WO2019058425A1 - Adhesive film for semiconductor device manufacture - Google Patents

Adhesive film for semiconductor device manufacture Download PDF

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Publication number
WO2019058425A1
WO2019058425A1 PCT/JP2017/033723 JP2017033723W WO2019058425A1 WO 2019058425 A1 WO2019058425 A1 WO 2019058425A1 JP 2017033723 W JP2017033723 W JP 2017033723W WO 2019058425 A1 WO2019058425 A1 WO 2019058425A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
film
carrier film
group
piece
Prior art date
Application number
PCT/JP2017/033723
Other languages
French (fr)
Japanese (ja)
Inventor
大久保　恵介
俊介 藤尾
昌典 夏川
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2017/033723 priority Critical patent/WO2019058425A1/en
Priority to JP2019543646A priority patent/JP7338469B2/en
Priority to PCT/JP2018/034514 priority patent/WO2019059189A1/en
Priority to KR1020207010061A priority patent/KR102528135B1/en
Priority to CN201880060553.2A priority patent/CN111133564B/en
Priority to SG11202002554XA priority patent/SG11202002554XA/en
Priority to TW107132902A priority patent/TWI827551B/en
Publication of WO2019058425A1 publication Critical patent/WO2019058425A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B32B7/14—Interconnection of layers using interposed adhesives or interposed materials with bonding properties applied in spaced arrangements, e.g. in stripes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present disclosure relates to an adhesive film used in a semiconductor device manufacturing process.
  • Patent Document 1 discloses an adhesive sheet (dicing die bonding sheet) having a function of fixing a semiconductor wafer in a dicing step and a function of bonding a semiconductor chip to a substrate in a die bonding step.
  • the present disclosure is useful for efficiently performing the bonding process in the manufacturing process of the semiconductor device, even if the area of the substrate to which the semiconductor chip is to be bonded is limited or the shape of the semiconductor chip is special. To provide an adhesive film.
  • the present disclosure provides an adhesive film for manufacturing a semiconductor device.
  • the adhesive film includes a belt-like carrier film having a width of 100 mm or less and a plurality of adhesive pieces arranged on the carrier film in the longitudinal direction of the carrier film.
  • a plurality of adhesive pieces arranged to be aligned on the carrier film can be sequentially picked up, and then each adhesive piece can be arranged in a predetermined area of the substrate, and the substrate and the semiconductor chip Can be carried out efficiently.
  • the bonding process can be performed more efficiently by the roll-to-roll method.
  • the shape of the adhesive piece may be appropriately set according to the shape of the region of the substrate to which the semiconductor chip is to be bonded or the shape of the semiconductor chip.
  • the size and the number of adhesive pieces disposed on the carrier film may be appropriately set according to the design of the semiconductor device to be manufactured.
  • the area of one adhesive strip can range from 10 to 200 mm 2 .
  • the percentage of the area of the surface of the carrier film covered by the plurality of adhesive pieces can be 10 to 60% based on the area of the carrier film.
  • An array of one or more adhesive strips may be formed on the carrier film.
  • the plurality of adhesive strips can be formed, for example, by stamping an adhesive layer formed to cover the surface of the carrier film.
  • the adhesion between the carrier film and the adhesive piece is It is preferably 0.5 to 18 N / m.
  • the adhesive film according to the present disclosure covers the second surface opposite to the first surface on the carrier film side of the adhesive strip, and may further include a protective member having the same shape as the adhesive strip. By covering the adhesive strip with the protective member, dust and the like can be prevented from adhering to the adhesive strip until the time of use.
  • the adhesive strip and the protective member can be formed by die cutting an adhesive layer formed to cover the surface of the carrier film and a protective film disposed to cover the adhesive layer.
  • the light transmittance of the protective member is preferably lower than the light transmittance of the carrier film.
  • the adhesion between the adhesive piece and the protective member is preferably 16 N / m or less.
  • the adhesion between the adhesive strip and the protective member is preferably 16 N / m or less after heat treatment at 100 ° C. for 10 minutes. .
  • the bonding process in the manufacturing process of the semiconductor device is efficiently performed.
  • Useful adhesive films are provided.
  • FIG. 1 is a perspective view schematically showing an embodiment of an adhesive film according to the present disclosure.
  • FIG. 2 is a cross-sectional view taken along the line II-II shown in FIG.
  • FIG. 3: is sectional drawing which shows typically the laminated body on which the carrier film, the adhesive bond layer, and the protective film were laminated
  • FIG. 4 is a perspective view showing how a plurality of adhesive pieces are formed on the carrier film by die cutting.
  • FIG. 5 is a cross-sectional view schematically showing how the adhesive strip and the protective member covering the adhesive strip are picked up from the carrier film.
  • (meth) acrylic means acrylic or methacrylic.
  • FIG. 1 is a perspective view schematically showing an adhesive film according to the present embodiment.
  • FIG. 2 is a cross-sectional view taken along the line II-II shown in FIG.
  • Adhesive films 10 shown in these figures are a band-like carrier film 1 having a width of 100 mm or less, and a plurality of carrier films 1 arranged on the carrier film 1 in the longitudinal direction (direction of arrow X shown in FIG. 1).
  • the adhesive strip 3p and the protective member 5p covering the surface F2 of the adhesive strip 3p and having the same shape as the adhesive strip 3p are provided.
  • the surface F2 (second surface) of the adhesive piece 3p is a surface opposite to the surface F1 (first surface) of the adhesive piece 3p on the carrier film 1 side.
  • the adhesive film 10 is applicable to various adhesion processes (for example, adhesion of a semiconductor chip and a substrate) in a manufacturing process of a semiconductor device.
  • a plurality of adhesive pieces 3p arranged to line up on the carrier film 1 can be sequentially picked up, and then each adhesive piece 3p can be arranged in a predetermined area of the substrate, and the substrate
  • the step of bonding the semiconductor chip to the semiconductor chip can be carried out efficiently.
  • the adhesive strip 3p shaped like a thick T is illustrated, but the shape of the adhesive strip is the shape of the area of the substrate to which the semiconductor chip is to be bonded, or The setting may be made as appropriate according to the shape of the semiconductor chip.
  • FIGS. 1 and 2 show the case where one row 3A of a plurality of adhesive pieces 3p is provided on the carrier film 1, two or more rows 3A are provided on the carrier film 1. It may be done.
  • the adhesive strip 3p in this embodiment is assumed to have a sufficiently small size, and the area of one adhesive strip 3p is, for example, 10 to 200 mm 2 , 20 to 160 mm 2 or 25 to 100 mm 2 . It may be.
  • the ratio of the area (area ratio of adhesive pieces) on the surface of the carrier film 1 and covered by the plurality of adhesive pieces 3p is, for example, 10 to 60% based on the area of the carrier film 1; It may be 10 to 35% or 15 to 33%.
  • the carrier film 1 is band-like and has a width of 100 mm or less.
  • the width of the carrier film 1 may be appropriately set in accordance with the size of the adhesive piece 3p disposed thereon and the number of rows 3A.
  • the width of the carrier film 1 is preferably 10 to 50 mm, and may be 10 to 30 mm or 10 to 20 mm.
  • the width of the carrier film 1 is 10 mm or more, when the roll-to-roll method is adopted, it is easy to prevent the deterioration in workability caused by the twisting of the carrier film 1.
  • the material of the carrier film 1 is not particularly limited as long as it can sufficiently withstand the tension applied in the manufacturing process of the adhesive film 10 and the manufacturing process of the semiconductor device.
  • the carrier film 1 is preferably transparent from the viewpoint of the visibility of the adhesive piece 3p and / or the protective member 5p disposed thereon.
  • the carrier film 1 may be a polyester film such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, polyvinyl acetate film, poly-4-methylpentene-1, ethylene-vinyl acetate co
  • a polyolefin film such as a polymer, a homopolymer or copolymer such as ethylene-ethyl acrylate copolymer, or a mixture thereof, a plastic film such as a polyvinyl chloride film or a polyimide film, or the like can be used.
  • the carrier film 1 may have a single layer structure or a multilayer structure.
  • the thickness of the carrier film 1 may be appropriately selected within a range that does not impair the workability, and is, for example, 10 to 200 ⁇ m, and may be 20 to 100 ⁇ m or 25 to 80 ⁇ m. These thickness ranges are practically acceptable and economically effective.
  • the carrier film 1 it is also possible to use a low surface energy film made of a fluorocarbon resin.
  • a film for example, A-63 (release treatment agent: modified silicone type) manufactured by Teijin Film Solutions Ltd., and A-31 (release treatment agent: Pt type manufactured by Teijin Film Solutions Ltd.) There are silicone type etc.
  • the surface of the carrier film 1 is separated from silicone release agent, fluorine release agent, long chain alkyl acrylate release agent, etc. You may form the release layer comprised from a mold agent.
  • the adhesion between the carrier film 1 and the adhesive strip 3p is preferably 0.5 to 18 N / m, more preferably 2 to 10 N / m, 2 to 6 N / m or 2 to 4 N / m. It may be m.
  • the adhesion is 0.5 N / m or more, careless peeling of the adhesive piece 3p from the carrier film 1 in the process of producing the adhesive film 10 can be easily prevented, and on the other hand, 18 N / m or less
  • the adhesion of the adhesive strip 3p to the carrier film 1 means 90 ° peel strength.
  • an adhesive layer of 20 mm in width made of the same composition as the adhesive strip 3p is formed on the carrier film 1
  • the prepared sample is prepared, which means the peel strength measured when the adhesive layer is peeled from the carrier film at an angle of 90 ° and a peeling speed of 50 mm / min.
  • the adhesive strip 3p is formed by simultaneously die-cutting the adhesive layer 3 formed to cover the surface of the carrier film 1 and the protective film 5 disposed to cover the adhesive layer 3 to form a protective member 5p. (See FIG. 4).
  • the thickness of the adhesive piece 3p may be appropriately selected within a range that does not impair the workability, and is, for example, 3 to 50 ⁇ m, and may be 5 to 40 ⁇ m or 7 to 30 ⁇ m. Sufficient adhesion can be easily secured by the thickness of the adhesive strip 3p being 3 ⁇ m or more, and the adhesive composition constituting the adhesive strip 3p can be protruded from the protective member 5p by being 50 ⁇ m or less It is easy to control.
  • the adhesive composition constituting the adhesive strip 3p only needs to have properties (for example, adhesiveness and heat resistance to heat of about 150 ° C.) that can be used without problems in the manufacturing process of the semiconductor device. What is used in the manufacturing process of the semiconductor device may be adopted appropriately.
  • the adhesive strip 3p preferably contains a thermoplastic resin, a thermosetting resin, a curing accelerator, and a filler, and may contain a photoreactive monomer, a photopolymerization initiator, and the like as necessary.
  • thermoplastic resin a resin having thermoplasticity or a resin having thermoplasticity at least in an uncured state and forming a crosslinked structure after heating can be used.
  • a thermoplastic resin as a tape for processing a semiconductor, a (meth) acrylic copolymer (hereinafter referred to as “reactive group-containing (meth) acrylic copolymer”) having a reactive group from the viewpoint of being excellent in shrinkage, heat resistance and peelability. It may be called "polymer”) is preferable.
  • the adhesive piece 3p may not include the thermosetting resin. That is, the aspect containing a reactive group containing (meth) acrylic copolymer, a hardening accelerator, and a filler may be sufficient.
  • a thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.
  • Examples of the (meth) acrylic copolymer include (meth) acrylic acid ester copolymers such as acrylic resin and acrylic rubber, and acrylic rubber is preferable.
  • the acrylic rubber preferably comprises an acrylic ester as a main component and is formed by copolymerization of a monomer selected from (meth) acrylic ester and acrylonitrile.
  • (meth) acrylic acid esters methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Examples thereof include isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and the like.
  • (meth) acrylic acid ester copolymer a copolymer containing butyl acrylate and acrylonitrile as a copolymer component, and a copolymer containing ethyl acrylate and acrylonitrile as a copolymer component are preferable.
  • the reactive group-containing (meth) acrylic copolymer is preferably a reactive group-containing (meth) acrylic copolymer containing a (meth) acrylic monomer having a reactive group as a copolymerization component.
  • a reactive group-containing (meth) acrylic copolymer can be obtained by copolymerizing a monomer composition containing a (meth) acrylic monomer having a reactive group and the above-described monomer. .
  • the reactive group is preferably an epoxy group, a carboxyl group, an acryloyl group, a methacryloyl group, a hydroxyl group or an episulfide group from the viewpoint of heat resistance improvement, and from the viewpoint of crosslinkability, an epoxy group and a carboxyl group are more preferable.
  • the reactive group-containing (meth) acrylic copolymer is preferably an epoxy group-containing (meth) acrylic copolymer containing a (meth) acrylic monomer having an epoxy group as a copolymerization component.
  • the (meth) acrylic monomer having an epoxy group glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexyl methyl acrylate, glycidyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, 3,4- Epoxy cyclohexyl methyl methacrylate and the like can be mentioned.
  • the (meth) acrylic monomer having a reactive group is preferably glycidyl acrylate or glycidyl methacrylate from the viewpoint of heat resistance.
  • the Tg of the thermoplastic resin is preferably ⁇ 50 ° C. to 50 ° C.
  • the Tg of the thermoplastic resin is 50 ° C. or less, the flexibility of the adhesive piece 3 p can be easily secured.
  • the unevenness is present when pasted to the adherend, it becomes easy to follow and has appropriate adhesiveness.
  • the Tg of the thermoplastic resin is ⁇ 50 ° C. or higher, it is easy to suppress the flexibility of the adhesive piece 3 p from becoming too high, and excellent handleability, adhesiveness, and releasability can be achieved.
  • the Tg of a thermoplastic resin is the midpoint glass transition temperature value obtained by differential scanning calorimetry (DSC). Specifically, the Tg of the thermoplastic resin is an intermediate value calculated by the method according to JIS K 7121: 1987, measuring the change in heat quantity under the conditions of a temperature rising rate of 10 ° C./min and a measuring temperature of -80 to 80 ° C. It is a point glass transition temperature.
  • the weight average molecular weight of the thermoplastic resin is preferably 100,000 or more and 2,000,000 or less.
  • the weight average molecular weight is 100,000 or more, heat resistance can be easily secured when used for temporary fixation.
  • the weight average molecular weight of the thermoplastic resin is more preferably 500,000 or more and 2,000,000 or less, and still more preferably 1,000,000 or more and 2,000,000 or less.
  • a weight average molecular weight is a polystyrene conversion value which used the calibration curve by standard polystyrene by the gel permeation chromatography method (GPC).
  • the total content of these is 0.1 to 20% by mass based on the total amount of the copolymerization component.
  • the content is preferably 0.5 to 15% by mass, and more preferably 1.0 to 10% by mass. If the content is within the above range, it is easy to achieve all of the flexibility, adhesiveness and releasability of the adhesive strip 3p to a higher level.
  • the (meth) acrylic copolymer having a reactive group as described above one obtained by a polymerization method such as pearl polymerization or solution polymerization may be used.
  • a polymerization method such as pearl polymerization or solution polymerization
  • commercially available products such as HTR-860P-3CSP (trade name, manufactured by Nagase ChemteX Co., Ltd.) may be used.
  • thermosetting resin Any thermosetting resin can be used without particular limitation as long as it can be cured by heat.
  • thermosetting resin epoxy resin, acrylic resin, silicone resin, phenol resin, thermosetting polyimide resin, polyurethane resin, melamine resin, urea resin, etc. may be mentioned. These can be used singly or in combination of two or more.
  • the epoxy resin is not particularly limited as long as it cures and has a heat-resistant function.
  • a bifunctional epoxy resin such as bisphenol A epoxy, a novolac epoxy resin such as phenol novolac epoxy resin, and a cresol novolac epoxy resin can be used.
  • the epoxy resin conventionally known ones such as polyfunctional epoxy resin, glycidyl amine type epoxy resin, heterocycle-containing epoxy resin, alicyclic epoxy resin and the like can be used.
  • Examples of the phenol novolac epoxy resin include Epicoat 152, Epicoat 154 (all manufactured by Mitsubishi Chemical Co., Ltd.), EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), DEN-438 (manufactured by Dow Chemical Co.) and the like.
  • o-cresol novolac type epoxy resin As o-cresol novolac type epoxy resin, YDCN-700-10 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 (all of them) Nippon Kayaku Co., Ltd., YDCN 701, YDCN 702, YDCN 703, YDCN 704 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
  • Epon 1031S made by Mitsubishi Chemical Corporation
  • araldite 0163 made by BASF Japan Ltd.
  • Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521 And EX-421, EX-411 and EX-321 all of which are manufactured by Nagase ChemteX Co., Ltd.
  • an amine type epoxy resin Epicoat 604 (made by Mitsubishi Chemical Corporation), YH-434 (made by Nippon Steel & Sumikin Chemical Co., Ltd.), TETRAD-X, TETRAD-C (all are made by Mitsubishi Chemical Co., Ltd.), ELM-120 (both) And Sumitomo Chemical Co., Ltd.).
  • heterocycle-containing epoxy resin examples include Araldite PT810 (manufactured by BASF Japan Ltd.), ERL 4234, ERL 4299, ERL 4221, and ERL 4206 (all manufactured by Union Carbide). These epoxy resins can be used singly or in combination of two or more.
  • the epoxy resin curing agent which is a part of the thermosetting resin component
  • a commonly used known resin can be used. Specifically, amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F, bisphenols having two or more phenolic hydroxyl groups in one molecule such as bisphenol S, phenol novolac resin And phenol resins such as bisphenol A novolac resin and cresol novolac resin.
  • phenol resins such as phenol novolac resin, bisphenol A novolac resin, and cresol novolac resin are preferable from the viewpoint of being excellent in electrolytic corrosion resistance at the time of moisture absorption.
  • the epoxy curing agent may be used simultaneously with the epoxy resin or may be used alone.
  • Phenolite LF 4871, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH 4170 (all manufactured by DIC Corporation, trade names), H-1 (Meiwa) Made by Kasei Co., Ltd., trade name, Epicure MP402FPY, Epicure YL6065, Epicure YLH129B65, Mirex XL, Mirex XLC, Mirex XLC-LL, Mirex RN, Mirex RS, Mirex VR (all are manufactured by Mitsubishi Chemical Corporation, etc.), etc. It is preferable to use a material having the following structure.
  • the content of the thermosetting resin in the adhesive piece 3p is preferably 10 to 500 parts by mass, more preferably 30 to 450 parts by mass, and still more preferably 50 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is easy to achieve the outstanding adhesiveness after thermosetting of adhesive piece 3p as content of a thermosetting resin is in a mentioned range.
  • adhesive piece 3p contains the (meth) acrylic copolymer which has an epoxy group
  • the hardening accelerator which promotes hardening of the epoxy group contained in the said acrylic copolymer.
  • curing accelerators that promote curing of epoxy groups include phenolic curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, imidazoline curing agents, triazine curing agents, and phosphine curing agents. It can be mentioned. Among these, from the viewpoint of rapid curing, heat resistance and releasability, an imidazole-based curing agent which can be expected to shorten the process time and improve the workability is preferable. These compounds can be used singly or in combination of two or more.
  • the content of the curing accelerator in the adhesive strip 3p is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 20 parts by mass, and more preferably 0.025 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Parts are more preferred. It exists in the tendency which can fully suppress the fall of storage stability, improving the hardenability of adhesive agent piece 3p as content of a hardening accelerator is in the said range.
  • the adhesive strip 3p preferably contains an inorganic filler.
  • the inorganic filler include metal fillers such as silver powder, gold powder and copper powder, and nonmetallic inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide and ceramic.
  • the inorganic filler can be selected according to the desired function.
  • the inorganic filler preferably has an organic group on the surface.
  • the surface of the inorganic filler is modified with an organic group, so that the dispersibility in an organic solvent when preparing a varnish for forming the adhesive strip 3p, and the high elastic modulus and the excellent peeling of the adhesive strip 3p It is easy to make
  • the inorganic filler having an organic group on the surface can be obtained, for example, by mixing a silane coupling agent represented by the following formula (B-1) and an inorganic filler and stirring at a temperature of 30 ° C. or more. It can be confirmed by UV measurement, IR measurement, XPS measurement or the like that the surface of the inorganic filler has been modified by the organic group.
  • X represents an organic group selected from the group consisting of phenyl group, glycidoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, vinyl group, isocyanate group and methacryloxy group;
  • Is an integer of 0 or 1 to 10.
  • R 11 , R 12 and R 13 each independently represent an alkyl group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group and isobutyl group.
  • the alkyl group having 1 to 10 carbon atoms is preferably a methyl group, an ethyl group and a pentyl group from the viewpoint of easy availability.
  • X is preferably an amino group, a glycidoxy group, a mercapto group and an isocyanate group, and more preferably a glycidoxy group and a mercapto group.
  • s in the formula (B-1) is preferably 0 to 5, and more preferably 0 to 4.
  • trimethoxyphenylsilane dimethyldimethoxyphenylsilane, triethoxyphenylsilane, dimethoxymethylphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycide Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltrie
  • 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane are preferable, trimethoxyphenylsilane, 3-glycidoxy Propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane are more preferred.
  • the silane coupling agent can be used singly or in combination of two or more.
  • the content of the coupling agent is preferably 0.01 to 50 parts by mass, and 0.05 to 20 parts by mass, with respect to 100 parts by mass of the inorganic filler, from the viewpoint of achieving a balance between heat resistance and storage stability.
  • the amount is more preferably 0.5 to 10 parts by mass from the viewpoint of heat resistance improvement.
  • the content of the inorganic filler in the adhesive piece 3p is preferably 600 parts by mass or less, more preferably 500 parts by mass or less, and 400 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. More preferable.
  • the lower limit of the content of the inorganic filler is not particularly limited, but is preferably 5 parts by mass or more, and more preferably 8 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin.
  • Adhesive piece 3 p may contain an organic filler.
  • the organic filler include carbon, rubber fillers, silicone particles, polyamide particles and polyimide particles. 300 mass parts or less are preferable with respect to 100 mass parts of thermoplastic resins, as for content of an organic filler, 200 mass parts or less are more preferable, and 100 mass parts or less are still more preferable.
  • the lower limit of the content of the organic filler is not particularly limited, but is preferably 5 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin.
  • the adhesive strip 3p may be diluted with an organic solvent, if necessary.
  • the organic solvent is not particularly limited, but can be determined in consideration of the volatility and the like at the time of film formation from the boiling point.
  • relatively low boiling point solvents such as methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene, etc. It is preferable from the viewpoint of difficulty in curing.
  • a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone and the like. These solvents can be used singly or in combination of two or more.
  • the protective member 5 p simultaneously cuts off the adhesive layer 3 formed so as to cover the surface of the carrier film 1 and the protective film 5 arranged so as to cover the adhesive layer 3 to form an adhesive piece 3 p. (See FIG. 4).
  • the protective member 5p according to the present embodiment is formed at the same time as the adhesive piece 3p by die cutting, and thus has substantially the same shape as the adhesive piece 3p.
  • the protective film 5 may be a film which can be punched out in the manufacturing process of the adhesive film 10 and can easily peel the protective member 5p from the adhesive piece 3p in the manufacturing process of the semiconductor device.
  • the adhesion between the adhesive strip 3p and the protective member 5p is preferably 16 N / m or less, more preferably 10 N / m or less, and 5 N / m or less or 4.5 N / m or less It is also good.
  • the adhesive strip 3p is made of a thermosetting resin composition, it is preferable that the adhesion of the protective member 5p to the adhesive strip 3p be in the above range after heat treatment at 100 ° C. for 10 minutes.
  • the adhesion is 16 N / m or less, the adhesive strip 3p in a state of being covered with the protective member 5p is temporarily crimped to an adherend (for example, a substrate) under conditions of 100 ° C. for 3 seconds, for example.
  • the adhesion of the protective member 5p to the adhesive strip 3p means 90 ° peel strength, and specifically, a protective film of the same width on a 20 mm wide adhesive layer made of the same composition as the adhesive strip 3p. Means a peel strength which is measured when the prepared sample is prepared and this protective film is peeled from the adhesive layer at an angle of 90 ° and a peeling speed of 300 mm / min.
  • polyester-based films such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, polyvinyl acetate film, poly-4-methylpentene-1, ethylene-vinyl acetate co
  • a polyolefin film such as a polymer, a homopolymer or copolymer such as ethylene-ethyl acrylate copolymer, or a mixture thereof, a plastic film such as a polyvinyl chloride film or a polyimide film, or the like can be used.
  • the protective film 5 may have a single layer structure or a multilayer structure.
  • the thickness of the protective film 5 may be appropriately selected within a range that does not impair the workability, and is, for example, 10 to 200 ⁇ m, and may be 20 to 100 ⁇ m or 25 to 80 ⁇ m. These thickness ranges are practically acceptable and economically effective.
  • the light transmittance of the protective member 5 p is preferably lower than the light transmittance of the carrier film 1.
  • a device such as a camera
  • the manufacturing method of the present embodiment includes the following steps.
  • FIG. 3 is sectional drawing which shows typically the laminated body 20 prepared by (A) process.
  • the laminate 20 can be produced as follows. First, the raw material resin composition of the adhesive layer 3 is dissolved in a solvent such as an organic solvent to prepare a varnished coating liquid. The coating liquid is applied onto the carrier film 1 and then the solvent is removed to form the adhesive layer 3.
  • the coating method may, for example, be a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method or a curtain coating method. Next, the protective film 5 is attached to the surface of the adhesive layer 3 under the conditions of normal temperature to 60 ° C. Thereby, the laminated body 20 can be obtained.
  • the laminated film is produced by bonding together the protective film 5 so that this may be covered, and this is cut
  • FIG. 4 is a perspective view showing how a plurality of adhesive pieces 3p and a protective member 5p covering the adhesive pieces 3p are formed on the carrier film 1 by die cutting in the (B) step.
  • the laminate 20 passes between the rotating body 51 having a plurality of blades 51 c for carrying out the die-cutting on the outer peripheral surface and the roll 52 paired with the rotating body 51.
  • An adhesive piece 3p and a protection member 5p according to the shape of the blade 51c are continuously formed on the carrier film 1.
  • the surface on the protective film 5 side of the laminate 20 faces the rotating body 51
  • the surface on the carrier film 1 side faces the roll 52.
  • the depth of the cut formed in the laminate 20 by the blade 51c by adjusting the distance between the rotation shaft 51a of the rotating body 51 and the rotation shaft 52a of the roll 52 or changing the height of the blade 51c Can be adjusted.
  • the laminate 20 which has passed between the rotating body 51 and the roll 52 is separated into the adhesive film 10 and the unnecessary portion 30 as shown in FIG. 4 and wound around each reel (not shown).
  • the unnecessary portion 30 includes the adhesive layer 3 and the protective film 5 in which the adhesive piece 3 p and the protective member 5 p are hollowed out.
  • FIG. 5 is a cross-sectional view schematically showing how the adhesive strip 3p and the protective member 5p covering the adhesive strip 3p are picked up from the carrier film 1.
  • FIG. 5 The adhesive film 10 is moved in the direction of the arrow shown in FIG. 5 while bringing the surface of the adhesive film 10 on the carrier film 1 side into contact with the wedge shaped member 60 in a state where a constant tension is applied to the adhesive film 10.
  • the front of the adhesive agent piece 3p and the protection member 5p will be in the state which floated from the carrier film 1.
  • FIG. 5 is a cross-sectional view schematically showing how the adhesive strip 3p and the protective member 5p covering the adhesive strip 3p are picked up from the carrier film 1.
  • the adhesive strip 3p and the protective member 5p are picked up by the pickup device 65 having a suction force.
  • the pickup device 65 having a suction force.
  • the adhesive strip 3p in a state of being covered by the protective member 5p is disposed at a predetermined position and direction of the substrate (not shown).
  • temporary pressure bonding of the adhesive piece 3p to the substrate is performed.
  • the temporary pressure bonding may be performed, for example, at a temperature of 60 to 150 ° C. and a pressing force of 0.05 to 1 MPa for 0.1 to 10 seconds.
  • the adhesive piece 3p is in close contact with the substrate to such an extent that the adhesive piece 3p is weak but does not peel off from the substrate.
  • the protective member 5p is peeled off from the adhesive piece 3p using an adhesive tape or the like.
  • the semiconductor chip After placing the semiconductor chip (not shown) on the surface of the adhesive piece 3p exposed by the peeling of the protective member 5p, the semiconductor chip is crimped to the substrate.
  • the pressure bonding may be performed, for example, at a temperature of 60 to 150 ° C. under a pressure of 0.05 to 1 MPa for 0.1 to 10 seconds.
  • this indication is not limited to the above-mentioned embodiment.
  • the case where the colored protective film 5 is used is illustrated so that the presence or absence, the direction, etc. of the protective member 5p can be grasped by a camera or the like, but instead of this, a predetermined protective member 5p is used.
  • the position of may be marked.
  • it is set as the aspect by which the adhesive agent piece 3p was colored it is not necessary to provide the protection member 5p.
  • the direction of the adhesive piece 3p does not matter (for example, when the shape of the adhesive piece 3p is circular), it is not necessary to identify the direction.
  • Example 1 (Preparation of adhesive varnish) An adhesive varnish was obtained by mixing the following materials and vacuum degassing.
  • Thermoplastic resin: HTR-860P-3 (trade name, manufactured by Nagase ChemteX Co., Ltd., glycidyl group-containing acrylic rubber, molecular weight 1,000,000, Tg-7 ° C.) 100 parts by mass
  • Thermosetting resin: YDCN-700-10 (Trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., o-cresol novolac epoxy resin, epoxy equivalent weight 210) 30 parts by mass
  • Thermosetting resin: LF-4871 (trade name, manufactured by DIC, bisphenol A epoxy resin, Epoxy equivalent 118) 95 parts by mass
  • Thermosetting resin: YDF-8170C (trade name, manufactured by Nippon Steel Sumikin Chemical Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent 157) 100 parts by mass Curing accelerator: 2PZ-CN (com
  • the adhesive varnish was coated on a surface release-treated polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film A-63) with a thickness of 50 ⁇ m. After the drying step, a film having a 25 ⁇ m-thick adhesive layer formed on one side of the polyethylene terephthalate film (carrier film) was obtained. A laminated film was obtained by laminating this film and a colored 50 ⁇ m-thick polyethylene film (manufactured by Tamapoly Co., Ltd., TDM-1). By slitting this laminated film to a width of 15 mm, a strip-like laminated body was obtained.
  • the laminated film obtained as described above was die-cut using the device having the configuration shown in FIG. 4 to obtain an adhesive film according to this example.
  • the shape of the adhesive piece was a shape (area: 29 mm 2 ) in which a corner of a part of a rectangle of about 7 mm in length ⁇ about 6 mm in width was missing.
  • the pitch P was about 9 mm.
  • the area ratio R of the adhesive piece was 23%.
  • Example 2 An adhesive film was produced in the same manner as in Example 1 except that the size and pitch of the adhesive pieces were changed.
  • Example 3 An adhesive film was produced in the same manner as in Example 2 except that a carrier film having a different surface treatment from that of the carrier film used in Example 2 was used and the shape of the adhesive piece was changed.
  • a carrier film a surface release-treated polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film A-53) having a thickness of 50 ⁇ m was used.
  • Example 4 An adhesive film was produced in the same manner as in Example 2 except that a protective film different from the protective film used in Example 2 was used.
  • a protective film a non-colored polyethylene film (manufactured by Tamapoly Corporation, trade name: NF-13, thickness: 20 ⁇ m) was used.
  • Example 5 An adhesive film was produced in the same manner as in Example 2 except that a protective film different from the protective film used in Example 2 was used.
  • a protective film a non-colored polyethylene film (manufactured by Tamapoly Corporation, trade name: GF-3, thickness: 30 ⁇ m) was used.
  • Example 6 An adhesive film was produced in the same manner as in Example 2 except that a carrier film different from the carrier film used in Example 2 was used.
  • a carrier film a polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film G2, thickness: 50 ⁇ m) not subjected to surface release treatment was used.
  • Example 7 An adhesive film was produced in the same manner as in Example 2 except that a carrier film different from the carrier film used in Example 2 was used.
  • a carrier film a polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film G2, thickness: 38 ⁇ m) not subjected to surface release treatment was used.
  • Example 8 An adhesive film was produced in the same manner as in Example 2 except that the size of the adhesive strip was changed.
  • Example 9 An adhesive film was produced in the same manner as in Example 2 except that the size of the adhesive strip was changed.
  • Light Transmittance V-570 (trade name) manufactured by JASCO Corporation is used to transmit light with a wavelength of 500 nm in a region where an adhesive strip and a protective member covering the adhesive film are provided on a carrier film. Measured.
  • Adhesion of protective film (90 ° peel strength)
  • a laminated film (carrier film / adhesive layer / protective film) not cut was cut into a width of 20 mm.
  • the protective film is upward while maintaining the angle of the protective film to the adhesive layer at 90 °.
  • the adhesive layer was peeled off from the protective film by pulling up. The pulling rate was 300 mm / min, and the measurement environment temperature was 23 ⁇ 2 ° C. The force required to pull it up was measured.
  • the adhesion between the protective film and the adhesive layer was calculated by substituting the measured value (mN) and the width (20 mm) of the sample into the following equation.
  • Adhesion (N / m) measured value (mN) / 20 (mm)
  • the bonding process in the manufacturing process of the semiconductor device is efficiently performed.
  • Useful adhesive films are provided.

Abstract

The present invention relates to an adhesive film for semiconductor device manufacture. This adhesive film includes a carrier film strip no more than 100 mm wide, and multiple adhesive pieces disposed on the carrier film and aligned in the longitudinal direction of the carrier film.

Description

半導体装置製造用接着フィルムAdhesive film for semiconductor device manufacturing
　本開示は、半導体装置の製造プロセスにおいて使用される接着フィルムに関する。 The present disclosure relates to an adhesive film used in a semiconductor device manufacturing process.
　従来、半導体装置は以下の工程を経て製造される。まず、ダイシング用粘着シートに半導体ウエハを貼り付け、その状態で半導体ウエハを半導体チップに個片化する。その後、ピックアップ工程、マウンティング工程、リフロー工程及びダイボンディング工程等が実施される。特許文献１は、ダイシング工程において半導体ウエハを固定する機能と、ダイボンディング工程において半導体チップを基板と接着させる機能とを併せ持つ粘接着シート（ダイシングダイボンディングシート）を開示する。 Conventionally, a semiconductor device is manufactured through the following steps. First, a semiconductor wafer is attached to a pressure-sensitive adhesive sheet for dicing, and in this state, the semiconductor wafer is singulated into semiconductor chips. Thereafter, a pickup process, a mounting process, a reflow process, a die bonding process, and the like are performed. Patent Document 1 discloses an adhesive sheet (dicing die bonding sheet) having a function of fixing a semiconductor wafer in a dicing step and a function of bonding a semiconductor chip to a substrate in a die bonding step.
特開２００７－２８８１７０号公報JP 2007-288170 A
　ところで、近年、スマートフォンに代表される小型デバイス向け半導体装置の進化に伴い、半導体装置の製造プロセスも従来と著しく変化している。例えば、特許文献１に記載の粘接着シート（ダイシングダイボンディングシート）を使用したダイシング工程及びダイボンディング工程を実施しないプロセス、あるいは、リフロー工程を実施しないプロセスの実用化が進められている。これに伴い、半導体装置の製造プロセスで使用される接着フィルムも新たな態様のものが求められている。かかる状況に加え、本発明者らは、半導体装置が搭載される小型デバイスの高機能化及び薄型化等に対応すべく、基板の限られた特定の領域に、これに応じた形状の半導体チップを接着するのに使い勝手のよい接着フィルムの開発を進めた。 By the way, in recent years, with the evolution of a semiconductor device for small devices represented by a smartphone, the manufacturing process of the semiconductor device is also significantly changed from the past. For example, the practical application of a process not performing a dicing process and a die bonding process using a tackiness adhesive sheet (dicing die bonding sheet) described in Patent Document 1 or a process not performing a reflow process has been advanced. Along with this, adhesive films used in the manufacturing process of semiconductor devices are also required to have new aspects. In addition to the above situation, the present inventors have developed a semiconductor chip having a shape corresponding to a limited specific area of the substrate in order to cope with the high functionalization and thinning of a small device on which the semiconductor device is mounted. We have developed an easy-to-use adhesive film for bonding
　本開示は、半導体チップが接着されるべき基板の領域に制限があったり、半導体チップの形状が特殊であったりしても、半導体装置の製造プロセスにおける接着工程を効率的に実施するのに有用な接着フィルムを提供することを目的とする。 The present disclosure is useful for efficiently performing the bonding process in the manufacturing process of the semiconductor device, even if the area of the substrate to which the semiconductor chip is to be bonded is limited or the shape of the semiconductor chip is special. To provide an adhesive film.
　本開示は半導体装置製造用接着フィルムを提供する。この接着フィルムは、幅１００ｍｍ以下の帯状のキャリアフィルムと、キャリアフィルム上にキャリアフィルムの長手方向に並ぶように配置されている複数の接着剤片とを備える。 The present disclosure provides an adhesive film for manufacturing a semiconductor device. The adhesive film includes a belt-like carrier film having a width of 100 mm or less and a plurality of adhesive pieces arranged on the carrier film in the longitudinal direction of the carrier film.
　この接着フィルムによれば、キャリアフィルム上に並ぶように配置された複数の接着剤片を順次ピックアップし、その後、各接着剤片を基板の所定の領域に配置することができ、基板と半導体チップとの接着工程を効率的に実施できる。例えば、帯状の接着フィルムをリールに巻いた態様とすれば、ロールｔｏロール方式によって、より一層効率的に接着工程を実施できる。接着剤片の形状は、半導体チップが接着されるべき基板の領域の形状、又は、半導体チップの形状に応じて適宜、設定すればよい。 According to this adhesive film, a plurality of adhesive pieces arranged to be aligned on the carrier film can be sequentially picked up, and then each adhesive piece can be arranged in a predetermined area of the substrate, and the substrate and the semiconductor chip Can be carried out efficiently. For example, if a band-like adhesive film is wound on a reel, the bonding process can be performed more efficiently by the roll-to-roll method. The shape of the adhesive piece may be appropriately set according to the shape of the region of the substrate to which the semiconductor chip is to be bonded or the shape of the semiconductor chip.
　キャリアフィルム上に配置される接着剤片のサイズ及び個数等は、製造する半導体装置の設計に応じて適宜設定すればよい。例えば、一つの接着剤片の面積は１０～２００ｍｍ２の範囲とすることができる。キャリアフィルムの表面であって複数の接着剤片によって覆われている領域の割合はキャリアフィルムの面積を基準として１０～６０％とすることができる。キャリアフィルム上には、一つ又は複数の、上記複数の接着剤片からなる列が形成されていてもよい。 The size and the number of adhesive pieces disposed on the carrier film may be appropriately set according to the design of the semiconductor device to be manufactured. For example, the area of one adhesive strip can range from 10 to 200 mm 2 . The percentage of the area of the surface of the carrier film covered by the plurality of adhesive pieces can be 10 to 60% based on the area of the carrier film. An array of one or more adhesive strips may be formed on the carrier film.
　複数の接着剤片は、例えば、キャリアフィルムの表面を覆うように形成された接着剤層を型抜きすることによって形成することができる。接着フィルムの加工性の観点（型抜きを行う際及びその後に、キャリアフィルムから接着剤片が不用意に剥離することを防止する点）から、キャリアフィルと接着剤片との間の密着力が０．５～１８Ｎ／ｍであることが好ましい。 The plurality of adhesive strips can be formed, for example, by stamping an adhesive layer formed to cover the surface of the carrier film. From the viewpoint of processability of the adhesive film (at the point of preventing inadvertent peeling of the adhesive piece from the carrier film during and after die cutting), the adhesion between the carrier film and the adhesive piece is It is preferably 0.5 to 18 N / m.
　本開示に係る接着フィルムは、接着剤片のキャリアフィルム側の第一面と反対側の第二面を覆っており、接着剤片と同じ形状を有する保護部材を更に備えてもよい。接着剤片を保護部材で覆った状態とすることで、使用するときまで埃等が接着剤片に付着することを防止できる。接着剤片及び保護部材は、キャリアフィルムの表面を覆うように形成された接着剤層と、接着剤層を覆うように配置された保護フィルムとを型抜きすることによって形成することができる。 The adhesive film according to the present disclosure covers the second surface opposite to the first surface on the carrier film side of the adhesive strip, and may further include a protective member having the same shape as the adhesive strip. By covering the adhesive strip with the protective member, dust and the like can be prevented from adhering to the adhesive strip until the time of use. The adhesive strip and the protective member can be formed by die cutting an adhesive layer formed to cover the surface of the carrier film and a protective film disposed to cover the adhesive layer.
　保護部材の光透過率はキャリアフィルムの光透過率よりも低いことが好ましい。かかる構成を採用することにより、接着剤片の位置をカメラ等のデバイスで認識することが可能となり、接着工程を完全自動化しやすい。 The light transmittance of the protective member is preferably lower than the light transmittance of the carrier film. By adopting such a configuration, it becomes possible to recognize the position of the adhesive strip with a device such as a camera, and it is easy to fully automate the bonding process.
　半導体チップと基板の接着工程の作業性の観点から、接着剤片と保護部材との間の密着力は１６Ｎ／ｍ以下であることが好ましい。例えば、接着剤片が熱硬化性を有する樹脂組成物からなる場合、１００℃で１０分の熱処理後において、接着剤片と保護部材との間の密着力は１６Ｎ／ｍ以下であることが好ましい。 From the viewpoint of the workability of the step of bonding the semiconductor chip and the substrate, the adhesion between the adhesive piece and the protective member is preferably 16 N / m or less. For example, when the adhesive strip is made of a thermosetting resin composition, the adhesion between the adhesive strip and the protective member is preferably 16 N / m or less after heat treatment at 100 ° C. for 10 minutes. .
　本開示によれば、半導体チップが接着されるべき基板の領域に制限があったり、半導体チップの形状が特殊であったりしても、半導体装置の製造プロセスにおける接着工程を効率的に実施するのに有用な接着フィルムが提供される。 According to the present disclosure, even if the area of the substrate to which the semiconductor chip is to be bonded is limited or the shape of the semiconductor chip is special, the bonding process in the manufacturing process of the semiconductor device is efficiently performed. Useful adhesive films are provided.
図１は本開示に係る接着フィルムの一実施形態を模式的に示す斜視図である。FIG. 1 is a perspective view schematically showing an embodiment of an adhesive film according to the present disclosure. 図２は図１に示すＩＩ－ＩＩ線における断面図である。FIG. 2 is a cross-sectional view taken along the line II-II shown in FIG. 図３はキャリアフィルム、接着剤層及び保護フィルムがこの順序で積層された積層体を模式的に示す断面図である。FIG. 3: is sectional drawing which shows typically the laminated body on which the carrier film, the adhesive bond layer, and the protective film were laminated | stacked in this order. 図４は型抜きによってキャリアフィルム上に複数の接着剤片が形成される様子を示す斜視図である。FIG. 4 is a perspective view showing how a plurality of adhesive pieces are formed on the carrier film by die cutting. 図５はキャリアフィルムから接着剤片及びこれを覆う保護部材がピックアップされる様子を模式的に示す断面図である。FIG. 5 is a cross-sectional view schematically showing how the adhesive strip and the protective member covering the adhesive strip are picked up from the carrier film.
　以下、図面を適宜参照しながら、本開示の実施形態について説明する。なお、本発明は以下の実施形態に限定されるものではない。本明細書において、（メタ）アクリルとは、アクリル又はメタクリルを意味する。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings as appropriate. The present invention is not limited to the following embodiments. In the present specification, (meth) acrylic means acrylic or methacrylic.
＜半導体装置製造用接着フィルム＞
　図１は本実施形態に係る接着フィルムを模式的に示す斜視図である。図２は図１に示すＩＩ－ＩＩ線における断面図である。これらの図に示す接着フィルム１０は、幅１００ｍｍ以下の帯状のキャリアフィルム１と、キャリアフィルム１上に、その長手方向（図１に示す矢印Ｘの方向）に並ぶように配置されている複数の接着剤片３ｐと、接着剤片３ｐの表面Ｆ２を覆っており且つ接着剤片３ｐと同じ形状を有する保護部材５ｐとを備える。図２に示すとおり、接着剤片３ｐの表面Ｆ２（第二面）は、接着剤片３ｐのキャリアフィルム１側の面Ｆ１（第一面）と反対側の面である。 <Adhesive film for manufacturing semiconductor devices>
FIG. 1 is a perspective view schematically showing an adhesive film according to the present embodiment. FIG. 2 is a cross-sectional view taken along the line II-II shown in FIG. Adhesive films 10 shown in these figures are a band-like carrier film 1 having a width of 100 mm or less, and a plurality of carrier films 1 arranged on the carrier film 1 in the longitudinal direction (direction of arrow X shown in FIG. 1). The adhesive strip 3p and the protective member 5p covering the surface F2 of the adhesive strip 3p and having the same shape as the adhesive strip 3p are provided. As shown in FIG. 2, the surface F2 (second surface) of the adhesive piece 3p is a surface opposite to the surface F1 (first surface) of the adhesive piece 3p on the carrier film 1 side.
　接着フィルム１０は、半導体装置の製造プロセスにおける種々の接着工程（例えば、半導体チップと基板の接着）に適用可能である。接着フィルム１０によれば、キャリアフィルム１上に並ぶように配置された複数の接着剤片３ｐを順次ピックアップし、その後、各接着剤片３ｐを基板の所定の領域に配置することができ、基板と半導体チップとの接着工程を効率的に実施できる。 The adhesive film 10 is applicable to various adhesion processes (for example, adhesion of a semiconductor chip and a substrate) in a manufacturing process of a semiconductor device. According to the adhesive film 10, a plurality of adhesive pieces 3p arranged to line up on the carrier film 1 can be sequentially picked up, and then each adhesive piece 3p can be arranged in a predetermined area of the substrate, and the substrate The step of bonding the semiconductor chip to the semiconductor chip can be carried out efficiently.
　本実施形態においては、図１に示すように、太いＴ字のような形状の接着剤片３ｐを例示したが、接着剤片の形状は半導体チップが接着されるべき基板の領域の形状、又は、半導体チップの形状に応じて適宜、設定すればよい。また、図１，２には、キャリアフィルム１上に、複数の接着剤片３ｐからなる列３Ａが一列設けられている場合を図示したが、二つ以上の列３Ａがキャリアフィルム１上に設けられていてもよい。 In this embodiment, as shown in FIG. 1, the adhesive strip 3p shaped like a thick T is illustrated, but the shape of the adhesive strip is the shape of the area of the substrate to which the semiconductor chip is to be bonded, or The setting may be made as appropriate according to the shape of the semiconductor chip. Although FIGS. 1 and 2 show the case where one row 3A of a plurality of adhesive pieces 3p is provided on the carrier film 1, two or more rows 3A are provided on the carrier film 1. It may be done.
　本実施形態における接着剤片３ｐは十分にサイズが小さいものを想定しており、一つの接着剤片３ｐの面積は、例えば、１０～２００ｍｍ２であり、２０～１６０ｍｍ２又は２５～１００ｍｍ２であってもよい。キャリアフィルム１の表面であって複数の接着剤片３ｐによって覆われている領域の割合（接着剤片の面積率）は、キャリアフィルム１の面積を基準として、例えば、１０～６０％であり、１０～３５％又は１５～３３％であってもよい。この面積率は、一つの接着剤片３ｐの面積Ａを、キャリアフィルム１上に設けられている接着剤片３ｐのピッチ（図１におけるピッチＰ）とキャリアフィルム１の幅（図１における幅Ｗ）との積で除すことによって算出してもよい。つまり、この面積率Ｒは、以下の式で算出される値としてもよい。
　　面積率Ｒ（％）＝Ａ／（Ｐ×Ｗ）×１００ The adhesive strip 3p in this embodiment is assumed to have a sufficiently small size, and the area of one adhesive strip 3p is, for example, 10 to 200 mm 2 , 20 to 160 mm 2 or 25 to 100 mm 2 . It may be. The ratio of the area (area ratio of adhesive pieces) on the surface of the carrier film 1 and covered by the plurality of adhesive pieces 3p is, for example, 10 to 60% based on the area of the carrier film 1; It may be 10 to 35% or 15 to 33%. This area ratio corresponds to the area A of one adhesive agent 3p, the pitch (pitch P in FIG. 1) of the adhesive agent 3p provided on the carrier film 1, and the width W in FIG. 1 of the carrier film 1 It may be calculated by dividing by the product of That is, the area ratio R may be a value calculated by the following equation.
Area ratio R (%) = A / (P × W) × 100
　以下、接着フィルム１０の構成について説明する。
［キャリアフィルム］
　キャリアフィルム１は、上述のとおり、帯状であって、１００ｍｍ以下の幅を有する。キャリアフィルム１の幅は、その上に配置する接着剤片３ｐのサイズ及び列３Ａの数に応じて適宜設定すればよい。例えば、図１に示すように、列３Ａの数が一つである場合、キャリアフィルム１の幅は１０～５０ｍｍであることが好ましく、１０～３０ｍｍ又は１０～２０ｍｍであってもよい。キャリアフィルム１の幅が１０ｍｍ以上であることで、ロールｔｏロール方式を採用した場合、キャリアフィルム１が捻れることに起因する作業性低下を防止しやすい。 Hereinafter, the configuration of the adhesive film 10 will be described.
[Carrier film]
As described above, the carrier film 1 is band-like and has a width of 100 mm or less. The width of the carrier film 1 may be appropriately set in accordance with the size of the adhesive piece 3p disposed thereon and the number of rows 3A. For example, as shown in FIG. 1, when the number of rows 3A is one, the width of the carrier film 1 is preferably 10 to 50 mm, and may be 10 to 30 mm or 10 to 20 mm. When the width of the carrier film 1 is 10 mm or more, when the roll-to-roll method is adopted, it is easy to prevent the deterioration in workability caused by the twisting of the carrier film 1.
　キャリアフィルム１の材質は、接着フィルム１０の製造プロセス及び半導体装置の製造プロセスにおいて加わる張力に十分に耐え得るものであれば、特に制限はない。キャリアフィルム１は、その上に配置される接着剤片３ｐ及び／又は保護部材５ｐの視認性の観点から、透明であることが好ましい。キャリアフィルム１としては、ポリエチレンテレフタレートフィルム等のポリエステル系フィルム、ポリテトラフルオロエチレンフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリビニルアセテートフィルム、ポリ－４－メチルペンテン－１、エチレン－酢酸ビニル共重合体、エチレン－アクリル酸エチル共重合体等の単独共重合体又は共重合体あるいはこれらの混合物等のポリオレフィン系フィルム、ポリ塩化ビニルフィルム、ポリイミドフィルム等のプラスチックフィルムなどを用いることができる。キャリアフィルム１は単層構造であっても、多層構造であってもよい。 The material of the carrier film 1 is not particularly limited as long as it can sufficiently withstand the tension applied in the manufacturing process of the adhesive film 10 and the manufacturing process of the semiconductor device. The carrier film 1 is preferably transparent from the viewpoint of the visibility of the adhesive piece 3p and / or the protective member 5p disposed thereon. The carrier film 1 may be a polyester film such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, polyvinyl acetate film, poly-4-methylpentene-1, ethylene-vinyl acetate co A polyolefin film such as a polymer, a homopolymer or copolymer such as ethylene-ethyl acrylate copolymer, or a mixture thereof, a plastic film such as a polyvinyl chloride film or a polyimide film, or the like can be used. The carrier film 1 may have a single layer structure or a multilayer structure.
　キャリアフィルム１の厚さは、作業性を損なわない範囲で適宜選択すればよく、例えば、１０～２００μｍであり、２０～１００μｍ又は２５～８０μｍであってもよい。これらの厚さの範囲は、実用的に問題なく、経済的にも有効な範囲である。 The thickness of the carrier film 1 may be appropriately selected within a range that does not impair the workability, and is, for example, 10 to 200 μm, and may be 20 to 100 μm or 25 to 80 μm. These thickness ranges are practically acceptable and economically effective.
　キャリアフィルム１に対する接着剤片３ｐの密着力を高めるために、キャリアフィルム１の表面に、コロナ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理等の化学的又は物理的表面処理を施してもよい。キャリアフィルム１として、フッ素樹脂からなる表面エネルギーの低いフィルムを用いることもできる。このようなフィルムとしては、例えば、帝人フィルムソリューション株式会社製のＡ－６３（離型処理剤：変性シリコーン系）、及び、帝人フィルムソリューション株式会社製のＡ－３１（離型処理剤：Ｐｔ系シリコーン系）等がある。 Chemical or physical treatment such as corona treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric shock exposure, ionizing radiation treatment, etc. on the surface of the carrier film 1 in order to enhance the adhesion of the adhesive strip 3p to the carrier film 1 You may surface-treat. As the carrier film 1, it is also possible to use a low surface energy film made of a fluorocarbon resin. As such a film, for example, A-63 (release treatment agent: modified silicone type) manufactured by Teijin Film Solutions Ltd., and A-31 (release treatment agent: Pt type manufactured by Teijin Film Solutions Ltd.) There are silicone type etc.
　キャリアフィルム１に対する接着剤片３ｐの密着力が過度に高くなることを防止するために、キャリアフィルム１の表面に、シリコーン系剥離剤、フッ素系剥離剤、長鎖アルキルアクリレート系剥離剤等の離型剤から構成される離型層を形成してもよい。 In order to prevent the adhesion of the adhesive strip 3p to the carrier film 1 from becoming excessively high, the surface of the carrier film 1 is separated from silicone release agent, fluorine release agent, long chain alkyl acrylate release agent, etc. You may form the release layer comprised from a mold agent.
　キャリアフィルム１と接着剤片３ｐとの間の密着力は０．５～１８Ｎ／ｍであることが好ましく、２～１０Ｎ／ｍであることがより好ましく、２～６Ｎ／ｍ又は２～４Ｎ／ｍであってもよい。この密着力が０．５Ｎ／ｍ以上であることで、接着フィルム１０を製造する過程においてキャリアフィルム１から接着剤片３ｐが不用意に剥離することを防止しやすく、他方、１８Ｎ／ｍ以下であることで、接着フィルム１０の使用時においてキャリアフィルム１から接着剤片３ｐ及びこれを覆う保護部材５ｐを安定的にピックアップしやすい。なお、キャリアフィルム１に対する接着剤片３ｐの密着力は、９０°ピール強度を意味し、具体的には、キャリアフィルム１上に接着剤片３ｐと同じ組成からなる幅２０ｍｍの接着剤層が形成された試料を準備し、この接着剤層を９０°の角度で且つ剥離速度５０ｍｍ／分でキャリアフィルムから剥離したときに測定されるピール強度を意味する。 The adhesion between the carrier film 1 and the adhesive strip 3p is preferably 0.5 to 18 N / m, more preferably 2 to 10 N / m, 2 to 6 N / m or 2 to 4 N / m. It may be m. When the adhesion is 0.5 N / m or more, careless peeling of the adhesive piece 3p from the carrier film 1 in the process of producing the adhesive film 10 can be easily prevented, and on the other hand, 18 N / m or less By using the adhesive film 10, it is easy to stably pick up the adhesive strip 3p and the protective member 5p covering the adhesive strip 3p from the carrier film 1 when the adhesive film 10 is used. The adhesion of the adhesive strip 3p to the carrier film 1 means 90 ° peel strength. Specifically, an adhesive layer of 20 mm in width made of the same composition as the adhesive strip 3p is formed on the carrier film 1 The prepared sample is prepared, which means the peel strength measured when the adhesive layer is peeled from the carrier film at an angle of 90 ° and a peeling speed of 50 mm / min.
［接着剤片］
　接着剤片３ｐは、キャリアフィルム１の表面を覆うように形成された接着剤層３と、接着剤層３を覆うように配置された保護フィルム５とを同時に型抜きすることにより、保護部材５ｐとともに形成されるものである（図４参照）。接着剤片３ｐの厚さは、作業性を損なわない範囲で適宜選択すればよく、例えば、３～５０μｍであり、５～４０μｍ又は７～３０μｍであってもよい。接着剤片３ｐの厚さが３μｍ以上であることで十分な接着性を確保しやすく、他方、５０μｍ以下であることで接着剤片３ｐを構成する接着剤組成物が保護部材５ｐからはみ出ることを抑制しやすい。 [Adhesive piece]
The adhesive strip 3p is formed by simultaneously die-cutting the adhesive layer 3 formed to cover the surface of the carrier film 1 and the protective film 5 disposed to cover the adhesive layer 3 to form a protective member 5p. (See FIG. 4). The thickness of the adhesive piece 3p may be appropriately selected within a range that does not impair the workability, and is, for example, 3 to 50 μm, and may be 5 to 40 μm or 7 to 30 μm. Sufficient adhesion can be easily secured by the thickness of the adhesive strip 3p being 3 μm or more, and the adhesive composition constituting the adhesive strip 3p can be protruded from the protective member 5p by being 50 μm or less It is easy to control.
　接着剤片３ｐを構成する接着剤組成物は、半導体装置の製造プロセスに問題なく使用し得る性質（例えば、接着性及び１５０℃程度の熱に対する耐熱性）を有していればよく、従来、半導体装置の製造プロセスにおいて使用されているものを適宜採用すればよい。接着剤片３ｐは、熱可塑性樹脂と、熱硬化性樹脂と、硬化促進剤と、フィラーとを含むことが好ましく、必要に応じ、光反応性モノマー及び光重合開始剤等を含んでもよい。 The adhesive composition constituting the adhesive strip 3p only needs to have properties (for example, adhesiveness and heat resistance to heat of about 150 ° C.) that can be used without problems in the manufacturing process of the semiconductor device. What is used in the manufacturing process of the semiconductor device may be adopted appropriately. The adhesive strip 3p preferably contains a thermoplastic resin, a thermosetting resin, a curing accelerator, and a filler, and may contain a photoreactive monomer, a photopolymerization initiator, and the like as necessary.
（熱可塑性樹脂）
　熱可塑性樹脂としては、熱可塑性を有する樹脂、又は少なくとも未硬化状態において熱可塑性を有し、加熱後に架橋構造を形成する樹脂を用いることができる。熱可塑性樹脂としては、半導体加工用テープとして、収縮性、耐熱性及び剥離性に優れる観点から、反応性基を有する（メタ）アクリル共重合体（以下、「反応性基含有（メタ）アクリル共重合体」という場合もある）が好ましい。
　熱可塑性樹脂として、反応性基含有（メタ）アクリル共重合体を含む場合、接着剤片３ｐは、熱硬化性樹脂を含まない態様でもよい。すなわち、反応性基含有（メタ）アクリル共重合体と、硬化促進剤と、フィラーとを含む態様でもよい。
　熱可塑性樹脂は、一種を単独で又は二種以上を組み合わせて用いることができる。 (Thermoplastic resin)
As the thermoplastic resin, a resin having thermoplasticity or a resin having thermoplasticity at least in an uncured state and forming a crosslinked structure after heating can be used. As a thermoplastic resin, as a tape for processing a semiconductor, a (meth) acrylic copolymer (hereinafter referred to as “reactive group-containing (meth) acrylic copolymer”) having a reactive group from the viewpoint of being excellent in shrinkage, heat resistance and peelability. It may be called "polymer") is preferable.
When the reactive group-containing (meth) acrylic copolymer is contained as the thermoplastic resin, the adhesive piece 3p may not include the thermosetting resin. That is, the aspect containing a reactive group containing (meth) acrylic copolymer, a hardening accelerator, and a filler may be sufficient.
A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.
　（メタ）アクリル共重合体としては、アクリル樹脂、アクリルゴム等の（メタ）アクリル酸エステル共重合体等が挙げられ、アクリルゴムが好ましい。アクリルゴムは、アクリル酸エステルを主成分とし、（メタ）アクリル酸エステル及びアクリロニトリルから選択されるモノマーの共重合により形成されるものが好ましい。 Examples of the (meth) acrylic copolymer include (meth) acrylic acid ester copolymers such as acrylic resin and acrylic rubber, and acrylic rubber is preferable. The acrylic rubber preferably comprises an acrylic ester as a main component and is formed by copolymerization of a monomer selected from (meth) acrylic ester and acrylonitrile.
　（メタ）アクリル酸エステルとしては、メチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ブチルアクリレート、イソブチルアクリレート、ヘキシルアクリレート、シクロヘキシルアクリレート、２－エチルヘキシルアクリレート、ラウリルアクリレート、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルアクリレート、ブチルメタクリレート、イソブチルメタクリレート、ヘキシルメタクリレート、シクロヘキシルメタクリレート、２－エチルヘキシルメタクリレート、ラウリルメタクリレート等が挙げられる。
　（メタ）アクリル酸エステル共重合体としては、共重合成分としてブチルアクリレート及びアクリロニトリルを含む共重合体、共重合成分としてエチルアクリレート及びアクリロニトリルを含む共重合体が好ましい。 As (meth) acrylic acid esters, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Examples thereof include isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and the like.
As the (meth) acrylic acid ester copolymer, a copolymer containing butyl acrylate and acrylonitrile as a copolymer component, and a copolymer containing ethyl acrylate and acrylonitrile as a copolymer component are preferable.
　反応性基含有（メタ）アクリル共重合体は、反応性基を有する（メタ）アクリルモノマーを共重合成分として含む反応性基含有（メタ）アクリル共重合体であることが好ましい。このような反応性基含有（メタ）アクリル共重合体は、反応性基を有する（メタ）アクリルモノマーと、上記のモノマーとが含まれる単量体組成物を共重合することにより得ることができる。 The reactive group-containing (meth) acrylic copolymer is preferably a reactive group-containing (meth) acrylic copolymer containing a (meth) acrylic monomer having a reactive group as a copolymerization component. Such a reactive group-containing (meth) acrylic copolymer can be obtained by copolymerizing a monomer composition containing a (meth) acrylic monomer having a reactive group and the above-described monomer. .
　反応性基としては、耐熱性向上の観点から、エポキシ基、カルボキシル基、アクリロイル基、メタクリロイル基、水酸基、エピスルフィド基が好ましく、中でも架橋性の点から、エポキシ基及びカルボキシル基がより好ましい。 The reactive group is preferably an epoxy group, a carboxyl group, an acryloyl group, a methacryloyl group, a hydroxyl group or an episulfide group from the viewpoint of heat resistance improvement, and from the viewpoint of crosslinkability, an epoxy group and a carboxyl group are more preferable.
　本実施形態において、反応性基含有（メタ）アクリル共重合体は、エポキシ基を有する（メタ）アクリルモノマーを共重合成分として含むエポキシ基含有（メタ）アクリル共重合体であることが好ましい。この場合、エポキシ基を有する（メタ）アクリルモノマーとしては、グリシジルアクリレート、４－ヒドロキシブチルアクリレートグリシジルエーテル、３，４－エポキシシクロヘキシルメチルアクリレート、グリシジルメタクリレート、４－ヒドロキシブチルメタクリレートグリシジルエーテル、３，４－エポキシシクロヘキシルメチルメタクリレート等が挙げられる。反応性基を有する（メタ）アクリルモノマーは、耐熱性の観点から、グリシジルアクリレート、グリシジルメタクリレートが好ましい。 In the present embodiment, the reactive group-containing (meth) acrylic copolymer is preferably an epoxy group-containing (meth) acrylic copolymer containing a (meth) acrylic monomer having an epoxy group as a copolymerization component. In this case, as the (meth) acrylic monomer having an epoxy group, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexyl methyl acrylate, glycidyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, 3,4- Epoxy cyclohexyl methyl methacrylate and the like can be mentioned. The (meth) acrylic monomer having a reactive group is preferably glycidyl acrylate or glycidyl methacrylate from the viewpoint of heat resistance.
　熱可塑性樹脂のＴｇは、－５０℃～５０℃であることが好ましい。熱可塑性樹脂のＴｇが５０℃以下であると、接着剤片３ｐの柔軟性を確保しやすい。また、被着体に貼り付ける際に凹凸が存在する場合、追随しやすくなり、適度な接着性を有するようになる。一方、熱可塑性樹脂のＴｇが－５０℃以上であると、接着剤片３ｐの柔軟性が高くなりすぎることを抑制しやすく、優れた取扱性及び接着性、剥離性を達成できる。 The Tg of the thermoplastic resin is preferably −50 ° C. to 50 ° C. When the Tg of the thermoplastic resin is 50 ° C. or less, the flexibility of the adhesive piece 3 p can be easily secured. In addition, when the unevenness is present when pasted to the adherend, it becomes easy to follow and has appropriate adhesiveness. On the other hand, when the Tg of the thermoplastic resin is −50 ° C. or higher, it is easy to suppress the flexibility of the adhesive piece 3 p from becoming too high, and excellent handleability, adhesiveness, and releasability can be achieved.
　熱可塑性樹脂のＴｇは、示差走査熱量測定（ＤＳＣ）によって得られる中間点ガラス転移温度値である。熱可塑性樹脂のＴｇは、具体的には、昇温速度１０℃／分、測定温度：－８０～８０℃の条件で熱量変化を測定し、ＪＩＳ　Ｋ　７１２１：１９８７に準拠した方法によって算出した中間点ガラス転移温度である。 The Tg of a thermoplastic resin is the midpoint glass transition temperature value obtained by differential scanning calorimetry (DSC). Specifically, the Tg of the thermoplastic resin is an intermediate value calculated by the method according to JIS K 7121: 1987, measuring the change in heat quantity under the conditions of a temperature rising rate of 10 ° C./min and a measuring temperature of -80 to 80 ° C. It is a point glass transition temperature.
　熱可塑性樹脂の重量平均分子量は、１０万以上２００万以下であることが好ましい。重量平均分子量が１０万以上であると、仮固定の用途で使用する場合、耐熱性を確保しやすくなる。一方、重量平均分子量が２００万以下であると、仮固定の用途で使用する場合、フローの低下及び貼付性の低下を抑制しやすい。上述した観点から、熱可塑性樹脂の重量平均分子量は、５０万以上２００万以下であることがより好ましく、１００万以上２００万以下であることが更に好ましい。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ）で標準ポリスチレンによる検量線を用いたポリスチレン換算値である。 The weight average molecular weight of the thermoplastic resin is preferably 100,000 or more and 2,000,000 or less. When the weight average molecular weight is 100,000 or more, heat resistance can be easily secured when used for temporary fixation. On the other hand, it is easy to suppress the fall of a flow, and the fall of patchability, when using for the use of temporary fixation as a weight average molecular weight is 2 million or less. From the viewpoint described above, the weight average molecular weight of the thermoplastic resin is more preferably 500,000 or more and 2,000,000 or less, and still more preferably 1,000,000 or more and 2,000,000 or less. In addition, a weight average molecular weight is a polystyrene conversion value which used the calibration curve by standard polystyrene by the gel permeation chromatography method (GPC).
　反応性基を有する（メタ）アクリル共重合体がグリシジルアクリレート又はグリシジルメタクリレートを共重合成分として含む場合、これらの含有量は合計で、共重合成分全量を基準として、０．１～２０質量％であることが好ましく、０．５～１５質量％であることがより好ましく、１．０～１０質量％であることが更に好ましい。含有量が上記範囲内であると、接着剤片３ｐの柔軟性、接着性及び剥離性の全てをより高水準に達成しやすい。 When the (meth) acrylic copolymer having a reactive group contains glycidyl acrylate or glycidyl methacrylate as a copolymerization component, the total content of these is 0.1 to 20% by mass based on the total amount of the copolymerization component. The content is preferably 0.5 to 15% by mass, and more preferably 1.0 to 10% by mass. If the content is within the above range, it is easy to achieve all of the flexibility, adhesiveness and releasability of the adhesive strip 3p to a higher level.
　上述のような反応性基を有する（メタ）アクリル共重合体としては、パール重合、溶液重合等の重合方法によって得られるものを用いてもよい。又は、ＨＴＲ－８６０Ｐ－３ＣＳＰ（商品名、ナガセケムテックス株式会社製）等の市販品を用いてもよい。 As the (meth) acrylic copolymer having a reactive group as described above, one obtained by a polymerization method such as pearl polymerization or solution polymerization may be used. Alternatively, commercially available products such as HTR-860P-3CSP (trade name, manufactured by Nagase ChemteX Co., Ltd.) may be used.
（熱硬化性樹脂）
　熱硬化性樹脂としては、熱により硬化する樹脂であれば特に制限なく用いることができる。熱硬化性樹脂としては、エポキシ樹脂、アクリル樹脂、シリコーン樹脂、フェノール樹脂、熱硬化型ポリイミド樹脂、ポリウレタン樹脂、メラミン樹脂、ユリア樹脂等が挙げられる。これらは、一種を単独で又は二種以上を組み合わせて用いることができる。 (Thermosetting resin)
Any thermosetting resin can be used without particular limitation as long as it can be cured by heat. As the thermosetting resin, epoxy resin, acrylic resin, silicone resin, phenol resin, thermosetting polyimide resin, polyurethane resin, melamine resin, urea resin, etc. may be mentioned. These can be used singly or in combination of two or more.
　エポキシ樹脂は、硬化して耐熱作用を有するものであれば特に限定されない。エポキシ樹脂は、ビスフェノールＡ型エポキシ等の二官能エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂などを用いることができる。エポキシ樹脂は、また、多官能エポキシ樹脂、グリシジルアミン型エポキシ樹脂、複素環含有エポキシ樹脂、脂環式エポキシ樹脂等、従来公知のものを用いることができる。 The epoxy resin is not particularly limited as long as it cures and has a heat-resistant function. As the epoxy resin, a bifunctional epoxy resin such as bisphenol A epoxy, a novolac epoxy resin such as phenol novolac epoxy resin, and a cresol novolac epoxy resin can be used. As the epoxy resin, conventionally known ones such as polyfunctional epoxy resin, glycidyl amine type epoxy resin, heterocycle-containing epoxy resin, alicyclic epoxy resin and the like can be used.
　ビスフェノールＡ型エポキシ樹脂としては、エピコート８０７、エピコート８１５、エピコート８２５、エピコート８２７、エピコート８２８、エピコート８３４、エピコート１００１、エピコート１００４、エピコート１００７、エピコート１００９（いずれも三菱ケミカル株式会社製）、ＤＥＲ－３３０、ＤＥＲ－３０１、ＤＥＲ－３６１（いずれもダウケミカル社製）、ＹＤ８１２５、ＹＤＦ８１７０（いずれも新日鉄住金化学株式会社製）等が挙げられる。
　フェノールノボラック型エポキシ樹脂としては、エピコート１５２、エピコート１５４（いずれも三菱ケミカル株式会社製）、ＥＰＰＮ－２０１（日本化薬株式会社製）、ＤＥＮ－４３８（ダウケミカル社製）等が挙げられる。
　ｏ－クレゾールノボラック型エポキシ樹脂としては、ＹＤＣＮ－７００－１０（新日鉄住金化学株式会社製）、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＥＯＣＮ－１０１２、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２７（いずれも日本化薬株式会社製）、ＹＤＣＮ７０１、ＹＤＣＮ７０２、ＹＤＣＮ７０３、ＹＤＣＮ７０４（いずれも新日鉄住金化学株式会社製）等が挙げられる。
　多官能エポキシ樹脂としては、Ｅｐｏｎ　１０３１Ｓ（三菱ケミカル株式会社製）、アラルダイト０１６３（ＢＡＳＦジャパン社製）、デナコールＥＸ－６１１、ＥＸ－６１４、ＥＸ－６１４Ｂ、ＥＸ－６２２、ＥＸ－５１２、ＥＸ－５２１、ＥＸ－４２１、ＥＸ－４１１、ＥＸ－３２１（いずれもナガセケムテックス株式会社製）等が挙げられる。
　アミン型エポキシ樹脂としては、エピコート６０４（三菱ケミカル株式会社製）、ＹＨ－４３４（新日鉄住金化学株式会社製）、ＴＥＴＲＡＤ－Ｘ、ＴＥＴＲＡＤ－Ｃ（いずれも三菱ケミカル株式会社製）、ＥＬＭ－１２０（住友化学株式会社製）等が挙げられる。
　複素環含有エポキシ樹脂としては、アラルダイトＰＴ８１０（ＢＡＳＦジャパン社製）、ＥＲＬ４２３４、ＥＲＬ４２９９、ＥＲＬ４２２１、ＥＲＬ４２０６（いずれもユニオンカーバイド社製）等が挙げられる。これらのエポキシ樹脂は、一種を単独で又は二種以上を組み合わせて用いることができる。 As bisphenol A type epoxy resin, Epi coat 807, Epi coat 815, Epi coat 825, Epi coat 827, Epi coat 828, Epi coat 834, Epi coat 1001, Epi coat 1004, Epi coat 1007, Epi coat 1009 (all are manufactured by Mitsubishi Chemical Corporation), DER-330 DER-301, DER-361 (all manufactured by Dow Chemical Co.), YD8125, YDF 8170 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like.
Examples of the phenol novolac epoxy resin include Epicoat 152, Epicoat 154 (all manufactured by Mitsubishi Chemical Co., Ltd.), EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), DEN-438 (manufactured by Dow Chemical Co.) and the like.
As o-cresol novolac type epoxy resin, YDCN-700-10 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 (all of them) Nippon Kayaku Co., Ltd., YDCN 701, YDCN 702, YDCN 703, YDCN 704 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.
As polyfunctional epoxy resin, Epon 1031S (made by Mitsubishi Chemical Corporation), araldite 0163 (made by BASF Japan Ltd.), Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521 And EX-421, EX-411 and EX-321 (all of which are manufactured by Nagase ChemteX Co., Ltd.).
As an amine type epoxy resin, Epicoat 604 (made by Mitsubishi Chemical Corporation), YH-434 (made by Nippon Steel & Sumikin Chemical Co., Ltd.), TETRAD-X, TETRAD-C (all are made by Mitsubishi Chemical Co., Ltd.), ELM-120 (both) And Sumitomo Chemical Co., Ltd.).
Examples of the heterocycle-containing epoxy resin include Araldite PT810 (manufactured by BASF Japan Ltd.), ERL 4234, ERL 4299, ERL 4221, and ERL 4206 (all manufactured by Union Carbide). These epoxy resins can be used singly or in combination of two or more.
　熱硬化樹脂成分の一部であるエポキシ樹脂硬化剤としては、通常用いられている公知の樹脂を使用することができる。具体的には、アミン類、ポリアミド、酸無水物、ポリスルフィド、三フッ化ホウ素、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳのようなフェノール性水酸基を１分子中に二個以上有するビスフェノール類、フェノールノボラック樹脂、ビスフェノールＡノボラック樹脂、クレゾールノボラック樹脂等のフェノール樹脂などが挙げられる。エポキシ樹脂硬化剤としては、特に、吸湿時の耐電食性に優れるという観点から、フェノールノボラック樹脂、ビスフェノールＡノボラック樹脂、クレゾールノボラック樹脂等のフェノール樹脂が好ましい。
　なお、エポキシ硬化剤は、エポキシ樹脂と同時に用いてもよいし、単独で用いてもよい。 As the epoxy resin curing agent which is a part of the thermosetting resin component, a commonly used known resin can be used. Specifically, amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F, bisphenols having two or more phenolic hydroxyl groups in one molecule such as bisphenol S, phenol novolac resin And phenol resins such as bisphenol A novolac resin and cresol novolac resin. As the epoxy resin curing agent, in particular, phenol resins such as phenol novolac resin, bisphenol A novolac resin, and cresol novolac resin are preferable from the viewpoint of being excellent in electrolytic corrosion resistance at the time of moisture absorption.
The epoxy curing agent may be used simultaneously with the epoxy resin or may be used alone.
　上記フェノール樹脂硬化剤の中でも、フェノライトＬＦ４８７１、フェノライトＴＤ－２０９０、フェノライトＴＤ－２１４９、フェノライトＶＨ－４１５０、フェノライトＶＨ４１７０（いずれもＤＩＣ株式会社製、商品名）、Ｈ－１（明和化成株式会社製、商品名）、エピキュアＭＰ４０２ＦＰＹ、エピキュアＹＬ６０６５、エピキュアＹＬＨ１２９Ｂ６５、ミレックスＸＬ、ミレックスＸＬＣ、ミレックスＸＬＣ－ＬＬ、ミレックスＲＮ、ミレックスＲＳ、ミレックスＶＲ（いずれも三菱ケミカル株式会社製、商品名）等の構造を有する材料を用いることが好ましい。 Among the above-mentioned phenol resin curing agents, Phenolite LF 4871, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH 4170 (all manufactured by DIC Corporation, trade names), H-1 (Meiwa) Made by Kasei Co., Ltd., trade name, Epicure MP402FPY, Epicure YL6065, Epicure YLH129B65, Mirex XL, Mirex XLC, Mirex XLC-LL, Mirex RN, Mirex RS, Mirex VR (all are manufactured by Mitsubishi Chemical Corporation, etc.), etc. It is preferable to use a material having the following structure.
　接着剤片３ｐにおける熱硬化性樹脂の含有量は、熱可塑性樹脂１００質量部に対して、１０～５００質量部が好ましく、３０～４５０質量部がより好ましく、５０～４００質量部が更に好ましい。熱硬化性樹脂の含有量が上記範囲内であると、接着剤片３ｐの熱硬化後の優れた密着性を達成しやすい。 The content of the thermosetting resin in the adhesive piece 3p is preferably 10 to 500 parts by mass, more preferably 30 to 450 parts by mass, and still more preferably 50 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is easy to achieve the outstanding adhesiveness after thermosetting of adhesive piece 3p as content of a thermosetting resin is in a mentioned range.
（硬化促進剤）
　硬化促進剤としては、イミダゾール類、ジシアンジアミド誘導体、ジカルボン酸ジヒドラジド、トリフェニルホスフィン、テトラフェニルホスホニウムテトラフェニルボレート、２－エチル－４－メチルイミダゾール－テトラフェニルボレート、１，８－ジアザビシクロ［５，４，０］ウンデセン－７－テトラフェニルボレート等が挙げられる。これらは、一種を単独で又は二種以上を組み合わせて用いることができる。 (Hardening accelerator)
As curing accelerators, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5,4, 0] Undecene-7-tetraphenyl borate and the like. These can be used singly or in combination of two or more.
　接着剤片３ｐがエポキシ基を有する（メタ）アクリル共重合体を含有する場合、係るアクリル共重合体に含まれるエポキシ基の硬化を促進する硬化促進剤を含有することが好ましい。エポキシ基の硬化を促進する硬化促進剤としては、フェノール系硬化剤、酸無水物系硬化剤、アミン系硬化剤、イミダゾール系硬化剤、イミダゾリン系硬化剤、トリアジン系硬化剤及びホスフィン系硬化剤が挙げられる。これらの中でも、速硬化性、耐熱性及び剥離性の観点から、工程時間の短縮及び作業性の向上が期待できるイミダゾール系硬化剤であることが好ましい。これらの化合物は、一種を単独で又は二種以上を組み合わせて用いることができる。 When adhesive piece 3p contains the (meth) acrylic copolymer which has an epoxy group, it is preferable to contain the hardening accelerator which promotes hardening of the epoxy group contained in the said acrylic copolymer. Examples of curing accelerators that promote curing of epoxy groups include phenolic curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents, imidazoline curing agents, triazine curing agents, and phosphine curing agents. It can be mentioned. Among these, from the viewpoint of rapid curing, heat resistance and releasability, an imidazole-based curing agent which can be expected to shorten the process time and improve the workability is preferable. These compounds can be used singly or in combination of two or more.
　接着剤片３ｐにおける硬化促進剤の含有量は、熱可塑性樹脂１００質量部に対して、０．０１～５０質量部が好ましく、０．０２～２０質量部がより好ましく、０．０２５～１０質量部が更に好ましい。硬化促進剤の含有量が上記範囲内であると、接着剤片３ｐの硬化性を向上させながら保存安定性の低下を十分抑制できる傾向にある。 The content of the curing accelerator in the adhesive strip 3p is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 20 parts by mass, and more preferably 0.025 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Parts are more preferred. It exists in the tendency which can fully suppress the fall of storage stability, improving the hardenability of adhesive agent piece 3p as content of a hardening accelerator is in the said range.
（無機フィラー）
　接着剤片３ｐは、無機フィラーを含有することが好ましい。無機フィラーとしては、銀粉、金粉、銅粉等の金属フィラー、シリカ、アルミナ、窒化ホウ素、チタニア、ガラス、酸化鉄、セラミック等の非金属無機フィラーなどが挙げられる。無機フィラーは所望する機能に応じて選択することができる。 (Inorganic filler)
The adhesive strip 3p preferably contains an inorganic filler. Examples of the inorganic filler include metal fillers such as silver powder, gold powder and copper powder, and nonmetallic inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide and ceramic. The inorganic filler can be selected according to the desired function.
　上記無機フィラーは表面に有機基を有するものが好ましい。無機フィラーの表面が有機基によって修飾されていることにより、接着剤片３ｐを形成するためのワニスを調製するときの有機溶剤への分散性、並びに接着剤片３ｐの高い弾性率及び優れた剥離性を両立しやすい。 The inorganic filler preferably has an organic group on the surface. The surface of the inorganic filler is modified with an organic group, so that the dispersibility in an organic solvent when preparing a varnish for forming the adhesive strip 3p, and the high elastic modulus and the excellent peeling of the adhesive strip 3p It is easy to make
　表面に有機基を有する無機フィラーは、例えば、下記式（Ｂ－１）で表されるシランカップリング剤と無機フィラーとを混合し、３０℃以上の温度で攪拌することにより得ることができる。無機フィラーの表面が有機基によって修飾されたことは、ＵＶ測定、ＩＲ測定、ＸＰＳ測定等で確認することが可能である。 The inorganic filler having an organic group on the surface can be obtained, for example, by mixing a silane coupling agent represented by the following formula (B-1) and an inorganic filler and stirring at a temperature of 30 ° C. or more. It can be confirmed by UV measurement, IR measurement, XPS measurement or the like that the surface of the inorganic filler has been modified by the organic group.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（Ｂ－１）中、Ｘは、フェニル基、グリシドキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、ビニル基、イソシアネート基及びメタクリロキシ基からなる群より選択される有機基を示し、ｓは０又は１～１０の整数を示し、Ｒ１１、Ｒ１２及びＲ１３は各々独立に、炭素数１～１０のアルキル基を示す。
　炭素数１～１０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、イソプロピル基、イソブチル基等が挙げられる。
　炭素数１～１０のアルキル基は、入手が容易であるという観点から、メチル基、エチル基及びペンチル基が好ましい。Ｘは、耐熱性の観点から、アミノ基、グリシドキシ基、メルカプト基及びイソシアネート基が好ましく、グリシドキシ基及びメルカプト基がより好ましい。式（Ｂ－１）中のｓは、高熱時のフィルム流動性を抑制し、耐熱性を向上させる観点から、０～５が好ましく、０～４がより好ましい。 In formula (B-1), X represents an organic group selected from the group consisting of phenyl group, glycidoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, vinyl group, isocyanate group and methacryloxy group; Is an integer of 0 or 1 to 10. R 11 , R 12 and R 13 each independently represent an alkyl group having 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group and isobutyl group. .
The alkyl group having 1 to 10 carbon atoms is preferably a methyl group, an ethyl group and a pentyl group from the viewpoint of easy availability. From the viewpoint of heat resistance, X is preferably an amino group, a glycidoxy group, a mercapto group and an isocyanate group, and more preferably a glycidoxy group and a mercapto group. From the viewpoint of suppressing film fluidity at high heat and improving heat resistance, s in the formula (B-1) is preferably 0 to 5, and more preferably 0 to 4.
　シランカップリング剤としては、トリメトキシフェニルシラン、ジメチルジメトキシフェニルシラン、トリエトキシフェニルシラン、ジメトキシメチルフェニルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、Ｎ－（１，３―ジメチルブチリデン）－３－（トリエトキシシリル）－１－プロパンアミン、Ｎ，Ｎ’―ビス（３－（トリメトキシシリル）プロピル）エチレンジアミン、ポリオキシエチレンプロピルトリアルコキシシラン、ポリエトキシジメチルシロキサン等が挙げられる。
　これらの中でも、３－アミノプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシランが好ましく、トリメトキシフェニルシラン、３－グリシドキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシランがより好ましい。シランカップリング剤は、一種を単独で又は二種以上を組み合わせて用いることができる。 As a silane coupling agent, trimethoxyphenylsilane, dimethyldimethoxyphenylsilane, triethoxyphenylsilane, dimethoxymethylphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycide Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-meta Ryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N'-bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylene propyltrialkoxysilane, polyethoxydimethyl siloxane and the like can be mentioned.
Among these, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane are preferable, trimethoxyphenylsilane, 3-glycidoxy Propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane are more preferred. The silane coupling agent can be used singly or in combination of two or more.
　上記カップリング剤の含有量は、耐熱性と保存安定性とのバランスを図る観点から、無機フィラー１００質量部に対して、０．０１～５０質量部が好ましく、０．０５～２０質量部がより好ましく、耐熱性向上の観点から、０．５～１０質量部が更に好ましい。 The content of the coupling agent is preferably 0.01 to 50 parts by mass, and 0.05 to 20 parts by mass, with respect to 100 parts by mass of the inorganic filler, from the viewpoint of achieving a balance between heat resistance and storage stability. The amount is more preferably 0.5 to 10 parts by mass from the viewpoint of heat resistance improvement.
　接着剤片３ｐにおける無機フィラーの含有量は、熱可塑性樹脂１００質量部に対し、６００質量部以下であることが好ましく、５００質量部以下であることがより好ましく、４００質量部以下であることが更に好ましい。無機フィラーの含有量の下限は特に制限はないが、熱可塑性樹脂１００質量部に対し、５質量部以上であることが好ましく、８質量部以上であることがより好ましい。無機フィラーの含有量を上記範囲とすることにより、熱硬化に伴う収縮を抑制できるとともに、接着剤片３ｐの高い弾性率及び優れた剥離性を両立しやすい。 The content of the inorganic filler in the adhesive piece 3p is preferably 600 parts by mass or less, more preferably 500 parts by mass or less, and 400 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. More preferable. The lower limit of the content of the inorganic filler is not particularly limited, but is preferably 5 parts by mass or more, and more preferably 8 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin. By making content of an inorganic filler into the said range, while being able to suppress the shrinkage | contraction accompanying thermosetting, it is easy to make compatible the high elastic modulus and the outstanding peelability of the adhesive piece 3p.
（有機フィラー）
　接着剤片３ｐは、有機フィラーを含有してもよい。有機フィラーとしては、カーボン、ゴム系フィラー、シリコーン系微粒子、ポリアミド微粒子、ポリイミド微粒子等が挙げられる。有機フィラーの含有量は、熱可塑性樹脂１００質量部に対し、３００質量部以下が好ましく、２００質量部以下がより好ましく、１００質量部以下が更により好ましい。有機フィラーの含有量の下限は特に制限はないが、熱可塑性樹脂１００質量部に対し、５質量部以上であることが好ましい。 (Organic filler)
Adhesive piece 3 p may contain an organic filler. Examples of the organic filler include carbon, rubber fillers, silicone particles, polyamide particles and polyimide particles. 300 mass parts or less are preferable with respect to 100 mass parts of thermoplastic resins, as for content of an organic filler, 200 mass parts or less are more preferable, and 100 mass parts or less are still more preferable. The lower limit of the content of the organic filler is not particularly limited, but is preferably 5 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin.
（有機溶剤）
　接着剤片３ｐは、必要に応じて、有機溶剤を用いて希釈してもよい。有機溶剤は特に限定されないが、製膜時の揮発性等を沸点から考慮して決めることができる。具体的には、メタノール、エタノール、２－メトキシエタノール、２－エトキシエタノール、２－ブトキシエタノール、メチルエチルケトン、アセトン、メチルイソブチルケトン、トルエン、キシレン等の比較的低沸点の溶剤が、製膜時にフィルムの硬化が進みにくいという観点から好ましい。また、製膜性を向上させる等の目的では、ジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン、シクロヘキサノン等の比較的高沸点の溶剤を使用することが好ましい。これらの溶剤は、一種を単独で又は二種以上を組み合わせて用いることができる。 (Organic solvent)
The adhesive strip 3p may be diluted with an organic solvent, if necessary. The organic solvent is not particularly limited, but can be determined in consideration of the volatility and the like at the time of film formation from the boiling point. Specifically, relatively low boiling point solvents such as methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene, etc. It is preferable from the viewpoint of difficulty in curing. Further, for the purpose of improving the film forming property, it is preferable to use a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone and the like. These solvents can be used singly or in combination of two or more.
［保護部材］
　保護部材５ｐは、キャリアフィルム１の表面を覆うように形成された接着剤層３と、接着剤層３を覆うように配置された保護フィルム５とを同時に型抜きすることにより、接着剤片３ｐとともに形成されるものである（図４参照）。本実施形態に係る保護部材５ｐは、型抜きによって接着剤片３ｐと同時に形成されるものであるから、接着剤片３ｐと実質的に同じ形状である。保護フィルム５としては、接着フィルム１０の製造プロセスにおいて打抜き加工が可能であり且つ半導体装置の製造プロセスにおいて接着剤片３ｐから保護部材５ｐを容易に剥離し得るものであればよい。 [Protective member]
The protective member 5 p simultaneously cuts off the adhesive layer 3 formed so as to cover the surface of the carrier film 1 and the protective film 5 arranged so as to cover the adhesive layer 3 to form an adhesive piece 3 p. (See FIG. 4). The protective member 5p according to the present embodiment is formed at the same time as the adhesive piece 3p by die cutting, and thus has substantially the same shape as the adhesive piece 3p. The protective film 5 may be a film which can be punched out in the manufacturing process of the adhesive film 10 and can easily peel the protective member 5p from the adhesive piece 3p in the manufacturing process of the semiconductor device.
　接着剤片３ｐと保護部材５ｐとの間の密着力は１６Ｎ／ｍ以下であることが好ましく、１０Ｎ／ｍ以下であることがより好ましく、５Ｎ／ｍ以下又は４．５Ｎ／ｍ以下であってもよい。特に、接着剤片３ｐが熱硬化性を有する樹脂組成物からなる場合、１００℃で１０分の熱処理後において、接着剤片３ｐに対する保護部材５ｐの密着力が上記範囲であることが好ましい。この密着力が１６Ｎ／ｍ以下であることで、保護部材５ｐで覆われた状態の接着剤片３ｐを、例えば、１００℃で３秒の条件で被着体（例えば、基板）に仮圧着させた後、接着剤片３ｐから保護部材５ｐを粘着テープ等で容易に剥離することができる。なお、接着剤片３ｐに対する保護部材５ｐの密着力は、９０°ピール強度を意味し、具体的には、接着剤片３ｐと同じ組成からなる幅２０ｍｍの接着剤層上に同じ幅の保護フィルムが配置された試料を準備し、この保護フィルムを９０°の角度で且つ剥離速度３００ｍｍ／分で接着剤層から剥離したときに測定されるピール強度を意味する。 The adhesion between the adhesive strip 3p and the protective member 5p is preferably 16 N / m or less, more preferably 10 N / m or less, and 5 N / m or less or 4.5 N / m or less It is also good. In particular, when the adhesive strip 3p is made of a thermosetting resin composition, it is preferable that the adhesion of the protective member 5p to the adhesive strip 3p be in the above range after heat treatment at 100 ° C. for 10 minutes. When the adhesion is 16 N / m or less, the adhesive strip 3p in a state of being covered with the protective member 5p is temporarily crimped to an adherend (for example, a substrate) under conditions of 100 ° C. for 3 seconds, for example. After that, the protective member 5p can be easily peeled off from the adhesive piece 3p with an adhesive tape or the like. The adhesion of the protective member 5p to the adhesive strip 3p means 90 ° peel strength, and specifically, a protective film of the same width on a 20 mm wide adhesive layer made of the same composition as the adhesive strip 3p. Means a peel strength which is measured when the prepared sample is prepared and this protective film is peeled from the adhesive layer at an angle of 90 ° and a peeling speed of 300 mm / min.
　保護フィルム５としては、ポリエチレンテレフタレートフィルム等のポリエステル系フィルム、ポリテトラフルオロエチレンフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリビニルアセテートフィルム、ポリ－４－メチルペンテン－１、エチレン－酢酸ビニル共重合体、エチレン－アクリル酸エチル共重合体等の単独共重合体又は共重合体あるいはこれらの混合物等のポリオレフィン系フィルム、ポリ塩化ビニルフィルム、ポリイミドフィルムなどのプラスチックフィルムなどを用いることができる。保護フィルム５は単層構造であっても、多層構造であってもよい。 As the protective film 5, polyester-based films such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, polyvinyl acetate film, poly-4-methylpentene-1, ethylene-vinyl acetate co A polyolefin film such as a polymer, a homopolymer or copolymer such as ethylene-ethyl acrylate copolymer, or a mixture thereof, a plastic film such as a polyvinyl chloride film or a polyimide film, or the like can be used. The protective film 5 may have a single layer structure or a multilayer structure.
　保護フィルム５の厚さは、作業性を損なわない範囲で適宜選択すればよく、例えば、１０～２００μｍであり、２０～１００μｍ又は２５～８０μｍであってもよい。これらの厚さの範囲は、実用的に問題なく、経済的にも有効な範囲である。 The thickness of the protective film 5 may be appropriately selected within a range that does not impair the workability, and is, for example, 10 to 200 μm, and may be 20 to 100 μm or 25 to 80 μm. These thickness ranges are practically acceptable and economically effective.
　保護部材５ｐの光透過率は、キャリアフィルム１の光透過率よりも低いことが好ましい。かかる構成を採用することにより、接着剤片３ｐの位置及び向き等をカメラ等のデバイスで認識することが可能となり、半導体装置の製造プロセスにおける接着工程を自動化しやすい。例えば、保護部材５ｐとして、波長５００ｎｍの光の透過率が１０％未満（より好ましくは７％未満）に着色されたものを使用することが好ましい。 The light transmittance of the protective member 5 p is preferably lower than the light transmittance of the carrier film 1. By adopting such a configuration, it is possible to recognize the position, orientation, and the like of the adhesive piece 3p with a device such as a camera, and it is easy to automate the bonding process in the manufacturing process of the semiconductor device. For example, it is preferable to use what protected the transmittance | permeability of light with a wavelength of 500 nm to less than 10% (more preferably less than 7%) as the protective member 5p.
＜接着フィルムの製造方法＞
　次に、接着フィルム１０の製造方法について説明する。本実施形態の製造方法は以下の工程を含む。
（Ａ）幅１００ｍｍ以下の帯状のキャリアフィルム１と、キャリアフィルム１の表面を覆うように形成された接着剤層３と、接着剤層３を覆うように配置された保護フィルム５と有する積層体２０を準備する工程。
（Ｂ）積層体２０における接着剤層３及び保護フィルム５を型抜きすることによって、キャリアフィルム１上にキャリアフィルム１の長手方向に並ぶように配置された複数の接着剤片３ｐを得る工程。 <Method of producing adhesive film>
Next, a method of manufacturing the adhesive film 10 will be described. The manufacturing method of the present embodiment includes the following steps.
(A) A laminate having a strip-like carrier film 1 having a width of 100 mm or less, an adhesive layer 3 formed so as to cover the surface of the carrier film 1 and a protective film 5 disposed so as to cover the adhesive layer 3 Step of preparing 20.
(B) A step of obtaining a plurality of adhesive pieces 3 p arranged on the carrier film 1 in the longitudinal direction of the carrier film 1 by die-cutting the adhesive layer 3 and the protective film 5 in the laminate 20.
　図３は、（Ａ）工程で準備する積層体２０を模式的に示す断面図である。積層体２０は以下のようにして作製することができる。まず、接着剤層３の原料樹脂組成物を有機溶剤等の溶媒に溶解させてワニス化した塗工液を準備する。この塗工液をキャリアフィルム１上に塗工した後、溶媒を除去することで接着剤層３を形成する。塗工方法としては、ナイフコート法、ロールコート法、スプレーコート法、グラビアコート法、バーコート法及びカーテンコート法等が挙げられる。次いで、接着剤層３の表面に保護フィルム５を常温～６０℃の条件で貼り合わせる。これにより、積層体２０を得ることができる。なお、幅の広いキャリアフィルムに接着剤層３を形成した後、これを覆うように保護フィルム５を貼り合わせることによって積層フィルムを作製し、これを１００ｍｍ以下の幅に切断（スリット）することによって積層体２０を得てもよい。 FIG. 3: is sectional drawing which shows typically the laminated body 20 prepared by (A) process. The laminate 20 can be produced as follows. First, the raw material resin composition of the adhesive layer 3 is dissolved in a solvent such as an organic solvent to prepare a varnished coating liquid. The coating liquid is applied onto the carrier film 1 and then the solvent is removed to form the adhesive layer 3. The coating method may, for example, be a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method or a curtain coating method. Next, the protective film 5 is attached to the surface of the adhesive layer 3 under the conditions of normal temperature to 60 ° C. Thereby, the laminated body 20 can be obtained. In addition, after forming the adhesive bond layer 3 in the carrier film with a wide width, the laminated film is produced by bonding together the protective film 5 so that this may be covered, and this is cut | disconnected by the width of 100 mm or less (slit) A laminate 20 may be obtained.
　図４は、（Ｂ）工程における型抜きによってキャリアフィルム１上に複数の接着剤片３ｐ及びこれを覆う保護部材５ｐが形成される様子を示す斜視図である。図４に示すように、型抜きを実施するための複数の刃５１ｃを外周面に有する回転体５１と、回転体５１と対をなすロール５２との間を積層体２０が通過することで、刃５１ｃの形状に応じた接着剤片３ｐ及び保護部材５ｐがキャリアフィルム１上に連続的に形成される。このとき、積層体２０は、保護フィルム５側の面が回転体５１に向き、キャリアフィルム１側の面がロール５２に向いている。回転体５１の回転軸５１ａと、ロール５２の回転軸５２ａとの距離を調整すること、又は、刃５１ｃの高さを変更することで、刃５１ｃによって積層体２０に形成される切込みの深さを調整することができる。 FIG. 4 is a perspective view showing how a plurality of adhesive pieces 3p and a protective member 5p covering the adhesive pieces 3p are formed on the carrier film 1 by die cutting in the (B) step. As shown in FIG. 4, the laminate 20 passes between the rotating body 51 having a plurality of blades 51 c for carrying out the die-cutting on the outer peripheral surface and the roll 52 paired with the rotating body 51. An adhesive piece 3p and a protection member 5p according to the shape of the blade 51c are continuously formed on the carrier film 1. At this time, the surface on the protective film 5 side of the laminate 20 faces the rotating body 51, and the surface on the carrier film 1 side faces the roll 52. The depth of the cut formed in the laminate 20 by the blade 51c by adjusting the distance between the rotation shaft 51a of the rotating body 51 and the rotation shaft 52a of the roll 52 or changing the height of the blade 51c Can be adjusted.
　回転体５１及びロール５２の間を通過した積層体２０は、図４に示すように、接着フィルム１０と、不要部分３０とに分離され、それぞれのリール（不図示）に巻き取られる。不要部分３０は、接着剤片３ｐ及び保護部材５ｐがくり抜かれた接着剤層３と保護フィルム５からなる。 The laminate 20 which has passed between the rotating body 51 and the roll 52 is separated into the adhesive film 10 and the unnecessary portion 30 as shown in FIG. 4 and wound around each reel (not shown). The unnecessary portion 30 includes the adhesive layer 3 and the protective film 5 in which the adhesive piece 3 p and the protective member 5 p are hollowed out.
＜接着フィルムの使用方法＞
　次に、接着フィルム１０の使用方法について説明する。図５はキャリアフィルム１から接着剤片３ｐ及びこれを覆う保護部材５ｐをピックアップされる様子を模式的に示す断面図である。接着フィルム１０に一定の張力を付与した状態で、くさび状部材６０に接着フィルム１０のキャリアフィルム１側の面を当接させながら、図５に示す矢印の方向に接着フィルム１０を移動させる。これにより、同図に示すように、接着剤片３ｐ及び保護部材５ｐの前方がキャリアフィルム１から浮いた状態となる。この状態のときに、例えば、吸引力を有するピックアップ装置６５で接着剤片３ｐ及び保護部材５ｐをピックアップする。例えば、ピックアップ装置６５として、保護部材５ｐを視認するカメラ等を備えたものを使用することで、接着剤片３ｐ及び保護部材５ｐの有無、並びに、向き等の情報を把握することが可能である。これらの情報に基づいて、その後の接着工程を適切に実施することができる。 <How to use adhesive film>
Next, how to use the adhesive film 10 will be described. FIG. 5 is a cross-sectional view schematically showing how the adhesive strip 3p and the protective member 5p covering the adhesive strip 3p are picked up from the carrier film 1. FIG. The adhesive film 10 is moved in the direction of the arrow shown in FIG. 5 while bringing the surface of the adhesive film 10 on the carrier film 1 side into contact with the wedge shaped member 60 in a state where a constant tension is applied to the adhesive film 10. Thereby, as shown to the same figure, the front of the adhesive agent piece 3p and the protection member 5p will be in the state which floated from the carrier film 1. As shown in FIG. In this state, for example, the adhesive strip 3p and the protective member 5p are picked up by the pickup device 65 having a suction force. For example, it is possible to grasp information such as the presence or absence of the adhesive piece 3p and the protective member 5p, and the direction by using the pickup device 65 provided with a camera or the like for visually recognizing the protective member 5p. . Based on these pieces of information, the subsequent bonding process can be appropriately performed.
　次いで、保護部材５ｐで覆われた状態の接着剤片３ｐを基板（不図示）の所定の位置及び向きに配置する。この状態のまま、基板に対する接着剤片３ｐの仮圧着を行う。仮圧着は、例えば、温度６０～１５０℃、押圧力０．０５～１ＭＰａの条件で０．１～１０秒にわたって行えばよい。仮圧着によって、接着剤片３ｐが基板に対して弱くではあるが基板から剥離しない程度に密着する。この状態で粘着テープ等を使用して保護部材５ｐを接着剤片３ｐから剥離する。保護部材５ｐの剥離によって露出した接着剤片３ｐの表面に半導体チップ（不図示）を配置した後、基板に対する半導体チップの圧着を行う。圧着は、例えば、温度６０～１５０℃、押圧力０．０５～１ＭＰａの条件で０．１～１０秒にわたって行えばよい。 Next, the adhesive strip 3p in a state of being covered by the protective member 5p is disposed at a predetermined position and direction of the substrate (not shown). In this state, temporary pressure bonding of the adhesive piece 3p to the substrate is performed. The temporary pressure bonding may be performed, for example, at a temperature of 60 to 150 ° C. and a pressing force of 0.05 to 1 MPa for 0.1 to 10 seconds. By the temporary pressure bonding, the adhesive piece 3p is in close contact with the substrate to such an extent that the adhesive piece 3p is weak but does not peel off from the substrate. In this state, the protective member 5p is peeled off from the adhesive piece 3p using an adhesive tape or the like. After placing the semiconductor chip (not shown) on the surface of the adhesive piece 3p exposed by the peeling of the protective member 5p, the semiconductor chip is crimped to the substrate. The pressure bonding may be performed, for example, at a temperature of 60 to 150 ° C. under a pressure of 0.05 to 1 MPa for 0.1 to 10 seconds.
　以上、本開示の実施形態について詳細に説明したが、本開示は上記実施形態に限定されるものではない。例えば、上記実施形態においては、保護部材５ｐの有無及び向き等をカメラ等で把握できるように、着色された保護フィルム５を使用する場合を例示したが、これの代わりに、保護部材５ｐの所定の位置にマークを付してもよい。また、接着剤片３ｐが着色された態様とすれば、保護部材５ｐは設けなくてもよい。なお、接着剤片３ｐの向きが問題とならない場合（例えば、接着剤片３ｐの形状が円形である場合）には、向きを識別する必要はない。 As mentioned above, although embodiment of this indication was described in detail, this indication is not limited to the above-mentioned embodiment. For example, in the above embodiment, the case where the colored protective film 5 is used is illustrated so that the presence or absence, the direction, etc. of the protective member 5p can be grasped by a camera or the like, but instead of this, a predetermined protective member 5p is used. The position of may be marked. Moreover, if it is set as the aspect by which the adhesive agent piece 3p was colored, it is not necessary to provide the protection member 5p. When the direction of the adhesive piece 3p does not matter (for example, when the shape of the adhesive piece 3p is circular), it is not necessary to identify the direction.
　以下、本開示について実施例に基づいて説明する。本開示は以下の実施例に限定されるものではない。 Hereinafter, the present disclosure will be described based on examples. The present disclosure is not limited to the following examples.
＜実施例１＞
（接着剤ワニスの調製）
　以下の材料を混合するとともに真空脱気することによって接着剤ワニスを得た。
・熱可塑性樹脂：ＨＴＲ－８６０Ｐ－３（商品名、ナガセケムテックス株式会社製、グリシジル基含有アクリルゴム、分子量１００万、Ｔｇ－７℃）１００質量部
・熱硬化性樹脂：ＹＤＣＮ－７００－１０（商品名、新日鉄住金化学株式会社製、ｏ－クレゾールノボラック型エポキシ樹脂、エポキシ当量２１０）３０質量部
・熱硬化性樹脂：ＬＦ－４８７１（商品名、ＤＩＣ株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１１８）９５質量部
・熱硬化性樹脂：ＹＤＦ－８１７０Ｃ（商品名、新日鉄住金化学株式会社製、ビスフェノールＦ型エポキシ樹脂、エポキシ当量１５７）１００質量部
・硬化促進剤：２ＰＺ－ＣＮ（商品名、四国化成工業株式会社製、イミダゾール化合物）０．３質量部
・表面処理フィラー：ＳＣ－２０５０－ＨＬＧ（商品名、株式会社アドマテックス製）３３０質量部
・シランカップリング剤：Ａ－１８９（商品名、ＮＵＣ株式会社製、γ－メルカプトプロピルトリメトキシシラン）０．９質量部
・シランカップリング剤：Ａ－１１６０（商品名、ＮＵＣ株式会社製、γ－ウレイドプロピルトリエトキシシラン）２質量部 Example 1
(Preparation of adhesive varnish)
An adhesive varnish was obtained by mixing the following materials and vacuum degassing.
Thermoplastic resin: HTR-860P-3 (trade name, manufactured by Nagase ChemteX Co., Ltd., glycidyl group-containing acrylic rubber, molecular weight 1,000,000, Tg-7 ° C.) 100 parts by mass Thermosetting resin: YDCN-700-10 (Trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., o-cresol novolac epoxy resin, epoxy equivalent weight 210) 30 parts by mass Thermosetting resin: LF-4871 (trade name, manufactured by DIC, bisphenol A epoxy resin, Epoxy equivalent 118) 95 parts by mass Thermosetting resin: YDF-8170C (trade name, manufactured by Nippon Steel Sumikin Chemical Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent 157) 100 parts by mass Curing accelerator: 2PZ-CN (commodity Name, manufactured by Shikoku Kasei Kogyo Co., Ltd., imidazole compound) 0.3 parts by mass, surface treated filler: SC-20 0-HLG (trade name, manufactured by Admatex Co., Ltd.) 330 parts by mass Silane coupling agent: A-189 (trade name, manufactured by NUC, γ-mercaptopropyltrimethoxysilane) 0.9 parts by mass Silane cup Ring agent: 2 parts by mass of A-1160 (trade name, manufactured by NUC Corporation, γ-ureidopropyltriethoxysilane)
（接着フィルムの作製）
　上記接着剤ワニスを、厚さ５０μｍの表面離型処理ポリエチレンテレフタレートフィルム（帝人フィルムソリューション株式会社製、商品名：テイジンテトロンフィルムＡ－６３）上に塗工した。乾燥工程を経て、上記ポリエチレンテレフタレートフィルム（キャリアフィルム）の一方の面に、厚さ２５μｍの接着剤層が形成されたフィルムを得た。このフィルムと、着色された厚さ５０μｍのポリエチレンフィルム（タマポリ株式会社製、ＴＤＭ－１）とを貼り合わせることによって、積層フィルムを得た。この積層フィルムを１５ｍｍ幅にスリットすることによって、帯状の積層体を得た。 (Production of adhesive film)
The adhesive varnish was coated on a surface release-treated polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film A-63) with a thickness of 50 μm. After the drying step, a film having a 25 μm-thick adhesive layer formed on one side of the polyethylene terephthalate film (carrier film) was obtained. A laminated film was obtained by laminating this film and a colored 50 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., TDM-1). By slitting this laminated film to a width of 15 mm, a strip-like laminated body was obtained.
　上記のようにして得た積層体に対して、図４に示す構成の装置を使用して型抜きを行うことで、本実施例に係る接着フィルムを得た。接着剤片の形状は、縦約７ｍｍ×横約６ｍｍの矩形の一部の角が欠けた形状（面積：２９ｍｍ２）とした。ピッチＰは約９ｍｍとした。接着剤片の面積率Ｒは２３％であった。 The laminated film obtained as described above was die-cut using the device having the configuration shown in FIG. 4 to obtain an adhesive film according to this example. The shape of the adhesive piece was a shape (area: 29 mm 2 ) in which a corner of a part of a rectangle of about 7 mm in length × about 6 mm in width was missing. The pitch P was about 9 mm. The area ratio R of the adhesive piece was 23%.
＜実施例２＞
　接着剤片のサイズ及びピッチを変更したことの他は、実施例１と同様にして接着フィルムを作製した。 Example 2
An adhesive film was produced in the same manner as in Example 1 except that the size and pitch of the adhesive pieces were changed.
＜実施例３＞
　実施例２で使用したキャリアフィルムと異なる表面処理が施されたキャリアフィルムを使用し且つ接着剤片の形状を変更したことの他は、実施例２と同様にして接着フィルムを作製した。キャリアフィルムとして、厚さ５０μｍの表面離型処理ポリエチレンテレフタレートフィルム（帝人フィルムソリューション株式会社製、商品名：テイジンテトロンフィルムＡ－５３）を使用した。 Example 3
An adhesive film was produced in the same manner as in Example 2 except that a carrier film having a different surface treatment from that of the carrier film used in Example 2 was used and the shape of the adhesive piece was changed. As a carrier film, a surface release-treated polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film A-53) having a thickness of 50 μm was used.
＜実施例４＞
　実施例２で使用した保護フィルムと異なる保護フィルムを使用したことの他は、実施例２と同様にして接着フィルムを作製した。保護フィルムとして、着色されていないポリエチレンフィルム(タマポリ株式会社製、商品名：ＮＦ－１３、厚さ：２０μｍ)を使用した。 Example 4
An adhesive film was produced in the same manner as in Example 2 except that a protective film different from the protective film used in Example 2 was used. As a protective film, a non-colored polyethylene film (manufactured by Tamapoly Corporation, trade name: NF-13, thickness: 20 μm) was used.
＜実施例５＞
　実施例２で使用した保護フィルムと異なる保護フィルムを使用したことの他は、実施例２と同様にして接着フィルムを作製した。保護フィルムとして、着色されていないポリエチレンフィルム(タマポリ株式会社製、商品名：ＧＦ－３、厚さ：３０μｍ)を使用した。 Example 5
An adhesive film was produced in the same manner as in Example 2 except that a protective film different from the protective film used in Example 2 was used. As a protective film, a non-colored polyethylene film (manufactured by Tamapoly Corporation, trade name: GF-3, thickness: 30 μm) was used.
＜実施例６＞
　実施例２で使用したキャリアフィルムと異なるキャリアフィルムを使用したことの他は、実施例２と同様にして接着フィルムを作製した。キャリアフィルムとして、表面離型処理がなされていないポリエチレンテレフタレートフィルム（帝人フィルムソリューション株式会社製、商品名：テイジンテトロンフィルムＧ２、厚さ：５０μｍ）を使用した。 Example 6
An adhesive film was produced in the same manner as in Example 2 except that a carrier film different from the carrier film used in Example 2 was used. As a carrier film, a polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film G2, thickness: 50 μm) not subjected to surface release treatment was used.
＜実施例７＞
　実施例２で使用したキャリアフィルムと異なるキャリアフィルムを使用したことの他は、実施例２と同様にして接着フィルムを作製した。キャリアフィルムとして、表面離型処理がなされていないポリエチレンテレフタレートフィルム（帝人フィルムソリューション株式会社製、商品名：テイジンテトロンフィルムＧ２、厚さ：３８μｍ）を使用した。 Example 7
An adhesive film was produced in the same manner as in Example 2 except that a carrier film different from the carrier film used in Example 2 was used. As a carrier film, a polyethylene terephthalate film (manufactured by Teijin Film Solutions Co., Ltd., trade name: Teijin Tetron Film G2, thickness: 38 μm) not subjected to surface release treatment was used.
＜実施例８＞
　接着剤片のサイズを変更したことの他は、実施例２と同様にして接着フィルムを作製した。 Example 8
An adhesive film was produced in the same manner as in Example 2 except that the size of the adhesive strip was changed.
＜実施例９＞
　接着剤片のサイズを変更したことの他は、実施例２と同様にして接着フィルムを作製した。 Example 9
An adhesive film was produced in the same manner as in Example 2 except that the size of the adhesive strip was changed.
　上記実施例に係る接着フィルムについて以下の項目の評価を行った。表１及び表２に結果を示す。
（１）接着剤片の面積率Ｒ
　表１に示す接着剤片の面積Ａ（ｍｍ２）、ピッチＰ（ｍｍ）及びキャリアフィルムの幅Ｗ（ｍｍ）を下記式に代入し、接着剤片の面積率Ｒ（％）を算出した。
　面積率Ｒ（％）＝Ａ／（Ｐ×Ｗ）×１００ The following items were evaluated about the adhesive film which concerns on the said Example. The results are shown in Tables 1 and 2.
(1) Area ratio R of adhesive pieces
The area A (mm 2 ) of the adhesive piece, the pitch P (mm), and the width W (mm) of the carrier film shown in Table 1 were substituted into the following equation to calculate the area ratio R (%) of the adhesive piece.
Area ratio R (%) = A / (P × W) × 100
（２）光透過率
　キャリアフィルム上に接着剤片及びこれを覆う保護部材が設けられている領域の波長５００ｎｍの光の透過率を日本分光株式会社製のＶ－５７０（商品名）を使用して測定した。 (2) Light Transmittance V-570 (trade name) manufactured by JASCO Corporation is used to transmit light with a wavelength of 500 nm in a region where an adhesive strip and a protective member covering the adhesive film are provided on a carrier film. Measured.
（３）キャリアフィルム密着力（９０°ピール強度）
　型抜きを行っていない積層フィルム（キャリアフィルム／接着剤層／保護フィルム）を２０ｍｍ幅に切り出した。両面テープを用い、キャリアフィルム側の面をアルミニウム板に貼り付けた後、保護フィルムを剥がした。その後、キャリアフィルムに対する接着剤層の角度を９０°に維持しながら、接着剤層を上方に引き上げることによってキャリアフィルムから接着剤層を剥離させた。引き上げ速度は５０ｍｍ／分とし、測定環境温度は２３±２℃とした。引き上げに要する力を測定した。この測定値（ｍＮ）及び試料の幅（２０ｍｍ）を下記式に代入することによって、キャリアフィルムと接着剤層と間の密着力を算出した。
　密着力（Ｎ／ｍ）＝測定値（ｍＮ）／２０（ｍｍ） (3) Carrier film adhesion (90 ° peel strength)
A laminated film (carrier film / adhesive layer / protective film) not cut was cut into a width of 20 mm. The surface on the carrier film side was attached to an aluminum plate using a double-sided tape, and then the protective film was peeled off. The adhesive layer was then peeled from the carrier film by pulling the adhesive layer upward while maintaining the angle of the adhesive layer to the carrier film at 90 °. The pulling rate was 50 mm / min, and the measurement environment temperature was 23 ± 2 ° C. The force required to pull it up was measured. The adhesion between the carrier film and the adhesive layer was calculated by substituting the measured value (mN) and the width (20 mm) of the sample into the following equation.
Adhesion (N / m) = measured value (mN) / 20 (mm)
（４）保護フィルム密着力（９０°ピール強度）
　型抜きを行っていない積層フィルム（キャリアフィルム／接着剤層／保護フィルム）を２０ｍｍ幅に切り出した。キャリアフィルムを剥がした後、両面テープを用い、接着剤層側の面をアルミニウム板に貼り付けた後、その後、接着剤層に対する保護フィルムの角度を９０°に維持しながら、保護フィルムを上方に引き上げることによって保護フィルムから接着剤層を剥離させた。引き上げ速度は３００ｍｍ／分とし、測定環境温度は２３±２℃とした。引き上げに要する力を測定した。この測定値（ｍＮ）及び試料の幅（２０ｍｍ）を下記式に代入することによって、保護フィルムと接着剤層との密着力を算出した。
　密着力（Ｎ／ｍ）＝測定値（ｍＮ）／２０（ｍｍ）
(4) Adhesion of protective film (90 ° peel strength)
A laminated film (carrier film / adhesive layer / protective film) not cut was cut into a width of 20 mm. After peeling off the carrier film, after using the double-sided tape and sticking the surface on the adhesive layer side to the aluminum plate, the protective film is upward while maintaining the angle of the protective film to the adhesive layer at 90 °. The adhesive layer was peeled off from the protective film by pulling up. The pulling rate was 300 mm / min, and the measurement environment temperature was 23 ± 2 ° C. The force required to pull it up was measured. The adhesion between the protective film and the adhesive layer was calculated by substituting the measured value (mN) and the width (20 mm) of the sample into the following equation.
Adhesion (N / m) = measured value (mN) / 20 (mm)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本開示によれば、半導体チップが接着されるべき基板の領域に制限があったり、半導体チップの形状が特殊であったりしても、半導体装置の製造プロセスにおける接着工程を効率的に実施するのに有用な接着フィルムが提供される。 According to the present disclosure, even if the area of the substrate to which the semiconductor chip is to be bonded is limited or the shape of the semiconductor chip is special, the bonding process in the manufacturing process of the semiconductor device is efficiently performed. Useful adhesive films are provided.
１…キャリアフィルム、３…接着剤層、３ｐ…接着剤片、５…保護フィルム、５ｐ…保護部材、１０…接着フィルム、Ｆ１…接着剤片の面（第一面）、Ｆ２…接着剤片の面（第二面） DESCRIPTION OF SYMBOLS 1 ... Carrier film, 3 ... Adhesive layer, 3p ... Adhesive piece, 5 ... Protective film, 5p ... Protective member, 10 ... Adhesive film, F1 ... Surface of adhesive piece (1st surface), F2 ... Adhesive piece Face (second face)

Claims (10)

  1. 　幅１００ｍｍ以下の帯状のキャリアフィルムと、
    　前記キャリアフィルム上に前記キャリアフィルムの長手方向に並ぶように配置されている複数の接着剤片と、
    を備える、半導体装置製造用接着フィルム。     Band-like carrier film with a width of 100 mm or less,
    A plurality of adhesive strips arranged on the carrier film in the longitudinal direction of the carrier film;
    An adhesive film for manufacturing a semiconductor device, comprising:
  2. 　前記接着剤片の面積が１０～２００ｍｍ２である、請求項１に記載の接着フィルム。 The adhesive film according to claim 1, wherein the area of the adhesive strip is 10 to 200 mm 2 .
  3. 　前記キャリアフィルムの表面であって前記複数の接着剤片によって覆われている領域の割合が前記キャリアフィルムの面積を基準として１０～６０％である、請求項１又は２に記載の接着フィルム。 The adhesive film according to claim 1 or 2, wherein the ratio of the area of the surface of the carrier film covered by the plurality of adhesive pieces is 10 to 60% based on the area of the carrier film.
  4. 　一つ又は複数の、前記複数の接着剤片からなる列が前記キャリアフィルム上に形成されている、請求項１～３のいずれか一項に記載の接着フィルム。 The adhesive film according to any one of the preceding claims, wherein one or more rows of the plurality of adhesive pieces are formed on the carrier film.
  5. 　前記接着剤片は、前記キャリアフィルムの表面を覆うように形成された接着剤層を型抜きすることによって形成されたものである、請求項１～４のいずれか一項に記載の接着フィルム。 The adhesive film according to any one of claims 1 to 4, wherein the adhesive piece is formed by die-cutting an adhesive layer formed so as to cover the surface of the carrier film.
  6. 　前記キャリアフィルムと前記接着剤片と間の密着力が０．５～１８Ｎ／ｍである、請求項１～５のいずれか一項に記載の接着フィルム。 The adhesive film according to any one of claims 1 to 5, wherein the adhesion between the carrier film and the adhesive piece is 0.5 to 18 N / m.
  7. 　前記接着剤片の前記キャリアフィルム側の第一面と反対側の第二面を覆っており、前記接着剤片と同じ形状を有する保護部材を更に備える、請求項１～６のいずれか一項に記載の接着フィルム。 The protective member which covers the 2nd surface on the opposite side to the 1st surface by the side of the said carrier film of the above-mentioned adhesive piece, and has the same shape as the above-mentioned adhesive piece is further provided with any one of Claims 1-6. Adhesive film as described in.
  8. 　前記接着剤片及び前記保護部材は、前記キャリアフィルムの表面を覆うように形成された接着剤層と、前記接着剤層を覆うように配置された保護フィルムとを型抜きすることによって形成されたものである、請求項７に記載の接着フィルム。 The adhesive piece and the protective member are formed by die cutting an adhesive layer formed so as to cover the surface of the carrier film and a protective film arranged so as to cover the adhesive layer. The adhesive film according to claim 7, which is one.
  9. 　前記保護部材の光透過率が前記キャリアフィルムの光透過率よりも低い、請求項７又は８に記載の接着フィルム。 The adhesive film according to claim 7 or 8, wherein the light transmittance of the protective member is lower than the light transmittance of the carrier film.
  10. 　前記接着剤片と前記保護部材との間の密着力が１６Ｎ／ｍ以下である、請求項７～９のいずれか一項に記載の接着フィルム。 The adhesive film according to any one of claims 7 to 9, wherein the adhesion between the adhesive piece and the protective member is 16 N / m or less.
PCT/JP2017/033723 2017-09-19 2017-09-19 Adhesive film for semiconductor device manufacture WO2019058425A1 (en)

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