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WO2017038919A1 - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
WO2017038919A1
WO2017038919A1 PCT/JP2016/075606 JP2016075606W WO2017038919A1 WO 2017038919 A1 WO2017038919 A1 WO 2017038919A1 JP 2016075606 W JP2016075606 W JP 2016075606W WO 2017038919 A1 WO2017038919 A1 WO 2017038919A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
sheet
mass
Prior art date
Application number
PCT/JP2016/075606
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
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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
Publication of WO2017038919A1 publication Critical patent/WO2017038919A1/en

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Classifications

    • 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 groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 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
    • 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

Definitions

  • the present invention relates to an adhesive sheet.
  • Patent Document 1 discloses a heat-resistant pressure-sensitive adhesive tape for manufacturing a semiconductor device, which is used when a substrate-less semiconductor chip that does not use a metal lead frame is sealed with a resin. Are listed.
  • An object of the present invention is to provide a pressure-sensitive adhesive sheet that can prevent destruction of the adherend when the pressure-sensitive adhesive sheet is peeled from the adherend.
  • a pressure-sensitive adhesive sheet used for sealing a semiconductor element on a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive, wherein the pressure-sensitive adhesive sheet A pressure-sensitive adhesive sheet having an adhesive force of 2.5 N / 25 mm or less in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer is attached to a polyimide film and heated at 190 ° C. for 1 hour is provided.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention has an adhesive force of 0.1 N / 25 mm or more in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer is attached to a polyimide film and heated at 190 ° C. for 1 hour. It is preferable that
  • the pressure-sensitive adhesive sheet according to one embodiment of the present invention preferably has an adhesive force to the polyimide film at room temperature before the heating of 0.1 N / 25 mm or more and 8.0 N / 25 mm or less.
  • 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 contains an acrylic copolymer mainly composed of 2-ethylhexyl acrylate.
  • the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
  • an adhesive sheet that can prevent the adherend from being destroyed when the adhesive sheet is peeled off from the adherend.
  • 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 and a pressure sensitive adhesive layer 12 containing a pressure sensitive adhesive.
  • the base material 11 has the 1st base material surface 11a and the 2nd base material surface 11b on the opposite side to the 1st base material surface 11a.
  • the adhesive layer 12 is laminated
  • a release sheet RL is laminated as shown in FIG.
  • the shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a tape shape and a label shape.
  • the substrate 11 is a member that supports the pressure-sensitive adhesive layer 12.
  • 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 oligomer contained in the polyester film is derived from a polyester-forming monomer, a dimer, a trimer, 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, 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 at 100 degrees C of the base material 11 is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring device.
  • 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.
  • 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 the adhesion and adhesive force. .
  • 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 contains 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 preferable, and this carboxyl group-containing monomer is preferable.
  • 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 adhesion aid preferably contains a rubber-based material having a reactive group (hereinafter sometimes referred to as “reactive adhesion aid”) or acetyl citrate triester as a main component.
  • reactive adhesion aid a rubber-based material having a reactive group
  • acetyl citrate triester a reactive adhesion assistant or acetyl citrate triester
  • 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.
  • 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.
  • including acetyl citrate triester as a main component means that the ratio of the mass of acetyl citrate triester to the total mass of the adhesion promoter exceeds 50 mass%.
  • 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 hydrogenated product of a polybutadiene type resin and a polybutadiene type resin is preferable, and the hydrogenated product of a polybutadiene type 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.
  • examples of the acetylcitrate triester-based adhesion assistant include tributyl acetylcitrate (ATBC).
  • the pressure-sensitive adhesive composition according to this 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-based 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 diisocyan
  • 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.
  • the crosslinking agent containing a compound having an isocyanate group as a main component 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. means.
  • 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.
  • Some of the aforementioned organo groups are 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) Some).
  • 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 above 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, PL-50T manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • 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
  • the addition reaction type silicone pressure-sensitive adhesive composition an 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 RL described later. After coating and bonding the base material 11 and the release sheet RL, heating or irradiating active energy rays to promote the crosslinking reaction of the silicone resin component and the silicone rubber component with the crosslinking agent can improve the stability of the adhesive force. From the aspect, it is 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. Heating at 60 ° C. or higher prevents the silicone resin component and silicone rubber component from being insufficiently cross-linked and prevents the adhesive force from becoming insufficient, and heating at 140 ° C. or lower causes heat shrinkage and wrinkles on the base sheet. Occurrence, deterioration, or discoloration can be prevented.
  • 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. Is mentioned. 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 cross-linked, resulting in insufficient adhesive force. 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. Irradiation with a dose of 1 Mrad or more can prevent the pressure-sensitive adhesive layer and the base sheet from being deteriorated or discolored, and can prevent the adhesiveness from becoming insufficient due to insufficient crosslinking. 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.
  • 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 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 acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer.
  • An adhesive composition is mentioned.
  • an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer.
  • 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 acrylic.
  • a certain adhesive composition 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 acrylic.
  • a pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, 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 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 acrylic.
  • a pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the pressure-sensitive adhesive aid is tributyl acetylcitrate (ATBC), and the cross-linking agent is an isocyanate-based cross-linking agent Things.
  • 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 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 release sheet RL is not particularly limited.
  • the release sheet RL preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate.
  • the release sheet RL may include a release agent layer only on one side of the release substrate, or may include 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-based resins, rubber-based elastomers (for example, butadiene-based resins and isoprene-based resins), long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and silicone-based resins. .
  • the thickness of the release sheet RL is not particularly limited.
  • the thickness of the release sheet RL is usually 20 ⁇ m or more and 200 ⁇ m or less, and preferably 25 ⁇ m or more and 150 ⁇ m or less.
  • 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 10 has a pressure-sensitive adhesive force (hereinafter referred to as “40 after heating”) on the polyimide film in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer 12 is attached to the polyimide film and heated at 190 ° C. for 1 hour.
  • adhesive strength in an atmosphere of ° C is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the adhesive sheet of 25 mm.
  • the adhesive strength of the pressure-sensitive adhesive sheet 10 under the above conditions is preferably 2.0 N / 25 mm or less, more preferably 1.5 N / 25 mm or less.
  • the lower limit of the adhesive strength of the adhesive sheet 10 under the above conditions is that the adhesive sheet 10 adheres when the substrate 11 or the adherend is deformed by heating. From the viewpoint of preventing the film from peeling off, it is preferably 0.1 N / 25 mm or more. If the adhesive strength of the pressure-sensitive adhesive sheet 10 under the above conditions (adhesive strength in a 40 ° C. atmosphere after heating) is 0.1 N / 25 mm or more, there is no possibility of destroying the package.
  • the adhesive strength of the adhesive sheet 10 under the above conditions (40 ° C. atmosphere after heating)
  • the lower limit of (adhesive strength) is more preferably 0.4 N / 25 mm or more, and further preferably 0.6 N / 25 mm or more.
  • the adhesive sheet 10 says the adhesive force with respect to the said polyimide film in the room temperature after sticking the adhesive layer 12 to a polyimide film, and heating at 190 degreeC for 1 hour (henceforth "the adhesive force in the room temperature after a heating”). May be 0.4 N / 25 mm or more and 10.0 N / 25 mm or less, and more preferably 1.1 N / 25 mm or more and 8.0 N / 25 mm or less. If the adhesive strength at room temperature after heating of the adhesive sheet 10 is in the above range, the adhesive sheet 10 does not peel off from the substrate 11 or the adherend at room temperature after heating. It can be easily peeled off by heating.
  • the adhesive sheet 10 has an adhesive force with respect to the polyimide film at room temperature before heating of 0.1 N / 25 mm or more and 8.0 N / 25 mm before heating from the viewpoint of preventing the sheet from unintentionally peeling off during the manufacturing process.
  • the room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower.
  • the adhesive force is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the adhesive sheet of 25 mm.
  • the manufacturing method of the adhesive sheet 10 is not particularly limited.
  • the adhesive sheet 10 is manufactured through the following processes. First, the pressure-sensitive adhesive composition is applied on the first base material surface 11a of the base material 11 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12. Then, release sheet RL is stuck so that adhesive layer 12 may be covered.
  • another manufacturing method of the adhesive sheet 10 it manufactures through the following processes. First, an adhesive composition is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12, and the first base material surface 11 a of the base material 11 is bonded to the pressure-sensitive adhesive layer 12.
  • a coating liquid pressure-sensitive adhesive liquid for application
  • the organic solvent include toluene, ethyl acetate, and methyl ethyl ketone.
  • the method for applying the coating liquid is not particularly limited. 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.
  • the coating liquid In order to prevent the organic solvent and the low boiling point component from remaining in the pressure-sensitive adhesive layer 12, it is preferable to apply the coating liquid to the substrate 11 or the release sheet RL, and then heat and dry the coating film.
  • 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.
  • PSP and WLP are mentioned as a form which packages a semiconductor element without using a metal lead frame. Since the pressure-sensitive adhesive sheet 10 according to this embodiment has a pressure-sensitive adhesive strength in a 40 ° C.
  • the adhesive sheet 10 is preferably used for a panel scale package.
  • the panel of the panel scale package include circular, oval, and quadrangular panels in plan view.
  • the diameter is preferably about 200 mm to 450 mm.
  • each side is preferably about 300 mm to 800 mm in size. If a panel is said size, when peeling the adhesive sheet 10 from a to-be-adhered body, it can peel favorably.
  • 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.
  • thermosetting step and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting.
  • each step will be described.
  • 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 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, a stealth dicing method, or the like 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 or the adhesive layer of the dicing sheet, 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-like 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 heat curing 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 heat-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 between the plate-like 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 plate member for example, a metal plate such as stainless steel can be used.
  • the pressure-sensitive adhesive sheet 10 is peeled off at 40 ° C., whereby the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained.
  • 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 by plate members from the reinforcing plate 41 side and the adhesive sheet 10 side, respectively. It is preferable to carry out a 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 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 adherend from being destroyed when the pressure-sensitive adhesive sheet is peeled from the adherend.
  • the adhesive sheet 10 may be a single wafer or may be provided in a state where a plurality of adhesive sheets 10 are laminated.
  • the pressure-sensitive adhesive layer 12 may be covered with the base material 11 of another pressure-sensitive adhesive sheet to be laminated.
  • the adhesive sheet 10 may be a long sheet or may be provided in a state of being wound in a roll. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
  • 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 passivation film such as polyimide resin may be provided on the circuit surface of the semiconductor chip CP.
  • the adhesive sheet 10 is more easily peeled off.
  • the sealing body 50 When the pressure-sensitive adhesive sheet 10 is peeled off, the sealing body 50 may be held by suction means such as a suction table. If it is the adhesive sheet 10, it can peel without destroying the sealing body 50, and it can peel, without moving the sealing body 50 from an adsorption
  • the pressure-sensitive adhesive sheets prepared in Examples 1 to 3 were cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (polyimide film).
  • adherend polyimide film
  • Kapton 100H product name
  • the peeling angle is 180 °
  • the peeling speed is 300 mm / min
  • the measuring instrument with a thermostat TENSILON manufactured by A & D
  • the adhesive strength at the time of peeling was measured.
  • the pressure-sensitive adhesive sheets prepared in Examples 1 to 3 were cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (polyimide film).
  • adherend polyimide film
  • Kapton 100H product name
  • This pressure-sensitive adhesive sheet with a polyimide film was heated under conditions of 190 ° C. and 1 hour using a thermostatic measuring instrument (TENSILON manufactured by A & D).
  • the peel angle was 180 °
  • the peel rate was 300 mm / min
  • the pressure-sensitive adhesive force after heating of the pressure-sensitive adhesive sheet was measured when the pressure-sensitive adhesive sheet was peeled from the polyimide film at room temperature and 40 ° C. atmosphere.
  • the pressure-sensitive adhesive sheets prepared in Examples 1 to 3 were cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (semiconductor wafer; diameter 150 mm, thickness 200 ⁇ m).
  • the pressure-sensitive adhesive sheet affixed to the semiconductor wafer was heated under conditions of 190 ° C. and 1 hour using a thermostatic measuring instrument (TENSILON manufactured by A & D). After the heating, the pressure-sensitive adhesive sheet was peeled from the semiconductor wafer in a 40 ° C. atmosphere at a peeling angle of 180 °, a peeling speed of 300 mm / min. The semiconductor wafer after peeling the adhesive sheet was visually observed, and the case where the wafer was not destroyed was designated as A, and the case where the wafer was destroyed was designated as B.
  • pressure-sensitive adhesive composition The following materials (polymer, pressure-sensitive adhesive, cross-linking agent, and diluting solvent) were blended and sufficiently stirred, and the pressure-sensitive adhesive liquid for application according to Example 1 (pressure-sensitive adhesive composition) Prepared).
  • 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 tributyl acetyl citrate (ATBC) [manufactured by Taoka Chemical Co., Ltd.], 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.
  • pressure-sensitive adhesive layer 38 Preparation of pressure-sensitive adhesive layer 38 ⁇ m transparent polyethylene terephthalate provided with a silicone release layer so that the thickness of the prepared pressure-sensitive adhesive liquid for coating after drying using a comma coater (registered trademark) is 50 ⁇ m. It is applied to the release layer side of a release film consisting of a 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. To produce a pressure-sensitive adhesive layer.
  • Example 2 The pressure-sensitive adhesive sheet according to Example 2 used 5 parts by mass (solid content) of a hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000) as a pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer. Other than that, it was produced in the same manner as in Example 1.
  • Example 3 The pressure-sensitive adhesive sheet according to Example 3 was produced in the same manner as in Example 2 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 2.
  • the polymer used in Example 3 was composed of 80.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, 12% by mass of N-acryloylmorpholine, and 0.2% by mass of acrylic acid. Prepared by copolymerization.
  • Table 1 shows the evaluation results of the pressure-sensitive adhesive sheets according to Examples 1 to 3.
  • the adhesive sheets according to Examples 1 to 3 were adhered to the polyimide film and heated at 190 ° C. for 1 hour, and the adhesive strength against the polyimide film at 40 ° C. was 2.5 N / 25 mm or less. The peelability of was good. Therefore, according to the pressure-sensitive adhesive sheets of Examples 1 to 3, it is considered that the adherend could be prevented from being destroyed.
  • Adhesive sheet 11 ... Base material, 12 ... Adhesive layer, 20 ... Frame member, 21 ... Opening

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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) and an adhesive agent layer (12) including an adhesive agent. After attaching the adhesive agent layer (12) of the adhesive sheet (10) to a polyimide film and performing heating at 190°C for 1 hour, the adhesive force with respect to the polyimide film in a 40°C atmosphere is 2.5 N/25 mm or less.

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.
　近年、半導体装置を製造する際に、チップを仮固定するための支持体として、粘着シートが用いられている。このような粘着シートとして、例えば、特許文献１には、金属製のリードフレームを用いない基板レス半導体チップを樹脂封止する際に、粘着して使用される半導体装置製造用耐熱性粘着テープが記載されている。 In recent years, an adhesive sheet has been used as a support for temporarily fixing a chip when manufacturing a semiconductor device. As such a pressure-sensitive adhesive sheet, for example, Patent Document 1 discloses a heat-resistant pressure-sensitive adhesive tape for manufacturing a semiconductor device, which is used when a substrate-less semiconductor chip that does not use a metal lead frame is sealed with a resin. Are listed.
特開２０１２－６２３７２号公報JP 2012-62372 A
　しかしながら、半導体装置の製造方法において、従来（１５０～１８０℃程度）よりも高い温度条件（１８０℃以上）で封止樹脂の熱硬化等のための加熱処理を行った場合、従来の粘着シートでは、加熱処理後に粘着シートを被着体から剥離する際に、被着体が破壊されてしまうという問題があった。この問題は、被着体が、例えば、ウエハレベルパッケージ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ；ＷＬＰ）、およびパネルスケールパッケージ（Ｐａｎｅｌ　Ｓｃａｌｅ　Ｐａｃｋａｇｅ；ＰＳＰ）等の場合に、特に顕著であった。 However, in the manufacturing method of the semiconductor device, when the heat treatment for thermosetting the sealing resin is performed under a temperature condition (180 ° C. or higher) higher than the conventional (about 150 to 180 ° C.), When the pressure-sensitive adhesive sheet is peeled from the adherend after the heat treatment, there has been a problem that the adherend is destroyed. This problem is particularly noticeable when the adherend is, for example, a wafer level package (WLP), a panel scale package (Panel Scale Package; PSP), or the like.
　本発明の目的は、粘着シートを被着体から剥離する際の被着体の破壊を防ぐ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 destruction of the adherend when the pressure-sensitive adhesive sheet is peeled from the adherend.
　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、を有し、前記粘着シートの前記粘着剤層をポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、４０℃雰囲気での前記ポリイミドフィルムに対する粘着力が２．５Ｎ／２５ｍｍ以下である、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, comprising a base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive, wherein the pressure-sensitive adhesive sheet A pressure-sensitive adhesive sheet having an adhesive force of 2.5 N / 25 mm or less in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer is attached to a polyimide film and heated at 190 ° C. for 1 hour is provided.
　本発明の一態様に係る粘着シートは、前記粘着剤層をポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、４０℃雰囲気での前記ポリイミドフィルムに対する粘着力が０．１Ｎ／２５ｍｍ以上であることが好ましい。 The pressure-sensitive adhesive sheet according to one aspect of the present invention has an adhesive force of 0.1 N / 25 mm or more in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer is attached to a polyimide film and heated at 190 ° C. for 1 hour. It is preferable that
　本発明の一態様に係る粘着シートは、前記加熱前の、室温における前記ポリイミドフィルムに対する粘着力が０．１Ｎ／２５ｍｍ以上８．０Ｎ／２５ｍｍ以下であることが好ましい。 The pressure-sensitive adhesive sheet according to one embodiment of the present invention preferably has an adhesive force to the polyimide film at room temperature before the heating of 0.1 N / 25 mm or more and 8.0 N / 25 mm or less.
　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, it is preferable that the acrylic pressure-sensitive adhesive composition contains an acrylic copolymer mainly composed of 2-ethylhexyl acrylate.
　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.
　本発明によれば、粘着シートを被着体から剥離する際の被着体の破壊を防ぐ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 an adhesive sheet that can prevent the adherend from being destroyed when the adhesive sheet is peeled off from the adherend.
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と、粘着剤を含む粘着剤層１２とを有する。
　基材１１は、第一基材面１１ａ、および第一基材面１１ａとは反対側の第二基材面１１ｂを有する。本実施形態の粘着シート１０においては、第一基材面１１ａに粘着剤層１２が積層されている。粘着剤層１２の上には、図１に示されているように、剥離シートＲＬが積層されている。
　粘着シート１０の形状は、例えば、テープ状、およびラベル状等、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 and a pressure sensitive adhesive layer 12 containing a pressure sensitive adhesive.
The base material 11 has the 1st base material surface 11a and the 2nd base material surface 11b on the opposite side to the 1st base material surface 11a. In the adhesive sheet 10 of this embodiment, the adhesive layer 12 is laminated | stacked on the 1st base material surface 11a. On the pressure-sensitive adhesive layer 12, a release sheet RL is laminated as shown in FIG.
The shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a tape shape and a label shape.
（基材）
　基材１１は、粘着剤層１２を支持する部材である。
　基材１１としては、例えば、合成樹脂フィルム等のシート材料等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、およ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.
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、及びトリマー等に由来する。 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 oligomer contained in the polyester film is derived from a polyester-forming monomer, a dimer, a trimer, 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以上であることが好ましく、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、基材１１の１００℃での貯蔵弾性率は、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, 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 addition, in this specification, the storage elastic modulus at 100 degrees C of the base material 11 is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring device. 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.
　基材１１と粘着剤層１２との密着性を高めるために、第一基材面１１ａは、プライマー処理、コロナ処理、およ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、およびウレタン系等の粘着剤が挙げられる。 In order to improve the adhesion between the substrate 11 and the pressure-sensitive adhesive layer 12, 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. 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、およ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、およ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、カルボキシル基およ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、およ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、反応性およ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、および（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、水酸基の反応性およ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」および「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、およ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、およ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、および（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、およ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、および（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、密着性およ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 the adhesion and adhesive force. .
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２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、およ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 contains 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およ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 preferable, and this carboxyl group-containing monomer is preferable. 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（以下、「反応性粘着助剤」ということもある。）またはアセチルクエン酸トリエステル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またはアセチルクエン酸トリエステルを含んでいると、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。
　本明細書において、アセチルクエン酸トリエステルを主成分として含むとは、粘着助剤全体の質量に占めるアセチルクエン酸トリエステルの質量の割合が５０質量％を超えることを意味する。 The adhesion aid preferably contains a rubber-based material having a reactive group (hereinafter sometimes referred to as “reactive adhesion aid”) or acetyl citrate triester as a main component. When the pressure-sensitive adhesive composition contains a reactive adhesion assistant or acetyl citrate triester, 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.
In the present specification, including acetyl citrate triester as a main component means that the ratio of the mass of acetyl citrate triester to the total mass of the adhesion promoter exceeds 50 mass%.
　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、アクリロイル基およ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、およ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－繰り返し単位および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。 Although it does not specifically limit as a rubber-type material, The hydrogenated product of a polybutadiene type resin and a polybutadiene type resin is preferable, and the hydrogenated product of a polybutadiene type 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、およ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、アクリロイル基およ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、およ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.
　本実施形態において、アセチルクエン酸トリエステル系の粘着助剤としては、例えば、アセチルクエン酸トリブチル（ＡＴＢＣ）等が挙げられる。 In this embodiment, examples of the acetylcitrate triester-based adhesion assistant include tributyl acetylcitrate (ATBC).
　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および粘着助剤の他に、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 this 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、およ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、およ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して含有する架橋剤とは、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-based 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 this specification, the crosslinking agent containing a compound having an isocyanate group as a main component 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. means.
　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、およ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、およびヒドロシリル基（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、およ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、およ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. Some of the aforementioned organo groups are 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) Some). 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）、および架橋剤とともに、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、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 above 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, PL-50T manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
　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との合計量に対して、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、粘着力および凝集力（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ＲＬに塗布し、基材１１と剥離シートＲＬ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, an 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 RL described later. After coating and bonding the base material 11 and the release sheet RL, heating or irradiating active energy rays to promote the crosslinking reaction of the silicone resin component and the silicone rubber component with the crosslinking agent can improve the stability of the adhesive force. From the aspect, it is 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て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. Heating at 60 ° C. or higher prevents the silicone resin component and silicone rubber component from being insufficiently cross-linked and prevents the adhesive force from becoming insufficient, and heating at 140 ° C. or lower causes heat shrinkage and wrinkles on the base sheet. 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. Is mentioned.
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て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、架橋不足により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したり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 cross-linked, resulting in insufficient adhesive force. 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. Irradiation with a dose of 1 Mrad or more can prevent the pressure-sensitive adhesive layer and the base sheet from being deteriorated or discolored, and can prevent the adhesiveness from becoming insufficient due to insufficient crosslinking. 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、およ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。 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.
　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。
　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。
　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。
　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。
　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、アセチルクエン酸トリブチル（ＡＴＢＣ）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。
　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。 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.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer. And an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer, wherein the tackifier includes a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent. An adhesive composition is mentioned.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer. And an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer, the pressure-sensitive adhesive composition in which the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both terminals, and the cross-linking agent is an isocyanate-based cross-linking agent. Can be mentioned.
As an example of the pressure-sensitive adhesive composition according to this 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 acrylic. An acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the tackifier includes a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent. A certain adhesive composition is mentioned.
As an example of the pressure-sensitive adhesive composition according to this 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 acrylic. A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, 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 Is mentioned.
As an example of the pressure-sensitive adhesive composition according to this 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 acrylic. A pressure-sensitive adhesive composition, which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the pressure-sensitive adhesive aid is tributyl acetylcitrate (ATBC), and the cross-linking agent is an isocyanate-based cross-linking agent Things.
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.
（剥離シート）
　剥離シートＲＬ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ＲＬ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ＲＬ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、およ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、およ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、およ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、および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、並びにシリコーン系樹脂等が挙げられる。 (Peeling sheet)
The release sheet RL is not particularly limited. For example, from the viewpoint of ease of handling, the release sheet RL preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate. Moreover, the release sheet RL may include a release agent layer only on one side of the release substrate, or may include 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-based resins, rubber-based elastomers (for example, butadiene-based resins and isoprene-based resins), long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and silicone-based resins. .
　剥離シートＲＬの厚みは、特に限定されない。剥離シートＲＬ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 RL is not particularly limited. The thickness of the release sheet RL is usually 20 μm or more and 200 μm or less, and preferably 25 μm or more and 150 μm or less.
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.
　本実施形態に係る粘着シート１０は、粘着剤層１２をポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、４０℃雰囲気での前記ポリイミドフィルムに対する粘着力（以下、「加熱後の４０℃雰囲気での粘着力」ということもある）が２．５Ｎ／２５ｍｍ以下である。
　なお、本明細書において、粘着力は、１８０°引き剥がし法により、剥離速度（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 the present embodiment has a pressure-sensitive adhesive force (hereinafter referred to as “40 after heating”) on the polyimide film in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer 12 is attached to the polyimide film and heated at 190 ° C. for 1 hour. Is sometimes referred to as "adhesive strength in an atmosphere of ° C") of 2.5 N / 25 mm or less.
In the present specification, the adhesive strength is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the adhesive sheet of 25 mm.
　前記条件下での粘着シート１０の粘着力（加熱後の４０℃雰囲気での粘着力）が２．５Ｎ／２５ｍｍ以下であると、加熱によって粘着シート１０及びパッケージが膨張することがなく、粘着シート１０とパッケージの間にせん断力が生じることもない。そのため、粘着シート１０を剥離する際に不具合が発生することもない。前記条件下での粘着シート１０の粘着力（加熱後の４０℃雰囲気での粘着力）は、好ましくは２．０Ｎ／２５ｍｍ以下であり、より好ましくは１．５Ｎ／２５ｍｍ以下である。
　前記条件下での粘着シート１０の粘着力（加熱後の４０℃雰囲気での粘着力）の下限値は、加熱によって基材１１または被着体が変形した場合に、粘着シート１０が被着体から剥がれ落ちることを防止する観点から、０．１Ｎ／２５ｍｍ以上であることが好ましい。前記条件下での粘着シート１０の粘着力（加熱後の４０℃雰囲気での粘着力）が０．１Ｎ／２５ｍｍ以上であれば、パッケージを破壊する恐れもない。
　また、被着体の被着面のサイズが、例えば４００ｍｍ×５００ｍｍ以上である場合（例えば、ＰＳＰのパッケージ等）には、前記条件下での粘着シート１０の粘着力（加熱後の４０℃雰囲気での粘着力）の下限値は、０．４Ｎ／２５ｍｍ以上であることがより好ましく、０．６Ｎ／２５ｍｍ以上であることがさらに好ましい。 When the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet 10 under the above conditions (pressure-sensitive adhesive strength in a 40 ° C. atmosphere after heating) is 2.5 N / 25 mm or less, the pressure-sensitive adhesive sheet 10 and the package are not expanded by heating, and the pressure-sensitive adhesive sheet There is no shearing force between 10 and the package. Therefore, no trouble occurs when the pressure-sensitive adhesive sheet 10 is peeled off. The adhesive strength of the pressure-sensitive adhesive sheet 10 under the above conditions (adhesive strength in a 40 ° C. atmosphere after heating) is preferably 2.0 N / 25 mm or less, more preferably 1.5 N / 25 mm or less.
The lower limit of the adhesive strength of the adhesive sheet 10 under the above conditions (adhesive strength in a 40 ° C. atmosphere after heating) is that the adhesive sheet 10 adheres when the substrate 11 or the adherend is deformed by heating. From the viewpoint of preventing the film from peeling off, it is preferably 0.1 N / 25 mm or more. If the adhesive strength of the pressure-sensitive adhesive sheet 10 under the above conditions (adhesive strength in a 40 ° C. atmosphere after heating) is 0.1 N / 25 mm or more, there is no possibility of destroying the package.
Moreover, when the size of the adherend surface of the adherend is, for example, 400 mm × 500 mm or more (for example, a PSP package), the adhesive strength of the adhesive sheet 10 under the above conditions (40 ° C. atmosphere after heating) The lower limit of (adhesive strength) is more preferably 0.4 N / 25 mm or more, and further preferably 0.6 N / 25 mm or more.
　また、粘着シート１０は、粘着剤層１２をポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、室温における前記ポリイミドフィルムに対する粘着力（以下、「加熱後の室温における粘着力」と言うこともある）が０．４Ｎ／２５ｍｍ以上１０．０Ｎ／２５ｍｍ以下であることが好ましく、１．１Ｎ／２５ｍｍ以上８．０Ｎ／２５ｍｍ以下であることがより好ましい。
　粘着シート１０の加熱後の室温における粘着力が、上記範囲の粘着力であれば、粘着シート１０は、加熱後の室温においては基材１１または被着体から剥がれ落ちることがなく、剥離時には、加熱することで容易に剥離することができる。 Moreover, the adhesive sheet 10 says the adhesive force with respect to the said polyimide film in the room temperature after sticking the adhesive layer 12 to a polyimide film, and heating at 190 degreeC for 1 hour (henceforth "the adhesive force in the room temperature after a heating"). May be 0.4 N / 25 mm or more and 10.0 N / 25 mm or less, and more preferably 1.1 N / 25 mm or more and 8.0 N / 25 mm or less.
If the adhesive strength at room temperature after heating of the adhesive sheet 10 is in the above range, the adhesive sheet 10 does not peel off from the substrate 11 or the adherend at room temperature after heating. It can be easily peeled off by heating.
　また、粘着シート１０は、製造プロセスの途中で意図せずシートが剥がれ落ちることを防止する観点から、加熱前の、室温における前記ポリイミドフィルムに対する粘着力が０．１Ｎ／２５ｍｍ以上８．０Ｎ／２５ｍｍ以下であることが好ましい。
　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、剥離速度（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。 In addition, the adhesive sheet 10 has an adhesive force with respect to the polyimide film at room temperature before heating of 0.1 N / 25 mm or more and 8.0 N / 25 mm before heating from the viewpoint of preventing the sheet from unintentionally peeling off during the manufacturing process. The following is preferable.
In this specification, the room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower. In this specification, the adhesive force is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the adhesive sheet of 25 mm.
（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。その後、粘着剤層１２を覆うように剥離シートＲＬを貼着する。
　また、粘着シート１０の別の製造方法としては、次のような工程を経て製造される。まず、剥離シートＲＬ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を形成し、この粘着剤層１２に基材１１の第一基材面１１ａを貼り合わせる。 (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 pressure-sensitive adhesive composition is applied on the first base material surface 11a of the base material 11 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12. Then, release sheet RL is stuck so that adhesive layer 12 may be covered.
Moreover, as another manufacturing method of the adhesive sheet 10, it manufactures through the following processes. First, an adhesive composition is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12, and the first base material surface 11 a of the base material 11 is bonded to the pressure-sensitive adhesive layer 12.
　粘着剤組成物を塗布して粘着剤層１２を形成する場合、有機溶媒で粘着剤組成物を希釈してコーティング液（塗布用粘着剤液）を調製して用いることが好ましい。有機溶媒としては、例えば、トルエン、酢酸エチル、およびメチルエチルケトン等が挙げられる。コーティング液を塗布する方法は、特に限定されない。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、およ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または剥離シートＲＬ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 pressure-sensitive adhesive composition is applied to form the pressure-sensitive adhesive layer 12, it is preferable to prepare and use a coating liquid (pressure-sensitive adhesive liquid for application) by diluting the pressure-sensitive adhesive composition with an organic solvent. Examples of the organic solvent include toluene, ethyl acetate, and methyl ethyl ketone. The method for applying the coating liquid is not particularly limited. 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 point component from remaining in the pressure-sensitive adhesive layer 12, it is preferable to apply the coating liquid to the substrate 11 or the release sheet RL, 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、ＰＳＰ及びＷＬＰが挙げられる。
　本実施形態に係る粘着シート１０は、加熱後の４０℃雰囲気での粘着力が２．５Ｎ／２５ｍｍ以下であることから、比較的大きな被着体であっても容易に剥離することができる。そのため、粘着シート１０は、パネルスケールパッケージに好ましく用いられる。
　パネルスケールパッケージのパネルとしては、例えば、平面視で円形、楕円形、および四角形等のパネルが挙げられる。例えば、パネルが円形である場合には、直径２００ｍｍ以上４５０ｍｍ以下程度のサイズであることが好ましい。また例えば、パネルが四角形の場合には、各々の辺が３００ｍｍ以上８００ｍｍ以下程度のサイズであることが好ましい。パネルが上記のサイズであれば、被着体から粘着シート１０を剥離する際に、良好に剥離することができる。 (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. PSP and WLP are mentioned as a form which packages a semiconductor element without using a metal lead frame.
Since the pressure-sensitive adhesive sheet 10 according to this embodiment has a pressure-sensitive adhesive strength in a 40 ° C. atmosphere after heating of 2.5 N / 25 mm or less, even a relatively large adherend can be easily peeled off. Therefore, the adhesive sheet 10 is preferably used for a panel scale package.
Examples of the panel of the panel scale package include circular, oval, and quadrangular panels in plan view. For example, when the panel is circular, the diameter is preferably about 200 mm to 450 mm. For example, when the panel is a quadrangle, each side is preferably about 300 mm to 800 mm in size. If a panel is said size, when peeling the adhesive sheet 10 from a to-be-adhered body, it can peel favorably.
（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、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.
Hereinafter, each step will be described.
・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。なお、粘着シート１０に剥離シートＲＬが貼着されている場合には、予め剥離シートＲＬを剥離する。
　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等が挙げられる。
　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. In addition, when peeling sheet RL is affixed on the adhesive sheet 10, peeling sheet RL is peeled previously.
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 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、ダイシングソー等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等を用いてもよい。 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, a stealth dicing method, or the like 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 or the adhesive layer of the dicing sheet, 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.
・封止工程および熱硬化工程
　図２Ｃには、粘着シート１０に貼着された半導体チップＣＰおよび枠部材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、エポキシ樹脂等が挙げられる。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、および硬化促進剤等が含まれていてもよい。
　封止樹脂３０で半導体チップＣＰおよび枠部材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および枠部材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および枠部材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および枠部材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硬化の温度条件範囲は、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 semiconductor chip CP and frame member 20 which were stuck to 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-like 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 heat curing 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および枠部材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 heat-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および枠部材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および枠部材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、加熱および圧力の条件は、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 molding 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および枠部材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、およ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。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。 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 between the plate-like 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. As the plate member, for example, a metal plate such as stainless steel can be used.
　熱硬化工程の後、粘着シート１０を４０℃の雰囲気下で剥離すると、封止樹脂３０で封止された半導体チップＣＰおよび枠部材２０が得られる。以下、これを封止体５０と称する場合がある。 After the thermosetting step, the pressure-sensitive adhesive sheet 10 is peeled off at 40 ° C., whereby 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および封止樹脂層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側および粘着シート１０側からそれぞれ板状部材で挟み込み、所定の温度、時間、およ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とを所定の温度およ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 by plate members from the reinforcing plate 41 side and the adhesive sheet 10 side, respectively. It is preferable to carry out a 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および封止樹脂層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および封止樹脂層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および封止樹脂層３０Ａにかかる負荷を低減しながら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および封止樹脂層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. If 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 the adhesive sheet 10 while bending the 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 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、粘着シートを被着体から剥離する際の被着体の破壊を防ぐことができる粘着シート１０を提供できる。 According to the present embodiment, it is possible to provide the pressure-sensitive adhesive sheet 10 that can prevent the adherend from being destroyed when the pressure-sensitive adhesive sheet is peeled from the adherend.
〔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.
　前記実施形態では、粘着シート１０の粘着剤層１２が剥離シートＲＬによって覆われてい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。
　また、粘着シート１０は、枚葉であってもよく、複数枚の粘着シート１０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１２は、積層される別の粘着シートの基材１１によって覆われていてもよい。
　また、粘着シート１０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１０は、ロールから繰り出されて所望のサイズに切断する等して使用することができる。 In the said embodiment, although the aspect in which the adhesive layer 12 of the adhesive sheet 10 was covered with the peeling sheet RL was mentioned as an example, this invention is not limited to such an aspect.
Moreover, the adhesive sheet 10 may be a single wafer or may be provided in a state where a plurality of adhesive sheets 10 are laminated. In this case, for example, the pressure-sensitive adhesive layer 12 may be covered with the base material 11 of another pressure-sensitive adhesive sheet to be laminated.
Moreover, the adhesive sheet 10 may be a long sheet or may be provided in a state of being wound in a roll. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
　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.
　前記実施形態において、半導体チップＣＰの回路面には、ポリイミド樹脂等のパッシベーション膜が設けられていてもよい。半導体チップＣＰの回路面にパッシベーション膜が設けられていると、粘着シート１０を剥離する際により剥離しやすい。 In the embodiment described above, a passivation film such as polyimide resin may be provided on the circuit surface of the semiconductor chip CP. When the passivation film is provided on the circuit surface of the semiconductor chip CP, the adhesive sheet 10 is more easily peeled off.
　粘着シート１０を剥離する際には、封止体５０を吸着テーブル等の吸着手段にて保持させてもよい。粘着シート１０であれば、封止体５０を破壊せずに剥離することができ、封止体５０を吸着テーブルから動かないようにして剥離することができる。 When the pressure-sensitive adhesive sheet 10 is peeled off, the sealing body 50 may be held by suction means such as a suction table. If it is the adhesive sheet 10, it can peel without destroying the sealing body 50, and it can peel, without moving the sealing body 50 from an adsorption | suction table.
　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.
＜易剥離性＞
［初期粘着力］
　実施例１～３で作製した粘着シートを２５ｍｍ幅に切断し、切断した粘着シートの粘着面を、被着体（ポリイミドフィルム）に貼付した。ポリイミドフィルムとしては、東レ・デュポン（株）製の厚さ２５μｍのカプトン１００Ｈ（製品名）を用いた。
　このポリイミドフィルム付き粘着シートを、剥離角度を１８０°とし、剥離速度（引っ張り速度）を３００ｍｍ／ｍｉｎとし、恒温槽付測定機（Ａ＆Ｄ社製　ＴＥＮＳＩＬＯＮ）を用いて、室温で粘着シートをポリイミドフィルムから剥離した際の粘着力を測定した。 <Easily peelable>
[Initial adhesive strength]
The pressure-sensitive adhesive sheets prepared in Examples 1 to 3 were cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (polyimide film). As the polyimide film, Kapton 100H (product name) having a thickness of 25 μm manufactured by Toray DuPont Co., Ltd. was used.
Using this pressure-sensitive adhesive sheet with a polyimide film, the peeling angle is 180 °, the peeling speed (pulling speed) is 300 mm / min, and the measuring instrument with a thermostat (TENSILON manufactured by A & D) is used to remove the pressure-sensitive adhesive sheet from the polyimide film at room temperature. The adhesive strength at the time of peeling was measured.
［加熱後の粘着力］
　実施例１～３で作製した粘着シートを２５ｍｍ幅に切断し、切断した粘着シートの粘着面を、被着体（ポリイミドフィルム）に貼付した。ポリイミドフィルムとしては、東レ・デュポン（株）製の厚さ２５μｍのカプトン１００Ｈ（製品名）を用いた。
　このポリイミドフィルム付き粘着シートを、恒温槽付測定機（Ａ＆Ｄ社製　ＴＥＮＳＩＬＯＮ）を用いて、１９０℃および１時間の条件で加熱した。加熱後、剥離角度を１８０°とし、剥離速度を３００ｍｍ／ｍｉｎとし、室温および４０℃雰囲気下で、粘着シートをポリイミドフィルムから剥離した際の、粘着シートの加熱後の粘着力を測定した。 [Adhesive strength after heating]
The pressure-sensitive adhesive sheets prepared in Examples 1 to 3 were cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (polyimide film). As the polyimide film, Kapton 100H (product name) having a thickness of 25 μm manufactured by Toray DuPont Co., Ltd. was used.
This pressure-sensitive adhesive sheet with a polyimide film was heated under conditions of 190 ° C. and 1 hour using a thermostatic measuring instrument (TENSILON manufactured by A & D). After heating, the peel angle was 180 °, the peel rate was 300 mm / min, and the pressure-sensitive adhesive force after heating of the pressure-sensitive adhesive sheet was measured when the pressure-sensitive adhesive sheet was peeled from the polyimide film at room temperature and 40 ° C. atmosphere.
［工程適正］
　実施例１～３で作製した粘着シートを２５ｍｍ幅に切断し、切断した粘着シートの粘着面を、被着体（半導体ウェハ；直径１５０ｍｍ、厚さ２００μｍ）に貼付した。
　半導体ウェハに貼付した粘着シートを、恒温槽付測定機（Ａ＆Ｄ社製　ＴＥＮＳＩＬＯＮ）を用いて、１９０℃および１時間の条件で加熱した。加熱後、剥離角度を１８０°とし、剥離速度を３００ｍｍ／ｍｉｎとし、４０℃雰囲気下で、粘着シートを半導体ウェハから剥離した。粘着シートを剥離した後の半導体ウェハを目視にて観察し、ウェハが破壊されていない場合をＡ、ウェハが破壊されている場合をＢとした。 [Process suitability]
The pressure-sensitive adhesive sheets prepared in Examples 1 to 3 were cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (semiconductor wafer; diameter 150 mm, thickness 200 μm).
The pressure-sensitive adhesive sheet affixed to the semiconductor wafer was heated under conditions of 190 ° C. and 1 hour using a thermostatic measuring instrument (TENSILON manufactured by A & D). After the heating, the pressure-sensitive adhesive sheet was peeled from the semiconductor wafer in a 40 ° C. atmosphere at a peeling angle of 180 °, a peeling speed of 300 mm / min. The semiconductor wafer after peeling the adhesive sheet was visually observed, and the case where the wafer was not destroyed was designated as A, and the case where the wafer was destroyed was designated as B.
〔粘着シートの作製〕
（実施例１） [Preparation of adhesive sheet]
Example 1
　（１）粘着剤組成物の調製
　以下の材料（ポリマー、粘着助剤、架橋剤、および希釈溶剤）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。 (1) Preparation of pressure-sensitive adhesive composition The following materials (polymer, pressure-sensitive adhesive, cross-linking agent, and diluting 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：アセチルクエン酸トリブチル（ＡＴＢＣ）〔田岡化学工業（株）製〕、５質量部（固形分） Adhesion aid: tributyl acetyl citrate (ATBC) [manufactured by Taoka Chemical Co., Ltd.], 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.
（２）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）を用いて乾燥後の厚さが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からなる剥離フィルム〔リンテック（株）製；ＳＰ－ＰＥＴ３８２１５０〕の剥離層面側に塗布し、９０℃および９０秒間の加熱を行い、続いて１１５℃および９０秒間の加熱を行い、塗膜を乾燥させて、粘着剤層を作製した。 (2) Preparation of pressure-sensitive adhesive layer 38 μm transparent polyethylene terephthalate provided with a silicone release layer so that the thickness of the prepared pressure-sensitive adhesive liquid for coating after drying using a comma coater (registered trademark) is 50 μm. It is applied to the release layer side of a release film consisting of a 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. To produce a pressure-sensitive adhesive layer.
（３）粘着シートの作製
　塗布用粘着剤液の塗膜を乾燥させた後、粘着剤層と、基材とを貼り合わせて、実施例１に係る粘着シートを得た。なお、基材として、透明ポリエチレンテレフタレートフィルム〔帝人デュポンフィルム（株）製；ＰＥＴ５０ＫＦＬ１２Ｄ、厚さ５０μｍ、１００℃における貯蔵弾性率３．１×１０９Ｐａ〕を用い、基材の易接着面に粘着剤層を貼り合わせた。 (3) Preparation of pressure-sensitive adhesive sheet After the coating film of the pressure-sensitive adhesive liquid for application was dried, the pressure-sensitive adhesive layer and the substrate were bonded together to obtain a pressure-sensitive adhesive sheet according to Example 1. In addition, a transparent polyethylene terephthalate film [manufactured by Teijin DuPont Films; PET 50KFL12D, thickness 50 μm, storage elastic modulus 3.1 × 10 9 Pa at 100 ° C.] is used as the base material, and it adheres to the easily adhesive surface of the base material. The agent layer was bonded.
（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粘着助剤として、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）を用いたこと以外は、実施例１と同様に作製した。 (Example 2)
The pressure-sensitive adhesive sheet according to Example 2 used 5 parts by mass (solid content) of a hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000) as a pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer. Other than that, it was produced in the same manner as in Example 1.
（実施例３）
　実施例３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２と異なること以外は、実施例２と同様に作製した。
　実施例３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、Ｎ－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 3)
The pressure-sensitive adhesive sheet according to Example 3 was produced in the same manner as in Example 2 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 2.
The polymer used in Example 3 was composed of 80.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, 12% by mass of N-acryloylmorpholine, and 0.2% by mass of acrylic acid. Prepared by copolymerization.
　表１に、実施例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 Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～３に係る粘着シートは、ポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、４０℃雰囲気でのポリイミドフィルムに対する粘着力が２．５Ｎ／２５ｍｍ以下であったため、加熱後の剥離性が良好であった。そのため、実施例１～３の粘着シートによれば、被着体の破壊を防止することができたと考えられる。 The adhesive sheets according to Examples 1 to 3 were adhered to the polyimide film and heated at 190 ° C. for 1 hour, and the adhesive strength against the polyimide film at 40 ° C. was 2.5 N / 25 mm or less. The peelability of was good. Therefore, according to the pressure-sensitive adhesive sheets of Examples 1 to 3, it is considered that the adherend could be prevented from being destroyed.
　１０…粘着シート、１１…基材、１２…粘着剤層、２０…枠部材、２１…開口部 10 ... Adhesive sheet, 11 ... Base material, 12 ... Adhesive layer, 20 ... Frame member, 21 ... Opening

Claims (7)

  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、を有し、
    　前記粘着シートの前記粘着剤層をポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、４０℃雰囲気での前記ポリイミドフィルムに対する粘着力が２．５Ｎ／２５ｍｍ以下である、
    　粘着シート。     A pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet,
    A substrate and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive,
    After the adhesive layer of the adhesive sheet is attached to a polyimide film and heated at 190 ° C. for 1 hour, the adhesive force to the polyimide film in a 40 ° C. atmosphere is 2.5 N / 25 mm or less.
    Adhesive sheet.
  2. 　前記粘着シートは、前記粘着剤層をポリイミドフィルムに貼付して１９０℃で１時間加熱した後の、４０℃雰囲気での前記ポリイミドフィルムに対する粘着力が０．１Ｎ／２５ｍｍ以上である、
    　請求項１に記載の粘着シート。     The pressure-sensitive adhesive sheet has a pressure-sensitive adhesive force of 0.1 N / 25 mm or more in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer is attached to a polyimide film and heated at 190 ° C. for 1 hour.
    The pressure-sensitive adhesive sheet according to claim 1.
  3. 　前記粘着シートは、前記加熱前の、室温における前記ポリイミドフィルムに対する粘着力が０．１Ｎ／２５ｍｍ以上８．０Ｎ／２５ｍｍ以下である、
    　請求項１または請求項２に記載の粘着シート。     The adhesive sheet has an adhesive force with respect to the polyimide film at room temperature before the heating is 0.1 N / 25 mm or more and 8.0 N / 25 mm or less.
    The pressure-sensitive adhesive sheet according to claim 1 or 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１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１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 mainly composed of 2-ethylhexyl acrylate.
    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.
PCT/JP2016/075606 2015-09-01 2016-09-01 Adhesive sheet WO2017038919A1 (en)

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