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WO2017038917A1 - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
WO2017038917A1
WO2017038917A1 PCT/JP2016/075604 JP2016075604W WO2017038917A1 WO 2017038917 A1 WO2017038917 A1 WO 2017038917A1 JP 2016075604 W JP2016075604 W JP 2016075604W WO 2017038917 A1 WO2017038917 A1 WO 2017038917A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
mass
layer
Prior art date
Application number
PCT/JP2016/075604
Other languages
French (fr)
Japanese (ja)
Inventor
高野　健
和浩 菊池
貴志 杉野
Original Assignee
リンテック株式会社
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 リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020187035736A priority Critical patent/KR102612643B1/en
Priority to KR1020177034192A priority patent/KR101930197B1/en
Priority to JP2017518161A priority patent/JP6148805B1/en
Priority to CN201680030959.7A priority patent/CN107636100B/en
Publication of WO2017038917A1 publication Critical patent/WO2017038917A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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 potential barriers, e.g. a 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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/003—Presence of epoxy resin in the primer coating
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/003—Presence of polyester in the primer coating
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Definitions

  • the present invention relates to an adhesive sheet.
  • Patent Document 1 discloses a mask sheet for suppressing adhesive residue of an adhesive and stably producing a QFN (Quad Flat Non-lead) semiconductor package.
  • a mask sheet is prepared using a specific heat-resistant film and a silicone-based pressure-sensitive adhesive to withstand an environment of 150 to 180 ° C. for 1 to 6 hours in a die attach process and a resin sealing process. It is stated that you get.
  • pressure-sensitive adhesive sheets are also used in processes where high temperature conditions such as 180 ° C. or higher and 200 ° C. or lower are imposed.
  • high-temperature process for example, when an inexpensive film (for example, a film such as polyethylene terephthalate) having a low heat resistance compared to a polyimide film or the like is used as a base material, the adhesive sheet is removed from the adherend after the process is completed. It was found that the surface of the adherend was contaminated when peeled off. It is thought that the cause of such contamination is that a low molecular weight component (oligomer) contained in the resin film used as the base material is deposited on the surface of the adherend.
  • oligomer a low molecular weight component contained in the resin film used as the base material
  • An object of the present invention is to provide a pressure-sensitive adhesive sheet that can prevent contamination of the surface of an adherend even after undergoing a process in which high-temperature conditions are imposed.
  • a pressure-sensitive adhesive sheet used for sealing a semiconductor element on a pressure-sensitive adhesive sheet which includes a base material, a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive, the base material, and the pressure-sensitive adhesive.
  • An pressure-sensitive adhesive sheet having an oligomer sealing layer provided between the layers is provided.
  • the oligomer sealing layer is a cured film obtained by curing a composition for an oligomer sealing layer containing an epoxy compound, a polyester compound, and a polyfunctional amino compound. Is preferred.
  • the composition for an oligomer sealing layer comprises (A) 50% by mass to 80% by mass of a bisphenol A type epoxy compound and (B) 5% by mass to 30% by mass. It is preferable to contain the following polyester compounds and (C) 10 to 40 mass% polyfunctional amino compounds.
  • the storage elastic modulus of the substrate at 100 ° C. is preferably 1 ⁇ 10 7 Pa or more.
  • the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
  • the acrylic pressure-sensitive adhesive composition preferably includes an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer.
  • the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
  • the oligomer sealing layer is provided on both surfaces of the base material.
  • the base material preferably contains a polyester resin.
  • FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
  • the pressure-sensitive adhesive sheet 10 has a base material 11, a pressure-sensitive adhesive layer 12, and an oligomer sealing layer 13.
  • the base material 11 has a first base material surface 11a and a second base material surface 11b opposite to the first base material surface 11a.
  • An oligomer sealing layer 13 is provided between the substrate 11 and the pressure-sensitive adhesive layer 12.
  • the oligomer sealing layer 13 is preferably laminated on the first base material surface 11 a, and the first base material surface 11 a is preferably covered with the oligomer sealing layer 13.
  • the shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a sheet shape, a tape shape, and a label shape.
  • the substrate 11 is a member that supports the pressure-sensitive adhesive layer 12 and the oligomer sealing layer 13.
  • a sheet material such as a synthetic resin film can be used.
  • synthetic resin films include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film.
  • examples of the substrate 11 include these cross-linked films and laminated films.
  • the base material 11 preferably includes a polyester-based resin, and more preferably includes a material having a polyester-based resin as a main component.
  • the material having a polyester-based resin as a main component means that the ratio of the mass of the polyester-based resin to the total mass of the material constituting the substrate is 50% by mass or more.
  • the polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins. Is preferred, and polyethylene terephthalate resin is more preferred.
  • a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film is more preferable.
  • the oligomers contained in the polyester film are derived from polyester-forming monomers, dimers, trimers, and the like.
  • the lower limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 ⁇ 10 7 Pa or more, and more preferably 1 ⁇ 10 8 Pa or more, from the viewpoint of dimensional stability during processing.
  • the upper limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 ⁇ 10 12 Pa or less from the viewpoint of workability.
  • the storage elastic modulus is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring apparatus.
  • the substrate to be measured is cut into a width of 5 mm and a length of 20 mm, and a viscoelasticity measuring device (manufactured by TA Instruments, DMAQ800) is used, and the storage viscoelasticity at 100 ° C. is measured at a frequency of 1 Hz and a tensile mode. taking measurement.
  • a viscoelasticity measuring device manufactured by TA Instruments, DMAQ800
  • the first substrate surface 11a may be subjected to at least one surface treatment such as a primer treatment, a corona treatment, and a plasma treatment in order to improve the adhesion with the oligomer sealing layer 13.
  • the first base material surface 11a of the base material 11 may be subjected to an adhesive treatment by applying an adhesive.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate include acrylic, rubber-based, silicone-based, and urethane-based pressure-sensitive adhesives.
  • the thickness of the substrate 11 is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 15 ⁇ m or more and 300 ⁇ m or less, and further preferably 20 ⁇ m or more and 250 ⁇ m or less.
  • the pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various types of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12.
  • Examples of the adhesive contained in the adhesive layer 12 include rubber-based, acrylic-based, silicone-based, polyester-based, and urethane-based.
  • the kind of adhesive is selected in consideration of the use and the kind of adherend to be attached.
  • the pressure-sensitive adhesive layer 12 preferably contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
  • the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer. . Moreover, when the adhesive layer 12 contains an acrylic adhesive composition, it is preferable that the acrylic copolymer and the adhesion promoter are included.
  • the acrylic copolymer is preferably a copolymer having 2-ethylhexyl acrylate as a main monomer.
  • the adhesive aid preferably contains a rubber-based material having a reactive group as a main component.
  • 2-ethylhexyl acrylate is the main monomer, and the ratio of the mass of the copolymer component derived from 2-ethylhexyl acrylate to the total mass of the acrylic copolymer is 50% by mass or more. Means.
  • the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, and 60% by mass or more and 95% by mass or less. It is more preferable that it is 80 mass% or more and 95 mass% or less, and it is still more preferable that it is 85 mass% or more and 93 mass% or less.
  • the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 50% by mass or more, the adhesive strength does not become too high after heating, and the adhesive sheet is more easily peeled off from the adherend, and 80% by mass or more. If it is, it will become still easier to peel. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, the initial adhesive force is insufficient and the substrate is deformed during heating, or the adhesive sheet is peeled off from the adherend due to the deformation. Can be prevented.
  • the type and number of copolymer components other than 2-ethylhexyl acrylate in the acrylic copolymer are not particularly limited.
  • a functional group-containing monomer having a reactive functional group is preferable.
  • a reactive functional group of a 2nd copolymer component when using the crosslinking agent mentioned later, it is preferable that it is a functional group which can react with the said crosslinking agent.
  • This reactive functional group is preferably at least one substituent selected from the group consisting of, for example, a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. These substituents are more preferable, and a carboxyl group is still more preferable.
  • Examples of the monomer having a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • carboxyl group-containing monomers acrylic acid is preferable from the viewpoint of reactivity and copolymerization.
  • a carboxyl group-containing monomer may be used independently and may be used in combination of 2 or more type.
  • Examples of the monomer having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 And (meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of hydroxyl reactivity and copolymerization.
  • a hydroxyl-containing monomer may be used independently and may be used in combination of 2 or more type.
  • “(meth) acrylic acid” is a notation used to represent both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
  • Examples of other copolymer components in the acrylic copolymer include (meth) acrylic acid alkyl esters having an alkyl group with 2 to 20 carbon atoms.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and (meth) acrylic acid n.
  • Examples of other copolymer components in the acrylic copolymer include, for example, alkoxyalkyl group-containing (meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring, and (meth) acrylic acid having an aromatic ring.
  • alkoxyalkyl group-containing (meth) acrylic acid ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
  • examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate.
  • examples of the (meth) acrylic acid ester having an aromatic ring examples include phenyl (meth) acrylate.
  • non-crosslinkable acrylamides examples include acrylamide and methacrylamide.
  • Examples of the (meth) acrylic acid ester having a non-crosslinkable tertiary amino group include (meth) acrylic acid (N, N-dimethylamino) ethyl and (meth) acrylic acid (N, N-dimethylamino). Propyl.
  • a copolymer component derived from a monomer having a nitrogen atom-containing ring is also preferable from the viewpoint of improving the polarity of the pressure-sensitive adhesive and improving adhesion and adhesive strength. .
  • Monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Examples include vinyl morpholine, N-vinyl caprolactam, and N- (meth) acryloyl morpholine.
  • N- (meth) acryloylmorpholine is preferable. These monomers may be used independently and may be used in combination of 2 or more type.
  • a carboxyl group-containing monomer or a hydroxyl group-containing monomer is preferable as the second copolymer component, and acrylic acid is more preferable.
  • the acrylic copolymer includes a copolymer component derived from 2-ethylhexyl acrylate and a copolymer component derived from acrylic acid
  • the copolymer component derived from acrylic acid occupies the total mass of the acrylic copolymer.
  • the mass ratio is preferably 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. If the ratio of acrylic acid is 1 mass% or less, when an adhesive composition contains a crosslinking agent, crosslinking of the acrylic copolymer can be prevented from proceeding too quickly.
  • the acrylic copolymer may contain a copolymer component derived from two or more kinds of functional group-containing monomers.
  • the acrylic copolymer may be a ternary copolymer.
  • an acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer and a hydroxyl group-containing monomer is preferred, and this carboxyl group-containing monomer is preferred.
  • the hydroxyl group-containing monomer is preferably 2-hydroxyethyl acrylate.
  • the ratio of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less, and the ratio of the mass of the copolymer component derived from acrylic acid is 1% by mass or less.
  • the balance is preferably a copolymer component derived from 2-hydroxyethyl acrylate.
  • the weight average molecular weight (Mw) of the acrylic copolymer is preferably from 300,000 to 2,000,000, more preferably from 600,000 to 1,500,000, and even more preferably from 800,000 to 1,200,000. preferable. If the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, the acrylic copolymer can be peeled without a residue of the adhesive on the adherend. When the weight average molecular weight Mw of the acrylic copolymer is 2 million or less, it can be reliably attached to the adherend.
  • the weight average molecular weight Mw of the acrylic copolymer is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.
  • the acrylic copolymer can be produced according to a conventionally known method using the above-mentioned various raw material monomers.
  • the form of copolymerization of the acrylic copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.
  • the content of the acrylic copolymer in the pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.
  • the adhesive aid preferably contains a rubber-based material having a reactive group as a main component.
  • the pressure-sensitive adhesive composition contains a reactive pressure-sensitive adhesive aid, the adhesive residue can be reduced.
  • the content of the adhesion assistant in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content rate of the adhesion promoter in an adhesive composition is 3 mass% or more, generation
  • including a rubber-based material having a reactive group as a main component means that the proportion of the mass of the rubber-based material having a reactive group in the total mass of the adhesive aid exceeds 50% by mass.
  • the ratio of the rubber-based material having a reactive group in the adhesion assistant is preferably more than 50% by mass, and more preferably 80% by mass or more. It is also preferable that the adhesion assistant is made of a rubber-based material having a substantially reactive group.
  • the reactive group is preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group. More preferably.
  • the reactive group possessed by the rubber material may be one type or two or more types.
  • the rubber-based material having a hydroxyl group may further have the aforementioned reactive group.
  • the number of reactive groups may be one per molecule constituting the rubber-based material, or two or more.
  • the rubber-based material is not particularly limited, but a polybutadiene-based resin and a hydrogenated product of a polybutadiene-based resin are preferable, and a hydrogenated product of a polybutadiene-based resin is more preferable.
  • the polybutadiene-based resin include resins having 1,4-repeating units, resins having 1,2-repeating units, and resins having both 1,4-repeating units and 1,2-repeating units.
  • the hydrogenated product of the polybutadiene resin of the present embodiment includes a hydride of a resin having these repeating units.
  • the polybutadiene resin and the hydrogenated product of the polybutadiene resin preferably have reactive groups at both ends.
  • the reactive groups at both ends may be the same or different.
  • the reactive groups at both ends are preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group. More preferred is a hydroxyl group.
  • both ends are hydroxyl groups.
  • the pressure-sensitive adhesive composition according to the present embodiment preferably contains a cross-linked product obtained by cross-linking a composition containing a cross-linking agent in addition to the acrylic copolymer and the pressure-sensitive adhesive aid.
  • the solid content of the pressure-sensitive adhesive composition substantially consists of a cross-linked product obtained by cross-linking the above-mentioned acrylic copolymer, the pressure-sensitive adhesive aid, and the cross-linking agent as described above.
  • “substantially” means that the solid content of the pressure-sensitive adhesive composition is composed only of the cross-linked product, excluding trace amounts of impurities that are inevitably mixed in the pressure-sensitive adhesive.
  • examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent.
  • These cross-linking agents may be used alone or in combination of two or more.
  • a crosslinking agent (isocyanate-based crosslinking agent) containing a compound having an isocyanate group as a main component is preferable.
  • isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
  • Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate,
  • the polyisocyanate compound may be a trimethylolpropane adduct-type modified product of the above-described compound, a burette-type modified product reacted with water, or an isocyanurate-type modified product having an isocyanurate ring.
  • crosslinking agent mainly comprising a compound having an isocyanate group means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. To do.
  • the content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If content of the crosslinking agent in an adhesive composition is in such a range, the adhesiveness of the layer (adhesive layer) containing an adhesive composition and a to-be-adhered body (for example, base material) will be improved. It is possible to shorten the curing period for stabilizing the adhesive property after the production of the adhesive sheet.
  • the isocyanate-based crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product).
  • the compound having an isocyanurate ring is preferably blended in an amount of 0.7 to 1.5 equivalents with respect to the hydroxyl equivalent of the acrylic copolymer. If the compounding quantity of the compound which has an isocyanurate ring is 0.7 equivalent or more, the adhesive strength will not become too high after heating, the adhesive sheet will be easily peeled off, and the adhesive residue can be reduced. If the compounding quantity of the compound which has an isocyanurate ring is 1.5 equivalent or less, it can prevent that an initial stage adhesive force becomes low too much, or can prevent a sticking fall.
  • the pressure-sensitive adhesive composition in this embodiment contains a crosslinking agent
  • the pressure-sensitive adhesive composition preferably further contains a crosslinking accelerator.
  • the crosslinking accelerator is preferably selected and used as appropriate according to the type of the crosslinking agent.
  • the pressure-sensitive adhesive composition contains a polyisocyanate compound as a crosslinking agent
  • a silicone-type adhesive composition contains an addition polymerization type silicone resin.
  • a silicone pressure-sensitive adhesive composition containing an addition polymerization type silicone resin is referred to as an addition reaction type silicone pressure-sensitive adhesive composition.
  • the addition reaction type silicone pressure-sensitive adhesive composition contains a main agent and a crosslinking agent.
  • the addition reaction type silicone pressure-sensitive adhesive composition has an advantage that it can be used only by primary curing at a low temperature and does not require secondary curing at a high temperature.
  • the conventional peroxide-curing silicone pressure-sensitive adhesive requires secondary curing at a high temperature such as 150 ° C. or higher. Therefore, by using the addition reaction type silicone pressure-sensitive adhesive composition, it is possible to produce a pressure-sensitive adhesive sheet at a relatively low temperature, use the base material 11 having excellent energy economy and relatively low heat resistance. Thus, the pressure-sensitive adhesive sheet 10 can be manufactured. Further, since no by-product is produced during curing unlike the peroxide-curing silicone pressure-sensitive adhesive, there are no problems such as odor and corrosion.
  • the addition reaction type silicone pressure-sensitive adhesive composition is usually composed of a main agent composed of a mixture of a silicone resin component and a silicone rubber component, a hydrosilyl group (SiH group) -containing crosslinking agent, and a curing catalyst used as necessary.
  • the silicone resin component is an organopolysiloxane having a network structure obtained by hydrolyzing organochlorosilane or organoalkoxysilane and then performing a dehydration condensation reaction.
  • the silicone rubber component is a diorganopolysiloxane having a linear structure.
  • both the silicone resin component and the silicone rubber component are a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like.
  • the aforementioned organo groups are partially vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth) acryloyl, (meth) acryloylmethyl, (meth) acryloylpropyl, and cyclohexenyl.
  • Substituting with an unsaturated group such as a group.
  • An organo group having a vinyl group that is easily available industrially is preferred.
  • crosslinking proceeds by an addition reaction between an unsaturated group and a hydrosilyl group to form a network structure, thereby exhibiting adhesiveness.
  • the number of unsaturated groups such as vinyl groups is usually from 0.05 to 3.0, preferably from 0.1 to 2.5, per 100 organo groups.
  • organopolysiloxane described above examples include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 per 100 methyl groups), Toray Dow Corning BY23-753 manufactured by the company (the number of vinyl groups is 0.1 per 100 methyl groups) and BY24-162 (the number of vinyl groups is 1.4 per 100 methyl groups) Things).
  • SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Toray Dow Corning can also be used.
  • organopolysiloxane which is a silicone resin component
  • silicone rubber component KS-3800 (manufactured by Shin-Etsu Chemical Co., Ltd.) 7.6 for 100 methyl groups), BY24-162 made by Toray Dow Corning (number of vinyl groups is 1.4 for 100 methyl groups), BY24- 843 (having no unsaturated group) and SD-7292 (the number of vinyl groups is 5.0 with respect to 100 methyl groups).
  • Specific examples of the addition reaction type silicone as described above are described in, for example, JP-A-10-219229.
  • the crosslinking agent is usually 0.5 to 10 hydrogen atoms bonded to silicon atoms, preferably 1 or more to one unsaturated group such as a vinyl group of the silicone resin component and the silicone rubber component. It mix
  • the number By setting the number to 0.5 or more, the reaction between the unsaturated group such as a vinyl group and the hydrosilyl group does not proceed completely, thereby preventing poor curing.
  • the addition reaction type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst together with the aforementioned addition reaction type silicone component (main agent comprising a silicone resin component and a silicone rubber component) and a crosslinking agent.
  • This curing catalyst is used to accelerate the hydrosilylation reaction between the unsaturated group in the silicone resin component and the silicone rubber component and the Si—H group in the crosslinking agent.
  • the curing catalyst is a platinum-based catalyst, that is, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol solution, a reaction product of chloroplatinic acid and an olefin compound, chloroplatinic acid and vinyl Examples thereof include a reaction product with a group-containing siloxane compound, a platinum-olefin complex, a platinum-vinyl group-containing siloxane complex, and a platinum-phosphorus complex.
  • Specific examples of the curing catalyst as described above are described in, for example, JP-A-2006-28311 and JP-A-10-147758. More specifically, commercially available products include SRX-212 manufactured by Toray Dow Corning and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
  • the blending amount of the curing catalyst is usually 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass ppm or more and 500 mass ppm or less with respect to the total amount of the silicone resin component and the silicone rubber component as platinum content.
  • curability is lowered and the crosslinking density is reduced, that is, the adhesive force and the cohesive force (holding force) are prevented from being reduced. While preventing, the stability of an adhesive layer can be hold
  • addition reaction type silicone pressure-sensitive adhesive composition adhesive force is exhibited even at room temperature by blending the above-mentioned components, but the addition reaction type silicone pressure-sensitive adhesive composition is applied to the substrate 11 or a release sheet described later. From the standpoint of stability of adhesive strength, the base material 11 and the release sheet are bonded together, and then a heating or active energy ray is irradiated to promote the crosslinking reaction of the silicone resin component and the silicone rubber component by the crosslinking agent. preferable.
  • the heating temperature is usually 60 ° C. or higher and 140 ° C. or lower, preferably 80 ° C. or higher and 130 ° C. or lower.
  • an active energy ray having energy quanta in an electromagnetic wave or a charged particle beam that is, an active light such as an ultraviolet ray or an electron beam
  • an active light such as an ultraviolet ray or an electron beam
  • a photopolymerization initiator is not required.
  • a photopolymerization initiator is present.
  • the photopolymerization initiator in the case of irradiation with ultraviolet rays is not particularly limited, and any photopolymerization initiator that has been conventionally used in ultraviolet curable resins can be appropriately selected and used. it can.
  • photopolymerization initiator examples include benzoins, benzophenones, acetophenones, ⁇ -hydroxy ketones, ⁇ -amino ketones, ⁇ -diketones, ⁇ -diketone dialkyl acetals, anthraquinones, thioxanthones, and other compounds. Etc. These photopolymerization initiators may be used alone or in combination of two or more. Further, the amount used is usually 0.01 parts by mass or more and 30 parts by mass or less, preferably 0.05 parts by mass with respect to 100 parts by mass of the total amount of the addition reaction type silicone component and the crosslinking agent used as the main agent. It is selected in the range of 20 parts by mass or less.
  • a pressure-sensitive adhesive sheet having a stable adhesive force can be obtained by crosslinking by irradiation with heat or active energy rays.
  • the acceleration voltage of the electron beam is generally 130 kV or more and 300 kV or less, preferably 150 kV or more and 250 kV or less. Irradiation at an acceleration voltage of 130 kV or more can prevent the silicone resin component and the silicone rubber component from being insufficiently crosslinked and prevent the adhesive force from becoming insufficient. By irradiation at an acceleration voltage of 300 kV or less, the adhesive It can prevent that a layer and a base material sheet deteriorate or discolor. A preferable range of the beam current is 1 mA or more and 100 mA or less.
  • the dose of the irradiated electron beam is preferably 1 Mrad to 70 Mrad, and more preferably 2 Mrad to 20 Mrad.
  • the irradiation amount in the case of ultraviolet irradiation is appropriately selected.
  • the light amount is from 100 mJ / cm 2 to 500 mJ / cm 2 and the illuminance is from 10 mW / cm 2 to 500 mW / cm 2 .
  • Heating and irradiation with active energy rays are preferably performed in a nitrogen atmosphere in order to prevent reaction inhibition by oxygen.
  • the thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the use of the pressure-sensitive adhesive sheet 10.
  • the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 ⁇ m or more and 60 ⁇ m or less, and more preferably 10 ⁇ m or more and 50 ⁇ m or less. If the thickness of the pressure-sensitive adhesive layer 12 is too thin, the pressure-sensitive adhesive layer 12 may not follow the irregularities on the circuit surface of the semiconductor chip, and a gap may be generated. For example, an interlayer insulating material and a sealing resin may enter the gap, and the wiring connection electrode pad on the chip circuit surface may be blocked.
  • the pressure-sensitive adhesive layer 12 When the thickness of the pressure-sensitive adhesive layer 12 is 5 ⁇ m or more, the pressure-sensitive adhesive layer 12 easily follows the unevenness of the chip circuit surface, and the generation of a gap can be prevented. If the thickness of the pressure-sensitive adhesive layer 12 is too thick, the semiconductor chip sinks into the pressure-sensitive adhesive layer, and there is a risk that a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip occurs. If such a step occurs, the wiring may be disconnected during rewiring. If the thickness of the pressure-sensitive adhesive layer 12 is 60 ⁇ m or less, a step is hardly generated.
  • the pressure-sensitive adhesive composition may contain other components as long as the effects of the present invention are not impaired.
  • other components that can be included in the pressure-sensitive adhesive composition include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, antiseptics, antifungal agents, and plastics. Agents, antifoaming agents, colorants, fillers, wettability adjusting agents and the like.
  • the addition reaction type silicone pressure-sensitive adhesive composition may contain non-reactive polyorganosiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane as additives.
  • the oligomer sealing layer 13 is a layer for preventing the low molecular weight component (oligomer) from entering the pressure-sensitive adhesive layer 12.
  • oligomer low molecular weight component
  • the oligomer sealing layer 13 preferably prevents the oligomer from entering the pressure-sensitive adhesive layer 12 even under a high temperature condition of 180 ° C. or higher and 200 ° C. or lower.
  • the material of the oligomer sealing layer 13 is not particularly limited as long as the oligomer can be prevented from entering the pressure-sensitive adhesive layer 12.
  • the oligomer sealing layer 13 is a cured film obtained by curing a composition for an oligomer sealing layer containing (A) an epoxy compound, (B) a polyester compound, and (C) a polyfunctional amino compound. Is preferred.
  • the composition for oligomer sealing layer may further contain (D) an acidic catalyst.
  • the epoxy compound is preferably a bisphenol A type epoxy compound.
  • the bisphenol A type epoxy compound include bisphenol A diglycidyl ether.
  • the weight average molecular weight (Mw) of the bisphenol A type epoxy compound is preferably 1 ⁇ 10 4 or more and 5 ⁇ 10 4 or less. If the weight average molecular weight (Mw) of the bisphenol A type epoxy compound is 1 ⁇ 10 4 or more, the crosslink density required for the film can be obtained, and the precipitation of the oligomer can be easily prevented. If the weight average molecular weight (Mw) is 5 ⁇ 10 4 or less, it is possible to prevent the film from becoming too hard.
  • the weight average molecular weight Mw is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
  • polyester compound (B) It does not specifically limit as a polyester compound, It can select from a well-known polyester compound suitably, and can be used.
  • the polyester compound is a resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid, and is a compound modified with a condensate of a dibasic acid and a dihydric alcohol or a non-drying oil fatty acid or the like
  • a convertible polyester compound that is a condensate of a dibasic acid and a trivalent or higher alcohol.
  • any of these polyester compounds can be used.
  • Examples of the polyhydric alcohol used as a raw material for the polyester compound include dihydric alcohols, trihydric alcohols, and tetrahydric or higher polyhydric alcohols.
  • Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol.
  • Examples of the trihydric alcohol include glycerin, trimethylolethane, and trimethylolpropane.
  • Examples of the tetrahydric or higher polyhydric alcohol include diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbit.
  • a polyhydric alcohol may be used individually by 1 type, and may be used in combination of 2 or more type.
  • polybasic acid examples include aromatic polybasic acids, aliphatic saturated polybasic acids, aliphatic unsaturated polybasic acids, and polybasic acids by Diels-Alder reaction.
  • aromatic polybasic acid examples include phthalic anhydride, terephthalic acid, isophthalic acid, and trimetic anhydride.
  • aliphatic saturated polybasic acid examples include succinic acid, adipic acid, and sebacic acid.
  • aliphatic unsaturated polybasic acid examples include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic anhydride.
  • Examples of the polybasic acid by Diels-Alder reaction include cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, and rosin-maleic anhydride adduct.
  • a polybasic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
  • non-drying oil fatty acid that is a modifier
  • examples of the non-drying oil fatty acid that is a modifier include octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid, or coconut oil. Linseed oil, tung oil, castor oil, dehydrated castor oil, soybean oil, safflower oil, and fatty acids thereof.
  • 1 type may be used independently and 2 or more types may be used in combination.
  • the polyester compound preferably has an active hydrogen group that serves as a base point for the crosslinking reaction.
  • the active hydrogen group include a hydroxyl group, a carboxyl group, and an amino group.
  • the polyester compound particularly preferably has a hydroxyl group.
  • the hydroxyl value of the polyester compound is preferably 5 mgKOH / g or more and 500 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 300 mgKOH / g or less.
  • the number average molecular weight (Mn) of the polyester compound is preferably 500 or more and 10,000 or less, and more preferably 1000 or more and 5000 or less.
  • the aforementioned number average molecular weight is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.
  • the glass transition temperature Tg of a polyester compound is 0 degreeC or more and 50 degrees C or less.
  • Mn number average molecular weight
  • Tg glass transition temperature
  • a polyfunctional amino compound As a polyfunctional amino compound, a melamine compound, a urea compound, a benzoguanamine compound, and diamine can be used, for example.
  • melamine compounds include hexamethoxymethyl melamine, methylated melamine compounds, and butylated melamine compounds.
  • urea compounds include methylated urea compounds and butylated urea compounds.
  • the benzoguanamine compound include a methylated benzoguanamine compound and a butylated benzoguanamine compound.
  • diamines examples include ethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N′-diphenylethylenediamine, and p-xylylenediamine. From the viewpoint of curability, hexamethoxymethyl melamine is preferred as the (C) polyfunctional amino compound.
  • Acidic catalyst examples include hydrochloric acid and p-toluenesulfonic acid.
  • the oligomer sealing layer 13 contains (A) bisphenol A type epoxy compound, (B) polyester compound, and (C) polyfunctional amino compound, respectively (A) 50 mass% or more 80 It may be a cured film obtained by curing a composition for an oligomer sealing layer containing at a blending ratio of 5% by mass or less, (B) 5% by mass to 30% by mass, and (C) 10% by mass or more and 40% by mass or less. preferable.
  • the effect of preventing the oligomer sealing layer 13 from entering the pressure-sensitive adhesive layer 12 by the oligomer sealing layer 13 can be improved.
  • composition for an oligomer sealing layer As a more specific example of the composition for an oligomer sealing layer according to the present embodiment, for example, the following examples of the composition for an oligomer sealing layer may be mentioned. It is not limited.
  • composition for an oligomer sealing layer As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst, A) an epoxy compound is a bisphenol A type epoxy compound, and (C) a polyfunctional amino compound includes a composition for an oligomer sealing layer, which is a melamine compound.
  • composition for an oligomer sealing layer As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst,
  • the A) epoxy compound is a bisphenol A type epoxy compound, the weight average molecular weight (Mw) of the (A) epoxy compound is 1 ⁇ 10 4 or more and 5 ⁇ 10 4 or less, and (C) the polyfunctional amino compound is melamine
  • Mw weight average molecular weight of the (A) epoxy compound is 1 ⁇ 10 4 or more and 5 ⁇ 10 4 or less
  • the polyfunctional amino compound is melamine
  • composition for an oligomer sealing layer As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst, A)
  • the epoxy compound is a bisphenol A type epoxy compound, the number average molecular weight (Mn) of the (B) polyester compound is 500 or more and 10,000 or less, and the glass transition temperature Tg of the (B) polyester compound is 0 ° C. or more.
  • the composition for oligomer sealing layers which is 50 degrees C or less and (C) polyfunctional amino compound is a melamine compound is mentioned.
  • composition for an oligomer sealing layer As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst,
  • the A) epoxy compound is a bisphenol A type epoxy compound, the weight average molecular weight (Mw) of the (A) epoxy compound is 1 ⁇ 10 4 or more and 5 ⁇ 10 4 or less, and (B) the number average molecular weight of the polyester compound ( Mn) is 500 or more and 10,000 or less, (B)
  • the glass transition temperature Tg of the polyester compound is 0 ° C. or more and 50 ° C. or less, and
  • the polyfunctional amino compound is a melamine compound for the oligomer sealing layer.
  • the thickness of the oligomer sealing layer 13 is preferably 50 nm or more and 500 nm or less, and more preferably 80 nm or more and 300 nm or less. If the thickness of the oligomer sealing layer 13 is 50 nm or more, the penetration of the oligomer into the pressure-sensitive adhesive layer 12 can be effectively prevented. If the thickness of the oligomer sealing layer 13 is 500 nm or less, it will become easy to wind up when the adhesive sheet 10 is wound around a core material in roll shape. Examples of the material of the core material include paper, plastic, and metal.
  • the pressure-sensitive adhesive sheet 10 preferably exhibits the following adhesive strength after heating.
  • the pressure-sensitive adhesive sheet 10 is adhered to an adherend (copper foil or polyimide film), heated at 100 ° C. and 30 minutes, subsequently heated at 180 ° C. and 30 minutes, and further at 190 ° C. and 1 ° C.
  • the adhesive strength of the adhesive layer 12 to the copper foil at room temperature and the adhesive strength of the adhesive layer 12 to the polyimide film at room temperature are 0.7 N / 25 mm or more and 2.0 N / 25 mm, respectively. The following is preferable.
  • the adhesive sheet 10 can be prevented from peeling off from the adherend when the substrate or adherend is deformed by heating. Moreover, if the adhesive force after a heating is 2.0 N / 25mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body.
  • room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower.
  • the adhesive strength is a value measured by a 180 ° peeling method at a pulling speed of 300 mm / min and a width of 25 mm of the adhesive sheet.
  • pressure-sensitive adhesive composition includes the following pressure-sensitive adhesive compositions, but the present invention is not limited to such examples.
  • An example of the pressure-sensitive adhesive composition according to this embodiment includes an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent, and the acrylic copolymer contains at least 2-ethylhexyl acrylate and a carboxyl group.
  • An example of the pressure-sensitive adhesive composition according to this embodiment includes an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent, and the acrylic copolymer contains at least 2-ethylhexyl acrylate and a carboxyl group.
  • a pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing a monomer and a hydroxyl group-containing monomer, wherein the adhesion assistant is a hydroxylated hydrogenated polybutadiene at both terminals, and the crosslinking agent is an isocyanate crosslinking agent Things.
  • an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, And an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the adhesion assistant contains a rubber-based material having a reactive group as a main component, and the crosslinking agent is an isocyanate-based crosslinking.
  • a pressure-sensitive adhesive composition which is an agent is mentioned.
  • an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Things.
  • the acrylic copolymer includes at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a monomer having a nitrogen atom-containing ring.
  • An acrylic copolymer obtained by polymerization is also preferred.
  • the acrylic copolymer contains at least 2-ethylhexyl acrylate, acrylic acid, 2-hydroxyethyl acrylate, and N- (meth) acryloylmorpholine.
  • An acrylic copolymer obtained by copolymerization is also preferred.
  • the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less.
  • the proportion of the mass of the copolymer component derived from the group-containing monomer is preferably 1% by mass or less, and the remainder is preferably another copolymer component.
  • the other copolymer component is a copolymer derived from a hydroxyl group-containing monomer. It preferably contains a polymer component.
  • the manufacturing method of the adhesive sheet 10 is not particularly limited.
  • the adhesive sheet 10 is manufactured through the following processes. First, the composition for oligomer sealing layers is apply
  • the composition for oligomer sealing layer When the composition for oligomer sealing layer is applied to form the oligomer sealing layer 13, and when the pressure-sensitive adhesive composition is applied to form the pressure-sensitive adhesive layer 12, the composition for oligomer sealing layer and the pressure-sensitive adhesive composition It is preferable to prepare a coating solution by diluting the product with an organic solvent.
  • organic solvent include aromatic solvents, aliphatic solvents, ester solvents, ketone solvents, and alcohol solvents.
  • the aromatic solvent include benzene, toluene, and xylene.
  • the aliphatic solvent include normal hexane and normal heptane.
  • Examples of the ester solvent include ethyl acetate and butyl acetate.
  • Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone.
  • Examples of the alcohol solvent include isopropyl alcohol and methanol.
  • Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, die coating, and gravure coating.
  • a crosslinking agent is blended in the pressure-sensitive adhesive composition, it is preferable to heat the coating film in order to promote the crosslinking reaction and improve the cohesive force.
  • the pressure-sensitive adhesive sheet 10 is used when sealing a semiconductor element.
  • the pressure-sensitive adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing a semiconductor element that is stuck on the pressure-sensitive adhesive sheet 10.
  • the pressure-sensitive adhesive sheet 10 is not used when sealing a semiconductor element mounted on a metal lead frame, but seals a semiconductor element that is stuck to the pressure-sensitive adhesive layer 12.
  • a panel scale package Panel Scale Package
  • WLP wafer Level Package
  • the pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process having a step of covering the semiconductor chip with a sealing resin and a step of thermosetting the sealing resin.
  • FIGS. 2A to 2E are schematic views illustrating the method for manufacturing the semiconductor device according to the present embodiment.
  • the manufacturing method of the semiconductor device according to the present embodiment includes a step of attaching the frame member 20 in which a plurality of openings 21 are formed on the adhesive sheet 10 (adhesive sheet attaching step), and an opening 21 of the frame member 20.
  • a step of bonding the semiconductor chip CP to the exposed adhesive layer 12 (bonding step), a step of covering the semiconductor chip CP with the sealing resin 30 (sealing step), and a step of thermosetting the sealing resin 30 ( A thermosetting step) and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting.
  • bonding step a step of bonding the semiconductor chip CP to the exposed adhesive layer 12
  • sealing step a step of covering the semiconductor chip CP with the sealing resin 30
  • a step of thermosetting the sealing resin 30 A thermosetting step
  • peeling the pressure-sensitive adhesive sheet 10 peeling step
  • the frame member 20 is formed in a lattice shape and has a plurality of openings 21.
  • the frame member 20 is preferably formed of a material having heat resistance. Examples of the material of the frame member 20 include metals such as copper and stainless steel, and heat resistant resins such as polyimide resin and glass epoxy resin.
  • the opening 21 is a hole that penetrates the front and back surfaces of the frame member 20.
  • the shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame.
  • the depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
  • FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
  • the semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces.
  • a semiconductor chip CP semiconductor element
  • the dicing apparatus is not particularly limited, and a known dicing apparatus can be used.
  • the dicing conditions are not particularly limited. Note that a laser dicing method or a stealth dicing method may be used instead of the dicing method using a dicing blade.
  • an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP.
  • the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding process, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
  • the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden.
  • the energy ray polymerizable compound When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced.
  • the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable.
  • UV ultraviolet rays
  • EB electron beams
  • the energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
  • the material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin.
  • the epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
  • the method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited. In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example.
  • the sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A.
  • the sheet-shaped sealing resin 30 it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being generated between the semiconductor chip CP and the frame member 20.
  • the temperature condition range for heating by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
  • a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used.
  • the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured.
  • Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
  • a transfer molding method may be employed.
  • the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device.
  • a fluid resin material is injected into the mold to cure the resin material.
  • the heating and pressure conditions are not particularly limited.
  • a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds.
  • the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
  • the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process).
  • the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. .
  • the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20.
  • corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
  • the sealing body 50 When the pressure-sensitive adhesive sheet 10 is peeled after the thermosetting step, the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained. Hereinafter, this may be referred to as a sealing body 50.
  • FIG. 2D The schematic diagram explaining the process of sticking the reinforcing member 40 to the sealing body 50 is shown by FIG. 2D.
  • a rewiring process and a bumping process for forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed.
  • a process (reinforcing member attaching process) of attaching the reinforcing member 40 to the sealing body 50 is performed as necessary. May be.
  • FIG. As illustrated in FIG. 2D, the sealing body 50 is supported in a state of being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
  • the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42.
  • the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a glass epoxy resin.
  • the adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50.
  • the adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
  • the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure.
  • the sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time.
  • the conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa.
  • a metal plate such as stainless steel can be used as the plate-like member.
  • FIG. 2E The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
  • the adhesive sheet 10 when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent.
  • peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree
  • the peeling angle ⁇ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A.
  • the peeling angle ⁇ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less.
  • the reinforcing member 40 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed. Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step).
  • a method for dividing the sealing body 50 into individual pieces is not particularly limited.
  • the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer.
  • the step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like.
  • the pressure-sensitive adhesive sheet 10 that can prevent the surface of the adherend from being contaminated even after a process in which high temperature conditions are imposed.
  • Examples of the adherend to which the adhesive layer 12 is in contact include the semiconductor chip CP and the frame member 20.
  • the semiconductor chip CP and the frame member 20 are exposed to high temperature conditions while being in contact with the pressure-sensitive adhesive layer 12. Since the pressure-sensitive adhesive sheet 10 includes the oligomer sealing layer 13 between the base material 11 and the pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive layer of the oligomer in the base material 11 even when the pressure-sensitive adhesive sheet 10 is exposed to high temperature conditions. Intrusion into 12 is prevented. Therefore, according to the pressure-sensitive adhesive sheet 10, it is possible to prevent contamination of the surfaces of the semiconductor chip CP and the frame member 20.
  • 2nd embodiment is different from 1st embodiment by the point which has an oligomer sealing layer on both surfaces of the base material of an adhesive sheet. Since the second embodiment is the same as the first embodiment in other points, the description is omitted or simplified.
  • FIG. 10 A of adhesive sheets The cross-sectional schematic of 10 A of adhesive sheets which concern on 2nd embodiment is shown by FIG. 10 A of adhesive sheets have the base material 11, the adhesive layer 12, the oligomer sealing layer 13 (1st oligomer sealing layer), and the oligomer sealing layer 14 (2nd oligomer sealing layer).
  • 10 A of adhesive sheets have the oligomer sealing layers 13 and 14 on both surfaces (the 1st base material surface 11a and the 2nd base material surface 11b) of the base material 11, respectively.
  • the oligomer sealing layer 13 is laminated on the first base material surface 11a
  • the oligomer sealing layer 14 is laminated on the second base material surface 11b.
  • the first base material surface 11 a is covered with the oligomer sealing layer 13 and the second base material surface 11 b is covered with the oligomer sealing layer 14. Similar to the first embodiment, an oligomer sealing layer 13 is provided between the base material 11 and the pressure-sensitive adhesive layer 12.
  • the shape of the pressure-sensitive adhesive sheet 10A can take any shape such as a sheet shape, a tape shape, and a label shape.
  • the oligomer sealing layer 13 (first oligomer sealing layer) is the same as in the first embodiment.
  • the oligomer sealing layer 14 (second oligomer sealing layer) is a layer for preventing oligomers that are heated and deposited on the second base material surface 11b of the base material 11 from adhering to and contaminating other members. is there.
  • the oligomer sealing layer 14 is preferably formed of the same material as the oligomer sealing layer 13.
  • the thickness of the oligomer sealing layer 14 is not particularly limited, and is preferably in the same range as the oligomer sealing layer 13 described in the first embodiment. As the thickness of the oligomer sealing layer is increased, the effect of the oligomer sealing is improved. For example, from the viewpoint of productivity and cost of the pressure-sensitive adhesive sheet, the thickness of the oligomer sealing layer 13 and the oligomer sealing layer 14 is 100 nm or more and 200 nm or less, or about 150 nm.
  • the manufacturing method of the pressure-sensitive adhesive sheet 10A is not particularly limited.
  • the adhesive sheet 10A is manufactured through the following steps. First, the composition for oligomer sealing layers is apply
  • the adhesive sheet 10A can also be used in the same manner as the adhesive sheet 10 according to the first embodiment, and can be used in the method for manufacturing a semiconductor device in the same manner as the adhesive sheet 10.
  • the pressure-sensitive adhesive sheet 10A As in the case of the pressure-sensitive adhesive sheet 10, it is possible to prevent the surface of the adherend from being contaminated even after a process in which high temperature conditions are imposed. Furthermore, according to the pressure-sensitive adhesive sheet 10A, the oligomer sealing layer 14 is also formed on the second base material surface 11b, so that the oligomer deposited on the second base material surface 11b adheres to members and devices other than the adherend. To prevent contamination. For example, in the method for manufacturing a semiconductor device, contamination of the plate-like member that comes into contact with the pressure-sensitive adhesive sheet 10A in the hot press process can be prevented.
  • the pressure-sensitive adhesive sheet may be a single sheet or may be provided in a state where a plurality of pressure-sensitive adhesive sheets are laminated.
  • the pressure-sensitive adhesive layer may be covered with a base material of another pressure-sensitive adhesive sheet to be laminated.
  • a long sheet may be sufficient as an adhesive sheet, and it may be provided in the state wound up by roll shape.
  • the pressure-sensitive adhesive sheet wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet may be covered with a release sheet.
  • the release sheet is not particularly limited.
  • the release sheet preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate.
  • the release sheet may be provided with a release agent layer only on one side of the release substrate, or may be provided with a release agent layer on both sides of the release substrate.
  • the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
  • the paper substrate include glassine paper, coated paper, and cast coated paper.
  • plastic film examples include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
  • release agent examples include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins.
  • the thickness of the release sheet is not particularly limited.
  • the thickness of the release sheet is usually from 20 ⁇ m to 200 ⁇ m, and preferably from 25 ⁇ m to 150 ⁇ m.
  • the thickness of the release agent layer is not particularly limited.
  • the thickness of the release agent layer is preferably 0.01 ⁇ m or more and 2.0 ⁇ m or less, and preferably 0.03 ⁇ m or more and 1.0 ⁇ m or less. More preferred.
  • the thickness of the plastic film is preferably 3 ⁇ m or more and 50 ⁇ m or less, and more preferably 5 ⁇ m or more and 40 ⁇ m or less.
  • the pressure-sensitive adhesive sheet having a release sheet is manufactured through the following steps, for example. First, a pressure-sensitive adhesive composition is applied on a release sheet to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12. Moreover, the oligomer sealing layer 13 is formed on the first base material surface 11a of the base material 11 as described in the above embodiment. The pressure-sensitive adhesive layer 12 on the release sheet and the oligomer sealing layer 13 on the substrate 11 are bonded together. In the case of the embodiment having the oligomer sealing layer 14, the pressure-sensitive adhesive layer 12 and the oligomer sealing layer 13 are bonded together after the oligomer sealing layers 13 and 14 are formed on both surfaces of the substrate 11.
  • the sealing resin 30 is a thermosetting resin
  • the present invention is not limited to such a mode.
  • the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
  • the adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
  • a semiconductor chip was attached to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to obtain a pressure-sensitive adhesive sheet with a semiconductor chip.
  • This adhesive sheet with a semiconductor chip was heated under the conditions of 190 ° C. and 1 hour. After heating, the adhesive sheet was peeled off.
  • the adherend surface of the semiconductor chip after peeling was observed with a digital microscope (manufactured by Keyence Co., Ltd., digital microscope; VHX-1000) to confirm the presence or absence of residues. The observation magnification was 500 times. The case where a residue was not confirmed was determined as “A”, and the case where a residue was confirmed was determined as “B”.
  • coating oligomer sealing agent liquid The following (A) bisphenol A type epoxy compound, (B) polyester compound, (C) polyfunctional amino compound and (D) acidic catalyst are blended and stirred sufficiently.
  • the oligomer sealing agent liquid for coating which concerns on Example 1 (composition for oligomer sealing layers) was prepared.
  • oligomer sealing layer The prepared oligomer sealing agent liquid for coating was applied to a biaxially stretched polyethylene terephthalate film ("Diafoil T-100" (trade name) manufactured by Mitsubishi Plastics, Inc., thickness 50 ⁇ m, at 100 ° C. It was uniformly coated on one surface of storage elastic modulus 3.2 ⁇ 10 9 Pa) by the Mayer bar coating method so that the thickness after drying was 150 nm. The coated film was passed through the oven, and the coating film was cured by heating to obtain an oligomer sealing layer. As conditions for blowing hot air in the oven, the temperature was set to 150 ° C., the wind speed was set to 8 m / min, and the processing speed in the oven was adjusted so that the coated film passed through the oven in 20 seconds.
  • a biaxially stretched polyethylene terephthalate film (“Diafoil T-100" (trade name) manufactured by Mitsubishi Plastics, Inc., thickness 50 ⁇ m, at 100 ° C. It was uniformly coated on one surface of storage elastic
  • Acrylic ester copolymer 40 parts by mass (solid content)
  • the acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
  • -Adhesion aid hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000), 5 parts by mass (solid content)
  • Crosslinking agent Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate; manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX), 3.5 parts by mass (solid content)
  • Diluting solvent Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
  • Example 2 The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
  • the polymer used in Example 2 was composed of 80.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, 12% by mass of 4-acryloylmorpholine, and 0.2% by mass of acrylic acid. Prepared by copolymerization.
  • the pressure-sensitive adhesive sheet according to Comparative Example 1 is the same as Example 1 except that the pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer is different from that in Example 1, the base material is different, and the oligomer sealing layer is not provided. It was prepared.
  • the adhesion promoter used in Comparative Example 1 is tributyl acetyl citrate [manufactured by Taoka Chemical Industry Co., Ltd.]. Note that tributyl acetylcitrate does not have the aforementioned reactive group.
  • the base material used in Comparative Example 1 is a polyethylene terephthalate film [manufactured by Mitsubishi Plastics; PET 50T-100, thickness 50 ⁇ m, storage elastic modulus at 100 ° C. 3.2 ⁇ 10 9 Pa].
  • the pressure-sensitive adhesive layer prepared on the surface of the release film was bonded to the base material to obtain a pressure-sensitive adhesive sheet according to Comparative Example 1.
  • Comparative Example 2 The pressure-sensitive adhesive sheet according to Comparative Example 2 was prepared in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer was different from that in Comparative Example 1.
  • the tackifier used in Comparative Example 2 is a hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000).
  • Comparative Example 3 The pressure-sensitive adhesive sheet according to Comparative Example 3 is different from Example 1 in that the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer is different, the thickness of the pressure-sensitive adhesive layer is different, the base material is different, and there is no oligomer sealing layer. Other than that, it was produced in the same manner as in Example 1. In Comparative Example 3, a silicone adhesive was used.
  • Silicone-based adhesive Ad1 (SD4580PSA) 18 parts by mass (solid content), Silicone-based adhesive Ad2 (SD4587L) 40 parts by mass (solid content), Catalyst Cat1 (NC-25 CAT) 0.3 part by mass (solid content), The catalyst Cat2 (CAT-SRX-212) 0.65 parts by mass (solid content) and the primer (BY24-712) 5 parts by mass (solid content) were blended and stirred thoroughly to give an adhesive solution for application (adhesion) Agent composition) was prepared.
  • the materials used for the pressure-sensitive adhesive composition of Comparative Example 3 are all manufactured by Toray Dow Corning Co., Ltd.
  • the pressure-sensitive adhesive liquid for coating according to Comparative Example 3 was applied to the release layer surface side of the release film and dried so that the thickness after drying was 30 ⁇ m, thereby preparing a pressure-sensitive adhesive layer. Drying conditions were 130 ° C. and 2 minutes.
  • the base material used in Comparative Example 3 was a polyethylene terephthalate film [Mitsubishi Resin Co., Ltd .; Diafoil PET50 T-100, thickness 50 ⁇ m, storage elastic modulus at 100 ° C. 3.2 ⁇ 10 9 Pa].
  • the pressure-sensitive adhesive layer prepared on the surface of the release film was bonded to the base material to obtain a pressure-sensitive adhesive sheet according to Comparative Example 3.
  • Table 1 shows the evaluation results of the pressure-sensitive adhesive sheets according to Example 1, Example 2, and Comparative Examples 1 to 3.
  • 10, 10A adhesive sheet, 11: base material, 12: adhesive layer, 13, 14: oligomer sealing layer.

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Abstract

Disclosed is an adhesive sheet (10) that is used at the time of sealing a semiconductor element on the adhesive sheet, the adhesive sheet (10) comprising: a substrate (11); an adhesive agent layer (12) including an adhesive agent; and an oligomer sealing layer (13) provided between the substrate (11) and the adhesive agent layer (12).

Description

粘着シートAdhesive sheet
　本発明は、粘着シートに関する。 The present invention relates to an adhesive sheet.
　半導体装置の製造工程で使用される粘着シートには、様々な特性が求められる。近年は、粘着シートには、高温条件が課される工程を経ても、製造工程で使用される装置、部材、及び被着体を汚さないことが求められる。さらに、高温条件の工程後、粘着シートを室温で剥離する際に、被着体等への粘着剤が残るという不具合（いわゆる糊残り）が少なく、かつ剥離力が小さいことも求められている。 Various properties are required for adhesive sheets used in the manufacturing process of semiconductor devices. In recent years, pressure-sensitive adhesive sheets are required not to contaminate devices, members, and adherends used in the manufacturing process even after a process in which high temperature conditions are imposed. Furthermore, after peeling off the pressure-sensitive adhesive sheet at room temperature after the process under high temperature conditions, it is also required that there are few problems (so-called adhesive residue) that the pressure-sensitive adhesive remains on the adherend and the like and that the peeling force is small.
　例えば、特許文献１には、粘着剤の糊残りを抑制し、安定してＱＦＮ（Ｑｕａｄ　Ｆｌａｔ　Ｎｏｎ－ｌｅａｄ）の半導体パッケージを生産するためのマスクシートが記載されている。特許文献１には、特定の耐熱フィルム及びシリコーン系粘着剤を用いてマスクシートを作製することによって、ダイアタッチ工程及び樹脂封止工程における１５０℃～１８０℃で１時間～６時間の環境に耐え得ると記載されている。 For example, Patent Document 1 discloses a mask sheet for suppressing adhesive residue of an adhesive and stably producing a QFN (Quad Flat Non-lead) semiconductor package. In Patent Document 1, a mask sheet is prepared using a specific heat-resistant film and a silicone-based pressure-sensitive adhesive to withstand an environment of 150 to 180 ° C. for 1 to 6 hours in a die attach process and a resin sealing process. It is stated that you get.
特開２００２－２７５４３５号公報JP 2002-275435 A
　近年、１８０℃以上２００℃以下のような高温条件が課される工程でも粘着シートが使用されている。このような高温の工程において、例えば、ポリイミドフィルム等に比べて耐熱性が低く安価なフィルム（例えば、ポリエチレンテレフタレート等のフィルム）を基材として使用した場合、工程終了後に被着体から粘着シートを剥がすと被着体の表面が汚染されることが分かった。このような汚染の原因としては、基材として用いた樹脂フィルム中に含まれる低分子量成分（オリゴマー）が被着体の表面に析出したことによると考えられる。例えば、粘着シートの粘着剤層に貼着された半導体素子を樹脂封止する工程で高温条件が課されると、半導体素子の表面が汚染され、半導体装置に不具合が生じる可能性がある。 In recent years, pressure-sensitive adhesive sheets are also used in processes where high temperature conditions such as 180 ° C. or higher and 200 ° C. or lower are imposed. In such a high-temperature process, for example, when an inexpensive film (for example, a film such as polyethylene terephthalate) having a low heat resistance compared to a polyimide film or the like is used as a base material, the adhesive sheet is removed from the adherend after the process is completed. It was found that the surface of the adherend was contaminated when peeled off. It is thought that the cause of such contamination is that a low molecular weight component (oligomer) contained in the resin film used as the base material is deposited on the surface of the adherend. For example, when a high temperature condition is imposed in the step of resin-sealing a semiconductor element attached to an adhesive layer of an adhesive sheet, the surface of the semiconductor element may be contaminated, causing a problem in the semiconductor device.
　本発明の目的は、高温条件が課される工程を経た後でも、被着体の表面の汚染を防止することができる粘着シートを提供することである。 An object of the present invention is to provide a pressure-sensitive adhesive sheet that can prevent contamination of the surface of an adherend even after undergoing a process in which high-temperature conditions are imposed.
　本発明の一態様によれば、粘着シート上の半導体素子を封止する際に使用される粘着シートであって、基材と、粘着剤を含む粘着剤層と、前記基材と前記粘着剤層との間に設けられたオリゴマー封止層と、を有する粘着シートが提供される。 According to one aspect of the present invention, there is provided a pressure-sensitive adhesive sheet used for sealing a semiconductor element on a pressure-sensitive adhesive sheet, which includes a base material, a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive, the base material, and the pressure-sensitive adhesive. An pressure-sensitive adhesive sheet having an oligomer sealing layer provided between the layers is provided.
　本発明の一態様に係る粘着シートにおいて、前記オリゴマー封止層は、エポキシ化合物と、ポリエステル化合物と、多官能アミノ化合物と、を含むオリゴマー封止層用組成物を硬化させた硬化皮膜であることが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the oligomer sealing layer is a cured film obtained by curing a composition for an oligomer sealing layer containing an epoxy compound, a polyester compound, and a polyfunctional amino compound. Is preferred.
　本発明の一態様に係る粘着シートにおいて、前記オリゴマー封止層用組成物は、（Ａ）５０質量％以上８０質量％以下のビスフェノールＡ型エポキシ化合物と、（Ｂ）５質量％以上３０質量％以下のポリエステル化合物と、（Ｃ）１０質量％以上４０質量％以下の多官能アミノ化合物と、を含むことが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the composition for an oligomer sealing layer comprises (A) 50% by mass to 80% by mass of a bisphenol A type epoxy compound and (B) 5% by mass to 30% by mass. It is preferable to contain the following polyester compounds and (C) 10 to 40 mass% polyfunctional amino compounds.
　本発明の一態様に係る粘着シートにおいて、前記基材の１００℃における貯蔵弾性率は、１×１０７Ｐａ以上であることが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the storage elastic modulus of the substrate at 100 ° C. is preferably 1 × 10 7 Pa or more.
　本発明の一態様に係る粘着シートにおいて、前記粘着剤層は、アクリル系粘着剤組成物またはシリコーン系粘着剤組成物を含有することが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
　本発明の一態様に係る粘着シートにおいて、前記アクリル系粘着剤組成物は、アクリル酸２－エチルヘキシルを主たるモノマーとするアクリル系共重合体を含むことが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the acrylic pressure-sensitive adhesive composition preferably includes an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer.
　本発明の一態様に係る粘着シートにおいて、前記シリコーン系粘着剤組成物は、付加重合型シリコーン樹脂を含むことが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, it is preferable that the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
　本発明の一態様に係る粘着シートにおいて、前記基材の両面に前記オリゴマー封止層を有することが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, it is preferable that the oligomer sealing layer is provided on both surfaces of the base material.
　本発明の一態様に係る粘着シートにおいて、前記基材は、ポリエステル系樹脂を含むことが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the base material preferably contains a polyester resin.
　本発明によれば、高温条件が課される工程を経た後でも、被着体の表面の汚染を防止することができる粘着シートを提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet that can prevent contamination of the surface of an adherend even after undergoing a process in which high temperature conditions are imposed.
第一実施形態に係る粘着シートの断面概略図である。It is a section schematic diagram of the adhesive sheet concerning a first embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第二実施形態に係る粘着シートの断面概略図である。It is a section schematic diagram of the adhesive sheet concerning a second embodiment.
〔第一実施形態〕
（粘着シート）
　図１には、本実施形態の粘着シート１０の断面概略図が示されている。
　粘着シート１０は、基材１１、粘着剤層１２及びオリゴマー封止層１３を有する。
　基材１１は、第一基材面１１ａ、及び第一基材面１１ａとは反対側の第二基材面１１ｂを有する。基材１１と粘着剤層１２との間にオリゴマー封止層１３が設けられている。粘着シート１０においては、第一基材面１１ａにオリゴマー封止層１３が積層されており、第一基材面１１ａがオリゴマー封止層１３によって被覆されていることが好ましい。
　粘着シート１０の形状は、例えば、シート状、テープ状、ラベル状などあらゆる形状をとり得る。 [First embodiment]
(Adhesive sheet)
FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
The pressure-sensitive adhesive sheet 10 has a base material 11, a pressure-sensitive adhesive layer 12, and an oligomer sealing layer 13.
The base material 11 has a first base material surface 11a and a second base material surface 11b opposite to the first base material surface 11a. An oligomer sealing layer 13 is provided between the substrate 11 and the pressure-sensitive adhesive layer 12. In the pressure-sensitive adhesive sheet 10, the oligomer sealing layer 13 is preferably laminated on the first base material surface 11 a, and the first base material surface 11 a is preferably covered with the oligomer sealing layer 13.
The shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a sheet shape, a tape shape, and a label shape.
（基材）
　基材１１は、粘着剤層１２及びオリゴマー封止層１３を支持する部材である。
　基材１１としては、例えば、合成樹脂フィルムなどのシート材料などを用いることができる。合成樹脂フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニル共重合体フィルム、アイオノマー樹脂フィルム、エチレン・（メタ）アクリル酸共重合体フィルム、エチレン・（メタ）アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、及びポリイミドフィルム等が挙げられる。その他、基材１１としては、これらの架橋フィルム及び積層フィルム等が挙げられる。 (Base material)
The substrate 11 is a member that supports the pressure-sensitive adhesive layer 12 and the oligomer sealing layer 13.
As the base material 11, for example, a sheet material such as a synthetic resin film can be used. Examples of synthetic resin films include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film. , Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, and polyimide film Etc. In addition, examples of the substrate 11 include these cross-linked films and laminated films.
　基材１１は、ポリエステル系樹脂を含むことが好ましく、ポリエステル系樹脂を主成分とする材料からなることがより好ましい。本明細書において、ポリエステル系樹脂を主成分とする材料とは、基材を構成する材料全体の質量に占めるポリエステル系樹脂の質量の割合が５０質量％以上であることを意味する。
　ポリエステル系樹脂としては、例えば、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリブチレンナフタレート樹脂、及びこれらの樹脂の共重合樹脂からなる群から選択されるいずれかの樹脂であることが好ましく、ポリエチレンテレフタレート樹脂がより好ましい。
　基材１１としては、ポリエチレンテレフタレートフィルム、またはポリエチレンナフタレートフィルムが好ましく、ポリエチレンテレフタレートフィルムがより好ましい。ポリエステルフィルムに含有するオリゴマーとしては、ポリエステル形成性モノマー、ダイマー、及びトリマーなどに由来する。 The base material 11 preferably includes a polyester-based resin, and more preferably includes a material having a polyester-based resin as a main component. In this specification, the material having a polyester-based resin as a main component means that the ratio of the mass of the polyester-based resin to the total mass of the material constituting the substrate is 50% by mass or more.
The polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins. Is preferred, and polyethylene terephthalate resin is more preferred.
As the base material 11, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film is more preferable. The oligomers contained in the polyester film are derived from polyester-forming monomers, dimers, trimers, and the like.
　基材１１の１００℃での貯蔵弾性率の下限は、加工時の寸法安定性の観点から、１×１０７Ｐａ以上が好ましく、１×１０８Ｐａ以上であることがより好ましい。基材１１の１００℃での貯蔵弾性率の上限は、加工適性の観点から１×１０１２Ｐａ以下であることが好ましい。なお、本明細書において、貯蔵弾性率は、動的粘弾性測定装置を用いて、ねじりせん断法により周波数１Ｈｚで測定した値である。測定する基材を幅５ｍｍ、長さ２０ｍｍに切断し、粘弾性測定機器（ティー・エイ・インスツルメント社製、ＤＭＡＱ８００）を使用し、周波数１Ｈｚ、引張モードにより、１００℃の貯蔵粘弾性を測定する。 The lower limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 × 10 7 Pa or more, and more preferably 1 × 10 8 Pa or more, from the viewpoint of dimensional stability during processing. The upper limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 × 10 12 Pa or less from the viewpoint of workability. In this specification, the storage elastic modulus is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring apparatus. The substrate to be measured is cut into a width of 5 mm and a length of 20 mm, and a viscoelasticity measuring device (manufactured by TA Instruments, DMAQ800) is used, and the storage viscoelasticity at 100 ° C. is measured at a frequency of 1 Hz and a tensile mode. taking measurement.
　第一基材面１１ａは、オリゴマー封止層１３との密着性を高めるために、プライマー処理、コロナ処理、及びプラズマ処理等の少なくともいずれかの表面処理が施されてもよい。基材１１の第一基材面１１ａには、粘着剤が塗布されて粘着処理が施されていてもよい。基材の粘着処理に用いられる粘着剤としては、例えば、アクリル系、ゴム系、シリコーン系、及びウレタン系等の粘着剤が挙げられる。 The first substrate surface 11a may be subjected to at least one surface treatment such as a primer treatment, a corona treatment, and a plasma treatment in order to improve the adhesion with the oligomer sealing layer 13. The first base material surface 11a of the base material 11 may be subjected to an adhesive treatment by applying an adhesive. Examples of the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate include acrylic, rubber-based, silicone-based, and urethane-based pressure-sensitive adhesives.
　基材１１の厚みは、１０μｍ以上５００μｍ以下であることが好ましく、１５μｍ以上３００μｍ以下であることがより好ましく、２０μｍ以上２５０μｍ以下であることがさらに好ましい。 The thickness of the substrate 11 is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, and further preferably 20 μm or more and 250 μm or less.
（粘着剤層）
　本実施形態に係る粘着剤層１２は、粘着剤組成物を含んでいる。この粘着剤組成物に含まれる粘着剤としては、特に限定されず、様々な種類の粘着剤を粘着剤層１２に適用できる。粘着剤層１２に含まれる粘着剤としては、例えば、ゴム系、アクリル系、シリコーン系、ポリエステル系、及びウレタン系が挙げられる。なお、粘着剤の種類は、用途及び貼着される被着体の種類等を考慮して選択される。粘着剤層１２は、アクリル系粘着剤組成物またはシリコーン系粘着剤組成物を含有することが好ましい。 (Adhesive layer)
The pressure-sensitive adhesive layer 12 according to this embodiment includes a pressure-sensitive adhesive composition. The pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various types of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12. Examples of the adhesive contained in the adhesive layer 12 include rubber-based, acrylic-based, silicone-based, polyester-based, and urethane-based. In addition, the kind of adhesive is selected in consideration of the use and the kind of adherend to be attached. The pressure-sensitive adhesive layer 12 preferably contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
・アクリル系粘着剤組成物
　粘着剤層１２がアクリル系粘着剤組成物を含む場合、アクリル系粘着剤組成物は、アクリル酸２－エチルヘキシルを主たるモノマーとするアクリル系共重合体を含むことが好ましい。
　また、粘着剤層１２がアクリル系粘着剤組成物を含む場合、アクリル系共重合体と、粘着助剤と、を含んでいることが好ましい。アクリル系共重合体は、アクリル酸２－エチルヘキシルを主たるモノマーとする共重合体であることが好ましい。粘着助剤は、反応性基を有するゴム系材料を主成分として含むことが好ましい。 Acrylic pressure-sensitive adhesive composition When the pressure-sensitive adhesive layer 12 contains an acrylic pressure-sensitive adhesive composition, the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer. .
Moreover, when the adhesive layer 12 contains an acrylic adhesive composition, it is preferable that the acrylic copolymer and the adhesion promoter are included. The acrylic copolymer is preferably a copolymer having 2-ethylhexyl acrylate as a main monomer. The adhesive aid preferably contains a rubber-based material having a reactive group as a main component.
　本明細書において、アクリル酸２－エチルヘキシルを主たるモノマーとするとは、アクリル系共重合体全体の質量に占めるアクリル酸２－エチルヘキシル由来の共重合体成分の質量の割合が５０質量％以上であることを意味する。本実施形態においては、アクリル系共重合体におけるアクリル酸２－エチルヘキシルに由来する共重合体成分の割合は、５０質量％以上９５質量％以下であることが好ましく、６０質量％以上９５質量％以下であることがより好ましく、８０質量％以上９５質量％以下であることがさらに好ましく、８５質量％以上９３質量％以下であることがさらにより好ましい。アクリル酸２－エチルヘキシルに由来する共重合体成分の割合が５０質量％以上であれば、加熱後に粘着力が高くなり過ぎず、被着体から粘着シートをより剥離し易くなり、８０質量％以上であればさらに剥離し易くなる。アクリル酸２－エチルヘキシルに由来する共重合体成分の割合が９５質量％以下であれば、初期密着力が不足して加熱時に基材が変形したり、その変形によって粘着シートが被着体から剥離したりすることを防止できる。 In this specification, 2-ethylhexyl acrylate is the main monomer, and the ratio of the mass of the copolymer component derived from 2-ethylhexyl acrylate to the total mass of the acrylic copolymer is 50% by mass or more. Means. In the present embodiment, the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, and 60% by mass or more and 95% by mass or less. It is more preferable that it is 80 mass% or more and 95 mass% or less, and it is still more preferable that it is 85 mass% or more and 93 mass% or less. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 50% by mass or more, the adhesive strength does not become too high after heating, and the adhesive sheet is more easily peeled off from the adherend, and 80% by mass or more. If it is, it will become still easier to peel. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, the initial adhesive force is insufficient and the substrate is deformed during heating, or the adhesive sheet is peeled off from the adherend due to the deformation. Can be prevented.
　アクリル系共重合体におけるアクリル酸２－エチルヘキシル以外の共重合体成分の種類及び数は、特に限定されない。例えば、第二の共重合体成分としては、反応性の官能基を有する官能基含有モノマーが好ましい。第二の共重合体成分の反応性官能基としては、後述する架橋剤を使用する場合には、当該架橋剤と反応し得る官能基であることが好ましい。この反応性官能基は、例えば、カルボキシル基、水酸基、アミノ基、置換アミノ基、及びエポキシ基からなる群から選択される少なくともいずれかの置換基であることが好ましく、カルボキシル基及び水酸基の少なくともいずれかの置換基であることがより好ましく、カルボキシル基であることが更に好ましい。 The type and number of copolymer components other than 2-ethylhexyl acrylate in the acrylic copolymer are not particularly limited. For example, as the second copolymer component, a functional group-containing monomer having a reactive functional group is preferable. As a reactive functional group of a 2nd copolymer component, when using the crosslinking agent mentioned later, it is preferable that it is a functional group which can react with the said crosslinking agent. This reactive functional group is preferably at least one substituent selected from the group consisting of, for example, a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. These substituents are more preferable, and a carboxyl group is still more preferable.
　カルボキシル基を有するモノマー（カルボキシル基含有モノマー）としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、及びシトラコン酸等のエチレン性不飽和カルボン酸が挙げられる。カルボキシル基含有モノマーの中でも、反応性及び共重合性の点から、アクリル酸が好ましい。カルボキシル基含有モノマーは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the monomer having a carboxyl group (carboxyl group-containing monomer) include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among the carboxyl group-containing monomers, acrylic acid is preferable from the viewpoint of reactivity and copolymerization. A carboxyl group-containing monomer may be used independently and may be used in combination of 2 or more type.
　水酸基を有するモノマー（水酸基含有モノマー）としては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、及び（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキルエステル等が挙げられる。水酸基含有モノマーの中でも、水酸基の反応性及び共重合性の点から、（メタ）アクリル酸２－ヒドロキシエチルが好ましい。水酸基含有モノマーは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。なお、本明細書における「（メタ）アクリル酸」は、「アクリル酸」及び「メタクリル酸」の双方を表す場合に用いる表記であり、他の類似用語についても同様である。 Examples of the monomer having a hydroxyl group (hydroxyl group-containing monomer) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 And (meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of hydroxyl reactivity and copolymerization. A hydroxyl-containing monomer may be used independently and may be used in combination of 2 or more type. In the present specification, “(meth) acrylic acid” is a notation used to represent both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
　エポキシ基を有するアクリル酸エステルとしては、例えば、グリシジルアクリレート、及びグリシジルメタクリレート等が挙げられる。 Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
　アクリル系共重合体におけるその他の共重合体成分としては、アルキル基の炭素数が２～２０の（メタ）アクリル酸アルキルエステルが挙げられる。（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、メタクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチル、及び（メタ）アクリル酸ステアリル等が挙げられる。これらの（メタ）アクリル酸アルキルエステルの中でも、粘着性をより向上させる観点から、アルキル基の炭素数が２～４の（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸ｎ－ブチルがより好ましい。（メタ）アクリル酸アルキルエステルは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of other copolymer components in the acrylic copolymer include (meth) acrylic acid alkyl esters having an alkyl group with 2 to 20 carbon atoms. Examples of the (meth) acrylic acid alkyl ester include, for example, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and (meth) acrylic acid n. -Hexyl, 2-ethylhexyl methacrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and ( Examples thereof include stearyl methacrylate. Among these (meth) acrylic acid alkyl esters, (meth) acrylic acid esters having an alkyl group with 2 to 4 carbon atoms are preferred, and n-butyl (meth) acrylate is more preferred from the viewpoint of further improving the adhesiveness. preferable. The (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
　アクリル系共重合体におけるその他の共重合体成分としては、例えば、アルコキシアルキル基含有（メタ）アクリル酸エステル、脂肪族環を有する（メタ）アクリル酸エステル、芳香族環を有する（メタ）アクリル酸エステル、非架橋性のアクリルアミド、非架橋性の３級アミノ基を有する（メタ）アクリル酸エステル、酢酸ビニル、及びスチレンからなる群から選択される少なくともいずれかのモノマーに由来する共重合体成分が挙げられる。
　アルコキシアルキル基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メトキシメチル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシメチル、及び（メタ）アクリル酸エトキシエチルが挙げられる。
　脂肪族環を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸シクロヘキシルが挙げられる。
　芳香族環を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸フェニルが挙げられる。
　非架橋性のアクリルアミドとしては、例えば、アクリルアミド、及びメタクリルアミドが挙げられる。
　非架橋性の３級アミノ基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸（Ｎ，Ｎ－ジメチルアミノ）エチル、及び（メタ）アクリル酸（Ｎ，Ｎ－ジメチルアミノ）プロピルが挙げられる。
　アクリル系共重合体におけるその他の共重合体成分としては、粘着剤の極性を向上させ、密着性及び粘着力を向上させる観点から、窒素原子含有環を有するモノマーに由来する共重合体成分も好ましい。
　窒素原子含有環を有するモノマーとしては、Ｎ－ビニル－２－ピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピペリドン、Ｎ－ビニルピペラジン、Ｎ－ビニルピラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、Ｎ－ビニルモルホリン、Ｎ－ビニルカプロラクタム、及びＮ－（メタ）アクリロイルモルホリン等が挙げられる。窒素原子含有環を有するモノマーとしては、Ｎ－（メタ）アクリロイルモルホリンが好ましい。
　これらのモノマーは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of other copolymer components in the acrylic copolymer include, for example, alkoxyalkyl group-containing (meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring, and (meth) acrylic acid having an aromatic ring. A copolymer component derived from at least one monomer selected from the group consisting of an ester, a non-crosslinkable acrylamide, a (meth) acrylic acid ester having a non-crosslinkable tertiary amino group, vinyl acetate, and styrene; Can be mentioned.
Examples of the alkoxyalkyl group-containing (meth) acrylic acid ester include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. .
Examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate.
Examples of the (meth) acrylic acid ester having an aromatic ring include phenyl (meth) acrylate.
Examples of non-crosslinkable acrylamides include acrylamide and methacrylamide.
Examples of the (meth) acrylic acid ester having a non-crosslinkable tertiary amino group include (meth) acrylic acid (N, N-dimethylamino) ethyl and (meth) acrylic acid (N, N-dimethylamino). Propyl.
As the other copolymer component in the acrylic copolymer, a copolymer component derived from a monomer having a nitrogen atom-containing ring is also preferable from the viewpoint of improving the polarity of the pressure-sensitive adhesive and improving adhesion and adhesive strength. .
Monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Examples include vinyl morpholine, N-vinyl caprolactam, and N- (meth) acryloyl morpholine. As the monomer having a nitrogen atom-containing ring, N- (meth) acryloylmorpholine is preferable.
These monomers may be used independently and may be used in combination of 2 or more type.
　本実施形態においては、第二の共重合体成分として、カルボキシル基含有モノマーまたは水酸基含有モノマーが好ましく、アクリル酸がより好ましい。アクリル系共重合体が、アクリル酸２－エチルヘキシル由来の共重合体成分、及びアクリル酸由来の共重合体成分を含む場合、アクリル系共重合体全体の質量に占めるアクリル酸由来の共重合体成分の質量の割合が１質量％以下であることが好ましく、０．１質量％以上０．５質量％以下であることがより好ましい。アクリル酸の割合が１質量％以下であれば、粘着剤組成物に架橋剤が含まれる場合にアクリル系共重合体の架橋が早く進行し過ぎることを防止できる。 In the present embodiment, a carboxyl group-containing monomer or a hydroxyl group-containing monomer is preferable as the second copolymer component, and acrylic acid is more preferable. When the acrylic copolymer includes a copolymer component derived from 2-ethylhexyl acrylate and a copolymer component derived from acrylic acid, the copolymer component derived from acrylic acid occupies the total mass of the acrylic copolymer. The mass ratio is preferably 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. If the ratio of acrylic acid is 1 mass% or less, when an adhesive composition contains a crosslinking agent, crosslinking of the acrylic copolymer can be prevented from proceeding too quickly.
　アクリル系共重合体は、２種類以上の官能基含有モノマー由来の共重合体成分を含んでいてもよい。例えば、アクリル系共重合体は、３元系共重合体であってもよい。アクリル系共重合体が３元系共重合体である場合、アクリル酸２－エチルヘキシル、カルボキシル基含有モノマー及び水酸基含有モノマーを共重合して得られるアクリル系共重合体が好ましく、このカルボキシル基含有モノマーは、アクリル酸であることが好ましく、水酸基含有モノマーは、アクリル酸２－ヒドロキシエチルであることが好ましい。アクリル系共重合体におけるアクリル酸２－エチルヘキシルに由来する共重合体成分の割合が８０質量％以上９５質量％以下であり、アクリル酸由来の共重合体成分の質量の割合が１質量％以下であり、残部がアクリル酸２－ヒドロキシエチル由来の共重合体成分であることが好ましい。 The acrylic copolymer may contain a copolymer component derived from two or more kinds of functional group-containing monomers. For example, the acrylic copolymer may be a ternary copolymer. When the acrylic copolymer is a ternary copolymer, an acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer and a hydroxyl group-containing monomer is preferred, and this carboxyl group-containing monomer is preferred. Is preferably acrylic acid, and the hydroxyl group-containing monomer is preferably 2-hydroxyethyl acrylate. The ratio of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less, and the ratio of the mass of the copolymer component derived from acrylic acid is 1% by mass or less. And the balance is preferably a copolymer component derived from 2-hydroxyethyl acrylate.
　アクリル系共重合体の重量平均分子量（Ｍｗ）は、３０万以上２００万以下であることが好ましく、６０万以上１５０万以下であることがより好ましく、８０万以上１２０万以下であることがさらに好ましい。アクリル系共重合体の重量平均分子量Ｍｗが３０万以上であれば、被着体への粘着剤の残渣なく剥離することができる。アクリル系共重合体の重量平均分子量Ｍｗが２００万以下であれば、被着体へ確実に貼り付けることができる。
　アクリル系共重合体の重量平均分子量Ｍｗは、ゲル・パーミエーション・クロマトグラフィー（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ；ＧＰＣ）法により測定される標準ポリスチレン換算値である。 The weight average molecular weight (Mw) of the acrylic copolymer is preferably from 300,000 to 2,000,000, more preferably from 600,000 to 1,500,000, and even more preferably from 800,000 to 1,200,000. preferable. If the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, the acrylic copolymer can be peeled without a residue of the adhesive on the adherend. When the weight average molecular weight Mw of the acrylic copolymer is 2 million or less, it can be reliably attached to the adherend.
The weight average molecular weight Mw of the acrylic copolymer is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.
　アクリル系共重合体は、前述の各種原料モノマーを用いて、従来公知の方法に従って製造することができる。 The acrylic copolymer can be produced according to a conventionally known method using the above-mentioned various raw material monomers.
　アクリル系共重合体の共重合の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、またはグラフト共重合体のいずれでもよい。
　本実施形態において、粘着剤組成物中のアクリル系共重合体の含有率は、４０質量％以上９０質量％以下であることが好ましく、５０質量％以上９０質量％以下であることがより好ましい。 The form of copolymerization of the acrylic copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.
In the present embodiment, the content of the acrylic copolymer in the pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.
　粘着助剤は、反応性基を有するゴム系材料を主成分として含むことが好ましい。粘着剤組成物が反応性粘着助剤を含んでいると、糊残りを減少させることができる。粘着剤組成物中の粘着助剤の含有率は、３質量％以上５０質量％以下であることが好ましく、５質量％以上３０質量％以下であることがより好ましい。粘着剤組成物中の粘着助剤の含有率が３質量％以上であれば、糊残りの発生を抑制でき、５０質量％以下であれば粘着力の低下を抑制できる。
　本明細書において、反応性基を有するゴム系材料を主成分として含むとは、粘着助剤全体の質量に占める反応性基を有するゴム系材料の質量の割合が５０質量％を超えることを意味する。本実施形態においては、粘着助剤における反応性基を有するゴム系材料の割合は、５０質量％超であることが好ましく、８０質量％以上であることがより好ましい。粘着助剤が実質的に反応性基を有するゴム系材料からなることも好ましい。 The adhesive aid preferably contains a rubber-based material having a reactive group as a main component. When the pressure-sensitive adhesive composition contains a reactive pressure-sensitive adhesive aid, the adhesive residue can be reduced. The content of the adhesion assistant in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content rate of the adhesion promoter in an adhesive composition is 3 mass% or more, generation | occurrence | production of adhesive residue can be suppressed, and if it is 50 mass% or less, the fall of adhesive force can be suppressed.
In the present specification, including a rubber-based material having a reactive group as a main component means that the proportion of the mass of the rubber-based material having a reactive group in the total mass of the adhesive aid exceeds 50% by mass. To do. In the present embodiment, the ratio of the rubber-based material having a reactive group in the adhesion assistant is preferably more than 50% by mass, and more preferably 80% by mass or more. It is also preferable that the adhesion assistant is made of a rubber-based material having a substantially reactive group.
　反応性基としては、水酸基、イソシアネート基、アミノ基、オキシラン基、酸無水物基、アルコキシ基、アクリロイル基及びメタクリロイル基からなる群より選択される一種以上の官能基であることが好ましく、水酸基であることがより好ましい。ゴム系材料が有する反応性基は、１種類でも、２種類以上でもよい。水酸基を有するゴム系材料は、さらに前述の反応性基を有していてもよい。また、反応性基の数は、ゴム系材料を構成する１分子中に１つでも、２つ以上でもよい。 The reactive group is preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group. More preferably. The reactive group possessed by the rubber material may be one type or two or more types. The rubber-based material having a hydroxyl group may further have the aforementioned reactive group. In addition, the number of reactive groups may be one per molecule constituting the rubber-based material, or two or more.
　ゴム系材料としては、特に限定されないが、ポリブタジエン系樹脂、及びポリブタジエン系樹脂の水素添加物が好ましく、ポリブタジエン系樹脂の水素添加物がより好ましい。
　ポリブタジエン系樹脂としては、１，４－繰り返し単位を有する樹脂、１，２－繰り返し単位を有する樹脂、並びに１，４－繰り返し単位及び１，２－繰り返し単位の両方を有する樹脂が挙げられる。本実施形態のポリブタジエン系樹脂の水素添加物は、これらの繰り返し単位を有する樹脂の水素化物も含む。 The rubber-based material is not particularly limited, but a polybutadiene-based resin and a hydrogenated product of a polybutadiene-based resin are preferable, and a hydrogenated product of a polybutadiene-based resin is more preferable.
Examples of the polybutadiene-based resin include resins having 1,4-repeating units, resins having 1,2-repeating units, and resins having both 1,4-repeating units and 1,2-repeating units. The hydrogenated product of the polybutadiene resin of the present embodiment includes a hydride of a resin having these repeating units.
　ポリブタジエン系樹脂、及びポリブタジエン系樹脂の水素添加物は、両末端にそれぞれ反応性基を有することが好ましい。両末端の反応性基は、同一でも異なっていてもよい。両末端の反応性基は、水酸基、イソシアネート基、アミノ基、オキシラン基、酸無水物基、アルコキシ基、アクリロイル基及びメタクリロイル基からなる群より選択される一種以上の官能基であることが好ましく、水酸基であることがより好ましい。ポリブタジエン系樹脂、及びポリブタジエン系樹脂の水素添加物においては、両末端が水酸基であることがより好ましい。 The polybutadiene resin and the hydrogenated product of the polybutadiene resin preferably have reactive groups at both ends. The reactive groups at both ends may be the same or different. The reactive groups at both ends are preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group. More preferred is a hydroxyl group. In the polybutadiene resin and the hydrogenated product of the polybutadiene resin, it is more preferable that both ends are hydroxyl groups.
　本実施形態に係る粘着剤組成物は、前述のアクリル系共重合体及び粘着助剤の他に、さらに架橋剤を配合した組成物を架橋させて得られる架橋物を含むことも好ましい。また、粘着剤組成物の固形分は、実質的に、前述のように前述のアクリル系共重合体と、粘着助剤と、架橋剤とを架橋させて得られる架橋物からなることも好ましい。ここで、実質的にとは、不可避的に粘着剤に混入してしまうような微量な不純物を除いて、粘着剤組成物の固形分が当該架橋物だけからなることを意味する。 The pressure-sensitive adhesive composition according to the present embodiment preferably contains a cross-linked product obtained by cross-linking a composition containing a cross-linking agent in addition to the acrylic copolymer and the pressure-sensitive adhesive aid. In addition, it is preferable that the solid content of the pressure-sensitive adhesive composition substantially consists of a cross-linked product obtained by cross-linking the above-mentioned acrylic copolymer, the pressure-sensitive adhesive aid, and the cross-linking agent as described above. Here, “substantially” means that the solid content of the pressure-sensitive adhesive composition is composed only of the cross-linked product, excluding trace amounts of impurities that are inevitably mixed in the pressure-sensitive adhesive.
　本実施形態において、架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤、アミン系架橋剤、及びアミノ樹脂系架橋剤が挙げられる。これらの架橋剤は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
　本実施形態において、粘着剤組成物の耐熱性及び粘着力を向上させる観点から、これら架橋剤の中でも、イソシアネート基を有する化合物を主成分として含有する架橋剤（イソシアネート系架橋剤）が好ましい。イソシアネート系架橋剤としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルメタン－２，４’－ジイソシアネート、３－メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、ジシクロヘキシルメタン－２，４’－ジイソシアネート、及びリジンイソシアネート等の多価イソシアネート化合物が挙げられる。
　また、多価イソシアネート化合物は、前述の化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、またはイソシアヌレート環を有するイソシアヌレート型変性体であってもよい。
　本明細書において、イソシアネート基を有する化合物を主成分とする架橋剤とは、架橋剤を構成する成分全体の質量に占めるイソシアネート基を有する化合物の質量の割合が５０質量％以上であることを意味する。 In the present embodiment, examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These cross-linking agents may be used alone or in combination of two or more.
In the present embodiment, from the viewpoint of improving the heat resistance and adhesive strength of the pressure-sensitive adhesive composition, among these crosslinking agents, a crosslinking agent (isocyanate-based crosslinking agent) containing a compound having an isocyanate group as a main component is preferable. Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
The polyisocyanate compound may be a trimethylolpropane adduct-type modified product of the above-described compound, a burette-type modified product reacted with water, or an isocyanurate-type modified product having an isocyanurate ring.
In the present specification, the term “crosslinking agent mainly comprising a compound having an isocyanate group” means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. To do.
　本実施形態において、粘着剤組成物中の架橋剤の含有量は、アクリル系共重合体１００質量部に対して、好ましくは０．１質量部以上２０質量部以下、より好ましくは１質量部以上１５質量部以下、さらに好ましくは５質量部以上１０質量部以下である。粘着剤組成物中の架橋剤の含有量がこのような範囲内であれば、粘着剤組成物を含む層（粘着剤層）と被着体（例えば、基材）との接着性を向上させることができ、粘着シートの製造後に粘着特性を安定化させるための養生期間を短縮できる。 In the present embodiment, the content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If content of the crosslinking agent in an adhesive composition is in such a range, the adhesiveness of the layer (adhesive layer) containing an adhesive composition and a to-be-adhered body (for example, base material) will be improved. It is possible to shorten the curing period for stabilizing the adhesive property after the production of the adhesive sheet.
　本実施形態においては、粘着剤組成物の耐熱性の観点から、イソシアネート系架橋剤は、イソシアヌレート環を有する化合物（イソシアヌレート型変性体）であることがさらに好ましい。イソシアヌレート環を有する化合物は、アクリル系共重合体の水酸基当量に対して、０．７当量以上１．５当量以下配合されていることが好ましい。イソシアヌレート環を有する化合物の配合量が０．７当量以上であれば、加熱後に粘着力が高くなり過ぎず、粘着シートを剥離し易くなり、糊残りを減少させることができる。イソシアヌレート環を有する化合物の配合量が１．５当量以下であれば、初期粘着力が低くなり過ぎることを防止したり、貼付性の低下を防止したりすることができる。 In the present embodiment, from the viewpoint of heat resistance of the pressure-sensitive adhesive composition, the isocyanate-based crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product). The compound having an isocyanurate ring is preferably blended in an amount of 0.7 to 1.5 equivalents with respect to the hydroxyl equivalent of the acrylic copolymer. If the compounding quantity of the compound which has an isocyanurate ring is 0.7 equivalent or more, the adhesive strength will not become too high after heating, the adhesive sheet will be easily peeled off, and the adhesive residue can be reduced. If the compounding quantity of the compound which has an isocyanurate ring is 1.5 equivalent or less, it can prevent that an initial stage adhesive force becomes low too much, or can prevent a sticking fall.
　本実施形態における粘着剤組成物が架橋剤を含む場合、粘着剤組成物は、架橋促進剤をさらに含むことが好ましい。架橋促進剤は、架橋剤の種類などに応じて、適宜選択して用いることが好ましい。例えば、粘着剤組成物が、架橋剤としてポリイソシアネート化合物を含む場合には、有機スズ化合物などの有機金属化合物系の架橋促進剤をさらに含むことが好ましい。 When the pressure-sensitive adhesive composition in this embodiment contains a crosslinking agent, the pressure-sensitive adhesive composition preferably further contains a crosslinking accelerator. The crosslinking accelerator is preferably selected and used as appropriate according to the type of the crosslinking agent. For example, when the pressure-sensitive adhesive composition contains a polyisocyanate compound as a crosslinking agent, it is preferable to further contain an organic metal compound-based crosslinking accelerator such as an organic tin compound.
・シリコーン系粘着剤組成物
　粘着剤層１２がシリコーン系粘着剤組成物を含む場合、シリコーン系粘着剤組成物は、付加重合型シリコーン樹脂を含むことが好ましい。本明細書において、付加重合型シリコーン樹脂を含むシリコーン系粘着剤組成物を付加反応型シリコーン系粘着剤組成物と称する。 -Silicone-type adhesive composition When the adhesive layer 12 contains a silicone-type adhesive composition, it is preferable that a silicone-type adhesive composition contains an addition polymerization type silicone resin. In the present specification, a silicone pressure-sensitive adhesive composition containing an addition polymerization type silicone resin is referred to as an addition reaction type silicone pressure-sensitive adhesive composition.
　付加反応型シリコーン系粘着剤組成物は、主剤、及び架橋剤を含有する。付加反応型シリコーン系粘着剤組成物は、低温での一次硬化だけで使用することが可能で、高温での２次硬化を必要としないという利点がある。ちなみに、従来の過酸化物硬化型シリコーン系粘着剤は１５０℃以上のような高温での２次硬化を必要とする。
　したがって、付加反応型シリコーン系粘着剤組成物を用いることにより、比較的低温での粘着シートの製造が可能となり、エネルギー経済性に優れており、かつ、比較的耐熱性の低い基材１１を用いて粘着シート１０を製造することも可能となる。また、過酸化物硬化型シリコーン系粘着剤のように硬化時に副生物を生じないので、臭気及び腐食などの問題もない。 The addition reaction type silicone pressure-sensitive adhesive composition contains a main agent and a crosslinking agent. The addition reaction type silicone pressure-sensitive adhesive composition has an advantage that it can be used only by primary curing at a low temperature and does not require secondary curing at a high temperature. Incidentally, the conventional peroxide-curing silicone pressure-sensitive adhesive requires secondary curing at a high temperature such as 150 ° C. or higher.
Therefore, by using the addition reaction type silicone pressure-sensitive adhesive composition, it is possible to produce a pressure-sensitive adhesive sheet at a relatively low temperature, use the base material 11 having excellent energy economy and relatively low heat resistance. Thus, the pressure-sensitive adhesive sheet 10 can be manufactured. Further, since no by-product is produced during curing unlike the peroxide-curing silicone pressure-sensitive adhesive, there are no problems such as odor and corrosion.
　付加反応型シリコーン系粘着剤組成物は、通常、シリコーン樹脂成分とシリコーンゴム成分との混合物からなる主剤、及びヒドロシリル基（ＳｉＨ基）含有の架橋剤、並びに必要に応じて使用される硬化触媒からなる。
　シリコーン樹脂成分は、オルガノクロルシランまたはオルガノアルコキシシランを加水分解した後、脱水縮合反応を行うことにより得られる網状構造のオルガノポリシロキサンである。
　シリコーンゴム成分は、直鎖構造を有するジオルガノポリシロキサンである。
　オルガノ基としては、シリコーン樹脂成分、及びシリコーンゴム成分ともに、メチル基、エチル基、プロピル基、ブチル基、フェニル基等である。前述のオルガノ基は、一部、ビニル基、ヘキセニル基、アリル基、ブテニル基、ペンテニル基、オクテニル基、（メタ）アクリロイル基、（メタ）アクリロイルメチル基、（メタ）アクリロイルプロピル基、及びシクロヘキセニル基のような不飽和基に置換されている。工業的に入手が容易なビニル基を有するオルガノ基が好ましい。付加反応型シリコーン系粘着剤組成物においては、不飽和基とヒドロシリル基との付加反応によって架橋が進行して網状の構造が形成され、粘着性が発現する。
　ビニル基のような不飽和基の数は、オルガノ基１００個に対して、通常０．０５個以上３．０個以下、好ましくは、０．１個以上２．５個以下である。オルガノ基１００個に対する不飽和基の数を０．０５個以上とすることにより、ヒドロシリル基との反応性が低下して硬化しにくくなるのを防止して適度な粘着力を付与することができる。オルガノ基１００個に対する不飽和基の数を３．０個以下とすることにより、粘着剤の架橋密度が高くなり粘着力及び凝集力が大きくなって被着面に悪影響を与えるのを防止する。 The addition reaction type silicone pressure-sensitive adhesive composition is usually composed of a main agent composed of a mixture of a silicone resin component and a silicone rubber component, a hydrosilyl group (SiH group) -containing crosslinking agent, and a curing catalyst used as necessary. Become.
The silicone resin component is an organopolysiloxane having a network structure obtained by hydrolyzing organochlorosilane or organoalkoxysilane and then performing a dehydration condensation reaction.
The silicone rubber component is a diorganopolysiloxane having a linear structure.
As the organo group, both the silicone resin component and the silicone rubber component are a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like. The aforementioned organo groups are partially vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth) acryloyl, (meth) acryloylmethyl, (meth) acryloylpropyl, and cyclohexenyl. Substituting with an unsaturated group such as a group. An organo group having a vinyl group that is easily available industrially is preferred. In the addition-reaction type silicone pressure-sensitive adhesive composition, crosslinking proceeds by an addition reaction between an unsaturated group and a hydrosilyl group to form a network structure, thereby exhibiting adhesiveness.
The number of unsaturated groups such as vinyl groups is usually from 0.05 to 3.0, preferably from 0.1 to 2.5, per 100 organo groups. By setting the number of unsaturated groups to 100 or more organo groups to 0.05 or more, it is possible to prevent the reactivity with the hydrosilyl group from being lowered and difficult to cure, and to impart an appropriate adhesive force. . By setting the number of unsaturated groups per 100 organo groups to 3.0 or less, the crosslinking density of the pressure-sensitive adhesive is increased, and the adhesive force and cohesive force are increased, thereby preventing adverse effects on the adherend surface.
　前述のようなオルガノポリシロキサンとしては、具体的には、信越化学工業社製のＫＳ－３７０３（ビニル基の数がメチル基１００個に対して０．６個であるもの）、東レ・ダウコーニング社製のＢＹ２３－７５３（ビニル基の数がメチル基１００個に対して０．１個であるもの）及びＢＹ２４－１６２（ビニル基の数がメチル基１００個に対して１．４個であるもの）などがある。また、東レ・ダウコーニング社製のＳＤ４５６０ＰＳＡ、ＳＤ４５７０ＰＳＡ、ＳＤ４５８０ＰＳＡ、ＳＤ４５８４ＰＳＡ、ＳＤ４５８５ＰＳＡ、ＳＤ４５８７Ｌ、及びＳＤ４５９２ＰＳＡなども使用することができる。
　前述のように、シリコーン樹脂成分であるオルガノポリシロキサンは、通常、シリコーンゴム成分と混合して使用されるが、シリコーンゴム成分としては、信越化学工業社製のＫＳ－３８００（ビニル基の数がメチル基１００個に対して７．６個であるもの）、東レ・ダウコーニング社製のＢＹ２４－１６２（ビニル基の数がメチル基１００個に対して１．４個であるもの）、ＢＹ２４－８４３（不飽和基を有していない）及びＳＤ－７２９２（ビニル基の数がメチル基１００個に対して５．０個であるもの）などが挙げられる。
　前述のような付加反応型シリコーンの具体例は、例えば、特開平１０－２１９２２９号公報に記載されている。 Specific examples of the organopolysiloxane described above include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 per 100 methyl groups), Toray Dow Corning BY23-753 manufactured by the company (the number of vinyl groups is 0.1 per 100 methyl groups) and BY24-162 (the number of vinyl groups is 1.4 per 100 methyl groups) Things). In addition, SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Toray Dow Corning can also be used.
As described above, organopolysiloxane, which is a silicone resin component, is usually used in a mixture with a silicone rubber component. As the silicone rubber component, KS-3800 (manufactured by Shin-Etsu Chemical Co., Ltd.) 7.6 for 100 methyl groups), BY24-162 made by Toray Dow Corning (number of vinyl groups is 1.4 for 100 methyl groups), BY24- 843 (having no unsaturated group) and SD-7292 (the number of vinyl groups is 5.0 with respect to 100 methyl groups).
Specific examples of the addition reaction type silicone as described above are described in, for example, JP-A-10-219229.
　架橋剤は、シリコーン樹脂成分及びシリコーンゴム成分のビニル基のような不飽和基１個に対して、通常、ケイ素原子に結合した水素原子０．５個以上１０個以下、好ましくは、１個以上２．５個以下になるように配合する。０．５個以上とすることにより、ビニル基のような不飽和基とヒドロシリル基との反応が完全には進行せずに硬化不良となるのを防止する。１０個以下とすることにより、架橋剤が未反応で残存して被着面に悪影響を与えるのを防止する。 The crosslinking agent is usually 0.5 to 10 hydrogen atoms bonded to silicon atoms, preferably 1 or more to one unsaturated group such as a vinyl group of the silicone resin component and the silicone rubber component. It mix | blends so that it may become 2.5 or less. By setting the number to 0.5 or more, the reaction between the unsaturated group such as a vinyl group and the hydrosilyl group does not proceed completely, thereby preventing poor curing. By setting the number to 10 or less, it is possible to prevent the crosslinking agent from remaining unreacted and adversely affecting the adherend surface.
　付加反応型シリコーン系粘着剤組成物は、前述の付加反応型シリコーン成分（シリコーン樹脂成分とシリコーンゴム成分とからなる主剤）、及び架橋剤とともに、硬化触媒を含有していることも好ましい。
　この硬化触媒は、シリコーン樹脂成分及びシリコーンゴム成分中の不飽和基と架橋剤中のＳｉ－Ｈ基とのヒドロシリル化反応を促進させるために使用される。
　硬化触媒としては、白金系の触媒、すなわち、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコール溶液との反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサン化合物との反応物、白金－オレフィン錯体、白金－ビニル基含有シロキサン錯体、及び白金－リン錯体等が挙げられる。前述のような硬化触媒の具体例は、例えば、特開２００６－２８３１１号公報及び特開平１０－１４７７５８号公報に記載されている。
　より具体的には、市販品として東レ・ダウコーニング社製のＳＲＸ-２１２、及び信越化学工業社製のＰＬ-５０Ｔなどが挙げられる。 The addition reaction type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst together with the aforementioned addition reaction type silicone component (main agent comprising a silicone resin component and a silicone rubber component) and a crosslinking agent.
This curing catalyst is used to accelerate the hydrosilylation reaction between the unsaturated group in the silicone resin component and the silicone rubber component and the Si—H group in the crosslinking agent.
The curing catalyst is a platinum-based catalyst, that is, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol solution, a reaction product of chloroplatinic acid and an olefin compound, chloroplatinic acid and vinyl Examples thereof include a reaction product with a group-containing siloxane compound, a platinum-olefin complex, a platinum-vinyl group-containing siloxane complex, and a platinum-phosphorus complex. Specific examples of the curing catalyst as described above are described in, for example, JP-A-2006-28311 and JP-A-10-147758.
More specifically, commercially available products include SRX-212 manufactured by Toray Dow Corning and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
　硬化触媒の配合量は白金分として、シリコーン樹脂成分とシリコーンゴム成分の合計量に対して、通常、５質量ｐｐｍ以上２０００質量ｐｐｍ以下、好ましくは、１０質量ｐｐｍ以上５００質量ｐｐｍ以下である。５質量ｐｐｍ以上とすることにより、硬化性が低下して架橋密度の低下、すなわち、粘着力及び凝集力（保持力）が低下するのを防ぎ、２０００質量ｐｐｍ以下とすることにより、コストアップを防ぐとともに粘着剤層の安定性を保持することができ、かつ、過剰に使用された硬化触媒が被着面に悪影響を与えるのを防止する。 The blending amount of the curing catalyst is usually 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass ppm or more and 500 mass ppm or less with respect to the total amount of the silicone resin component and the silicone rubber component as platinum content. By setting the content to 5 mass ppm or more, curability is lowered and the crosslinking density is reduced, that is, the adhesive force and the cohesive force (holding force) are prevented from being reduced. While preventing, the stability of an adhesive layer can be hold | maintained, and it prevents that the curing catalyst used excessively has a bad influence on a to-be-adhered surface.
　付加反応型シリコーン系粘着剤組成物においては、前述の各成分を配合することにより常温でも粘着力が発現するが、付加反応型シリコーン系粘着剤組成物を基材１１または後記する剥離シートに塗布し、基材１１と剥離シートとを貼り合わせた後、加熱または活性エネルギー線を照射してシリコーン樹脂成分とシリコーンゴム成分の架橋剤による架橋反応を促進させることが粘着力の安定性の面から好ましい。 In the addition reaction type silicone pressure-sensitive adhesive composition, adhesive force is exhibited even at room temperature by blending the above-mentioned components, but the addition reaction type silicone pressure-sensitive adhesive composition is applied to the substrate 11 or a release sheet described later. From the standpoint of stability of adhesive strength, the base material 11 and the release sheet are bonded together, and then a heating or active energy ray is irradiated to promote the crosslinking reaction of the silicone resin component and the silicone rubber component by the crosslinking agent. preferable.
　加熱で架橋反応を促進させる場合の加熱温度は通常は、６０℃以上１４０℃以下、好ましくは、８０℃以上１３０℃以下である。６０℃以上で加熱することにより、シリコーン樹脂成分とシリコーンゴム成分の架橋が不足し、粘着力が不十分になるのを防止し、１４０℃以下で加熱することにより基材シートに熱収縮しわが生じたり、劣化したり、変色したりするのを防止することができる。 When the crosslinking reaction is accelerated by heating, the heating temperature is usually 60 ° C. or higher and 140 ° C. or lower, preferably 80 ° C. or higher and 130 ° C. or lower. By heating at 60 ° C. or higher, the crosslinking between the silicone resin component and the silicone rubber component is insufficient, and the adhesive strength is prevented from becoming insufficient. Occurrence, deterioration, or discoloration can be prevented.
　活性エネルギー線を照射して架橋反応を促進させる場合、電磁波または荷電粒子線の中でエネルギー量子を有する活性エネルギー線、すなわち、紫外線などの活性光または電子線などを利用できる。電子線を照射して架橋させる場合、光重合開始剤を必要としないが、紫外線などの活性光を照射して架橋させる場合には、光重合開始剤を存在させることが好ましい。
　紫外線照射させる場合の光重合開始剤としては、特に制限はなく、従来、紫外線硬化型樹脂に慣用されている光重合開始剤の中から、任意の光重合開始剤を適宜選択して用いることができる。この光重合開始剤としては、例えば、ベンゾイン類、ベンゾフェノン類、アセトフェノン類、α－ヒドロキシケトン類、α－アミノケトン類、α－ジケトン類、α－ジケトンジアルキルアセタール類、アントラキノン類、チオキサントン類、その他化合物などが挙げられる。
　これらの光重合開始剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、その使用量は、主剤として用いられる前記付加反応型シリコーン成分と架橋剤との合計量１００質量部に対し、通常、０．０１質量部以上３０質量部以下、好ましくは０．０５質量部以上２０質量部以下の範囲で選定される。
　加熱または活性エネルギー線を照射して架橋することにより、安定した粘着力を有する粘着シートが得られる。 When the active energy ray is irradiated to promote the crosslinking reaction, an active energy ray having energy quanta in an electromagnetic wave or a charged particle beam, that is, an active light such as an ultraviolet ray or an electron beam can be used. In the case of crosslinking by irradiation with an electron beam, a photopolymerization initiator is not required. However, in the case of crosslinking by irradiation with active light such as ultraviolet rays, it is preferable that a photopolymerization initiator is present.
The photopolymerization initiator in the case of irradiation with ultraviolet rays is not particularly limited, and any photopolymerization initiator that has been conventionally used in ultraviolet curable resins can be appropriately selected and used. it can. Examples of the photopolymerization initiator include benzoins, benzophenones, acetophenones, α-hydroxy ketones, α-amino ketones, α-diketones, α-diketone dialkyl acetals, anthraquinones, thioxanthones, and other compounds. Etc.
These photopolymerization initiators may be used alone or in combination of two or more. Further, the amount used is usually 0.01 parts by mass or more and 30 parts by mass or less, preferably 0.05 parts by mass with respect to 100 parts by mass of the total amount of the addition reaction type silicone component and the crosslinking agent used as the main agent. It is selected in the range of 20 parts by mass or less.
A pressure-sensitive adhesive sheet having a stable adhesive force can be obtained by crosslinking by irradiation with heat or active energy rays.
　活性エネルギー線の一つである電子線を照射して架橋する場合の電子線の加速電圧は、一般的には、１３０ｋＶ以上３００ｋＶ以下、好ましくは１５０ｋＶ以上２５０ｋＶ以下である。１３０ｋＶ以上の加速電圧で照射することにより、シリコーン樹脂成分とシリコーンゴム成分の架橋が不足し、粘着力が不十分になるのを防ぐことができ、３００ｋＶ以下の加速電圧で照射することにより粘着剤層及び基材シートが劣化したり変色したりするのを防止することができる。ビーム電流の好ましい範囲は１ｍＡ以上１００ｍＡ以下である。
　照射される電子線の線量は１Ｍｒａｄ以上７０Ｍｒａｄ以下が好ましく、２Ｍｒａｄ以上２０Ｍｒａｄ以下がより好ましい。１Ｍｒａｄ以上の線量で照射することにより粘着剤層及び基材シートが劣化したり変色したりするのを防止し、架橋不足による粘着性が不十分になるのを防止することができる。７０Ｍｒａｄ以下の線量で照射することにより、粘着剤層が劣化したり変色することによる凝集力の低下を防止し、基材シートが劣化したり収縮したりするのを防止することができる。
　紫外線照射の場合の照射量としては、適宜選択されるが、光量は、１００ｍＪ／ｃｍ２以上５００ｍＪ／ｃｍ２以下、照度は、１０ｍＷ／ｃｍ２以上５００ｍＷ／ｃｍ２以下である。
　加熱及び活性エネルギー線の照射は、酸素による反応阻害を防止するため、窒素雰囲気下で行うのが好ましい。 In the case of crosslinking by irradiating an electron beam which is one of the active energy rays, the acceleration voltage of the electron beam is generally 130 kV or more and 300 kV or less, preferably 150 kV or more and 250 kV or less. Irradiation at an acceleration voltage of 130 kV or more can prevent the silicone resin component and the silicone rubber component from being insufficiently crosslinked and prevent the adhesive force from becoming insufficient. By irradiation at an acceleration voltage of 300 kV or less, the adhesive It can prevent that a layer and a base material sheet deteriorate or discolor. A preferable range of the beam current is 1 mA or more and 100 mA or less.
The dose of the irradiated electron beam is preferably 1 Mrad to 70 Mrad, and more preferably 2 Mrad to 20 Mrad. By irradiating with a dose of 1 Mrad or more, the adhesive layer and the base sheet can be prevented from deteriorating or discoloring, and the adhesiveness due to insufficient crosslinking can be prevented from becoming insufficient. By irradiating with a dose of 70 Mrad or less, it is possible to prevent the cohesive force from being reduced due to deterioration or discoloration of the pressure-sensitive adhesive layer, and it is possible to prevent the base sheet from being deteriorated or contracted.
The irradiation amount in the case of ultraviolet irradiation is appropriately selected. The light amount is from 100 mJ / cm 2 to 500 mJ / cm 2 and the illuminance is from 10 mW / cm 2 to 500 mW / cm 2 .
Heating and irradiation with active energy rays are preferably performed in a nitrogen atmosphere in order to prevent reaction inhibition by oxygen.
　粘着剤層１２の厚みは、粘着シート１０の用途に応じて適宜決定される。本実施形態において、粘着剤層１２の厚みは、５μｍ以上６０μｍ以下であることが好ましく、１０μｍ以上５０μｍ以下であることがより好ましい。粘着剤層１２の厚みが薄過ぎると、半導体チップの回路面の凹凸に粘着剤層１２が追従できずに隙間が生じるおそれがある。その隙間に、例えば、層間絶縁材及び封止樹脂等が入り込み、チップ回路面の配線接続用の電極パッドが塞がれるおそれがある。粘着剤層１２の厚みが５μｍ以上であれば、チップ回路面の凹凸に粘着剤層１２が追従し易くなり、隙間の発生を防止できる。また、粘着剤層１２の厚みが厚過ぎると、半導体チップが粘着剤層に沈み込んでしまい、半導体チップ部分と、半導体チップを封止する樹脂部分との段差が生じるおそれがある。このような段差が生じると再配線の際に配線が断線するおそれがある。粘着剤層１２の厚みが６０μｍ以下であれば、段差が生じ難くなる。 The thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the use of the pressure-sensitive adhesive sheet 10. In the present embodiment, the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 μm or more and 60 μm or less, and more preferably 10 μm or more and 50 μm or less. If the thickness of the pressure-sensitive adhesive layer 12 is too thin, the pressure-sensitive adhesive layer 12 may not follow the irregularities on the circuit surface of the semiconductor chip, and a gap may be generated. For example, an interlayer insulating material and a sealing resin may enter the gap, and the wiring connection electrode pad on the chip circuit surface may be blocked. When the thickness of the pressure-sensitive adhesive layer 12 is 5 μm or more, the pressure-sensitive adhesive layer 12 easily follows the unevenness of the chip circuit surface, and the generation of a gap can be prevented. If the thickness of the pressure-sensitive adhesive layer 12 is too thick, the semiconductor chip sinks into the pressure-sensitive adhesive layer, and there is a risk that a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip occurs. If such a step occurs, the wiring may be disconnected during rewiring. If the thickness of the pressure-sensitive adhesive layer 12 is 60 μm or less, a step is hardly generated.
　本実施形態において、粘着剤組成物には、本発明の効果を損なわない範囲で、その他の成分が含まれていてもよい。粘着剤組成物に含まれ得るその他の成分としては、例えば、有機溶媒、難燃剤、粘着付与剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、防腐剤、防黴剤、可塑剤、消泡剤、着色剤、フィラー、及び濡れ性調整剤などが挙げられる。
　付加反応型シリコーン系粘着剤組成物には、添加剤として、ポリジメチルシロキサン及びポリメチルフェニルシロキサンのような非反応性のポリオルガノシロキサンが含まれていてもよい。 In the present embodiment, the pressure-sensitive adhesive composition may contain other components as long as the effects of the present invention are not impaired. Examples of other components that can be included in the pressure-sensitive adhesive composition include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, antiseptics, antifungal agents, and plastics. Agents, antifoaming agents, colorants, fillers, wettability adjusting agents and the like.
The addition reaction type silicone pressure-sensitive adhesive composition may contain non-reactive polyorganosiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane as additives.
（オリゴマー封止層）
　オリゴマー封止層１３は、粘着剤層１２に低分子量成分（オリゴマー）が浸入することを防止するための層である。高温条件に粘着シート１０が曝されると、基材１１中に含まれるオリゴマーは、加熱により基材１１表面に析出し、オリゴマー封止層１３が設けられていない場合には、粘着剤層１２へと浸入し、さらには、粘着剤層１２を通過して、粘着剤層１２の表面まで到達すると考えられる。オリゴマー封止層１３は、１８０℃以上２００℃以下の高温条件下においても、粘着剤層１２へのオリゴマーの浸入を防止することが好ましい。 (Oligomer sealing layer)
The oligomer sealing layer 13 is a layer for preventing the low molecular weight component (oligomer) from entering the pressure-sensitive adhesive layer 12. When the pressure-sensitive adhesive sheet 10 is exposed to a high temperature condition, the oligomer contained in the base material 11 is deposited on the surface of the base material 11 by heating, and when the oligomer sealing layer 13 is not provided, the pressure-sensitive adhesive layer 12 is provided. It is thought that it penetrates into the surface and further passes through the pressure-sensitive adhesive layer 12 and reaches the surface of the pressure-sensitive adhesive layer 12. The oligomer sealing layer 13 preferably prevents the oligomer from entering the pressure-sensitive adhesive layer 12 even under a high temperature condition of 180 ° C. or higher and 200 ° C. or lower.
　オリゴマー封止層１３の材質は、オリゴマーが粘着剤層１２に浸入することを防止できれば、特に限定されない。
　例えば、オリゴマー封止層１３は、（Ａ）エポキシ化合物と、（Ｂ）ポリエステル化合物と、（Ｃ）多官能アミノ化合物と、を含むオリゴマー封止層用組成物を硬化させた硬化皮膜であることが好ましい。オリゴマー封止層用組成物は、硬化反応を促進するために、更に、（Ｄ）酸性触媒を含んでいても良い。 The material of the oligomer sealing layer 13 is not particularly limited as long as the oligomer can be prevented from entering the pressure-sensitive adhesive layer 12.
For example, the oligomer sealing layer 13 is a cured film obtained by curing a composition for an oligomer sealing layer containing (A) an epoxy compound, (B) a polyester compound, and (C) a polyfunctional amino compound. Is preferred. In order to accelerate the curing reaction, the composition for oligomer sealing layer may further contain (D) an acidic catalyst.
・（Ａ）エポキシ化合物
　（Ａ）エポキシ化合物は、ビスフェノールＡ型エポキシ化合物であることが好ましい。ビスフェノールＡ型エポキシ化合物としては、ビスフェノールＡジグリシジルエーテル等を挙げることができる。ビスフェノールＡ型エポキシ化合物の重量平均分子量（Ｍｗ）は、１×１０４以上５×１０４以下であることが好ましい。ビスフェノールＡ型エポキシ化合物の重量平均分子量（Ｍｗ）が１×１０４以上であれば、膜として必要な架橋密度が得られ、オリゴマーの析出を防止し易くなる。重量平均分子量（Ｍｗ）が５×１０４以下であれば、皮膜が硬くなりすぎることを防止できる。重量平均分子量Ｍｗは、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定される標準ポリスチレン換算値である。 -(A) Epoxy Compound (A) The epoxy compound is preferably a bisphenol A type epoxy compound. Examples of the bisphenol A type epoxy compound include bisphenol A diglycidyl ether. The weight average molecular weight (Mw) of the bisphenol A type epoxy compound is preferably 1 × 10 4 or more and 5 × 10 4 or less. If the weight average molecular weight (Mw) of the bisphenol A type epoxy compound is 1 × 10 4 or more, the crosslink density required for the film can be obtained, and the precipitation of the oligomer can be easily prevented. If the weight average molecular weight (Mw) is 5 × 10 4 or less, it is possible to prevent the film from becoming too hard. The weight average molecular weight Mw is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
・（Ｂ）ポリエステル化合物
　（Ｂ）ポリエステル化合物としては、特に限定されず、公知のポリエステル化合物の中から適宜選択して用いることができる。ポリエステル化合物としては、具体的には、多価アルコールと多塩基酸との縮合反応によって得られる樹脂であって、二塩基酸と二価アルコールとの縮合物若しくは不乾性油脂肪酸等で変性した化合物である不転化性ポリエステル化合物、及び二塩基酸と三価以上のアルコールとの縮合物である転化性ポリエステル化合物等が挙げられる。本実施形態においては、これらのポリエステル化合物のいずれも使用することができる。 -(B) Polyester compound (B) It does not specifically limit as a polyester compound, It can select from a well-known polyester compound suitably, and can be used. Specifically, the polyester compound is a resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid, and is a compound modified with a condensate of a dibasic acid and a dihydric alcohol or a non-drying oil fatty acid or the like And a convertible polyester compound that is a condensate of a dibasic acid and a trivalent or higher alcohol. In the present embodiment, any of these polyester compounds can be used.
　（Ｂ）ポリエステル化合物の原料として用いられる多価アルコールとしては、二価アルコール、三価アルコール、及び四価以上の多価アルコールが挙げられる。
　二価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、トリメチレングリコール、テトラメチレングリコール、及びネオペンチルグリコールが挙げられる。
　三価アルコールとしては、例えば、グリセリン、トリメチロールエタン、及びトリメチロールプロパンが挙げられる。
　四価以上の多価アルコールとしては、例えば、ジグリセリン、トリグリセリン、ペンタエリスリトール、ジペンタエリスリトール、マンニット、及びソルビットが挙げられる。
　多価アルコールは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (B) Examples of the polyhydric alcohol used as a raw material for the polyester compound include dihydric alcohols, trihydric alcohols, and tetrahydric or higher polyhydric alcohols.
Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol.
Examples of the trihydric alcohol include glycerin, trimethylolethane, and trimethylolpropane.
Examples of the tetrahydric or higher polyhydric alcohol include diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbit.
A polyhydric alcohol may be used individually by 1 type, and may be used in combination of 2 or more type.
　多塩基酸としては、例えば、芳香族多塩基酸、脂肪族飽和多塩基酸、脂肪族不飽和多塩基酸、及びディールズ・アルダー反応による多塩基酸が挙げられる。
　芳香族多塩基酸としては、例えば、無水フタル酸、テレフタル酸、イソフタル酸、及び無水トリメット酸が挙げられる。
　脂肪族飽和多塩基酸としては、例えば、コハク酸、アジピン酸、及びセバシン酸が挙げられる。
　脂肪族不飽和多塩基酸としては、例えば、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、及び無水シトラコン酸が挙げられる。
　ディールズ・アルダー反応による多塩基酸としては、例えば、シクロペンタジエン－無水マレイン酸付加物、テルペン－無水マレイン酸付加物、及びロジン－無水マレイン酸付加物が挙げられる。
　多塩基酸は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the polybasic acid include aromatic polybasic acids, aliphatic saturated polybasic acids, aliphatic unsaturated polybasic acids, and polybasic acids by Diels-Alder reaction.
Examples of the aromatic polybasic acid include phthalic anhydride, terephthalic acid, isophthalic acid, and trimetic anhydride.
Examples of the aliphatic saturated polybasic acid include succinic acid, adipic acid, and sebacic acid.
Examples of the aliphatic unsaturated polybasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic anhydride.
Examples of the polybasic acid by Diels-Alder reaction include cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, and rosin-maleic anhydride adduct.
A polybasic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
　変性剤である不乾性油脂肪酸等としては、例えば、オクチル酸、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレイン酸、エレオステアリン酸、リシノレイン酸、脱水リシノレイン酸、あるいはヤシ油、アマニ油、キリ油、ヒマシ油、脱水ヒマシ油、大豆油、サフラワー油、及びこれらの脂肪酸等を挙げることができる。これら変性剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。また、ポリエステル化合物としても、１種を単独で用いても良く、２種以上を組み合わせて用いてもよい。 Examples of the non-drying oil fatty acid that is a modifier include octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid, or coconut oil. Linseed oil, tung oil, castor oil, dehydrated castor oil, soybean oil, safflower oil, and fatty acids thereof. One of these modifiers may be used alone, or two or more thereof may be used in combination. Moreover, also as a polyester compound, 1 type may be used independently and 2 or more types may be used in combination.
　（Ｂ）ポリエステル化合物は、架橋反応の基点となる活性水素基を有していることが好ましい。活性水素基としては、例えば、水酸基、カルボキシル基、及びアミノ基が挙げられる。ポリエステル化合物は、水酸基を有していることが特に好ましい。ポリエステル化合物の水酸基価は、５ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下であることが好ましく、１０ｍｇＫＯＨ／ｇ以上３００ｍｇＫＯＨ／ｇ以下であることがより好ましい。 (B) The polyester compound preferably has an active hydrogen group that serves as a base point for the crosslinking reaction. Examples of the active hydrogen group include a hydroxyl group, a carboxyl group, and an amino group. The polyester compound particularly preferably has a hydroxyl group. The hydroxyl value of the polyester compound is preferably 5 mgKOH / g or more and 500 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 300 mgKOH / g or less.
　（Ｂ）ポリエステル化合物の数平均分子量（Ｍｎ）は、５００以上１００００以下であることが好ましく、１０００以上５０００以下であることがより好ましい。前述の数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した標準ポリスチレン換算の値である。 (B) The number average molecular weight (Mn) of the polyester compound is preferably 500 or more and 10,000 or less, and more preferably 1000 or more and 5000 or less. The aforementioned number average molecular weight is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.
　（Ｂ）ポリエステル化合物のガラス転移温度Ｔｇは、０℃以上５０℃以下であることが好ましい。
　前述の範囲の数平均分子量（Ｍｎ）及びガラス転移温度Ｔｇを有するポリエステル化合物を使用することによりオリゴマー封止層１３を形成する硬化皮膜に適度な柔軟性を付与することができる。ガラス転移温度Ｔｇは、ＪＩＳ　Ｋ　７１２１に準拠し、入力補償示差走査熱量測定装置を用いて、－８０℃から２５０℃の温度範囲で、捕外ガラス転移開始温度を測定し、ガラス転移温度Ｔｇを求めた。 (B) It is preferable that the glass transition temperature Tg of a polyester compound is 0 degreeC or more and 50 degrees C or less.
By using a polyester compound having a number average molecular weight (Mn) and a glass transition temperature Tg in the above-mentioned range, moderate flexibility can be imparted to the cured film forming the oligomer sealing layer 13. The glass transition temperature Tg is measured in accordance with JIS K 7121, using an input compensated differential scanning calorimeter, in the temperature range from −80 ° C. to 250 ° C., and the glass transition temperature Tg is measured. Asked.
・（Ｃ）多官能アミノ化合物
　（Ｃ）多官能アミノ化合物としては、例えば、メラミン化合物、尿素化合物、ベンゾグアナミン化合物、及びジアミン類を用いることができる。
　メラミン化合物としては、例えば、ヘキサメトキシメチルメラミン、メチル化メラミン化合物、及びブチル化メラミン化合物が挙げられる。
　尿素化合物としては、例えば、メチル化尿素化合物、及びブチル化尿素化合物が挙げられる。
　ベンゾグアナミン化合物としては、例えば、メチル化ベンゾグアナミン化合物、及びブチル化ベンゾグアナミン化合物が挙げられる。
　ジアミン類としては、例えば、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、Ｎ，Ｎ’－ジフェニルエチレンジアミン、及びｐ－キシリレンジアミンが挙げられる。
　硬化性の観点から、（Ｃ）多官能アミノ化合物としては、ヘキサメトキシメチルメラミンが好ましい。 -(C) Polyfunctional amino compound (C) As a polyfunctional amino compound, a melamine compound, a urea compound, a benzoguanamine compound, and diamine can be used, for example.
Examples of melamine compounds include hexamethoxymethyl melamine, methylated melamine compounds, and butylated melamine compounds.
Examples of urea compounds include methylated urea compounds and butylated urea compounds.
Examples of the benzoguanamine compound include a methylated benzoguanamine compound and a butylated benzoguanamine compound.
Examples of diamines include ethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N′-diphenylethylenediamine, and p-xylylenediamine.
From the viewpoint of curability, hexamethoxymethyl melamine is preferred as the (C) polyfunctional amino compound.
・（Ｄ）酸性触媒
　酸性触媒（Ｄ）としては、例えば、塩酸、及びｐ－トルエンスルホン酸が挙げられる。 -(D) Acidic catalyst Examples of the acidic catalyst (D) include hydrochloric acid and p-toluenesulfonic acid.
・硬化皮膜
　本実施形態において、オリゴマー封止層１３は、（Ａ）ビスフェノールＡ型エポキシ化合物、（Ｂ）ポリエステル化合物、及び（Ｃ）多官能アミノ化合物を、それぞれ、（Ａ）５０質量％以上８０質量％以下、（Ｂ）５質量％以上３０質量％以下、及び（Ｃ）１０質量％以上４０質量％以下の配合率で含むオリゴマー封止層用組成物を硬化させた硬化皮膜であることが好ましい。（Ｄ）酸性触媒をオリゴマー封止層用組成物に配合する場合は、（Ｄ）成分の含有量を１質量％以上５質量％以下とすることが好ましい。
　前述の範囲の配合率のオリゴマー封止層用組成物を硬化させた硬化皮膜によれば、オリゴマー封止層１３による粘着剤層１２へのオリゴマーの浸入を防止する効果を向上させることができる。 -Cured film In this embodiment, the oligomer sealing layer 13 contains (A) bisphenol A type epoxy compound, (B) polyester compound, and (C) polyfunctional amino compound, respectively (A) 50 mass% or more 80 It may be a cured film obtained by curing a composition for an oligomer sealing layer containing at a blending ratio of 5% by mass or less, (B) 5% by mass to 30% by mass, and (C) 10% by mass or more and 40% by mass or less. preferable. (D) When mix | blending an acidic catalyst with the composition for oligomer sealing layers, it is preferable that content of (D) component shall be 1 mass% or more and 5 mass% or less.
According to the cured film obtained by curing the composition for the oligomer sealing layer having the blending ratio in the above range, the effect of preventing the oligomer sealing layer 13 from entering the pressure-sensitive adhesive layer 12 by the oligomer sealing layer 13 can be improved.
　本実施形態に係るオリゴマー封止層用組成物のより具体的な例としては、例えば、以下のようなオリゴマー封止層用組成物の例が挙げられるが、本発明は、このような例に限定されない。 As a more specific example of the composition for an oligomer sealing layer according to the present embodiment, for example, the following examples of the composition for an oligomer sealing layer may be mentioned. It is not limited.
　本実施形態に係るオリゴマー封止層用組成物の一例として、（Ａ）エポキシ化合物と、（Ｂ）ポリエステル化合物と、（Ｃ）多官能アミノ化合物と、（Ｄ）酸性触媒と、を含み、（Ａ）エポキシ化合物は、ビスフェノールＡ型エポキシ化合物であり、（Ｃ）多官能アミノ化合物は、メラミン化合物であるオリゴマー封止層用組成物が挙げられる。 As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst, A) an epoxy compound is a bisphenol A type epoxy compound, and (C) a polyfunctional amino compound includes a composition for an oligomer sealing layer, which is a melamine compound.
　本実施形態に係るオリゴマー封止層用組成物の一例として、（Ａ）エポキシ化合物と、（Ｂ）ポリエステル化合物と、（Ｃ）多官能アミノ化合物と、（Ｄ）酸性触媒と、を含み、（Ａ）エポキシ化合物は、ビスフェノールＡ型エポキシ化合物であり、（Ａ）エポキシ化合物の重量平均分子量（Ｍｗ）が１×１０４以上５×１０４以下であり、（Ｃ）多官能アミノ化合物は、メラミン化合物であるオリゴマー封止層用組成物が挙げられる。 As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst, The A) epoxy compound is a bisphenol A type epoxy compound, the weight average molecular weight (Mw) of the (A) epoxy compound is 1 × 10 4 or more and 5 × 10 4 or less, and (C) the polyfunctional amino compound is melamine The composition for oligomer sealing layers which is a compound is mentioned.
　本実施形態に係るオリゴマー封止層用組成物の一例として、（Ａ）エポキシ化合物と、（Ｂ）ポリエステル化合物と、（Ｃ）多官能アミノ化合物と、（Ｄ）酸性触媒と、を含み、（Ａ）エポキシ化合物は、ビスフェノールＡ型エポキシ化合物であり、（Ｂ）ポリエステル化合物の数平均分子量（Ｍｎ）は、５００以上１００００以下であり、（Ｂ）ポリエステル化合物のガラス転移温度Ｔｇは、０℃以上５０℃以下であり、（Ｃ）多官能アミノ化合物は、メラミン化合物であるオリゴマー封止層用組成物が挙げられる。 As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst, A) The epoxy compound is a bisphenol A type epoxy compound, the number average molecular weight (Mn) of the (B) polyester compound is 500 or more and 10,000 or less, and the glass transition temperature Tg of the (B) polyester compound is 0 ° C. or more. The composition for oligomer sealing layers which is 50 degrees C or less and (C) polyfunctional amino compound is a melamine compound is mentioned.
　本実施形態に係るオリゴマー封止層用組成物の一例として、（Ａ）エポキシ化合物と、（Ｂ）ポリエステル化合物と、（Ｃ）多官能アミノ化合物と、（Ｄ）酸性触媒と、を含み、（Ａ）エポキシ化合物は、ビスフェノールＡ型エポキシ化合物であり、（Ａ）エポキシ化合物の重量平均分子量（Ｍｗ）が１×１０４以上５×１０４以下であり、（Ｂ）ポリエステル化合物の数平均分子量（Ｍｎ）は、５００以上１００００以下であり、（Ｂ）ポリエステル化合物のガラス転移温度Ｔｇは、０℃以上５０℃以下であり、（Ｃ）多官能アミノ化合物は、メラミン化合物であるオリゴマー封止層用組成物が挙げられる。 As an example of the composition for an oligomer sealing layer according to this embodiment, (A) an epoxy compound, (B) a polyester compound, (C) a polyfunctional amino compound, and (D) an acidic catalyst, The A) epoxy compound is a bisphenol A type epoxy compound, the weight average molecular weight (Mw) of the (A) epoxy compound is 1 × 10 4 or more and 5 × 10 4 or less, and (B) the number average molecular weight of the polyester compound ( Mn) is 500 or more and 10,000 or less, (B) The glass transition temperature Tg of the polyester compound is 0 ° C. or more and 50 ° C. or less, and (C) the polyfunctional amino compound is a melamine compound for the oligomer sealing layer. A composition.
・オリゴマー封止層の膜厚
　オリゴマー封止層１３の厚さは、５０ｎｍ以上５００ｎｍ以下であることが好ましく、８０ｎｍ以上３００ｎｍ以下であることがより好ましい。オリゴマー封止層１３の厚さが５０ｎｍ以上であれば、粘着剤層１２へのオリゴマーの浸入を効果的に防止できる。オリゴマー封止層１３の厚さが５００ｎｍ以下であれば、粘着シート１０をコア材にロール状に巻き取る際に巻き取り易くなる。コア材の材質としては、例えば、紙製、プラスチック製、及び金属製が挙げられる。 -Thickness of the oligomer sealing layer The thickness of the oligomer sealing layer 13 is preferably 50 nm or more and 500 nm or less, and more preferably 80 nm or more and 300 nm or less. If the thickness of the oligomer sealing layer 13 is 50 nm or more, the penetration of the oligomer into the pressure-sensitive adhesive layer 12 can be effectively prevented. If the thickness of the oligomer sealing layer 13 is 500 nm or less, it will become easy to wind up when the adhesive sheet 10 is wound around a core material in roll shape. Examples of the material of the core material include paper, plastic, and metal.
　本実施形態に係る粘着シート１０は、加熱後に、次のような粘着力を示すことが好ましい。まず、粘着シート１０を被着体（銅箔またはポリイミドフィルム）に貼着させ、１００℃及び３０分間の条件で加熱し、続いて１８０℃及び３０分間の条件で加熱し、さらに１９０℃及び１時間の条件で加熱した後、粘着剤層１２の銅箔に対する室温での粘着力、及び粘着剤層１２のポリイミドフィルムに対する室温での粘着力が、それぞれ０．７Ｎ／２５ｍｍ以上２．０Ｎ／２５ｍｍ以下であることが好ましい。このような加熱を行った後の粘着力が０．７Ｎ／２５ｍｍ以上であれば、加熱によって基材または被着体が変形した場合に粘着シート１０が被着体から剥離することを防止できる。また、加熱後の粘着力が２．０Ｎ／２５ｍｍ以下であれば、剥離力が高くなり過ぎず、粘着シート１０を被着体から剥離し易い。なお、本明細書において室温とは、２２℃以上２４℃以下の温度である。本明細書において、粘着力は、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分、粘着シートの幅２５ｍｍにて測定した値である。 The pressure-sensitive adhesive sheet 10 according to this embodiment preferably exhibits the following adhesive strength after heating. First, the pressure-sensitive adhesive sheet 10 is adhered to an adherend (copper foil or polyimide film), heated at 100 ° C. and 30 minutes, subsequently heated at 180 ° C. and 30 minutes, and further at 190 ° C. and 1 ° C. After heating under the conditions of time, the adhesive strength of the adhesive layer 12 to the copper foil at room temperature and the adhesive strength of the adhesive layer 12 to the polyimide film at room temperature are 0.7 N / 25 mm or more and 2.0 N / 25 mm, respectively. The following is preferable. If the adhesive strength after performing such heating is 0.7 N / 25 mm or more, the adhesive sheet 10 can be prevented from peeling off from the adherend when the substrate or adherend is deformed by heating. Moreover, if the adhesive force after a heating is 2.0 N / 25mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body. In this specification, room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower. In this specification, the adhesive strength is a value measured by a 180 ° peeling method at a pulling speed of 300 mm / min and a width of 25 mm of the adhesive sheet.
　本実施形態に係る粘着剤組成物のより具体的な例としては、例えば、以下のような粘着剤組成物の例が挙げられるが、本発明は、このような例に限定されない。
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤と、を含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、カルボキシル基含有モノマー、及び水酸基含有モノマーを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、反応性基を有するゴム系材料を主成分として含み、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。 More specific examples of the pressure-sensitive adhesive composition according to this embodiment include the following pressure-sensitive adhesive compositions, but the present invention is not limited to such examples.
An example of the pressure-sensitive adhesive composition according to this embodiment includes an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent, and the acrylic copolymer contains at least 2-ethylhexyl acrylate and a carboxyl group. An acrylic copolymer obtained by copolymerization of a monomer and a hydroxyl group-containing monomer, wherein the adhesive aid contains a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent And a pressure-sensitive adhesive composition.
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤と、を含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、カルボキシル基含有モノマー、及び水酸基含有モノマーを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、両末端水酸基水素化ポリブタジエンであり、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。 An example of the pressure-sensitive adhesive composition according to this embodiment includes an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent, and the acrylic copolymer contains at least 2-ethylhexyl acrylate and a carboxyl group. A pressure-sensitive adhesive composition, which is an acrylic copolymer obtained by copolymerizing a monomer and a hydroxyl group-containing monomer, wherein the adhesion assistant is a hydroxylated hydrogenated polybutadiene at both terminals, and the crosslinking agent is an isocyanate crosslinking agent Things.
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤と、を含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、アクリル酸、及びアクリル酸２－ヒドロキシエチルを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、反応性基を有するゴム系材料を主成分として含み、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。 As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, And an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the adhesion assistant contains a rubber-based material having a reactive group as a main component, and the crosslinking agent is an isocyanate-based crosslinking. A pressure-sensitive adhesive composition which is an agent is mentioned.
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤と、を含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、アクリル酸及びアクリル酸２－ヒドロキシエチルを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、両末端水酸基水素化ポリブタジエンであり、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。 As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Things.
　本実施形態に係る粘着剤組成物のこれらの例においては、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、カルボキシル基含有モノマー、水酸基含有モノマー、及び窒素原子含有環を有するモノマーを共重合して得られるアクリル系共重合体であることも好ましい。
　本実施形態に係る粘着剤組成物のこれらの例においては、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、アクリル酸、アクリル酸２－ヒドロキシエチル、及びＮ－（メタ）アクリロイルモルホリンを共重合して得られるアクリル系共重合体であることも好ましい。
　本実施形態に係る粘着剤組成物のこれらの例においては、前記アクリル系共重合体におけるアクリル酸２－エチルヘキシルに由来する共重合体成分の割合が８０質量％以上９５質量％以下であり、カルボキシル基含有モノマー由来の共重合体成分の質量の割合が１質量％以下であり、残部が他の共重合体成分であることが好ましく、他の共重合体成分としては、水酸基含有モノマー由来の共重合体成分を含むことが好ましい。 In these examples of the pressure-sensitive adhesive composition according to this embodiment, the acrylic copolymer includes at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a monomer having a nitrogen atom-containing ring. An acrylic copolymer obtained by polymerization is also preferred.
In these examples of the pressure-sensitive adhesive composition according to this embodiment, the acrylic copolymer contains at least 2-ethylhexyl acrylate, acrylic acid, 2-hydroxyethyl acrylate, and N- (meth) acryloylmorpholine. An acrylic copolymer obtained by copolymerization is also preferred.
In these examples of the pressure-sensitive adhesive composition according to this embodiment, the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less. The proportion of the mass of the copolymer component derived from the group-containing monomer is preferably 1% by mass or less, and the remainder is preferably another copolymer component. The other copolymer component is a copolymer derived from a hydroxyl group-containing monomer. It preferably contains a polymer component.
（粘着シートの製造方法）
　粘着シート１０の製造方法は、特に限定されない。
　例えば、粘着シート１０は、次のような工程を経て製造される。
　まず、基材１１の第一基材面１１ａの上にオリゴマー封止層用組成物を塗布し、塗膜を形成する。次に、この塗膜を加熱及び硬化させて、オリゴマー封止層１３となる硬化皮膜を形成する。加熱硬化の条件としては、例えば、１２０℃以上１７０℃以下で、５秒間以上５分間以内である。
　次に、オリゴマー封止層１３の上に粘着剤組成物を塗布し、塗膜を形成する。次に、この塗膜を乾燥させて、粘着剤層１２を形成する。 (Method for producing adhesive sheet)
The manufacturing method of the adhesive sheet 10 is not particularly limited.
For example, the adhesive sheet 10 is manufactured through the following processes.
First, the composition for oligomer sealing layers is apply | coated on the 1st base material surface 11a of the base material 11, and a coating film is formed. Next, this coating film is heated and cured to form a cured film that becomes the oligomer sealing layer 13. The heat curing conditions are, for example, 120 ° C. or more and 170 ° C. or less and 5 seconds or more and 5 minutes or less.
Next, an adhesive composition is applied on the oligomer sealing layer 13 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12.
　オリゴマー封止層用組成物を塗布してオリゴマー封止層１３を形成する場合、及び粘着剤組成物を塗布して粘着剤層１２を形成する場合、オリゴマー封止層用組成物及び粘着剤組成物を有機溶媒で希釈して、コーティング液を調製して用いることが好ましい。
　コーティング液の調製に用いる有機溶媒としては、特に限定されない。有機溶媒としては、例えば、芳香族系溶媒、脂肪族系溶媒、エステル系溶媒、ケトン系溶媒、及びアルコール系溶媒が挙げられる。芳香族系溶媒としては、例えば、ベンゼン、トルエン、及びキシレンが挙げられる。脂肪族系溶媒としては、例えば、ノルマルヘキサン、及びノルマルヘプタンが挙げられる。エステル系溶媒としては、例えば、酢酸エチル、及び酢酸ブチルが挙げられる。ケトン系溶媒としては、例えば、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、及びシクロペンタノンが挙げられる。アルコール系溶媒としては、例えば、イソプロピルアルコール、及びメタノールが挙げられる。
　塗布方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールナイフコート法、ロールコート法、ブレードコート法、ダイコート法、及びグラビアコート法等が挙げられる。
　有機溶媒及び低沸点成分がオリゴマー封止層１３、及び粘着剤層１２に残留することを防ぐため、コーティング液を基材１１に塗布した後、塗膜を加熱して乾燥させることが好ましい。
　粘着剤組成物に架橋剤が配合されている場合には、架橋反応を進行させて凝集力を向上させるためにも、塗膜を加熱することが好ましい。 When the composition for oligomer sealing layer is applied to form the oligomer sealing layer 13, and when the pressure-sensitive adhesive composition is applied to form the pressure-sensitive adhesive layer 12, the composition for oligomer sealing layer and the pressure-sensitive adhesive composition It is preferable to prepare a coating solution by diluting the product with an organic solvent.
It does not specifically limit as an organic solvent used for preparation of a coating liquid. Examples of the organic solvent include aromatic solvents, aliphatic solvents, ester solvents, ketone solvents, and alcohol solvents. Examples of the aromatic solvent include benzene, toluene, and xylene. Examples of the aliphatic solvent include normal hexane and normal heptane. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone. Examples of the alcohol solvent include isopropyl alcohol and methanol.
Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, die coating, and gravure coating.
In order to prevent the organic solvent and the low-boiling component from remaining in the oligomer sealing layer 13 and the pressure-sensitive adhesive layer 12, it is preferable to apply the coating liquid to the substrate 11 and then heat and dry the coating film.
When a crosslinking agent is blended in the pressure-sensitive adhesive composition, it is preferable to heat the coating film in order to promote the crosslinking reaction and improve the cohesive force.
（粘着シートの使用）
　粘着シート１０は、半導体素子を封止する際に使用される。粘着シート１０は、金属製リードフレームに搭載されておらず、粘着シート１０上に貼着された状態の半導体素子を封止する際に使用されることが好ましい。具体的には、粘着シート１０は、金属製リードフレームに搭載された半導体素子を封止する際に使用されるのではなく、粘着剤層１２に貼着された状態の半導体素子を封止する際に使用されることが好ましい。金属製リードフレームを用いずに半導体素子をパッケージングする形態としては、パネルスケールパッケージ（Ｐａｎｅｌ　Ｓｃａｌｅ　Ｐａｃｋａｇｅ；ＰＳＰ）及びウエハレベルパッケージ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ；ＷＬＰ）が挙げられる。
　粘着シート１０は、複数の開口部が形成された枠部材を粘着シート１０に貼着させる工程と、前記枠部材の開口部にて露出する粘着剤層１２に半導体チップを貼着させる工程と、前記半導体チップを封止樹脂で覆う工程と、前記封止樹脂を熱硬化させる工程と、を有するプロセスにおいて使用されることが好ましい。 (Use of adhesive sheet)
The pressure-sensitive adhesive sheet 10 is used when sealing a semiconductor element. The pressure-sensitive adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing a semiconductor element that is stuck on the pressure-sensitive adhesive sheet 10. Specifically, the pressure-sensitive adhesive sheet 10 is not used when sealing a semiconductor element mounted on a metal lead frame, but seals a semiconductor element that is stuck to the pressure-sensitive adhesive layer 12. Preferably used. As a form of packaging a semiconductor element without using a metal lead frame, a panel scale package (Panel Scale Package; PSP) and a wafer level package (Wafer Level Package; WLP) can be cited.
The pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process having a step of covering the semiconductor chip with a sealing resin and a step of thermosetting the sealing resin.
（半導体装置の製造方法）
　本実施形態に係る粘着シート１０を用いて半導体装置を製造する方法を説明する。
　図２Ａ～図２Ｅには、本実施形態に係る半導体装置の製造方法を説明する概略図が示されている。
　本実施形態に係る半導体装置の製造方法は、粘着シート１０に複数の開口部２１が形成された枠部材２０を貼着させる工程（粘着シート貼着工程）と、枠部材２０の開口部２１にて露出する粘着剤層１２に半導体チップＣＰを貼着させる工程（ボンディング工程）と、半導体チップＣＰを封止樹脂３０で覆う工程（封止工程）と、封止樹脂３０を熱硬化させる工程（熱硬化工程）と、熱硬化させた後、粘着シート１０を剥離する工程（剥離工程）と、を実施する。必要に応じて、熱硬化工程の後に、封止樹脂３０で封止された封止体５０に補強部材４０を貼着させる工程（補強部材貼着工程）を実施してもよい。以下に各工程について説明する。 (Method for manufacturing semiconductor device)
A method for manufacturing a semiconductor device using the pressure-sensitive adhesive sheet 10 according to this embodiment will be described.
2A to 2E are schematic views illustrating the method for manufacturing the semiconductor device according to the present embodiment.
The manufacturing method of the semiconductor device according to the present embodiment includes a step of attaching the frame member 20 in which a plurality of openings 21 are formed on the adhesive sheet 10 (adhesive sheet attaching step), and an opening 21 of the frame member 20. A step of bonding the semiconductor chip CP to the exposed adhesive layer 12 (bonding step), a step of covering the semiconductor chip CP with the sealing resin 30 (sealing step), and a step of thermosetting the sealing resin 30 ( A thermosetting step) and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting. As needed, you may implement the process (reinforcing member sticking process) of sticking the reinforcement member 40 to the sealing body 50 sealed with the sealing resin 30 after the thermosetting process. Each step will be described below.
・粘着シート貼着工程
　図２Ａには、粘着シート１０の粘着剤層１２に枠部材２０を貼着させる工程を説明する概略図が示されている。
　本実施形態に係る枠部材２０は、格子状に形成され、複数の開口部２１を有する。枠部材２０は、耐熱性を有する材質で形成されていることが好ましい。枠部材２０の材質としては、例えば、銅及びステンレス等の金属、並びにポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂などが挙げられる。
　開口部２１は、枠部材２０の表裏面を貫通する孔である。開口部２１の形状は、半導体チップＣＰを枠内に収容可能であれば、特に限定されない。開口部２１の孔の深さも、半導体チップＣＰを収容可能であれば、特に限定されない。 -Adhesive sheet sticking process The schematic explaining the process of sticking the frame member 20 to the adhesive layer 12 of the adhesive sheet 10 is shown by FIG. 2A.
The frame member 20 according to the present embodiment is formed in a lattice shape and has a plurality of openings 21. The frame member 20 is preferably formed of a material having heat resistance. Examples of the material of the frame member 20 include metals such as copper and stainless steel, and heat resistant resins such as polyimide resin and glass epoxy resin.
The opening 21 is a hole that penetrates the front and back surfaces of the frame member 20. The shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame. The depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
・ボンディング工程
　図２Ｂには、粘着剤層１２に半導体チップＣＰを貼着させる工程を説明する概略図が示されている。
　枠部材２０に粘着シート１０を貼着させると、それぞれの開口部２１において開口部２１の形状に応じて粘着剤層１２が露出する。各開口部２１の粘着剤層１２に半導体チップＣＰを貼着させる。半導体チップＣＰを、その回路面を粘着剤層１２で覆うように貼着させる。 Bonding Step FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
When the pressure-sensitive adhesive sheet 10 is adhered to the frame member 20, the pressure-sensitive adhesive layer 12 is exposed in each opening 21 according to the shape of the opening 21. The semiconductor chip CP is adhered to the adhesive layer 12 of each opening 21. The semiconductor chip CP is stuck so that its circuit surface is covered with the adhesive layer 12.
　半導体チップＣＰの製造は、例えば、回路が形成された半導体ウエハの裏面を研削するバックグラインド工程、及び半導体ウエハを個片化するダイシング工程を実施することにより製造する。ダイシング工程では、半導体ウエハをダイシングシートの接着剤層に貼着させ、ダイシングソーなどの切断手段を用いて半導体ウエハを個片化することで半導体チップＣＰ（半導体素子）が得られる。
　ダイシング装置は、特に限定されず、公知のダイシング装置を用いることができる。また、ダイシングの条件についても、特に限定されない。なお、ダイシングブレードを用いてダイシングする方法に代えて、レーザーダイシング法またはステルスダイシング法などを用いてもよい。 The semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces. In the dicing step, a semiconductor chip CP (semiconductor element) is obtained by sticking the semiconductor wafer to the adhesive layer of the dicing sheet and separating the semiconductor wafer using a cutting means such as a dicing saw.
The dicing apparatus is not particularly limited, and a known dicing apparatus can be used. Also, the dicing conditions are not particularly limited. Note that a laser dicing method or a stealth dicing method may be used instead of the dicing method using a dicing blade.
　ダイシング工程の後、ダイシングシートを引き延ばして、複数の半導体チップＣＰ間の間隔を拡げるエキスパンド工程を実施してもよい。エキスパンド工程を実施することで、コレット等の搬送手段を用いて半導体チップＣＰをピックアップすることができる。また、エキスパンド工程を実施することで、ダイシングシートの接着剤層の接着力が減少し、半導体チップＣＰがピックアップし易くなる。
　ダイシングシートの接着剤組成物、または接着剤層にエネルギー線重合性化合物が配合されている場合には、ダイシングシートの基材側から接着剤層にエネルギー線を照射し、エネルギー線重合性化合物を硬化させる。エネルギー線重合性化合物を硬化させると、接着剤層の凝集力が高まり、接着剤層の接着力を低下させることができる。エネルギー線としては、例えば、紫外線（ＵＶ）及び電子線（ＥＢ）等が挙げられ、紫外線が好ましい。エネルギー線の照射は、半導体ウエハの貼付後、半導体チップの剥離（ピックアップ）前のいずれの段階で行ってもよい。例えば、ダイシングの前もしくは後にエネルギー線を照射してもよいし、エキスパンド工程の後にエネルギー線を照射してもよい。 After the dicing process, an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP. By carrying out the expanding step, the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding process, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
When the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden. When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced. Examples of the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable. The energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
・封止工程及び熱硬化工程
　図２Ｃには、粘着シート１０に貼着された半導体チップＣＰ及び枠部材２０を封止する工程を説明する概略図が示されている。
　封止樹脂３０の材質は、熱硬化性樹脂であり、例えば、エポキシ樹脂などが挙げられる。封止樹脂３０として用いられるエポキシ樹脂には、例えば、フェノール樹脂、エラストマー、無機充填材、及び硬化促進剤などが含まれていてもよい。
　封止樹脂３０で半導体チップＣＰ及び枠部材２０を覆う方法は、特に限定されない。
　本実施形態では、シート状の封止樹脂３０を用いた態様を例に挙げて説明する。シート状の封止樹脂３０を半導体チップＣＰ及び枠部材２０を覆うように載置し、封止樹脂３０を加熱硬化させて、封止樹脂層３０Ａを形成する。このようにして、半導体チップＣＰ及び枠部材２０が封止樹脂層３０Ａに埋め込まれる。シート状の封止樹脂３０を用いる場合には、真空ラミネート法により半導体チップＣＰ及び枠部材２０を封止することが好ましい。この真空ラミネート法により、半導体チップＣＰと枠部材２０との間に空隙が生じることを防止できる。真空ラミネート法による加熱の温度条件範囲は、例えば、８０℃以上１２０℃以下である。 -Sealing process and thermosetting process The schematic diagram explaining the process of sealing the semiconductor chip CP and the frame member 20 which were affixed on the adhesive sheet 10 is shown by FIG. 2C.
The material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin. The epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
The method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited.
In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example. The sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A. When the sheet-shaped sealing resin 30 is used, it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being generated between the semiconductor chip CP and the frame member 20. The temperature condition range for heating by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
　封止工程では、シート状の封止樹脂３０がポリエチレンテレフタレート等の樹脂シートに支持された積層シートを用いてもよい。この場合、半導体チップＣＰ及び枠部材２０を覆うように積層シートを載置した後、樹脂シートを封止樹脂３０から剥離して、封止樹脂３０を加熱硬化させてもよい。このような積層シートとしては、例えば、ＡＢＦフィルム（味の素ファインテクノ株式会社製）が挙げられる。 In the sealing step, a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used. In this case, after the laminated sheet is placed so as to cover the semiconductor chip CP and the frame member 20, the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured. Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
　半導体チップＣＰ及び枠部材２０を封止する方法としては、トランスファーモールド法を採用してもよい。この場合、例えば、封止装置の金型の内部に、粘着シート１０に貼着された半導体チップＣＰ及び枠部材２０を収容する。この金型の内部に流動性の樹脂材料を注入し、樹脂材料を硬化させる。トランスファーモールド法の場合、加熱及び圧力の条件は、特に限定されない。トランスファーモールド法における通常の条件の一例として、１５０℃以上の温度と、４ＭＰａ以上１５ＭＰａ以下の圧力を３０秒以上３００秒以下の間維持する。その後、加圧を解除し、封止装置から硬化物を取り出してオーブン内に静置して、１５０℃以上の温度を２時間以上１５時間以下、維持する。このようにして、半導体チップＣＰ及び枠部材２０を封止する。 As a method for sealing the semiconductor chip CP and the frame member 20, a transfer molding method may be employed. In this case, for example, the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device. A fluid resin material is injected into the mold to cure the resin material. In the case of the transfer mold method, the heating and pressure conditions are not particularly limited. As an example of normal conditions in the transfer molding method, a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds. Thereafter, the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
　前述の封止工程においてシート状の封止樹脂３０を用いる場合、封止樹脂３０を熱硬化させる工程（熱硬化工程）の前に、第一加熱プレス工程を実施してもよい。第一加熱プレス工程においては、封止樹脂３０で被覆された半導体チップＣＰ及び枠部材２０付き粘着シート１０を両面から板状部材で挟み込み、所定の温度、時間、及び圧力の条件下でプレスする。第一加熱プレス工程を実施することにより、封止樹脂３０が半導体チップＣＰと枠部材２０との空隙にも充填され易くなる。また、加熱プレス工程を実施することにより、封止樹脂３０により構成される封止樹脂層３０Ａの凹凸を平坦化することもできる。 When the sheet-shaped sealing resin 30 is used in the above-described sealing process, the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process). In the first heating press step, the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. . By performing the first heat pressing step, the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20. Moreover, the unevenness | corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
　熱硬化工程の後、粘着シート１０を剥離すると、封止樹脂３０で封止された半導体チップＣＰ及び枠部材２０が得られる。以下、これを封止体５０と称する場合がある。 When the pressure-sensitive adhesive sheet 10 is peeled after the thermosetting step, the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained. Hereinafter, this may be referred to as a sealing body 50.
・補強部材貼着工程
　図２Ｄには、封止体５０に補強部材４０を貼着させる工程を説明する概略図が示されている。
　粘着シート１０を剥離した後、露出した半導体チップＣＰの回路面に対して再配線層を形成する再配線工程及びバンプ付け工程が実施される。このような再配線工程及びバンプ付け工程における封止体５０の取り扱い性を向上させるため、必要に応じて、封止体５０に補強部材４０を貼着させる工程（補強部材貼着工程）を実施してもよい。補強部材貼着工程を実施する場合には、粘着シート１０を剥離する前に実施することが好ましい。図２Ｄに示すように、封止体５０は、粘着シート１０及び補強部材４０によって挟まれた状態で支持されている。 -Reinforcing member sticking process The schematic diagram explaining the process of sticking the reinforcing member 40 to the sealing body 50 is shown by FIG. 2D.
After the adhesive sheet 10 is peeled off, a rewiring process and a bumping process for forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed. In order to improve the handleability of the sealing body 50 in such a rewiring process and a bumping process, a process (reinforcing member attaching process) of attaching the reinforcing member 40 to the sealing body 50 is performed as necessary. May be. When implementing a reinforcement member sticking process, it is preferable to carry out before peeling the adhesive sheet 10. FIG. As illustrated in FIG. 2D, the sealing body 50 is supported in a state of being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
　本実施形態では、補強部材４０は、耐熱性の補強板４１と、耐熱性の接着層４２とを備える。補強板４１としては、例えば、ガラスエポキシ樹脂等の耐熱性樹脂を含む板状の部材が挙げられる。接着層４２は、補強板４１と封止体５０とを接着させる。接着層４２としては、補強板４１及び封止樹脂層３０Ａの材質に応じて適宜選択される。 In the present embodiment, the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42. Examples of the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a glass epoxy resin. The adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50. The adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
　補強部材貼着工程では、封止体５０の封止樹脂層３０Ａと補強板４１との間に接着層４２を挟み込み、さらに補強板４１側及び粘着シート１０側からそれぞれ板状部材で挟み込み、所定の温度、時間、及び圧力の条件下でプレスする第二加熱プレス工程を実施することが好ましい。第二加熱プレス工程により、封止体５０と補強部材４０とを仮固定する。第二加熱プレス工程の後に、接着層４２を硬化させるために、仮固定された封止体５０と補強部材４０とを所定の温度及び時間の条件下で加熱することが好ましい。加熱硬化の条件は、接着層４２の材質に応じて適宜設定され、例えば、１８５℃、８０分間、及び２．４ＭＰａの条件である。第二加熱プレス工程においても、板状部材としては、例えば、ステンレス等の金属板を用いることができる。 In the reinforcing member sticking step, the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure. The sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time. The conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa. Also in the second heat pressing step, as the plate-like member, for example, a metal plate such as stainless steel can be used.
・剥離工程
　図２Ｅには、粘着シート１０を剥離する工程を説明する概略図が示されている。
　本実施形態では、粘着シート１０の基材１１が屈曲可能である場合、粘着シート１０を屈曲させながら、枠部材２０、半導体チップＣＰ及び封止樹脂層３０Ａから容易に剥離することができる。剥離角度θは、特に限定されないが、９０度以上の剥離角度θで粘着シート１０を剥離することが好ましい。剥離角度θが９０度以上であれば、粘着シート１０を、枠部材２０、半導体チップＣＰ及び封止樹脂層３０Ａから容易に剥離することができる。剥離角度θは、９０度以上１８０度以下が好ましく、１３５度以上１８０度以下がより好ましい。このように粘着シート１０を屈曲させながら剥離を行うことで、枠部材２０、半導体チップＣＰ及び封止樹脂層３０Ａにかかる負荷を低減しながらの剥離することができ、粘着シート１０の剥離による、半導体チップＣＰ及び封止樹脂層３０Ａの損傷を抑制することができる。粘着シート１０を剥離した後、前述の再配線工程及びバンプ付け工程等が実施される。粘着シート１０の剥離後、再配線工程及びバンプ付け工程等の実施前に、必要に応じて、前述の補強部材貼着工程を実施してもよい。 -Peeling process The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
In this embodiment, when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent. Although peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree | times or more. When the peeling angle θ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A. The peeling angle θ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less. By peeling off the pressure-sensitive adhesive sheet 10 in this way, it is possible to peel it while reducing the load applied to the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A. Damage to the semiconductor chip CP and the sealing resin layer 30A can be suppressed. After the pressure-sensitive adhesive sheet 10 is peeled off, the above-described rewiring process and bumping process are performed. After the pressure-sensitive adhesive sheet 10 is peeled off, before the rewiring step and the bumping step, etc., the aforementioned reinforcing member sticking step may be performed as necessary.
　補強部材４０を貼着させた場合、再配線工程及びバンプ付け工程等が実施された後、補強部材４０による支持が不要になった段階で、補強部材４０を封止体５０から剥離する。
　その後、封止体５０を半導体チップＣＰ単位で個片化する（個片化工程）。封止体５０を個片化させる方法は特に限定されない。例えば、前述の半導体ウエハをダイシングする際に使用した方法と同様の方法で個片化させることができる。封止体５０を個片化させる工程は、封止体５０をダイシングシート等に貼着させた状態で実施してもよい。封止体５０を個片化することで、半導体チップＣＰ単位の半導体パッケージが製造され、この半導体パッケージは、実装工程においてプリント配線基板等に実装される。 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed.
Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step). A method for dividing the sealing body 50 into individual pieces is not particularly limited. For example, the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer. The step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like. By separating the sealing body 50 into individual pieces, a semiconductor package in units of the semiconductor chip CP is manufactured, and this semiconductor package is mounted on a printed wiring board or the like in a mounting process.
　本実施形態によれば、高温条件が課される工程を経た後でも、被着体の表面の汚染を防止することができる粘着シート１０を提供できる。
　粘着剤層１２が接する被着体としては、例えば、半導体チップＣＰ及び枠部材２０である。半導体チップＣＰ及び枠部材２０は、粘着剤層１２に接した状態で高温条件に曝される。粘着シート１０は、基材１１と粘着剤層１２との間にオリゴマー封止層１３を含んでいるため、粘着シート１０が高温条件に曝されても、基材１１中のオリゴマーの粘着剤層１２への浸入が防止される。それゆえ、粘着シート１０によれば、半導体チップＣＰ及び枠部材２０の表面の汚染を防止することができる。 According to the present embodiment, it is possible to provide the pressure-sensitive adhesive sheet 10 that can prevent the surface of the adherend from being contaminated even after a process in which high temperature conditions are imposed.
Examples of the adherend to which the adhesive layer 12 is in contact include the semiconductor chip CP and the frame member 20. The semiconductor chip CP and the frame member 20 are exposed to high temperature conditions while being in contact with the pressure-sensitive adhesive layer 12. Since the pressure-sensitive adhesive sheet 10 includes the oligomer sealing layer 13 between the base material 11 and the pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive layer of the oligomer in the base material 11 even when the pressure-sensitive adhesive sheet 10 is exposed to high temperature conditions. Intrusion into 12 is prevented. Therefore, according to the pressure-sensitive adhesive sheet 10, it is possible to prevent contamination of the surfaces of the semiconductor chip CP and the frame member 20.
〔第二実施形態〕
　第二実施形態は、粘着シートの基材両面にオリゴマー封止層を有する点で、第一実施形態と相違する。第二実施形態は、その他の点において第一実施形態と同様であるため、説明を省略または簡略化する。 [Second Embodiment]
2nd embodiment is different from 1st embodiment by the point which has an oligomer sealing layer on both surfaces of the base material of an adhesive sheet. Since the second embodiment is the same as the first embodiment in other points, the description is omitted or simplified.
　図３には、第二実施形態に係る粘着シート１０Ａの断面概略図が示されている。
　粘着シート１０Ａは、基材１１、粘着剤層１２、オリゴマー封止層１３（第一オリゴマー封止層）及びオリゴマー封止層１４（第二オリゴマー封止層）を有する。
　粘着シート１０Ａは、基材１１の両面（第一基材面１１ａ及び第二基材面１１ｂ）にそれぞれオリゴマー封止層１３，１４を有する。粘着シート１０Ａにおいては、第一基材面１１ａにオリゴマー封止層１３が積層され、第二基材面１１ｂにオリゴマー封止層１４が積層されている。第一基材面１１ａがオリゴマー封止層１３によって被覆され、第二基材面１１ｂがオリゴマー封止層１４によって被覆されていることが好ましい。第一実施形態と同様、基材１１と粘着剤層１２との間にオリゴマー封止層１３が設けられている。粘着シート１０Ａの形状も、シート状、テープ状、ラベル状などあらゆる形状をとり得る。 The cross-sectional schematic of 10 A of adhesive sheets which concern on 2nd embodiment is shown by FIG.
10 A of adhesive sheets have the base material 11, the adhesive layer 12, the oligomer sealing layer 13 (1st oligomer sealing layer), and the oligomer sealing layer 14 (2nd oligomer sealing layer).
10 A of adhesive sheets have the oligomer sealing layers 13 and 14 on both surfaces (the 1st base material surface 11a and the 2nd base material surface 11b) of the base material 11, respectively. In the pressure-sensitive adhesive sheet 10A, the oligomer sealing layer 13 is laminated on the first base material surface 11a, and the oligomer sealing layer 14 is laminated on the second base material surface 11b. It is preferable that the first base material surface 11 a is covered with the oligomer sealing layer 13 and the second base material surface 11 b is covered with the oligomer sealing layer 14. Similar to the first embodiment, an oligomer sealing layer 13 is provided between the base material 11 and the pressure-sensitive adhesive layer 12. The shape of the pressure-sensitive adhesive sheet 10A can take any shape such as a sheet shape, a tape shape, and a label shape.
　オリゴマー封止層１３（第一オリゴマー封止層）は、第一実施形態と同様である。
　オリゴマー封止層１４（第二オリゴマー封止層）は、加熱されて基材１１の第二基材面１１ｂに析出するオリゴマーが他の部材に付着して汚染することを防止するための層である。オリゴマー封止層１４は、オリゴマー封止層１３と同様の材質で形成されていることが好ましい。 The oligomer sealing layer 13 (first oligomer sealing layer) is the same as in the first embodiment.
The oligomer sealing layer 14 (second oligomer sealing layer) is a layer for preventing oligomers that are heated and deposited on the second base material surface 11b of the base material 11 from adhering to and contaminating other members. is there. The oligomer sealing layer 14 is preferably formed of the same material as the oligomer sealing layer 13.
　オリゴマー封止層１４の厚さは、特に限定されず、第一実施形態で説明したオリゴマー封止層１３と同様の範囲の厚さであることが好ましい。オリゴマー封止層の厚さが増すほど、オリゴマー封止の効果は向上するが、例えば、粘着シートの生産性及びコストの観点からすると、オリゴマー封止層１３及びオリゴマー封止層１４の厚さは、１００ｎｍ以上２００ｎｍ以下でもよく、１５０ｎｍ程度でもよい。 The thickness of the oligomer sealing layer 14 is not particularly limited, and is preferably in the same range as the oligomer sealing layer 13 described in the first embodiment. As the thickness of the oligomer sealing layer is increased, the effect of the oligomer sealing is improved. For example, from the viewpoint of productivity and cost of the pressure-sensitive adhesive sheet, the thickness of the oligomer sealing layer 13 and the oligomer sealing layer 14 is 100 nm or more and 200 nm or less, or about 150 nm.
　粘着シート１０Ａの製造方法も特に限定されない。
　例えば、粘着シート１０Ａは、次のような工程を経て製造される。まず、基材１１の第一基材面１１ａの上にオリゴマー封止層用組成物を塗布し、塗膜を形成する。次に、この塗膜を加熱及び硬化させて、オリゴマー封止層１３を形成する。次に、基材１１の第二基材面１１ｂの上にオリゴマー封止層用組成物を塗布し、塗膜を形成する。次に、この塗膜を加熱及び硬化させて、オリゴマー封止層１４を形成する。次に、オリゴマー封止層１３の上に粘着剤組成物を塗布し、塗膜を形成する。次に、この塗膜を乾燥させて、粘着剤層１２を形成する。 The manufacturing method of the pressure-sensitive adhesive sheet 10A is not particularly limited.
For example, the adhesive sheet 10A is manufactured through the following steps. First, the composition for oligomer sealing layers is apply | coated on the 1st base material surface 11a of the base material 11, and a coating film is formed. Next, this coating film is heated and cured to form the oligomer sealing layer 13. Next, the composition for oligomer sealing layers is apply | coated on the 2nd base material surface 11b of the base material 11, and a coating film is formed. Next, this coating film is heated and cured to form the oligomer sealing layer 14. Next, an adhesive composition is applied on the oligomer sealing layer 13 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12.
　粘着シート１０Ａも、第一実施形態に係る粘着シート１０と同様の使用方法が適用可能であり、粘着シート１０と同様に半導体装置の製造方法において使用できる。 The adhesive sheet 10A can also be used in the same manner as the adhesive sheet 10 according to the first embodiment, and can be used in the method for manufacturing a semiconductor device in the same manner as the adhesive sheet 10.
　粘着シート１０Ａによれば、粘着シート１０と同様、高温条件が課される工程を経た後でも、被着体の表面の汚染を防止することができる。
　さらに、粘着シート１０Ａによれば、第二基材面１１ｂにもオリゴマー封止層１４が形成されているので、第二基材面１１ｂに析出したオリゴマーが被着体以外の部材及び装置に付着して汚染することを防止できる。例えば、半導体装置の製造方法において、加熱プレス工程で粘着シート１０Ａと接触する板状部材の汚染を防止することができる。 According to the pressure-sensitive adhesive sheet 10A, as in the case of the pressure-sensitive adhesive sheet 10, it is possible to prevent the surface of the adherend from being contaminated even after a process in which high temperature conditions are imposed.
Furthermore, according to the pressure-sensitive adhesive sheet 10A, the oligomer sealing layer 14 is also formed on the second base material surface 11b, so that the oligomer deposited on the second base material surface 11b adheres to members and devices other than the adherend. To prevent contamination. For example, in the method for manufacturing a semiconductor device, contamination of the plate-like member that comes into contact with the pressure-sensitive adhesive sheet 10A in the hot press process can be prevented.
〔実施形態の変形〕
　本発明は、前記実施形態に限定されず、本発明の目的を達成できる範囲での変形及び改良等は、本発明に含まれる。なお、以下の説明では、前記実施形態で説明した部材等と同一であれば、同一符号を付してその説明を省略または簡略化する。 [Modification of Embodiment]
The present invention is not limited to the above-described embodiment, but includes modifications and improvements as long as the object of the present invention can be achieved. In the following description, if it is the same as the member described in the above embodiment, the same reference numeral is given and the description is omitted or simplified.
　また、粘着シートは、枚葉であってもよく、複数枚の粘着シートが積層された状態で提供されてもよい。この場合、例えば、粘着剤層は、積層される別の粘着シートの基材によって覆われていてもよい。
　また、粘着シートは、長尺状のシートであってもよく、ロール状に巻き取られた状態で提供されてもよい。ロール状に巻き取られた粘着シートは、ロールから繰り出されて所望のサイズに切断するなどして使用することができる。 Further, the pressure-sensitive adhesive sheet may be a single sheet or may be provided in a state where a plurality of pressure-sensitive adhesive sheets are laminated. In this case, for example, the pressure-sensitive adhesive layer may be covered with a base material of another pressure-sensitive adhesive sheet to be laminated.
Moreover, a long sheet may be sufficient as an adhesive sheet, and it may be provided in the state wound up by roll shape. The pressure-sensitive adhesive sheet wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
　粘着シートの粘着剤層は、剥離シートによって覆われていてもよい。剥離シートとしては、特に限定されない。例えば、取り扱い易さの観点から、剥離シートは、剥離基材と、剥離基材の上に剥離剤が塗布されて形成された剥離剤層とを備えることが好ましい。また、剥離シートは、剥離基材の片面のみに剥離剤層を備えていてもよいし、剥離基材の両面に剥離剤層を備えていてもよい。剥離基材としては、例えば、紙基材、この紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙、並びにプラスチックフィルム等が挙げられる。紙基材としては、グラシン紙、コート紙、及びキャストコート紙等が挙げられる。プラスチックフィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリエチレンナフタレート等のポリエステルフィルム、並びにポリプロピレン及びポリエチレン等のポリオレフィンフィルム等が挙げられる。剥離剤としては、例えば、オレフィン系樹脂、ゴム系エラストマー（例えば、ブタジエン系樹脂、イソプレン系樹脂等）、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂、及びシリコーン系樹脂が挙げられる。 The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet may be covered with a release sheet. The release sheet is not particularly limited. For example, from the viewpoint of ease of handling, the release sheet preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate. Moreover, the release sheet may be provided with a release agent layer only on one side of the release substrate, or may be provided with a release agent layer on both sides of the release substrate. Examples of the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film. Examples of the paper substrate include glassine paper, coated paper, and cast coated paper. Examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. Examples of the release agent include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins.
　剥離シートの厚みは、特に限定されない。剥離シートの厚みは、通常、２０μｍ以上２００μｍ以下であり、２５μｍ以上１５０μｍ以下であることが好ましい。
　剥離剤層の厚みは、特に限定されない。剥離剤を含む溶液を塗布して剥離剤層を形成する場合、剥離剤層の厚みは、０．０１μｍ以上２．０μｍ以下であることが好ましく、０．０３μｍ以上１．０μｍ以下であることがより好ましい。
　剥離基材としてプラスチックフィルムを用いる場合、当該プラスチックフィルムの厚みは、３μｍ以上５０μｍ以下であることが好ましく、５μｍ以上４０μｍ以下であることがより好ましい。 The thickness of the release sheet is not particularly limited. The thickness of the release sheet is usually from 20 μm to 200 μm, and preferably from 25 μm to 150 μm.
The thickness of the release agent layer is not particularly limited. When a release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 μm or more and 2.0 μm or less, and preferably 0.03 μm or more and 1.0 μm or less. More preferred.
When a plastic film is used as the peeling substrate, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 40 μm or less.
　剥離シートを有する粘着シートは、例えば、次のような工程を経て製造される。まず、剥離シートの上に粘着剤組成物を塗布し、塗膜を形成する。次に、塗膜を乾燥させて、粘着剤層１２を形成する。また、前記実施形態で説明したように基材１１の第一基材面１１ａにオリゴマー封止層１３を形成しておく。剥離シート上の粘着剤層１２と、基材１１上のオリゴマー封止層１３とを貼り合わせる。オリゴマー封止層１４を有する態様の場合には、基材１１の両面にオリゴマー封止層１３，１４を形成した後に、粘着剤層１２と、オリゴマー封止層１３とを貼り合わせる。 The pressure-sensitive adhesive sheet having a release sheet is manufactured through the following steps, for example. First, a pressure-sensitive adhesive composition is applied on a release sheet to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12. Moreover, the oligomer sealing layer 13 is formed on the first base material surface 11a of the base material 11 as described in the above embodiment. The pressure-sensitive adhesive layer 12 on the release sheet and the oligomer sealing layer 13 on the substrate 11 are bonded together. In the case of the embodiment having the oligomer sealing layer 14, the pressure-sensitive adhesive layer 12 and the oligomer sealing layer 13 are bonded together after the oligomer sealing layers 13 and 14 are formed on both surfaces of the substrate 11.
　前記実施形態では、封止樹脂３０の材質として熱硬化性樹脂である場合を例に挙げて説明したが、本発明はこのような態様に限定されない。例えば、封止樹脂３０は、紫外線等のエネルギー線で硬化するエネルギー線硬化性樹脂でもよい。 In the above embodiment, the case where the sealing resin 30 is a thermosetting resin has been described as an example, but the present invention is not limited to such a mode. For example, the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
　前記実施形態では、半導体装置の製造方法の説明において、枠部材２０を粘着シート１０に貼着させる態様を例に挙げて説明したが、本発明はこのような態様に限定されない。粘着シート１０は、枠部材を用いずに半導体素子を封止する半導体装置の製造方法において使用されてもよい。 In the above embodiment, in the description of the method for manufacturing a semiconductor device, an example in which the frame member 20 is attached to the adhesive sheet 10 has been described as an example, but the present invention is not limited to such an embodiment. The adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
　以下、実施例を挙げて本発明をさらに詳細に説明する。本発明はこれら実施例に何ら限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.
〔評価方法〕
　粘着シートの評価は、以下に示す方法に従って行った。 〔Evaluation methods〕
Evaluation of the pressure-sensitive adhesive sheet was performed according to the following method.
[残渣物の確認]
　粘着シートの粘着剤層に半導体チップを貼着し、半導体チップ付き粘着シートを得た。
　この半導体チップ付き粘着シートを、１９０℃及び１時間の条件で加熱した。加熱後、粘着シートを剥離した。剥離後の半導体チップの被着面をデジタル顕微鏡（（株）キーエンス製、デジタルマイクロスコープ；ＶＨＸ－１０００）にて観察し、残渣の有無を確認した。観察倍率は、５００倍とした。残渣物が確認されなかった場合を「Ａ」と判定し、残渣物が確認された場合を「Ｂ」と判定した。 [Confirmation of residue]
A semiconductor chip was attached to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to obtain a pressure-sensitive adhesive sheet with a semiconductor chip.
This adhesive sheet with a semiconductor chip was heated under the conditions of 190 ° C. and 1 hour. After heating, the adhesive sheet was peeled off. The adherend surface of the semiconductor chip after peeling was observed with a digital microscope (manufactured by Keyence Co., Ltd., digital microscope; VHX-1000) to confirm the presence or absence of residues. The observation magnification was 500 times. The case where a residue was not confirmed was determined as “A”, and the case where a residue was confirmed was determined as “B”.
　なお、残渣物が基材に由来するオリゴマーであるか否かの確認は、次に示す方法により行った。ラマン分光分析法を用いて残渣物のスペクトルを測定し、スペクトルと粘着シートの基材の特徴とが合致したことから、残渣物が基材に由来するオリゴマーであることを確認した。 Note that whether or not the residue was an oligomer derived from the base material was confirmed by the following method. The spectrum of the residue was measured using Raman spectroscopy, and the spectrum and the characteristics of the base material of the pressure-sensitive adhesive sheet were matched, confirming that the residue was an oligomer derived from the base material.
〔粘着シートの作製〕
（実施例１） [Preparation of adhesive sheet]
Example 1
（１）塗布用オリゴマー封止剤液の調製
　下記（Ａ）ビスフェノールＡ型エポキシ化合物、（Ｂ）ポリエステル化合物、（Ｃ）多官能アミノ化合物及び（Ｄ）酸性触媒を配合し、十分に撹拌して、実施例１に係る塗布用オリゴマー封止剤液（オリゴマー封止層用組成物）を調製した。 (1) Preparation of coating oligomer sealing agent liquid The following (A) bisphenol A type epoxy compound, (B) polyester compound, (C) polyfunctional amino compound and (D) acidic catalyst are blended and stirred sufficiently. The oligomer sealing agent liquid for coating which concerns on Example 1 (composition for oligomer sealing layers) was prepared.
　（Ａ）ビスフェノールＡ型エポキシ化合物
　　ＤＩＣ社製「ＥＰＩＣＬＯＮ　Ｈ－３６０」（商品名）、固形分濃度：４０質量％、重量平均分子量：２５０００ (A) Bisphenol A type epoxy compound “EPICLON H-360” (trade name) manufactured by DIC, solid content concentration: 40 mass%, weight average molecular weight: 25000
　（Ｂ）ポリエステル化合物
　　東洋紡績社製「バイロンＧＫ６８０」（商品名）、数平均分子量：６０００、ガラス転移温度：１０℃ (B) Polyester compound “Byron GK680” (trade name) manufactured by Toyobo Co., Ltd., number average molecular weight: 6000, glass transition temperature: 10 ° C.
　（Ｃ）多官能アミノ化合物
　　ヘキサメトキシメチルメラミン、日本サイテックインダストリーズ社製「サイメル３０３」（商品名） (C) Polyfunctional amino compound Hexamethoxymethylmelamine, “Cymel 303” (trade name) manufactured by Nippon Cytec Industries, Ltd.
　（Ｄ）酸性触媒
　　ｐ－トルエンスルホン酸のメタノール溶液（固形分濃度５０質量％） (D) Acidic catalyst p-Toluenesulfonic acid in methanol solution (solid content concentration 50 mass%)
　具体的には、上記（Ａ）ビスフェノールＡ型エポキシ化合物１００質量部に、上記（Ｂ）ポリエステル化合物のトルエン希釈溶液（固形分濃度：３０％）１４．２９質量部、及び上記（Ｃ）ヘキサメトキシメチルメラミン１１．４質量部を加え、さらに、トルエン／メチルエチルケトン＝５０質量％／５０質量％の混合溶剤で固形分が３質量％になるように希釈し、撹拌した。撹拌後の溶液に（Ｄ）ｐ－トルエンスルホン酸のメタノール溶液（固形分濃度５０質量％）を２．９質量部（（Ａ）ビスフェノールＡ型エポキシ化合物１００質量部に対して）添加して、塗布用オリゴマー封止剤液を得た。 Specifically, 100 parts by mass of the (A) bisphenol A type epoxy compound, 14.29 parts by mass of a toluene diluted solution of the (B) polyester compound (solid content concentration: 30%), and the above (C) hexamethoxy 11.4 parts by mass of methylmelamine was added, and the mixture was further diluted with a mixed solvent of toluene / methyl ethyl ketone = 50% by mass / 50% by mass so that the solid content became 3% by mass and stirred. 2.9 parts by mass of methanol solution (solid content concentration 50% by mass) of (D) p-toluenesulfonic acid (based on 100 parts by mass of (A) bisphenol A type epoxy compound) was added to the stirred solution, An oligomer sealing agent solution for coating was obtained.
（２）オリゴマー封止層の作製
　調製した塗布用オリゴマー封止剤液を、二軸延伸ポリエチレンテレフタレートフィルム（三菱樹脂社製「ダイヤホイル　Ｔ－１００」（商品名）、厚さ５０μｍ、１００℃における貯蔵弾性率３．２×１０９Ｐａ）の一方の面に乾燥後の厚さが１５０ｎｍとなるようにマイヤーバーコート法にて均一に塗布した。塗布後のフィルムをオーブンの内部を通過させ、塗膜を加熱硬化させて、オリゴマー封止層を得た。オーブンにおける熱風の吹き出し条件としては、温度を１５０℃とし、風速を８ｍ／ｍｉｎとし、オーブンにおける加工速度としては、塗布後のフィルムがオーブン内部を２０秒で通過するように調整した。 (2) Preparation of oligomer sealing layer The prepared oligomer sealing agent liquid for coating was applied to a biaxially stretched polyethylene terephthalate film ("Diafoil T-100" (trade name) manufactured by Mitsubishi Plastics, Inc., thickness 50 μm, at 100 ° C. It was uniformly coated on one surface of storage elastic modulus 3.2 × 10 9 Pa) by the Mayer bar coating method so that the thickness after drying was 150 nm. The coated film was passed through the oven, and the coating film was cured by heating to obtain an oligomer sealing layer. As conditions for blowing hot air in the oven, the temperature was set to 150 ° C., the wind speed was set to 8 m / min, and the processing speed in the oven was adjusted so that the coated film passed through the oven in 20 seconds.
（３）粘着剤組成物の作製
　以下の材料（ポリマー、粘着助剤、架橋剤、及び希釈溶剤）を配合し、十分に撹拌して、実施例１に係る塗布用粘着剤液（粘着剤組成物）を調製した。 (3) Production of pressure-sensitive adhesive composition The following materials (polymer, pressure-sensitive adhesive, cross-linking agent, and dilution solvent) were blended and sufficiently stirred, and the pressure-sensitive adhesive liquid for application according to Example 1 (pressure-sensitive adhesive composition) Prepared).
・ポリマー：アクリル酸エステル共重合体、４０質量部（固形分）
　アクリル酸エステル共重合体は、アクリル酸２－エチルヘキシル９２．８質量％と、アクリル酸２－ヒドロキシエチル７．０質量％と、アクリル酸０．２質量％とを共重合して調製した。 -Polymer: Acrylic ester copolymer, 40 parts by mass (solid content)
The acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
・粘着助剤：両末端水酸基水素化ポリブタジエン〔日本曹達（株）製；ＧＩ－１０００〕、５質量部（固形分） -Adhesion aid: hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000), 5 parts by mass (solid content)
・架橋剤：ヘキサメチレンジイソシアネートを有する脂肪族系イソシアネート（ヘキサメチレンジイソシアネートのイソシアヌレート型変性体）〔日本ポリウレタン工業（株）製；コロネートＨＸ〕、３．５質量部（固形分） Crosslinking agent: Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate; manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX), 3.5 parts by mass (solid content)
・希釈溶剤：メチルエチルケトンを用い、塗布用粘着剤液の固形分濃度は、３０質量％に調製した。 Diluting solvent: Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
（４）粘着剤層の作製
　調製した塗布用粘着剤液を、コンマコーター（登録商標）を用いて乾燥後の膜厚が５０μｍになるように、シリコーン系剥離層を設けた３８μｍの透明ポリエチレンテレフタレートフィルム剥離フィルム〔リンテック（株）製；ＳＰ－ＰＥＴ３８２１５０〕の剥離層面側に塗布し、９０℃及び９０秒間の加熱を行い、続いて１１５℃及び９０秒間の加熱を行い、塗膜を乾燥させた。 (4) Preparation of pressure-sensitive adhesive layer 38 μm of transparent polyethylene terephthalate provided with a silicone-based release layer so that the thickness of the prepared pressure-sensitive adhesive liquid for application using a comma coater (registered trademark) after drying is 50 μm. It was applied to the release layer side of a film release film [manufactured by Lintec Corporation; SP-PET382150], heated at 90 ° C. for 90 seconds, and then heated at 115 ° C. for 90 seconds to dry the coating film. .
（５）粘着シートの作製
　剥離フィルムの表面上に作製された粘着剤層と、基材の表面上に作製されたオリゴマー封止層とを貼り合わせて実施例１に係る粘着シートを得た。 (5) Production of pressure-sensitive adhesive sheet The pressure-sensitive adhesive layer produced on the surface of the release film and the oligomer sealing layer produced on the surface of the substrate were bonded together to obtain a pressure-sensitive adhesive sheet according to Example 1.
（実施例２）
　実施例２に係る粘着シートは、粘着剤層に含まれるポリマーが実施例１と異なること以外は、実施例１と同様に作製した。
　実施例２で用いたポリマーは、アクリル酸２－エチルヘキシル８０．８質量％と、アクリル酸２－ヒドロキシエチル７質量％と、４－アクリロイルモルホリン１２質量％と、アクリル酸０．２質量％とを共重合して調製した。 (Example 2)
The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
The polymer used in Example 2 was composed of 80.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, 12% by mass of 4-acryloylmorpholine, and 0.2% by mass of acrylic acid. Prepared by copolymerization.
（比較例１）
　比較例１に係る粘着シートは、粘着剤層に含まれる粘着助剤が実施例１と異なること、基材が異なること、並びにオリゴマー封止層を有さないこと以外は、実施例１と同様に作製した。
　比較例１で用いた粘着助剤は、アセチルクエン酸トリブチル〔田岡化学工業（株）製〕である。なお、アセチルクエン酸トリブチルは、前述の反応性基を有さない。
　比較例１で用いた基材は、ポリエチレンテレフタレートフィルム〔三菱樹脂社製；ＰＥＴ５０Ｔ-１００、厚さ５０μｍ、１００℃における貯蔵弾性率３．２×１０９Ｐａ〕である。剥離フィルムの表面上に作製された粘着剤層と、基材とを貼り合わせて比較例１に係る粘着シートを得た。 (Comparative Example 1)
The pressure-sensitive adhesive sheet according to Comparative Example 1 is the same as Example 1 except that the pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer is different from that in Example 1, the base material is different, and the oligomer sealing layer is not provided. It was prepared.
The adhesion promoter used in Comparative Example 1 is tributyl acetyl citrate [manufactured by Taoka Chemical Industry Co., Ltd.]. Note that tributyl acetylcitrate does not have the aforementioned reactive group.
The base material used in Comparative Example 1 is a polyethylene terephthalate film [manufactured by Mitsubishi Plastics; PET 50T-100, thickness 50 μm, storage elastic modulus at 100 ° C. 3.2 × 10 9 Pa]. The pressure-sensitive adhesive layer prepared on the surface of the release film was bonded to the base material to obtain a pressure-sensitive adhesive sheet according to Comparative Example 1.
（比較例２）
　比較例２に係る粘着シートは、粘着剤層に含まれる粘着助剤が比較例１と異なること以外は、比較例１と同様に作製した。
　比較例２で用いた粘着助剤は、両末端水酸基水素化ポリブタジエン〔日本曹達（株）製；ＧＩ－１０００〕である。 (Comparative Example 2)
The pressure-sensitive adhesive sheet according to Comparative Example 2 was prepared in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer was different from that in Comparative Example 1.
The tackifier used in Comparative Example 2 is a hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000).
（比較例３）
　比較例３に係る粘着シートは、粘着剤層に含まれる粘着剤が実施例１と異なること、粘着剤層の厚みが異なること、基材が異なること、並びにオリゴマー封止層を有さないこと以外は、実施例１と同様に作製した。
　比較例３では、シリコーン系粘着剤を用いた。
　比較例３においては、
　　シリコーン系粘着剤Ａｄ１（ＳＤ４５８０ＰＳＡ）１８質量部（固形分）、
　　シリコーン系粘着剤Ａｄ２（ＳＤ４５８７Ｌ）４０質量部（固形分）、
　　触媒Ｃａｔ１（ＮＣ－２５　ＣＡＴ）０．３質量部（固形分）、
　　触媒Ｃａｔ２（ＣＡＴ－ＳＲＸ－２１２）０．６５質量部（固形分）、及び
　　プライマー（ＢＹ２４－７１２）５質量部（固形分）を配合し、十分に撹拌して、塗布用粘着剤液（粘着剤組成物）を調製した。比較例３の粘着剤組成物に用いた材料は、いずれも東レ・ダウコーニング（株）製である。
　比較例３に係る塗布用粘着剤液を、乾燥後の厚みが３０μｍとなるように剥離フィルムの剥離層面側に塗布及び乾燥して粘着剤層を作製した。乾燥条件は、１３０℃及び２分間とした。比較例３で用いた基材は、ポリエチレンテレフタレートフィルム〔三菱樹脂社製；ダイヤホイル　ＰＥＴ５０　Ｔ－１００、厚さ５０μｍ、１００℃における貯蔵弾性率３．２×１０９Ｐａ〕を用いた。剥離フィルムの表面上に作製された粘着剤層と、基材とを貼り合わせて比較例３に係る粘着シートを得た。 (Comparative Example 3)
The pressure-sensitive adhesive sheet according to Comparative Example 3 is different from Example 1 in that the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer is different, the thickness of the pressure-sensitive adhesive layer is different, the base material is different, and there is no oligomer sealing layer. Other than that, it was produced in the same manner as in Example 1.
In Comparative Example 3, a silicone adhesive was used.
In Comparative Example 3,
Silicone-based adhesive Ad1 (SD4580PSA) 18 parts by mass (solid content),
Silicone-based adhesive Ad2 (SD4587L) 40 parts by mass (solid content),
Catalyst Cat1 (NC-25 CAT) 0.3 part by mass (solid content),
The catalyst Cat2 (CAT-SRX-212) 0.65 parts by mass (solid content) and the primer (BY24-712) 5 parts by mass (solid content) were blended and stirred thoroughly to give an adhesive solution for application (adhesion) Agent composition) was prepared. The materials used for the pressure-sensitive adhesive composition of Comparative Example 3 are all manufactured by Toray Dow Corning Co., Ltd.
The pressure-sensitive adhesive liquid for coating according to Comparative Example 3 was applied to the release layer surface side of the release film and dried so that the thickness after drying was 30 μm, thereby preparing a pressure-sensitive adhesive layer. Drying conditions were 130 ° C. and 2 minutes. The base material used in Comparative Example 3 was a polyethylene terephthalate film [Mitsubishi Resin Co., Ltd .; Diafoil PET50 T-100, thickness 50 μm, storage elastic modulus at 100 ° C. 3.2 × 10 9 Pa]. The pressure-sensitive adhesive layer prepared on the surface of the release film was bonded to the base material to obtain a pressure-sensitive adhesive sheet according to Comparative Example 3.
　表１に実施例１、実施例２、及び比較例１～３に係る粘着シートの評価結果を示す。 Table 1 shows the evaluation results of the pressure-sensitive adhesive sheets according to Example 1, Example 2, and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　比較例１～３に係る粘着シートはオリゴマー封止層を粘着剤層と基材との間に有していなかったため、１９０℃の高温条件下に曝されて、被着体（半導体チップ）表面に残渣物が析出したと考えられる。
　一方、実施例１及び実施例２に係る粘着シートはオリゴマー封止層を粘着剤層と基材との間に有していたため、１９０℃の高温条件下に曝されても、被着体（半導体チップ）表面に残渣物が析出しなかったと考えられる。 Since the pressure-sensitive adhesive sheets according to Comparative Examples 1 to 3 did not have an oligomer sealing layer between the pressure-sensitive adhesive layer and the substrate, they were exposed to a high temperature condition of 190 ° C., and the surface of the adherend (semiconductor chip) It is thought that a residue was deposited on the surface.
On the other hand, since the pressure-sensitive adhesive sheets according to Example 1 and Example 2 had the oligomer sealing layer between the pressure-sensitive adhesive layer and the base material, the adherend ( It is considered that no residue was deposited on the surface of the semiconductor chip).
　１０，１０Ａ…粘着シート、１１…基材、１２…粘着剤層、１３，１４…オリゴマー封止層。 10, 10A: adhesive sheet, 11: base material, 12: adhesive layer, 13, 14: oligomer sealing layer.

Claims (9)

  1. 　粘着シート上の半導体素子を封止する際に使用される粘着シートであって、
    　基材と、
    　粘着剤を含む粘着剤層と、
    　前記基材と前記粘着剤層との間に設けられたオリゴマー封止層と、を有する
    　粘着シート。     A pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet,
    A substrate;
    An adhesive layer containing an adhesive,
    An oligomer sealing layer provided between the substrate and the pressure-sensitive adhesive layer.
  2. 　前記オリゴマー封止層は、エポキシ化合物と、ポリエステル化合物と、多官能アミノ化合物と、を含むオリゴマー封止層用組成物を硬化させた硬化皮膜である、
    　請求項１に記載の粘着シート。     The oligomer sealing layer is a cured film obtained by curing a composition for an oligomer sealing layer containing an epoxy compound, a polyester compound, and a polyfunctional amino compound.
    The pressure-sensitive adhesive sheet according to claim 1.
  3. 　前記オリゴマー封止層用組成物は、
    （Ａ）５０質量％以上８０質量％以下のビスフェノールＡ型エポキシ化合物と、
    （Ｂ）５質量％以上３０質量％以下のポリエステル化合物と、
    （Ｃ）１０質量％以上４０質量％以下の多官能アミノ化合物と、
    を含む、
    　請求項２に記載の粘着シート。     The oligomer sealing layer composition is:
    (A) 50 mass% or more and 80 mass% or less of bisphenol A type epoxy compound,
    (B) 5% by mass or more and 30% by mass or less of a polyester compound;
    (C) 10% by mass or more and 40% by mass or less of a polyfunctional amino compound;
    including,
    The pressure-sensitive adhesive sheet according to claim 2.
  4. 　前記基材の１００℃における貯蔵弾性率は、１×１０７Ｐａ以上である、
    　請求項１から請求項３のいずれか一項に記載の粘着シート。     The storage elastic modulus at 100 ° C. of the substrate is 1 × 10 7 Pa or more.
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 3.
  5. 　前記粘着剤層は、アクリル系粘着剤組成物またはシリコーン系粘着剤組成物を含有する、
    　請求項１から請求項４のいずれか一項に記載の粘着シート。     The pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 4.
  6. 　前記アクリル系粘着剤組成物は、アクリル酸２－エチルヘキシルを主たるモノマーとするアクリル系共重合体を含む、
    　請求項５に記載の粘着シート。     The acrylic pressure-sensitive adhesive composition includes an acrylic copolymer having 2-ethylhexyl acrylate as a main monomer.
    The pressure-sensitive adhesive sheet according to claim 5.
  7. 　前記シリコーン系粘着剤組成物は、付加重合型シリコーン樹脂を含む、
    　請求項５に記載の粘着シート。     The silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
    The pressure-sensitive adhesive sheet according to claim 5.
  8. 　前記基材の両面に前記オリゴマー封止層を有する、
    　請求項１から請求項７のいずれか一項に記載の粘着シート。     Having the oligomer sealing layer on both sides of the substrate;
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 7.
  9. 　前記基材は、ポリエステル系樹脂を含む、
    　請求項１から請求項８のいずれか一項に記載の粘着シート。     The base material includes a polyester-based resin,
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 8.
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