductor wafers formed by dicing the semiconductor wafers are less likely to be peeled off from the adhesive tape 1 .

(架橋劑) 　　作為架橋劑，可以適當使用與丙烯酸酯系共聚物具有的官能基反應者。丙烯酸酯系共聚物的官能基為羥基之場合可適宜使用異氰酸酯系架橋劑，丙烯酸酯系共聚物的官能基為羧基之場合可適宜使用環氧系架橋劑。 　　此外，架橋劑的添加量，架橋劑中之、與丙烯酸酯系共聚物具有的官能基反應之官能基的總量，相對於丙烯酸酯系共聚物的官能基，最好為1mol當量以上之量。(Bridging agent) As the bridging agent, one that reacts with the functional group possessed by the acrylate-based copolymer can be appropriately used. When the functional group of the acrylate-based copolymer is a hydroxyl group, an isocyanate-based bridging agent can be suitably used, and when the functional group of the acrylate-based copolymer is a carboxyl group, an epoxy-based bridging agent can be suitably used. In addition, the addition amount of the bridging agent and the total amount of functional groups in the bridging agent that react with the functional groups of the acrylate-based copolymer are preferably 1 mol equivalent or more relative to the functional groups of the acrylate-based copolymer. .

(光聚合開始劑) 　　光聚合開始劑，係具有在對黏著膠帶1照射放射線後生成自由基、使放射線碳-碳雙鍵開裂而開始聚合反應之作用。 　　作為光聚合開始劑，例如，可列舉安息香甲基醚、安息香乙醚、安息香丙醚、安息香異丙醚、安息香異丁醚、二苯基甲酮、苯甲醯苯甲酸、3,3’-二甲基-4-甲氧二苯甲酮、聚乙烯二苯基甲酮、α-羥基環己基苯基甲酮、4-(2-羥乙氧)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、對甲氧苯乙酮、2,2-二甲氧基-2-對苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1、二甲基苯偶醯縮酮、塞噸酮、2-氯塞噸酮、2-甲基塞噸酮、2-乙基塞噸酮、2-異丙基塞噸酮、2-十二基塞噸酮、2,4-二氯塞噸酮、2,4-二甲基塞噸酮、2,4-二乙基塞噸酮、2,4-二異丙基塞噸酮、二苯基乙二酮、安息香、2-甲基-2-羥基苯丙酮、2-萘磺醯氯、1-醯苯-1,1-丙二酮-2-(o-乙氧羰基)肟等。這些可以單獨使用，亦可組合2種以上使用。(Photopolymerization Initiator) The photopolymerization initiator has the function of generating radicals after irradiating the adhesive tape 1 with radiation, cleaving the carbon-carbon double bond of the radiation, and starting the polymerization reaction. As the photopolymerization initiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, benzoin benzoic acid, 3,3'-dibenzoin can be mentioned. Methyl-4-methoxybenzophenone, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ) ketone, α-hydroxy-α,α'-dimethylacetophenone, p-methoxyacetophenone, 2,2-dimethoxy-2-p-phenylacetophenone, 2,2-diethyl acetophenone Oxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1, dimethylbenzyl ketal, saxanthone, 2- Chlorxanthone, 2-methylxanthone, 2-ethylxanthone, 2-isopropylxanthone, 2-dodecylxanthone, 2,4-dichloroxanthone, 2 ,4-Dimethyl saxanthone, 2,4-diethyl saxanthone, 2,4-diisopropyl saxanthone, diphenylethanone, benzoin, 2-methyl-2-hydroxyl Propiophenone, 2-naphthalenesulfonyl chloride, 1-benzene-1,1-propanedione-2-(o-ethoxycarbonyl) oxime, etc. These may be used alone or in combination of two or more.

＜底膠層＞ 　　如上述，於本實施形態之黏著膠帶1，亦可因應黏著膠帶1之製造條件或製造後的黏著膠帶1之使用條件等，在基材2與黏著劑層3之間，設置配合基材種類之底膠層。藉由設置底膠層，提升基材2與黏著劑層3之密貼力。<Primer layer> As described above, in the adhesive tape 1 of the present embodiment, the adhesive tape 1 may be formed between the base material 2 and the adhesive layer 3 in accordance with the manufacturing conditions of the adhesive tape 1 or the use conditions of the adhesive tape 1 after manufacture, etc. Set the primer layer to match the type of substrate. By providing the primer layer, the adhesion between the substrate 2 and the adhesive layer 3 is enhanced.

＜剝離襯墊＞ 　　此外，亦可在黏著劑層3之與基材2相反之表面側(一方的表面側)，因應必要而設置剝離襯墊。可以使用為剝離襯墊之物並未特別限制，例如，可列舉聚乙烯、聚丙烯、聚對苯二甲酸乙二醇酯等合成樹脂，或紙類等。此外，在剝離襯墊的表面，為了提高黏著劑層3的剝離性，亦可實施利用聚矽氧系剝離處理劑、長鏈烷基系剝離處理劑、氟系剝離處理劑等之剝離處理。剝離襯墊的厚度並無特別限定，可適宜使用10μm以上200μm以下之厚度。<Release liner> In addition, a release liner may be provided on the surface side (one surface side) opposite to the base material 2 of the adhesive layer 3 as necessary. What can be used as a release liner is not particularly limited, and examples thereof include synthetic resins such as polyethylene, polypropylene, and polyethylene terephthalate, paper, and the like. In addition, in order to improve the releasability of the adhesive layer 3 on the surface of the release liner, a release treatment using a polysiloxane-based release treatment agent, a long-chain alkyl-based release treatment agent, a fluorine-based release treatment agent, or the like may be performed. The thickness of the release liner is not particularly limited, and a thickness of 10 μm or more and 200 μm or less can be suitably used.

＜黏著膠帶之製造方法＞ 　　圖2係說明黏著膠帶1之製造方法之流程圖。 　　首先，準備基材2(步驟101：基材準備製程)。 　　其次，製作供形成黏著劑層3用的黏著劑層3用塗布溶液(黏著劑層形成用塗布溶液)(步驟102：塗布溶液製作製程)。塗布溶液，係包含黏著劑層3的成分之丙烯酸酯系共聚物、放射線硬化性低聚物、與架橋劑。然後，可以藉由將這些投入溶媒、進行攪拌來製作塗布溶液。作為溶媒，例如，可以使用甲苯或乙酸乙酯等泛用的有機溶劑。<Method of Manufacturing Adhesive Tape> FIG. 2 is a flowchart illustrating a method of manufacturing the adhesive tape 1. FIG. First, prepare substrate 2 (step 101: substrate preparation process). Next, a coating solution for the adhesive layer 3 (coating solution for forming the adhesive layer) for forming the adhesive layer 3 is prepared (step 102: coating solution preparation process). The coating solution contains the acrylate-based copolymer, the radiation curable oligomer, and the bridging agent of the components of the adhesive layer 3 . Then, a coating solution can be prepared by putting these into a solvent and stirring. As the solvent, for example, general-purpose organic solvents such as toluene and ethyl acetate can be used.

然後，使用於步驟102製作出的黏著劑層3用塗布溶液，在基材2上形成黏著劑層3(步驟103：黏著劑層形成製程)。 　　作為在基材2上形成黏著劑層3之方法，可以採用在基材2上直接塗布黏著劑層3用塗布溶液並予以乾燥之方法，或者，在剝離襯墊上塗布黏著劑層3用塗布溶液並予以乾燥、之後在黏著劑層3上貼合基材2之方法之任一種方法。 　　然後，將形成的黏著劑層3藉由於例如40℃～60℃的環境下陳化並與丙烯酸酯系共聚物與架橋劑交聯化而使之熱硬化(步驟104：熱硬化製程)。Then, the adhesive layer 3 is formed on the substrate 2 using the coating solution for the adhesive layer 3 produced in step 102 (step 103 : the adhesive layer forming process). As a method of forming the adhesive layer 3 on the substrate 2, a method of directly applying the coating solution for the adhesive layer 3 on the substrate 2 and drying, or applying a coating solution for the adhesive layer 3 to the release liner can be adopted. Any of the methods in which the solution is dried, and then the substrate 2 is attached to the adhesive layer 3 . Then, the formed adhesive layer 3 is thermally hardened by aging in an environment of, for example, 40° C. to 60° C. and cross-linking with the acrylate-based copolymer and the bridging agent (step 104 : thermal hardening process).

根據以上詳述之本實施形態，黏著劑層3所含的丙烯酸酯系共聚物的官能基(羥基、羧基中之任一種官能基)，係與架橋劑的官能基反應。此外，黏著劑層3所含的放射線硬化性低聚物，重量平均分子量Mw為500以上6000以下且在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下。According to the present embodiment described in detail above, the functional group (either of a hydroxyl group and a carboxyl group) of the acrylate-based copolymer contained in the adhesive layer 3 reacts with the functional group of the bridging agent. In addition, the radiation curable oligomer contained in the adhesive layer 3 has a weight average molecular weight Mw of 500 or more and 6000 or less, has three or more radiation polymerizable carbon-carbon double bonds in the molecule, and has a hydroxyl value of 3 mgKOH/g or less.

本實施形態之黏著膠帶1，係可以用於將半導體晶圓切割而形成個個半導體晶片之場合。特別是，能適用於將在表面具有活性面的半導體晶圓切割而形成個個半導體晶片之場合。The adhesive tape 1 of the present embodiment can be used in a case where individual semiconductor chips are formed by dicing a semiconductor wafer. In particular, it can be applied to the case where individual semiconductor wafers are formed by dicing a semiconductor wafer having an active surface on the surface.

亦即，根據本實施形態之黏著膠帶1，在具有活性面的半導體晶圓黏貼黏著膠帶1之場合，藉由對黏著膠帶1照射放射線使黏著劑層3硬化，可充分減低黏著劑層3的黏著力。這場合，使利用切割被形成的個個半導體晶片變得容易自黏著膠帶1剝離。 　　從而，即使是對研削半導體晶圓而成為活性面的半導體晶圓的表面黏貼本實施形態的黏著膠帶1之場合，都可良好地進行切割、或利用切割被形成的個個半導體晶片之拾取。That is, according to the adhesive tape 1 of the present embodiment, when the adhesive tape 1 is adhered to a semiconductor wafer having an active surface, the adhesive layer 3 is cured by irradiating the adhesive tape 1 with radiation, so that the adhesive layer 3 can be sufficiently reduced. Adhesion. In this case, the individual semiconductor wafers formed by dicing are easily peeled off from the adhesive tape 1 . Therefore, even in the case where the adhesive tape 1 of the present embodiment is pasted on the surface of the semiconductor wafer that has been ground to become an active surface, dicing or picking up of individual semiconductor wafers formed by dicing can be performed well.

又，本實施形態之黏著膠帶1，可以是被捲成滾軸狀之形態，抑或層積幅度寬廣的薄片之形態。此外，抑或將該等形態的黏著膠帶1切斷成預先決定的大小而被形成的薄片狀或膠帶狀之形態。In addition, the adhesive tape 1 of the present embodiment may be wound in a roll shape, or may be a form of laminating sheets with a wide width. In addition, the adhesive tape 1 of these forms may be cut into a predetermined size and formed into a sheet-like or tape-like form.

＜半導體晶片之製造方法＞ 　　圖3係說明使用本實施形態的黏著膠帶1之半導體晶片之製造方法之流程圖。此外，圖4(a)～(d)係圖示使用本實施形態的黏著膠帶1之半導體晶片之製造例。<Manufacturing method of semiconductor wafer> FIG. 3 is a flowchart illustrating a manufacturing method of a semiconductor wafer using the adhesive tape 1 of the present embodiment. In addition, FIG.4(a)-(d) has shown the manufacture example of the semiconductor wafer using the adhesive tape 1 of this embodiment.

首先，如圖4(a)所示，準備例如在以矽為主成分的基板101上搭載複數積體電路102之半導體晶圓100(步驟201：準備製程)。 　　接著，研削半導體晶圓100之與搭載積體電路102的面相反側的面，將半導體晶圓100形成預先決定的厚度(步驟202：研削製程)。此時，未圖示，但在半導體晶圓100之搭載積體電路102之面黏貼保護膠帶。保護膠帶會在切斷(切割)製程之前被剝下。 　　然後，以半導體晶圓100的研削面與黏著膠帶1的黏著劑層3相對向之方式，將黏著膠帶1對於半導體晶圓100黏貼(步驟203：黏貼製程)。於步驟202藉由在研削半導體晶圓100後立即黏貼黏著膠帶1，於半導體晶圓100的表面存在活性原子之狀態下，在半導體晶圓100黏貼黏著膠帶1。First, as shown in FIG. 4( a ), for example, a semiconductor wafer 100 on which a plurality of integrated circuits 102 are mounted on a substrate 101 mainly composed of silicon is prepared (step 201 : preparation process). Next, the surface of the semiconductor wafer 100 opposite to the surface on which the integrated circuit 102 is mounted is ground, and the semiconductor wafer 100 is formed into a predetermined thickness (step 202: grinding process). At this time, although not shown, a protective tape is pasted on the surface of the semiconductor wafer 100 on which the integrated circuit 102 is mounted. The protective tape is peeled off before the severing (dicing) process. Then, the adhesive tape 1 is adhered to the semiconductor wafer 100 in such a manner that the grinding surface of the semiconductor wafer 100 is opposite to the adhesive layer 3 of the adhesive tape 1 (step 203 : the sticking process). In step 202 , the adhesive tape 1 is affixed to the semiconductor wafer 100 in a state where active atoms exist on the surface of the semiconductor wafer 100 by affixing the adhesive tape 1 immediately after grinding the semiconductor wafer 100 .

在此，於黏貼製程，一般上，使用推壓黏著膠帶1的推壓滾筒等，而在半導體晶圓100黏貼黏著膠帶1。此外，抑或藉由於可以加壓的容器(例如，高壓鍋等)中使半導體晶圓100與黏著膠帶1疊合、將容器內予以加壓，而在半導體晶圓100黏貼黏著膠帶1。再者，抑或於減壓室(真空室)內，在半導體晶圓100黏貼黏著膠帶1。Here, in the sticking process, generally, the sticking tape 1 is sticked to the semiconductor wafer 100 by using a pressing roller or the like for pressing the sticking tape 1 . Alternatively, the adhesive tape 1 may be adhered to the semiconductor wafer 100 by stacking the semiconductor wafer 100 and the adhesive tape 1 in a pressurizable container (eg, a pressure cooker, etc.) and pressurizing the container. Furthermore, the adhesive tape 1 is attached to the semiconductor wafer 100 in a decompression chamber (vacuum chamber).

接著，如圖4(b)所示，於貼合黏著膠帶1與半導體晶圓100之狀態下，沿著切斷預定線X，將半導體晶圓100利用切塊機等切斷(步驟204：切斷製程)。如圖4(c)所示，於此例，進行全切入半導體晶圓100之所謂全切(full cut)。Next, as shown in FIG. 4( b ), in the state where the adhesive tape 1 and the semiconductor wafer 100 are bonded together, the semiconductor wafer 100 is cut along the planned cutting line X using a dicing machine or the like (step 204 : cutting process). As shown in FIG. 4( c ), in this example, a so-called full cut in which the semiconductor wafer 100 is completely cut is performed.

在此，於切斷製程，一般上，為了去除摩擦熱或防止切斷屑附著而邊對被黏貼黏著膠帶的半導體晶圓供給洗淨水、邊使用例如旋轉的刀片將半導體晶圓100切斷成預先決定的大小。又，為了利用切割被形成的個個半導體晶片的拾取容易進行，在切斷製程後，亦可進行黏著膠帶1的拉長(擴展)。Here, in the dicing process, generally, the semiconductor wafer 100 is diced using, for example, a rotating blade while supplying cleaning water to the semiconductor wafer to which the adhesive tape is attached in order to remove frictional heat or prevent the adhesion of dicing chips. into a predetermined size. In addition, in order to easily pick up the individual semiconductor wafers formed by dicing, after the cutting process, the adhesive tape 1 may be elongated (expanded).

接著，藉由對黏著膠帶1照射放射線，使黏著劑層3硬化･收縮、使黏著劑層3的黏著力降低(步驟205：照射製程)。 　　接著，如圖4(d)所示，進行將藉由切斷半導體晶圓100而被形成的半導體晶片200自黏著膠帶1剝離之所謂拾取(步驟206：剝離製程)。 　　作為該拾取的方法，例如，可列舉將半導體晶片200自黏著膠帶1側利用針300而上推，將被上推的半導體晶片200、使用拾取裝置(未圖示)自黏著膠帶1剝離之方法等。Next, by irradiating the adhesive tape 1 with radiation, the adhesive layer 3 is hardened and shrunk, and the adhesive force of the adhesive layer 3 is reduced (step 205 : irradiation process). Next, as shown in FIG. 4( d ), a so-called pick-up in which the semiconductor wafer 200 formed by cutting the semiconductor wafer 100 is peeled off from the adhesive tape 1 is performed (step 206 : peeling process). As a method of picking up, for example, the semiconductor wafer 200 is pushed up from the adhesive tape 1 side with the needle 300, and the semiconductor wafer 200 pushed up is peeled off from the adhesive tape 1 using a pickup device (not shown). Wait.

又，於圖4(a)~(d)說明之方法，係使用黏著膠帶1之半導體晶片200之製造方法之一例，黏著膠帶1之使用方法，則並不以上述方法為限。亦即，本實施形態之黏著膠帶1，只要是在切割時，被黏貼在半導體晶圓100者，則可不受限定於上述方法來使用。 [實施例]4(a)-(d) is an example of a method of manufacturing the semiconductor wafer 200 using the adhesive tape 1, and the method of using the adhesive tape 1 is not limited to the above method. That is, the adhesive tape 1 of the present embodiment can be used without being limited to the above-mentioned method as long as it is adhered to the semiconductor wafer 100 during dicing. [Example]

以下，用實施例更詳細說明本發明。本發明，只要不逸脫其要旨則並不以這些實施例為限定。Hereinafter, the present invention will be described in more detail with examples. The present invention is not limited to these Examples unless it deviates from the gist.

製作圖1所示之黏著膠帶1，進行評價。 [黏著膠帶1之製作] (實施例1) 　　於本實施例，作為基材2，使用厚度90μm之聚烯烴(PO)系薄膜。The adhesive tape 1 shown in FIG. 1 was produced and evaluated. [Production of Adhesive Tape 1] (Example 1) In this example, as the base material 2, a polyolefin (PO)-based film with a thickness of 90 μm was used.

其次，在基材2一方的表面側，以以下作法形成黏著劑層3。 　　首先，藉由以偶氮二異丁腈(AIBN)作為開始劑、使50質量部的丙烯酸2-乙基己基、3質量部的丙烯酸2-羥基乙基、37質量部的甲基丙烯酸甲酯、與10質量部的N-乙烯基-2-咯烷酮於乙酸乙酯溶媒中進行自由基共聚合，製作出具有羥基之丙烯酸酯系共聚物(固體濃度：35質量%)。在此，甲基丙烯酸甲酯，係為了調整黏著劑層3的硬度而使用。Next, the adhesive layer 3 is formed on one surface side of the base material 2 by the following method. First, by using azobisisobutyronitrile (AIBN) as a starting agent, 50 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of 2-hydroxyethyl acrylate, and 37 parts by mass of methyl methacrylate , and 10 mass parts of N-vinyl-2-rolidone were radically copolymerized in an ethyl acetate solvent to produce an acrylate-based copolymer (solid concentration: 35 mass %) having a hydroxyl group. Here, methyl methacrylate is used for adjusting the hardness of the adhesive layer 3 .

接著，在乙酸乙酯，溶解製作出的丙烯酸酯系共聚物、放射線硬化性聚氨酯丙烯酸酯系低聚物、作為異氰酸酯系架橋劑之Tosoh(股)公司製Coronate(登錄商標)L、與作為光聚合開始劑之BASF Japan(股)公司製的IRGACURE(登錄商標)369，製作出黏著劑層3用之塗布溶液。 　　在此，塗布溶液的配合組成，係相對於丙烯酸酯系共聚物100質量部(固體)，作成放射線硬化性聚氨酯丙烯酸酯系低聚物為120質量部(固體)、Coronate L為7.5質量部(固體)、IRGACURE 369為1.0質量部(固體)、乙酸乙酯為343質量部。 　　放射線硬化性聚氨酯丙烯酸酯系低聚物，係使用重量平均分子量Mw為1000、羥基價為1mgKOH/g、放射線聚合性碳-碳雙鍵之數為6個者。Next, the prepared acrylate-based copolymer, radiation-curable urethane acrylate-based oligomer, Coronate (registered trademark) L by Tosoh Co., Ltd. as an isocyanate-based bridging agent, and light as a bridging agent were dissolved in ethyl acetate. IRGACURE (registered trademark) 369 manufactured by BASF Japan Co., Ltd., which is a polymerization initiator, was used to prepare a coating solution for the adhesive layer 3 . Here, the compounding composition of the coating solution is 120 parts by mass (solids) for the radiation-curable urethane acrylate-based oligomer and 7.5 parts by mass (solids) for Coronate L relative to 100 parts by mass (solids) of the acrylate-based copolymer. solid), IRGACURE 369 was 1.0 parts by mass (solids), and ethyl acetate was 343 parts by mass. As the radiation-curable urethane acrylate-based oligomer, a weight-average molecular weight Mw of 1,000, a hydroxyl value of 1 mgKOH/g, and a radiation-polymerizable carbon-carbon double bond of 6 were used.

然後，在以使乾燥後的黏著劑層3的厚度成為10μm之方式，在剝離襯墊(厚度38μm、聚酯膜)的剝離處理面側塗布上述塗布溶液並藉由以溫度100℃加熱3分鐘使之乾燥之後，在黏著劑層3上貼合基材2，製作出黏著膠帶1。之後，將黏著膠帶1以溫度40℃保存72小時而使黏著劑層3硬化。 　　利用以上製程製作出本實施例之黏著膠帶1。Then, the above-mentioned coating solution was applied to the release-treated surface side of the release liner (thickness 38 μm, polyester film) so that the thickness of the adhesive layer 3 after drying was 10 μm, and heated at a temperature of 100° C. for 3 minutes. After drying, the base material 2 is bonded to the adhesive layer 3, and the adhesive tape 1 is produced. After that, the adhesive tape 1 was stored at a temperature of 40° C. for 72 hours to harden the adhesive layer 3 . The adhesive tape 1 of this embodiment is produced by using the above process.

(實施例2～12) 　　對於實施例1，如圖5所示針對放射線硬化性胺甲酸乙酯低聚物進行變更以外，與實施例1同樣作法製作黏著膠帶1。(Examples 2 to 12) The adhesive tape 1 was produced in the same manner as in Example 1 except that the radiation curable urethane oligomer was changed as shown in Fig. 5 in Example 1.

(實施例13) 　　相對於實施例1，針對丙烯酸酯系共聚物，藉由將3質量部的丙烯酸2-羥基乙基變更成1質量部的甲基丙烯酸作成具有羧基之丙烯酸酯系共聚物，針對架橋劑，將異氰酸酯系架橋劑之Coronate L:7.5質量部進行變更成環氧系架橋劑之日本共榮社化學(股)公司製的Epolight 40E:2.5質量部以外，與實施例1同樣作法製作黏著膠帶1。 [比較例](Example 13) With respect to Example 1, an acrylate-based copolymer having a carboxyl group was prepared by changing 3 parts by mass of 2-hydroxyethyl acrylate to 1 part by mass of methacrylic acid for the acrylate-based copolymer, For the bridging agent, the same procedure as in Example 1 was carried out, except that Coronate L: 7.5 mass part of the isocyanate-based bridging agent was changed to Epolight 40E: 2.5 mass part manufactured by Nippon Kyeisha Chemical Co., Ltd., which was an epoxy-based bridging agent Make adhesive tape 1. [Comparative example]

(比較例1～4) 　　對於實施例1，如圖5所示針對放射線硬化性胺甲酸乙酯低聚物進行變更以外，與實施例1同樣作法製作黏著膠帶。其中於比較例1，放射線硬化性低聚物的分子中之放射線聚合性碳-碳結合之數，為低於下限值之2個。此外，於比較例2，放射線硬化性低聚物的重量平均分子量Mw，為低於下限值之200。此外，於比較例3，放射線硬化性低聚物的重量平均分子量Mw，為超過上限值之6500。此外，於比較例4，放射線硬化性低聚物的羥基價，為超過上限值之5mgKOH/g。(Comparative Examples 1 to 4) In Example 1, an adhesive tape was produced in the same manner as in Example 1, except that the radiation-curable urethane oligomer was changed as shown in FIG. 5 . However, in Comparative Example 1, the number of radiation-polymerizable carbon-carbon bonds in the molecule of the radiation-curable oligomer was two below the lower limit. Moreover, in Comparative Example 2, the weight average molecular weight Mw of the radiation curable oligomer was 200 lower than the lower limit. Moreover, in Comparative Example 3, the weight average molecular weight Mw of the radiation curable oligomer was 6500 which exceeded the upper limit. In addition, in Comparative Example 4, the hydroxyl value of the radiation curable oligomer was 5 mgKOH/g exceeding the upper limit.

[評價方法] (1)黏著力試驗 　　針對實施例1~13及比較例1~4之黏著膠帶，進行黏著力試驗。 　　具體上，對剛鏡面研磨後的半導體晶圓，黏貼黏著膠帶，於溫度23℃及濕度50%之氛圍下保持7日。又，為了在半導體晶圓的研削面被形成自然氧化膜之前黏貼黏著膠帶，而在半導體晶圓研削後5分鐘以內黏貼黏著膠帶。 　　接著，對黏著膠帶照射紫外線(累計光量:300mJ/cm2 )。然後，在23±3℃的環境下，朝沿著黏著膠帶的表面之方向施力並以拉伸速度300m/分拉伸黏著膠帶、自半導體晶圓剝下黏著膠帶，進行對半導體晶圓的黏著力之評價。亦即，針對黏著力，為了自半導體晶圓剝下黏著膠帶所必需的力為0.15N/10mm以下時作成○的評價、比0.15N/10mm還大時則作成×的評價。又，以○的評價為合格。[Evaluation method] (1) Adhesion test For the adhesive tapes of Examples 1 to 13 and Comparative Examples 1 to 4, an adhesion test was performed. Specifically, an adhesive tape was affixed to the semiconductor wafer just after mirror polishing, and it was kept for 7 days in an atmosphere with a temperature of 23° C. and a humidity of 50%. Furthermore, in order to apply the adhesive tape before the natural oxide film is formed on the ground surface of the semiconductor wafer, the adhesive tape is pasted within 5 minutes after the semiconductor wafer is ground. Next, the adhesive tape was irradiated with ultraviolet rays (cumulative light intensity: 300 mJ/cm 2 ). Then, in an environment of 23±3°C, the adhesive tape was stretched at a tensile speed of 300 m/min by applying force in the direction along the surface of the adhesive tape, and the adhesive tape was peeled off from the semiconductor wafer, and the semiconductor wafer was attached to the semiconductor wafer. Adhesion evaluation. That is, regarding the adhesive force, when the force necessary to peel the adhesive tape from the semiconductor wafer is 0.15 N/10 mm or less, an evaluation of ○ is made, and when it is greater than 0.15 N/10 mm, an evaluation of x is made. In addition, the evaluation of ○ was regarded as a pass.

(2)拾取試驗 　　針對實施例1~13及比較例1~4之黏著膠帶，進行拾取試驗。 　　具體而言，使用DISCO(股)公司製的DAG810(商品名)來研削半導體晶圓作成厚度50μm之後，對活性原子存在之半導體晶圓的表面黏貼黏著膠帶。之後，使用DISCO(股)公司製的DFD651(商品名，給送速度:50mm/min)來進行切割，形成個個大小為100mm2 的半導體晶片之後，從黏著膠帶的基材側照射紫外線(累計光量:300mJ/cm2 )。然後，在進行拉長黏著膠帶(擴展)之後，使用Daitron(股)公司製的WCS-700(商品名，針數:5支)來進行半導體晶圓之拾取，評價拾取性。 　　亦即，對任意50個半導體元件進行拾取，針對所有半導體元件沒有破裂且拾取成功時設為◎的評價。此外，針對1個以上5個以下半導體元件發生破裂、而餘下的半導體元件沒有破裂且拾取成功時設為○的評價。此外，針對6個以上半導體元件發生破裂時設為×的評價。又，以○或◎的評價為合格。(2) Pick-up test With respect to the adhesive tapes of Examples 1 to 13 and Comparative Examples 1 to 4, a pick-up test was performed. Specifically, after grinding a semiconductor wafer to a thickness of 50 μm using DAG810 (trade name) manufactured by DISCO Co., Ltd., an adhesive tape was applied to the surface of the semiconductor wafer containing active atoms. After that, it was diced using DFD651 (trade name, feed speed: 50 mm/min) manufactured by DISCO Co., Ltd. to form semiconductor wafers each having a size of 100 mm 2 , and then irradiated with ultraviolet rays (cumulative Light quantity: 300mJ/cm 2 ). Then, after the adhesive tape was stretched (expanded), the semiconductor wafer was picked up using WCS-700 (trade name, number of pins: 5 pieces) manufactured by Daitron Co., Ltd., and the pick-up property was evaluated. That is, 50 arbitrary semiconductor elements were picked up, and the evaluation of ⊚ when all the semiconductor elements were not cracked and picked up was successful. In addition, about one or more semiconductor elements cracked and 5 or less semiconductor elements were cracked, and the remaining semiconductor elements were not cracked and were picked up successfully, it was made into the evaluation of (circle). In addition, the evaluation of x was made when cracks occurred in 6 or more semiconductor elements. In addition, the evaluation of ○ or ◎ was considered acceptable.

(3)貯藏彈性係數之測定 　　針對實施例1~13及比較例1~4之黏著膠帶，測定各個黏著劑層放射線照射･硬化後之貯藏彈性係數。 　　具體而言，製作試料使塗布･乾燥調製出的各個黏著劑層之乾燥後的厚度為500μm，對黏著劑層照射紫外線(累計光量:300mJ/cm2 )之後，使用Hitachi High-Tech Science(股)公司製的黏彈性測量裝置DMA6100(商品名)，測定動態黏彈性，求出貯藏彈性係數。測定條件，設定頻率1Hz、升溫速度2℃/分，以23℃的數值作為貯藏彈性係數。(3) Measurement of storage elastic modulus For the adhesive tapes of Examples 1 to 13 and Comparative Examples 1 to 4, the storage elastic modulus of each adhesive layer after radiation irradiation and curing was measured. Specifically, samples were prepared so that the thickness after drying of each adhesive layer prepared by coating and drying was 500 μm, and the adhesive layer was irradiated with ultraviolet rays (cumulative light intensity: 300 mJ/cm 2 ), and then the adhesive layer was irradiated with Hitachi High-Tech Science Co., Ltd. ) Viscoelasticity measuring device DMA6100 (trade name) manufactured by the company measures the dynamic viscoelasticity, and obtains the storage elastic coefficient. As for the measurement conditions, a frequency of 1 Hz, a temperature increase rate of 2° C./min, and a value of 23° C. were set as the storage elastic coefficient.

[評價結果] 　　將評價結果顯示於圖5。 　　針對實施例1~13之黏著膠帶，黏著力試驗之黏著力皆為○之良好結果、合格。 　　此外，針對實施例1~13之黏著膠帶，拾取試驗之拾取性為◎或○之良好結果、皆合格。 　　再者，詳細比較實施例時，實施例5由於放射線硬化性低聚物之羥基價為3mgKOH/g之上限值，拾取性稍差(半導體元件之破裂數:1個)。 　　此外，實施例8由於放射線硬化性低聚物的含有量為比較少的50質量部，所以貯藏彈性係數稍低、為7.0×105 Pa，拾取性稍差(半導體元件之破裂數:2個)。 　　此外，實施例9由於放射線硬化性低聚物的重量平均分子量Mw為800、稍微低，含有量為170質量部、稍微多，所以貯藏彈性係數稍高、為1.0×109 Pa，拾取性微差(半導體元件之破裂數:1個)。 　　此外，實施例11由於放射線硬化性低聚物的含有量為稍多的180質量部，所以貯藏彈性係數微高、為7.5×108 Pa，拾取性微差(半導體元件之破裂數:1個)。 　　此外，實施例12由於放射線硬化性低聚物的含有量為比較多的190質量部，所以貯藏彈性係數稍高、為1.0×109 Pa，拾取性稍差(半導體元件之破裂數:2個)。[Evaluation Results] The evaluation results are shown in FIG. 5 . For the adhesive tapes of Examples 1 to 13, the adhesive force of the adhesive force test was all good results of ○ and passed. In addition, with respect to the adhesive tapes of Examples 1 to 13, the pick-up properties of the pick-up test were good results of ⊚ or ◯, which were all acceptable. Further, when comparing the examples in detail, in Example 5, since the hydroxyl valence of the radiation-curable oligomer was the upper limit of 3 mgKOH/g, the pick-up property was slightly inferior (the number of cracks in the semiconductor element: 1). In addition, in Example 8, since the content of the radiation-curable oligomer was relatively small at 50 parts by mass, the storage elastic modulus was slightly low at 7.0×10 5 Pa, and the pick-up property was slightly poor (the number of cracks in the semiconductor element: 2 pieces) ). In addition, in Example 9, since the weight average molecular weight Mw of the radiation curable oligomer is 800, which is slightly low, and the content is 170 parts by mass, which is slightly more, the storage elastic modulus is slightly high, 1.0×10 9 Pa, and the pick-up property is slightly high. Poor (number of cracks in semiconductor elements: 1). In addition, in Example 11, since the content of the radiation-curable oligomer was slightly more than 180 parts by mass, the storage elastic modulus was slightly high at 7.5×10 8 Pa, and the pick-up property was slightly poor (the number of cracks in the semiconductor element: 1 piece) ). In addition, in Example 12, since the content of the radiation-curable oligomer was relatively large at 190 parts by mass, the storage elastic modulus was slightly high at 1.0×10 9 Pa, and the pick-up property was slightly inferior (the number of cracks in the semiconductor element: 2 pieces) ).

相對地，針對比較例1、比較例3、4之黏著膠帶，在黏著力試驗，黏著劑層之黏著力過大則為X的評價、為不合格。 　　此外，針對比較例1~4之黏著膠帶，針對拾取試驗之拾取性，皆為X的評價、為不合格。 　　亦即，比較例1，放射線硬化性低聚物的分子中之放射線聚合性碳-碳結合之數為低於下限值之2個，在放射線照射後黏著劑層無法充分硬化･收縮而黏著力未充分降低，因而，變成不易將個片化的半導體晶片自黏著膠帶剝離，拾取性低。 　　此外，於比較例2，放射線硬化性低聚物的重量平均分子量Mw為低於下限值之200，在放射線照射後黏著力降低，但因低聚物彼此的交聯密度變高之影響致使變硬、彎曲彈性係數變高，因而，在將個片化的半導體晶片自黏著膠帶剝離時發生破裂，拾取性低。 　　此外，於比較例3，放射線硬化性低聚物的重量平均分子量Mw，為超過上限值之6500，在放射線照射後黏著劑層無法充分硬化･收縮而黏著力未充分降低，因而，變成不易將個片化的半導體晶片自黏著膠帶剝離，拾取性低。 　　此外，於比較例4，放射線硬化性低聚物的羥基價，為超過上限值之5mgKOH/g，在對剛鏡面研磨後的半導體晶圓黏貼黏著膠帶時黏著力變得過大，即使照射放射線也未使黏著力充分降低，因而，變成不易將個片化的半導體晶片自黏著膠帶剝離，拾取性低。On the other hand, with respect to the adhesive tapes of Comparative Example 1, Comparative Examples 3 and 4, in the adhesive force test, if the adhesive force of the adhesive layer is too large, the evaluation is X, which is unacceptable. In addition, with respect to the adhesive tapes of Comparative Examples 1 to 4, the pick-up properties in the pick-up test were all evaluated as X, and were considered unacceptable. That is, in Comparative Example 1, the number of radiation-polymerizable carbon-carbon bonds in the molecules of the radiation-curable oligomer was less than 2 of the lower limit, and the adhesive layer was not sufficiently hardened and shrunk after irradiation with radiation and adhered. Since the force was not sufficiently reduced, it was difficult to separate the individualized semiconductor wafers from the adhesive tape, and the pick-up property was low. In addition, in Comparative Example 2, the weight average molecular weight Mw of the radiation-curable oligomer was less than 200 of the lower limit, and the adhesive force decreased after irradiation with radiation, but the cross-linking density between the oligomers increased. Since it becomes hard and the flexural elastic modulus becomes high, when the individualized semiconductor wafer is peeled off from the adhesive tape, a crack occurs, and the pick-up property is low. In addition, in Comparative Example 3, the weight-average molecular weight Mw of the radiation-curable oligomer was 6500, which exceeded the upper limit value, and the adhesive layer was not sufficiently cured and shrunk after radiation irradiation, and the adhesive force was not sufficiently lowered, so it was difficult to The individualized semiconductor wafer is peeled off from the adhesive tape, and the pick-up property is low. In addition, in Comparative Example 4, the hydroxyl valence of the radiation-curable oligomer was 5 mgKOH/g exceeding the upper limit, and the adhesive force became too large when the adhesive tape was applied to the semiconductor wafer just after mirror polishing, and even if the radiation was irradiated Since the adhesive force was not sufficiently lowered, it was difficult to separate the individualized semiconductor wafers from the adhesive tape, and the pick-up property was low.

根據實施例1~13及比較例1~4之結果確認，需要丙烯酸酯系共聚物，作為官能基而具有羥基、羧基中之任一種，及放射線硬化性低聚物，重量平均分子量Mw為500以上6000以下且在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下。From the results of Examples 1 to 13 and Comparative Examples 1 to 4, it was confirmed that an acrylate-based copolymer having either a hydroxyl group or a carboxyl group as a functional group, and a radiation curable oligomer, and a weight-average molecular weight Mw of 500 were required. More than 6000 or less, having 3 or more radiation polymerizable carbon-carbon double bonds in the molecule, and having a hydroxyl value of 3 mgKOH/g or less.

1‧‧‧黏著膠帶2‧‧‧基材3‧‧‧黏著劑層1‧‧‧Adhesive tape 2‧‧‧Substrate 3‧‧‧Adhesive layer

圖1係圖示適用本實施形態之黏著膠帶之構成一例。 　　圖2係說明黏著膠帶之製造方法之流程圖。 　　圖3係說明半導體晶片之製造方法之流程圖。 　　圖4(a)～(d)係圖示使用黏著膠帶之半導體晶片之製造例。 　　圖5係圖示實施例及比較例。FIG. 1 shows an example of the configuration of the adhesive tape to which the present embodiment is applied. Figure 2 is a flow chart illustrating a method of manufacturing the adhesive tape. FIG. 3 is a flow chart illustrating a method of manufacturing a semiconductor wafer. Figures 4(a) to (d) show examples of manufacturing semiconductor wafers using adhesive tapes. Fig. 5 shows examples and comparative examples.

1‧‧‧黏著膠帶 1‧‧‧Adhesive tape

2‧‧‧基材 2‧‧‧Substrate

3‧‧‧黏著劑層 3‧‧‧Adhesive layer

Claims (4)

一種切割用黏著膠帶，其特徵係具有基材、與設置在前述基材的至少一方的表面側之黏著劑層；前述黏著劑層係至少具備：作為官能基而具有羥基之丙烯酸酯系共聚物、重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物、以及具有與該丙烯酸酯系共聚物所具有的羥基反應的官能基之架橋劑；前述架橋劑的前述官能基的總量，相對於前述丙烯酸酯系共聚物所具有的羥基，為1mol當量以上；前述黏著劑層，其被照射放射線且硬化之後的貯藏彈性係數為1.0×106Pa以上7.0×108Pa以下。 An adhesive tape for dicing, characterized by comprising a base material and an adhesive layer provided on at least one surface side of the base material; the adhesive layer at least includes: an acrylate-based copolymer having a hydroxyl group as a functional group , A radiation curable oligomer having a weight average molecular weight Mw of 500 or more and 6000 or less, having 3 or more radiation polymerizable carbon-carbon double bonds in the molecule and having a hydroxyl value of 3 mgKOH/g or less, and having a copolymerization with the acrylate system The bridging agent of the functional group that reacts with the hydroxyl group possessed by the bridging agent; the total amount of the functional group of the bridging agent is 1 mol equivalent or more with respect to the hydroxyl group possessed by the acrylate copolymer; the adhesive layer is irradiated The storage elastic modulus after radiation and hardening is 1.0×10 6 Pa or more and 7.0×10 8 Pa or less. 如申請專利範圍第1項記載之切割用黏著膠帶，其中前述黏著劑層，在將前述丙烯酸酯系共聚物設為100質量部時，包含前述放射線硬化性低聚物80質量部以上180質量部以下。 The adhesive tape for dicing according to claim 1, wherein the adhesive layer contains 80 parts by mass or more and 180 parts by mass of the radiation-curable oligomer when the acrylate-based copolymer is set at 100 parts by mass. the following. 一種切割用黏著膠帶之製造方法，其特徵係包含：準備基材之基材準備製程；製作用以形成黏著劑層之塗布溶液且至少包含 作為官能基而具有羥基之丙烯酸酯系共聚物、重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物、以及具有與該丙烯酸酯系共聚物所具有的羥基反應的官能基之架橋劑之塗布溶液之塗布溶液製作製程；使用前述塗布溶液，在前述基材的至少一方的表面側形成前述黏著劑層之黏著劑層形成製程；與包含使前述丙烯酸酯系共聚物與前述架橋劑交聯的處理、使形成的前述黏著劑層熱硬化之熱硬化製程；前述架橋劑的前述官能基的總量，相對於前述丙烯酸酯系共聚物所具有的羥基，為1mol當量以上；前述黏著劑層，其被照射放射線且硬化之後的貯藏彈性係數為1.0×106Pa以上7.0×108Pa以下。 A manufacturing method of an adhesive tape for dicing, which is characterized by comprising: a substrate preparation process for preparing a substrate; preparing a coating solution for forming an adhesive layer and at least comprising an acrylate-based copolymer having a hydroxyl group as a functional group, weight A radiation-curable oligomer having an average molecular weight Mw of 500 or more and 6000 or less, having three or more radiation-polymerizable carbon-carbon double bonds in the molecule, and having a hydroxyl valence of 3 mgKOH/g or less, and a radiation-curable oligomer having an affinity with the acrylate-based copolymer. A process for producing a coating solution for a coating solution of a bridging agent having a functional group reactive with a hydroxyl group; a process for forming an adhesive layer for forming the above-mentioned adhesive layer on at least one surface side of the above-mentioned substrate using the above-mentioned coating solution; The treatment of the crosslinking of the acrylate copolymer and the aforementioned bridging agent, and the thermal curing process of thermally curing the aforementioned adhesive layer formed; The hydroxyl group is 1 mol equivalent or more, and the adhesive layer has a storage elastic modulus of 1.0×10 6 Pa or more and 7.0×10 8 Pa or less after being irradiated with radiation and hardened. 一種半導體晶片之製造方法，其特徵係包含對於複數半導體元件被形成在基板上的元件用基板、黏貼切割用黏著膠帶之黏貼製程，將黏貼前述切割用黏著膠帶的前述元件用基板、切斷成複數半導體晶片之切斷製程，對於黏貼在前述半導體晶片的前述切割用黏著膠帶照射放射線、使該切割用黏著膠帶的黏著力降低之照射製程，與 將前述半導體晶片自黏著力降低的前述切割用黏著膠帶剝離之剝離製程；前述切割用黏著膠帶係具有基材、與設置在前述基材的至少一方的表面側之黏著劑層；前述黏著劑層係至少具備：作為官能基而具有羥基之丙烯酸酯系共聚物、重量平均分子量Mw為500以上6000以下並在分子中具有3個以上放射線聚合性碳-碳雙鍵且羥基價為3mgKOH/g以下之放射線硬化性低聚物、以及具有與該丙烯酸酯系共聚物所具有的羥基反應的官能基之架橋劑；前述架橋劑的前述官能基的總量，相對於前述丙烯酸酯系共聚物所具有的羥基，為1mol當量以上；前述黏著劑層，其被照射放射線且硬化之後的貯藏彈性係數為1.0×106Pa以上7.0×108Pa以下。A method of manufacturing a semiconductor wafer, which is characterized by comprising a process of attaching a substrate for a device on which a plurality of semiconductor elements are formed on a substrate, and an adhesive tape for dicing, and cutting the substrate for a device to which the adhesive tape for dicing is pasted, and cutting into pieces. The dicing process of a plurality of semiconductor wafers, the irradiation process of irradiating the above-mentioned adhesive tape for dicing attached to the above-mentioned semiconductor wafer with radiation to reduce the adhesive force of the adhesive tape for dicing, and the above-mentioned dicing process for reducing the self-adhesive force of the semiconductor wafer. The peeling process for peeling the adhesive tape; the adhesive tape for dicing has a substrate and an adhesive layer disposed on at least one surface side of the substrate; the adhesive layer at least has: acrylic acid having a hydroxyl group as a functional group Ester-based copolymers, radiation-curable oligomers having a weight average molecular weight Mw of not less than 500 and not more than 6,000, having 3 or more radiation-polymerizable carbon-carbon double bonds in the molecule, and having a hydroxyl value of not more than 3 mgKOH/g; and The bridging agent for the functional group of the hydroxyl group of the acrylate copolymer; the total amount of the functional groups in the bridging agent is 1 mol equivalent or more with respect to the hydroxyl group of the acrylate copolymer; the adhesive layer , which is irradiated with radiation and has a storage elastic modulus of 1.0×10 6 Pa or more and 7.0×10 8 Pa or less.
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