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TWI860425B - Adhesive tape for dicing and method for manufacturing semiconductor chip - Google Patents

Adhesive tape for dicing and method for manufacturing semiconductor chip Download PDF

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TWI860425B
TWI860425B TW109140310A TW109140310A TWI860425B TW I860425 B TWI860425 B TW I860425B TW 109140310 A TW109140310 A TW 109140310A TW 109140310 A TW109140310 A TW 109140310A TW I860425 B TWI860425 B TW I860425B
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silicone resin
silicone
adhesive
mass
adhesive tape
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TW109140310A
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Chinese (zh)
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TW202132525A (en
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増田晃良
下田敬之
酒井貴広
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日商麥克賽爾股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • H10P72/7402
    • H10P95/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/50Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Engineering & Computer Science (AREA)
  • Dicing (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)

Abstract

一種切割用黏著膠帶,其係具備基材與黏著劑層,黏著劑層係由黏著劑組成物所構成,該黏著劑組成物包含:混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂、作為交聯劑之1分子中具有至少2個以上之矽原子鍵結氫原子之有機聚矽氧烷、作為熱聚合起始劑之過氧化物、光感應鉑(Pt)觸媒;其中,矽氧膠(G)與矽氧樹脂(R)之混合比率為40.0/ 60.0~56.0/44.0之範圍,矽氧膠(G)包含由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk ),且矽原子鍵結烯基之含量為7.0×10-7 ~5.5×10-6 mol/g之範圍。An adhesive tape for cutting has a base material and an adhesive layer. The adhesive layer is composed of an adhesive composition. The adhesive composition includes: a silicone resin mixed with silicone glue (G) and silicone resin (R), an organic polysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule as a crosslinking agent, a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst; wherein the mixing ratio of silicone glue (G) to silicone resin (R) is 40.0/ The silicone gel (G) includes silicone gel (G alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group, and the content of the silicon atom-bonded alkenyl group is in the range of 7.0×10 -7 ~5.5×10 -6 mol/g.

Description

切割用黏著膠帶及半導體晶片之製造方法Adhesive tape for dicing and method for manufacturing semiconductor chip

本發明係關於成為半導體晶片材料之半導體材料在切割時所使用之切割用黏著膠帶,及使用切割用黏著膠帶之半導體晶片之製造方法。The present invention relates to a dicing adhesive tape used when dicing a semiconductor material that becomes a semiconductor chip material, and a method for manufacturing a semiconductor chip using the dicing adhesive tape.

以往,作為用來製作具有LED(發光二極體)等之半導體晶片所使用之切割用黏著膠帶,已知有具有由丙烯酸系樹脂所構成之接著劑層之黏著膠帶(參照專利文獻1)。 又,作為用來製作具有LED等之半導體晶片所切割用黏著膠帶,已知有具有由矽氧系樹脂所構成之黏著劑層之黏著膠帶(參照專利文獻2、專利文獻3)。 並且,作為使用切割用黏著膠帶來製作半導體晶片之方法,在基板上形成有複數半導體元件之半導體元件基板之基板側貼附黏著膠帶,藉由切割機來裁切半導體元件基板之方法(參照專利文獻4)。 [先前技術文獻] [專利文獻]Conventionally, as a dicing adhesive tape used for manufacturing semiconductor chips having LEDs (light emitting diodes), there is known an adhesive tape having an adhesive layer composed of an acrylic resin (see Patent Document 1). Also, as a dicing adhesive tape used for manufacturing semiconductor chips having LEDs, there is known an adhesive tape having an adhesive layer composed of a silicone resin (see Patent Document 2 and Patent Document 3). Furthermore, as a method for manufacturing semiconductor chips using a dicing adhesive tape, there is a method in which an adhesive tape is attached to a substrate side of a semiconductor element substrate having a plurality of semiconductor elements formed on the substrate, and the semiconductor element substrate is cut by a dicing machine (see Patent Document 4). [Prior art literature] [Patent literature]

[專利文獻1] 日本特開2013-38408號公報 [專利文獻2] 日本特開2015-050216號公報 [專利文獻3] 日本特開2016-122812號公報 [專利文獻4] 日本特開2005-93503號公報[Patent Document 1] Japanese Patent Publication No. 2013-38408 [Patent Document 2] Japanese Patent Publication No. 2015-050216 [Patent Document 3] Japanese Patent Publication No. 2016-122812 [Patent Document 4] Japanese Patent Publication No. 2005-93503

[發明所欲解決之課題][The problem that the invention wants to solve]

另一方面,近年來作為製作藉由切割而經個片化之半導體晶片之方法,已提出有在複數半導體元件被密封樹脂或螢光體等之被覆材所被覆之半導體材料上貼附黏著膠帶進行切割之技術,即對應所謂之晶圓級CSP(晶片尺寸封裝)製程之技術。 因此,在半導體元件經被覆材所被覆之半導體材料上貼附黏著膠帶之情況,根據黏著膠帶中之黏著劑層之構成或被覆材之素材等,而有黏著力不足,藉由切割而經個片化之半導體晶片進行飛散的情況。又,為了抑制半導體晶片之飛散,若將黏著劑層之滾球黏性或黏著力設計成較高時,從黏著膠帶剝離取得之半導體晶片之際,會有黏著劑仍附著於半導體晶片之狀態下殘留,即產生所謂殘膠的情況。On the other hand, in recent years, as a method for producing semiconductor chips that are cut into individual pieces by dicing, a technique has been proposed in which an adhesive tape is attached to a semiconductor material in which a plurality of semiconductor elements are covered with a coating material such as a sealing resin or a fluorescent body, and then cut. This technique corresponds to the so-called wafer-level CSP (chip size package) process. Therefore, when an adhesive tape is attached to a semiconductor material in which a semiconductor element is covered with a coating material, there is a possibility that the adhesive force is insufficient, depending on the composition of the adhesive layer in the adhesive tape or the material of the coating material, and the semiconductor chips that are cut into individual pieces by dicing may scatter. Furthermore, in order to suppress the scattering of semiconductor chips, if the rolling ball viscosity or adhesive force of the adhesive layer is designed to be higher, when the semiconductor chip is peeled off from the adhesive tape, some adhesive will remain attached to the semiconductor chip, which is the so-called adhesive residue.

本發明之目的在於提供一種對於具有經被覆材所被覆之複數半導體元件之半導體材料具有良好之黏著力(adhesive strength)及黏力(tack strength),並且在將藉由切割而經個片化之半導體晶片予以時,半導體晶片上之殘膠受到抑制之切割用黏著膠帶,及使用此之半導體晶片之製造方法。 [用以解決課題之手段]The purpose of the present invention is to provide an adhesive tape for dicing that has good adhesive strength and tack strength for a semiconductor material having a plurality of semiconductor elements coated with a coating material, and that suppresses the residual adhesive on the semiconductor chip when the semiconductor chip is cut into individual pieces by dicing, and a method for manufacturing a semiconductor chip using the same. [Means for solving the problem]

本發明者等基於該目的,精心研討關於切割用黏著膠帶之黏著劑層之結果,發現若將黏著劑層作成由對於至少包含(1)包含由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠之矽氧系樹脂、(2)具有矽原子鍵結氫原子(SiH基)之交聯劑,及(3)由過氧化物所構成之熱聚合起始劑之特定樹脂組成物,再添加(4)光感應鉑(Pt)觸媒之黏著劑組成物所構成者,且將矽氧系樹脂中之矽氧膠(silicone gum)與矽氧樹脂(silicone resin)之混合比率,以及矽氧系樹脂全體中之矽原子鍵結烯基之含量作成指定之範圍,則對於具有經被覆材所被覆之複數半導體元件之導體材料具有安定且良好之黏著力,並且在將藉由切割而經個片化之半導體晶片予以剝離時,對於半導體晶片之殘膠就會受到抑制,進而完成了本發明。 即,發現藉由將切割用黏著膠帶之黏著劑層作成由將矽氧膠與矽氧樹脂以指定之比率混合,且對於具有指定量之矽原子鍵結烯基之矽氧系樹脂,添加交聯劑與熱聚合起始劑與光感應鉑(Pt)觸媒之黏著組成物所構成者,即能達成以下之效果。首先,將具有經被覆材所被覆之複數半導體元件之半導體材料分割成複數半導體晶片時,黏著劑層在經過將該黏著劑層形成於基材上用之加熱・乾燥步驟之際,由於藉由熱聚合起始劑而矽氧系樹脂之一部分成為經過交聯・硬化(第1階段之交聯反應)之狀態,故藉由該黏著劑層之適度凝聚力所賦予之安定且良好之黏力及黏著力,從而發現在切割時經個片化之半導體晶片之飛散會受到抑制。又另一方面,從切割用黏著膠帶剝離藉由切割而經個片化之半導體晶片時,由於藉由對黏著劑層照射紫外線等之光,而黏著劑組成物中之光感應鉑(Pt)觸媒受到活性化,在矽氧系樹脂中之矽氧膠所具有之矽原子鍵結烯基與交聯劑所具有之矽原子鍵結氫原子(SiH基)之間第2階段之交聯反應(加成反應)受到促進,從而交聯密度更加變高,故在與光照射前相比,黏著劑組成物之凝聚力更加變大。其結果係黏著劑層之黏力適度地降低,以及在保持力試驗中之破壞模式成為「界面剝離」,或在保持力試驗中成為「不會落下」者。藉此,半導體晶片之來自切割用黏著膠帶之拾取性變得良好,且發現對於半導體晶片之殘膠受到抑制。Based on this purpose, the inventors of the present invention have carefully studied the adhesive layer of the adhesive tape for dicing and found that if the adhesive layer is made of a silicone resin comprising at least (1) silicone gum composed of an organic polysiloxane containing an olefin group bonded to a silicon atom, (2) a crosslinking agent having a hydrogen atom (SiH group) bonded to a silicon atom, and (3) a specific resin composition composed of a thermal polymerization initiator composed of a peroxide, and (4) an adhesive composition comprising a photosensitive platinum (Pt) catalyst is added, and the silicone gum in the silicone resin is mixed with the silicone resin. By setting the mixing ratio of the silicon-based resin and the content of the silicon-atom-bonded olefinic groups in the entire silicone resin to a specified range, the conductive material having multiple semiconductor elements coated by the coating material has stable and good adhesion, and when the semiconductor chip that has been cut into individual pieces by dicing is peeled off, the residual adhesive on the semiconductor chip is suppressed, thereby completing the present invention. That is, it was found that the following effects can be achieved by making the adhesive layer of the dicing adhesive tape into an adhesive composition composed of a mixture of silicone glue and silicone resin in a specified ratio, and adding a crosslinking agent, a thermal polymerization initiator and a photosensitive platinum (Pt) catalyst to a silicone resin having a specified amount of silicon atom-bonded alkenyl groups. First, when a semiconductor material having a plurality of semiconductor elements coated with a coating material is divided into a plurality of semiconductor chips, the adhesive layer undergoes a heating and drying step for forming the adhesive layer on the substrate. Since a portion of the silicone resin is crosslinked and hardened (the first stage of the crosslinking reaction) by the thermal polymerization initiator, the moderate cohesion of the adhesive layer provides a stable and good adhesive force and adhesion, thereby suppressing the scattering of the individual semiconductor chips during dicing. On the other hand, when the semiconductor chip that has been cut into pieces is peeled off from the dicing adhesive tape, the photosensitive platinum (Pt) catalyst in the adhesive composition is activated by irradiating the adhesive layer with light such as ultraviolet rays, and the second-stage cross-linking reaction (addition reaction) between the silicon atom-bonded olefin groups possessed by the silicone in the silicone resin and the silicon atom-bonded hydrogen atoms (SiH groups) possessed by the cross-linking agent is promoted, thereby further increasing the cross-linking density. Therefore, the cohesive force of the adhesive composition is further increased compared to before light irradiation. As a result, the adhesive force of the adhesive layer was moderately reduced, and the failure mode in the holding force test became "interface peeling" or "no drop" in the holding force test. As a result, the pickup property of the semiconductor chip from the dicing adhesive tape became good, and it was found that the residual adhesive on the semiconductor chip was suppressed.

本發明之切割用黏著膠帶,其特徵為具備基材與層合於該基材之黏著劑層,且係將半導體材料分割成複數之半導體晶片時所使用之切割用黏著膠帶,其中,前述半導體材料具有經被覆材所被覆之複數之半導體元件,前述黏著劑層係由黏著劑組成物所構成,該黏著劑組成物包含:混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂、作為對於該矽氧系樹脂之交聯劑、作為熱聚合起始劑之過氧化物,及光感應鉑(Pt)觸媒;該交聯劑為1分子中具有至少2個以上之矽原子鍵結氫原子(SiH基)之有機聚矽氧烷,前述矽氧系樹脂全體中之矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))在以質量比計為40.0/60.0~56.0/44.0之範圍,前述矽氧膠(G)包含:由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk ),且前述矽氧系樹脂全體中之前述矽原子鍵結烯基之含量為7.0×10-7 mol/g以上5.5×10-6 mol/g以下之範圍。 在此,其特徵係可作成複數之前述半導體元件係對於藉由前述被覆材所密封之前述半導體材料,從該被覆材側來貼附所使用者,且該被覆材係由矽氧樹脂所構成者。 又,其特徵係可作成前述黏著劑層中,該黏著劑組成物所含之前述交聯劑之前述矽原子鍵結氫原子(SiH基)之含量(總量)對前述黏著劑組成物所含之前述矽氧系樹脂全體中之前述矽原子鍵結烯基之含量(總量)的莫耳比率(SiH基/矽原子鍵結烯基)為2.0以上10.0以下之範圍。 又,其特徵係可作成前述黏著劑層中,相對於前述矽氧系樹脂全體之固體成分100質量份,前述黏著劑組成物中之前述過氧化物之含量在以固體成分計為0.10質量份以上3.00質量份以下之範圍。 又,其特徵係可作成前述黏著劑層之前述過氧化物為二醯基過氧化物類。 又,其特徵係可作成前述黏著劑層中,相對於前述矽氧系樹脂全體之固體成分100質量份,前述黏著劑組成物中之前述光感應鉑(Pt)觸媒之含量在以固體成分計為0.10質量份以上3.00質量份以下之範圍。 又,其特徵係可作成前述黏著劑層中,前述矽氧系樹脂全體中之前述矽原子鍵結烯基之含量為2.9×10-6 mol/g以上4.1×10-6 mol/g以下之範圍。 又,其特徵係可作成依據JIS Z 0237(2009)之黏著特性係全部滿足下述條件(a)~(c)。 (a)對於BA-SUS試驗板之光照射前之黏著力為2.8N/ 10mm以上5.5N/10mm以下之範圍。 (b)傾斜式滾球黏性試驗(ball tack test)(傾斜角30°,溫度23℃,相對濕度50%RH)中之球號(ball number)之值在將光照射前之球號之值設為BN0,將光照射後之球號之值設為BN1時,則為BN0>BN1之關係。 (c)光照射後之保持力試驗(溫度40℃,相對濕度33%RH,放置時間2880分)中,落下時之破壞現象為前述黏著劑層與BA-SUS試驗板之界面剝離,或,該保持力試驗中不會落下。The dicing adhesive tape of the present invention is characterized by having a substrate and an adhesive layer laminated on the substrate, and is used when a semiconductor material is divided into a plurality of semiconductor chips, wherein the semiconductor material has a plurality of semiconductor elements coated by a coating material, and the adhesive layer is composed of an adhesive composition, and the adhesive composition includes: a silicone resin mixed with a silicone glue (G) and a silicone resin (R), a crosslinking agent for the silicone resin, and a thermal polymerization agent. The initiator is a peroxide, and a photosensitive platinum (Pt) catalyst; the crosslinking agent is an organic polysiloxane having at least two silicon-atom-bonded hydrogen atoms (SiH groups) in one molecule; the mixing ratio ((G)/(R)) of the silicone glue (G) and the silicone resin (R) in the silicone resin as a whole is in the range of 40.0/60.0 to 56.0/44.0 in terms of mass ratio; the silicone glue (G) comprises: a silicone glue (G) composed of an organic polysiloxane containing a silicon-atom-bonded olefin group; alk ), and the content of the aforementioned silicon atom-bonded olefin groups in the aforementioned silicon-oxide resin as a whole is in the range of 7.0×10 -7 mol/g or more and 5.5×10 -6 mol/g or less. Here, it is characterized in that a plurality of the aforementioned semiconductor elements can be made to be attached to the aforementioned semiconductor material sealed by the aforementioned covering material from the side of the covering material, and the covering material is composed of silicon-oxide resin. Furthermore, the adhesive layer can be made such that the molar ratio (SiH group/silicon atom bonded olefin group) of the aforementioned crosslinking agent and the aforementioned silicon atom bonded hydrogen atom (SiH group) contained in the adhesive composition to the aforementioned silicon atom bonded olefin group content (total) in the aforementioned silicon-oxygen resin contained in the aforementioned adhesive composition is in the range of 2.0 to 10.0. Furthermore, the adhesive layer can be made such that the content of the aforementioned peroxide in the aforementioned adhesive composition is in the range of 0.10 to 3.00 parts by mass based on the solid content, relative to 100 parts by mass of the solid content of the aforementioned silicon-oxygen resin. Furthermore, the adhesive layer can be made such that the aforementioned peroxide is a diacyl peroxide. Furthermore, the adhesive layer can be made such that the content of the aforementioned photosensitive platinum (Pt) catalyst in the aforementioned adhesive composition is in the range of 0.10 mass parts to 3.00 mass parts in terms of solid content relative to 100 mass parts of the entire solid content of the aforementioned silicone resin. Furthermore, the adhesive layer can be made such that the content of the aforementioned silicon atom-bonded olefinic group in the entire silicone resin is in the range of 2.9×10 -6 mol/g to 4.1×10 -6 mol/g. In addition, the adhesive properties according to JIS Z 0237 (2009) can be made to meet the following conditions (a) to (c). (a) The adhesive force of the BA-SUS test plate before light irradiation is in the range of 2.8N/10mm to 5.5N/10mm. (b) In the ball tack test (tilt angle 30°, temperature 23°C, relative humidity 50%RH), the ball number value before light irradiation is set as BN0 and the ball number value after light irradiation is set as BN1, and the relationship of BN0>BN1 is achieved. (c) In the retention test after light irradiation (temperature 40°C, relative humidity 33%RH, placement time 2880 minutes), the damage phenomenon when falling is the interface between the above-mentioned adhesive layer and the BA-SUS test plate peeling off, or there is no falling in the retention test.

又,在採用其他觀點時,本發明所適用之半導體晶片之製造方法為一種半導體晶片之製造方法,其係包含,貼附步驟:其係對於由矽氧樹脂所構成之密封樹脂所密封之複數之前述半導體元件已形成於基板上之半導體元件基板,將上述之切割用黏著膠帶,從該密封樹脂側進行貼附;切割步驟:其係將已貼附前述切割用黏著膠帶之前述半導體元件基板切割成複數之半導體晶片;照射步驟:其係對前述半導體元件基板之前述切割用黏著膠帶照射光;及,剝離步驟:其係從前述複數之半導體晶片剝下前述切割用黏著膠帶。 [發明效果]Furthermore, when adopting other viewpoints, the manufacturing method of the semiconductor chip to which the present invention is applied is a manufacturing method of the semiconductor chip, which comprises, a bonding step: for a semiconductor element substrate on which a plurality of the aforementioned semiconductor elements are formed on a substrate and sealed by a sealing resin composed of a silicone resin, the above-mentioned dicing adhesive tape is bonded from the side of the sealing resin; a cutting step: for cutting the above-mentioned semiconductor element substrate to which the above-mentioned dicing adhesive tape is attached into a plurality of semiconductor chips; an irradiation step: for irradiating the above-mentioned dicing adhesive tape of the above-mentioned semiconductor element substrate with light; and a peeling step: for peeling the above-mentioned dicing adhesive tape from the above-mentioned plurality of semiconductor chips. [Effect of the invention]

根據本發明,可提供對於對於複數之半導體元件經被覆材所被覆之半導體材料,在光照射前之階段具有良好之黏著力及黏力,並且在光照射後將藉由切割而經個片化之半導體晶片予以剝離之情況,具有半導體晶片之良好拾取性,且同時對於半導體晶片之殘膠受到抑制之切割用黏著膠帶,及使用此之半導體晶片之製造方法。According to the present invention, there can be provided a semiconductor material coated with a coating material having good adhesion and tackiness before light irradiation, and having good pickup properties for semiconductor chips when peeling off individual semiconductor chips by dicing after light irradiation, and at the same time, an adhesive tape for dicing in which residual adhesive of the semiconductor chips is suppressed, and a method for manufacturing semiconductor chips using the same.

以下,參照附件圖式面來詳細說明關於本發明之實施形態。 [黏著膠帶之構成] 圖1為展示適用本實施形態之切割用黏著膠帶1(以下,單稱為黏著膠帶1)之構成一例的圖。本實施形態之黏著膠帶1為例如,LED(發光二極體)或功率半導體等之具有半導體元件之半導體晶片之製造步驟中,使用於切割成為半導體晶片之基礎之半導體材料。Hereinafter, the embodiment of the present invention will be described in detail with reference to the attached drawings. [Composition of Adhesive Tape] Figure 1 is a diagram showing an example of the composition of an adhesive tape 1 for cutting (hereinafter, simply referred to as adhesive tape 1) applicable to the present embodiment. The adhesive tape 1 of the present embodiment is a semiconductor material used as a basis for cutting into semiconductor chips in the manufacturing process of semiconductor chips having semiconductor elements such as LEDs (light emitting diodes) or power semiconductors.

如圖1所示,黏著膠帶1係具有在基材2上層合黏著劑層3之構成。 尚且,雖有省略圖示,但、黏著膠帶1在基材2與黏著劑層3之間因應必要亦可具備提高基材2與黏著劑層3之密著性用之錨塗層。又,基材2之表面(與黏著劑層3面對之面為相反側之面)上亦可施加表面處理。並且,黏著劑層3之表面(與基材2面對之面為相反側之面)亦可具備剝離襯墊(peeling liner)。As shown in FIG. 1 , the adhesive tape 1 has a structure in which an adhesive layer 3 is laminated on a substrate 2. Also, although not shown in the figure, the adhesive tape 1 may also have an anchor coating layer between the substrate 2 and the adhesive layer 3 to improve the adhesion between the substrate 2 and the adhesive layer 3 as necessary. In addition, a surface treatment may be applied to the surface of the substrate 2 (the surface opposite to the surface facing the adhesive layer 3). Furthermore, the surface of the adhesive layer 3 (the surface opposite to the surface facing the substrate 2) may also have a peeling liner.

<基材> 本實施形態之基材2係由會讓紫外線等之光穿透之材料所構成。作為基材2之材料,只要係紫外線等之光能穿透,即並未係受到特別限定者,可使用例如紫外線等之光能穿透之塑膠等。尚且,在此,紫外線等之光能穿透並非係意指紫外線等之光之穿透率為100%者,只要係至少藉由黏著劑層3所包含之後述之光感應鉑(Pt)觸媒而能促進矽氧系樹脂與交聯劑之加成反應之程度之光能夠穿透即可。<Substrate> The substrate 2 of this embodiment is made of a material that allows ultraviolet light to penetrate. The material of the substrate 2 is not particularly limited as long as it allows ultraviolet light to penetrate. For example, plastics that allow ultraviolet light to penetrate can be used. Moreover, here, the ability of ultraviolet light to penetrate does not mean that the transmittance of ultraviolet light is 100%, as long as the light can penetrate to the extent that the addition reaction between the silicone resin and the crosslinking agent can be promoted by the photosensitive platinum (Pt) catalyst described later contained in the adhesive layer 3.

作為基材2之材料,具體地可使用如聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚苯硫醚、雙軸延伸聚丙烯、脂肪族聚醯亞胺(透明性聚醯亞胺)、聚環烯烴、氟系樹脂、聚烯烴樹脂等之樹脂膜。又,因應用途,基材2也可使用例如,層合聚對酞酸乙二酯與聚烯烴樹脂膜而成之複合膜、及該等複合膜再與樹脂膜層合而成之複合膜、使用共擠出而作成複數層之樹脂膜等。 其中,作為基材2,以使用將聚對酞酸乙二酯作為主成分之材料為佳。As the material of the substrate 2, specifically, resin films such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxially oriented polypropylene, aliphatic polyimide (transparent polyimide), polycycloolefin, fluorine resin, polyolefin resin, etc. can be used. In addition, depending on the application, the substrate 2 can also use, for example, a composite film formed by laminating polyethylene terephthalate and polyolefin resin films, a composite film formed by laminating these composite films with resin films, a resin film made of multiple layers by co-extrusion, etc. Among them, as the substrate 2, it is preferable to use a material having polyethylene terephthalate as the main component.

<黏著劑層> 本實施形態之黏著劑層3係由黏著劑組成物所構成,該黏著劑組成物含有:混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂、1分子中具有至少2個以上之矽原子鍵結氫原子(SiH基)之對矽氧系樹脂之交聯劑、作為熱聚合起始劑之過氧化物,及光感應鉑(Pt)觸媒。 矽氧系樹脂係由混合樹脂所構成,該混合樹脂係以指定比率來摻合「包含由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )之矽氧膠(G)」,與「由有機聚矽氧烷所構成之矽氧樹脂(R)」者。以下,依序說明關於構成黏著劑層3之黏著劑組成物所包含之各成分。<Adhesive layer> The adhesive layer 3 of the present embodiment is composed of an adhesive composition, which contains: a silicone resin mixed with a silicone gel (G) and a silicone resin (R), a crosslinking agent for the silicone resin having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule, a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst. The silicone resin is composed of a mixed resin in which "silicone glue (G) composed of an organic polysiloxane containing an olefinic group bonded to a silicon atom (G alk )" and "silicone resin (R) composed of an organic polysiloxane" are mixed at a specified ratio. The following describes the components of the adhesive composition constituting the adhesive layer 3 in order.

(矽氧系樹脂) 本實施形態之矽氧系樹脂係由混合樹脂所構成,該混合樹脂係將「包含由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )之矽氧膠(G)」,與「由有機聚矽氧烷所構成之矽氧樹脂(R)」,以成為40.0/60.0~56.0/44.0之範圍之方式來摻合者。即,由矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))在以質量比計係以成為40.0/60.0~ 56.0/44.0之範圍之方式來摻合的混合樹脂所構成。 又,矽氧系樹脂係以矽氧系樹脂全體中之矽原子鍵結烯基之含量成為7.0×10-7 mol/g以上5.5×10-6 mol/g以下之範圍之方式來構成,較佳係以成為2.9×10-6 mol/g以上4.1× 10-5 mol/g以下之範圍之方式來構成。在此「mol/g」係意指「矽氧系樹脂全體之固體成分每1g之物質量」。(Silicone-based resin) The silicone-based resin of the present embodiment is composed of a mixed resin, wherein "silicone gel ( G ) composed of an organic polysiloxane containing alkenyl groups bonded to silicon atoms" and "silicone resin (R) composed of an organic polysiloxane" are mixed in a ratio ranging from 40.0/60.0 to 56.0/44.0. That is, the mixed resin is composed of a silicone gel (G) and a silicone resin (R) in a mixing ratio ((G)/(R)) in the range of 40.0/60.0 to 56.0/44.0 in terms of mass ratio. Furthermore, the silicone resin is composed in a manner that the content of silicon atom-bonded olefin groups in the entire silicone resin is in the range of 7.0× 10-7 mol/g to 5.5× 10-6 mol/g, preferably in the range of 2.9× 10-6 mol/g to 4.1× 10-5 mol/g. Here, "mol/g" means "the mass per 1g of the solid component of the entire silicone resin".

矽氧系樹脂全體中之矽原子鍵結烯基之含量若未滿7.0×10-7 mol/g,對黏著膠帶1照射紫外線等之光時,由矽氧膠所具有之矽原子鍵結烯基與交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之第2階段之交聯反應(加成反應)所成之交聯密度之提升會變得不充分,黏著劑變得難以硬化,且凝聚力變得不易提升。於此情況,無法取得所欲之黏力低下或保持力試驗中之破壞模式,在將黏著膠帶1使用於半導體元件基板等之切割後,在將取得之半導體晶片等從黏著膠帶1剝離之際,有經個片化之半導體晶片之拾取性變差之憂慮,或有半導體晶片等變得容易產生殘膠的憂慮。 另一方面,矽氧系樹脂全體中之矽原子鍵結烯基之含量若超過5.5×10-6 mol/g,在構成黏著劑層3之黏著劑組成物之矽氧系樹脂中矽氧膠(G)之混合比率為高時,根據熱聚合起始劑之種類或含量不同,則有在紫外線等之光照射前之階段下,矽氧系樹脂之硬化(第1階段之交聯反應)因熱聚合起始劑而過度進行,而黏著劑層3變得過硬的情況。於此情況,若將黏著膠帶1使用於半導體元件基板等之切割,在裁切半導體元件基板等時,則有裁切片之半導體晶片等從黏著膠帶1剝離後變得容易飛散之憂慮。If the content of silicon-bonded olefin groups in the entire silicone resin is less than 7.0×10 -7 mol/g, when the adhesive tape 1 is irradiated with ultraviolet light or the like, the increase in crosslinking density caused by the second-stage crosslinking reaction (addition reaction) between silicon-bonded olefin groups of the silicone adhesive and silicon-bonded hydrogen atoms (SiH groups) of the crosslinking agent will become insufficient, and the adhesive will be difficult to harden and the cohesive force will be difficult to increase. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. When the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become prone to residual adhesive. On the other hand, if the content of silicon atom-bonded alkenyl groups in the entire silicone resin exceeds 5.5×10 -6 mol/g, when the mixing ratio of silicone glue (G) in the silicone resin constituting the adhesive composition of the adhesive layer 3 is high, depending on the type or content of the thermal polymerization initiator, the curing of the silicone resin (the first stage cross-linking reaction) may proceed excessively due to the thermal polymerization initiator at the stage before irradiation with ultraviolet rays or the like, and the adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for cutting semiconductor device substrates, when cutting the semiconductor device substrates, there is a concern that the semiconductor chips of the cut pieces may be easily scattered after being peeled off from the adhesive tape 1.

矽氧系樹脂全體中之矽原子鍵結烯基之含量係可藉由進行相對於矽氧系樹脂不揮發成分之1 H-NMR(核磁共振)光譜測量,並求出烯基之共振訊號面積(積分值)來算出。詳細則如後述。The content of silicon-atom-bonded alkenyl groups in the entire silicone resin can be calculated by measuring the 1 H-NMR (nuclear magnetic resonance) spectrum relative to the non-volatile components of the silicone resin and finding the resonance signal area (integral value) of the alkenyl groups. The details are described below.

尚且,本實施形態之矽氧系樹脂只要「矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))」及「矽原子鍵結烯基之含量」在上述範圍內,亦可包含:由不含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(G0 )。即,矽氧膠(G)可為「由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )」之單獨物或該等2種以上之混合物,也可為「由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )」與「由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )」之混合物或該等2種以上之混合物。Furthermore, the silicone resin of the present embodiment may also include silicone gel (G 0 ) composed of an organic polysiloxane containing no silicon atom-bonded olefinic group, as long as the "mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin ( R )" and the "content of silicon atom-bonded olefinic group" are within the above ranges. That is, the silicone gel (G) may be a single "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G alk )" or a mixture of two or more thereof, or a mixture of a "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G alk )" and a "silicone gel composed of an organic polysiloxane not containing an alkenyl group bonded to a silicon atom (G 0 )" or a mixture of two or more thereof.

以下,更加詳細說明關於矽氧系樹脂所包含之「由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )」、「由不含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(G0 )」與「由不含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧樹脂(R)」。 尚且,在以下之說明中,有將由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )記載成含有矽原子鍵結烯基之矽氧膠(Galk ),或單純記載成矽氧膠(Galk )的情況。同樣地有將由不含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(G0 )記載成不含有矽原子鍵結烯基之矽氧膠(G0 ),或單純記載成矽氧膠(G0 )的情況。並且,有將由有機聚矽氧烷所構成之矽氧樹脂(R)單純記載成矽氧樹脂(R)的情況。The following is a more detailed description of the silicone resins including "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G alk )", "silicone gel composed of an organic polysiloxane not containing an alkenyl group bonded to a silicon atom (G 0 )", and "silicone resin (R) composed of an organic polysiloxane not containing an alkenyl group bonded to a silicon atom". Furthermore, in the following description, silicone gel (G alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group may be described as silicone gel containing a silicon atom-bonded alkenyl group (G alk ) or simply as silicone gel (G alk ). Similarly, silicone gel (G 0 ) composed of an organic polysiloxane not containing a silicon atom-bonded alkenyl group may be described as silicone gel not containing a silicon atom-bonded alkenyl group (G 0 ) or simply as silicone gel (G 0 ). Furthermore, there are cases where a silicone resin (R) composed of an organic polysiloxane is simply described as a silicone resin (R).

(由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )) 本實施形態中之由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )只要係一般使用作為加成反應型矽氧系樹脂者,即,平均1分子中含有至少2個矽原子鍵結烯基者即可,而並非矽受到特別限定者。 具體而言,作為矽氧膠(Galk ),可使用矽原子鍵結烯基之含量在1.0×10-6 mol/g以上1.0×10-1 mol/g以下之範圍者。本實施形態中,從控制黏著劑層3之黏著特性,或使用市售品時之取得容易度之觀點,以使用矽原子鍵結烯基之含量為1.7×10-6 mol/g以上1.0×10-2 mol/g以下之範圍者為佳。該矽氧膠(Galk )係以上述之混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂全體中之烯基之含量成為7.0×10-7 mol/g以上5.5×10-6 mol/g以下之範圍之方式,而可單獨使用1種,亦可併用2種以上。(Silicon oxide gel (G alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group) The silicone oxide gel (G alk ) composed of an organic polysiloxane containing a silicon atom-bonded alkenyl group in this embodiment can be any silicone oxide resin generally used as an addition reaction type silicone resin, that is, any silicone oxide resin containing at least two silicon atom-bonded alkenyl groups in an average of one molecule, and the silicone oxide is not particularly limited. Specifically, the silicone oxide gel (G alk ) can contain a silicon atom-bonded alkenyl group content in the range of 1.0×10 -6 mol/g or more and 1.0×10 -1 mol/g or less. In this embodiment, from the viewpoint of controlling the adhesive properties of the adhesive layer 3 or the ease of obtaining when using commercial products, it is preferred to use a silicon atom-bonded olefinic group content in the range of 1.7× 10-6 mol/g or more and 1.0× 10-2 mol/g or less. The silicone gel (G alk ) is such that the olefinic group content in the silicone resin as a whole, which is a mixture of the silicone gel (G) and the silicone resin (R), is in the range of 7.0× 10-7 mol/g or more and 5.5× 10-6 mol/g or less. One type may be used alone or two or more types may be used in combination.

作為構成矽氧膠(Galk )之含有矽原子鍵結烯基之有機聚矽氧烷之分子構造,可舉出例如,主鏈部分係由二有機矽氧烷單位之重複所構成之直鏈狀構造、該分子構造之一部分包含分支鏈之構造、分支鏈狀構造,或環狀體構造。其中,從紫外線等之光照射後之黏著劑之機械強度及物性等之觀點,以直鏈狀構造之有機聚矽氧烷為佳。As the molecular structure of the organic polysiloxane containing silicon atoms bonded to alkenyl groups constituting silicone gel ( Galk ), for example, a straight chain structure consisting of a main chain portion composed of repeated two organic siloxane units, a structure in which a part of the molecular structure includes a branched chain structure, a branched chain structure, or a ring structure can be cited. Among them, from the perspective of the mechanical strength and physical properties of the adhesive after irradiation with ultraviolet light, etc., the organic polysiloxane with a straight chain structure is preferred.

由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )可為油狀或生橡膠狀之任一者,以生橡膠狀為佳。在油狀之情況,由有機聚矽氧烷所構成之矽氧膠(Galk )之黏度在25℃下,以1,000mPa・s以上為佳。黏度若未滿1,000mPa・s,則有紫外線等之光照射前後之黏著劑無法展現所欲之黏著特性的憂慮,或黏著劑層3與基材2之密著性變差的憂慮。在生橡膠狀之情況,使由有機聚矽氧烷所構成之矽氧膠(Galk )成為30質量%濃度之方式以甲苯來溶解時之黏度在25℃下,以100,000mPa・s以下為佳。黏度若超過100,000mPa・s,則有調製黏著劑組成物時之攪拌變得困難的憂慮。尚且,由有機聚矽氧烷所構成之矽氧膠(Galk )之黏度係能以B型旋轉黏度計(使用BM型轉子,以下相同)來測量。Silicone glue (G alk ) composed of organopolysiloxane containing silicon atoms bonded to alkenyl groups can be either oily or rubbery, with the rubbery form being preferred. In the case of oily form, the viscosity of silicone glue (G alk ) composed of organopolysiloxane is preferably 1,000 mPa·s or more at 25°C. If the viscosity is less than 1,000 mPa·s, there is a concern that the adhesive before and after irradiation with ultraviolet light or the like may not exhibit the desired adhesive properties, or that the adhesion between the adhesive layer 3 and the substrate 2 may deteriorate. In the case of raw rubber, the viscosity of silicone gel (G alk ) composed of organic polysiloxane is preferably 100,000 mPa・s or less at 25°C when dissolved in toluene at a concentration of 30 mass%. If the viscosity exceeds 100,000 mPa・s, stirring may become difficult when preparing the adhesive composition. In addition, the viscosity of silicone gel (G alk ) composed of organic polysiloxane can be measured with a B-type rotational viscometer (using a BM-type rotor, the same below).

由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )係可舉出例如,下述一般式(1)或一般式(2)所示者,但並非係受到該等所限定者。Silicone gel ( Galk ) composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom may be represented by the following general formula (1) or general formula (2), but is not limited thereto.

在此,上述一般式(1)、一般式(2)中,R1 係互相獨立為不具有脂肪族不飽和鍵之1價烴基,X為含烯基之有機基。a為0~3之整數,m為0以上之整數,n為100以上之整數,但a與m不會同時為0,只有a為0時,m為2以上之整數。m+n為上述由有機聚矽氧烷所構成之矽氧膠(Galk )在25℃之黏度會成為1,000mPa・s以上之值。Here, in the above general formula (1) and general formula (2), R1 is independently a monovalent hydrocarbon group without an aliphatic unsaturated bond, and X is an organic group containing an alkenyl group. a is an integer of 0 to 3, m is an integer greater than 0, and n is an integer greater than 100, but a and m are not both 0, and only when a is 0, m is an integer greater than 2. m+n is a value at which the viscosity of the silicone gel ( Galk ) composed of the above organic polysiloxane at 25°C becomes 1,000 mPa・s or more.

作為R1 ,以碳數1~10,較佳為碳數1~7之不具有脂肪族不飽和鍵之1價烴基為佳。可舉出例如,甲基、乙基、丙基、及丁基等之烷基;環己基等之環烷基;及苯基、及甲苯基等之芳基等,尤其係以甲基或苯基為佳。R 1 is preferably a monovalent alkyl group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and having no aliphatic unsaturated bond. Examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl. Methyl or phenyl is particularly preferred.

作為X,以碳數2~10之含烯基之有機基為佳。可舉出例如,乙烯基、烯丙基、己烯基、辛烯基、丙烯醯基丙基、丙烯醯基甲基、甲基丙烯醯基丙基、丙烯醯氧基丙基、丙烯醯氧基甲基、甲基丙烯醯氧基丙基、甲基丙烯醯氧基甲基、環己烯基乙基、及乙烯氧基丙基等。其中亦以乙烯基、烯丙基等之低級烯基為佳,從工業性觀點,尤其係以乙烯基為佳。烯基之鍵結位置並無特別限定,可在分子鏈末端、分子鏈側鏈或分子鏈末端與分子鏈側鏈雙方。X is preferably an organic group containing an alkenyl group having 2 to 10 carbon atoms. Examples thereof include vinyl, allyl, hexenyl, octenyl, acrylylpropyl, acrylylmethyl, methacrylpropyl, acryloxypropyl, acryloxymethyl, methacryloxypropyl, methacryloxymethyl, cyclohexenylethyl, and vinyloxypropyl. Among them, lower alkenyl groups such as vinyl and allyl are preferred, and vinyl is particularly preferred from an industrial point of view. The bonding position of the alkenyl group is not particularly limited, and may be at the molecular chain end, the molecular chain side chain, or both the molecular chain end and the molecular chain side chain.

烯基之數係根據矽氧系黏著劑所含之由有機聚矽氧烷所構成之矽氧樹脂(R)之含量、交聯劑之種類・添加量,與其他之添加成分之平衡等,而適當範圍會改變,故無法一概而論,例如,相對於有機聚矽氧烷之有機基100個,通常係以0.1個以上3.0個以下之範圍為佳。且,以在該比率之範圍內,以成為上述黏度範圍之方式來調整分子量,並以有機聚矽氧烷平均1分子中之上述烯基之數成為至少2個之方式來進行調整為佳。烯基之數在相對於有機聚矽氧烷之有機基100個,若未滿0.1個,則在對黏著膠帶1照射紫外線等之光時,利用矽氧膠(Galk )所具有之矽原子鍵結烯基,與對矽氧系樹脂之交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之第2階段之交聯反應(加成反應)而得之交聯密度之提升會變得不充分,黏著劑變得難以硬化,且凝聚力變得不易提升。於此情況,無法取得所欲之黏力低下或保持力試驗中之破壞模式,在將黏著膠帶1使用於半導體元件基板等之切割後,在將取得之半導體晶片等從黏著膠帶1剝離之際,有經個片化之半導體晶片之拾取性變差之憂慮,或有半導體晶片等變得容易產生殘膠的憂慮。另一方面,烯基之數在相對於有機聚矽氧烷之有機基100個,若超過3.0個,在構成黏著劑層3之黏著劑組成物之矽氧系樹脂中矽氧膠(G)之混合比率為高時,根據熱聚合起始劑之種類或含量不同,則有在紫外線等之光照射前之階段下,矽氧系樹脂之硬化(第1階段之交聯反應)因熱聚合起始劑而過度進行,而黏著劑層3變得過硬的情況。於此情況,若將黏著膠帶1使用於半導體元件基板等之切割,在裁切半導體元件基板等時,則有裁切片之半導體晶片等從黏著膠帶1剝離後變得容易飛散之憂慮。The number of alkenyl groups varies depending on the content of silicone resin (R) composed of organopolysiloxane contained in the silicone adhesive, the type and amount of crosslinking agent, and the balance of other additives, so it is impossible to generalize. For example, it is usually preferably in the range of 0.1 to 3.0 relative to 100 organic groups of organopolysiloxane. And, within the range of this ratio, the molecular weight is adjusted in a manner to achieve the above-mentioned viscosity range, and it is preferably adjusted in a manner that the number of alkenyl groups in an average molecule of organopolysiloxane is at least 2. If the number of alkenyl groups is less than 0.1 relative to 100 organic groups of the organopolysiloxane, when the adhesive tape 1 is irradiated with ultraviolet light or the like, the increase in crosslinking density obtained by the second-stage crosslinking reaction (addition reaction) between the alkenyl groups bonded to silicon atoms of the silicone glue ( Galk ) and the hydrogen atoms (SiH groups) bonded to silicon atoms of the crosslinking agent of the silicone resin will become insufficient, and the adhesive will be difficult to harden and the cohesive force will be difficult to increase. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. When the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become prone to residual adhesive. On the other hand, if the number of alkenyl groups exceeds 3.0 with respect to 100 organic groups of the organopolysiloxane, when the mixing ratio of the silicone glue (G) in the silicone resin constituting the adhesive composition of the adhesive layer 3 is high, depending on the type or content of the thermal polymerization initiator, the curing (first stage cross-linking reaction) of the silicone resin may proceed excessively due to the thermal polymerization initiator at the stage before irradiation with ultraviolet light or the like, and the adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for cutting semiconductor device substrates, when cutting the semiconductor device substrates, there is a concern that the semiconductor chips of the cut pieces may be easily scattered after being peeled off from the adhesive tape 1.

作為此種含有矽原子鍵結烯基之矽氧膠(Galk )之具體例,可舉出如分子鏈兩末端經二甲基乙烯基矽氧基封鏈之二甲基聚矽氧烷、分子鏈兩末端經二甲基乙烯基矽氧基封鏈之二甲基矽氧烷・甲基乙烯基矽氧烷共聚物、分子鏈兩末端經二甲基乙烯基矽氧基封鏈之二甲基矽氧烷・甲基苯基矽氧烷共聚物、分子鏈兩末端經二甲基乙烯基矽氧基封鏈之甲基苯基聚矽氧烷、分子鏈兩末端經三甲基矽氧基封鏈之二甲基矽氧烷・甲基乙烯基矽氧烷共聚物、分子鏈兩末端經三甲基矽氧基封鏈之二甲基矽氧烷・甲基乙烯基矽氧烷・甲基苯基矽氧烷共聚物、分子鏈兩末端經三甲基矽氧基封鏈之二甲基矽氧烷・甲基己烯基矽氧烷共聚物、分子鏈兩末端經二甲基乙烯基矽氧基封鏈之二甲基矽氧烷・甲基己烯基矽氧烷共聚物、分子鏈兩末端經二甲基己烯基矽氧基封鏈之二甲基矽氧烷・甲基己烯基矽氧烷共聚物等。Specific examples of such silicone gels containing alkenyl groups bonded to silicon atoms include dimethyl polysiloxane having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, dimethyl siloxane-methyl vinyl siloxane copolymer having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, dimethyl siloxane-methyl phenyl siloxane copolymer having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, methyl phenyl polysiloxane having dimethylvinylsiloxy groups chain-blocked at both ends of the molecular chain, dimethyl siloxane-methyl vinyl siloxane copolymer having trimethyl siloxy groups chain-blocked at both ends of the molecular chain, and dimethyl siloxane-methyl phenyl siloxane copolymer having trimethyl siloxy groups chain-blocked at both ends of the molecular chain. Vinyl siloxane copolymer, dimethylsiloxane, methylvinylsiloxane, methylphenylsiloxane copolymer with trimethylsiloxy groups chain-blocked at both ends of the molecular chain, dimethylsiloxane, methylhexenylsiloxane copolymer with trimethylsiloxy groups chain-blocked at both ends of the molecular chain, dimethylsiloxane, methylhexenylsiloxane copolymer with dimethylvinylsiloxane groups chain-blocked at both ends of the molecular chain, dimethylsiloxane, methylhexenylsiloxane copolymer with dimethylhexenylsiloxane groups chain-blocked at both ends of the molecular chain, etc.

(由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )) 本實施形態中之由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )只要係一般使用作為過氧化物硬化型矽氧系樹脂者,即,不含有矽原子鍵結烯基者即可,並非係受到特別限定者。 作為此種構成矽氧膠(G0 )之有機聚矽氧烷之分子構造,可舉出例如,主鏈部分係由二有機矽氧烷單位之重複所構成之直鏈狀構造、該分子構造之一部分包含分支鏈之構造、分支鏈狀構造、或環狀體構造。(Silicone gel (G 0 ) composed of an organic polysiloxane containing no silicon atom-bonded alkenyl group) The silicone gel (G 0 ) composed of an organic polysiloxane containing no silicon atom-bonded alkenyl group in the present embodiment is not particularly limited as long as it is generally used as a peroxide-curable silicone resin, that is, it does not contain a silicon atom-bonded alkenyl group. Examples of the molecular structure of the organic polysiloxane constituting the silicone gel (G 0 ) include a straight chain structure in which the main chain portion is composed of repeated two organic polysiloxane units, a structure in which a part of the molecular structure includes a branched chain structure, a branched chain structure, or a ring structure.

由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )可為油狀或生橡膠狀之任一者,以生橡膠狀為佳。在油狀之情況,由有機聚矽氧烷所構成之矽氧膠(G0 )之黏度在25℃下,以1,000mPa・s以上為佳。黏度若未滿1,000mPa・s,則有在紫外線等之光照射前後之黏著劑無法展現所欲黏著特性之憂慮,或有黏著劑層3與基材2之密著性變差的憂慮。再生橡膠狀之情況,使由有機聚矽氧烷所構成之矽氧膠(G0 )成為30質量%濃度之方式以甲苯溶解時之黏度在25℃下,以100,000mPa・s以下為佳。黏度若超過100,000mPa・s,則有調製黏著劑組成物時之攪拌變得困難的憂慮。尚且,由有機聚矽氧烷所構成之矽氧膠(G0 )之黏度係能使用B型旋轉黏度計來測量。The silicone glue (G 0 ) composed of the organopolysiloxane containing no silicon atom-bonded alkenyl group may be either oily or rubbery, with the rubbery being preferred. In the case of oily state, the viscosity of the silicone glue (G 0 ) composed of the organopolysiloxane is preferably 1,000 mPa·s or more at 25°C. If the viscosity is less than 1,000 mPa·s, there is a concern that the adhesive may not exhibit the desired adhesive properties before and after irradiation with ultraviolet light or the adhesion between the adhesive layer 3 and the substrate 2 may deteriorate. In the case of recycled rubber, the viscosity of silicone rubber (G 0 ) composed of organic polysiloxane at 30 mass% concentration when dissolved in toluene is preferably 100,000 mPa·s or less at 25°C. If the viscosity exceeds 100,000 mPa·s, stirring may become difficult when preparing the adhesive composition. In addition, the viscosity of silicone rubber (G 0 ) composed of organic polysiloxane can be measured using a B-type rotational viscometer.

由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )係可舉出例如,下述一般式(3)或一般式(4)所示者,但並非係受到該等所限定者。The silicone gel (G 0 ) composed of an organic polysiloxane having no silicon atom-bonded alkenyl group may be, for example, one represented by the following general formula (3) or general formula (4), but is not limited thereto.

在此,上述一般式(3)、一般式(4)中,R4 係互相獨立為不具有脂肪族不飽和鍵之1價烴基,t為100以上之整數,且係由上述二有機聚矽氧烷所構成之矽氧膠(G0 )在25℃之黏度成為1,000mPa・s以上之值。Here, in the general formula (3) and the general formula (4), R 4 is independently a monovalent hydrocarbon group having no aliphatic unsaturated bond, t is an integer greater than 100, and the viscosity of the silicone gel (G 0 ) composed of the two organopolysiloxanes is greater than 1,000 mPa·s at 25°C.

作為R4 ,以碳數1~10,較佳為碳數1~7之不具有脂肪族不飽和鍵之1價烴基為佳。可舉出例如,甲基、乙基、丙基、及丁基等之烷基;環己基等之環烷基;及苯基、及甲苯基等之芳基等,尤其係以甲基為佳。R 4 is preferably a monovalent alkyl group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and having no aliphatic unsaturated bond. Examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl. Methyl is particularly preferred.

(由有機聚矽氧烷所構成之矽氧樹脂(R)) 本實施形態中之由有機聚矽氧烷所構成之矽氧樹脂(R)為具有R2 3 SiO0.5 單位(M單位)及SiO2 單位(Q單位)之有機聚矽氧烷,一般矽氧系黏著劑所使用之所謂稱為MQ樹脂者。該由有機聚矽氧烷所構成之矽氧樹脂(R)係基本上在分子內不具有烯基,且係可使用以往公知者。R2 為碳數1~10之1價烴基,可舉出如作為上述之R1 所例示者。構成矽氧樹脂(R)之有機聚矽氧烷係以R2 3 SiO0.5 單位/SiO2 單位之莫耳比成為0.5以上1.7以下之範圍來含有R2 3 SiO0.5 單位及SiO2 單位為佳。R2 3 SiO0.5 單位/SiO2 單位之莫耳比若未滿0.5,則有取得之黏著劑層3之黏著力或黏力降低的情況。另一方面,R2 3 SiO0.5 單位/SiO2 單位之莫耳比若超過1.7,則有取得之黏著劑層3之黏著力或保持力降低的情況。尚且,構成矽氧樹脂(R)之有機聚矽氧烷亦可具有OH基。於此情況,相對於有機聚矽氧烷之總質量,OH基之含量係以4.0質量%以下為佳。OH基之含量若超過4.0質量%,則有黏著劑之硬化性降低的憂慮。(Silicone resin (R) composed of organopolysiloxane) The silicone resin (R) composed of organopolysiloxane in this embodiment is an organopolysiloxane having R 2 3 SiO 0.5 units (M units) and SiO 2 units (Q units), and is generally a so-called MQ resin used in silicone adhesives. The silicone resin (R) composed of organopolysiloxane basically does not have an alkenyl group in the molecule, and a conventionally known one can be used. R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include those exemplified as R 1 above. The organopolysiloxane constituting the silicone resin (R) preferably contains R 2 3 SiO 0.5 units and SiO 2 units in a molar ratio of R 2 3 SiO 0.5 units/SiO 2 units of 0.5 to 1.7. If the molar ratio of R 2 3 SiO 0.5 units/SiO 2 units is less than 0.5, the adhesion or adhesive force of the obtained adhesive layer 3 may be reduced. On the other hand, if the molar ratio of R 2 3 SiO 0.5 units/SiO 2 units exceeds 1.7, the adhesion or retention of the obtained adhesive layer 3 may be reduced. Furthermore, the organopolysiloxane constituting the silicone resin (R) may also have an OH group. In this case, the OH group content is preferably 4.0 mass % or less relative to the total mass of the organopolysiloxane. If the OH group content exceeds 4.0 mass %, there is a concern that the curability of the adhesive may be reduced.

上述有機聚矽氧烷係亦可併用2種以上。又,上述有機聚矽氧烷在不損及本發明之特性範圍內,亦可具有R2 SiO1.5 單位(T單位)及/或R2 2 SiO單位(D單位)。The above-mentioned organopolysiloxane may be used in combination of two or more kinds. Furthermore, the above-mentioned organopolysiloxane may have R 2 SiO 1.5 units (T units) and/or R 2 2 SiO units (D units) within a range not impairing the properties of the present invention.

「由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )」與「由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )」與「由有機聚矽氧烷所構成之矽氧樹脂(R)」通常係單純地混合使用即可。又,在含有上述一般式(2)所示之有機聚矽氧烷作為由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk )的情況,或,在含有上述一般式(4)所示之有機聚矽氧烷作為由不含有矽原子鍵結烯基之有機聚矽氧烷所構成矽氧膠(G0 )的情況,只要不損及本發明之特性,也可使用作為預先使矽氧膠(Galk )與矽氧樹脂(R),或使矽氧膠(G0 )與矽氧樹脂(R)進行反應而得之(部分)縮合反應物。Usually, "silicone gel composed of an organic polysiloxane containing an alkenyl group bonded to a silicon atom (G alk )", "silicone gel composed of an organic polysiloxane containing no alkenyl group bonded to a silicon atom (G 0 )", and "silicone resin composed of an organic polysiloxane (R)" can be simply mixed for use. Furthermore, when the organopolysiloxane represented by the general formula (2) is contained as a silicone gel (G alk ) composed of an organopolysiloxane containing an alkenyl group bonded to a silicon atom, or when the organopolysiloxane represented by the general formula (4) is contained as a silicone gel (G 0 ) composed of an organopolysiloxane containing no alkenyl group bonded to a silicon atom, as long as the characteristics of the present invention are not impaired, the silicone gel (G alk ) may be used as a (partial) condensation reaction product obtained by reacting the silicone gel (G alk ) with the silicone resin (R) or reacting the silicone gel (G 0 ) with the silicone resin (R) in advance.

(矽氧系樹脂全體中之矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))) 本實施形態之黏著劑層3所含之矽氧系樹脂全體中,矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))在以質量比計為40.0/60.0~56.0/44.0之範圍。在此,併用2種以上之矽氧膠(G)時,將各自之矽氧膠(G)之合計量視為矽氧系樹脂全體中之矽氧膠(G)之質量。例如,在併用矽氧膠(Galk )與矽氧膠(G0 )作為矽氧膠(G)時,矽氧系樹脂全體中之矽氧膠(G)之質量為矽氧膠(Galk )之質量與矽氧膠(G0 )之質量之合計量。同樣地,在併用2種以上之矽氧樹脂(R)時,也將各自之矽氧樹脂之合計量視為矽氧系樹脂全體中之矽氧樹脂(R)之質量。(Mixture ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) in the whole silicone resin) In the whole silicone resin contained in the adhesive layer 3 of the present embodiment, the mixture ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) is in the range of 40.0/60.0 to 56.0/44.0 in terms of mass ratio. Here, when two or more silicone glues (G) are used in combination, the total amount of the respective silicone glues (G) is regarded as the mass of the silicone glue (G) in the whole silicone resin. For example, when silicone glue (G alk ) and silicone glue (G 0 ) are used together as silicone glue (G), the mass of silicone glue (G) in the entire silicone resin is the sum of the mass of silicone glue (G alk ) and the mass of silicone glue (G 0 ). Similarly, when two or more silicone resins (R) are used together, the sum of the respective silicone resins is also regarded as the mass of silicone resin (R) in the entire silicone resin.

本實施形態之黏著劑層3所含之矽氧系樹脂全體中,矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))若未滿上述範圍之下限值,對黏著膠帶1照射紫外線等之光之際,利用矽氧膠(G)所具有之矽原子鍵結烯基與對於矽氧系樹脂之交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之第2階段之交聯反應(加成反應)而得之交聯密度之提升之賦予則變得不充分,黏著劑變得難以硬化,且凝聚力變得不易提升。於此情況,無法取得所欲之黏力低下或保持力試驗中之破壞模式,在將黏著膠帶1使用於半導體元件基板等之切割後,在將取得之半導體晶片等從黏著膠帶1剝離之際,有經個片化之半導體晶片之拾取性變差之憂慮,或有半導體晶片等變得容易產生殘膠的憂慮。If the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) in the silicone resin contained in the adhesive layer 3 of the present embodiment is less than the lower limit of the above range, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the crosslinking density obtained by the second-stage crosslinking reaction (addition reaction) between the silicon atom-bonded olefin groups of the silicone gel (G) and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent for the silicone resin is insufficiently imparted, and the adhesive becomes difficult to harden and the cohesive force becomes difficult to improve. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. When the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become prone to residual adhesive.

另一方面,本實施形態之黏著劑層3所含之矽氧系樹脂全體中,矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))若超過上述範圍之上限值,在紫外線等之光照射前之階段,則有矽氧系樹脂之硬化(第1階段之交聯反應)因熱聚合起始劑而過度進行,黏著劑層3變得過硬的情況。於此情況,若將黏著膠帶1使用於半導體元件基板等之切割,在裁切半導體元件基板等時,則有裁切片之半導體晶片等從黏著膠帶1剝離後變得容易飛散之憂慮。On the other hand, if the mixing ratio ((G)/(R)) of the silicone resin (G) and the silicone resin (R) in the entire silicone resin contained in the adhesive layer 3 of the present embodiment exceeds the upper limit of the above range, the curing of the silicone resin (the first stage crosslinking reaction) may excessively proceed due to the thermal polymerization initiator before irradiation with ultraviolet light, and the adhesive layer 3 may become too hard. In this case, if the adhesive tape 1 is used for cutting semiconductor device substrates, when cutting the semiconductor device substrates, there is a concern that the cut semiconductor chips may be easily scattered after being peeled off from the adhesive tape 1.

相對於此,本實施形態之黏著劑層3所含之矽氧系樹脂全體中,藉由將矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))作成在上述40.0/60.0~56.0/44.0之範圍,即能實現以下之效果。即,在紫外線等之光照射前之階段,由於黏著劑層3會因熱聚合起始劑而矽氧系樹脂之一部成為經交聯・硬化(第1階段交聯反應)之狀態,故變得能對黏著劑層3賦予在切割時裁切片之半導體晶片等之飛散不會產生之適當黏著力及黏力。另一方面,紫外線等之光照射後,黏著劑層3之矽氧系樹脂由於係以如上述般矽氧系樹脂全體中之矽原子鍵結烯基之含量成為7.0×10-7 mol/g以上5.5×10-6 mol/g以下之範圍之方式來構成,故在矽氧膠(G)所具有之矽原子鍵結烯基與對於矽氧系樹脂之交聯劑所具有之矽原子鍵結氫原子(SiH基)之間第2階段之交聯反應(加成反應)會充分進行。藉此,由於黏著劑層3之硬化更加進行,從而交聯密度變高,凝聚力更加提升,故變得能取得所欲之黏力降低或保持力試驗中之破壞模式。其結果變得能實現將黏著膠帶1使用於半導體元件基板等之切割後,將取得之半導體晶片等從黏著膠帶1剝離時之良好拾取性,且同時抑制對於半導體晶片等之殘膠。In contrast, in the adhesive layer 3 of the present embodiment, the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) is made within the range of 40.0/60.0 to 56.0/44.0, thereby achieving the following effects. That is, in the stage before irradiation with ultraviolet light or the like, the adhesive layer 3 is partially crosslinked and hardened (first stage crosslinking reaction) by the thermal polymerization initiator, so that the adhesive layer 3 is given appropriate adhesion and tackiness that prevents the semiconductor chips cut into pieces from flying when dicing. On the other hand, after irradiation with ultraviolet light or the like, the silicone resin of the adhesive layer 3 is constituted in such a manner that the content of the silicon-atom-bonded olefinic groups in the silicone resin as a whole is in the range of 7.0×10 -7 mol/g or more and 5.5×10 -6 mol/g or less, so the second-stage crosslinking reaction (addition reaction) between the silicon-atom-bonded olefinic groups of the silicone glue (G) and the silicon-atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent for the silicone resin is fully carried out. As a result, the curing of the adhesive layer 3 is further carried out, thereby increasing the crosslinking density and further improving the cohesive force, so that the desired adhesion reduction or the destruction mode in the retention test can be obtained. As a result, after the adhesive tape 1 is used for dicing a semiconductor element substrate, etc., good pickup performance can be achieved when the obtained semiconductor chip etc. is peeled off from the adhesive tape 1, and at the same time, residual adhesive on the semiconductor chip etc. can be suppressed.

尤其,上述矽氧系樹脂全體中之矽原子鍵結烯基之含量係以作成2.9×10-6 mol/g以上4.1×10-6 mol/g以下之範圍為佳。於此情況,由於變得容易控制黏著劑層3之凝聚力,故能實現具有更安定切割特性之黏著膠帶1。In particular, the content of silicon-bonded olefin groups in the silicone resin as a whole is preferably in the range of 2.9×10 -6 mol/g or more and 4.1×10 -6 mol/g or less. In this case, since the cohesive force of the adhesive layer 3 is easily controlled, the adhesive tape 1 having more stable cutting characteristics can be realized.

又,作為本發明之混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂,也可使用將以下例示之市售材料予以適宜組合並混合調製者。在此,「適宜組合並混合調製者」係意指「以黏著劑層3之矽氧系樹脂全體中之矽原子鍵結烯基之含量成為7.0×10-7 mol/g以上5.5×10-6 mol/g以下之範圍,矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))成為40.0/60.0~56.0/44.0之範圍之方式,來適合組合各個材料並混合調製者」。作為適宜組合並混合調製用之各個市售材料,可舉出例如,以下材料(1)~(4)等。Furthermore, as the silicone resin of the present invention, which is a mixture of silicone glue (G) and silicone resin (R), the commercially available materials listed below may be appropriately combined and mixed. Here, "appropriately combined and mixed" means "appropriately combining and mixing the materials in such a way that the content of silicon atom-bonded alkenyl groups in the entire silicone resin of the adhesive layer 3 is in the range of 7.0×10 -7 mol/g or more and 5.5×10 -6 mol/g or less, and the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) is in the range of 40.0/60.0 to 56.0/44.0". Examples of commercially available materials that can be suitably combined and mixed for preparation include the following materials (1) to (4).

作為含有矽原子鍵結烯基之矽氧系樹脂,可舉出如(1)矽氧膠(Galk )與矽氧樹脂(R)係以指定比率混合之市售之加成反應型矽氧系黏著劑,或(2)將矽氧膠(Galk )作為主成分之加成反應型矽氧系離型劑等。又,作為不含有矽原子鍵結烯基之矽氧系樹脂,可舉出如(3)矽氧膠(G0 )與矽氧樹脂(R)係以指定比率混合之市售之過氧化物硬化型矽氧系黏著劑,或(4)市售之矽之樹脂(R)之單獨物等。本發明中,在適合組合該等市售之各個材料並混合調製時,以至少包含(2)之加成反應型矽氧系離型劑為佳,又以除此之外再更含有(1)之加成反應型矽氧系黏著劑為更佳。Examples of silicone resins containing alkenyl groups bonded to silicon atoms include (1) commercially available addition reaction type silicone adhesives in which silicone glue (G alk ) and silicone resin (R) are mixed at a specified ratio, or (2) addition reaction type silicone release agents containing silicone glue (G alk ) as a main component. Examples of silicone resins not containing alkenyl groups bonded to silicon atoms include (3) commercially available peroxide curing type silicone adhesives in which silicone glue (G 0 ) and silicone resin (R) are mixed at a specified ratio, or (4) commercially available silicone resin (R) alone. In the present invention, when the commercially available materials are appropriately combined and mixed, it is preferred to contain at least the addition reaction type silicone-oxygen release agent of (2), and it is more preferred to further contain the addition reaction type silicone-oxygen adhesive of (1).

如上述般,作為含有矽原子鍵結烯基之矽氧系樹脂,可使用如(1)矽氧膠(Galk )與矽氧樹脂(R)係以指定比率混合之市售之加成反應型矽氧系黏著劑,或(2)將矽氧膠(Galk )作為主成分之市售之加成反應型矽氧系離型劑等。以下,例示關於具體之市售材料。As described above, as the silicone resin containing a silicon atom-bonded olefinic group, (1) a commercially available addition reaction type silicone adhesive in which silicone glue (G alk ) and silicone resin (R) are mixed at a specified ratio, or (2) a commercially available addition reaction type silicone release agent having silicone glue (G alk ) as a main component can be used. Specific commercially available materials are exemplified below.

(1)加成反應型矽氧系黏著劑 作為上述市售之加成反應型矽氧系黏著劑,只要係一般使用作為矽氧系黏著膠帶用之矽氧系黏著劑者,即無特別限定。具體地可使用例如,信越化學工業股份有限公司製之KR-3700、KR-3701、X-40-3237-1、X-40-3240、X-40-3291-1、X-40-3229、X-40-3270、X-40-3306(皆為商品名)、邁圖高新材料公司製之TSR1512、TSR1516、XR37-B9204(皆為商品名)、陶氏東麗股份有限公司製之SD4580、SD4584、SD4585、SD4560、SD4564、SD4565、SD4570、SD4574、SD4575、SD4600PFC、SD4593、DC7651ADHESIVE(皆為商品名)等之型號中,未添加鉑(Pt)系觸媒及後述交聯劑的類型。尚且,雖也可使用已添加交聯劑之類型,但在已添加之交聯劑所具有之矽原子鍵結氫原子(SiH基)之含量為不明之情況,該含量係可藉由後述之1 H-NMR(核磁共振)光譜測量之分析等來求出。(1) Addition reaction type silicone adhesive As the above-mentioned commercially available addition reaction type silicone adhesive, there is no particular limitation as long as it is a silicone adhesive generally used for silicone adhesive tapes. Specifically, for example, KR-3700, KR-3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40-3270, X-40-3306 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., TSR1512, TSR1516, XR37-B9204 ( In the models such as SD4580, SD4584, SD4585, SD4560, SD4564, SD4565, SD4570, SD4574, SD4575, SD4600PFC, SD4593, and DC7651ADHESIVE (all trade names) manufactured by Dow Toray Co., Ltd., no platinum (Pt) catalyst and the crosslinking agent described below are added. In addition, although the type with the crosslinking agent added can also be used, the content of silicon atom-bonded hydrogen atoms (SiH groups) in the added crosslinking agent is unknown, and the content can be obtained by analysis such as 1 H-NMR (nuclear magnetic resonance) spectroscopy measurement described below.

(2)加成反應型矽氧系離型劑 作為上述市售之加成反應型矽氧系離型劑,只要係一般使用作為黏著膠帶用之矽氧系離型膜之離型處理劑者,即無特別限定。具體地可使用例如,陶氏東麗股份有限公司製之LTC750A、LTC310、LTC300B(皆為商品名)、信越化學工業股份有限公司製之KS3600、KS778(皆為商品名)、邁圖高新材料公司製之TPR6710、TPR6700(皆為商品名)等。於此情況,也係可使用未添加交聯劑之類型及已添加有交聯劑之類型的任一者,已添加之交聯劑所具有之矽原子鍵結氫原子(SiH基)之含量係可藉由1 H-NMR(核磁共振)光譜測量之分析等來求出。(2) Addition reaction type silicone release agent The commercially available addition reaction type silicone release agent is not particularly limited as long as it is a release treatment agent generally used as a silicone release film for adhesive tapes. Specifically, for example, LTC750A, LTC310, LTC300B (all trade names) manufactured by Dow Toray Industries, Ltd., KS3600, KS778 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., TPR6710, TPR6700 (all trade names) manufactured by Maitu Advanced Materials Co., Ltd., etc. can be used. In this case, either the type without adding a crosslinking agent or the type with adding a crosslinking agent may be used, and the content of silicon atom-bonded hydrogen atoms (SiH groups) in the added crosslinking agent can be determined by analysis such as 1 H-NMR (nuclear magnetic resonance) spectroscopy measurement.

上述市售之加成反應型矽氧系黏著劑中之矽氧膠(G)與矽氧樹脂(R)之混合比率為不明之情況,該混合比率係可藉由29 Si-NMR(核磁共振)光譜測量,從D單位與Q單位之鋒面積比(矽氧膠:矽氧樹脂=D單位:Q單位)來求出。又,也可從藉由凝膠滲透層析(GPC)所測量之個別之鋒面積之比率來求出。In the case where the mixing ratio of silicone glue (G) and silicone resin (R) in the above commercially available addition reaction silicone adhesive is unknown, the mixing ratio can be obtained from the face area ratio of D unit to Q unit (silicone glue: silicone resin = D unit: Q unit) by 29 Si-NMR (nuclear magnetic resonance) spectroscopy measurement. Alternatively, it can be obtained from the ratio of individual face areas measured by gel permeation chromatography (GPC).

又,作為不含有矽原子鍵結烯基之矽氧系樹脂,可使用如,以指定比率混合有矽氧膠(G0 )與矽氧樹脂(R)之市售之過氧化物硬化型矽氧系黏著劑,或市售之矽氧樹脂(R)之單獨物等。以下,例示關於具體之市售材料。As the silicone resin containing no silicon atom-bonded alkenyl group, for example, a commercially available peroxide-curable silicone adhesive in which silicone glue (G 0 ) and silicone resin (R) are mixed at a predetermined ratio, or a commercially available silicone resin (R) alone can be used. Specific commercially available materials are exemplified below.

(3)過氧化物硬化型矽氧系黏著劑 作為上述市售之過氧化物硬化型矽氧系黏著劑,只要係一般使用作為矽氧系黏著膠帶用之矽氧系黏著劑者,即並無特別限定。具體地可舉出例如,信越化學工業股份有限公司製之KR-100、KR-101-10(皆為商品名)、邁圖高新材料公司製之YR3340、YR3286、PSA610-SM、XR37-B6722、YF3897(皆為商品名)、陶氏東麗股份有限公司製之SH4280、SH4282、SE4200、BY24-717、BY24-715、Q2-7735(皆為商品名)等。(3) Peroxide-curing silicone adhesives The above-mentioned commercially available peroxide-curing silicone adhesives are not particularly limited as long as they are silicone adhesives generally used for silicone adhesive tapes. Specific examples include KR-100 and KR-101-10 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., YR3340, YR3286, PSA610-SM, XR37-B6722, and YF3897 (all trade names) manufactured by Maitu Advanced Materials Co., Ltd., and SH4280, SH4282, SE4200, BY24-717, BY24-715, and Q2-7735 (all trade names) manufactured by Dow Toray Industries, Inc.

(4)矽氧樹脂 作為市售之矽氧樹脂(R)之單獨物,具體地可舉出例如,邁圖高新材料公司製之YF3800、XF3905、YF3057、YF3807、YF3802、YF3897、XC96-723、2D SILANOL FLUID(皆為商品名)等。(4) Silicone resin Specific examples of commercially available silicone resins (R) include YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XC96-723, and 2D SILANOL FLUID (all trade names) manufactured by Maitu High-Tech Materials Co., Ltd.

上述市售之過氧化物硬化型矽氧系黏著劑中之矽氧膠(G)與矽氧樹脂(R)之混合比率為不明之情況,該混合比率係與上述同樣地可藉由29 Si-NMR(核磁共振)光譜測量,從D單位與Q單位之鋒面積比(矽氧膠:矽氧樹脂=D單位:Q單位)來求出。又,也可從藉由凝膠滲透層析(GPC)所測量之個別之鋒面積之比率來求出。In the case where the mixing ratio of silicone glue (G) and silicone resin (R) in the above-mentioned commercially available peroxide-curing silicone adhesive is unknown, the mixing ratio can be obtained from the face area ratio of D unit to Q unit (silicone glue: silicone resin = D unit: Q unit) by 29 Si-NMR (nuclear magnetic resonance) spectroscopy measurement in the same manner as above. Alternatively, it can be obtained from the ratio of individual face areas measured by gel permeation chromatography (GPC).

該等市售之矽氧系樹脂係如上述般,在以黏著劑層3之矽氧系樹脂全體中之矽原子鍵結烯基之含量成為7.0×10-7 mol/g以上5.5×10-6 mol/g以下之範圍,矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))成為40.0/60.0 ~56.0/44.0之範圍之方式來適宜組合並混合調製之狀態下使用即可。作為使用該等市售之矽氧系樹脂時之為佳之態樣例,具體而言,例如,將(a)對加成反應型矽氧系黏著劑添加有加成反應型矽氧系離型劑之矽氧系樹脂,或(b)對該等更添加過氧化物硬化型矽氧系黏著劑及/或矽氧樹脂(R)之矽氧系樹脂使用作為構成黏著劑層3之黏著劑組成物之主成分即可。 尚且,本實施形態之說明中,「作為主成分」係意指將黏著劑組成物之固體成分設為100質量份時佔75質量份以上,以90質量份以上為佳,較佳為95質量份以上。The commercially available silicone resins can be used in a state of being appropriately combined and mixed so that the content of silicon atom-bonded alkenyl groups in the silicone resin as a whole of the adhesive layer 3 is in the range of 7.0×10 -7 mol/g to 5.5×10 -6 mol/g, and the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) is in the range of 40.0/60.0 to 56.0/44.0. As a preferred example of using these commercially available silicone resins, specifically, for example, (a) a silicone resin to which an addition-reaction silicone release agent is added to an addition-reaction silicone adhesive, or (b) a silicone resin to which a peroxide-curing silicone adhesive and/or silicone resin (R) is further added, can be used as the main component of the adhesive composition constituting the adhesive layer 3. Moreover, in the description of this embodiment, "as the main component" means that the solid component of the adhesive composition accounts for 75 parts by mass or more, preferably 90 parts by mass or more, and more preferably 95 parts by mass or more, when the solid component of the adhesive composition is set to 100 parts by mass.

(交聯劑) 本實施形態中之交聯劑係藉由紫外線等之光照射於黏著劑層3,而展現作為對於矽氧系黏著劑之交聯劑之功能。即,本實施形態中之交聯劑係藉由將紫外線等之光照射於黏著劑層3,而矽氧系黏著劑中之光感應鉑(Pt)觸媒受到活性化之際,為了使其對於矽氧系樹脂所含之矽氧膠(Galk )所具有之矽原子鍵結烯基進行加成反應,而使黏著劑層3進行交聯所使用者。由於藉由交聯劑而矽氧系樹脂進行交聯且黏著劑層3硬化而交聯密度變高,故在與紫外線等之光照射之前相比,黏著劑層3之凝聚力增加。 作為交聯劑,使用1分子中具有至少2個,較佳為3個以上之矽原子鍵結氫原子(SiH基)之有機聚矽氧烷(有機氫聚矽氧烷)。以下之說明中,有將具有矽原子鍵結氫原子(SiH基)之有機聚矽氧烷單純記載成有機氫聚矽氧烷的情況。(Crosslinking agent) The crosslinking agent in this embodiment functions as a crosslinking agent for the silicone adhesive by irradiating the adhesive layer 3 with light such as ultraviolet rays. That is, the crosslinking agent in this embodiment is used to crosslink the adhesive layer 3 by irradiating the adhesive layer 3 with light such as ultraviolet rays, so that the photosensitive platinum (Pt) catalyst in the silicone adhesive is activated and reacts with the silicon atom-bonded olefin group of the silicone glue ( Galk ) contained in the silicone resin. Since the silicone resin is crosslinked by the crosslinking agent and the adhesive layer 3 is cured and the crosslinking density is increased, the cohesive force of the adhesive layer 3 is increased compared to before the irradiation with ultraviolet light or the like. As the crosslinking agent, an organic polysiloxane (organic hydropolysiloxane) having at least two, preferably three or more silicon-atom-bonded hydrogen atoms (SiH groups) in one molecule is used. In the following description, an organic polysiloxane having silicon-atom-bonded hydrogen atoms (SiH groups) may be simply described as an organic hydropolysiloxane.

作為使用當作為交聯劑之有機氫聚矽氧烷之分子構造,可例示例如,直鏈狀、一部分具有分支之直鏈狀、分支鏈狀、網狀。有機氫聚矽氧烷之25℃之黏度係以1mPa・s以上5,000mPa・s以下之範圍為佳。尚且,上述黏度係可使用B型旋轉黏度計進行測量。The molecular structure of the organohydropolysiloxane used as a crosslinking agent may be, for example, a linear chain, a linear chain partially branched, a branched chain, or a network. The viscosity of the organohydropolysiloxane at 25°C is preferably in the range of 1 mPa・s to 5,000 mPa・s. The above viscosity can be measured using a B-type rotational viscometer.

使用作為交聯劑之有機氫聚矽氧烷係可使用以往公知者。例如,作為該有機氫聚矽氧烷,可舉出如下述一般式(5)或一般式(6)所示者,但並非係受到該等所限定者。The organohydropolysiloxane used as the crosslinking agent may be a conventionally known one. For example, the organohydropolysiloxane may be one represented by the following general formula (5) or general formula (6), but the present invention is not limited thereto.

在此,一般式(5)、一般式(6)中,R3 為碳數1~10之1價烴基,b為0或1,p及q為整數,且係有機氫聚矽氧烷在25℃之黏度成為1mPa・s以上5,000mPa・s以下之值。r為2以上之整數,s為0以上之整數,且r+s≧3,以8≧r+s≧3為佳。有機氫聚矽氧烷係可為2種以上之混合物。Here, in general formula (5) and general formula (6), R 3 is a monovalent alkyl group having 1 to 10 carbon atoms, b is 0 or 1, p and q are integers, and the viscosity of the organohydropolysiloxane at 25°C is a value of 1 mPa·s or more and 5,000 mPa·s or less. r is an integer of 2 or more, s is an integer of 0 or more, and r+s≧3, preferably 8≧r+s≧3. The organohydropolysiloxane may be a mixture of two or more types.

R3 為碳數1~10,較佳為碳數1~7之1價烴基。可舉出例如,甲基、乙基、丙基、及丁基等之烷基;環己基等之環烷基;及苯基、及甲苯基等之芳基、乙烯基及烯丙基等之烯基,尤其係以甲基或苯基為佳。R 3 is a monovalent alkyl group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. Examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl; and alkenyl groups such as vinyl and allyl. Methyl or phenyl is particularly preferred.

本實施形態之黏著劑層3中使用作為交聯劑之有機氫聚矽氧烷之含量由於係根據矽氧膠(Galk )之矽原子鍵結烯基之含量及有機氫聚矽氧烷所具有之矽原子鍵結氫原子之含量之平衡,而其適當之範圍會改變,故無法一概而論,通常係以例如,黏著劑組成物所包含之交聯劑之矽原子鍵結氫原子(SiH基)之含量(總量)對構成黏著劑層3之黏著劑組成物所含之矽氧系樹脂之矽原子鍵結烯基之含量(總量)之莫耳比率成為2.0以上10.0以下之範圍之量為佳。The content of the organohydropolysiloxane used as a crosslinking agent in the adhesive layer 3 of the present embodiment is determined by the balance between the content of silicon-bonded olefinic groups of the silicone gel ( Galk ) and the content of silicon-bonded hydrogen atoms of the organohydropolysiloxane, and its appropriate range varies and cannot be generalized. Generally, for example, the molar ratio of the content (total amount) of silicon-bonded hydrogen atoms (SiH groups) of the crosslinking agent contained in the adhesive composition to the content (total amount) of silicon-bonded olefinic groups of the silicone resin contained in the adhesive composition constituting the adhesive layer 3 is preferably in the range of 2.0 to 10.0.

有機氫聚矽氧烷之含量在未滿上述下限值之情況,對黏著膠帶1照射紫外線等之光之際,利用矽氧膠所具有之矽原子鍵結烯基與交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之第2階段之交聯反應(加成反應)而得之交聯密度之提升則變得不充分,黏著劑變得難以硬化,且凝聚力變得不易提升。於此情況,無法取得所欲之黏力低下或保持力試驗中之破壞模式,在將黏著膠帶1使用於半導體元件基板等之切割後,在將取得之半導體晶片等從黏著膠帶1剝離之際,有經個片化之半導體晶片之拾取性變差之憂慮,或有半導體晶片等變得容易產生殘膠的憂慮。When the content of the organohydropolysiloxane is less than the above lower limit, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the crosslinking density obtained by the second-stage crosslinking reaction (addition reaction) between the silicon atom-bonded olefin groups of the silicone adhesive and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent becomes insufficient, and the adhesive becomes difficult to harden and the cohesive force becomes difficult to improve. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. When the adhesive tape 1 is used to cut the semiconductor element substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become prone to residual adhesive.

另一方面,有機氫聚矽氧烷之含量在超過上述上限值之情況,未反應之有機氫聚矽氧烷會有污染半導體晶片的憂慮。又,有未反應之有機氫聚矽氧烷中之矽原子鍵結氫原子(SiH基)會與空氣中之氧或水分反應而轉換成SiOH,且黏著劑層3對被黏著物之黏著力變大,經個片化之半導體晶片之拾取性變差的憂慮。On the other hand, if the content of the organohydropolysiloxane exceeds the above upper limit, there is a concern that the unreacted organohydropolysiloxane may contaminate the semiconductor chip. In addition, there is a concern that the silicon atom-bonded hydrogen atom (SiH group) in the unreacted organohydropolysiloxane may react with oxygen or moisture in the air to be converted into SiOH, and the adhesive layer 3 may have a greater adhesion to the adherend, thereby deteriorating the pickup properties of the individualized semiconductor chips.

本實施形態之黏著劑層3中之交聯劑之含量係如上述般,將黏著劑層3中之,交聯劑全體之矽原子鍵結氫原子(SiH基)之含量(總量)對矽氧系樹脂全體之矽原子鍵結烯基之含量(總量)之莫耳比率調整成上述範圍內即可。作為滿足該範圍之交聯劑之含量,雖係根據交聯劑所具有之矽原子鍵結氫原子(SiH基)之數而不同,例如,相對於構成黏著劑層3之黏著劑組成物所含之矽氧系樹脂全體之固體成分100質量份,以使交聯劑以固體成分計成為0.20質量份以上20.00質量份以下之範圍之方式來添加即可。The content of the crosslinking agent in the adhesive layer 3 of the present embodiment is as described above, and the molar ratio of the content (total amount) of the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent in the adhesive layer 3 to the content (total amount) of the silicon atom-bonded olefin group of the silicon-oxygen resin in the adhesive layer 3 is adjusted to be within the above range. The content of the crosslinking agent that satisfies the above range varies depending on the number of silicon atom-bonded hydrogen atoms (SiH groups) possessed by the crosslinking agent. For example, the crosslinking agent may be added in a range of 0.20 parts by mass to 20.00 parts by mass based on the solid content, relative to 100 parts by mass of the entire solid content of the silicone-based resin contained in the adhesive composition constituting the adhesive layer 3.

藉由將黏著劑層3中之交聯劑對矽氧系樹脂之含量作成上述範圍,將半導體晶片從切割用黏著膠帶剝離之際,藉由將紫外線等之光照射於黏著劑層3,使矽氧系黏著劑中之光感應鉑(Pt)觸媒受到活性化,從而矽氧系樹脂中之矽氧膠(Galk )所具有之矽原子鍵結烯基與對於該矽氧系樹脂之交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之第2階段之交聯反應(加成反應)受到促進,交聯密度變高,在與紫外線等之光照射前相比,黏著劑之凝聚力變大。其結果係變得能實現黏著劑層3之黏力適度降低,將半導體晶片等從黏著膠帶1剝離時之良好拾取性,並且能抑制對於半導體晶片等之殘膠。By setting the content of the crosslinking agent in the adhesive layer 3 to the silicone resin within the above range, when the semiconductor chip is peeled off from the dicing adhesive tape, the light such as ultraviolet rays is irradiated to the adhesive layer 3, so that the photosensitive platinum (Pt) catalyst in the silicone adhesive is activated, thereby promoting the second stage crosslinking reaction (addition reaction) between the silicon atom-bonded olefin group of the silicone glue (G alk ) in the silicone resin and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent for the silicone resin, thereby increasing the crosslinking density and increasing the cohesive force of the adhesive compared to before the irradiation with the light such as ultraviolet rays. As a result, the adhesive force of the adhesive layer 3 can be appropriately reduced, and good pickup performance can be achieved when the semiconductor chip or the like is peeled off from the adhesive tape 1, and residual adhesive on the semiconductor chip or the like can be suppressed.

作為交聯劑,只要係一般使用作為加成反應型矽氧系黏著劑之交聯劑者,即,1分子中具有至少2個矽原子鍵結氫原子(SiH基)之有機聚矽氧烷(有機氫聚矽氧烷)即可,而並非係受到特別限定者。具體地可舉出例如,信越化學股份有限公司製之X-92-122(商品名)、陶氏東麗股份有限公司製之BY24-741(商品名)等。尚且,該等交聯劑所具有之矽原子鍵結氫原子(SiH基)之含量為之情況,該含量係可藉由後述之1 H-NMR(核磁共振)光譜測量之分析等來求出。As the crosslinking agent, any crosslinking agent generally used as an addition reaction type silicone adhesive, that is, an organopolysiloxane (organohydropolysiloxane) having at least two silicon atom-bonded hydrogen atoms (SiH groups) in one molecule can be used, and there is no particular limitation. Specifically, for example, X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and BY24-741 (trade name) manufactured by Dow Toray Industries, Ltd. can be cited. Moreover, the content of silicon atom-bonded hydrogen atoms (SiH groups) possessed by such crosslinking agents can be determined by analysis such as 1 H-NMR (nuclear magnetic resonance) spectroscopy measurement described later.

(光感應鉑(Pt)觸媒) 光感應鉑(Pt)觸媒係使用於藉由紫外線等之光照射而促進由構成黏著劑層3之矽氧系樹脂與交聯劑之加成反應(矽氫化)所成之硬化者用。為了促進由矽氧系黏著劑中之矽氧膠(Galk )所具有之矽原子鍵結烯基與交聯劑所具有之矽原子鍵結氫原子(SiH基)之加成反應所得之硬化而能使用之光之波長係以240nm以上400nm以下之範圍為佳。 作為光感應鉑(Pt)觸媒,從光感應性及反應速度為良好之觀點,以使用光活性環戊二烯基鉑(IV)化合物為佳。(Photosensitive platinum (Pt) catalyst) Photosensitive platinum (Pt) catalyst is used to promote the curing of the silicone resin and the crosslinking agent constituting the adhesive layer 3 by irradiation with light such as ultraviolet rays. In order to promote the curing obtained by the addition reaction of the silicon atom-bonded olefin group of the silicone glue ( Galk ) in the silicone adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent, the wavelength of light that can be used is preferably in the range of 240nm to 400nm. As the photosensitive platinum (Pt) catalyst, a photoactive cyclopentadienyl platinum (IV) compound is preferably used from the viewpoint of good photosensitivity and reaction speed.

作為該光活性環戊二烯基鉑(IV)化合物,並非係受到特別限定者,可舉出例如,(環戊二烯基)二甲基三甲基矽基甲基鉑、(環戊二烯基)二乙基三甲基矽基甲基鉑、(環戊二烯基)二丙基三甲基矽基甲基鉑、(環戊二烯基)二異丙基三甲基矽基甲基鉑、(環戊二烯基)二烯丙基三甲基矽基甲基鉑、(環戊二烯基)二苄基三甲基矽基甲基鉑、(環戊二烯基)二甲基三乙基矽基甲基鉑、(環戊二烯基)二甲基三丙基矽基甲基鉑、(環戊二烯基)二甲基三異丙基矽基甲基鉑、(環戊二烯基)二甲基三苯基矽基甲基鉑、(環戊二烯基)二甲基二甲基苯基矽基甲基鉑、(環戊二烯基)二甲基甲基二苯基矽基甲基鉑、(環戊二烯基)二甲基二甲基(三甲基矽氧基)矽基甲基鉑、(環戊二烯基)二甲基二甲基(二甲基乙烯基矽氧基)矽基甲基鉑、[(1’-萘基)環戊二烯基]三甲基矽基甲基鉑、[(2’-萘基)環戊二烯基]三甲基矽基甲基鉑、[1-甲基-3-(1’-萘基)環戊二烯基]三甲基矽基甲基鉑、[1-甲基-3-(2’-萘基)環戊二烯基]三甲基矽基甲基鉑、[(4’-聯苯基)環戊二烯基]三甲基矽基甲基鉑、[1-(4’-聯苯基)-3-甲基環戊二烯基]三甲基矽基甲基鉑、[(9’-菲基)環戊二烯基]三甲基矽基甲基鉑、[1-甲基-3-(9’-菲基)環戊二烯基]三甲基矽基甲基鉑、[1-(2’-蒽基)-3-甲基環戊二烯基]三甲基矽基甲基鉑、[(2’-蒽基)環戊二烯基]三甲基矽基甲基鉑、[(1’-芘基)環戊二烯基]三甲基矽基甲基鉑、[1-甲基-3-(1’-芘基)環戊二烯基]三甲基矽基甲基鉑等。The photoactive cyclopentadienyl platinum (IV) compound is not particularly limited, and examples thereof include (cyclopentadienyl) dimethyl trimethyl silyl methyl platinum, (cyclopentadienyl) diethyl trimethyl silyl methyl platinum, (cyclopentadienyl) dipropyl trimethyl silyl methyl platinum, (cyclopentadienyl) diisopropyl trimethyl silyl methyl platinum, (cyclopentadienyl) diallyl trimethyl silyl methyl platinum, (cyclopentadienyl) dibenzyl trimethyl silyl methyl platinum, (cyclopentadienyl) dimethyl triethylsilylmethyl platinum, (cyclopentadienyl)dimethyltripropylsilylmethyl platinum, (cyclopentadienyl)dimethyltriisopropylsilylmethyl platinum, (cyclopentadienyl)dimethyltriphenylsilylmethyl platinum, (cyclopentadienyl)dimethyldimethylphenylsilylmethyl platinum, (cyclopentadienyl)dimethylmethyldiphenylsilylmethyl platinum, (cyclopentadienyl)dimethyldimethyl(trimethylsiloxy)silylmethyl platinum, (cyclopentadienyl)dimethyldimethyl(dimethylvinylsiloxy)silyl Methylplatinum, [(1'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [(2'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [1-methyl-3-(1'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [1-methyl-3-(2'-naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum, [(4'-biphenylyl)cyclopentadienyl]trimethylsilylmethylplatinum, [1-(4'-biphenylyl)-3-methylcyclopentadienyl]trimethylsilylmethylplatinum methyl platinum, [(9'-phenanthrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, [1-methyl-3-(9'-phenanthrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, [1-(2'-anthryl)-3-methylcyclopentadienyl]trimethylsilylmethyl platinum, [(2'-anthryl)cyclopentadienyl]trimethylsilylmethyl platinum, [(1'-pyrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, [1-methyl-3-(1'-pyrenyl)cyclopentadienyl]trimethylsilylmethyl platinum, and the like.

上述化合物中之環戊二烯基環係亦可經甲基、氯、氟、三甲基矽基、三乙基矽基、二甲基苯基矽基、甲基二苯基矽基、三苯基矽基、苯基、氟苯基、氯苯基、甲氧基、萘基、聯苯基、蒽基、芘基、2-苄醯基萘、噻噸酮、2-氯噻噸酮、2-異丙基噻噸酮、蒽醌、1-氯蒽醌、苯乙酮、二苯甲酮、9,10-二甲基蒽、9,10-二氯蒽,及經選自該等之中之1以上之基所取代之環戊二烯基環所取代。 又,上述化合物中,環戊二烯基環也可被η5-茀基取代。The cyclopentadienyl ring in the above compounds may be substituted by methyl, chlorine, fluorine, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, phenyl, fluorophenyl, chlorophenyl, methoxy, naphthyl, biphenyl, anthracenyl, pyrene, 2-benzylanthracene, thiothione, 2-chlorothiothione, 2-isopropylthiothione, anthraquinone, 1-chloroanthraquinone, acetophenone, benzophenone, 9,10-dimethylanthracene, 9,10-dichloroanthracene, and a cyclopentadienyl ring substituted by one or more groups selected from the above. In addition, in the above compounds, the cyclopentadienyl ring may be substituted by η5-fluorenyl.

作為上述化合物中之環戊二烯基環,以未經取代者,經1個以上芳香族有機基所取代者,經1個以上脂肪族有機基所取代者、經1個以上芳香族有機基與1個以上脂肪族有機基所取代者為佳。又,作為取代環戊二烯基環之有機基,以萘基、聯苯基、蒽基、菲基及芘基為佳。The cyclopentadienyl ring in the above-mentioned compound is preferably unsubstituted, substituted with one or more aromatic organic groups, substituted with one or more aliphatic organic groups, or substituted with one or more aromatic organic groups and one or more aliphatic organic groups. In addition, the organic group substituted with the cyclopentadienyl ring is preferably naphthyl, biphenyl, anthracenyl, phenanthrenyl, and pyrenyl.

本實施形態之黏著劑層3中之光感應鉑(Pt)觸媒之含量只要係因紫外線等之光照射,而能促進矽氧系黏著劑中之矽氧膠(Galk )所具有之矽原子鍵結烯基與交聯劑所具有之矽原子鍵結氫原子(SiH基)之加成反應者,即並非係受到特別限定者。本實施形態之黏著劑層3中之光感應鉑(Pt)觸媒之含量,例如,相對於構成黏著劑層3之黏著劑組成物中之矽氧系樹脂全體固體成分100質量份,以固體成分計以0.10質量份以上3.00質量份以下之範圍為佳,以0.20質量份〜1.00質量份之範圍為較佳。光感應鉑(Pt)觸媒之含量在未滿0.10質量份之情況,在對黏著膠帶1照射紫外線等之光之際,矽氧膠所具有之矽原子鍵結烯基與交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之交聯反應(加成反應)會無法充分進行,交聯密度之提升變得不充足,黏著劑難以硬化,且凝聚力變得難以提升。於此情況,無法取得所欲之黏力低下或保持力試驗中之破壞模式,在將黏著膠帶1使用於半導體元件基板等之切割後,在將取得之半導體晶片等從黏著膠帶1剝離之際,有經個片化之半導體晶片之拾取性變差之憂慮,或有半導體晶片等變得容易產生殘膠的憂慮。另一方面,光感應鉑(Pt)觸媒之含量在超過3.00質量份之情況,由於上述交聯反應(加成反應)會充分地進行,例如即使為10.0質量份之含量,作為黏著膠帶1之特性仍不會有特別問題,但從經濟性之觀點,則為不佳。The content of the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the present embodiment is not particularly limited as long as it can promote the addition reaction between the silicon atom-bonded olefin groups of the silicone glue ( Galk ) in the silicone adhesive and the silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent under irradiation with light such as ultraviolet rays. The content of the photosensitive platinum (Pt) catalyst in the adhesive layer 3 of the present embodiment is, for example, preferably in the range of 0.10 to 3.00 parts by mass, and more preferably in the range of 0.20 to 1.00 parts by mass, based on the solid content, relative to 100 parts by mass of the total solid content of the silicone resin in the adhesive composition constituting the adhesive layer 3. When the content of the photosensitive platinum (Pt) catalyst is less than 0.10 parts by weight, when the adhesive tape 1 is irradiated with light such as ultraviolet rays, the crosslinking reaction (addition reaction) between the silicon atom-bonded olefin group of the silicone adhesive and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent cannot be fully performed, and the crosslinking density is insufficiently increased, the adhesive is difficult to harden, and the cohesive force is difficult to increase. In this case, the desired low adhesive force or failure mode in the holding force test cannot be obtained. When the adhesive tape 1 is used for cutting the semiconductor device substrate, etc., and the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that the pickup property of the individualized semiconductor chip will deteriorate, or there is a concern that the semiconductor chip will become easy to produce adhesive residue. On the other hand, when the content of the photosensitive platinum (Pt) catalyst exceeds 3.00 parts by mass, the above-mentioned crosslinking reaction (addition reaction) will fully proceed. For example, even if the content is 10.0 parts by mass, there will be no special problem as the characteristics of the adhesive tape 1, but from the perspective of economic efficiency, it is not good.

(熱聚合起始劑) 作為本實施形態中之熱聚合起始劑,使用過氧化物,更具體而言,使用有機過氧化物。本實施形態中之熱聚合起始劑係為了對照射紫外線等之光前之黏著膠帶1之黏著劑層3賦予在切割時裁切片之半導體晶片等不會產生飛散之適當黏著力及黏力所使用者。即,藉由在形成黏著劑層3時之加熱・乾燥步驟中被施加之熱,而黏著劑層3中之熱聚合起始劑產生自由基。其後,該自由基主要係攻擊矽氧系樹脂中之矽氧膠(G)之甲基或烯基之一部分來形成亞甲基鏈,使黏著劑層3適度地交聯、硬化。具體而言,認為最初係甲基與烯基進行反應,與此同時,或接續其後,在甲基彼此,或交聯部分與甲基之間進行交聯反應者。藉此,對黏著劑層3賦予適度之凝聚力,其結果係在切割時,能安定地實現裁切片之半導體晶片等之飛散不會產生之適當黏著力及黏力。(Thermal polymerization initiator) As the thermal polymerization initiator in this embodiment, a peroxide is used, more specifically, an organic peroxide is used. The thermal polymerization initiator in this embodiment is used to give the adhesive layer 3 of the adhesive tape 1 before irradiation with ultraviolet light or the like, so that the semiconductor chips cut into pieces do not fly away during dicing. That is, the thermal polymerization initiator in the adhesive layer 3 generates free radicals by heat applied in the heating and drying step when forming the adhesive layer 3. Thereafter, the free radicals mainly attack a part of the methyl or alkenyl group of the silicone glue (G) in the silicone resin to form a methylene chain, so that the adhesive layer 3 is appropriately crosslinked and hardened. Specifically, it is considered that the methyl groups react with the alkenyl groups first, and at the same time or subsequently, the methyl groups react with each other or with the crosslinking part and the methyl groups. This imparts a moderate cohesive force to the adhesive layer 3, and as a result, a suitable adhesion and tackiness can be stably achieved without causing the semiconductor chips of the cut pieces to fly apart during dicing.

作為使用當作熱聚合起始劑之過氧化物,只要係會分解產生遊離氧自由基者,即並非係受到特別限定者,可舉出例如,二苄醯基過氧化物、4,4’-二甲基二苄醯基過氧化物、3,3’-二甲基二苄醯基過氧化物、2,2’-二甲基二苄醯基過氧化物、2,2’,4,4’-四氯二苄醯基過氧化物、二異丁醯基過氧化物、二月桂醯基過氧化物、二異壬醯基過氧化物等之1分鐘半衰期溫度為85℃以上135℃以下之二醯基過氧化物類;二異丙苯基過氧化物、t-丁基-異丙苯基過氧化物、2,5-二甲基-2,5-二(t-丁基過氧基)己烷、1,1´-二-t-丁基過氧基-3,3,5-三亞甲基環己烷、1,3-二-(t-丁基過氧基)-二異丙基苯等之1分鐘半衰期溫度為170℃~200℃之二烷基過氧化物類等。作為市售品,例如,作為二醯基過氧化物類,可舉出如日油股份有限公司製之Nyper BMT-K40、Nyper BW(皆為商品名)等,作為二烷基過氧化物類,可舉出如日油股份有限公司製之Perbutyl C、 Percumyl D、Perbutyl P(皆為商品名)等。The peroxide used as the thermal polymerization initiator is not particularly limited as long as it decomposes to generate free oxygen radicals, and examples thereof include dibenzyl peroxide, 4,4'-dimethyldibenzyl peroxide, 3,3'-dimethyldibenzyl peroxide, 2,2'-dimethyldibenzyl peroxide, 2,2',4,4'-tetrachlorodibenzyl peroxide, diisobutyl peroxide, dilauryl peroxide, and diisononanoyl peroxide. The half-life temperature of 1 minute is between 85℃ and 135℃ for diacyl peroxides, such as diisopropyl peroxide, t-butyl-isopropyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1´-di-t-butylperoxy-3,3,5-trimethylenecyclohexane, 1,3-di-(t-butylperoxy)-diisopropylbenzene, etc., and the half-life temperature of 1 minute is between 170℃ and 200℃ for dialkyl peroxides. As commercial products, for example, as diacyl peroxides, there are Nyper BMT-K40 and Nyper BW (both trade names) manufactured by NOF Corporation, and as dialkyl peroxides, there are Perbutyl C, Percumyl D, and Perbutyl P (both trade names) manufactured by NOF Corporation.

上述之過氧化物在從確保黏著膠帶1之基材2之變形溫度(耐熱性)、紫外線等之光照射前狀態下之矽氧膠(Galk )之烯基殘存量之觀點,以使用1分鐘半衰期溫度為85℃~135℃程度之二醯基過氧化物類為佳。即,在與使用二烷基過氧化物類(1分鐘半衰期溫度為170℃~200℃程度)之情況相比,在使用二醯基過氧化物類作為過氧化物的情況,於形成黏著劑層3時之加熱・乾燥步驟中,即使在黏著膠帶1之基材2不易熱變形之低加熱溫度、短乾燥時間下,仍能分解。並且,比起矽氧膠(G)之甲基與烯基之反應,矽氧膠(G)之甲基彼此之反應會容易優先地進行,且能預先確保更多在紫外線等之光照射時,藉由與交聯劑所具有之矽原子鍵結氫原子(SiH基)之加成反應(第2階段之交聯反應)而用來使黏著劑層3之交聯密度更加提升所必須之矽氧膠(Galk )之烯基之殘存量。The above-mentioned peroxide is preferably a diacyl peroxide having a half-life temperature of about 85°C to 135°C in terms of ensuring the deformation temperature (heat resistance) of the substrate 2 of the adhesive tape 1 and the residual amount of alkenyl in the silicone glue ( Galk ) before irradiation with ultraviolet light or the like. That is, when a diacyl peroxide is used as the peroxide, it can be decomposed even at a low heating temperature and a short drying time in which the substrate 2 of the adhesive tape 1 is not easily deformed by heat, compared to the case of using a dialkyl peroxide (a half-life temperature of about 170°C to 200°C in one minute). Furthermore, the reaction between the methyl groups of silicone (G) is more likely to proceed preferentially than the reaction between the methyl groups of silicone (G) and the alkenyl groups, and more residual amounts of alkenyl groups of silicone (G) necessary for increasing the crosslinking density of the adhesive layer 3 by addition reaction with silicon atom-bonded hydrogen atoms (SiH groups) of the crosslinking agent (the second stage of crosslinking reaction) when irradiated with ultraviolet light or the like can be ensured in advance.

黏著劑層3中之上述熱聚合起始劑之含量由於係根據加熱溫度・時間、所使用之有機過氧化物之分解溫度(1分鐘半衰期溫度)或矽氧膠(G)之混合比率等而相異,故無法一概而論,例如,相對於黏著劑層3中之矽氧系樹脂全體之固體成分100質量份,以固體成分計以0.10質量份以上3.00質量份以下之範圍為佳,以0.50質量份以上2.00質量份以下之範圍為較佳,以0.70質量份以上1.80質量份以下之範圍為特佳。相對於黏著劑層3中之矽氧系樹脂全體之固體成分100質量份,黏著劑層3中之熱聚合起始劑之含量在以固體成分計未滿0.10質量份時,在照射紫外線等之光之前之階段,黏著劑層3之由熱聚合起始劑所成之矽氧系樹脂之交聯・硬化(第1階段交聯反應)變得不充足。藉此,矽氧系樹脂全體之矽氧膠(G)之比率為多時,則有起因於矽氧膠(G)成分而黏著劑層3變軟之憂慮。於此情況,在半導體元件基板等之切割時,切割之振動變得容易傳達至黏著劑層3而振動幅度變大,且會有例如,半導體元件基板從基準位置偏移之憂慮。且,伴隨於此,有在經個片化之半導體晶片上產生缺損(chipping)之憂慮,或有每一個個別半導體晶片在大小上產生偏差的憂慮。又,也有黏著劑層3之黏著力或黏力降低之憂慮。於此情況,該若將黏著膠帶1使用於半導體元件基板等之切割,在裁切半導體元件基板等時,則有裁切片之半導體晶片等從黏著膠帶1剝離後變得容易飛散之憂慮。 另一方面,熱聚合起始劑之含量超過3.00質量份時,在照射紫外線等之光之前階段,根據熱聚合起始劑之種類或加熱溫度・時間,會有矽氧系樹脂之交聯・硬化(第1階段交聯反應)因熱聚合起始劑而過度進行,黏著劑層3變得過硬的情況。於此情況,若將黏著膠帶1使用於半導體元件基板等之切割,在裁切半導體元件基板等時,則有裁切片之半導體晶片等從黏著膠帶1剝離後變得容易飛散之憂慮。又,有熱聚合起始劑本身,或源自熱聚合起始劑之分解生成物之成分殘留於被黏著物而污染被黏著物的憂慮。The content of the thermal polymerization initiator in the adhesive layer 3 varies depending on the heating temperature and time, the decomposition temperature (1 minute half-life temperature) of the organic peroxide used, or the mixing ratio of the silicone glue (G), so it is impossible to generalize. For example, relative to 100 parts by mass of the solid content of the silicone resin in the adhesive layer 3, the solid content is preferably in the range of 0.10 parts by mass to 3.00 parts by mass, more preferably in the range of 0.50 parts by mass to 2.00 parts by mass, and particularly preferably in the range of 0.70 parts by mass to 1.80 parts by mass. When the content of the thermal polymerization initiator in the adhesive layer 3 is less than 0.10 parts by mass in terms of solid content relative to 100 parts by mass of the entire solid content of the silicone resin in the adhesive layer 3, the crosslinking and curing (first stage crosslinking reaction) of the silicone resin formed by the thermal polymerization initiator in the adhesive layer 3 becomes insufficient before irradiation with ultraviolet light or the like. As a result, when the ratio of the silicone gel (G) in the entire silicone resin is high, there is a concern that the adhesive layer 3 becomes soft due to the silicone gel (G) component. In this case, when cutting the semiconductor device substrate, the vibration of the cutting becomes easy to be transmitted to the adhesive layer 3 and the vibration amplitude becomes larger, and there is a concern that, for example, the semiconductor device substrate is offset from the reference position. And, along with this, there is a concern that defects (chipping) will occur on the individualized semiconductor chips, or there is a concern that each individual semiconductor chip will have a deviation in size. In addition, there is also a concern that the adhesive force or adhesive force of the adhesive layer 3 will decrease. In this case, if the adhesive tape 1 is used for cutting the semiconductor device substrate, when cutting the semiconductor device substrate, there is a concern that the cut semiconductor chips will easily fly away after being peeled off from the adhesive tape 1. On the other hand, when the content of the thermal polymerization initiator exceeds 3.00 parts by mass, the crosslinking and curing of the silicone resin (first stage crosslinking reaction) may be excessively advanced by the thermal polymerization initiator before irradiation with ultraviolet light or the like, depending on the type of the thermal polymerization initiator or the heating temperature and time, and the adhesive layer 3 may become too hard. In this case, when the adhesive tape 1 is used for cutting semiconductor device substrates or the like, when the semiconductor device substrates or the like are cut, there is a concern that the semiconductor chips or the like of the cut pieces may be easily scattered after being peeled off from the adhesive tape 1. In addition, there is a concern that the thermal polymerization initiator itself or the components derived from the decomposition products of the thermal polymerization initiator remain on the adherend and contaminate the adherend.

本實施形態之矽氧系黏著劑層係由黏著劑組成物所構成者,該黏著劑組成物係包含:混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂、作為對矽氧系樹脂之交聯劑之1分子中具有至少2個以上之矽原子鍵結氫原子(SiH基)之有機聚矽氧烷、作為熱聚合起始劑之過氧化物,及光感應鉑(Pt)觸媒作為主成分,但不損及本發明之效果範圍內,亦可含有其他成分。作為其他成分,可舉出如凝聚力提升劑、補強填充劑、剝離控制劑等。The silicone adhesive layer of the present embodiment is composed of an adhesive composition, which includes: a silicone resin mixed with silicone glue (G) and silicone resin (R), an organic polysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) in one molecule as a crosslinking agent for the silicone resin, a peroxide as a thermal polymerization initiator, and a photosensitive platinum (Pt) catalyst as main components, but other components may also be contained within the scope of the effect of the present invention. As other components, cohesion enhancers, reinforcing fillers, peeling control agents, etc. can be cited.

(凝聚力提升劑) 凝聚力提升劑係為了提升黏著劑層3之凝聚力,因應必要所使用者。作為凝聚力提升劑,並非係受到特別限定者,可使用例如多官能硫醇。作為由多官能硫醇所構成之凝聚力提升劑,可舉出例如,昭和電工股份有限公司製之Kalenz(註冊商標)MT-PE1、Kalenz MT-NR1等。(Cohesion enhancer) The cohesion enhancer is used as needed to enhance the cohesion of the adhesive layer 3. The cohesion enhancer is not particularly limited, and for example, polyfunctional thiol can be used. Examples of cohesion enhancers composed of polyfunctional thiol include Kalenz (registered trademark) MT-PE1 and Kalenz MT-NR1 manufactured by Showa Denko Co., Ltd.

但,多官能硫醇不會與構成黏著劑層3之黏著劑組成物中之矽氧系樹脂相溶,故為了使用多官能硫醇作為凝聚力提升劑,則有必要使用矽氧系樹脂與多官能硫醇之相溶化劑。作為相溶化劑,並非係受到特別限定者,可舉出例如,具有巰基之矽烷耦合劑之信越化學工業股份有限公司製之KBM-802、KBM-803(皆為商品名)、陶氏東麗股份有限公司製之SH6062(商品名)等。 對黏著劑層3使用凝聚力提升劑時,相對於矽氧系樹脂全體之固體成分100質量份,凝聚力提升劑之添加量在以固體成分計,以6質量份以下之範圍為佳。相對於矽氧系樹脂全體之固體成分100質量份,凝聚力提升劑之添加量在以固體成分計超過6質量份時,即使添加相溶化劑,矽氧系樹脂與凝聚力提升劑之多官能硫醇仍會有進行相分離之憂慮。However, polyfunctional thiol is not compatible with the silicone resin in the adhesive composition constituting the adhesive layer 3. Therefore, in order to use polyfunctional thiol as a cohesive agent, it is necessary to use a compatibilizer for silicone resin and polyfunctional thiol. The compatibilizer is not particularly limited, and examples thereof include KBM-802 and KBM-803 (both trade names) manufactured by Shin-Etsu Chemical Co., Ltd., which are silane coupling agents having a silane group, and SH6062 (trade name) manufactured by Dow Toray Industries, Ltd., etc. When a cohesion enhancer is used for the adhesive layer 3, the amount of the cohesion enhancer added is preferably within a range of 6 parts by mass or less based on 100 parts by mass of the solid content of the entire silicone resin. If the amount of the cohesion enhancer added exceeds 6 parts by mass based on 100 parts by mass of the solid content of the entire silicone resin, even if a compatibilizer is added, there is still a concern that the silicone resin and the multifunctional thiol of the cohesion enhancer will separate into phases.

(補強填充劑) 補強填充劑係為了提升黏著劑層3之強度,因應必要所使用者。作為補強填充劑,並非係受到特別限定者,可舉出例如,日本Aerosil 股份有限公司製之Aerosil(註冊商標)130、Aerosil 200、Aerosil 300、股份有限公司德山製之Reolosil(註冊商標)QS-102、Reolosil QS-30、DSL.日本股份有限公司製之Carplex(註冊商標)80、PPG製之Hi-Sil(註冊商標)-233-D等。(Reinforcing filler) Reinforcing fillers are used as necessary to increase the strength of the adhesive layer 3. Reinforcing fillers are not particularly limited, and examples thereof include Aerosil (registered trademark) 130, Aerosil 200, Aerosil 300 manufactured by Japan Aerosil Co., Ltd., Reolosil (registered trademark) QS-102, Reolosil QS-30 manufactured by Tokuyama Co., Ltd., Carplex (registered trademark) 80 manufactured by DSL. Japan Co., Ltd., and Hi-Sil (registered trademark) -233-D manufactured by PPG.

(剝離控制劑) 剝離控制劑係為了更加減低在紫外線等之光照射後之黏著劑層3之黏著力,因應必要所使用者。作為剝離控制劑,並非係受到特別限定者,可舉出例如,矽氧油等之輕剝離添加劑。但,剝離控制劑之添加量為多時,由於會有因滲出而污染被黏著物表面之憂慮,故以在被黏著物表面之污染程度能夠容許之範圍內進行添加為佳。(Peeling control agent) Peeling control agents are used as necessary to further reduce the adhesion of the adhesive layer 3 after exposure to ultraviolet light or the like. Peeling control agents are not particularly limited, and examples thereof include light peeling additives such as silicone oil. However, when the amount of peeling control agent added is large, there is a concern that the surface of the adherend may be contaminated by seepage, so it is better to add the amount within the range that the contamination level of the adherend surface can be tolerated.

<黏著劑層之厚度> 黏著劑層3之厚度係以10μm以上100μm以下之範圍為佳,以20μm以上40μm以下之範圍為較佳。黏著劑層3之厚度在未滿10μm時,由於黏著劑層3所含之矽氧系黏著劑之厚度變薄,故黏著膠帶1之黏著力容易降低。另一方面,黏著劑層3之厚度比100μm還厚時,則有黏著劑層3之凝集破壞變得容易產生之憂慮。且,將黏著膠帶1使用於半導體元件基板等之切割後,在將取得之半導體晶片等從黏著膠帶1剝離之際,有半導體晶片等上變得容易產生殘膠的憂慮。又,在半導體元件基板等之切割時,切割之振動變得容易傳達至黏著劑層3,而有例如半導體元件基板從基準位置偏移之憂慮。且,伴隨於此,有經個片化之半導體晶片上產生缺損(chipping)之憂慮,或有每一個個別半導體晶片在大小上產生偏差的憂慮。<Thickness of adhesive layer> The thickness of the adhesive layer 3 is preferably in the range of 10μm to 100μm, and more preferably in the range of 20μm to 40μm. When the thickness of the adhesive layer 3 is less than 10μm, the thickness of the silicone adhesive contained in the adhesive layer 3 becomes thinner, so the adhesive force of the adhesive tape 1 is likely to decrease. On the other hand, when the thickness of the adhesive layer 3 is thicker than 100μm, there is a concern that the coagulation and destruction of the adhesive layer 3 becomes more likely to occur. Furthermore, after the adhesive tape 1 is used to cut the semiconductor device substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, there is a concern that residual adhesive is likely to be generated on the semiconductor chip. Furthermore, when the semiconductor device substrate is cut, the vibration of the cutting is likely to be transmitted to the adhesive layer 3, and there is a concern that, for example, the semiconductor device substrate is shifted from the reference position. And, accompanying this, there is a concern that defects (chipping) are generated on the individualized semiconductor chips, or there is a concern that each individual semiconductor chip has a deviation in size.

<錨塗層> 如上述般,本實施形態之黏著膠帶1中,因應黏著膠帶1之製造條件或製造後之黏著膠帶1之使用條件等,亦可在基材2與黏著劑層3之間配合基材2之種類來設置錨塗層,或施加電暈處理等之表面處理。藉此,變得能改善基材2與黏著劑層3之密著力。<Anchor coating> As described above, in the adhesive tape 1 of this embodiment, depending on the manufacturing conditions of the adhesive tape 1 or the use conditions of the adhesive tape 1 after manufacturing, an anchor coating may be provided between the substrate 2 and the adhesive layer 3, or a surface treatment such as a corona treatment may be applied depending on the type of the substrate 2. This improves the adhesion between the substrate 2 and the adhesive layer 3.

<表面處理> 也可在基材2之表面(與黏著劑層3面對之面為反對側之面)上施加剝離性改良處理等之表面處理。作為基材2之表面處理所使用之處理劑,並非係受到特別限定者,可使用例如,長鏈烷基乙烯基單體聚合物、氟化烷基乙烯基單體聚合物、聚乙烯醇胺甲酸酯、胺基醇酸(amino alkyd)系樹脂等之非矽氧系之剝離處理劑等。作為此種非矽氧系之剝離處理劑,可舉出例如,獅王特殊化學股份有限公司製之Peeloil(註冊商標)1050、Peeloil 1200等。<Surface treatment> The surface of the substrate 2 (the surface opposite to the adhesive layer 3) may be subjected to a surface treatment such as a release-improving treatment. The treatment agent used for the surface treatment of the substrate 2 is not particularly limited, and non-silicone-based release agents such as long-chain alkyl vinyl monomer polymers, fluorinated alkyl vinyl monomer polymers, polyvinyl alcohol urethane, and amino alkyd resins may be used. Examples of such non-silicone-based release agents include Peeloil (registered trademark) 1050 and Peeloil 1200 manufactured by Lion Special Chemicals Co., Ltd.

<剝離襯墊> 又,黏著劑層3之表面(與基材2面對之面為反對側之面)在因應必要亦可設置剝離襯墊。作為剝離襯墊,可使用如對紙、聚乙烯、聚丙烯、聚對酞酸乙二酯等之膜施加有提高與黏著劑層3所含之矽氧系黏著劑之離型性用之剝離處理者。作為剝離襯墊之剝離處理所使用之材料,並無特別限定,可使用例如,氟烷基變性矽氧、長鏈烷基乙烯基單體聚合物、胺基醇酸系樹脂等之材料。<Peel-off pad> In addition, a peel-off pad may be provided on the surface of the adhesive layer 3 (the surface opposite to the substrate 2) as necessary. As the peel-off pad, a film such as paper, polyethylene, polypropylene, polyethylene terephthalate, etc., which has been subjected to a peel-off treatment for improving the release property of the silicone adhesive contained in the adhesive layer 3, may be used. The material used for the peel-off treatment of the peel-off pad is not particularly limited, and materials such as fluoroalkyl modified silicone, long-chain alkyl vinyl monomer polymer, aminoalkyd resin, etc. may be used.

<黏著膠帶之厚度> 作為具有如以上說明之構成之黏著膠帶1之全體厚度係以20μm以上200μm以下之範圍為佳。 黏著膠帶1之厚度在為未滿20μm時,在將黏著膠帶1使用半導體元件基板等之切割時,有變得難以將已形成之半導體晶片等從黏著膠帶1剝離取下的情況。 另一方面,黏著膠帶1之厚度超過200μm時,將黏著膠帶1貼附於半導體元件基板之際,黏著膠帶1會變得難以追隨形成於半導體元件基板之貼附面上之凹凸。於此情況,黏著膠帶1與半導體元件基板等之接著面積變小,在切割之際會有半導體晶片等變得容易飛散之憂慮。<Thickness of Adhesive Tape> The overall thickness of the adhesive tape 1 having the structure described above is preferably in the range of 20 μm to 200 μm. When the thickness of the adhesive tape 1 is less than 20 μm, it may become difficult to peel off the formed semiconductor chip from the adhesive tape 1 when the adhesive tape 1 is used to cut the semiconductor device substrate. On the other hand, when the thickness of the adhesive tape 1 exceeds 200 μm, it may become difficult for the adhesive tape 1 to follow the unevenness formed on the attachment surface of the semiconductor device substrate when the adhesive tape 1 is attached to the semiconductor device substrate. In this case, the contact area between the adhesive tape 1 and the semiconductor device substrate etc. becomes smaller, and there is a concern that the semiconductor chip etc. may be easily scattered during dicing.

[黏著膠帶之製造方法] 接著,說明關於本實施形態之黏著膠帶1之製造方法。尚且,以下所說明之黏著膠帶1之製造方法僅為舉例,黏著膠帶1之製造方法並非係受此所限定者。[Manufacturing method of adhesive tape] Next, the manufacturing method of the adhesive tape 1 of this embodiment is described. The manufacturing method of the adhesive tape 1 described below is only an example, and the manufacturing method of the adhesive tape 1 is not limited to this.

在製造黏著膠帶1之際,首先在甲苯或乙酸乙酯等之泛用之有機溶劑中使上述之矽氧系黏著劑、交聯劑、光感應鉑(Pt)觸媒等之成分溶解,而取得黏著劑溶液。接著,使用逗點塗布機(comma coater)等,在因應必要已進行表面處理或錨塗層之形成之基材2之表面上,將該黏著劑溶液以成為預先決定之厚度之方式進行塗布。 其次,藉由使用乾燥爐來加熱已塗佈黏著劑溶液之基材2,使黏著劑溶液乾燥・硬化,而形成黏著劑層3。作為加熱・乾燥之條件,由於也係取決於熱聚合起始劑之半衰期溫度等,故無法一概而論,可參照例如,日本特開2012-107125等揭示之條件。具體而言,例如,對基材2塗佈黏著劑層3用之黏著劑溶液,在乾燥爐之前半區域部,以40~90℃之溫度來階段性地提高溫度進行初期乾燥後,在乾燥爐之後半區域部,以120~200℃之溫度範圍來進行1~5分鐘之加熱乾燥,並捲取作為輥狀之原料捲即可,但並不受限於此。 藉由以上之步驟,如圖1所示般,可取得在基材2之上層合有黏著劑層3之黏著膠帶1。本實施形態中,於此階段中,黏著劑層3係藉由熱聚合起始劑而成為矽氧系樹脂之一部經交聯・硬化(第1階段交聯反應)之狀態。When manufacturing the adhesive tape 1, first, the above-mentioned silicone adhesive, crosslinking agent, photosensitive platinum (Pt) catalyst and other components are dissolved in a general organic solvent such as toluene or ethyl acetate to obtain an adhesive solution. Then, the adhesive solution is applied to the surface of the substrate 2, which has been subjected to surface treatment or anchor coating as necessary, in a predetermined thickness using a comma coater or the like. Next, the adhesive solution is dried and hardened by heating the substrate 2 on which the adhesive solution has been applied using a drying oven to form an adhesive layer 3. As for the conditions of heating and drying, it is also dependent on the half-life temperature of the thermal polymerization initiator, etc., so it is impossible to generalize. For example, the conditions disclosed in Japanese Patent Publication No. 2012-107125 can be referred to. Specifically, for example, the adhesive solution for applying the adhesive layer 3 to the substrate 2 is gradually increased at a temperature of 40 to 90°C in the front half of the drying furnace for initial drying, and then heated and dried at a temperature range of 120 to 200°C for 1 to 5 minutes in the rear half of the drying furnace, and then rolled up as a raw material roll, but it is not limited to this. Through the above steps, as shown in FIG1 , an adhesive tape 1 having an adhesive layer 3 laminated on a substrate 2 can be obtained. In this embodiment, at this stage, the adhesive layer 3 is a state in which a portion of the silicone resin is crosslinked and hardened (first stage crosslinking reaction) by a thermal polymerization initiator.

[黏著膠帶之使用方法] 本實施形態之黏著膠帶1係在LED(發光二極體)或功率半導體等之具有半導體元件之半導體晶片之製造步驟中,使用於成為半導體晶片基礎之半導體材料之切割者。[How to use the adhesive tape] The adhesive tape 1 of this embodiment is used for cutting semiconductor materials that become the basis of semiconductor chips in the manufacturing process of semiconductor chips having semiconductor elements such as LEDs (light emitting diodes) or power semiconductors.

具體而言,黏著膠帶1係為了取得半導體晶片所使用者,該半導體晶片係將在由樹脂或陶瓷等所構成之基板上已形成有複數LED元件或功率半導體元件等之半導體元件之半導體元件基板予以切割並經個片化之半導體晶片者。在此,基板上已形成有複數半導體元件之半導體元件基板通常為了從溫度或濕度等之外部環境來保護半導體元件,而有設置以被覆半導體元件之方式來設置作為被覆材之一例之密封樹脂的情況。 本實施形態之黏著膠帶1尤其係能更佳使用於設置有密封樹脂之半導體元件基板之切割。Specifically, the adhesive tape 1 is used to obtain a semiconductor chip, which is a semiconductor chip obtained by cutting and individualizing a semiconductor element substrate on which a plurality of semiconductor elements such as LED elements or power semiconductor elements are formed on a substrate made of resin or ceramic. Here, the semiconductor element substrate on which a plurality of semiconductor elements are formed is usually provided with a sealing resin as an example of a covering material in order to protect the semiconductor element from an external environment such as temperature or humidity. The adhesive tape 1 of this embodiment can be particularly preferably used for cutting a semiconductor element substrate provided with a sealing resin.

作為裁切設置有密封樹脂之半導體元件基板而取得複數半導體晶片用之方法,以往已知有例如以下之方法。 首先,從半導體元件基板之基板側貼附切割用之黏著膠帶,並且藉由切割機等從會形成半導體元件之側來裁切半導體元件基板。且,藉由從黏著膠帶剝下藉由裁切所形成之個別半導體晶片,而取得複數之半導體晶片。As a method for obtaining a plurality of semiconductor chips by cutting a semiconductor element substrate provided with a sealing resin, the following method is known in the past. First, an adhesive tape for cutting is attached to the substrate side of the semiconductor element substrate, and the semiconductor element substrate is cut from the side where the semiconductor element is formed by a dicing machine or the like. Then, the individual semiconductor chips formed by cutting are peeled off from the adhesive tape to obtain a plurality of semiconductor chips.

但,如此般在從半導體元件基板之基板側貼附切割用黏著膠帶並進行裁切半導體元件基板之情況,有在裁切面(半導體晶片之基板側面)上產生缺少即所謂之下陷,或裁切面變粗糙等之課題。 因此,近年來為了解決此種課題,已提出對於半導體元件基板,不僅在基板側,也在形成半導體元件之側,即從密封半導體元件之密封樹脂側貼附切割用之黏著膠帶,進而裁切半導體元件基板之方法。However, when the semiconductor device substrate is cut by attaching a dicing adhesive tape from the substrate side of the semiconductor device substrate, there is a problem that a defect, i.e., a depression, or a roughening of the cut surface (the substrate side of the semiconductor chip) occurs on the cut surface. Therefore, in recent years, in order to solve such a problem, a method has been proposed in which a dicing adhesive tape is attached not only to the substrate side but also to the side where the semiconductor device is formed, i.e., from the sealing resin side where the semiconductor device is sealed, and then the semiconductor device substrate is cut.

在此,作為LED或功率半導體等之半導體元件用之密封樹脂,以往係利用電特性或耐熱性優異之環氧樹脂,環氧樹脂在使用於高輸出之LED或功率半導體之情況,在使用於短波長LED之情況,或根據半導體晶片之使用環境等,而有容易變色的問題。Here, as a sealing resin for semiconductor elements such as LEDs and power semiconductors, epoxy resins with excellent electrical properties or heat resistance have been used in the past. However, epoxy resins have the problem of easy discoloration when used for high-output LEDs or power semiconductors, when used for short-wavelength LEDs, or depending on the use environment of the semiconductor chip.

相對於此,由於與環氧樹脂相比,不引起因熱或光所造成之變色的理由,近年來使用矽氧樹脂作為LED或功率半導體等之半導體元件用之密封樹脂的情況為多。更具體而言,使用含有甲基及苯基之雙方或單方作為官能基之矽氧樹脂,即含有甲基之矽氧樹脂、含有苯基之矽氧樹脂、含有甲基與苯基雙方之矽氧樹脂的情況為多。In contrast, silicone resins are less likely to discolor due to heat or light than epoxy resins, so in recent years silicone resins are often used as sealing resins for semiconductor components such as LEDs and power semiconductors. More specifically, silicone resins containing either or both methyl and phenyl groups as functional groups, i.e., silicone resins containing methyl groups, silicone resins containing phenyl groups, and silicone resins containing both methyl groups and phenyl groups, are often used.

藉由使用矽氧樹脂作為半導體元件之密封樹脂,而可抑制因熱或光所造成之密封樹脂之變色。又,矽氧樹脂係可將光穿透率調整成高達88%以上(波長400~ 800nm),且可將折射率調整成1.41以上1.57以下之範圍。因此,半導體元件為LED之情況,藉由折射率更高之矽氧樹脂作為密封樹脂,而能有效率地將來自LED之放射光取出至封裝之外部。上述矽氧樹脂之中,在與使用含有甲基之矽氧樹脂之情況相比,藉由使用含有苯基之矽氧樹脂,由於能更加提高密封材之折射率,從而謀求之放射光之更高效率化。By using silicone resin as a sealing resin for semiconductor components, discoloration of the sealing resin caused by heat or light can be suppressed. In addition, silicone resin can adjust the light transmittance to be as high as 88% or more (wavelength 400~800nm), and the refractive index can be adjusted to a range of 1.41 or more and 1.57 or less. Therefore, when the semiconductor component is an LED, by using a silicone resin with a higher refractive index as a sealing resin, the radiated light from the LED can be efficiently taken out to the outside of the package. Among the above-mentioned silicone resins, by using a silicone resin containing phenyl, the refractive index of the sealing material can be further increased compared to the case of using a silicone resin containing methyl, thereby seeking a higher efficiency of the radiated light.

作為含有甲基之矽氧樹脂,並非係受到特別限定者,可舉出例如,信越化學工業股份有限公司製之KER-2300、KER-2460、KER-2500N、KER-2600、KER-2700、KER-2900、X-32-2528(皆為商品名)、邁圖高新材料公司製之IVS4312、IVS4312、XE14-C2042、IVS4542、IVS4546、IVS4622、IVS4632、IVS4742、IVS4752、IVSG3445、IVSG0810、IVSG5778、XE13-C2479、IVSM4500(皆為商品名)、陶氏東麗股份有限公司製之OE-6351、OE-6336、OE-6301(皆為商品名)等。 作為含有甲基與苯基之矽氧樹脂,並非係受到特別限定者,可舉出例如,信越化學工業股份有限公司製KER-6075、KER-6150、KER-6020(皆為商品名)等。 作為含有苯基之矽氧樹脂,並非係受到特別限定者,可舉出例如,信越化學工業股份有限公司製KER-6110、KER-6000、KER-6200、ASP-1111、ASP-1060、ASP-1120、ASP-1050P(皆為商品名)、邁圖高新材料公司製之XE14-C2508(商品名)、陶氏東麗股份有限公司製之OE-6520、OE-6550、OE-6631、OE-6636、OE-6635、OE-6630(皆為商品名)等。Examples of silicone resins containing methyl groups are not particularly limited, and include KER-2300, KER-2460, KER-2500N, KER-2600, KER-2700, KER-2900, and X-32-2528 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., and IVS4312, IVS4312, and XE14-C20 manufactured by Maitu Advanced Materials Co., Ltd. 42, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG0810, IVSG5778, XE13-C2479, IVSM4500 (all trade names), OE-6351, OE-6336, OE-6301 (all trade names) manufactured by Dow Toray Co., Ltd., etc. Silicone resins containing methyl and phenyl groups are not particularly limited, and examples thereof include KER-6075, KER-6150, KER-6020 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., etc. Examples of silicone resins containing phenyl groups are not particularly limited, and include KER-6110, KER-6000, KER-6200, ASP-1111, ASP-1060, ASP-1120, and ASP-1050P (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd., XE14-C2508 (trade name) manufactured by Maitu Advanced Materials Co., Ltd., and OE-6520, OE-6550, OE-6631, OE-6636, OE-6635, and OE-6630 (all trade names) manufactured by Dow Toray Industries, Inc.

另一方面,作為以往為了裁切半導體元件所使用之切割用之黏著膠帶,係使用例如黏著劑層係由丙烯酸樹脂系之黏著劑所構成之黏著膠帶。 但,在將此種以往之黏著膠帶從半導體元件基板之形成半導體元件之側(密封樹脂側)來貼附而進行半導體元件基板之切割時,例如,在密封樹脂與黏著膠帶之黏著力為不充分之情況,則有產生在切割時半導體晶片飛散等之問題的憂慮。On the other hand, as a dicing adhesive tape used in the past for cutting semiconductor elements, an adhesive tape whose adhesive layer is composed of an acrylic resin-based adhesive is used. However, when such a conventional adhesive tape is attached from the side of the semiconductor element substrate where the semiconductor element is formed (sealing resin side) to cut the semiconductor element substrate, for example, if the adhesion between the sealing resin and the adhesive tape is insufficient, there is a concern that the semiconductor chip may fly during cutting.

尤其,例如在與以往使用作為密封樹脂之環氧樹脂等相比,上述矽氧樹脂具有高離型性性質。因此,對於使用矽氧樹脂作為密封樹脂之半導體元件基板,在貼附例如黏著劑層係由丙烯酸樹脂系之黏著劑所構成之黏著膠帶之情況,密封樹脂之矽氧樹脂與黏著膠帶之接著力變得容易變小。其結果係在切割半導體元件基板之際變得更容易產生半導體晶片飛散等之問題。In particular, the silicone resin has a high release property compared to epoxy resins used as sealing resins in the past. Therefore, when a semiconductor device substrate using silicone resin as a sealing resin is attached with an adhesive tape whose adhesive layer is composed of an acrylic resin-based adhesive, the adhesion between the silicone resin of the sealing resin and the adhesive tape is likely to decrease. As a result, problems such as semiconductor chip scattering are more likely to occur when the semiconductor device substrate is cut.

相對於此,本實施形態之黏著膠帶1係如上述般,由於黏著劑層3係藉由黏著劑組成物所構成,且該黏著劑組成物包含:以適當比率來混合矽氧膠(G)與矽氧樹脂(R)且具有指定量之矽原子鍵結烯基之矽氧系樹脂與熱聚合起始劑,從而黏著劑層3係藉由熱聚合起始劑而矽氧系樹脂之一部成為經交聯・硬化(第1階段交聯反應)之狀態,故在進行切割半導體元件基板時,即使從由矽氧樹脂所構成之密封樹脂側來貼附使用之情況,仍能安定且良好地保持半導體元件基板對密封樹脂之黏著力及黏力。且,與以往之黏著膠帶相比,在進行半導體元件基板之切割時,仍能抑制半導體晶片之飛散等之產生。 另一方面,構成黏著劑層3之黏著劑組成物藉由一同含有上述之矽氧系樹脂與光感應鉑(Pt)觸媒及交聯劑,藉由照射紫外線等之光,而矽氧系樹脂中之光感應鉑(Pt)觸媒受到活性化,矽氧系樹脂中之矽氧膠(Galk )所具有之矽原子鍵結烯基與對於該矽氧系樹脂之交聯劑所具有之矽原子鍵結氫原子(SiH基)之間之第2階段之交聯反應(加成反應)受到促進而交聯密度變高,故黏著劑之凝聚力在與紫外線等之光照射前相比更加變大。其結果係黏著劑層3之黏力適度地降低,以及在保持力試驗中之破壞模式為「界面剝離」或在保持力試驗中成為「不會落下」者。藉此,可實現將半導體晶片等從黏著膠帶1剝離時之良好拾取性,並且變得能抑制對於半導體晶片等之殘膠。In contrast, the adhesive tape 1 of the present embodiment is as described above, since the adhesive layer 3 is formed by an adhesive composition, and the adhesive composition includes: a silicone resin (G) and a silicone resin (R) mixed in an appropriate ratio and having a specified amount of silicon atom-bonded alkenyl groups and a thermal polymerization initiator, thereby the adhesive layer 3 Because part of the silicone resin is crosslinked and hardened (first stage crosslinking reaction) by the thermal polymerization initiator, when cutting the semiconductor device substrate, even if it is attached from the sealing resin side composed of silicone resin, the adhesion and adhesion of the semiconductor device substrate to the sealing resin can be maintained stably and well. Moreover, compared with the conventional adhesive tape, when cutting the semiconductor device substrate, the scattering of semiconductor chips can be suppressed. On the other hand, the adhesive composition constituting the adhesive layer 3 contains the above-mentioned silicone resin, photosensitive platinum (Pt) catalyst and crosslinking agent together. When irradiated with light such as ultraviolet rays, the photosensitive platinum (Pt) catalyst in the silicone resin is activated, and the second-stage crosslinking reaction (addition reaction) between the silicon atom-bonded olefin group of the silicone gel ( Galk ) in the silicone resin and the silicon atom-bonded hydrogen atom (SiH group) of the crosslinking agent to the silicone resin is promoted, thereby increasing the crosslinking density. Therefore, the cohesive force of the adhesive becomes greater than before irradiation with light such as ultraviolet rays. As a result, the adhesive force of the adhesive layer 3 is appropriately reduced, and the failure mode in the holding force test is "interface peeling" or "no falling" in the holding force test. As a result, good pickup performance when peeling the semiconductor chip from the adhesive tape 1 can be achieved, and residual adhesive on the semiconductor chip can be suppressed.

以下,詳細說明關於本實施形態之黏著膠帶1之使用方法,及使用本實施形態之黏著膠帶1之半導體晶片之製造方法。圖2(a)~(e)為展示使用本實施形態之黏著膠帶1之半導體晶片之製造方法的圖。 尚且,在此係舉出使用黏著膠帶1來製造具有LED元件作為半導體元件之半導體晶片之情況為例進行說明。又,以下所說明之方法為黏著膠帶1之使用方法,及使用黏著膠帶1之導體晶片之製造方法之一例,但並非係受到以下之方法所限定者。The following describes in detail the method for using the adhesive tape 1 of the present embodiment and the method for manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment. Figures 2(a) to (e) are diagrams showing the method for manufacturing a semiconductor chip using the adhesive tape 1 of the present embodiment. Moreover, the method described below is an example of the method for using the adhesive tape 1 and the method for manufacturing a semiconductor chip having an LED element as a semiconductor element, but is not limited to the following method.

本實施形態係首先在例如由樹脂材料或陶瓷等所構成之基板101上搭載複數之半導體元件102而製作半導體元件基板100。尚且,半導體元件102例如為LED元件,雖省略圖示,但例如係包含藉由通而進行發光之發光層等之複數半導體層經層合所構成,且在上部形成有電極者。 其次,使用由矽氧系樹脂所構成之密封樹脂103來密封在半導體元件基板100之基板101上所形成之複數半導體元件(密封步驟)。尚且,該例係藉由密封樹脂103來整體密封複數半導體元件102,亦可藉由密封樹脂103來個別密封個別之半導體元件102。In this embodiment, a plurality of semiconductor elements 102 are mounted on a substrate 101 made of, for example, a resin material or ceramic to produce a semiconductor element substrate 100. The semiconductor element 102 is, for example, an LED element, which is not shown in the figure, but is composed of a plurality of semiconductor layers such as a light-emitting layer that emits light through a channel, and an electrode is formed on the upper part. Next, a sealing resin 103 made of a silicon-based resin is used to seal the plurality of semiconductor elements formed on the substrate 101 of the semiconductor element substrate 100 (sealing step). In this example, the plurality of semiconductor elements 102 are sealed as a whole by the sealing resin 103, and individual semiconductor elements 102 can also be sealed individually by the sealing resin 103.

接著,如圖2(a)所示,黏著膠帶1之黏著劑層3係以面對半導體元件基板100之密封樹脂103之方式來貼合黏著膠帶1與半導體元件基板100(貼附步驟)。 其次,如圖2(b)、(c)所示,在已貼合黏著膠帶1與半導體元件基板100之狀態下,沿著裁切預定線X,藉由切割機等來裁切半導體元件基板100(切斷步驟)。該例係從基板101側裁切已貼附黏著膠帶1之半導體元件基板100。又,如圖2(c)所示,該例係將半導體元件基板100在厚度方向上全部切入,即進行所謂之全切割。Next, as shown in FIG. 2(a), the adhesive layer 3 of the adhesive tape 1 is bonded to the semiconductor element substrate 100 in a manner that faces the sealing resin 103 of the semiconductor element substrate 100 (bonding step). Next, as shown in FIG. 2(b) and (c), in a state where the adhesive tape 1 and the semiconductor element substrate 100 have been bonded, the semiconductor element substrate 100 is cut along the predetermined cutting line X by a cutting machine or the like (cutting step). In this example, the semiconductor element substrate 100 to which the adhesive tape 1 has been bonded is cut from the side of the substrate 101. In addition, as shown in FIG. 2(c), in this example, the semiconductor element substrate 100 is completely cut in the thickness direction, i.e., the so-called full cutting is performed.

接著,如圖2(d)所示,對於已貼附在半導體元件基板100上之黏著膠帶1,從基材2側照射紫外線等之光(照射步驟)。如上述般,基材2係由紫外線等之光會穿透之材質所構成。因此,藉由對黏著膠帶1從基材2側照射紫外線等之光,紫外線等之光會穿透基材2而照射於黏著劑層3。 本實施形態之黏著膠帶1中,由於黏著劑層3具有光感應鉑(Pt)觸媒,藉由紫外線等之光照射於黏著劑層3,光感應鉑(Pt)觸媒進行活性化,從而促進黏著劑層3中之含有矽原子鍵結烯基之矽氧系樹脂與交聯劑之第2階段之交聯反應(加成反應)。藉此,在與照射紫外線等之光之前相比,黏著劑層3之交聯密度,即凝聚力更加增加,黏著劑層3之黏力降低。Next, as shown in FIG. 2( d ), the adhesive tape 1 attached to the semiconductor device substrate 100 is irradiated with light such as ultraviolet rays from the substrate 2 side (irradiation step). As described above, the substrate 2 is made of a material through which light such as ultraviolet rays can penetrate. Therefore, by irradiating the adhesive tape 1 with light such as ultraviolet rays from the substrate 2 side, the light such as ultraviolet rays can penetrate the substrate 2 and irradiate the adhesive layer 3. In the adhesive tape 1 of the present embodiment, since the adhesive layer 3 has a photosensitive platinum (Pt) catalyst, the photosensitive platinum (Pt) catalyst is activated by irradiating the adhesive layer 3 with light such as ultraviolet rays, thereby promoting the second-stage crosslinking reaction (addition reaction) between the silicone resin containing silicon atoms bonded to alkenyl groups and the crosslinking agent in the adhesive layer 3. As a result, the crosslinking density, i.e., the cohesive force, of the adhesive layer 3 is further increased compared to before irradiation with light such as ultraviolet rays, and the adhesive force of the adhesive layer 3 is reduced.

接著,從黏著膠帶1剝下(拾取)藉由裁切半導體元件基板100而形成之半導體晶片200,如圖2(e)所示,而能取得經個片化之半導體晶片200(剝離步驟)。Next, the semiconductor chip 200 formed by cutting the semiconductor device substrate 100 is peeled off (picked up) from the adhesive tape 1, as shown in FIG. 2(e), and the individualized semiconductor chips 200 can be obtained (peeling step).

如上述般,本實施形態之黏著膠帶1之黏著劑層3係由黏著劑組成物來構成,且該黏著劑組成物包含:以適當比率來混合矽氧膠(G)與矽氧樹脂(R)且具有指定量之矽原子鍵結烯基之矽氧系樹脂與熱聚合起始劑。藉此,在將黏著膠帶1使用於切割時,可安定且良好地保持對於半導體元件基板100之黏著膠帶1之黏著力及黏力。 尤其,近年來作為密封半導體元件102之密封樹脂103,諸多係使用高離型性之矽氧樹脂。相對於此,本實施形態之黏著膠帶1藉由具有上述之構成,即使對於由矽氧樹脂所構成之密封樹脂103,仍具有良好之黏著力及黏力。 其結果係本實施形態之黏著膠帶1在使用於半導體元件基板100之切割時,仍可抑制半導體晶片200之飛散。As described above, the adhesive layer 3 of the adhesive tape 1 of the present embodiment is composed of an adhesive composition, and the adhesive composition includes: a silicone resin having a specified amount of silicon atom-bonded olefin groups and a thermal polymerization initiator, in which silicone glue (G) and silicone resin (R) are mixed in an appropriate ratio. Thus, when the adhesive tape 1 is used for cutting, the adhesive force and adhesion of the adhesive tape 1 to the semiconductor device substrate 100 can be stably and well maintained. In particular, in recent years, as the sealing resin 103 for sealing the semiconductor device 102, many silicone resins with high release properties are used. In contrast, the adhesive tape 1 of the present embodiment has the above-mentioned structure, and has good adhesion and tack even to the sealing resin 103 composed of silicone resin. As a result, the adhesive tape 1 of the present embodiment can still suppress the scattering of the semiconductor chip 200 when used for cutting the semiconductor element substrate 100.

並且,本實施形態之黏著膠帶1之包含構成黏著劑層3之矽氧系樹脂而成之黏著劑組成物係如上述般,具有與密封樹脂103之良好黏著力,且具有高離型性之性質。 即,本實施形態之黏著膠帶1係例如包含:藉由紫外線等之光照射而促進黏著劑層3中之含有矽原子鍵結烯基之矽氧系樹脂與交聯劑之加成反應的光感應鉑(Pt)觸媒。且,藉由在裁切步驟之後,剝離步驟前隔著基材2而對黏著劑層3照射紫外線等之光,而光感應鉑(Pt)觸媒受到活性化,在黏著劑層3中含有矽原子鍵結烯基之矽氧系樹脂與交聯劑之加成反應受到促進,在與照射紫外線等之光之前相比,可使黏著劑層3中之交聯密度更加提高,即係使凝聚力更加增加,且使黏著劑層3之黏力降低。藉此,在剝離步驟中,從黏著膠帶1剝下(拾取)藉由切割半導體元件基板100而得之半導體晶片200之際,可抑制半導體晶片200上黏著劑之附著,即所謂殘膠之發生。又,可實現將半導體晶片200從黏著膠帶1剝離時之良好拾取性。Furthermore, the adhesive composition of the adhesive tape 1 of the present embodiment, which includes the silicone resin constituting the adhesive layer 3, has good adhesion to the sealing resin 103 as described above, and has a high release property. That is, the adhesive tape 1 of the present embodiment includes, for example: a photosensitive platinum (Pt) catalyst that promotes the addition reaction of the silicone resin containing silicon atom-bonded alkenyl groups in the adhesive layer 3 and the crosslinking agent by irradiation with light such as ultraviolet rays. Furthermore, by irradiating the adhesive layer 3 with ultraviolet light or the like through the substrate 2 after the cutting step and before the peeling step, the photosensitive platinum (Pt) catalyst is activated, and the addition reaction between the silicone resin containing silicon atoms bonded to alkenes in the adhesive layer 3 and the crosslinking agent is promoted. Compared with before irradiation with ultraviolet light or the like, the crosslinking density in the adhesive layer 3 can be further increased, that is, the cohesive force is further increased, and the adhesive force of the adhesive layer 3 is reduced. Thus, in the peeling step, when the semiconductor chip 200 obtained by cutting the semiconductor device substrate 100 is peeled off (picked up) from the adhesive tape 1, the adhesion of the adhesive on the semiconductor chip 200, i.e., the occurrence of so-called residual adhesive, can be suppressed. In addition, good pickup performance when the semiconductor chip 200 is peeled off from the adhesive tape 1 can be achieved.

尚且,上述已說明了對於基板上形成有複數半導體元件之半導體元件基板,從密封樹脂側貼附黏著膠帶1來進行切割而取得經個片化之半導體晶片的方法。然而,本實施形態之黏著膠帶1之用途並非係受此限定者。 本實施形態之黏著膠帶1係亦可使用於用來取得例如在晶片尺寸封裝LED之製造中,切割複數之LED元件係被作為被覆材之一例之螢光體所被覆之半導體材料,而經個片化之晶片尺寸封裝LED。尚且,螢光體係指在樹脂材料或陶瓷等中分散有螢光材料之構件。Furthermore, the above has described a method for obtaining individualized semiconductor chips by cutting a semiconductor element substrate having a plurality of semiconductor elements formed on the substrate by attaching an adhesive tape 1 from the sealing resin side. However, the use of the adhesive tape 1 of this embodiment is not limited to this. The adhesive tape 1 of this embodiment can also be used to obtain individualized chip-size packaged LEDs by cutting a plurality of LED elements, for example, in the manufacture of chip-size packaged LEDs, by using a semiconductor material coated with a fluorescent body as an example of a coating material. Furthermore, a fluorescent body refers to a component in which a fluorescent material is dispersed in a resin material or ceramics.

近年來伴隨晶片尺寸封裝LED之小型化,在切割時經個片化之晶片尺寸封裝LED有容易飛散之傾向。相對於此,藉由使用具有上述構成之本實施形態之黏著膠帶1,變得能良好地保持螢光體與黏著劑層3之接著力,且能抑制經個片化之晶片尺寸封裝LED之飛散。 又,切割後,藉由對黏著劑層3照射紫外線等之光使黏力降低,從而變得容易從黏著膠帶1剝離經個片化之晶片尺寸封裝LED,並且可抑制在已剝離之晶片尺寸封裝LED上之殘膠產生。 [實施例]In recent years, with the miniaturization of chip-size packaged LEDs, the chip-size packaged LEDs that have been cut into individual pieces tend to scatter easily during cutting. In contrast, by using the adhesive tape 1 of the present embodiment having the above-mentioned structure, it is possible to maintain good adhesion between the phosphor and the adhesive layer 3, and to suppress the scattering of the chip-size packaged LEDs that have been cut into individual pieces. In addition, after cutting, by irradiating the adhesive layer 3 with light such as ultraviolet rays to reduce the adhesive force, it becomes easy to peel off the chip-size packaged LEDs that have been cut into individual pieces from the adhesive tape 1, and the generation of residual adhesive on the peeled chip-size packaged LEDs can be suppressed. [Example]

接著,使用實施例及比較例更加具體地說明本發明。尚且,本發明並非係受到以下之實施例所限定者。Next, the present invention will be described in more detail using embodiments and comparative examples. However, the present invention is not limited to the following embodiments.

為了調整實施例及比較例所使用之各種黏著劑組成物,使用下述之矽氧系樹脂(a)~(j)作為黏著劑組成物之主成分,使用下述之具有矽原子鍵結氫原子(SiH)之有機聚矽氧烷(有機氫聚矽氧烷)(m)及(n)作為交聯劑。In order to adjust the various adhesive compositions used in the embodiments and comparative examples, the following silicone resins (a) to (j) are used as the main components of the adhesive compositions, and the following organopolysiloxanes (organohydropolysiloxanes) (m) and (n) having silicon atom-bonded hydrogen atoms (SiH) are used as crosslinking agents.

矽氧系樹脂(a)~(d)皆為含有矽原子鍵結烯基之矽氧膠(Galk )與矽氧樹脂(R)之混合物,其混合比率及矽原子鍵結烯基含量互為相異。該矽氧膠(Galk )係使用重量平均分子量(Mw)約50萬之分子鏈兩末端二甲基乙烯基矽氧基封鏈二甲基矽氧烷・甲基乙烯基矽氧烷共聚物,該矽氧樹脂(R)係使用重量平均分子量(Mw)約5,000之具有R2 3 SiO0.5 單位(M單位)及SiO2 單位(Q單位)之有機聚矽氧烷(MQ樹脂)。Silicone resins (a) to (d) are mixtures of silicone gel (G alk ) containing silicon-bonded alkenyl groups and silicone resin (R), and the mixing ratio and the content of silicon-bonded alkenyl groups are different from each other. The silicone gel (G alk ) uses a dimethylsiloxane-methylvinylsiloxane copolymer with a weight average molecular weight (Mw) of about 500,000 and dimethylvinylsiloxy groups at both ends of the molecular chain, and the silicone resin (R) uses an organic polysiloxane (MQ resin) with a weight average molecular weight (Mw) of about 5,000 and R 2 3 SiO 0.5 units (M units) and SiO 2 units (Q units).

又,矽氧系樹脂(e)及(f)皆為含有矽原子鍵結烯基之矽氧膠(Galk )之單獨物,且矽原子鍵結烯基含量互為相異。矽氧系樹脂(e)之矽氧膠(Galk )係使用重量平均分子量(Mw)約30萬之分子鏈兩末端二甲基己烯基矽氧基封鏈二甲基矽氧烷・甲基己烯基矽氧烷共聚物,矽氧系樹脂(f)之矽氧膠(Galk )係使用重量平均分子量(Mw)約20萬之分子鏈兩末端二甲基乙烯基矽氧基封鏈二甲基矽氧烷聚合物。In addition, both silicone resins (e) and (f) are single products of silicone gel (G alk ) containing silicon-bonded alkenyl groups, and the contents of silicon-bonded alkenyl groups are different from each other. The silicone gel (G alk ) of silicone resin (e) is a dimethylsiloxane-methylhexenylsiloxane copolymer with a weight average molecular weight (Mw) of about 300,000 and dimethylhexenylsiloxy groups at both ends of the molecular chain blocked, and the silicone gel (G alk ) of silicone resin (f) is a dimethylsiloxane polymer with a weight average molecular weight (Mw) of about 200,000 and dimethylvinylsiloxy groups at both ends of the molecular chain blocked.

並且,矽氧系樹脂(g)~(i)皆為不含有矽原子鍵結烯基之矽氧膠(G0 )與矽氧樹脂(R)之混合物,其混合比率互為相異。該矽氧膠(G0 )係使用重量平均分子量(Mw)約50萬之二甲基矽氧烷聚合物,該矽氧樹脂(R)係使用重量平均分子量(Mw)約5,000之具有R2 3 SiO0.5 單位(M單位)及SiO2 單位(Q單位)之有機聚矽氧烷(MQ樹脂)。Furthermore, the silicone resins (g) to (i) are all mixtures of silicone gel (G 0 ) and silicone resin (R) that do not contain silicon atom-bonded alkenyl groups, and the mixing ratios thereof are different from each other. The silicone gel (G 0 ) uses a dimethylsiloxane polymer with a weight average molecular weight (Mw) of about 500,000, and the silicone resin (R) uses an organic polysiloxane (MQ resin) with a weight average molecular weight (Mw) of about 5,000 and having R 2 3 SiO 0.5 units (M units) and SiO 2 units (Q units).

更進一步,矽氧系樹脂(j)為矽氧樹脂(R)之單獨物,該矽氧樹脂(R)係使用重量平均分子量(Mw)約5,000之具有R2 3 SiO0.5 單位(M單位)及SiO2 單位(Q單位)之有機聚矽氧烷(MQ樹脂)。Furthermore, the silicone resin (j) is a single silicone resin (R), and the silicone resin (R) is an organic polysiloxane (MQ resin) having a weight average molecular weight (Mw) of about 5,000 and having R 2 3 SiO 0.5 units (M units) and SiO 2 units (Q units).

・矽氧系樹脂(a) 矽氧膠(Galk )與矽氧樹脂(R)之混合物 (Galk )/(R)=40.0質量%/60.0質量% 烯基(乙烯基)含量:2.0×10-6 mol/g・Silicone resin (a) A mixture of silicone gel (G alk ) and silicone resin (R): (G alk )/(R) = 40.0 mass%/60.0 mass% Alkenyl (vinyl) content: 2.0×10 -6 mol/g

・矽氧系樹脂(b) 矽氧膠(Galk )與矽氧樹脂(R)之混合物 (Galk )/(R)=35.0質量%/65.0質量% 烯基(乙烯基)含量:1.8×10-6 mol/g・Silicone resin (b) A mixture of silicone gel (G alk ) and silicone resin (R): (G alk )/(R) = 35.0 mass%/65.0 mass% Alkenyl (vinyl) content: 1.8×10 -6 mol/g

・矽氧系樹脂(c) 矽氧膠(Galk )與矽氧樹脂(R)之混合物 (Galk )/(R)=50.0質量%/50.0質量% 烯基(乙烯基)含量:2.5×10-6 mol/g・Silicone resin (c) A mixture of silicone gel (G alk ) and silicone resin (R) (G alk )/(R) = 50.0 mass%/50.0 mass% Alkenyl (vinyl) content: 2.5×10 -6 mol/g

・矽氧系樹脂(d) 矽氧膠(Galk )與矽氧樹脂(R)之混合物 (Galk )/(R)=70.0質量%/30.0質量% 烯基(乙烯基)含量:3.5×10-6 mol/g・Silicone resin (d) A mixture of silicone gel (G alk ) and silicone resin (R): (G alk )/(R) = 70.0 mass%/30.0 mass% Alkenyl (vinyl) content: 3.5×10 -6 mol/g

・矽氧系樹脂(e) 矽氧膠(Galk )單質 烯基(己烯基)含量:2.0×10-4 mol/g・Silicone resin (e) Silicone gel (G alk ) single olefin (hexenyl) content: 2.0×10 -4 mol/g

・矽氧系樹脂(f) 矽氧膠(Galk )單質 烯基(乙烯基)含量:2.7×10-3 mol/g・Silicone resin (f) Silicone gel (G alk ) single vinyl content: 2.7×10 -3 mol/g

・矽氧系樹脂(g) 矽氧膠(G0 )與矽氧樹脂(R)之混合物 (G0 )/(R)=50.0質量%/50.0質量% 不含有烯基・Silicone resin (g) A mixture of silicone gel (G 0 ) and silicone resin (R) (G 0 )/(R)=50.0 mass%/50.0 mass% Does not contain olefinic

・矽氧系樹脂(h) 矽氧膠(G0 )與矽氧樹脂(R)之混合物 (G0 )/(R)=40.0質量%/60.0質量% 不含有烯基・Silicone resin (h) A mixture of silicone gel (G 0 ) and silicone resin (R) (G 0 )/(R) = 40.0 mass%/60.0 mass% Does not contain olefinic

・矽氧系樹脂(i) 矽氧膠(G0 )與矽氧樹脂(R)之混合物 (G0 )/(R)=60.0質量%/40.0質量% 不含有烯基・Silicone resin (i) A mixture of silicone gel (G 0 ) and silicone resin (R) (G 0 )/(R) = 60.0 mass%/40.0 mass% Does not contain olefinic

・矽氧系樹脂(j) 矽氧樹脂(R)單質 不含有烯基・Silicone resin (j) Silicone resin (R) single substance Does not contain olefin

・交聯劑(m) 有機氫聚矽氧烷 SiH基含量:2.0×10-2 mol/g・Crosslinking agent (m) Organic hydropolysiloxane SiH group content: 2.0×10 -2 mol/g

・交聯劑(n) 有機氫聚矽氧烷 SiH基含量:2.4×10-3 mol/g・Crosslinking agent (n) Organic hydropolysiloxane SiH group content: 2.4×10 -3 mol/g

尚且,上述使用之矽氧系樹脂之烯基含量及交聯劑之SiH基含量係藉由測量500MHz之1 H-NMR(核磁共振)光譜來進行定量。具體而言,使上述矽氧系樹脂脂不揮發成分充分溶解於包含二甲亞碸作為內部標準試料之重氯仿,使用日本電子股份有限公司製NMR裝置“JNM・ECA500”(製品名)來測量1 H-NMR(核磁共振)光譜。其次,求出測量光譜中之內部標準試料之二甲亞碸之共振訊號面積(積分值)與烯基之共振訊號面積(積分值),並從該比率算出矽氧系樹脂每1g(固體成分)之烯基之含量。又,關於交聯劑之SiH基含量也係同樣地操作,測量1 H-NMR光譜,求出測量光譜中之內部標準試料之二甲亞碸之共振訊號面積(積分值)與SiH基之共振訊號面積(積分值),並從該比率算出交聯劑每1g(固體成分)之SiH基之含量。尚且,交聯劑係從最初就已添加於矽氧系樹脂中之情況,從該1 H-NMR光譜同時算出烯基與SiH基之含量即可。Furthermore, the alkenyl content of the silicone resin and the SiH group content of the crosslinking agent used above are quantitatively determined by measuring 500MHz 1H -NMR (nuclear magnetic resonance) spectrum. Specifically, the non-volatile components of the silicone resin are fully dissolved in heavy chloroform containing dimethyl sulfoxide as an internal standard sample, and the 1H -NMR (nuclear magnetic resonance) spectrum is measured using the NMR device "JNM・ECA500" (product name) manufactured by JEOL Ltd. Next, the resonance signal area (integral value) of dimethyl sulfoxide as an internal standard sample and the resonance signal area (integral value) of the alkenyl group in the measured spectrum are calculated, and the alkenyl content per 1g (solid content) of the silicone resin is calculated from the ratio. The SiH group content of the crosslinking agent is similarly calculated by measuring the 1 H-NMR spectrum, finding the resonance signal area (integral value) of dimethyl sulfoxide, an internal standard sample, and the resonance signal area (integral value) of the SiH group in the measured spectrum, and calculating the SiH group content per 1g (solid content) of the crosslinking agent from the ratio. In addition, when the crosslinking agent is added to the silicone resin from the beginning, the contents of the alkenyl group and the SiH group can be calculated simultaneously from the 1 H-NMR spectrum.

1.黏著膠帶之製作 (實施例1) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(e)與矽氧系樹脂(g)與矽氧系樹脂(j)以質量比(e)/(g)/(j)成為2.72/83.43/13.85之方式來混合之矽氧系樹脂(S1)在甲苯中進行稀釋・攪拌,而調製出矽氧樹脂(S1)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S1)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為44.4/ 55.6,烯基含量為5.4×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(g)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。1. Preparation of Adhesive Tape (Example 1) <Preparation of Silicone Resin Solution> A silicone resin (S1) in which a silicone resin (e), a silicone resin (g) and a silicone resin (j) are mixed in a mass ratio (e)/(g)/(j) of 2.72/83.43/13.85 is diluted and stirred in toluene to prepare a silicone resin (S1) solution (solid content concentration 30 mass %). The silicone resin (S1) has a mixing ratio ((G)/(R)) of 44.4/55.6 of silicone gel (G) and silicone resin (R), and an olefin content of 5.4×10 -6 mol/g. Here, the total mass of silicone gel (G) is the total mass of "silicone gel (G alk ) of silicone resin (e)" and "silicone gel (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone gel (R) of silicone resin (g)" and "silicone gel (R) of silicone resin (j)".

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為8.82/91.18之方式來混合之交聯劑(C1)在甲苯進行稀釋・攪拌,而調製出交聯劑(C1)溶液(固體成分濃度20質量%)。該交聯劑(C1)之SiH基含量為4.0×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C1) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 8.82/91.18 was diluted and stirred in toluene to prepare a crosslinking agent (C1) solution (solid content 20 mass%). The SiH group content of the crosslinking agent (C1) was 4.0×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機(disper),對於上述矽氧系樹脂(S1)溶液333.00質量份(固體成分換算100質量份),摻合交聯劑(C1)溶液3.00質量份(固體成分換算0.60質量份、SiH基/烯基之莫耳比=4.4)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”4.18質量份(固體成分換算1.67質量份,固體成分濃度40質量%)並均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液4.47質量份(固體成分換算0.67質量份),並均勻地進行攪拌・混合而製作出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, using a disper, 333.00 parts by mass of the above-mentioned silicone resin (S1) solution (100 parts by mass as solid content), 3.00 parts by mass of the crosslinking agent (C1) solution (0.60 parts by mass as solid content, SiH group/olefin molar ratio = 4.4), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide] were mixed. 4.18 parts by mass (1.67 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were added and stirred and mixed uniformly. Next, 4.47 parts by mass (0.67 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and stirred and mixed uniformly to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為58μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 58 μm after drying is obtained.

(實施例2) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(e)與矽氧系樹脂(h)與矽氧系樹脂(j)以質量比(e)/(h)/(j)成為1.19/96.99/1.82之方式來混合之矽氧系樹脂(S2)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S2)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S2)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為40.0/ 60.0,烯基含量為2.4×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(h)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(h)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。(Example 2) <Preparation of Silicone Resin Solution> Silicone resin (S2) mixed with silicone resin (e) and silicone resin (h) and silicone resin (j) in a mass ratio (e)/(h)/(j) of 1.19/96.99/1.82 was diluted and stirred in toluene to prepare a silicone resin (S2) solution (solid content concentration 30 mass %). The silicone resin (S2) was a silicone gel (G) and a silicone resin (R) in a mixing ratio ((G)/(R)) of 40.0/60.0, and the alkenyl content was 2.4×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (e)" and "silicone glue (G 0 ) of silicone resin (h)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (h)" and "silicone resin (R) of silicone resin (j)".

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為2.83/97.17之方式來混合之交聯劑(C2)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C2)溶液(固體成分濃度20質量%)。該交聯劑(C2)之SiH基含量為2.9×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C2) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 2.83/97.17 was diluted and stirred in toluene to prepare a crosslinking agent (C2) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C2) was 2.9×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S2)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C2)溶液4.10質量份(固體成分換算0.82質量份,SiH基/烯基之莫耳比=10.0)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”3.85質量份(固體成分換算1.54質量份,固體成分濃度40質量%),並均一地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液6.47質量份(固體成分換算0.97質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S2) solution (100 parts by mass in terms of solid content) was mixed with 4.10 parts by mass of the crosslinking agent (C2) solution (0.82 parts by mass in terms of solid content, SiH group/olefin molar ratio = 10.0), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 3.85 parts by mass (1.54 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were added and stirred and mixed uniformly. Next, 6.47 parts by mass (0.97 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and stirred and mixed uniformly to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度12μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。且,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為10μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為22μm之黏著膠帶1。Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 12 μm. The adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of the drying furnace, and is dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the back half of the drying furnace is 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 10 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone is attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 22 μm after drying is obtained.

(實施例3) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(e)與矽氧系樹脂(g)與矽氧系樹脂(j)以質量比(e)/(g)/(j)成為2.09/87.26/10.65之方式來混合之矽氧系樹脂(S3)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S3)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S3)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為45.7/ 54.3,烯基含量為4.2×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(g)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。(Example 3) <Preparation of Silicone Resin Solution> Silicone resin (S3) mixed with silicone resin (e) and silicone resin (g) and silicone resin (j) in a mass ratio (e)/(g)/(j) of 2.09/87.26/10.65 was diluted and stirred in toluene to prepare a silicone resin (S3) solution (solid content concentration 30 mass %). The silicone resin (S3) has a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 45.7/54.3, and an olefin content of 4.2×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (e)" and "silicone glue (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (g)" and "silicone resin (R) of silicone resin (j)".

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為9.63/90.37之方式來混合之交聯劑(C3)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C3)溶液(固體成分濃度20質量%)。該交聯劑(C3)之SiH基含量為4.1×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C3) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 9.63/90.37 was diluted and stirred in toluene to prepare a crosslinking agent (C3) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C3) was 4.1×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S3)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C3)溶液2.10質量份(固體成分換算0.42質量份,SiH基/烯基之莫耳比=4.2)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”4.38質量份(固體成分換算1.75質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液3.13質量份(固體成分換算0.47質量份),均勻地進行攪拌・混合而製作出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S3) solution (100 parts by mass in terms of solid content) was mixed with 2.10 parts by mass of the crosslinking agent (C3) solution (0.42 parts by mass in terms of solid content, SiH group/olefin molar ratio = 4.2), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 4.38 parts by mass (1.75 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were uniformly stirred and mixed. Next, 3.13 parts by mass (0.47 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度50μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為40μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為90μm之黏著膠帶1。Next, the adhesive solution is applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 50 μm. Thereafter, the adhesive solution applied to the substrate 2 is initially dried in stages at a temperature of 40 to 90°C in the front half of the drying furnace, and is dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace is 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 40 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone is attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 90 μm after drying is obtained.

(實施例4) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(b)與矽氧系樹脂(e)與矽氧系樹脂(g)以質量比(b)/(e)/(g)成為49.51/0.97/49.52之方式來混合之矽氧系樹脂(S4)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S4)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S4)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為43.1/ 56.9,烯基含量為2.8×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(b)之矽氧膠(Galk )」與矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(b)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」之合計量。(Example 4) <Preparation of Silicone Resin Solution> Silicone resin (S4) mixed with silicone resin (b), silicone resin (e) and silicone resin (g) in a mass ratio (b)/(e)/(g) of 49.51/0.97/49.52 was diluted and stirred in toluene to prepare a silicone resin (S4) solution (solid content concentration 30 mass %). The silicone resin (S4) has a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 43.1/56.9, and an olefin content of 2.8×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (b)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (b)" and "silicone resin (R) of silicone resin (g)".

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為5.50/94.50之方式來混合之交聯劑(C4)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C4)溶液(固體成分濃度20質量%)。該交聯劑(C4)之SiH基含量為3.4×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C4) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 5.50/94.50 was diluted and stirred in toluene to prepare a crosslinking agent (C4) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C4) was 3.4×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S4)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C4)溶液1.75質量份(固體成分換算0.35質量份、SiH基/烯基之莫耳比=4.1)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”2.48質量份(固體成分換算0.99質量份、固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液2.67質量份(固體成分換算0.40質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S4) solution (100 parts by mass as solid content) was mixed with 1.75 parts by mass of the crosslinking agent (C4) solution (0.35 parts by mass as solid content, SiH group/olefin molar ratio = 4.1), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 2.48 parts by mass (0.99 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were uniformly stirred and mixed. Next, 2.67 parts by mass (0.40 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and the mixture was uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度125μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為145μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 125 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 145 μm after drying is obtained.

(實施例5) 以下述操作來調製矽氧系樹脂(S5)溶液,且在黏著劑溶液之製作中,除了將矽氧系樹脂(S4)溶液變更為矽氧系樹脂(S5)溶液,將交聯劑(C4)溶液之摻合量變更為2.10質量份(固體成分換算0.42質量份、SiH基/烯基之莫耳比=4.1),將有機過氧化物溶液之摻合量變更為1.93質量份(固體成分換算0.77質量份),將光感應鉑(Pt)觸媒溶液之摻合量變更為3.20質量份(固體成分換算0.48質量份),且將黏著劑層3之乾燥後之厚度變更為38μm以外,其他係與實施例4同樣地操作而取得乾燥後之總厚為58μm之黏著膠帶1。(Example 5) The following operation is used to prepare the silicone resin (S5) solution. In the preparation of the adhesive solution, in addition to changing the silicone resin (S4) solution to the silicone resin (S5) solution, the amount of the crosslinking agent (C4) solution is changed to 2.10 parts by mass (0.42 parts by mass in terms of solid content, SiH group/olefin molar ratio = 4.1), and the organic peroxide solution is added to the silicone resin (S5) solution. The adhesive tape 1 having a total thickness of 58 μm after drying is obtained by the same operation as in Example 4, except that the amount of the mixed liquid is changed to 1.93 mass parts (0.77 mass parts as solid component conversion), the amount of the mixed photosensitive platinum (Pt) catalyst solution is changed to 3.20 mass parts (0.48 mass parts as solid component conversion), and the thickness of the adhesive layer 3 after drying is changed to 38 μm.

<矽氧系樹脂溶液之調製> 使矽氧系樹脂(b)與矽氧系樹脂(e)與矽氧系樹脂(g)以質量比(b)/(e)/(g)成為60.37/1.18/38.45之方式來混合之矽氧系樹脂(S5)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S5)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S5)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為41.5/ 58.5,烯基含量為3.4×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(b)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(b)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」之合計量。<Preparation of Silicone Resin Solution> Silicone resin (S5) mixed with silicone resin (b) and silicone resin (e) and silicone resin (g) at a mass ratio (b)/(e)/(g) of 60.37/1.18/38.45 was diluted and stirred in toluene to prepare a silicone resin (S5) solution (solid content concentration 30 mass%). The silicone resin (S5) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 41.5/58.5, and an olefin content of 3.4×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (b)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (b)" and "silicone resin (R) of silicone resin (g)".

(實施例6) 以下述操作來調製矽氧系樹脂(S6)溶液,且在黏著劑溶液之製作中,除了將矽氧系樹脂(S5)溶液變更為矽氧系樹脂(S6)溶液,將交聯劑(C4)溶液之摻合量變更為1.40質量份(固體成分換算0.28質量份,SiH基/烯基之莫耳比=4.1),將有機過氧化物溶液之摻合量變更為2.98質量份(固體成分換算1.19質量份),將光感應鉑(Pt)觸媒溶液之摻合量變更為2.13質量份(固體成分換算0.32質量份)以外,其他係與實施例5同樣地操作而取得乾燥後之總厚為58μm之黏著膠帶1。(Example 6) The following operation is used to prepare a silicone resin (S6) solution. In the preparation of the adhesive solution, in addition to changing the silicone resin (S5) solution to a silicone resin (S6) solution, the amount of the crosslinking agent (C4) solution is changed to 1.40 parts by mass (0.28 parts by mass in terms of solid content, SiH group/olefin molar ratio = 4. 1), except that the amount of the organic peroxide solution was changed to 2.98 parts by mass (1.19 parts by mass as solid content), and the amount of the photosensitive platinum (Pt) catalyst solution was changed to 2.13 parts by mass (0.32 parts by mass as solid content), the other operations were the same as those in Example 5 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

<矽氧系樹脂溶液之調製> 使矽氧系樹脂(b)與矽氧系樹脂(e)與矽氧系樹脂(g)以質量比(b)/(e)/(g)成為39.69/0.78/59.53之方式來混合之矽氧系樹脂(S6)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S6)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S6)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為44.4/ 55.6,烯基含量為2.3×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(b)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(b)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」之合計量。<Preparation of Silicone Resin Solution> Silicone resin (S6) mixed with silicone resin (b) and silicone resin (e) and silicone resin (g) at a mass ratio (b)/(e)/(g) of 39.69/0.78/59.53 was diluted and stirred in toluene to prepare a silicone resin (S6) solution (solid content concentration 30 mass%). The silicone resin (S6) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 44.4/55.6, and an olefin content of 2.3×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (b)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (b)" and "silicone resin (R) of silicone resin (g)".

(實施例7) 以下述操作來調製矽氧系樹脂(S7)溶液,且在黏著劑溶液之製作中,除了將矽氧系樹脂(S5)溶液變更為矽氧系樹脂(S7)溶液,將交聯劑(C4)溶液之摻合量變更為1.75質量份(固體成分換算0.35質量份,SiH基/烯基之莫耳比=4.0),將有機過氧化物溶液之摻合量變更為2.48質量份(固體成分換算0.99質量份),將光感應鉑(Pt)觸媒溶液之摻合量變更為2.67質量份(固體成分換算0.40質量份)以外,其他係與實施例5同樣地操作而取得乾燥後之總厚為58μm之黏著膠帶1。(Example 7) The following operation is used to prepare a silicone resin (S7) solution. In the preparation of the adhesive solution, in addition to changing the silicone resin (S5) solution to a silicone resin (S7) solution, the amount of the crosslinking agent (C4) solution is changed to 1.75 parts by mass (0.35 parts by mass in terms of solid content, SiH group/olefin molar ratio = 4. 0), the amount of the organic peroxide solution was changed to 2.48 mass parts (0.99 mass parts in terms of solid content), and the amount of the photosensitive platinum (Pt) catalyst solution was changed to 2.67 mass parts (0.40 mass parts in terms of solid content). Other operations were performed in the same manner as in Example 5 to obtain an adhesive tape 1 having a total thickness of 58 μm after drying.

<矽氧系樹脂溶液之調製> 使矽氧系樹脂(a)與矽氧系樹脂(e)與矽氧系樹脂(g)以質量比(a)/(e)/(g)成為49.51/0.98/49.51之方式來混合之矽氧系樹脂(S7)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S7)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S7)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為45.5/ 54.5,烯基含量為2.9×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(a)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(a)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」之合計量。<Preparation of Silicone Resin Solution> Silicone resin (S7) mixed with silicone resin (a), silicone resin (e) and silicone resin (g) at a mass ratio (a)/(e)/(g) of 49.51/0.98/49.51 was diluted and stirred in toluene to prepare a silicone resin (S7) solution (solid content concentration 30 mass%). The silicone resin (S7) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 45.5/54.5, and an olefin content of 2.9×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (a)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone glue (R) of silicone resin (a)" and "silicone glue (R) of silicone resin (g)".

(實施例8) 以下述操作來調製矽氧系樹脂(S8)溶液,且在黏著劑溶液之製作中,除了將矽氧系樹脂(S5)溶液變更為矽氧系樹脂(S8)溶液,將交聯劑(C4)溶液之摻合量變更為1.40質量份(固體成分換算0.28質量份,SiH基/烯基之莫耳比=3.7),將有機過氧化物溶液之摻合量變更為2.95質量份(固體成分換算1.18質量份),將光感應鉑(Pt)觸媒溶液之摻合量變更為2.13質量份(固體成分換算0.32質量份)以外,其他係與實施例5同樣地操作而取得乾燥後之總厚為58μm之黏著膠帶1。(Example 8) The following operation is used to prepare a silicone resin (S8) solution. In the preparation of the adhesive solution, in addition to changing the silicone resin (S5) solution to a silicone resin (S8) solution, the amount of the crosslinking agent (C4) solution is changed to 1.40 parts by mass (0.28 parts by mass in terms of solid content, SiH group/olefin molar ratio = 3. 7), except that the blending amount of the organic peroxide solution was changed to 2.95 mass parts (1.18 mass parts in terms of solid content), and the blending amount of the photosensitive platinum (Pt) catalyst solution was changed to 2.13 mass parts (0.32 mass parts in terms of solid content), the other operations were carried out in the same manner as in Example 5 to obtain an adhesive tape 1 with a total thickness of 58 μm after drying.

<矽氧系樹脂溶液之調製> 使矽氧系樹脂(c)與矽氧系樹脂(e)與矽氧系樹脂(h)與矽氧系樹脂(j)以質量比(c)/(e)/(h)/(j)成為39.46/0.77/59.18/ 0.59之方式來混合之矽氧系樹脂(S8)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S8)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S8)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為56.0/44.0,烯基含量為2.5×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(c)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(h)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(c)之矽氧樹脂(R)」與「矽氧系樹脂(h)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。<Preparation of silicone resin solution> A silicone resin (S8) in which a silicone resin (c), a silicone resin (e), a silicone resin (h), and a silicone resin (j) were mixed at a mass ratio of (c)/(e)/(h)/(j) of 39.46/0.77/59.18/0.59 was diluted and stirred in toluene to prepare a silicone resin (S8) solution (solid content concentration: 30 mass %). The silicone resin (S8) has a mixing ratio ((G)/(R)) of 56.0/44.0 of silicone glue (G) and silicone resin (R), and an olefin content of 2.5×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (c)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (h)". The total mass of the silicone resin (R) is the total mass of the silicone resin (R) of the silicone resin (c), the silicone resin (R) of the silicone resin (h), and the silicone resin (R) of the silicone resin (j).

(實施例9) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(b)與矽氧系樹脂(e)與矽氧系樹脂(g)與矽氧系樹脂(j)以質量比(b)/(e)/(g)/(j)成為33.14/0.07/66.29/ 0.50之方式來混合之矽氧系樹脂(S9)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S9)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S9)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為44.8/55.2,烯基含量為7.1×10-7 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(b)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(b)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。(Example 9) <Preparation of silicone resin solution> A silicone resin (S9) in which silicone resin (b), silicone resin (e), silicone resin (g) and silicone resin (j) are mixed in a mass ratio of (b)/(e)/(g)/(j) of 33.14/0.07/66.29/0.50 is diluted and stirred in toluene to prepare a silicone resin (S9) solution (solid content concentration 30 mass %). The silicone resin (S9) has a mixing ratio ((G)/(R)) of 44.8/55.2 of silicone glue (G) and silicone resin (R), and an olefin content of 7.1×10 -7 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (b)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". The total mass of the silicone resin (R) is the total mass of the silicone resin (R) of the silicone resin (b), the silicone resin (R) of the silicone resin (g), and the silicone resin (R) of the silicone resin (j).

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為0.58/99.42之方式來混合之交聯劑(C5)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C5)溶液(固體成分濃度20質量%)。該交聯劑(C5)之SiH基含量為2.5×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C5) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 0.58/99.42 was diluted and stirred in toluene to prepare a crosslinking agent (C5) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C5) was 2.5×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S9)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C5)溶液1.10質量份(固體成分換算0.22質量份,SiH基/烯基之莫耳比=7.8)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”2.90質量份(固體成分換算1.16質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液1.80質量份(固體成分換算0.27質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S9) solution (100 parts by mass in terms of solid content) was mixed with 1.10 parts by mass of the crosslinking agent (C5) solution (0.22 parts by mass in terms of solid content, SiH group/olefin molar ratio = 7.8), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 2.90 parts by mass (1.16 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were uniformly stirred and mixed. Next, 1.80 parts by mass (0.27 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為25μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為63μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 25 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 63 μm after drying is obtained.

(實施例10) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(c)與矽氧系樹脂(e)與矽氧系樹脂(g)與矽氧系樹脂(j)以質量比(c)/(e)/(g)/(j)成為48.91/1.45/48.91/ 0.73之方式來混合之矽氧系樹脂(S10)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S10)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S10)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為50.4/49.6,烯基含量為4.1×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(c)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(c)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。(Example 10) <Preparation of a silicone resin solution> A silicone resin (S10) in which a silicone resin (c), a silicone resin (e), a silicone resin (g), and a silicone resin (j) are mixed in a mass ratio of (c)/(e)/(g)/(j) of 48.91/1.45/48.91/0.73 is diluted and stirred in toluene to prepare a silicone resin (S10) solution (solid content concentration: 30 mass %). The silicone resin (S10) has a mixing ratio ((G)/(R)) of 50.4/49.6 of silicone glue (G) and silicone resin (R), and an olefin content of 4.1×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (c)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". The total mass of the silicone resin (R) is the total mass of the silicone resin (R) of the silicone resin (c), the silicone resin (R) of the silicone resin (g), and the silicone resin (R) of the silicone resin (j).

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為8.04/91.9之方式來混合之交聯劑(C6)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C6)溶液(固體成分濃度20質量%)。該交聯劑(C6)之SiH基含量為3.8×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C6) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 8.04/91.9 was diluted and stirred in toluene to prepare a crosslinking agent (C6) solution (solid content 20 mass%). The SiH group content of the crosslinking agent (C6) was 3.8×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S10)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C6)溶液1.75質量份(固體成分換算0.35質量份,SiH基/烯基之莫耳比=3.3)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”1.83質量份(固體成分換算0.73質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液2.60質量份(固體成分換算0.39質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S10) solution (100 parts by mass as solid content) was mixed with 1.75 parts by mass of the crosslinking agent (C6) solution (0.35 parts by mass as solid content, SiH group/olefin molar ratio = 3.3), organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide] using a disperser. 1.83 parts by mass (0.73 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were added and stirred and mixed uniformly. Next, 2.60 parts by mass (0.39 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and stirred and mixed uniformly to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為58μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 58 μm after drying is obtained.

(比較例1) 以下述操作來調製矽氧系樹脂(S11)溶液,除了將矽氧系樹脂(S1)溶液變更為矽氧系樹脂(S11)溶液,且在黏著劑溶液之製作中,並未摻合交聯劑及有機過氧化物,將光感應鉑(Pt)觸媒溶液之摻合量變更為5.33質量份(固體成分換算0.80質量份),將黏著劑層3之乾燥後之厚度變更為35μm以外,其他係與實施例1同樣地操作而取得乾燥後之總厚為73μm之黏著膠帶1。(Comparative Example 1) The following operation was used to prepare a silicone resin (S11) solution, except that the silicone resin (S1) solution was changed to a silicone resin (S11) solution, and in the preparation of the adhesive solution, no crosslinking agent and organic peroxide were mixed, the mixing amount of the photosensitive platinum (Pt) catalyst solution was changed to 5.33 parts by mass (0.80 parts by mass in terms of solid content), and the thickness of the adhesive layer 3 after drying was changed to 35μm. The other operations were the same as those of Example 1 to obtain an adhesive tape 1 with a total thickness of 73μm after drying.

<矽氧系樹脂溶液之調製> 使矽氧系樹脂(a)與矽氧系樹脂(f)以質量比(a)/(f)成為99.90/0.10之方式來混合之矽氧系樹脂(S11)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S11)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S11)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為40.1/59.9,烯基含量為4.7×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(a)之矽氧膠(Galk )」與「矽氧系樹脂(f)之矽氧膠(Galk )」之合計量。又,矽氧樹脂(R)之總質量為矽氧系樹脂(a)之矽氧樹脂(R)之量。<Preparation of Silicone Resin Solution> Silicone resin (S11) mixed with silicone resin (a) and silicone resin (f) at a mass ratio (a)/(f) of 99.90/0.10 was diluted and stirred in toluene to prepare a silicone resin (S11) solution (solid content concentration 30 mass%). The silicone resin (S11) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 40.1/59.9, and an olefin content of 4.7×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (a)" and "silicone glue (G alk ) of silicone resin (f)". In addition, the total mass of silicone resin (R) is the amount of silicone resin (R) of silicone resin (a).

(比較例2) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(b)與矽氧系樹脂(e)與矽氧系樹脂(g)以質量比(b)/(e)/(g)成為49.28/1.45/49.28之方式來混合之矽氧系樹脂(S12)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S12)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S12)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為43.3/56.7,烯基含量為3.8×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(b)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(g)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(b)之矽氧樹脂(R)」與「矽氧系樹脂(g)之矽氧樹脂(R)」之合計量。(Comparative Example 2) <Preparation of Silicone Resin Solution> Silicone resin (S12) mixed with silicone resin (b) and silicone resin (e) and silicone resin (g) at a mass ratio (b)/(e)/(g) of 49.28/1.45/49.28 was diluted and stirred in toluene to prepare a silicone resin (S12) solution (solid content concentration 30 mass %). The silicone resin (S12) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 43.3/56.7, and an olefin content of 3.8×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (b)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (g)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (b)" and "silicone resin (R) of silicone resin (g)".

<交聯劑溶液之調製> 接著,與實施例10同樣地操作而調製出交聯劑(C6)溶液(固體成分濃度20質量%)。<Preparation of crosslinking agent solution> Then, the same operation as in Example 10 was performed to prepare a crosslinking agent (C6) solution (solid content concentration 20 mass %).

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S12)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C6)溶液1.75質量份(固體成分換算0.35質量份,SiH基/烯基之莫耳比=3.6)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”2.48質量份(固體成分換算0.99質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合陶氏東麗股份有限公司製鉑(Pt)金屬系觸媒“NC-25”(商品名,固體成分濃度25質量%)之溶液2.96質量份(固體成分換算0.74質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, 333.00 parts by mass of the above-mentioned silicone resin (S12) solution (100 parts by mass as solid content) was mixed with 1.75 parts by mass of the crosslinking agent (C6) solution (0.35 parts by mass as solid content, SiH group/olefin molar ratio = 3.6), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 2.48 parts by mass (0.99 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were added and uniformly stirred and mixed. Next, 2.96 parts by mass (0.74 parts by mass as solid content) of a solution of platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Co., Ltd. were added using a disperser and uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成於乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,而取得乾燥後之總厚為58μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with fluoroalkyl modified silicone was attached to the adhesive layer 3. In this way, an adhesive tape 1 having a total thickness of 58 μm after drying is obtained.

(比較例3) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(e)與矽氧系樹脂(h)以質量比(e)/(h)成為0.26/99.74之方式來混合之矽氧系樹脂(S13)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S13)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S13)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為40.2/59.8,烯基含量為5.2×10-7 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(h)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為矽氧系樹脂(h)之矽氧樹脂(R)之量。(Comparative Example 3) <Preparation of Silicone Resin Solution> Silicone resin (S13) mixed with silicone resin (e) and silicone resin (h) at a mass ratio (e)/(h) of 0.26/99.74 was diluted and stirred in toluene to prepare a silicone resin (S13) solution (solid content concentration 30 mass %). The silicone resin (S13) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 40.2/59.8, and an olefin content of 5.2×10 -7 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (e)" and "silicone glue (G 0 ) of silicone resin (h)". In addition, the total mass of silicone resin (R) is the amount of silicone resin (R) of silicone resin (h).

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為1.15/98.85之方式來混合之交聯劑(C7)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C7)溶液(固體成分濃度20質量%)。該交聯劑(C7)之SiH基含量為2.6×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C7) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 1.15/98.85 was diluted and stirred in toluene to prepare a crosslinking agent (C7) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C7) was 2.6×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S13)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C7)溶液2.20質量份(固體成分換算0.44質量份,SiH基/烯基之莫耳比=22.2)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”4.98質量份(固體成分換算1.99質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液3.53質量份(固體成分換算0.53質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, using a disperser, 333.00 parts by mass of the above-mentioned silicone resin (S13) solution (100 parts by mass in terms of solid content) was mixed with 2.20 parts by mass of the crosslinking agent (C7) solution (0.44 parts by mass in terms of solid content, SiH group/olefin molar ratio = 22.2), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 4.98 parts by mass (1.99 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were uniformly stirred and mixed. Next, 3.53 parts by mass (0.53 parts by mass as solid content) of a photosensitive platinum (Pt) catalyst "trimethyl (methylcyclopentadienyl) platinum (IV)" manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene to a solution having a solid content concentration of 15% by mass and mixed using a disperser, and the mixture was uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,取得乾燥後之總厚為58μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.

(比較例4) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(e)與矽氧系樹脂(i)與矽氧系樹脂(j)以質量比(e)/(i)/(j)成為4.67/79.44/15.89之方式來混合之矽氧系樹脂(S14)在甲苯中進行稀釋・攪拌,而調製出矽氧樹脂(S14)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S14)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為52.3/ 47.7,烯基含量為9.4×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(i)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(i)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。(Comparative Example 4) <Preparation of Silicone Resin Solution> Silicone resin (S14) mixed with silicone resin (e) and silicone resin (i) and silicone resin (j) in a mass ratio (e)/(i)/(j) of 4.67/79.44/15.89 was diluted and stirred in toluene to prepare a silicone resin (S14) solution (solid content concentration 30 mass %). The silicone resin (S14) had a mixing ratio ((G)/(R)) of silicone gel (G) and silicone resin (R) of 52.3/47.7, and an olefin content of 9.4×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (e)" and "silicone glue (G 0 ) of silicone resin (i)". In addition, the total mass of silicone resin (R) is the total mass of "silicone resin (R) of silicone resin (i)" and "silicone resin (R) of silicone resin (j)".

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為14.88/85.12之方式來混合之交聯劑(C8)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C8)溶液(固體成分濃度20質量%)。該交聯劑(C8)之SiH基含量為5.0×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C8) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 14.88/85.12 was diluted and stirred in toluene to prepare a crosslinking agent (C8) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C8) was 5.0×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S14)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C8)溶液3.10質量份(固體成分換算0.62質量份,SiH基/烯基之莫耳比=3.3)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”1.20質量份(固體成分換算0.48質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合以甲苯將西格瑪奧瑞奇日本合同公司製之光感應鉑(Pt)觸媒“三甲基(甲基環戊二烯基)鉑(IV)”稀釋成固體成分濃度15質量%之溶液4.27質量份(固體成分換算0.64質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, using a disperser, 333.00 parts by mass of the above-mentioned silicone resin (S14) solution (100 parts by mass in terms of solid content) was mixed with 3.10 parts by mass of the crosslinking agent (C8) solution (0.62 parts by mass in terms of solid content, SiH group/olefin molar ratio = 3.3), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 1.20 parts by mass (0.48 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were uniformly stirred and mixed. Next, 4.27 parts by mass (0.64 parts by mass as solid content) of a solution having a solid content concentration of 15% by mass of "trimethyl (methylcyclopentadienyl) platinum (IV)" of a photosensitive platinum (Pt) catalyst manufactured by Sigma-Aldrich Japan Contract Co., Ltd. was diluted with toluene and mixed using a disperser, and uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,取得乾燥後之總厚為58μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.

(比較例5) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(b)與矽氧系樹脂(e)與矽氧系樹脂(h)與矽氧系樹脂(j)以質量比(b)/(e)/(h)/(j)成為47.29/0.69/47.29 /4.73之方式來混合之矽氧系樹脂(S15)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S15)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S15)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為36.2/63.8,烯基含量為2.3×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(b)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(h)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(b)之矽氧樹脂(R)」與「矽氧系樹脂(h)之矽氧樹脂(R)」與「矽氧系樹脂(j)之矽氧樹脂(R)」之合計量。(Comparative Example 5) <Preparation of a silicone resin solution> A silicone resin (S15) in which a silicone resin (b), a silicone resin (e), a silicone resin (h), and a silicone resin (j) were mixed in a mass ratio of (b)/(e)/(h)/(j) of 47.29/0.69/47.29/4.73 was diluted and stirred in toluene to prepare a silicone resin (S15) solution (solid content concentration: 30 mass %). The silicone resin (S15) has a mixing ratio ((G)/(R)) of 36.2/63.8 of silicone gel (G) and silicone resin (R), and an olefin content of 2.3×10 -6 mol/g. Here, the total mass of silicone gel (G) is the total mass of "silicone gel (G alk ) of silicone resin (b)", "silicone gel (G alk ) of silicone resin (e)", and "silicone gel (G 0 ) of silicone resin (h)". The total mass of the silicone resin (R) is the total mass of the silicone resin (R) of the silicone resin (b), the silicone resin (R) of the silicone resin (h), and the silicone resin (R) of the silicone resin (j).

<交聯劑溶液之調製> 接著,使交聯劑(m)與交聯劑(n)以質量比(m)/(n)成為4.19/95.81之方式來混合之交聯劑(C9)在甲苯中進行稀釋・攪拌,而調製出交聯劑(C9)溶液(固體成分濃度20質量%)。該交聯劑(C9)之SiH基含量為3.1×10-3 mol/g。<Preparation of crosslinking agent solution> Next, crosslinking agent (C9) mixed with crosslinking agent (m) and crosslinking agent (n) at a mass ratio (m)/(n) of 4.19/95.81 was diluted and stirred in toluene to prepare a crosslinking agent (C9) solution (solid content concentration 20 mass%). The SiH group content of the crosslinking agent (C9) was 3.1×10 -3 mol/g.

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S15)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C9)溶液1.65質量份(固體成分換算0.33質量份,SiH基/烯基之莫耳比=4.4)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”2.38質量份(固體成分換算0.95質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機來摻合陶氏東麗股份有限公司製鉑(Pt)金屬系觸媒“NC-25”(商品名,固體成分濃度25質量%)之溶液2.53質量份(固體成分換算0.38質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, using a disperser, 333.00 parts by mass of the above-mentioned silicone resin (S15) solution (100 parts by mass as solid content) was mixed with 1.65 parts by mass of the crosslinking agent (C9) solution (0.33 parts by mass as solid content, SiH group/olefin molar ratio = 4.4), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 2.38 parts by mass (0.95 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were added and uniformly stirred and mixed. Next, 2.53 parts by mass (0.38 parts by mass as solid content) of a solution of platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Co., Ltd. were added using a disperser and uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為30μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,取得乾燥後之總厚為68μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 30 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 68 μm after drying was obtained.

(比較例6) <矽氧系樹脂溶液之調製> 使矽氧系樹脂(d)與矽氧系樹脂(e)與矽氧系樹脂(i)以質量比(d)/(e)/(i)成為49.28/1.45/49.28之方式來混合之矽氧系樹脂(S16)在甲苯中進行稀釋・攪拌,而調製出矽氧系樹脂(S16)溶液(固體成分濃度30質量%)。該矽氧系樹脂(S16)係矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為65.5/34.5,烯基含量為4.6×10-6 mol/g。在此,矽氧膠(G)之總質量為「矽氧系樹脂(d)之矽氧膠(Galk )」與「矽氧系樹脂(e)之矽氧膠(Galk )」與「矽氧系樹脂(i)之矽氧膠(G0 )」之合計量。又,矽氧樹脂(R)之總質量為「矽氧系樹脂(d)之矽氧樹脂(R)」與「矽氧系樹脂(i)之矽氧樹脂(R)」之合計量。(Comparative Example 6) <Preparation of Silicone Resin Solution> Silicone resin (S16) in which silicone resin (d) and silicone resin (e) and silicone resin (i) were mixed in a mass ratio (d)/(e)/(i) of 49.28/1.45/49.28 was diluted and stirred in toluene to prepare a silicone resin (S16) solution (solid content concentration 30 mass %). The silicone resin (S16) had a mixing ratio ((G)/(R)) of 65.5/34.5 between silicone gel (G) and silicone resin (R), and an olefin content of 4.6×10 -6 mol/g. Here, the total mass of silicone glue (G) is the total mass of "silicone glue (G alk ) of silicone resin (d)", "silicone glue (G alk ) of silicone resin (e)", and "silicone glue (G 0 ) of silicone resin (i)". In addition, the total mass of silicone resin (R) is the total mass of "silicone glue (R) of silicone resin (d)" and "silicone glue (R) of silicone resin (i)".

<交聯劑溶液之調製> 接著,與實施例10同樣地操作而調製出交聯劑(C6)溶液(固體成分濃度20質量%)。<Preparation of crosslinking agent solution> Then, the same operation as in Example 10 was performed to prepare a crosslinking agent (C6) solution (solid content concentration 20 mass %).

<黏著劑溶液之製作> 接著,使用分散機,對於上述矽氧系樹脂(S16)溶液333.00質量份(固體成分換算100質量份)摻合交聯劑(C6)溶液1.75質量份(固體成分換算0.35質量份,SiH基/烯基之莫耳比=2.9)、日油股份有限公司製之有機過氧化物[(二-(3-甲基苄醯基)過氧化物、苄醯基(3-甲基苄醯基)過氧化物、二苄醯基過氧化物之混合物]溶液“Nyper BMT-40K(商品名,1分鐘半衰期溫度:131.1℃)”2.48質量份(固體成分換算0.99質量份,固體成分濃度40質量%),均勻地進行攪拌・混合。其次,使用分散機摻合陶氏東麗股份有限公司製鉑(Pt)金屬系觸媒“NC-25”(商品名,固體成分濃度25質量%)之溶液2.60質量份(固體成分換算0.39質量份),均勻地進行攪拌・混合而調製出塗佈用黏著劑溶液。<Preparation of adhesive solution> Next, using a disperser, 333.00 parts by mass of the above-mentioned silicone resin (S16) solution (100 parts by mass as solid content) was mixed with 1.75 parts by mass of the crosslinking agent (C6) solution (0.35 parts by mass as solid content, SiH group/olefin molar ratio = 2.9), and organic peroxide solution "Nyper" manufactured by NOF Corporation [a mixture of di-(3-methylbenzyl) peroxide, benzyl (3-methylbenzyl) peroxide, and dibenzyl peroxide]. 2.48 parts by mass (0.99 parts by mass as solid content, solid content concentration 40% by mass) of "BMT-40K (trade name, 1 minute half-life temperature: 131.1°C)" were added and uniformly stirred and mixed. Next, 2.60 parts by mass (0.39 parts by mass as solid content) of a solution of a platinum (Pt) metal catalyst "NC-25" (trade name, solid content concentration 25% by mass) manufactured by Dow Toray Industries, Ltd. were added using a disperser and uniformly stirred and mixed to prepare a coating adhesive solution.

接著,將該黏著劑溶液塗佈於厚度38μm之由聚對酞酸乙二酯(PET)膜所構成之基材2上。其後,將塗佈於基材2上之黏著劑溶液在乾燥爐之前半部中,在40~90℃之溫度下階段性地進行初期乾燥,並且,使其在設置於乾燥爐後半部之熱處理之最高溫度成為160℃之區域乾燥3分鐘使黏著劑層3加熱・硬化,而形成乾燥後之厚度為20μm之黏著劑層3。其次,將經氟烷基變性矽氧來離型處理之剝離襯墊貼合於黏著劑層3。藉此,取得乾燥後之總厚為58μm之黏著膠帶1。Next, the adhesive solution was applied to a substrate 2 made of a polyethylene terephthalate (PET) film with a thickness of 38 μm. Thereafter, the adhesive solution applied to the substrate 2 was staged for initial drying at a temperature of 40 to 90°C in the front half of the drying furnace, and was dried for 3 minutes in a zone where the highest temperature of the heat treatment set in the rear half of the drying furnace was 160°C to heat and harden the adhesive layer 3, thereby forming an adhesive layer 3 with a thickness of 20 μm after drying. Next, a release pad treated with a fluoroalkyl modified silicone was attached to the adhesive layer 3. Thus, an adhesive tape 1 having a total thickness of 58 μm after drying was obtained.

將實施例1~10、及比較例1~6所製作之黏著膠帶1中之構成及黏著劑層3之組成展示於表1~表3。The structures of the adhesive tapes 1 and the compositions of the adhesive layer 3 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 are shown in Tables 1 to 3.

2.評價方法 接著,說明關於黏著膠帶1之評價方法。 (1)黏著力試驗(UV照射前) 對於實施例1~10及比較例1~6所製作之黏著膠帶1,根據黏著膠帶・黏著片試驗方法(JIS Z 0237(2009))記載之方法,實施對BA-SUS黏著力試驗(撕離黏著力試驗)。 具體而言,使已將剝離襯墊剝下之黏著膠帶1貼附於經過輝面退火(BA)處理之表面粗度(Ra)50±25nm之不鏽鋼板(SUS304),使質量2000g之輥輪以5mm/s之速度來回1次進行壓著。接著,放置20~40分後,使用拉升試驗機,對不鏽鋼板朝180°方向以5mm/s之速度來撕離,並測量相對於研磨SUS板之黏著力。 尚且,黏著力試驗係對照射紫外線(UV)前之黏著膠帶1實施者。又,作為黏著力試驗之結果,在考慮到將黏著膠帶1使用於半導體材料之切割時之固定力,以2.4N/ 10mm以上為佳,從藉由切割而經個片化之半導體晶片等之拾取性之觀點,以5.5N/10mm以下為佳。較佳為2.8N/ 10mm以上、5.5N/10mm以下。2. Evaluation method Next, the evaluation method of the adhesive tape 1 is described. (1) Adhesion test (before UV irradiation) The adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were subjected to a BA-SUS adhesion test (peel-off adhesion test) according to the method described in Adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)). Specifically, the adhesive tape 1 from which the peel-off liner had been peeled off was attached to a stainless steel plate (SUS304) having a surface roughness (Ra) of 50±25nm and subjected to buffing annealing (BA) treatment, and a roller with a mass of 2000g was pressed back and forth once at a speed of 5mm/s. Then, after leaving it for 20 to 40 minutes, use a pull-up tester to tear off the stainless steel plate in the 180° direction at a speed of 5mm/s, and measure the adhesion relative to the polished SUS plate. Moreover, the adhesion test is performed on the adhesive tape 1 before irradiation with ultraviolet rays (UV). In addition, as a result of the adhesion test, considering that the fixing force of the adhesive tape 1 when used for cutting semiconductor materials is preferably 2.4N/10mm or more, and from the perspective of the pick-up of semiconductor chips that are cut into pieces by cutting, it is preferably 5.5N/10mm or less. It is better to be 2.8N/10mm or more and 5.5N/10mm or less.

(2)滾球黏性試驗 (2-1)初期(UV照射前)滾球黏性之測量 對於實施例1~10及比較例1~6所製作之照射UV前之黏著膠帶1,根據黏著膠帶・黏著片試驗方法(JIS Z 0237 (2009))記載之方法來實施滾球黏性試驗。(2) Rolling ball adhesion test (2-1) Measurement of initial (before UV irradiation) rolling ball adhesion For the adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 before UV irradiation, a rolling ball adhesion test was performed according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)).

(2-2)UV照射後滾球黏性之測量 從實施例1~10及比較例1~6所製作之個別之黏著膠帶1之基材側照射UV,在溫度23℃、濕度50±5%RH之條件下放置20~40分鐘後,剝下個別黏著膠帶1之剝離襯墊,根據黏著膠帶・黏著片試驗方法(JIS Z 0237(2009))記載之方法,與初期(UV照射前)滾球黏性同樣地進行滾球黏性試驗。 UV之照射係使用高壓水銀燈,以波長365nm之UV成為累積光量1200mJ/cm2 之方式進行調整來照射。尚且,關於將累積光量作成3000mJ/cm2 時之滾球黏性,也係同樣地進行測量,但由於並未發現與將累積光量作成1200mJ/cm2 時之差別,故在此將累積光量作為1200mJ/cm2 來進行評價。(2-2) Measurement of roller ball adhesion after UV irradiation The substrate side of each adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 was irradiated with UV and placed at a temperature of 23°C and a humidity of 50±5%RH for 20 to 40 minutes. The peeling pad of each adhesive tape 1 was then peeled off and the roller ball adhesion test was performed in the same manner as the initial (before UV irradiation) roller ball adhesion test according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)). The UV irradiation was performed using a high-pressure mercury lamp and was adjusted so that the UV with a wavelength of 365nm became an accumulated light amount of 1200mJ/ cm2 . Furthermore, the rolling ball viscosity was measured in the same manner when the integrated light amount was set to 3000mJ/ cm2 , but no difference was found when the integrated light amount was set to 1200mJ/ cm2 , so the integrated light amount was set to 1200mJ/ cm2 for evaluation.

作為滾球黏性試驗之結果,在考慮到藉由切割而經個片化之半導體晶片等之拾取性時,與初期(UV照射前)滾球黏性(滾球No.)相比,UV照射後滾球黏性(滾球No.)係以較低為佳。即,將UV照射前之球號之值設為BN0,將UV照射後之球號之值設為BN1時,以BN0>BN1之關係為佳。該關係係意指藉由UV照射而黏著劑層3之第2階段之交聯反應受到促進,而凝聚力比UV照射前還要增加。As a result of the rolling ball adhesion test, when considering the pick-up properties of semiconductor chips that have been cut into pieces by dicing, the rolling ball adhesion (roller ball No.) after UV irradiation is preferably lower than the initial (before UV irradiation) rolling ball adhesion (roller ball No.). That is, when the value of the ball number before UV irradiation is set as BN0 and the value of the ball number after UV irradiation is set as BN1, the relationship of BN0>BN1 is preferred. This relationship means that the cross-linking reaction of the second stage of the adhesive layer 3 is promoted by UV irradiation, and the cohesion is increased compared to before UV irradiation.

(3)保持力試驗 (3-1)初期(UV照射前)保持力之測量 對於實施例1~10及比較例1~6所製作之照射UV前之黏著膠帶1,根據黏著膠帶・黏著片試驗方法(JIS Z 0237 (2009))記載之方法來實施保持力試驗。 具體而言,將個別之黏著膠帶1之剝離襯墊剝下,將黏著劑層3貼附於經過耐水研磨紙研磨之不鏽鋼板(SUS304),在裝載指定重量之狀態下,保持在溫度40℃、濕度33%RH之條件下,測量黏著膠帶1從不鏽鋼板剝離落下為止之經過時間(落下時間(分))。並且,觀察黏著膠帶1從不鏽鋼板剝離時之破壞模式(黏著劑層3與不鏽鋼板之間之破壞模式為界面剝離或凝集破壞)。尚且,保持力試驗之落下時間之測量係進行到2880分鐘為止。又,作為後述之表4~表6所示之保持力試驗之結果,展示落下時間(分)及黏著膠帶1之破壞模式。(3) Holding force test (3-1) Measurement of initial (before UV irradiation) holding force The holding force test was conducted on the adhesive tapes 1 produced in Examples 1 to 10 and Comparative Examples 1 to 6 before UV irradiation according to the method described in the adhesive tape and adhesive sheet test method (JIS Z 0237 (2009)). Specifically, the peeling pad of each adhesive tape 1 was peeled off, and the adhesive layer 3 was attached to a stainless steel plate (SUS304) polished with water-resistant abrasive paper. The adhesive tape 1 was loaded with a specified weight and kept at a temperature of 40°C and a humidity of 33% RH. The time (falling time (min)) from the time the adhesive tape 1 peeled off the stainless steel plate and fell off was measured. Furthermore, the failure mode of the adhesive tape 1 when it is peeled off from the stainless steel plate is observed (the failure mode between the adhesive layer 3 and the stainless steel plate is interface peeling or cohesion failure). Moreover, the measurement of the drop time of the holding force test is carried out until 2880 minutes. In addition, the drop time (minutes) and the failure mode of the adhesive tape 1 are displayed as the results of the holding force test shown in Tables 4 to 6 described later.

(3-2)UV照射後保持力之測量 與上述UV照射後之滾球黏性之測量記載之條件同樣地進行對黏著膠帶1照射UV並放置後,與初期保持力同樣地進行保持力試驗。(3-2) Measurement of holding power after UV irradiation The adhesive tape 1 was irradiated with UV and left to stand under the same conditions as the measurement of rolling ball viscosity after UV irradiation described above, and then the holding power test was performed in the same manner as the initial holding power test.

(3-3)關於保持力與破壞模式之關係 在此,說明關於黏著膠帶1之保持力與破壞模式之關係。圖3係展示黏著劑層3中之矽氧系樹脂之交聯密度,與黏著膠帶1之保持力試驗之結果(落下時間)之關係的模式圖。 如圖3所示,黏著膠帶1中,隨著黏著劑層3中之矽氧系樹脂之交聯密度變高,由保持力試驗所成之黏著膠帶1對不鏽鋼板之破壞模式則係呈現[黏著劑層3之凝集破壞(落下)]→[保持(不會落下)]→[黏著劑層3與不鏽鋼板之界面剝離(落下)]之變化。(3-3) Relationship between holding force and failure mode Here, the relationship between the holding force and failure mode of the adhesive tape 1 is described. Figure 3 is a schematic diagram showing the relationship between the crosslinking density of the silicone resin in the adhesive layer 3 and the result of the holding force test of the adhesive tape 1 (falling time). As shown in FIG. 3 , in the adhesive tape 1 , as the cross-linking density of the silicone resin in the adhesive layer 3 increases, the damage mode of the adhesive tape 1 to the stainless steel plate from the retention test shows a change from [aggregation damage of the adhesive layer 3 (falling)] → [retention (no falling)] → [interface peeling (falling) between the adhesive layer 3 and the stainless steel plate].

又,如圖3所示,在黏著膠帶1之破壞模式為凝集破壞之區域中,黏著膠帶1之保持力(落下時間)係隨著黏著劑層3中之矽氧系樹脂之交聯密度變高而上升。 另一方面,如圖3所示,黏著膠帶1之破壞模式為界面剝離之區域中,黏著膠帶1之保持力(落下時間)係隨著黏著劑層3中之矽氧系樹脂之交聯密度變高而降低。此推測係隨著矽氧系樹脂之交聯密度變高而黏著劑層3之凝聚力上升,從而黏著膠帶1之黏著力降低,其結果係黏著膠帶容易從不鏽鋼板剝離而落下所致。Furthermore, as shown in FIG3 , in the region where the failure mode of the adhesive tape 1 is coagulation failure, the holding force (drop time) of the adhesive tape 1 increases as the crosslinking density of the silicone resin in the adhesive layer 3 increases. On the other hand, as shown in FIG3 , in the region where the failure mode of the adhesive tape 1 is interface peeling, the holding force (drop time) of the adhesive tape 1 decreases as the crosslinking density of the silicone resin in the adhesive layer 3 increases. This is speculated to be because as the cross-linking density of the silicone resin increases, the cohesive force of the adhesive layer 3 increases, thereby reducing the adhesive force of the adhesive tape 1, resulting in the adhesive tape being easily peeled off from the stainless steel plate and falling off.

作為保持力試驗之結果,至少係以UV照射後之破壞模式為保持或界面剝離為佳,至少係以UV照射後之破壞模式為界面剝離為較佳,以初期(UV照射前)及UV照射後之破壞模式皆為界面剝離為更佳。又,在初期(UV照射前)與UV照射後之破壞模式皆為界面剝離之情況,落下時間在從將黏著膠帶1使用於切割半導體材料時之固定力之觀點,初期(UV照射前)係以盡可能地長,或不會落下為佳,在UV照射後,從藉由切割而經個片化之半導體晶片等之拾取性之觀點,以與初期(UV照射前)相比為較短為佳。 於此情況,將黏著膠帶1使用於半導體元件基板等之切割後,將取得之半導體晶片等從黏著膠帶1剝離之際,藉由對黏著膠帶1照射UV,而半導體晶片等上變得不易產生殘膠。As the result of the holding force test, it is preferred that the damage mode after UV irradiation is at least holding or interface peeling, it is more preferred that the damage mode after UV irradiation is interface peeling, and it is more preferred that the damage mode both in the initial stage (before UV irradiation) and after UV irradiation is interface peeling. In addition, in the case where the damage mode both in the initial stage (before UV irradiation) and after UV irradiation is interface peeling, the falling time is preferably as long as possible or does not fall off in the initial stage (before UV irradiation) from the perspective of the fixing force when the adhesive tape 1 is used to cut semiconductor materials, and after UV irradiation, it is preferred that it is shorter than the initial stage (before UV irradiation) from the perspective of the pick-up of semiconductor chips that are cut into pieces. In this case, after the adhesive tape 1 is used for dicing a semiconductor device substrate, when the obtained semiconductor chip is peeled off from the adhesive tape 1, the adhesive tape 1 is irradiated with UV, so that it becomes difficult for residual adhesive to be generated on the semiconductor chip.

(4)對矽氧樹脂殘膠試驗 對於實施例1~10及比較例1~6所製作之黏著膠帶1,實施相對於矽氧樹脂之殘膠試驗。 首先,將LED裝置用矽氧樹脂之含有甲基之矽氧樹脂(信越化學工業股份有限公司製KER-2500N(商品名))之A劑與B劑以混合比1:1進行混合而製作出混合液。將該混合液塗佈於不鏽鋼板,在100℃×1小時,其後150℃×2小時之條件下進行加熱使其硬化,而製作出矽氧試驗片A。 同樣地使LED裝置用矽氧樹脂之含有苯基之矽氧樹脂(信越化學工業股份有限公司製之KER-6110(商品名))之A劑與B劑以混合比3:7進行混合而製作出混合液。將該混合液塗佈於不鏽鋼板,在100℃×2小時,其後150℃×5小時之條件下進行加熱使其硬化而製作出矽氧試驗片B。(4) Silicone resin residue test The adhesive tape 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 was subjected to a silicone resin residue test. First, agent A and agent B of a methyl silicone resin for LED devices (KER-2500N (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a mixing ratio of 1:1 to prepare a mixed solution. The mixed solution was applied to a stainless steel plate and heated at 100°C for 1 hour and then at 150°C for 2 hours to cure, thereby preparing a silicone test piece A. Similarly, agent A and agent B of a phenyl-containing silicone resin for LED devices (KER-6110 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a mixing ratio of 3:7 to prepare a mixed solution. The mixed solution was applied to a stainless steel plate and heated at 100°C for 2 hours and then at 150°C for 5 hours to cure, thereby preparing a silicone test piece B.

接著,剝下黏著膠帶1之剝離襯墊,將黏著劑層3分別貼附於矽氧試驗片A、B,使質量2000g之輥輪以5mm/s之速度來回1次進行壓著。接著,與UV照射後之滾球黏性之測量記載之條件同樣地,從黏著膠帶1之基材2側照射UV後,在溫度40℃、濕度90%RH之環境下放置120小時。其後,返回室溫,將黏著膠帶1以相對於矽氧試驗片A、B為90°之方向,以800mm/s~1200mm/s之速度來撕離,並以目視來確認對於矽氧試驗片A、B之殘膠。Next, peel off the peeling pad of the adhesive tape 1, and attach the adhesive layer 3 to the silicone test pieces A and B respectively, and press the adhesive with a roller of mass 2000g at a speed of 5mm/s once. Next, after irradiating the adhesive tape 1 with UV from the substrate 2 side, place it in an environment of temperature 40℃ and humidity 90%RH for 120 hours, similar to the conditions recorded in the measurement of rolling ball adhesion after UV irradiation. Afterwards, the surface was returned to room temperature, and the adhesive tape 1 was torn off at a speed of 800 mm/s to 1200 mm/s in a direction of 90° relative to the silicone test pieces A and B, and the residual adhesive on the silicone test pieces A and B was visually confirmed.

(5)對環氧樹脂殘膠試驗 對於實施例1~10及比較例1~6所製作之黏著膠帶1實施對於環氧樹脂之殘膠試驗。 對於由使玻璃布基材含浸有環氧樹脂之環氧樹脂板(日光化成股份有限公司製NL-EG-23(商品名))所構成之環氧試驗片,貼附已剝下剝離襯墊之黏著膠帶1之黏著劑層3,使質量2000g之輥輪以5mm/s之速度來回1次進行壓著。接著,與UV照射後之滾球黏性之測量記載之條件同樣地,從黏著膠帶1之基材2側照射UV後,在溫度40℃、濕度90%RH之環境下放置120小時。其後,返回室溫,將黏著膠帶1以相對於環氧試驗片為90°之方向,以800mm/s~ 1200mm/s之速度來撕離,並以目視確認對於環氧試驗片之殘膠。(5) Epoxy resin residue test The epoxy resin residue test was performed on the adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6. An epoxy test sheet consisting of an epoxy resin sheet (NL-EG-23 (trade name) manufactured by Nikko Chemical Co., Ltd.) in which a glass cloth substrate is impregnated with epoxy resin was attached to the adhesive layer 3 of the adhesive tape 1 from which the peeling liner had been peeled off, and a roller with a mass of 2000 g was pressed back and forth once at a speed of 5 mm/s. Next, the adhesive tape 1 was irradiated with UV from the substrate 2 side under the same conditions as those in the measurement of the rolling ball adhesion after UV irradiation, and then placed in an environment of 40°C and 90%RH for 120 hours. After that, it was returned to room temperature, and the adhesive tape 1 was torn off at a speed of 800mm/s to 1200mm/s in a direction of 90° relative to the epoxy test piece, and the residual adhesive on the epoxy test piece was visually confirmed.

對矽氧樹脂殘膠試驗、及對環氧樹脂殘膠試驗係根據以下之判斷基準來進行評價。尚且,將A或B之評價當作合格者。 A:試驗片之每單位面積100%之範圍內無殘膠 B:試驗片之每單位面積未滿2%之範圍發現殘膠 C:試驗片之每單位面積2%以上未滿5%之範圍發現殘膠 D:試驗片之每單位面積5%以上之範圍發現殘膠,或,試驗片之邊緣部分發現殘膠The silicone resin residual test and the epoxy resin residual test are evaluated based on the following judgment criteria. In addition, the evaluation of A or B is considered to be qualified. A: No residual adhesive is found within 100% of the test piece per unit area B: Residual adhesive is found within less than 2% of the test piece per unit area C: Residual adhesive is found within 2% or more but less than 5% of the test piece per unit area D: Residual adhesive is found within more than 5% of the test piece per unit area, or, Residual adhesive is found at the edge of the test piece

(6)切割試驗 對於實施例1~10及比較例1~6所製作之黏著膠帶1實施切割試驗。 具體而言,首先將造型用環氧樹脂(日立化成股份有限公司製CEL-400ZHF40-W75G(商品名))放入模具,在密封壓力50kgf/cm2 (491N/cm2 )、密封材之厚度0.3mm、加熱溫度150℃×300秒之條件下使其加熱硬化,而製作出圓板狀(直徑200mm(8吋))之切割試驗片。 接著,將已剝下剝離襯墊之黏著膠帶1之黏著劑層3貼附於切割用環,切下從環溢出之部分後,再貼合氟系剝離膜(Nippa股份有限公司製SS1A(商品名),厚度75μm)。接著,使質量2000g之輥輪來回而將黏著膠帶1與環部分予以壓著。接著,剝下氟系剝離膜,對環中央部分之黏著劑層3貼合切割試驗片並進行壓著。(6) Cutting Test The adhesive tapes 1 prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were subjected to a cutting test. Specifically, a molding epoxy resin (CEL-400ZHF40-W75G (trade name) manufactured by Hitachi Chemical Co., Ltd.) was first placed in a mold and heated and hardened under the conditions of a sealing pressure of 50 kgf/cm 2 (491 N/cm 2 ), a sealing material thickness of 0.3 mm, and a heating temperature of 150° C. for 300 seconds to prepare a circular plate-shaped (diameter 200 mm (8 inches)) cutting test piece. Next, the adhesive layer 3 of the adhesive tape 1 from which the peeling pad has been peeled off is attached to the cutting ring, and after the portion that overflows from the ring is cut off, a fluorine-based peeling film (SS1A (trade name) manufactured by Nippa Co., Ltd., thickness 75μm) is attached. Next, a roller with a mass of 2000g is moved back and forth to press the adhesive tape 1 and the ring portion. Next, the fluorine-based peeling film is peeled off, and the cutting test piece is attached to the adhesive layer 3 in the center of the ring and pressed.

並且,使用東京精密股份有限公司製切割裝置(A-WD-100A(商品名)),利用股份有限公司DISCO製之切割刀片,將切割試驗片與黏著膠帶1一同地裁切成10mm×10mm之晶片。此時,計算測量經飛散之晶片個數,來進行切割試驗中之固定力之評價。 接著,對於個片化成10mm×10mm之晶片上所貼附之黏著膠帶1,與UV照射後滾球黏性之測量記載之條件同樣地照射UV。其後,從黏著膠帶1拾取經個片化之晶片,並以目視確認有無晶片上之殘膠來進行切割試驗中之殘膠評價。又,在拾取晶片之際,計算測量拾取失敗之晶片個數來進行切割試驗中之拾取性之評價。Furthermore, using a dicing device (A-WD-100A (trade name)) manufactured by Tokyo Seimitsu Co., Ltd., and a dicing blade manufactured by DISCO Co., Ltd., the dicing test piece and the adhesive tape 1 were cut into 10mm×10mm chips. At this time, the number of chips that were scattered was calculated and measured to evaluate the fixing force in the dicing test. Then, the adhesive tape 1 attached to the chip that was diced into 10mm×10mm was irradiated with UV under the same conditions as the measurement of the rolling ball viscosity after UV irradiation. After that, the individualized chip was picked up from the adhesive tape 1, and the residual adhesive on the chip was visually confirmed to evaluate the residual adhesive in the dicing test. In addition, when picking up the wafers, the number of wafers that failed to be picked up is calculated and measured to evaluate the picking performance in the dicing test.

切割試驗中之固定力係根據以下之判斷基準來進行評價。尚且,將A或B之評價視為合格。 A:經飛散之晶片數為100個中0個,且未發現晶片之缺損 B:經飛散之晶片數為100個中1個,且未發現晶片之缺損 C:經飛散之晶片數為100個中2個,且未發現晶片之缺損 D:經飛散之晶片數為100個中3個以上,或發現晶片之缺損The fixing force in the dicing test is evaluated based on the following judgment criteria. However, the evaluation of A or B is considered to be qualified. A: The number of scattered chips is 0 out of 100, and no chip defects are found B: The number of scattered chips is 1 out of 100, and no chip defects are found C: The number of scattered chips is 2 out of 100, and no chip defects are found D: The number of scattered chips is 3 or more out of 100, or chip defects are found

切割試驗中之殘膠係根據以下之判斷基準來進行評價。尚且,將A之評價視為合格。 A:晶片上未發現殘膠 D:晶片上發現殘膠,或晶片之側面看到黏著劑之牽絲The adhesive residue in the dicing test is evaluated based on the following judgment criteria. In this case, the evaluation of A is considered qualified. A: No adhesive residue is found on the chip D: Adhesive residue is found on the chip, or adhesive strands are seen on the side of the chip

切割試驗中之拾取性係根據以下之判斷基準來進行評價。尚且,將A或B之評價視為合格。 A:拾取失敗之晶片個數為100個中0個 B:拾取失敗之晶片個數為100個中1個 C:拾取失敗之晶片個數為100個中2個 D:拾取失敗之晶片個數為100個中3個以上The pick-up performance in the dicing test is evaluated based on the following judgment criteria. In addition, the evaluation of A or B is considered to be qualified. A: The number of chips that failed to be picked up is 0 out of 100 B: The number of chips that failed to be picked up is 1 out of 100 C: The number of chips that failed to be picked up is 2 out of 100 D: The number of chips that failed to be picked up is 3 or more out of 100

3.試驗結果 將有關對於實施例1~10、及比較例1~6之黏著膠帶1之評價結果展示於表4~6。3. Test results The evaluation results of the adhesive tape 1 of Examples 1 to 10 and Comparative Examples 1 to 6 are shown in Tables 4 to 6.

如表4、5所示,確認到黏著劑層係滿足本發明要件之實施例1~10之黏著膠帶1在黏著力試驗、滾球黏性試驗、保持力試驗、對矽氧樹脂殘膠試驗、對環氧樹脂殘膠試驗、及切割試驗(固定力、殘膠及拾取性)之任一者皆可取得為佳之結果。As shown in Tables 4 and 5, the adhesive tape 1 of Examples 1 to 10, which is confirmed to have an adhesive layer that meets the requirements of the present invention, can obtain good results in any of the adhesion test, rolling ball viscosity test, holding force test, silicone resin residue test, epoxy resin residue test, and cutting test (fixing force, residue, and pickup).

藉此,確認到實施例1~10之黏著膠帶1係有用作為半導體材料之切割用黏著膠帶,更具體而言,有用作為半導體元件基板之從密封樹脂側來貼附而使用於切割之切割用黏著膠帶。Thus, it was confirmed that the adhesive tape 1 of Examples 1 to 10 is useful as an adhesive tape for dicing semiconductor materials, and more specifically, is useful as an adhesive tape for dicing semiconductor device substrates that is adhered from the sealing resin side and used for dicing.

其中,亦以矽氧系樹脂全體中之矽原子鍵結烯基之含量為2.9×10-6 mol/g以上4.1×10-6 mol/g以下之範圍之實施例5、7及10之黏著膠帶1,在與其他實施例之黏著膠帶1相比,在全部試驗項目之評價結果皆為良好。尚且,該實施例5、7及10之矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為41.5/58.5~50.4/49.6之範圍。Among them, the adhesive tapes 1 of Examples 5, 7 and 10, in which the content of silicon atom-bonded olefin groups in the entire silicone resin is in the range of 2.9×10 -6 mol/g or more and 4.1×10 -6 mol/g or less, have good evaluation results in all test items compared with the adhesive tapes 1 of other Examples. Moreover, the mixing ratio ((G)/(R)) of the silicone glue (G) and the silicone resin (R) of Examples 5, 7 and 10 is in the range of 41.5/58.5 to 50.4/49.6.

相對於此,如表6所示,確認到黏著劑層3為不滿足本發明要件之比較例1~6之黏著膠帶1在對矽氧樹脂殘膠試驗、對環氧樹脂殘膠試驗、及切割試驗(固定力、殘膠及拾取性)之任一試驗結果中皆為比實施例1~10還差之結果。In contrast, as shown in Table 6, the adhesive tapes 1 of Comparative Examples 1 to 6, which were confirmed to have adhesive layer 3 that did not meet the requirements of the present invention, showed results worse than those of Examples 1 to 10 in any of the test results of the silicone resin residue test, the epoxy resin residue test, and the cutting test (fixing force, residue, and pickup).

具體而言,黏著劑層3為不包含交聯劑及熱聚合起始劑之比較例1之黏著膠帶1由於即使施予加熱或UV照射仍不會引起矽氧系樹脂之交聯反應,故在UV照射前後,在滾球黏性試驗及保持力試驗之結果並未發現變化,從而凝聚力不足。因此,在用來確認實用性之對矽氧樹脂殘膠試驗及對環氧樹脂殘膠試驗及對環氧樹脂殘膠試驗中,發現諸多殘膠。又,在切割試驗中,如上述般由於並未發現UV照射後之凝聚力增加,故切割試驗片之晶片之拾取性差,且晶片上發現殘膠。Specifically, the adhesive tape 1 of Comparative Example 1 in which the adhesive layer 3 does not contain a crosslinking agent and a thermal polymerization initiator does not cause a crosslinking reaction of the silicone resin even when heated or UV irradiated, so there is no change in the results of the rolling ball viscosity test and the holding force test before and after UV irradiation, and the cohesion is insufficient. Therefore, in the silicone resin residue test, the epoxy resin residue test, and the epoxy resin residue test used to confirm the practicality, many residues were found. In addition, in the cutting test, as mentioned above, since the cohesion after UV irradiation was not increased, the pick-up property of the wafer of the cut test piece was poor, and residues were found on the wafer.

又,黏著劑層3不包含光感應鉑(Pt)觸媒,而包含通常之鉑(Pt)觸媒之比較例2之黏著膠帶1,在UV照射前之初期,凝聚力雖會增加,但即使施加UV照射,仍凝聚力仍不會增加,在UV照射前後,在滾球黏性試驗及保持力試驗之結果並未發現變化。因此,在對矽氧樹脂殘膠試驗及對環氧樹脂殘膠試驗中,發現諸多殘膠。又,即使在切割試驗中,切割試驗片之晶片拾取性也些許為差,且晶片上發現些微多的殘膠。In addition, in the adhesive tape 1 of Comparative Example 2, in which the adhesive layer 3 does not include a photosensitive platinum (Pt) catalyst but includes a conventional platinum (Pt) catalyst, the cohesion increases in the initial stage before UV irradiation, but the cohesion does not increase even after UV irradiation, and no change is found in the results of the rolling ball adhesion test and the holding force test before and after UV irradiation. Therefore, a lot of adhesive residues are found in the silicone resin residue test and the epoxy resin residue test. In addition, even in the cutting test, the chip pickup of the cutting test piece is slightly poor, and a little more adhesive residue is found on the chip.

並且,黏著劑層3中之矽氧系樹脂中之矽原子鍵結烯基之含量為未滿本發明要件之下限值之比較例3之黏著膠帶1,在UV照射前後,在滾球黏性試驗及保持力試驗之結果並未發現變化,由UV照射所成之黏著劑層3之凝聚力增加效果並不充分。因此,在對矽氧樹脂殘膠試驗及對環氧樹脂殘膠試驗中發現諸多殘膠。又,即使在切割試驗中,切割試驗片之晶片拾取性也差,且晶片上發現殘膠。Furthermore, the adhesive tape 1 of Comparative Example 3, in which the content of silicon-atom-bonded olefin groups in the silicone resin in the adhesive layer 3 was less than the lower limit of the requirements of the present invention, showed no change in the results of the rolling ball adhesion test and the holding force test before and after UV irradiation, and the cohesion increase effect of the adhesive layer 3 formed by UV irradiation was not sufficient. Therefore, a lot of adhesive residues were found in the silicone resin residue test and the epoxy resin residue test. Moreover, even in the dicing test, the wafer pickup of the diced test piece was poor, and adhesive residues were found on the wafer.

更進一步,黏著劑層3中之矽氧系樹脂中之矽原子鍵結烯基之含量為超過本發明要件之上限值之比較例4之黏著膠帶1,在切割試驗中,切割試驗片之固定力為低,在切割時發現諸多晶片之飛散。此推測係在UV照射前之階段,即,在將黏著劑層3形成於基材2上用之加熱・乾燥步驟中,藉由熱聚合起始劑而黏著劑層3中之矽氧系樹脂之矽氧膠(G)之交聯反應早已進行,且進行硬化變得過硬所致。尚且,在對矽氧樹脂殘膠試驗及對環氧樹脂殘膠試驗中並未發現殘膠。又,即使在切割試驗中,對於並未飛散之晶片也並未發現殘膠。Furthermore, in the adhesive tape 1 of Comparative Example 4, in which the content of silicon atom-bonded olefin groups in the silicone resin in the adhesive layer 3 exceeded the upper limit of the requirements of the present invention, the fixing force of the cut test piece was low in the cutting test, and many chips were found to fly during cutting. This is speculated to be because the cross-linking reaction of the silicone glue (G) of the silicone resin in the adhesive layer 3 has already proceeded by the thermal polymerization initiator in the stage before UV irradiation, that is, in the heating and drying step for forming the adhesive layer 3 on the substrate 2, and the hardening has been too hard. Furthermore, no adhesive residue was found in the silicone resin residue test or the epoxy resin residue test. Also, no adhesive residue was found in the dicing test even on the wafers that did not scatter.

更進一步,矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為未滿本發明要件之下限值之比較例5之黏著膠帶1,由於幾乎不會幫助黏著劑層3之交聯之矽氧樹脂(R)為多,故由UV照射所成之黏著劑層3之凝聚力之增加效果並無不充分。因此,在對矽氧樹脂殘膠試驗及對環氧樹脂殘膠試驗中,發現些許多之殘膠。又,在切割試驗中,切割試驗片之晶片拾取性也些許為差,且晶片上發現些微多的殘膠。Furthermore, in the adhesive tape 1 of Comparative Example 5, in which the mixing ratio ((G)/(R)) of silicone glue (G) and silicone resin (R) is less than the lower limit of the requirements of the present invention, the silicone resin (R) which hardly helps the cross-linking of the adhesive layer 3 is large, so the effect of increasing the cohesive force of the adhesive layer 3 by UV irradiation is not insufficient. Therefore, in the silicone resin residue test and the epoxy resin residue test, a lot of residue was found. In addition, in the dicing test, the chip pickup of the diced test piece was also slightly poor, and a little bit of residue was found on the chip.

更進一步,黏著劑層3中之矽氧系樹脂中之矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))為超過本發明要件之上限值之比較例6之黏著膠帶1,在切割試驗中,切割試驗片之固定力為低,且切割時發現諸多晶片之飛散。此推測係在UV照射前之階段,即,在將黏著劑層3形成於基材2上用之加熱・乾燥步驟中,藉由熱聚合起始劑而黏著劑層3中之矽氧系樹脂之矽氧膠(G)之交聯反應早已進行,且進行硬化變得過硬所致。 尚且,在對矽氧樹脂殘膠試驗及對環氧樹脂殘膠試驗中並未發現殘膠。又,即使在切割試驗中,對於並未飛散之晶片也並未發現殘膠。Furthermore, in the adhesive tape 1 of Comparative Example 6, in which the mixing ratio ((G)/(R)) of the silicone glue (G) and the silicone resin (R) in the silicone resin in the adhesive layer 3 exceeded the upper limit of the requirements of the present invention, the fixing force of the cut test piece was low in the cutting test, and many chips were found to fly during cutting. This is speculated to be due to the fact that the crosslinking reaction of the silicone glue (G) of the silicone resin in the adhesive layer 3 had already proceeded by the thermal polymerization initiator in the stage before UV irradiation, that is, in the heating and drying step for forming the adhesive layer 3 on the substrate 2, and the curing was too hard. Furthermore, no adhesive residue was found in the silicone resin residue test or the epoxy resin residue test. Also, no adhesive residue was found in the dicing test even on the wafers that did not scatter.

1:黏著膠帶 2:基材 3:黏著劑層 100:半導體元件基板 101:基板 102:半導體元件 103:密封樹脂 200:半導體晶片1: Adhesive tape 2: Base material 3: Adhesive layer 100: Semiconductor component substrate 101: Substrate 102: Semiconductor component 103: Sealing resin 200: Semiconductor chip

[圖1]展示適用本實施形態之切割用黏著膠帶之構成一例的圖。 [圖2(a)~(e)]為展示使用本實施形態之黏著膠帶之半導體晶片之製造方法的圖。 [圖3]展示黏著劑層中之矽氧系樹脂之交聯密度,與黏著膠帶1之保持力試驗之結果(落下時間)之關係的模式圖。[FIG. 1] is a diagram showing an example of the structure of the dicing adhesive tape applicable to the present embodiment. [FIG. 2(a) to (e)] is a diagram showing a method for manufacturing a semiconductor chip using the adhesive tape of the present embodiment. [FIG. 3] is a schematic diagram showing the relationship between the crosslinking density of the silicone resin in the adhesive layer and the result of the holding force test of the adhesive tape 1 (falling time).

1:黏著膠帶 1: Adhesive tape

2:基材 2: Base material

3:黏著劑層 3: Adhesive layer

Claims (9)

一種切割用黏著膠帶,其係具備基材與層合於該基材之黏著劑層,且將半導體材料分割成複數之半導體晶片時所使用之切割用黏著膠帶,其中,前述半導體材料具有經被覆材所被覆之複數之半導體元件,前述黏著劑層係由黏著劑組成物所構成,該黏著劑組成物包含:混合有矽氧膠(G)與矽氧樹脂(R)之矽氧系樹脂、作為對於該矽氧系樹脂之交聯劑、作為熱聚合起始劑之過氧化物,及光感應鉑(Pt)觸媒,該交聯劑為1分子中具有至少2個以上之矽原子鍵結氫原子(SiH基)之有機聚矽氧烷,前述矽氧系樹脂全體中之矽氧膠(G)與矽氧樹脂(R)之混合比率((G)/(R))在以質量比計為40.0/60.0~56.0/44.0之範圍,前述矽氧膠(G)包含:由含有矽原子鍵結烯基之有機聚矽氧烷所構成之矽氧膠(Galk),且前述矽氧系樹脂全體中之前述矽原子鍵結烯基之含量為7.0×10-7mol/g以上5.5×10-6mol/g以下之範圍。 A dicing adhesive tape comprises a substrate and an adhesive layer laminated on the substrate, and is used when a semiconductor material is divided into a plurality of semiconductor chips, wherein the semiconductor material has a plurality of semiconductor elements coated by a coating material, and the adhesive layer is composed of an adhesive composition, wherein the adhesive composition comprises: a silicone resin mixed with a silicone glue (G) and a silicone resin (R), a crosslinking agent for the silicone resin, and a thermal polymerization initiator. The crosslinking agent is an organic polysiloxane having at least two silicon-atom-bonded hydrogen atoms (SiH groups) in one molecule, and the mixing ratio ((G)/(R)) of the silicone gel (G) and the silicone resin (R) in the silicone resin as a whole is in the range of 40.0/60.0 to 56.0/44.0 in terms of mass ratio. The silicone gel (G) comprises: a silicone gel (G) composed of an organic polysiloxane containing a silicon-atom-bonded olefin group; alk ), and the content of the aforementioned silicon atom-bonded olefinic groups in the aforementioned silicon-oxygen-based resin as a whole is in the range of 7.0×10 -7 mol/g or more and 5.5×10 -6 mol/g or less. 如請求項1之切割用黏著膠帶,其中複數之前述半導體元件係對於藉由前述被覆材所密封之前述半導體材料,從該被覆材側來貼附所使用,且該被覆材係由矽氧樹脂所構成者。 As in claim 1, the dicing adhesive tape, wherein the plurality of the aforementioned semiconductor elements are used for attaching the aforementioned semiconductor material sealed by the aforementioned covering material from the side of the covering material, and the covering material is composed of silicone resin. 如請求項1或2之切割用黏著膠帶,其中 前述黏著劑層中,該黏著劑組成物所含之前述交聯劑之前述矽原子鍵結氫原子(SiH基)之含量(總量)對前述黏著劑組成物所含之前述矽氧系樹脂全體中之前述矽原子鍵結烯基之含量(總量)的莫耳比率(SiH基/矽原子鍵結烯基)為2.0以上10.0以下之範圍。 As claimed in claim 1 or 2, the adhesive tape for dicing, wherein In the aforementioned adhesive layer, the molar ratio (SiH group/silicon atom bonded olefin group) of the aforementioned crosslinking agent contained in the adhesive composition to the aforementioned silicon atom bonded olefin group content (total amount) in the aforementioned silicone resin contained in the aforementioned adhesive composition is in the range of 2.0 to 10.0. 如請求項1或2之切割用黏著膠帶,其中前述黏著劑層中,相對於前述矽氧系樹脂全體之固體成分100質量份,前述黏著劑組成物中之前述過氧化物之含量在以固體成分計為0.10質量份以上3.00質量份以下之範圍。 As in claim 1 or 2, the adhesive tape for cutting, wherein in the adhesive layer, the content of the aforementioned peroxide in the aforementioned adhesive composition is in the range of 0.10 mass parts to 3.00 mass parts in terms of solid content relative to 100 mass parts of the total solid content of the aforementioned silicone resin. 如請求項1或2之切割用黏著膠帶,其中前述黏著劑層之前述過氧化物為二醯基過氧化物類。 As in claim 1 or 2, the adhesive tape for cutting, wherein the peroxide mentioned above in the adhesive layer is a diacyl peroxide. 如請求項1或2之切割用黏著膠帶,其中前述黏著劑層中,相對於前述矽氧系樹脂全體之固體成分100質量份,前述黏著劑組成物中之前述光感應鉑(Pt)觸媒之含量以固體成分計為0.10質量份以上3.00質量份以下之範圍。 As in claim 1 or 2, the adhesive tape for cutting, wherein in the adhesive layer, the content of the aforementioned photosensitive platinum (Pt) catalyst in the aforementioned adhesive composition is in the range of 0.10 mass parts to 3.00 mass parts in terms of solid content relative to 100 mass parts of the total solid content of the aforementioned silicone resin. 如請求項1或2之切割用黏著膠帶,其中前述黏著劑層中,前述矽氧系樹脂全體中之前述矽原子鍵結烯基之含量為2.9×10-6mol/g以上4.1×10-6mol/g以下之範圍。 The dicing adhesive tape of claim 1 or 2, wherein in the adhesive layer, the content of the silicon atom-bonded olefin groups in the entire silicone resin is in the range of 2.9×10 -6 mol/g to 4.1×10 -6 mol/g. 如請求項1或2之切割用黏著膠帶,其中依據JIS Z 0237(2009)之黏著特性係全部滿足下述條件(a)~(c): (a)對於BA-SUS試驗板之光照射前之黏著力為2.8N/10mm以上5.5N/10mm以下之範圍;(b)傾斜式滾球黏性試驗(ball tack test)(傾斜角30°,溫度23℃,相對濕度50%RH)中之球號(ball number)之值在將光照射前之球號之值設為BN0,將光照射後之球號之值設為BN1時,為BN0>BN1之關係;(c)光照射後之保持力試驗(溫度40℃,相對濕度33%RH,放置時間2880分)中,落下時之破壞現象為前述黏著劑層與BA-SUS試驗板之界面剝離,或,該保持力試驗中不會落下。 For the adhesive tape for cutting as claimed in claim 1 or 2, the adhesive properties according to JIS Z 0237 (2009) satisfy all of the following conditions (a) to (c): (a) The adhesive force before light exposure to the BA-SUS test plate is within the range of 2.8 N/10 mm to 5.5 N/10 mm; (b) The ball number (ball tack test) in the ball tack test (tilt angle 30°, temperature 23°C, relative humidity 50% RH) is (c) In the retention test after light irradiation (temperature 40°C, relative humidity 33%RH, placement time 2880 minutes), the damage phenomenon when falling is the interface between the aforementioned adhesive layer and the BA-SUS test plate peeling off, or the test plate does not fall off in the retention test. 一種半導體晶片之製造方法,其係包含,貼附步驟:其係對於由矽氧樹脂所構成之密封樹脂所密封之複數之前述半導體元件已形成於基板上之半導體元件基板,將如請求項1至8中任一項之切割用黏著膠帶,從該密封樹脂側進行貼附;切割步驟:其係將已貼附前述切割用黏著膠帶之前述半導體元件基板切割成複數之半導體晶片;照射步驟:其係對前述半導體元件基板之前述切割用黏著膠帶照射光;及,剝離步驟:其係從前述複數之半導體晶片剝下前述切割用黏著膠帶。 A method for manufacturing a semiconductor chip comprises: an attaching step: attaching a dicing adhesive tape as described in any one of claims 1 to 8 from the side of a sealing resin formed by a silicone resin to a semiconductor element substrate on which a plurality of the aforementioned semiconductor elements have been formed on the substrate; a cutting step: cutting the aforementioned semiconductor element substrate to which the aforementioned dicing adhesive tape has been attached into a plurality of semiconductor chips; an irradiation step: irradiating the aforementioned dicing adhesive tape of the aforementioned semiconductor element substrate with light; and a peeling step: peeling the aforementioned dicing adhesive tape from the aforementioned plurality of semiconductor chips.
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