WO2018158858A1 - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
WO2018158858A1
WO2018158858A1 PCT/JP2017/007979 JP2017007979W WO2018158858A1 WO 2018158858 A1 WO2018158858 A1 WO 2018158858A1 JP 2017007979 W JP2017007979 W JP 2017007979W WO 2018158858 A1 WO2018158858 A1 WO 2018158858A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
mass
acrylic
Prior art date
Application number
PCT/JP2017/007979
Other languages
French (fr)
Japanese (ja)
Inventor
高野　健
和浩 菊池
泰紀 柄澤
恵美 淵
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2017541407A priority Critical patent/JP6220488B1/en
Priority to KR1020197022476A priority patent/KR102661574B1/en
Priority to PCT/JP2017/007979 priority patent/WO2018158858A1/en
Priority to CN201780087025.1A priority patent/CN110383438B/en
Priority to TW106136619A priority patent/TWI813547B/en
Publication of WO2018158858A1 publication Critical patent/WO2018158858A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an adhesive sheet.
  • chip size package (CSP) technology has attracted attention as a mounting technology.
  • CSP chip size package
  • WLP wafer level package
  • a chip to be fixed on a substrate needs to be fixed on another support. Therefore, for example, when manufacturing a semiconductor device, an adhesive sheet is used as a support for temporarily fixing a chip (Patent Document 1 and Patent Document 2).
  • the circuit surface of the semiconductor element is fixed to the adhesive layer of the adhesive sheet.
  • On the circuit surface of the semiconductor element there is a stepped portion such as a dicing line at the periphery of the semiconductor element.
  • sealing resin embeds the clearance gap between a level
  • the sealing resin cannot fill the gap between the stepped portion and the pressure-sensitive adhesive layer, and a void is formed. If such a gap is formed, the smoothness of the circuit surface of the semiconductor element becomes insufficient, and a problem may occur when forming a pattern on the circuit surface. Therefore, the adhesive sheet is required to have a property that the sealing resin can easily fill the gap between the stepped portion and the adhesive layer (hereinafter sometimes referred to as “filling property”).
  • An object of the present invention is to provide a pressure-sensitive adhesive sheet that can achieve both resin leakage prevention and filling properties when a semiconductor element on a pressure-sensitive adhesive sheet is sealed.
  • the present invention is a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet
  • the pressure-sensitive adhesive sheet includes a base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition.
  • the surface free energy of the pressure-sensitive adhesive layer has a 10 mJ / m 2 or more 22 mJ / m 2 or less, and a storage modulus at 100 ° C. of the pressure-sensitive adhesive layer a (Pa), the thickness of the pressure-sensitive adhesive layer B
  • a pressure-sensitive adhesive sheet having a numerical value calculated by the following relational expression (1) of 1.5 ⁇ 10 ⁇ 5 or more is provided.
  • the contact angle of 1-bromonaphthalene with respect to the pressure-sensitive adhesive layer is preferably 65 ° or more.
  • the numerical value calculated by the following relational expression (2) is preferably 1.5 ⁇ 10 ⁇ 10 or more.
  • the storage elastic modulus of the substrate at 100 ° C. is preferably 1 ⁇ 10 7 Pa or more.
  • the pressure-sensitive adhesive layer is preferably made of an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive layer is preferably made of an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer.
  • the proportion of the mass of the copolymer component derived from the (meth) acrylic acid alkyl ester in the total mass of the acrylic copolymer is 90% by mass or more. Is preferred.
  • the alkyl of the (meth) acrylic acid alkyl ester preferably has 6 to 8 carbon atoms.
  • the acrylic copolymer preferably includes an acrylic copolymer containing 2-ethyl hexyl (meth) acrylate as a main monomer.
  • the acrylic copolymer preferably includes a copolymer component derived from a monomer having a hydroxyl group.
  • the ratio of the copolymer component derived from the monomer having a hydroxyl group in the mass of the entire acrylic copolymer is preferably 3% by mass or more.
  • the acrylic copolymer does not include a copolymer component derived from a monomer having a carboxyl group, or includes a copolymer component derived from a monomer having a carboxyl group. And it is preferable that the ratio of the mass of the copolymer component derived from the monomer which has the said carboxyl group to the mass of the said whole acrylic copolymer is 1 mass% or less.
  • the acrylic pressure-sensitive adhesive composition preferably contains a pressure-sensitive adhesive auxiliary containing an oligomer having a hydrocarbon skeleton.
  • the pressure-sensitive adhesive layer is made of a silicone-based pressure-sensitive adhesive composition, and the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
  • FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
  • the pressure-sensitive adhesive sheet 10 has a base material 11 and a pressure-sensitive adhesive layer 12 containing a pressure-sensitive adhesive composition.
  • the base material 11 has a first base material surface 11a and a second base material surface 11b opposite to the first base material surface 11a.
  • 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 surface free energy of the pressure-sensitive adhesive layer 12 is at 10 mJ / m 2 or more 22 mJ / m 2 or less, and a storage modulus at 100 ° C. of the pressure-sensitive adhesive layer 12 A (Pa )
  • the numerical value calculated by the following relational expression (1) needs to be 1.5 ⁇ 10 ⁇ 5 or more.
  • the surface free energy of the pressure-sensitive adhesive layer 12 is 10 mJ / m 2 or more 22 mJ / m 2 or less, excellent semiconductor device on the adhesive sheet 10 to the filling of the time of sealing, sealing the semiconductor elements on the adhesive sheet 10
  • the sealing resin can fill the gap between the step portion of the semiconductor element and the pressure-sensitive adhesive layer.
  • the numerical value calculated by the relational expression (1) is 1.5 ⁇ 10 ⁇ 5 or more, when the pressure-sensitive adhesive sheet of this embodiment is used as a support when sealing a semiconductor chip, Resin leakage can be prevented.
  • the surface free energy of the pressure-sensitive adhesive layer 12 can be measured by the following method. Specifically, first, contact angles of water, diiodomethane, and 1-bromonaphthalene with respect to the pressure-sensitive adhesive layer 12 are measured using a contact angle measuring device (“DM701” manufactured by Kyowa Interface Science Co., Ltd.). The amount of each droplet is 2 ⁇ L. From these measured values, the surface free energy can be calculated by the Kitazaki-Hatabe method.
  • the storage elastic modulus of the pressure-sensitive adhesive layer is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring device.
  • the surface free energy of the pressure-sensitive adhesive layer is more preferably 12 mJ / m 2 or more and 21.5 mJ / m 2 or less.
  • the contact angle of 1-bromonaphthalene is preferably 65 ° or more, preferably 67 ° or more, and more preferably 68 ° or more.
  • the upper limit of the contact angle of 1-bromonaphthalene is preferably 75 ° or less, and more preferably 72 ° or less.
  • the following methods are mentioned as a method of adjusting the value of these surface free energy and a contact angle.
  • the values of the surface free energy and the contact angle can be adjusted by changing the composition of the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive layer 12.
  • the numerical value calculated by the relational expression (1) is preferably 2.0 ⁇ 10 ⁇ 5 or more, more preferably 5.0 ⁇ 10 ⁇ 5 or more.
  • the upper limit of the numerical value calculated by the relational expression (1) is not particularly limited.
  • the pressure-sensitive adhesive sheet is preferably 1.0 ⁇ 10 ⁇ 2 or less because the pressure-sensitive adhesive sheet can be easily produced at low cost.
  • the pressure-sensitive adhesive sheet 10 preferably has a numerical value calculated by the following relational expression (2) of 1.5 ⁇ 10 ⁇ 10 or more, more preferably 5.0 ⁇ 10 ⁇ 10 or more, and still more preferably 1. It is 0 ⁇ 10 ⁇ 9 or more.
  • the pressure-sensitive adhesive sheet 10 preferably exhibits the following pressure-sensitive adhesive strength after heating.
  • the pressure-sensitive adhesive sheet 10 is adhered to an adherend (copper foil or polyimide film), heated at 100 ° C. and 30 minutes, subsequently heated at 180 ° C. and 30 minutes, and further at 190 ° C. and 1 ° C.
  • the adhesive strength of the adhesive layer 12 to the copper foil at room temperature and the adhesive strength of the adhesive layer 12 to the polyimide film at room temperature are 0.7 N / 25 mm or more and 2.0 N / 25 mm, respectively. The following is preferable.
  • the adhesive sheet 10 can be prevented from peeling off from the adherend when the substrate or the adherend is deformed by heating. Moreover, if the adhesive force after performing the above-mentioned heating is 2.0 N / 25 mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body.
  • room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower.
  • the adhesive strength is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the pressure sensitive adhesive sheet of 25 mm, specifically, the method described in the examples. Measured in
  • 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 proportion of the mass of the polyester-based resin in the entire material constituting the base material 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.
  • 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 of the tensile elastic modulus measured at a frequency of 1 Hz using a 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. Measure.
  • 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 adhesive material is apply
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate 11 include pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, 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 a rubber adhesive, an acrylic adhesive, a silicone adhesive, a polyester adhesive, and a urethane adhesive.
  • 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 is preferably made of an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition, and more preferably made of an acrylic pressure-sensitive adhesive composition. When the pressure-sensitive adhesive layer 12 is made of an acrylic pressure-sensitive adhesive composition, the pressure-sensitive adhesive (so-called adhesive residue) remaining on the surface of the adherend when the pressure-sensitive adhesive sheet 10 is peeled from the adherend can be reduced. .
  • an acrylic adhesive composition contains an acrylic copolymer.
  • a part or all of the alkyl acrylate ester (CH 2 ⁇ CR 1 COOR 2 ) has an alkyl group R 2 having 6 to 8 carbon atoms (meta )
  • Acrylic acid alkyl ester is preferred.
  • (meth) acrylic acid alkyl esters in which the alkyl group R 2 has 6 to 8 carbon atoms include n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Isooctyl acrylate, n-octyl (meth) acrylate, and the like.
  • R 2 is an alkyl group of straight or branched chain.
  • the alkyl group R 2 preferably has 8 carbon atoms, more preferably 2-ethylhexyl (meth) acrylate, and more preferably 2-ethylhexyl acrylate.
  • the acrylic copolymer preferably includes an acrylic copolymer containing 2-ethylhexyl (meth) acrylate as a main monomer.
  • the main monomer is 2-ethylhexyl (meth) acrylate
  • the ratio of the weight of the copolymer component derived from 2-ethylhexyl (meth) acrylate to the total weight of the acrylic copolymer is It means 50% by mass or more.
  • Examples of the (meth) acrylic acid alkyl ester in which the alkyl group R 2 has 1 to 5 or 9 to 20 carbon atoms include, for example, methyl (meth) acrylate, (meth) acrylic Ethyl acetate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, (meth) acrylic Examples include myristyl acid, palmityl (meth) acrylate, and stearyl (meth) acrylate.
  • the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
  • “(meth) acrylic acid” is a notation used to represent both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the first copolymer component in the acrylic copolymer is a (meth) acrylic acid alkyl ester
  • a copolymer component other than the (meth) acrylic acid alkyl ester in the acrylic copolymer hereinafter referred to as “th”
  • the type and number of “second copolymer component” are not particularly limited.
  • the second copolymer component 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.
  • the reactive functional group include a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group.
  • 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. Examples include acids.
  • 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.
  • hydroxyl group-containing monomer examples include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 3- And (meth) acrylic acid hydroxyalkyl esters such as hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 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.
  • Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
  • the second copolymer component in the acrylic copolymer in addition to the above, for example, an alkoxyalkyl group-containing (meth) acrylic acid ester, a (meth) acrylic acid ester having an aromatic ring, non-crosslinkable acrylamide And a copolymer component derived from at least one monomer selected from the group consisting of (meth) acrylic acid ester having a non-crosslinkable tertiary amino group, vinyl acetate, and styrene.
  • alkoxyalkyl group-containing (meth) acrylic acid ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. It is done.
  • examples of the (meth) acrylic acid ester having an aromatic ring include phenyl (meth) acrylate.
  • 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). And propyl. These monomers may be used independently and may be used in combination of 2 or more type.
  • the acrylic copolymer preferably includes a copolymer component derived from a monomer having a hydroxyl group.
  • the acrylic copolymer contains a copolymer component derived from a monomer having a hydroxyl group, when a crosslinking agent described later is used, the crosslinking density with the hydroxyl group as a crosslinking point can be increased. This is effective in preventing chip displacement.
  • the ratio of the mass of the copolymer component derived from the monomer having a hydroxyl group to the total mass of the acrylic copolymer is preferably 3% by mass or more.
  • the proportion of the mass of the copolymer component derived from the hydroxyl group-containing monomer is 3% by mass or more, resin leakage can be more effectively prevented.
  • the ratio of the mass of the copolymer component derived from the monomer having a hydroxyl group to the total mass of the acrylic copolymer is preferably 9.9% by mass or less.
  • the acrylic copolymer preferably does not contain a copolymer component derived from a monomer having a carboxyl group.
  • the acrylic copolymer includes a copolymer component derived from a monomer having a carboxyl group, and the copolymer component derived from the monomer having a carboxyl group occupies the mass of the entire acrylic copolymer.
  • the mass ratio is preferably 1% by mass or less, and more preferably 0.05% by mass or more and 1% by mass or less.
  • 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.
  • the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, the pressure-sensitive adhesive sheet can be peeled without a residue of pressure-sensitive adhesive on the adherend. If the weight average molecular weight Mw of an acrylic copolymer is 2 million or less, an adhesive sheet can be reliably affixed on a to-be-adhered body.
  • the weight average molecular weight (Mw) of the acrylic copolymer is a standard polystyrene conversion 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 may be any of a block copolymer, a random copolymer, or a graft copolymer.
  • the proportion of the mass of the acrylic copolymer in the total mass of the acrylic pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and 50% by mass or more and 90% by mass or less. It is more preferable that
  • an acrylic adhesive composition contains an acrylic copolymer and an adhesion aid.
  • the acrylic pressure-sensitive adhesive composition contains a pressure-sensitive adhesive agent, the initial tack of the pressure-sensitive adhesive sheet is improved, and peeling when the pressure-sensitive adhesive sheet is attached to the frame can be prevented.
  • the adhesion promoter contained in the acrylic pressure-sensitive adhesive composition contains an oligomer having a hydrocarbon skeleton. The oligomer is preferably a polymer having a molecular weight of less than 10,000.
  • the acrylic pressure-sensitive adhesive composition contains an adhesion assistant containing an oligomer having a hydrocarbon skeleton, and in addition, the increase in surface free energy can be suppressed and the filling property can be improved.
  • the oligomer having a hydrocarbon skeleton preferably has a reactive group.
  • the oligomer having a hydrocarbon skeleton and having a reactive group may be referred to as a hydrocarbon-based reactive adhesion aid.
  • the pressure-sensitive adhesive composition contains a hydrocarbon-based reactive pressure-sensitive adhesion assistant, the adhesive residue can be reduced.
  • the reactive group in the adhesion promoter is one or more 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. It is preferably a functional group, more preferably a hydroxyl group.
  • One type or two or more types of reactive groups may be included in the adhesion aid.
  • the adhesion promoter having a hydroxyl group may further have another reactive group described above.
  • the number of reactive groups may be one per molecule constituting the adhesion aid, or two or more.
  • the oligomer having a hydrocarbon skeleton is preferably a rubber-based material from the viewpoint of reducing the surface free energy of the pressure-sensitive adhesive layer and preventing adhesive residue.
  • the rubber-based material is not particularly limited, but a polybutadiene-based resin and a hydrogenated product of a polybutadiene-based resin are preferable, and a hydrogenated product of a polybutadiene-based resin is more preferable.
  • the polybutadiene-based resin include resins having 1,4-repeating units, resins having 1,2-repeating units, and resins having both 1,4-repeating units and 1,2-repeating units.
  • the hydrogenated product of the polybutadiene resin of the present embodiment includes a hydride of a resin having these repeating units.
  • the polybutadiene-based resin and the hydrogenated product of the polybutadiene-based resin preferably each have a reactive group 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 preferably, it is a hydroxyl group.
  • both ends are hydroxyl groups.
  • the adhesion promoter contains acetyl citrate triester.
  • the pressure-sensitive adhesive composition contains acetyl citrate triester, adhesive residue can be reduced.
  • examples of the acetylcitrate triester-based tackifier include tributyl acetylcitrate (ATBC).
  • the ratio of the mass of the adhesion assistant to the mass of the entire 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 proportion of the mass of the oligomer having a hydrocarbon skeleton in the mass of the entire pressure-sensitive adhesive composition is 3% by mass or more and 50% by mass or less. Is preferable, and more preferably 5% by mass or more and 30% by mass or less.
  • the acrylic pressure-sensitive adhesive composition according to this embodiment includes a cross-linked product obtained by cross-linking a composition containing the above-mentioned acrylic copolymer and a cross-linking agent.
  • the acrylic pressure-sensitive adhesive composition according to this embodiment is obtained by cross-linking a composition obtained by blending the above-mentioned acrylic copolymer, a hydrocarbon-based reactive adhesive aid, and a cross-linking agent. It is also preferable to include a product.
  • 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 cross-linking agent that is a compound having an isocyanate group 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
  • polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of these compounds, a burette type modified product reacted with water, or an isocyanurate type modified product having an isocyanurate ring.
  • the content of the crosslinking agent in the acrylic 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 with respect to 100 parts by mass of the acrylic copolymer. Part to 15 parts by mass, more preferably 5 parts to 10 parts by mass. If content of the crosslinking agent in an acrylic adhesive composition is in such a range, it will become easy to adjust the storage elastic modulus in 100 degreeC of the adhesive layer 12 to the above-mentioned range.
  • 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 so that the isocyanate group is 0.7 equivalent or more and 1.5 equivalent or less 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 acrylic pressure-sensitive adhesive composition in the present embodiment contains a crosslinking agent
  • the acrylic 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 acrylic pressure-sensitive adhesive composition contains a polyisocyanate compound as a cross-linking agent
  • a silicone adhesive composition contains a silicone resin, and it is preferable that an addition polymerization type silicone resin is included.
  • 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 (addition polymerization type silicone resin) 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 low temperature and does not require secondary curing at high temperature.
  • the conventional peroxide curable 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 curable 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.
  • organo group examples include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, both of the silicone resin component and the silicone rubber component.
  • the aforementioned organo groups are partially vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth) acryloyl, (meth) acryloylmethyl, (meth) acryloylpropyl, and cyclohexenyl. It is substituted with an unsaturated group such as a group.
  • An organo group having a vinyl group that is easily available industrially is preferred.
  • cross-linking proceeds by an addition reaction between the unsaturated group in the main agent and the hydrosilyl group in the cross-linking agent to form a network structure, thereby exhibiting adhesiveness.
  • the number of unsaturated groups such as vinyl groups is usually 0.05 or more and 3.0 or less, preferably 0.1 or more and 2.5, per 100 organo groups. It is as follows. 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 appropriate adhesive strength. . 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.
  • organopolysiloxane as described above examples include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 with respect to 100 methyl groups), Toray Dow BY23-753 manufactured by Corning Co., Ltd. (the number of vinyl groups is 0.1 with respect to 100 methyl groups), and BY24-162 (the number of vinyl groups is 1.4 with respect to 100 methyl groups). Etc.).
  • SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Toray Dow Corning Co., Ltd. can also be used.
  • organopolysiloxane which is a silicone resin component
  • silicone rubber component KS-3800 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is methyl) is used. 7.6 for 100 groups), BY24-162 manufactured by Toray Dow Corning Co., Ltd. (for which the number of vinyl groups is 1.4 for 100 methyl groups), BY24- 843 (having no unsaturated group), SD-7292 (having 5.0 vinyl groups per 100 methyl groups), and the like.
  • addition polymerization type silicone resin as described above are described in, for example, JP-A-10-219229.
  • the cross-linking agent usually has 0.5 to 10 hydrogen atoms bonded to silicon atoms, preferably 1 to one unsaturated group (vinyl group, etc.) 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 (vinyl group and the like) and the hydrosilyl group does not proceed completely, thereby preventing poor curing.
  • the addition reaction type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst together with the aforementioned addition reaction type silicone component (main agent comprising a silicone resin component and a silicone rubber component) and a crosslinking agent.
  • This curing catalyst is used for promoting the hydrosilylation reaction between the unsaturated group in the silicone resin component and the silicone rubber component and the SiH 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, examples of commercially available products include SRX-212 manufactured by Toray Dow Corning Co., Ltd., and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
  • the blending amount thereof is usually 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass, with respect to the total amount of the silicone resin component and the silicone rubber component as platinum content. It is mass ppm or more and 500 mass ppm or less.
  • 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.
  • the silicone resin component and the silicone rubber component by the crosslinking agent are irradiated with heat or active energy rays. It is preferable to promote the crosslinking reaction.
  • a pressure-sensitive adhesive sheet having a stable adhesive force can be obtained by crosslinking by irradiation with heat or active energy rays.
  • 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. Heating at 140 ° C. or lower causes heat shrinkage to the substrate. Wrinkles can be prevented from being deteriorated or discolored.
  • 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 crosslinking by ultraviolet irradiation is not particularly limited, and any photopolymerization initiator conventionally used in an ultraviolet curable resin is appropriately selected and used. be able to.
  • 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.
  • 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.
  • the acceleration voltage of 130 kV or more it is possible to prevent the adhesive force from becoming insufficient due to insufficient crosslinking between the silicone resin component and the silicone rubber component.
  • By irradiating with an acceleration voltage of 300 kV or less It can prevent that an adhesive layer and a base material 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 or more and 70 Mrad or less, and more preferably 2 Mrad or more and 20 Mrad or less.
  • a dose of 1 Mrad or more it is possible to prevent the pressure-sensitive adhesive layer and the substrate from being deteriorated or discolored, and to prevent the adhesiveness from becoming insufficient due to insufficient crosslinking.
  • a dose of 70 Mrad or less it is possible to prevent a decrease in cohesive force due to deterioration or discoloration of the pressure-sensitive adhesive layer, and it is possible to prevent the base material from being deteriorated or contracted.
  • the irradiation amount in the case of ultraviolet irradiation is appropriately selected.
  • the light amount is preferably 100 mJ / cm 2 or more and 500 mJ / cm 2 or less, and the illuminance is preferably 10 mW / cm 2 or more and 500 mW / cm 2 or less.
  • 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 a non-reactive polyorganosiloxane such as polydimethylsiloxane and polymethylphenylsiloxane as an additive.
  • 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 acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer wherein the adhesion assistant contains 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.
  • 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 obtained by copolymerizing a hydroxyl group-containing monomer the pressure-sensitive adhesive composition is a hydroxylated hydrogenated polybutadiene at both terminals, and the crosslinking agent is an isocyanate-based crosslinking 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 An acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the adhesion assistant contains a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent And a pressure-sensitive adhesive composition.
  • an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Things.
  • the 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.
  • 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. Therefore, for example, there is no possibility that the interlayer insulating material, the sealing resin, and the like enter the gaps in the irregularities on the circuit surface of the semiconductor chip, and the electrode pads for wiring connection on the chip circuit surface are blocked.
  • the semiconductor chip When the thickness of the pressure-sensitive adhesive layer 12 is 60 ⁇ m or less, the semiconductor chip is unlikely to sink into the pressure-sensitive adhesive layer, and a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip is less likely to occur. Therefore, there is no fear that the wiring is disconnected due to a step during rewiring.
  • 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 (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), polyolefin films (for example, polypropylene, polyethylene, and the like), and the like.
  • 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 release agent is preferably a non-silicone-based release agent.
  • 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 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.
  • a panel scale package (PSP), WLP, or the like can be given as a form of packaging a semiconductor element without using a metal lead frame.
  • the pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process having a step of covering the semiconductor chip with a sealing resin and a step of thermosetting the sealing resin.
  • FIGS. 2A to 2E are schematic views illustrating the method for manufacturing the semiconductor device according to the present embodiment.
  • the manufacturing method of the semiconductor device according to the present embodiment includes a step of attaching the frame member 20 in which a plurality of openings 21 are formed on the adhesive sheet 10 (adhesive sheet attaching step), and an opening 21 of the frame member 20.
  • a step of bonding the semiconductor chip CP to the exposed adhesive layer 12 (bonding step), a step of covering the semiconductor chip CP with the sealing resin 30 (sealing step), and a step of thermosetting the sealing resin 30 ( A thermosetting step) and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting.
  • 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 separating 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 step, 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-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A.
  • the temperature condition range for heat curing by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
  • the sheet-shaped sealing resin 30 When the sheet-shaped sealing resin 30 is used, the sheet-shaped sealing resin is solid before the sealing step. Therefore, the filling property may be inferior to using a liquid sealing resin.
  • the adhesive sheet 10 of the present embodiment since the surface free energy of the pressure-sensitive adhesive layer 12 is 10 mJ / m 2 or more 22 mJ / m 2 or less, even the sealing resin is a sheet-like, excellent in filling property, this step It is possible to prevent the occurrence of problems in
  • a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used.
  • the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured.
  • Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
  • a transfer molding method may be employed.
  • the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device.
  • a fluid resin material is injected into the mold to cure the resin material.
  • the heating and pressure conditions are not particularly limited.
  • a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds.
  • the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
  • the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process).
  • the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. .
  • the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20.
  • corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
  • the plate member for example, a metal plate such as stainless steel can be used.
  • the sealing body 50 When the pressure-sensitive adhesive sheet 10 is peeled after the thermosetting step, the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained. Hereinafter, this may be referred to as a sealing body 50.
  • FIG. 2D The schematic diagram explaining the process of sticking the reinforcing member 40 to the sealing body 50 is shown by FIG. 2D.
  • a rewiring process and a bumping process for forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed.
  • a process (reinforcing member attaching process) of attaching the reinforcing member 40 to the sealing body 50 is performed as necessary. May be.
  • FIG. As illustrated in FIG. 2D, the sealing body 50 is supported in a state of being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
  • the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42.
  • the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a polyimide resin and 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 preferably a glass cloth including a thermoplastic resin.
  • the thermoplastic resin contained bismaleimide triazine resin (BT resin) is preferable.
  • the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure.
  • the sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time.
  • the conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa.
  • a metal plate such as stainless steel can be used as the plate-like member.
  • FIG. 2E The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
  • peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree
  • peeling angle ⁇ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A.
  • the peeling angle ⁇ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less.
  • the temperature atmosphere at the time of peeling the pressure-sensitive adhesive sheet 10 may be room temperature, but when there is a concern about the destruction of each member of the adherend and the interface between the members at the time of peeling, the pressure-sensitive adhesive of the pressure-sensitive adhesive
  • the pressure-sensitive adhesive sheet 10 may be peeled in a temperature atmosphere higher than room temperature.
  • the temperature atmosphere higher than room temperature is preferably in the range of 30 to 60 ° C, more preferably in the range of 35 to 50 ° C.
  • 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 adhesive sheet 10 can prevent resin leakage when sealing the semiconductor element on the adhesive sheet and has good filling properties when sealing the semiconductor element on the adhesive sheet. Can provide. Moreover, according to the manufacturing method of the semiconductor device using the adhesive sheet 10 of this embodiment, resin leakage can be prevented and the chip can be prevented from flowing or floating. Therefore, the yield of semiconductor devices is improved. Moreover, according to the manufacturing method of the semiconductor device using the adhesive sheet 10 of the present embodiment, in the sealing process, as shown in FIG. 3, the sealing resin 30 is formed on the peripheral portion of the circuit surface CPA of the semiconductor chip CP. A gap S between a certain stepped portion CPB and the pressure-sensitive adhesive layer 12 can be embedded.
  • the height dimension x of the step between the step portion CPB and the circuit surface CPA is usually 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 5 ⁇ m or less. As the height dimension x is smaller, the sealing resin 30 is less likely to fill the gap S. However, if the height dimension x is equal to or greater than the lower limit, the sealing resin 30 can fill the gap S.
  • the width dimension y of the stepped portion CPB is usually 1 ⁇ m or more and 100 ⁇ m or less, and preferably 5 ⁇ m or more and 50 ⁇ m or less. The larger the width dimension y, the harder the sealing resin 30 fills the gap S. However, the sealing resin 30 can embed the gap S as long as the upper limit is not reached.
  • the adhesive sheet 10 may be a sheet piece, and may be provided in a state in which 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 pressure-sensitive adhesive sheet 10 may be a belt-like sheet or may be provided in a state of being wound in a roll shape. 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 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.
  • Example 1 The coating adhesive solution in Example 1 was applied to a release film (“PET3801”, manufactured by Lintec Corporation) using a comma coater (registered trademark), and then dried (drying conditions: 90 ° C., 90 seconds, and 115 ° C., 90 seconds), a layer having a thickness of 30 ⁇ m was formed, and this was laminated to produce a circular measurement sample having a thickness of 1 mm and a diameter of 8 mm.
  • the storage elastic modulus (Pa) at 100 ° C. of the obtained measurement sample was measured by a torsional shear method using a viscoelasticity measuring device (MCR manufactured by Anton Paar Japan).
  • the heating rate was 5 ° C./min, and the measurement frequency was 1 Hz.
  • the coating adhesive solutions in Examples 2 to 5 and Comparative Examples 1 to 3 the storage elastic modulus (Pa) at 100 ° C. of the obtained measurement samples was measured in the same manner as described above.
  • the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet produced in Example 1 was applied to an adherend (polyimide film) with a load of 2 kgf.
  • adherend polyimide film
  • Kapton 100H product name
  • This polyimide film-attached pressure-sensitive adhesive sheet is stored for 0.5 hours in an environment of 25 ° C. and 50% relative humidity, and then using a thermostat (PHH-202, manufactured by ESPEC Corporation) under the conditions of 190 ° C. and 1 hour. After heating, the pressure-sensitive adhesive sheet with a polyimide film was stored for 1 hour in an environment of 25 ° C. and 50% relative humidity.
  • the adhesive strength of the adhesive sheet was measured by a 180 ° peeling method in an environment of 25 ° C. and 50% relative humidity.
  • a measuring device a measuring device with a thermostatic bath (manufactured by A & D, TENSILON) was used, the tensile speed was 300 mm / min, and the width of the adhesive sheet was 25 mm.
  • the adhesive strength of the adhesive sheets was measured in the same manner as described above.
  • Sealing conditions were such that the preheating temperature of the vacuum heating and pressurization laminator table and the diaphragm was 100 ° C., and the sealing was performed for 60 seconds by vacuuming, 30 seconds in the Dynamic press mode, and 10 seconds in the Static press mode. . After that, the state of the interface between the chip and the pressure-sensitive adhesive sheet is confirmed with a digital microscope through the pressure-sensitive adhesive sheet. If the interlayer insulating resin penetrates 10 ⁇ m or more from the end of the chip between the chip and the pressure-sensitive adhesive sheet, there is a resin leak. Less than the case was regarded as no resin leakage. For the pressure-sensitive adhesive sheets prepared in Examples 2 to 5 and Comparative Examples 1 to 3, the resin leakage prevention property was evaluated in the same manner as described above.
  • the surface free energy of the pressure-sensitive adhesive layer was measured by the following method. Specifically, first, using a contact angle measuring device (“DM701” manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angles of water, diiodomethane and 1-bromonaphthalene to the pressure-sensitive adhesive layer produced in Example 1 were measured. did. The amount of each droplet was 2 ⁇ L. Then, the surface free energy was calculated from these measured values by the Kitasaki-Hatabe method. For the pressure-sensitive adhesive layers prepared in Examples 2 to 5 and Comparative Examples 1 to 3, the contact angles were measured in the same manner as described above, and the surface free energy was calculated from these measured values.
  • DM701 manufactured by Kyowa Interface Chemical Co., Ltd.
  • the distance between adjacent chips was set such that the distance between the centers of the rectangular shapes of the chips was 5 mm.
  • the semiconductor chip on the adhesive sheet is sealed with a sealing resin (ABF film manufactured by Ajinomoto Fine Techno Co., Ltd., GX LE-T15B) using a vacuum heating and pressure laminator (“7024HP5” manufactured by ROHM and HAAS). (Sealing process).
  • the sealing conditions are as follows.
  • Example 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 coating according to Example 1 (pressure-sensitive adhesive composition) Prepared).
  • -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.
  • the weight average molecular weight of the obtained polymer was 850,000.
  • Adhesion aid hydroxylated hydrogenated polybutadiene at both ends (Nippon Soda Co., Ltd .; GI-1000), 5 parts by mass (solid content)
  • Crosslinking agent Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate) [manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX], 3.5 parts by mass (solid content)
  • Diluting solvent Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
  • Example 2 (1) Preparation of pressure-sensitive adhesive composition
  • a silicone-based pressure-sensitive adhesive was used.
  • Silicone-based adhesive A (SD4580PSA) 18 parts by mass (solid content) 40 parts by mass (solid content) of silicone-based adhesive B (SD-4487L), Catalyst A (NC-25CAT) 0.3 parts by mass (solid content)
  • Catalyst B (CAT-SRX-212) 0.65 parts by mass (solid content)
  • Silicone dispersion BY-24-712) 5 parts by mass (solid content) was mixed with toluene as a diluent solvent so that the solid content was 20% by mass and stirred sufficiently to prepare a coating pressure-sensitive adhesive liquid (pressure-sensitive adhesive composition) according to Example 2.
  • the materials used for the pressure-sensitive adhesive composition of Example 2 are all manufactured by Toray Dow Corning Co., Ltd.
  • Example 3 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying the pressure-sensitive adhesive liquid for coating was 30 ⁇ m.
  • Example 4 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying of the pressure-sensitive adhesive liquid for coating was 40 ⁇ m.
  • Example 5 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying the pressure-sensitive adhesive liquid for coating was 50 ⁇ m.
  • Example 1 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying the pressure-sensitive adhesive liquid for coating was 10 ⁇ m.
  • Example 2 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the polymer of Example 1 was changed to the following composition.
  • the acrylic ester copolymer comprises a copolymer of 80.8% by mass of 2-ethylhexyl acrylate, 12% by mass of acryloylmorpholine, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid. Prepared by polymerization. The weight average molecular weight of the obtained polymer was 760,000.
  • Comparative Example 3 A pressure-sensitive adhesive sheet was prepared in the same manner as in Comparative Example 2 except that the thickness of the pressure-sensitive adhesive in Comparative Example 2 was changed to 20 ⁇ m.
  • Table 1 shows the evaluation results of the pressure-sensitive adhesive sheets according to Examples 1 to 5 and Comparative Examples 1 to 3.
  • the pressure-sensitive adhesive sheets according to Examples 1-5 the numerical values surface free energy of the pressure-sensitive adhesive layer is 10 mJ / m 2 or more 22 mJ / m 2 or less, and is calculated by A ⁇ B 2 Is 1.5 ⁇ 10 ⁇ 5 or more, it was confirmed that the filling property is good and the resin leakage can be prevented.
  • the adhesive sheet according to Comparative Example 1 has a numerical value calculated by A ⁇ B 2 of less than 1.5 ⁇ 10 ⁇ 5 , so it is considered that resin leakage could not be prevented.
  • the pressure-sensitive adhesive sheets according to Comparative Examples 2 to 3 are considered to be inferior in filling property when sealing semiconductor elements on the pressure-sensitive adhesive sheet because the surface free energy of the pressure-sensitive adhesive layer exceeds 22 mJ / m 2. .

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Abstract

Provided is an adhesive sheet (10) used in a case where a semiconductor element is sealed on an adhesive sheet, wherein: the adhesive sheet is provided with a base material (11) and an adhesive agent layer that contains an adhesive agent composition (12); the surface free energy of the adhesive agent layer (12) is in the range of 10–22 mJ/m2; and if the storage elastic modulus of the adhesive agent layer (12) at 100°C is A (Pa) and the thickness of the adhesive agent layer (12) is B (m), the numerical value calculated using the relational expression (1) is at least 1.5 × 10− 5. (1): A×B2

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、実装技術において、チップサイズパッケージ（Ｃｈｉｐ　Ｓｉｚｅ　Ｐａｃｋａｇｅ；ＣＳＰ）技術が注目されている。この技術のうち、ウェハレベルパッケージ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ；ＷＬＰ）に代表される基板を用いないチップのみの形態のパッケージについては、小型化と高集積の面で特に注目されている。このようなＷＬＰ等の製造方法においては、従来、基板上に固定するチップを、別の支持体上に固定することが必要となる。そこで、例えば、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（特許文献１及び特許文献２）。 In recent years, chip size package (CSP) technology has attracted attention as a mounting technology. Of these technologies, a chip-only package that does not use a substrate typified by a wafer level package (WLP) has attracted particular attention in terms of miniaturization and high integration. In such a manufacturing method of WLP or the like, conventionally, a chip to be fixed on a substrate needs to be fixed on another support. Therefore, for example, when manufacturing a semiconductor device, an adhesive sheet is used as a support for temporarily fixing a chip (Patent Document 1 and Patent Document 2).
特開２０１２－０５９９３４号公報JP 2012-059934 A 特開２００４－０１４９３０号公報JP 2004-014930 A
　しかしながら、従来の粘着シートを用いて半導体装置を製造すると、粘着シートに貼着された半導体チップを封止する際に、封止樹脂が漏れて、チップと粘着シートの間に入り込み、半導体チップが流されたり、浮いてしまったりするという問題があった。 However, when a semiconductor device is manufactured using a conventional pressure-sensitive adhesive sheet, when a semiconductor chip attached to the pressure-sensitive adhesive sheet is sealed, the sealing resin leaks and enters between the chip and the pressure-sensitive adhesive sheet. There was a problem of being washed away or floating.
　また例えば、粘着シートを用いて半導体装置を製造する場合には、半導体素子の回路面が、粘着シートの粘着剤層に固定されることになる。半導体素子の回路面には、半導体素子の周縁部に、ダイシングライン等の段差部がある。そして、粘着シート上の半導体素子を封止する際には、封止樹脂が段差部と粘着剤層との隙間を埋め込むことになる。
　しかしながら、封止樹脂の種類によっては、封止樹脂が段差部と粘着剤層との隙間を埋め込むことができず、空隙ができることが分かった。そして、このような空隙ができると、半導体素子の回路面の平滑性が不十分となり、回路面のパターン形成の際に問題が生じるおそれがある。そこで、粘着シートには、封止樹脂が段差部と粘着剤層との隙間を埋め込みやすいという性質（以下、「フィリング性」と称する場合がある。）が求められる。 For example, when manufacturing a semiconductor device using an adhesive sheet, the circuit surface of the semiconductor element is fixed to the adhesive layer of the adhesive sheet. On the circuit surface of the semiconductor element, there is a stepped portion such as a dicing line at the periphery of the semiconductor element. And when sealing the semiconductor element on an adhesive sheet, sealing resin embeds the clearance gap between a level | step-difference part and an adhesive layer.
However, it has been found that depending on the type of the sealing resin, the sealing resin cannot fill the gap between the stepped portion and the pressure-sensitive adhesive layer, and a void is formed. If such a gap is formed, the smoothness of the circuit surface of the semiconductor element becomes insufficient, and a problem may occur when forming a pattern on the circuit surface. Therefore, the adhesive sheet is required to have a property that the sealing resin can easily fill the gap between the stepped portion and the adhesive layer (hereinafter sometimes referred to as “filling property”).
　本発明の目的は、粘着シート上の半導体素子を封止する際の、樹脂漏れ防止性とフィリング性とを両立することができる粘着シートを提供することである。 An object of the present invention is to provide a pressure-sensitive adhesive sheet that can achieve both resin leakage prevention and filling properties when a semiconductor element on a pressure-sensitive adhesive sheet is sealed.
　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、当該粘着シートは、基材と粘着剤組成物を含む粘着剤層とを備え、前記粘着剤層の表面自由エネルギーが１０ｍJ／ｍ２以上２２ｍJ／ｍ２以下であり、かつ、前記粘着剤層の１００℃における貯蔵弾性率をＡ（Ｐａ）、前記粘着剤層の厚みをＢ（ｍ）としたとき、下記関係式（１）により算出される数値が１．５×１０－５以上である粘着シートが提供される。 According to one aspect of the present invention, it is a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive sheet includes a base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition. the surface free energy of the pressure-sensitive adhesive layer has a 10 mJ / m 2 or more 22 mJ / m 2 or less, and a storage modulus at 100 ° C. of the pressure-sensitive adhesive layer a (Pa), the thickness of the pressure-sensitive adhesive layer B When (m) is indicated, a pressure-sensitive adhesive sheet having a numerical value calculated by the following relational expression (1) of 1.5 × 10 −5 or more is provided.
　　Ａ×Ｂ２　　　　　（１） A × B 2 (1)
　本発明の一態様に係る粘着シートにおいて、前記粘着剤層に対する１－ブロモナフタレンの接触角が６５°以上であることが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the contact angle of 1-bromonaphthalene with respect to the pressure-sensitive adhesive layer is preferably 65 ° or more.
　本発明の一態様に係る粘着シートにおいて、下記関係式（２）により算出される数値が１．５×１０－１０以上であることが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the numerical value calculated by the following relational expression (2) is preferably 1.5 × 10 −10 or more.
　　Ａ×Ｂ３　　　　　（２） A × B 3 (2)
　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からなることが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the pressure-sensitive adhesive layer is preferably made of 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、前記粘着剤層は、アクリル系粘着剤組成物からなり、前記アクリル系粘着剤組成物は、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 embodiment of the present invention, the pressure-sensitive adhesive layer is preferably made of an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer.
　本発明の一態様に係る粘着シートにおいて、前記アクリル系共重合体全体の質量に占める、（メタ）アクリル酸アルキルエステルに由来する共重合体成分の質量の割合が、９０質量％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 proportion of the mass of the copolymer component derived from the (meth) acrylic acid alkyl ester in the total mass of the acrylic copolymer is 90% by mass or more. Is preferred.
　本発明の一態様に係る粘着シートにおいて、前記（メタ）アクリル酸アルキルエステルにおけるアルキルの炭素数が６～８であることが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the alkyl of the (meth) acrylic acid alkyl ester preferably has 6 to 8 carbon atoms.
　本発明の一態様に係る粘着シートにおいて、前記アクリル系共重合体は、（メタ）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 embodiment of the present invention, the acrylic copolymer preferably includes an acrylic copolymer containing 2-ethyl hexyl (meth) acrylate as a main monomer.
　本発明の一態様に係る粘着シートにおいて、前記アクリル系共重合体は、水酸基を有するモノマーに由来する共重合体成分を含むことが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the acrylic copolymer preferably includes a copolymer component derived from a monomer having a hydroxyl group.
　本発明の一態様に係る粘着シートにおいて、前記アクリル系共重合体全体の質量に占める、前記水酸基を有するモノマーに由来する共重合体成分の割合が、３質量％以上であることが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, the ratio of the copolymer component derived from the monomer having a hydroxyl group in the mass of the entire acrylic copolymer is preferably 3% by mass or more.
　本発明の一態様に係る粘着シートにおいて、前記アクリル系共重合体は、カルボキシル基を有するモノマーに由来する共重合体成分を含まない、またはカルボキシル基を有するモノマーに由来する共重合体成分を含み、かつ、前記アクリル系共重合体全体の質量に占める、前記カルボキシル基を有するモノマーに由来する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い。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the acrylic copolymer does not include a copolymer component derived from a monomer having a carboxyl group, or includes a copolymer component derived from a monomer having a carboxyl group. And it is preferable that the ratio of the mass of the copolymer component derived from the monomer which has the said carboxyl group to the mass of the said whole acrylic copolymer is 1 mass% or less.
　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、炭化水素骨格を有するオリゴマーを含む粘着助剤を含有することが好ましい。 In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the acrylic pressure-sensitive adhesive composition preferably contains a pressure-sensitive adhesive auxiliary containing an oligomer having a hydrocarbon skeleton.
　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、シリコーン系粘着剤組成物からなり、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 pressure-sensitive adhesive layer is made of a silicone-based pressure-sensitive adhesive composition, and the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
　本発明によれば、粘着シート上の半導体素子を封止する際の、樹脂漏れ防止性とフィリング性とを両立することができる粘着シートを提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet that can achieve both resin leakage prevention and filling properties when sealing semiconductor elements on the pressure-sensitive adhesive sheet.
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. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程における封止工程後の半導体素子を示す断面図である。It is sectional drawing which shows the semiconductor element after the sealing process in the 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、粘着剤組成物を含む粘着剤層１２とを有する。
　基材１１は、第一基材面１１ａ、及び第一基材面１１ａとは反対側の第二基材面１１ｂを有する。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、及びラベル状等、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 composition.
The base material 11 has a first base material surface 11a and a second base material surface 11b opposite to the first base material surface 11a. 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.
　本実施形態に係る粘着シート１０は、粘着剤層１２の表面自由エネルギーが１０ｍＪ／ｍ２以上２２ｍＪ／ｍ２以下であり、かつ、粘着剤層１２の１００℃での貯蔵弾性率をＡ（Ｐａ）、粘着剤層１２の厚みをＢ（ｍ）としたとき、下記関係式（１）により算出される数値が１．５×１０－５以上であることが必要である。 The pressure-sensitive adhesive sheet 10 according to the present embodiment, the surface free energy of the pressure-sensitive adhesive layer 12 is at 10 mJ / m 2 or more 22 mJ / m 2 or less, and a storage modulus at 100 ° C. of the pressure-sensitive adhesive layer 12 A (Pa ) When the thickness of the pressure-sensitive adhesive layer 12 is B (m), the numerical value calculated by the following relational expression (1) needs to be 1.5 × 10 −5 or more.
　　　　Ａ×Ｂ２　　　　　（１） A × B 2 (1)
　粘着剤層１２の表面自由エネルギーが１０ｍＪ／ｍ２以上２２ｍＪ／ｍ２以下であれば、粘着シート１０上の半導体素子を封止する際のフィリング性に優れ、粘着シート１０上の半導体素子を封止する際に、封止樹脂が半導体素子の段差部と粘着剤層との隙間を埋め込むことができる。
　また、前記関係式（１）により算出される数値が１．５×１０－５以上であると、本実施形態の粘着シートを、半導体チップを封止する際の支持体として用いた際に、樹脂漏れを防ぐことができる。 If the surface free energy of the pressure-sensitive adhesive layer 12 is 10 mJ / m 2 or more 22 mJ / m 2 or less, excellent semiconductor device on the adhesive sheet 10 to the filling of the time of sealing, sealing the semiconductor elements on the adhesive sheet 10 When stopping, the sealing resin can fill the gap between the step portion of the semiconductor element and the pressure-sensitive adhesive layer.
Further, when the numerical value calculated by the relational expression (1) is 1.5 × 10 −5 or more, when the pressure-sensitive adhesive sheet of this embodiment is used as a support when sealing a semiconductor chip, Resin leakage can be prevented.
　なお、本明細書において、粘着剤層１２の表面自由エネルギーは、次に示す方法により測定できる。具体的には、まず、接触角測定装置（協和界面科学株式会社製の「ＤＭ７０１」）を用いて、粘着剤層１２に対する水、ジヨードメタン、及び１－ブロモナフタレンの接触角を測定する。それぞれの液滴の量は２μＬとする。そして、これらの測定値から、北崎－畑法により、表面自由エネルギーを算出できる。
　また、本明細書において、粘着剤層の貯蔵弾性率は、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。 In the present specification, the surface free energy of the pressure-sensitive adhesive layer 12 can be measured by the following method. Specifically, first, contact angles of water, diiodomethane, and 1-bromonaphthalene with respect to the pressure-sensitive adhesive layer 12 are measured using a contact angle measuring device (“DM701” manufactured by Kyowa Interface Science Co., Ltd.). The amount of each droplet is 2 μL. From these measured values, the surface free energy can be calculated by the Kitazaki-Hatabe method.
In this specification, the storage elastic modulus of the pressure-sensitive adhesive layer is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring device.
　本実施形態において、粘着剤層の表面自由エネルギーは、１２ｍＪ／ｍ２以上２１．５ｍＪ／ｍ２以下であることがより好ましい。 In the present embodiment, the surface free energy of the pressure-sensitive adhesive layer is more preferably 12 mJ / m 2 or more and 21.5 mJ / m 2 or less.
　本実施形態においては、フィリング性の観点から、１－ブロモナフタレンの接触角は、６５°以上であることが好ましく、６７°以上であることが好ましく、６８°以上であることがより好ましい。１－ブロモナフタレンの接触角の上限としては、７５°以下が好ましく、７２°以下がより好ましい。
　なお、これら表面自由エネルギー及び接触角の値を調整する方法としては、以下のような方法が挙げられる。例えば、粘着剤層１２で用いる粘着剤組成物の組成を変更することで、表面自由エネルギー及び接触角の値を調整できる。 In the present embodiment, from the viewpoint of filling properties, the contact angle of 1-bromonaphthalene is preferably 65 ° or more, preferably 67 ° or more, and more preferably 68 ° or more. The upper limit of the contact angle of 1-bromonaphthalene is preferably 75 ° or less, and more preferably 72 ° or less.
In addition, the following methods are mentioned as a method of adjusting the value of these surface free energy and a contact angle. For example, the values of the surface free energy and the contact angle can be adjusted by changing the composition of the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive layer 12.
　本実施形態において、前記関係式（１）により算出される数値は、好ましくは２．０×１０－５以上であり、より好ましくは５．０×１０－５以上である。 In the present embodiment, the numerical value calculated by the relational expression (1) is preferably 2.0 × 10 −5 or more, more preferably 5.0 × 10 −5 or more.
　前記関係式（１）により算出される数値の上限は、特に限定されない。粘着シートを低コストで容易に製造できることから、１．０×１０－２以下であることが好ましい。 The upper limit of the numerical value calculated by the relational expression (1) is not particularly limited. The pressure-sensitive adhesive sheet is preferably 1.0 × 10 −2 or less because the pressure-sensitive adhesive sheet can be easily produced at low cost.
　粘着シート１０は、下記関係式（２）により算出される数値が１．５×１０－１０以上であることが好ましく、より好ましくは５．０×１０－１０以上であり、さらに好ましくは１．０×１０－９以上である。 The pressure-sensitive adhesive sheet 10 preferably has a numerical value calculated by the following relational expression (2) of 1.5 × 10 −10 or more, more preferably 5.0 × 10 −10 or more, and still more preferably 1. It is 0 × 10 −9 or more.
　　　　Ａ×Ｂ３　　　　　（２） A × B 3 (2)
　前記関係式（２）により算出される数値が１．５×１０－１０以上であれば、樹脂漏れをより効果的に防止することができる。 If the numerical value calculated by the relational expression (2) is 1.5 × 10 −10 or more, resin leakage can be more effectively prevented.
　本実施形態に係る粘着シート１０は、加熱後に、次のような粘着力を示すことが好ましい。まず、粘着シート１０を被着体（銅箔またはポリイミドフィルム）に貼着させ、１００℃及び３０分間の条件で加熱し、続いて１８０℃及び３０分間の条件で加熱し、さらに１９０℃及び１時間の条件で加熱した後、粘着剤層１２の銅箔に対する室温での粘着力、及び粘着剤層１２のポリイミドフィルムに対する室温での粘着力が、それぞれ０．７Ｎ／２５ｍｍ以上２．０Ｎ／２５ｍｍ以下であることが好ましい。前述の加熱を行った後の粘着力が０．７Ｎ／２５ｍｍ以上であれば、加熱によって基材または被着体が変形した場合に粘着シート１０が被着体から剥離することを防止できる。また、前述の加熱を行った後の粘着力が２．０Ｎ／２５ｍｍ以下であれば、剥離力が高くなり過ぎず、粘着シート１０を被着体から剥離し易い。
　なお、本明細書において室温とは、２２℃以上２４℃以下の温度である。本明細書において、粘着力は、１８０°引き剥がし法により、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り、具体的には、実施例に記載の方法で測定される。 The pressure-sensitive adhesive sheet 10 according to this embodiment preferably exhibits the following pressure-sensitive adhesive strength after heating. First, the pressure-sensitive adhesive sheet 10 is adhered to an adherend (copper foil or polyimide film), heated at 100 ° C. and 30 minutes, subsequently heated at 180 ° C. and 30 minutes, and further at 190 ° C. and 1 ° C. After heating under the conditions of time, the adhesive strength of the adhesive layer 12 to the copper foil at room temperature and the adhesive strength of the adhesive layer 12 to the polyimide film at room temperature are 0.7 N / 25 mm or more and 2.0 N / 25 mm, respectively. The following is preferable. If the adhesive strength after the above heating is 0.7 N / 25 mm or more, the adhesive sheet 10 can be prevented from peeling off from the adherend when the substrate or the adherend is deformed by heating. Moreover, if the adhesive force after performing the above-mentioned heating is 2.0 N / 25 mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body.
In this specification, room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower. In 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 pressure sensitive adhesive sheet of 25 mm, specifically, the method described in the examples. Measured in
（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、及びポリイミドフィルム等が挙げられる。その他、基材１１としては、これらの架橋フィルム及び積層フィルム等が挙げられる。 (Base material)
The substrate 11 is a member that supports the pressure-sensitive adhesive layer 12.
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。 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 proportion of the mass of the polyester-based resin in the entire material constituting the base material 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.
　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、粘弾性測定機器を用いて、周波数１Ｈｚで測定した引張弾性率の値である。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℃の貯蔵粘弾率を測定する。 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 of the tensile elastic modulus measured at a frequency of 1 Hz using a 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. Measure.
　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、及びプラズマ処理等の少なくともいずれかの表面処理が施されていてもよい。また、基材１１と粘着剤層１２との密着性を高めるために、基材１１の第一基材面１１ａには、粘着剤が塗布されて予備的な粘着処理が施されていてもよい。基材１１の粘着処理に用いられる粘着剤としては、例えば、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、及びウレタン系粘着剤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. Moreover, in order to improve the adhesiveness of the base material 11 and the adhesive layer 12, the adhesive material is apply | coated to the 1st base material surface 11a of the base material 11, and the preliminary adhesion process may be performed. . Examples of the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate 11 include pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, 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、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、及びウレタン系粘着剤等が挙げられる。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からなることが好ましく、アクリル系粘着剤組成物からなることがより好ましい。粘着剤層１２がアクリル系粘着剤組成物からなることにより、粘着シート１０を被着体から剥離した際の、被着体表面等に残る粘着剤（いわゆる、糊残り）を減少させることができる。 (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 a rubber adhesive, an acrylic adhesive, a silicone adhesive, a polyester adhesive, and a urethane adhesive. 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 is preferably made of an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition, and more preferably made of an acrylic pressure-sensitive adhesive composition. When the pressure-sensitive adhesive layer 12 is made of an acrylic pressure-sensitive adhesive composition, the pressure-sensitive adhesive (so-called adhesive residue) remaining on the surface of the adherend when the pressure-sensitive adhesive sheet 10 is peeled from the adherend can be reduced. .
・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からなる場合、アクリル系粘着剤組成物は、アクリル系共重合体を含むことが好ましい。この場合、アクリル系共重合体は、（メタ）アクリル酸アルキルエステル（ＣＨ２＝ＣＲ１ＣＯＯＲ２（Ｒ１は水素またはメチル基、Ｒ２は直鎖、分岐鎖または環状（脂環式）のアルキル基））に由来する共重合体成分を含むことが好ましい。また、粘着剤層の表面自由エネルギーを調整する観点から、アクリル酸アルキルエステル（ＣＨ２＝ＣＲ１ＣＯＯＲ２）の一部または全部が、アルキル基Ｒ２の炭素数が６～８である（メタ）アクリル酸アルキルエステルであることが好ましい。アルキル基Ｒ２の炭素数が６～８である（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、及び（メタ）アクリル酸ｎ－オクチル等が挙げられる。これらの中でも、Ｒ２が直鎖または分岐鎖のアルキル基であることが好ましい。また、アルキル基Ｒ２の炭素数が８であるものが好ましく、（メタ）アクリル酸２－エチルヘキシルがより好ましく、アクリル酸２－エチルヘキシルがさらに好ましい。
　本実施形態においては、アクリル系共重合体は、（メタ）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。
　本明細書において、（メタ）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、（メタ）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。 -Acrylic adhesive composition When the adhesive layer 12 consists of an acrylic adhesive composition, it is preferable that an acrylic adhesive composition contains an acrylic copolymer. In this case, the acrylic copolymer is a (meth) acrylic acid alkyl ester (CH 2 = CR 1 COOR 2 (R 1 is hydrogen or methyl group, R 2 is linear, branched or cyclic (alicyclic)). It preferably contains a copolymer component derived from an alkyl group)). From the viewpoint of adjusting the surface free energy of the pressure-sensitive adhesive layer, a part or all of the alkyl acrylate ester (CH 2 ═CR 1 COOR 2 ) has an alkyl group R 2 having 6 to 8 carbon atoms (meta ) Acrylic acid alkyl ester is preferred. Examples of (meth) acrylic acid alkyl esters in which the alkyl group R 2 has 6 to 8 carbon atoms include n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Isooctyl acrylate, n-octyl (meth) acrylate, and the like. Among these, it is preferred that R 2 is an alkyl group of straight or branched chain. The alkyl group R 2 preferably has 8 carbon atoms, more preferably 2-ethylhexyl (meth) acrylate, and more preferably 2-ethylhexyl acrylate.
In the present embodiment, the acrylic copolymer preferably includes an acrylic copolymer containing 2-ethylhexyl (meth) acrylate as a main monomer.
In the present specification, the main monomer is 2-ethylhexyl (meth) acrylate, and the ratio of the weight of the copolymer component derived from 2-ethylhexyl (meth) acrylate to the total weight of the acrylic copolymer is It means 50% by mass or more.
　アルキル基Ｒ２の炭素数が１～５または９～２０の、（メタ）アクリル酸アルキルエステル（前記ＣＨ２＝ＣＲ１ＣＯＯＲ２）としては、例えば、（メタ）アクリル酸メチル、（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－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。
　（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。
　なお、本明細書における「（メタ）アクリル酸」は、「アクリル酸」及び「メタクリル酸」の双方を表す場合に用いる表記であり、他の類似用語についても同様である。 Examples of the (meth) acrylic acid alkyl ester (the CH 2 ═CR 1 COOR 2 ) in which the alkyl group R 2 has 1 to 5 or 9 to 20 carbon atoms include, for example, methyl (meth) acrylate, (meth) acrylic Ethyl acetate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, (meth) acrylic Examples include myristyl acid, palmityl (meth) acrylate, and stearyl (meth) acrylate.
The (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
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.
　本実施形態においては、アクリル系共重合体は、前記ＣＨ２＝ＣＲ１ＣＯＯＲ２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。
　本明細書において、ＣＨ２＝ＣＲ１ＣＯＯＲ２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、ＣＨ２＝ＣＲ１ＣＯＯＲ２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。
　粘着剤層の表面自由エネルギーを調整する観点から、アクリル系共重合体全体の質量に占める、（メタ）アクリル酸アルキルエステル（前記ＣＨ２＝ＣＲ１ＣＯＯＲ２）に由来する共重合体成分の質量の割合が、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、８０質量％以上であることがさらに好ましく、９０質量％以上であることがさらにより好ましい。（メタ）アクリル酸アルキルエステル（前記ＣＨ２＝ＣＲ１ＣＯＯＲ２）に由来する共重合体成分の質量の割合は、初期密着力の向上等の観点から、９６質量％以下であることが好ましい。 In the present embodiment, the acrylic copolymer preferably contains an acrylic copolymer which said CH 2 = CR 1 COOR 2 as a main monomer.
In this specification, when CH 2 = CR 1 COOR 2 is the main monomer, the proportion of the mass of the copolymer component derived from CH 2 = CR 1 COOR 2 in the total mass of the acrylic copolymer is 50 masses. It means that it is more than%.
From the viewpoint of adjusting the surface free energy of the pressure-sensitive adhesive layer, the mass of the copolymer component derived from the (meth) acrylic acid alkyl ester (CH 2 = CR 1 COOR 2 ) in the total mass of the acrylic copolymer. Is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more. The proportion of the mass of the copolymer component derived from the (meth) acrylic acid alkyl ester (CH 2 = CR 1 COOR 2 ) is preferably 96% by mass or less from the viewpoint of improving the initial adhesion.
　アクリル系共重合体における第一の共重合体成分が（メタ）アクリル酸アルキルエステルである場合、当該アクリル系共重合体における（メタ）アクリル酸アルキルエステル以外の共重合体成分（以下、「第二の共重合体成分」と称する）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。この反応性の官能基としては、例えば、カルボキシル基、水酸基、アミノ基、置換アミノ基、及びエポキシ基等が挙げられる。 When the first copolymer component in the acrylic copolymer is a (meth) acrylic acid alkyl ester, a copolymer component other than the (meth) acrylic acid alkyl ester in the acrylic copolymer (hereinafter referred to as “th” The type and number of “second copolymer component” 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. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group.
　カルボキシル基を有するモノマー（以下、「カルボキシル基含有モノマー」と称する場合がある）としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、及びシトラコン酸等のエチレン性不飽和カルボン酸が挙げられる。カルボキシル基含有モノマーの中でも、反応性及び共重合性の点から、アクリル酸が好ましい。カルボキシル基含有モノマーは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the monomer having a carboxyl group (hereinafter sometimes referred to as “carboxyl group-containing monomer”) include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Examples include acids. 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（以下、「水酸基含有モノマー」と称する場合がある）としては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、及び（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキルエステル等が挙げられる。水酸基含有モノマーの中でも、水酸基の反応性及び共重合性の点から、（メタ）アクリル酸２－ヒドロキシエチルが好ましい。水酸基含有モノマーは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the monomer having a hydroxyl group (hereinafter sometimes referred to as “hydroxyl group-containing monomer”) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 3- And (meth) acrylic acid hydroxyalkyl esters such as hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 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.
　エポキシ基を有するアクリル酸エステルとしては、例えば、グリシジルアクリレート、及びグリシジルメタクリレート等が挙げられる。 Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
　アクリル系共重合体における第二の共重合体成分としては、上記の他、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、芳香族環を有する（メタ）アクリル酸エステル、非架橋性のアクリルアミド、非架橋性の３級アミノ基を有する（メタ）アクリル酸エステル、酢酸ビニル、及びスチレンからなる群から選択される少なくともいずれかのモノマーに由来する共重合体成分が挙げられる。 As the second copolymer component in the acrylic copolymer, in addition to the above, for example, an alkoxyalkyl group-containing (meth) acrylic acid ester, a (meth) acrylic acid ester having an aromatic ring, non-crosslinkable acrylamide And a copolymer component derived from at least one monomer selected from the group consisting of (meth) acrylic acid ester having a non-crosslinkable tertiary amino group, vinyl acetate, and styrene.
　アルコキシアルキル基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メトキシメチル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシメチル、及び（メタ）アクリル酸エトキシエチル等が挙げられる。
　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等が挙げられる。
　非架橋性のアクリルアミドとしては、例えば、アクリルアミド、及びメタクリルアミド等が挙げられる。
　非架橋性の３級アミノ基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸（Ｎ，Ｎ－ジメチルアミノ）エチル、及び（メタ）アクリル酸（Ｎ，Ｎ－ジメチルアミノ）プロピル等が挙げられる。
　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 the alkoxyalkyl group-containing (meth) acrylic acid ester include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. It is done.
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). And propyl.
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、アクリル系共重合体は、水酸基を有するモノマーに由来する共重合体成分を含むことが好ましい。
　アクリル系共重合体が、水酸基を有するモノマーに由来する共重合体成分を含むことで、後述する架橋剤を使用する場合に、水酸基を架橋点とした架橋密度を上昇させることができ、樹脂漏れを防止できるため、チップずれ防止に効果的である。
　アクリル系共重合体全体の質量に占める、水酸基を有するモノマーに由来する共重合体成分の質量の割合は、３質量％以上であることが好ましい。水酸基含有モノマーに由来する共重合体成分の質量の割合が３質量％以上であれば、樹脂漏れをより効果的に防止することができる。
　フィリング性を向上させる観点から、アクリル系共重合体全体の質量に占める、水酸基を有するモノマーに由来する共重合体成分の質量の割合は、９．９質量％以下であることが好ましい。 In the present embodiment, the acrylic copolymer preferably includes a copolymer component derived from a monomer having a hydroxyl group.
When the acrylic copolymer contains a copolymer component derived from a monomer having a hydroxyl group, when a crosslinking agent described later is used, the crosslinking density with the hydroxyl group as a crosslinking point can be increased. This is effective in preventing chip displacement.
The ratio of the mass of the copolymer component derived from the monomer having a hydroxyl group to the total mass of the acrylic copolymer is preferably 3% by mass or more. If the proportion of the mass of the copolymer component derived from the hydroxyl group-containing monomer is 3% by mass or more, resin leakage can be more effectively prevented.
From the viewpoint of improving the filling property, the ratio of the mass of the copolymer component derived from the monomer having a hydroxyl group to the total mass of the acrylic copolymer is preferably 9.9% by mass or less.
　本実施形態において、表面自由エネルギーの増大を防ぐ観点から、アクリル系共重合体は、カルボキシル基を有するモノマーに由来する共重合体成分を含まないことも好ましい。または、アクリル系共重合体は、カルボキシル基を有するモノマーに由来する共重合体成分を含み、かつ、前記アクリル系共重合体全体の質量に占める、前記カルボキシル基を有するモノマー由来の共重合体成分の質量の割合が１質量％以下であることも好ましく、０．０５質量％以上１質量％以下であることがより好ましい。 In this embodiment, from the viewpoint of preventing an increase in surface free energy, the acrylic copolymer preferably does not contain a copolymer component derived from a monomer having a carboxyl group. Alternatively, the acrylic copolymer includes a copolymer component derived from a monomer having a carboxyl group, and the copolymer component derived from the monomer having a carboxyl group occupies the mass of the entire acrylic copolymer. The mass ratio is preferably 1% by mass or less, and more preferably 0.05% by mass or more and 1% by mass or less.
　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粘着シートを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、粘着シートを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. When the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, the pressure-sensitive adhesive sheet can be peeled without a residue of pressure-sensitive adhesive on the adherend. If the weight average molecular weight Mw of an acrylic copolymer is 2 million or less, an adhesive sheet can be reliably affixed on a to-be-adhered body.
The weight average molecular weight (Mw) of the acrylic copolymer is a standard polystyrene conversion 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。 The form of copolymerization of the acrylic copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, or a graft copolymer.
　本実施形態において、アクリル系粘着剤組成物全体の質量に占める、アクリル系共重合体の質量の割合は、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。 In the present embodiment, the proportion of the mass of the acrylic copolymer in the total mass of the acrylic pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and 50% by mass or more and 90% by mass or less. It is more preferable that
　本実施形態において、粘着剤層１２がアクリル系粘着剤組成物からなる場合、アクリル系粘着剤組成物は、アクリル系共重合体と、粘着助剤と、を含有することが好ましい。アクリル系粘着剤組成物が粘着助剤を含有することで、粘着シートの初期タックが向上し、粘着シートをフレームに貼付した時の剥がれを防止できる。
　本実施形態において、アクリル系粘着剤組成物が含有する粘着助剤は、炭化水素骨格を有するオリゴマーを含んでいることが好ましい。オリゴマーは、分子量１０，０００未満の重合体であることが好ましい。
　アクリル系粘着剤組成物が炭化水素骨格を有するオリゴマーを含む粘着助剤を含有することで、上記の効果に加えて、表面自由エネルギーの増大を抑制し、フィリング性を向上させることができる。
　炭化水素骨格を有するオリゴマーは、反応性基を有することが好ましい。炭化水素骨格を有し、かつ、反応性基を有するオリゴマーを、以下、炭化水素系反応性粘着助剤ということもある。粘着剤組成物が炭化水素系反応性粘着助剤を含んでいると、糊残りを減少させることができる。
　本実施形態において、粘着助剤における反応性基としては、水酸基、イソシアネート基、アミノ基、オキシラン基、酸無水物基、アルコキシ基、アクリロイル基、及びメタクリロイル基からなる群より選択される一種以上の官能基であることが好ましく、水酸基であることがより好ましい。粘着助剤が有する反応性基は、１種類でも、２種類以上でもよい。水酸基を有する粘着助剤は、さらに前述の別の反応性基を有していてもよい。また、反応性基の数は、粘着助剤を構成する１分子中に１つでも、２つ以上でもよい。 In this embodiment, when the adhesive layer 12 consists of an acrylic adhesive composition, it is preferable that an acrylic adhesive composition contains an acrylic copolymer and an adhesion aid. When the acrylic pressure-sensitive adhesive composition contains a pressure-sensitive adhesive agent, the initial tack of the pressure-sensitive adhesive sheet is improved, and peeling when the pressure-sensitive adhesive sheet is attached to the frame can be prevented.
In this embodiment, it is preferable that the adhesion promoter contained in the acrylic pressure-sensitive adhesive composition contains an oligomer having a hydrocarbon skeleton. The oligomer is preferably a polymer having a molecular weight of less than 10,000.
In addition to the above effects, the acrylic pressure-sensitive adhesive composition contains an adhesion assistant containing an oligomer having a hydrocarbon skeleton, and in addition, the increase in surface free energy can be suppressed and the filling property can be improved.
The oligomer having a hydrocarbon skeleton preferably has a reactive group. Hereinafter, the oligomer having a hydrocarbon skeleton and having a reactive group may be referred to as a hydrocarbon-based reactive adhesion aid. When the pressure-sensitive adhesive composition contains a hydrocarbon-based reactive pressure-sensitive adhesion assistant, the adhesive residue can be reduced.
In the present embodiment, the reactive group in the adhesion promoter is one or more 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. It is preferably a functional group, more preferably a hydroxyl group. One type or two or more types of reactive groups may be included in the adhesion aid. The adhesion promoter having a hydroxyl group may further have another reactive group described above. In addition, the number of reactive groups may be one per molecule constituting the adhesion aid, or two or more.
　炭化水素骨格を有するオリゴマーは、粘着剤層の表面自由エネルギーの低下と、糊残りの防止の観点から、ゴム系材料であることが好ましい。ゴム系材料としては、特に限定されないが、ポリブタジエン系樹脂、及びポリブタジエン系樹脂の水素添加物が好ましく、ポリブタジエン系樹脂の水素添加物がより好ましい。
　ポリブタジエン系樹脂としては、１，４－繰り返し単位を有する樹脂、１，２－繰り返し単位を有する樹脂、並びに１，４－繰り返し単位及び１，２－繰り返し単位の両方を有する樹脂が挙げられる。本実施形態のポリブタジエン系樹脂の水素添加物は、これらの繰り返し単位を有する樹脂の水素化物も含む。 The oligomer having a hydrocarbon skeleton is preferably a rubber-based material from the viewpoint of reducing the surface free energy of the pressure-sensitive adhesive layer and preventing adhesive residue. The rubber-based material is not particularly limited, but a polybutadiene-based resin and a hydrogenated product of a polybutadiene-based resin are preferable, and a hydrogenated product of a polybutadiene-based resin is more preferable.
Examples of the polybutadiene-based resin include resins having 1,4-repeating units, resins having 1,2-repeating units, and resins having both 1,4-repeating units and 1,2-repeating units. The hydrogenated product of the polybutadiene resin of the present embodiment includes a hydride of a resin having these repeating units.
　ゴム系材料が反応性基を有する場合、ポリブタジエン系樹脂、及びポリブタジエン系樹脂の水素添加物は、両末端にそれぞれ反応性基を有することが好ましい。両末端の反応性基は、同一でも異なっていてもよい。両末端の反応性基は、水酸基、イソシアネート基、アミノ基、オキシラン基、酸無水物基、アルコキシ基、アクリロイル基、及びメタクリロイル基からなる群より選択される一種以上の官能基であることが好ましく、水酸基であることがより好ましい。ポリブタジエン系樹脂、及びポリブタジエン系樹脂の水素添加物においては、両末端が水酸基であることがより好ましい。 When the rubber-based material has a reactive group, the polybutadiene-based resin and the hydrogenated product of the polybutadiene-based resin preferably each have a reactive group 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 preferably, it 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、粘着助剤は、アセチルクエン酸トリエステルを含むことも好ましい。粘着剤組成物が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。
　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, it is also preferable that the adhesion promoter contains acetyl citrate triester. When the pressure-sensitive adhesive composition contains acetyl citrate triester, adhesive residue can be reduced.
In the present embodiment, examples of the acetylcitrate triester-based tackifier include tributyl acetylcitrate (ATBC).
　粘着剤組成物全体の質量に占める、粘着助剤の質量の割合は、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。
　また、粘着助剤が、炭化水素骨格を有するオリゴマーを含む場合、粘着剤組成物全体の質量に占める、炭化水素骨格を有するオリゴマーの質量の割合は、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。 The ratio of the mass of the adhesion assistant to the mass of the entire 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.
Moreover, when the adhesion assistant includes an oligomer having a hydrocarbon skeleton, the proportion of the mass of the oligomer having a hydrocarbon skeleton in the mass of the entire pressure-sensitive adhesive composition is 3% by mass or more and 50% by mass or less. Is preferable, and more preferably 5% by mass or more and 30% by mass or less.
　本実施形態に係るアクリル系粘着剤組成物は、前述のアクリル系共重合体と、さらに架橋剤と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、本実施形態に係るアクリル系粘着剤組成物は、前述のアクリル系共重合体と、炭化水素系反応性粘着助剤と、さらに架橋剤と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。 It is also preferable that the acrylic pressure-sensitive adhesive composition according to this embodiment includes a cross-linked product obtained by cross-linking a composition containing the above-mentioned acrylic copolymer and a cross-linking agent.
In addition, the acrylic pressure-sensitive adhesive composition according to this embodiment is obtained by cross-linking a composition obtained by blending the above-mentioned acrylic copolymer, a hydrocarbon-based reactive adhesive aid, and a cross-linking agent. It is also preferable to include a product.
　本実施形態において、架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤、アミン系架橋剤、及びアミノ樹脂系架橋剤等が挙げられる。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。 In this 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.
　本実施形態において、アクリル系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である架橋剤（イソシアネート系架橋剤）が好ましい。イソシアネート系架橋剤としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルメタン－２，４’－ジイソシアネート、３－メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、ジシクロヘキシルメタン－２，４’－ジイソシアネート、及びリジンイソシアネート等の多価イソシアネート化合物が挙げられる。
　また、多価イソシアネート化合物は、これら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。 In the present embodiment, from the viewpoint of improving the heat resistance and adhesive strength of the acrylic pressure-sensitive adhesive composition, among these cross-linking agents, a cross-linking agent (isocyanate-based cross-linking agent) that is a compound having an isocyanate group 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.
Further, the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of these compounds, a burette type modified product reacted with water, or an isocyanurate type modified product having an isocyanurate ring.
　本実施形態において、アクリル系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。アクリル系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、粘着剤層１２の１００℃での貯蔵弾性率を、上述の範囲に調整することが容易となる。 In the present embodiment, the content of the crosslinking agent in the acrylic 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 with respect to 100 parts by mass of the acrylic copolymer. Part to 15 parts by mass, more preferably 5 parts to 10 parts by mass. If content of the crosslinking agent in an acrylic adhesive composition is in such a range, it will become easy to adjust the storage elastic modulus in 100 degreeC of the adhesive layer 12 to the above-mentioned range.
　本実施形態においては、アクリル系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、イソシアネート基が０．７当量以上１．５当量以下となるように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 acrylic 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 so that the isocyanate group is 0.7 equivalent or more and 1.5 equivalent or less 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アクリル系粘着剤組成物が架橋剤を含む場合、当該アクリル系粘着剤組成物は、架橋促進剤をさらに含むことが好ましい。架橋促進剤は、架橋剤の種類等に応じて、適宜選択して用いることが好ましい。例えば、アクリル系粘着剤組成物が、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、有機スズ化合物等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 acrylic pressure-sensitive adhesive composition in the present embodiment contains a crosslinking agent, the acrylic 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 acrylic pressure-sensitive adhesive composition contains a polyisocyanate compound as a cross-linking agent, it is preferable to further contain an organic metal compound-based cross-linking 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からなる場合、シリコーン系粘着剤組成物は、シリコーン樹脂を含むことが好ましく、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 adhesive composition When the adhesive layer 12 consists of a silicone adhesive composition, it is preferable that a silicone adhesive composition contains a silicone resin, and it is preferable that an addition polymerization type silicone resin is included. 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.
　本実施形態において、付加反応型シリコーン系粘着剤組成物は、主剤（付加重合型シリコーン樹脂）、及び架橋剤を含有する。付加反応型シリコーン系粘着剤組成物は、低温での一次硬化だけで使用することが可能で、高温での二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二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、臭気及び腐食等の問題もない。 In the present embodiment, the addition reaction type silicone pressure-sensitive adhesive composition contains a main agent (addition polymerization type silicone resin) 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 low temperature and does not require secondary curing at high temperature. Incidentally, the conventional peroxide curable 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 curable silicone pressure-sensitive adhesive, there are no problems such as odor and corrosion.
　付加反応型シリコーン系粘着剤組成物は、通常、シリコーン樹脂成分とシリコーンゴム成分との混合物からなる主剤、及びヒドロシリル基（ＳｉＨ基）含有の架橋剤、並びに必要に応じて使用される硬化触媒からなる。
　シリコーン樹脂成分は、オルガノクロルシランまたはオルガノアルコキシシランを加水分解した後、脱水縮合反応を行うことにより得られる網状構造のオルガノポリシロキサンである。
　シリコーンゴム成分は、直鎖構造を有するジオルガノポリシロキサンである。
　オルガノ基としては、シリコーン樹脂成分、及びシリコーンゴム成分ともに、例えば、メチル基、エチル基、プロピル基、ブチル基、及びフェニル基等である。前述のオルガノ基は、一部、ビニル基、ヘキセニル基、アリル基、ブテニル基、ペンテニル基、オクテニル基、（メタ）アクリロイル基、（メタ）アクリロイルメチル基、（メタ）アクリロイルプロピル基、及びシクロヘキセニル基等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、主剤における不飽和基と、架橋剤における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。 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.
Examples of the organo group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, both of the silicone resin component and the silicone rubber component. The aforementioned organo groups are partially vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth) acryloyl, (meth) acryloylmethyl, (meth) acryloylpropyl, and cyclohexenyl. It is substituted 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-based pressure-sensitive adhesive composition, cross-linking proceeds by an addition reaction between the unsaturated group in the main agent and the hydrosilyl group in the cross-linking agent to form a network structure, thereby exhibiting adhesiveness.
　シリコーン樹脂成分において、ビニル基等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、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。 In the silicone resin component, the number of unsaturated groups such as vinyl groups is usually 0.05 or more and 3.0 or less, preferably 0.1 or more and 2.5, per 100 organo groups. It is as follows. 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 appropriate adhesive strength. . 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、信越化学工業株式会社製の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・ダウコーニング株式会社製の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）等がある。また、東レ・ダウコーニング株式会社製のＳＤ４５６０ＰＳＡ、ＳＤ４５７０ＰＳＡ、ＳＤ４５８０ＰＳＡ、ＳＤ４５８４ＰＳＡ、ＳＤ４５８５ＰＳＡ、ＳＤ４５８７Ｌ、及びＳＤ４５９２ＰＳＡ等も使用することができる。 Specific examples of the organopolysiloxane as described above include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 with respect to 100 methyl groups), Toray Dow BY23-753 manufactured by Corning Co., Ltd. (the number of vinyl groups is 0.1 with respect to 100 methyl groups), and BY24-162 (the number of vinyl groups is 1.4 with respect to 100 methyl groups). Etc.). In addition, SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Toray Dow Corning Co., Ltd. can also be used.
　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、シリコーンゴム成分としては、信越化学工業株式会社製の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・ダウコーニング株式会社製の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）等が挙げられる。 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. (the number of vinyl groups is methyl) is used. 7.6 for 100 groups), BY24-162 manufactured by Toray Dow Corning Co., Ltd. (for which the number of vinyl groups is 1.4 for 100 methyl groups), BY24- 843 (having no unsaturated group), SD-7292 (having 5.0 vinyl groups per 100 methyl groups), and the like.
　前述のような付加重合型シリコーン樹脂（付加型シリコーン）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 addition polymerization type silicone resin (addition 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不飽和基（ビニル基等）１個に対して、通常、ケイ素原子に結合した水素原子が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、不飽和基（ビニル基等）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 cross-linking agent usually has 0.5 to 10 hydrogen atoms bonded to silicon atoms, preferably 1 to one unsaturated group (vinyl group, etc.) 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 (vinyl group and the like) and the hydrosilyl group does not proceed completely, thereby preventing poor curing. By setting the number to 10 or less, it is possible to prevent the crosslinking agent from remaining unreacted and adversely affecting the adherend surface.
　付加反応型シリコーン系粘着剤組成物は、前述の付加反応型シリコーン成分（シリコーン樹脂成分とシリコーンゴム成分とからなる主剤）、及び架橋剤とともに、硬化触媒を含有していることも好ましい。
　この硬化触媒は、シリコーン樹脂成分及びシリコーンゴム成分中の不飽和基と、架橋剤中のＳｉＨ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、例えば東レ・ダウコーニング株式会社製のＳＲＸ-２１２、及び信越化学工業株式会社製のＰＬ-５０Ｔ等が挙げられる。 The addition reaction type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst together with the aforementioned addition reaction type silicone component (main agent comprising a silicone resin component and a silicone rubber component) and a crosslinking agent.
This curing catalyst is used for promoting the hydrosilylation reaction between the unsaturated group in the silicone resin component and the silicone rubber component and the SiH 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, examples of commercially available products include SRX-212 manufactured by Toray Dow Corning Co., Ltd., and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
　硬化触媒が白金系の触媒である場合、その配合量は、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。配合量を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、すなわち、粘着力及び凝集力（保持力）が低下するのを防ぎ、２０００質量ｐｐｍ以下とすることにより、コストアップを防ぐとともに粘着剤層の安定性を保持することができ、かつ、過剰に使用された硬化触媒が被着面に悪影響を与えるのを防止する。 When the curing catalyst is a platinum-based catalyst, the blending amount thereof is usually 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass, with respect to the total amount of the silicone resin component and the silicone rubber component as platinum content. It is mass ppm or more and 500 mass ppm or less. By setting the blending amount to 5 mass ppm or more, curability is reduced and the crosslinking density, that is, the adhesive force and cohesive force (holding force) is prevented from being decreased, and by setting it to 2000 mass ppm or less, the cost is increased. And the stability of the pressure-sensitive adhesive layer can be maintained, and the excessively used curing catalyst is prevented from adversely affecting the adherend 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とを付加反応型シリコーン系粘着剤組成物を介して貼り合わせた後、加熱または活性エネルギー線を照射して、架橋剤によるシリコーン樹脂成分とシリコーンゴム成分との架橋反応を促進させることが、好ましい。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。 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 through the addition reaction type silicone pressure-sensitive adhesive composition, the silicone resin component and the silicone rubber component by the crosslinking agent are irradiated with heat or active energy rays. It is preferable to promote the crosslinking reaction. A pressure-sensitive adhesive sheet having a stable adhesive force can be obtained by crosslinking by irradiation with heat or active energy rays.
　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と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 promoted 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. Heating at 140 ° C. or lower causes heat shrinkage to the substrate. Wrinkles can be prevented from being deteriorated or discolored.
　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、紫外線等の活性光または電子線等を利用できる。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、紫外線等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。
　紫外線照射により架橋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、その他化合物等が挙げられる。
　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。 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 crosslinking by ultraviolet irradiation is not particularly limited, and any photopolymerization initiator conventionally used in an ultraviolet curable resin is appropriately selected and used. be able to. 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.
　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と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以下であることが好ましい。
　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ことが好ましい。 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. By irradiating with an acceleration voltage of 130 kV or more, it is possible to prevent the adhesive force from becoming insufficient due to insufficient crosslinking between the silicone resin component and the silicone rubber component. By irradiating with an acceleration voltage of 300 kV or less, It can prevent that an adhesive layer and a base material 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 or more and 70 Mrad or less, and more preferably 2 Mrad or more and 20 Mrad or less. By irradiating with a dose of 1 Mrad or more, it is possible to prevent the pressure-sensitive adhesive layer and the substrate from being deteriorated or discolored, and to 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 a decrease in cohesive force due to deterioration or discoloration of the pressure-sensitive adhesive layer, and it is possible to prevent the base material from being deteriorated or contracted.
The irradiation amount in the case of ultraviolet irradiation is appropriately selected. The light amount is preferably 100 mJ / cm 2 or more and 500 mJ / cm 2 or less, and the illuminance is preferably 10 mW / cm 2 or more and 500 mW / cm 2 or less.
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、及び濡れ性調整剤等が挙げられる。
　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等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 a non-reactive polyorganosiloxane such as polydimethylsiloxane and polymethylphenylsiloxane as an additive.
　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。 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 adhesion assistant contains 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, 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 is a hydroxylated hydrogenated polybutadiene at both terminals, and the crosslinking agent is an isocyanate-based crosslinking agent Is mentioned.
As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and An acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the adhesion assistant contains a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent And a pressure-sensitive adhesive composition.
As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Things.
　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。そのため、例えば、層間絶縁材及び封止樹脂等が半導体チップの回路面の凹凸の隙間に入り込み、チップ回路面の配線接続用の電極パッドが塞がれる等のおそれがない。粘着剤層１２の厚みが６０μｍ以下であれば、半導体チップが粘着剤層に沈み込み難く、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難くなる。そのため、再配線の際に段差により配線が断線する等のおそれがない。 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. 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. Therefore, for example, there is no possibility that the interlayer insulating material, the sealing resin, and the like enter the gaps in the irregularities on the circuit surface of the semiconductor chip, and the electrode pads for wiring connection on the chip circuit surface are blocked. When the thickness of the pressure-sensitive adhesive layer 12 is 60 μm or less, the semiconductor chip is unlikely to sink into the pressure-sensitive adhesive layer, and a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip is less likely to occur. Therefore, there is no fear that the wiring is disconnected due to a step during rewiring.
（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、及びプラスチックフィルム等が挙げられる。紙基材としては、グラシン紙、コート紙、及びキャストコート紙等が挙げられる。プラスチックフィルムとしては、ポリエステルフィルム（例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリエチレンナフタレート等）、並びにポリオレフィンフィルム（例えば、ポリプロピレン、及びポリエチレン等）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、及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。粘着剤層が、シリコーン系粘着剤組成物からなる場合には、剥離剤は、非シリコーン系の剥離剤であることが好ましい。 (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 (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), polyolefin films (for example, polypropylene, polyethylene, and the like), and the like.
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. . When the pressure-sensitive adhesive layer is composed of a silicone-based pressure-sensitive adhesive composition, the release agent is preferably a non-silicone-based release agent.
　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.
（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、及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、及びグラビアコート法等が挙げられる。
　有機溶媒及び低沸点成分が粘着剤層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、パネルスケールパッケージ（Ｐａｎｅｌ　Ｓｃａｌｅ　Ｐａｃｋａｇｅ；ＰＳＰ）及びＷＬＰ等が挙げられる。
　粘着シート１０は、複数の開口部が形成された枠部材を粘着シート１０に貼着させる工程と、前記枠部材の開口部にて露出する粘着剤層１２に半導体チップを貼着させる工程と、前記半導体チップを封止樹脂で覆う工程と、前記封止樹脂を熱硬化させる工程と、を有するプロセスにおいて使用されることが好ましい。 (Use of adhesive sheet)
The pressure-sensitive adhesive sheet 10 is used when sealing a semiconductor element. The pressure-sensitive adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing a semiconductor element that is stuck on the pressure-sensitive adhesive sheet 10. Specifically, the pressure-sensitive adhesive sheet 10 is not used when sealing a semiconductor element mounted on a metal lead frame, but seals a semiconductor element that is stuck to the pressure-sensitive adhesive layer 12. Preferably used. As a form of packaging a semiconductor element without using a metal lead frame, a panel scale package (PSP), WLP, or the like can be given.
The pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process having a step of covering the semiconductor chip with a sealing resin and a step of thermosetting the sealing resin.
（半導体装置の製造方法）
　本実施形態に係る粘着シート１０を用いて半導体装置を製造する方法を説明する。
　図２Ａ～図２Ｅには、本実施形態に係る半導体装置の製造方法を説明する概略図が示されている。
　本実施形態に係る半導体装置の製造方法は、粘着シート１０に複数の開口部２１が形成された枠部材２０を貼着させる工程（粘着シート貼着工程）と、枠部材２０の開口部２１にて露出する粘着剤層１２に半導体チップＣＰを貼着させる工程（ボンディング工程）と、半導体チップＣＰを封止樹脂３０で覆う工程（封止工程）と、封止樹脂３０を熱硬化させる工程（熱硬化工程）と、熱硬化させた後、粘着シート１０を剥離する工程（剥離工程）と、を実施する。必要に応じて、熱硬化工程の後に、封止樹脂３０で封止された封止体５０に補強部材４０を貼着させる工程（補強部材貼着工程）を実施してもよい。
　以下、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の粘着剤層１２上に剥離シート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 the peeling sheet RL is stuck on the adhesive layer 12 of the adhesive sheet 10, the peeling sheet RL is peeled beforehand.
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ェハの裏面を研削するバックグラインド工程、及び半導体ウェ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、半導体ウェハの裏面をダイシングシートの接着剤層に貼着し、ダイシングソー等の切断手段を用いて半導体ウェ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 separating the semiconductor wafer into individual pieces. In the dicing process, a semiconductor chip CP (semiconductor element) is obtained by sticking the back surface of 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を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、半導体ウェハの貼付後、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 step, 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.
・封止工程及び熱硬化工程
　図２Ｃには、粘着シート１０に貼着された半導体チップＣＰ及び枠部材２０を封止する工程を説明する概略図が示されている。
　封止樹脂３０の材質は、熱硬化性樹脂であり、例えば、エポキシ樹脂等が挙げられる。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、及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及び枠部材２０を覆う方法は、特に限定されない。本実施形態では、シート状の封止樹脂３０を用いた態様を例に挙げて説明する。シート状の封止樹脂３０を半導体チップＣＰ及び枠部材２０を覆うように載置し、封止樹脂３０を加熱硬化させて、封止樹脂層３０Ａを形成する。このようにして、半導体チップＣＰ及び枠部材２０が封止樹脂層３０Ａに埋め込まれる。シート状の封止樹脂３０を用いる場合には、真空ラミネート法により半導体チップＣＰ及び枠部材２０を封止することが好ましい。この真空ラミネート法により、半導体チップＣＰと枠部材２０との間に空隙が生じることを防止できる。真空ラミネート法による加熱硬化の温度条件範囲は、例えば、８０℃以上１２０℃以下である。シート状の封止樹脂３０を用いる場合、封止工程前において、シート状の封止樹脂は固体である。そのため、液状の封止樹脂を用いるよりも、フィリング性に劣る場合がある。本実施形態の粘着シート１０は、粘着剤層１２の表面自由エネルギーが１０ｍＪ／ｍ２以上２２ｍＪ／ｍ２以下であるため、封止樹脂がシート状であっても、フィリング性に優れ、本工程での不具合の発生を防止することができる。 -Sealing process and thermosetting process The schematic diagram explaining the process of sealing the semiconductor chip CP and the frame member 20 which were affixed on the adhesive sheet 10 is shown by FIG. 2C.
The material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin. The epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
The method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited. In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example. The sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A. When the sheet-shaped sealing resin 30 is used, it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being generated between the semiconductor chip CP and the frame member 20. The temperature condition range for heat curing by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less. When the sheet-shaped sealing resin 30 is used, the sheet-shaped sealing resin is solid before the sealing step. Therefore, the filling property may be inferior to using a liquid sealing resin. The adhesive sheet 10 of the present embodiment, since the surface free energy of the pressure-sensitive adhesive layer 12 is 10 mJ / m 2 or more 22 mJ / m 2 or less, even the sealing resin is a sheet-like, excellent in filling property, this step It is possible to prevent the occurrence of problems in
　封止工程では、シート状の封止樹脂３０がポリエチレンテレフタレート等の樹脂シートに支持された積層シートを用いてもよい。この場合、半導体チップＣＰ及び枠部材２０を覆うように積層シートを載置した後、樹脂シートを封止樹脂３０から剥離して、封止樹脂３０を加熱硬化させてもよい。このような積層シートとしては、例えば、ＡＢＦフィルム（味の素ファインテクノ株式会社製）等が挙げられる。 In the sealing step, a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used. In this case, after the laminated sheet is placed so as to cover the semiconductor chip CP and the frame member 20, the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured. Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
　半導体チップＣＰ及び枠部材２０を封止する方法としては、トランスファーモールド法を採用してもよい。この場合、例えば、封止装置の金型の内部に、粘着シート１０に貼着された半導体チップＣＰ及び枠部材２０を収容する。この金型の内部に流動性の樹脂材料を注入し、樹脂材料を硬化させる。トランスファーモールド法の場合、加熱及び圧力の条件は、特に限定されない。トランスファーモールド法における通常の条件の一例として、１５０℃以上の温度と、４ＭＰａ以上１５ＭＰａ以下の圧力を、３０秒以上３００秒以下の間維持する。その後、加圧を解除し、封止装置から硬化物を取り出してオーブン内に静置して、１５０℃以上の温度を、２時間以上１５時間以下、維持する。このようにして、半導体チップＣＰ及び枠部材２０を封止する。 As a method for sealing the semiconductor chip CP and the frame member 20, a transfer molding method may be employed. In this case, for example, the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device. A fluid resin material is injected into the mold to cure the resin material. In the case of the transfer mold method, the heating and pressure conditions are not particularly limited. As an example of normal conditions in the transfer mold method, a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds. Thereafter, the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
　前述の封止工程においてシート状の封止樹脂３０を用いる場合、封止樹脂３０を熱硬化させる工程（熱硬化工程）の前に、第一加熱プレス工程を実施してもよい。第一加熱プレス工程においては、封止樹脂３０で被覆された半導体チップＣＰ及び枠部材２０付き粘着シート１０を両面から板状部材で挟み込み、所定の温度、時間、及び圧力の条件下でプレスする。第一加熱プレス工程を実施することにより、封止樹脂３０が半導体チップＣＰと枠部材２０との空隙にも充填され易くなる。また、加熱プレス工程を実施することにより、封止樹脂３０により構成される封止樹脂層３０Ａの凹凸を平坦化することもできる。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 by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. . By performing the first heat pressing step, the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20. Moreover, the unevenness | corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process. 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を剥離すると、封止樹脂３０で封止された半導体チップＣＰ及び枠部材２０が得られる。以下、これを封止体５０と称する場合がある。 When the pressure-sensitive adhesive sheet 10 is peeled after the thermosetting step, the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained. Hereinafter, this may be referred to as a sealing body 50.
・補強部材貼着工程
　図２Ｄには、封止体５０に補強部材４０を貼着させる工程を説明する概略図が示されている。
　粘着シート１０を剥離した後、露出した半導体チップＣＰの回路面に対して再配線層を形成する再配線工程及びバンプ付け工程が実施される。
　このような再配線工程及びバンプ付け工程における封止体５０の取り扱い性を向上させるため、必要に応じて、封止体５０に補強部材４０を貼着させる工程（補強部材貼着工程）を実施してもよい。補強部材貼着工程を実施する場合には、粘着シート１０を剥離する前に実施することが好ましい。図２Ｄに示すように、封止体５０は、粘着シート１０及び補強部材４０によって挟まれた状態で支持されている。 -Reinforcing member sticking process The schematic diagram explaining the process of sticking the reinforcing member 40 to the sealing body 50 is shown by FIG. 2D.
After the adhesive sheet 10 is peeled off, a rewiring process and a bumping process for forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed.
In order to improve the handleability of the sealing body 50 in such a rewiring process and a bumping process, a process (reinforcing member attaching process) of attaching the reinforcing member 40 to the sealing body 50 is performed as necessary. May be. When implementing a reinforcement member sticking process, it is preferable to carry out before peeling the adhesive sheet 10. FIG. As illustrated in FIG. 2D, the sealing body 50 is supported in a state of being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
　本実施形態では、補強部材４０は、耐熱性の補強板４１と、耐熱性の接着層４２とを備える。
　補強板４１としては、例えば、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を含む板状の部材が挙げられる。
　接着層４２は、補強板４１と封止体５０とを接着させる。接着層４２としては、補強板４１及び封止樹脂層３０Ａの材質に応じて適宜選択される。例えば、封止樹脂層３０Ａがエポキシ系樹脂を含み、補強板４１がガラスエポキシ樹脂を含んでいる場合には、接着層４２としては、熱可塑性樹脂を含んだガラスクロスが好ましく、接着層４２に含まれる熱可塑性樹脂としては、ビスマレイミドトリアジン樹脂（ＢＴレジン）が好ましい。 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 polyimide resin and 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. For example, when the sealing resin layer 30A includes an epoxy resin and the reinforcing plate 41 includes a glass epoxy resin, the adhesive layer 42 is preferably a glass cloth including a thermoplastic resin. As the thermoplastic resin contained, bismaleimide triazine resin (BT resin) is preferable.
　補強部材貼着工程では、封止体５０の封止樹脂層３０Ａと補強板４１との間に接着層４２を挟み込み、さらに補強板４１側及び粘着シート１０側からそれぞれ板状部材で挟み込み、所定の温度、時間、及び圧力の条件下でプレスする第二加熱プレス工程を実施することが好ましい。第二加熱プレス工程により、封止体５０と補強部材４０とを仮固定する。第二加熱プレス工程の後に、接着層４２を硬化させるために、仮固定された封止体５０と補強部材４０とを所定の温度及び時間の条件下で加熱することが好ましい。加熱硬化の条件は、接着層４２の材質に応じて適宜設定され、例えば、１８５℃、８０分間、及び２．４ＭＰａの条件である。第二加熱プレス工程においても、板状部材としては、例えば、ステンレス等の金属板を用いることができる。 In the reinforcing member sticking step, the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure. The sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time. The conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa. Also in the second heat pressing step, as the plate-like member, for example, a metal plate such as stainless steel can be used.
・剥離工程
　図２Ｅには、粘着シート１０を剥離する工程を説明する概略図が示されている。
　本実施形態では、粘着シート１０の基材１１が屈曲可能であるため、粘着シート１０を屈曲させながら、枠部材２０、半導体チップＣＰ及び封止樹脂層３０Ａから容易に剥離することができる。剥離角度θは、特に限定されないが、９０度以上の剥離角度θで粘着シート１０を剥離することが好ましい。剥離角度θが９０度以上であれば、粘着シート１０を、枠部材２０、半導体チップＣＰ及び封止樹脂層３０Ａから容易に剥離することができる。剥離角度θは、９０度以上１８０度以下が好ましく、１３５度以上１８０度以下がより好ましい。このように粘着シート１０を屈曲させながら剥離を行うことで、枠部材２０、半導体チップＣＰ及び封止樹脂層３０Ａにかかる負荷を低減しながら剥離することができ、粘着シート１０の剥離による、半導体チップＣＰ及び封止樹脂層３０Ａの損傷を抑制することができる。粘着シート１０を剥離する際の温度雰囲気は、室温であってもよいが、剥離時における被着体の各部材及び部材間の界面の破壊が懸念される場合には、粘着剤の粘着性の低下を目的として、室温よりも高い温度雰囲気において粘着シート１０を剥離してもよい。室温よりも高い温度雰囲気としては、３０～６０℃の範囲が好ましく、３５～５０℃の範囲がより好ましい。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, since the base material 11 of the adhesive sheet 10 can be bent, it can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while the adhesive sheet 10 is bent. Although peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree | times or more. When the peeling angle θ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A. The peeling angle θ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less. By peeling the adhesive sheet 10 while bending the adhesive sheet 10 in this way, the peeling can be performed 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. The temperature atmosphere at the time of peeling the pressure-sensitive adhesive sheet 10 may be room temperature, but when there is a concern about the destruction of each member of the adherend and the interface between the members at the time of peeling, the pressure-sensitive adhesive of the pressure-sensitive adhesive For the purpose of lowering, the pressure-sensitive adhesive sheet 10 may be peeled in a temperature atmosphere higher than room temperature. The temperature atmosphere higher than room temperature is preferably in the range of 30 to 60 ° C, more preferably in the range of 35 to 50 ° C. 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、前述の半導体ウェ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、粘着シート上の半導体素子を封止する際の樹脂漏れを防止することができ、かつ粘着シート上の半導体素子を封止する際に良好なフィリング性を有する粘着シート１０を提供できる。また、本実施形態の粘着シート１０を用いた半導体装置の製造方法によれば、樹脂漏れを防止でき、チップが流されたり、浮いたりすることを防止できる。そのため、半導体装置の歩留まりが向上する。
　また、本実施形態の粘着シート１０を用いた半導体装置の製造方法によれば、封止工程において、図３に示すように、封止樹脂３０が、半導体チップＣＰの回路面ＣＰＡにおける周縁部にある段差部ＣＰＢと、粘着剤層１２との隙間Ｓを埋め込むことができる。
　段差部ＣＰＢと回路面ＣＰＡとの段差の高さ寸法ｘは、通常、０．１μｍ以上１０μｍ以下であり、好ましくは、０．５μｍ以上５μｍ以下である。この高さ寸法ｘが小さいほど、封止樹脂３０が隙間Ｓを埋め込み難くなるが、前記下限以上であれば、封止樹脂３０が隙間Ｓを埋め込むことができる。
　段差部ＣＰＢの幅寸法ｙは、通常、１μｍ以上１００μｍ以下であり、好ましくは、５μｍ以上５０μｍ以下である。この幅寸法ｙが大きいほど、封止樹脂３０が隙間Ｓを埋め込み難くなるが、前記上限以下であれば、封止樹脂３０が隙間Ｓを埋め込むことができる。 According to this embodiment, the adhesive sheet 10 can prevent resin leakage when sealing the semiconductor element on the adhesive sheet and has good filling properties when sealing the semiconductor element on the adhesive sheet. Can provide. Moreover, according to the manufacturing method of the semiconductor device using the adhesive sheet 10 of this embodiment, resin leakage can be prevented and the chip can be prevented from flowing or floating. Therefore, the yield of semiconductor devices is improved.
Moreover, according to the manufacturing method of the semiconductor device using the adhesive sheet 10 of the present embodiment, in the sealing process, as shown in FIG. 3, the sealing resin 30 is formed on the peripheral portion of the circuit surface CPA of the semiconductor chip CP. A gap S between a certain stepped portion CPB and the pressure-sensitive adhesive layer 12 can be embedded.
The height dimension x of the step between the step portion CPB and the circuit surface CPA is usually 0.1 μm or more and 10 μm or less, preferably 0.5 μm or more and 5 μm or less. As the height dimension x is smaller, the sealing resin 30 is less likely to fill the gap S. However, if the height dimension x is equal to or greater than the lower limit, the sealing resin 30 can fill the gap S.
The width dimension y of the stepped portion CPB is usually 1 μm or more and 100 μm or less, and preferably 5 μm or more and 50 μm or less. The larger the width dimension y, the harder the sealing resin 30 fills the gap S. However, the sealing resin 30 can embed the gap S as long as the upper limit is not reached.
〔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、シート片であってもよく、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、帯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 sheet piece, and may be provided in a state in which 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.
Further, the pressure-sensitive adhesive sheet 10 may be a belt-like sheet or may be provided in a state of being wound in a roll shape. 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の材質が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 embodiment, the case where the material of 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.
　前記実施形態において、半導体装置の製造方法における各工程については、必ず全ての工程を実施しなければならないわけではなく、一部の工程を省略し得る。 In the above-described embodiment, all the steps in the semiconductor device manufacturing method do not necessarily have to be performed, and some steps may be omitted.
　前記実施形態では、半導体装置の製造方法の説明において、枠部材２０を粘着シート１０に貼着させる態様を例に挙げて説明したが、本発明はこのような態様に限定されない。粘着シート１０は、枠部材を用いずに半導体素子を封止する半導体装置の製造方法において使用されてもよい。 In the above embodiment, in the description of the method for manufacturing a semiconductor device, an example in which the frame member 20 is attached to the adhesive sheet 10 has been described as an example, but the present invention is not limited to such an embodiment. The adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
　以下、実施例を挙げて本発明をさらに詳細に説明する。本発明はこれら実施例に何ら限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.
〔評価方法〕
　粘着シートの評価は、以下に示す方法に従って行った。
［貯蔵弾性率］
　実施例１における塗布用粘着剤液を、剥離フィルム（リンテック株式会社製、「ＰＥＴ３８０１」）に、コンマコーター（登録商標）を用いて塗布した後、乾燥（乾燥条件：９０℃、９０秒、及び１１５℃、９０秒）して、厚さ３０μｍの層を形成し、これを積層して厚さ１ｍｍ、直径８ｍｍの円形の測定用試料を作製した。得られた測定用試料の１００℃における貯蔵弾性率（Ｐａ）を、粘弾性測定装置（アントンパール・ジャパン製　ＭＣＲ）を用いて、ねじりせん断法により測定した。昇温速度は５℃／分、測定周波数は１Ｈｚとした。
　実施例２～５及び比較例１～３における塗布用粘着剤液を用いて、上記と同様にして、得られた測定用試料の１００℃における貯蔵弾性率（Ｐａ）を測定した。 〔Evaluation methods〕
Evaluation of the pressure-sensitive adhesive sheet was performed according to the following method.
[Storage modulus]
The coating adhesive solution in Example 1 was applied to a release film (“PET3801”, manufactured by Lintec Corporation) using a comma coater (registered trademark), and then dried (drying conditions: 90 ° C., 90 seconds, and 115 ° C., 90 seconds), a layer having a thickness of 30 μm was formed, and this was laminated to produce a circular measurement sample having a thickness of 1 mm and a diameter of 8 mm. The storage elastic modulus (Pa) at 100 ° C. of the obtained measurement sample was measured by a torsional shear method using a viscoelasticity measuring device (MCR manufactured by Anton Paar Japan). The heating rate was 5 ° C./min, and the measurement frequency was 1 Hz.
Using the coating adhesive solutions in Examples 2 to 5 and Comparative Examples 1 to 3, the storage elastic modulus (Pa) at 100 ° C. of the obtained measurement samples was measured in the same manner as described above.
［粘着力］
　被着体（ポリイミドフィルム）に、２ｋｇｆの荷重をかけて実施例１で作製した粘着シートの粘着面を貼付した。ポリイミドフィルムとしては、東レ・デュポン株式会社製の厚さ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、２５℃５０％相対湿度の環境下で０．５時間保管した後、恒温器（エスペック株式会社製、ＰＨＨ－２０２）を用いて、１９０℃及び１時間の条件で加熱した後、ポリイミドフィルム付き粘着シートを、２５℃５０％相対湿度の環境下で１時間保管した。その後、２５℃５０％相対湿度の環境下で、１８０°引き剥がし法により、粘着シートの粘着力を測定した。なお、測定機として、恒温槽付測定機（株式会社Ａ＆Ｄ製、ＴＥＮＳＩＬＯＮ）を用い、引張速度は３００ｍｍ／分、粘着シートの幅は２５ｍｍとした。
　実施例２～５及び比較例１～３で作製した粘着シートについても、上記と同様にして、粘着シートの粘着力を測定した。 [Adhesive force]
The pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet produced in Example 1 was applied to an adherend (polyimide film) with a load of 2 kgf. As the polyimide film, Kapton 100H (product name) having a thickness of 25 μm manufactured by Toray DuPont Co., Ltd. was used. This polyimide film-attached pressure-sensitive adhesive sheet is stored for 0.5 hours in an environment of 25 ° C. and 50% relative humidity, and then using a thermostat (PHH-202, manufactured by ESPEC Corporation) under the conditions of 190 ° C. and 1 hour. After heating, the pressure-sensitive adhesive sheet with a polyimide film was stored for 1 hour in an environment of 25 ° C. and 50% relative humidity. Thereafter, the adhesive strength of the adhesive sheet was measured by a 180 ° peeling method in an environment of 25 ° C. and 50% relative humidity. In addition, as a measuring device, a measuring device with a thermostatic bath (manufactured by A & D, TENSILON) was used, the tensile speed was 300 mm / min, and the width of the adhesive sheet was 25 mm.
For the adhesive sheets prepared in Examples 2 to 5 and Comparative Examples 1 to 3, the adhesive strength of the adhesive sheets was measured in the same manner as described above.
［樹脂漏れ防止性］
　実施例１で作製した粘着シートの粘着面に、鏡面加工が施されたシリコンチップ（２．３ｍｍ×１．７ｍｍ×０．２ｍｍ厚み）８０００個を、鏡面加工面が接するように８０行１００列の配置で設置した。この際、チップの２．３ｍｍの長さの辺と平行な方向と、チップの配列の列方向が一致するようにした。また、隣り合うチップ同士の距離は、チップの長方形形状の中心間の距離が５ｍｍとなるようにした。層間絶縁樹脂（味の素ファインケミカル製ＡＢＦ；Ｔ－１５Ｂ）で、粘着シート上のチップを、真空加熱加圧ラミネーター（ＲＯＨＭ　ａｎｄ　ＨＡＡＳ社製；７０２４ＨＰ５）を用いて封止した。封止条件は、真空加熱加圧ラミネーターのテーブル及びダイアフラムの予熱温度をともに１００℃とし、真空引きで６０秒、Ｄｙｎａｍｉｃ　ｐｒｅｓｓモードで３０秒、Ｓｔａｔｉｃ　ｐｒｅｓｓモードで１０秒の条件で封止を行った。
　その後、粘着シート越しに、チップと粘着シートとの界面の状態をデジタル顕微鏡で確認し、チップ／粘着シート間に層間絶縁樹脂がチップ端部から１０μｍ以上侵入していれば樹脂漏れ有りとし、１０μｍ未満の場合を樹脂漏れなしとした。
　実施例２～５及び比較例１～３で作製した粘着シートについても、上記と同様にして、樹脂漏れ防止性を評価した。 [Resin leakage prevention]
8000 silicon chips (2.3 mm × 1.7 mm × 0.2 mm thickness) that have been mirror-finished on the adhesive surface of the adhesive sheet prepared in Example 1 are 80 rows and 100 columns so that the mirror-finished surface is in contact. Was installed. At this time, the direction parallel to the 2.3 mm long side of the chip was aligned with the column direction of the chip array. Further, the distance between adjacent chips was set such that the distance between the centers of the rectangular shapes of the chips was 5 mm. The chip on the adhesive sheet was sealed with an interlayer insulating resin (ABF of Ajinomoto Fine Chemical; T-15B) using a vacuum heating and pressure laminator (manufactured by ROHM and HAAS; 7024HP5). Sealing conditions were such that the preheating temperature of the vacuum heating and pressurization laminator table and the diaphragm was 100 ° C., and the sealing was performed for 60 seconds by vacuuming, 30 seconds in the Dynamic press mode, and 10 seconds in the Static press mode. .
After that, the state of the interface between the chip and the pressure-sensitive adhesive sheet is confirmed with a digital microscope through the pressure-sensitive adhesive sheet. If the interlayer insulating resin penetrates 10 μm or more from the end of the chip between the chip and the pressure-sensitive adhesive sheet, there is a resin leak. Less than the case was regarded as no resin leakage.
For the pressure-sensitive adhesive sheets prepared in Examples 2 to 5 and Comparative Examples 1 to 3, the resin leakage prevention property was evaluated in the same manner as described above.
［表面自由エネルギー及び接触角］
　粘着剤層の表面自由エネルギーは、次に示す方法により測定した。具体的には、まず、接触角測定装置（協和界面化学株式会社製の「ＤＭ７０１」）を用いて、実施例１で作製した粘着剤層に対する水、ジヨードメタン及び１－ブロモナフタレンの接触角を測定した。それぞれの液滴の量は２μＬとした。そして、これらの測定値から、北崎－畑法により、表面自由エネルギーを算出した。
　実施例２～５及び比較例１～３で作製した粘着剤層についても、上記と同様にして、接触角を測定し、これらの測定値から表面自由エネルギーを算出した。 [Surface free energy and contact angle]
The surface free energy of the pressure-sensitive adhesive layer was measured by the following method. Specifically, first, using a contact angle measuring device (“DM701” manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angles of water, diiodomethane and 1-bromonaphthalene to the pressure-sensitive adhesive layer produced in Example 1 were measured. did. The amount of each droplet was 2 μL. Then, the surface free energy was calculated from these measured values by the Kitasaki-Hatabe method.
For the pressure-sensitive adhesive layers prepared in Examples 2 to 5 and Comparative Examples 1 to 3, the contact angles were measured in the same manner as described above, and the surface free energy was calculated from these measured values.
［フィリング性評価］
　実施例１で作製した粘着シートの粘着面に半導体チップ（鏡面加工が施されたシリコンチップ、チップサイズ：２．３ｍｍ×１．７ｍｍ、チップ厚み：０．２ｍｍ、段差部と回路面との段差の高さ寸法ｘ：１μｍ、段差部の幅寸法ｙ：３０μｍ（株式会社アルバック製、Ｄｅｋｔａｋ１５０で測定。））８０００個を、粘着シートの粘着面と半導体チップの回路面とが接するように、８０行１００列の配置で設置した。この際、チップの２．３ｍｍの長さの辺と平行な方向と、チップの配列の列方向が一致するようにした。また、隣り合うチップ同士の距離は、チップの長方形形状の中心間の距離が５ｍｍとなるようにした。その後、封止樹脂（味の素ファインテクノ株式会社製ＡＢＦフィルム、ＧＸ　ＬＥ－Ｔ１５Ｂ）で粘着シート上の半導体チップを、真空加熱加圧ラミネーター（ＲＯＨＭ　ａｎｄ　ＨＡＡＳ社製の「７０２４ＨＰ５」）を用いて封止した（封止工程）。封止条件は、下記の通りである。
　・予熱温度：テーブル及びダイアフラムとも１００℃
　・真空引き：６０秒間
　・ダイナミックプレスモード：３０秒間
　・スタティックプレスモード：１０秒間
　そして、封止工程後の粘着シート上の半導体チップを顕微鏡にて観察し（それぞれの半導体チップの全周囲）、半導体チップの段差部と粘着剤層との隙間に封止樹脂が埋め込まれているか否かを確認した。隙間に封止樹脂が埋め込まれている場合を「Ａ」と判定し、隙間に封止樹脂が埋め込まれていないか、或いは、隙間にボイドが発生した場合を「Ｂ」と判定した。
　実施例２～５及び比較例１～３で作製した粘着シートについても、上記と同様にして、フィリング性を評価した。 [Filling property evaluation]
Semiconductor chip (silicon chip with mirror finish, chip size: 2.3 mm × 1.7 mm, chip thickness: 0.2 mm, level difference between the stepped portion and the circuit surface on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet produced in Example 1 The height dimension x: 1 μm, the width dimension y of the stepped part: 30 μm (manufactured by ULVAC, Inc., measured with Dektak 150)) 80 so that the adhesive surface of the adhesive sheet and the circuit surface of the semiconductor chip are in contact with each other. Installed in an arrangement of 100 rows and 100 columns. At this time, the direction parallel to the 2.3 mm long side of the chip was aligned with the column direction of the chip array. Further, the distance between adjacent chips was set such that the distance between the centers of the rectangular shapes of the chips was 5 mm. Thereafter, the semiconductor chip on the adhesive sheet is sealed with a sealing resin (ABF film manufactured by Ajinomoto Fine Techno Co., Ltd., GX LE-T15B) using a vacuum heating and pressure laminator (“7024HP5” manufactured by ROHM and HAAS). (Sealing process). The sealing conditions are as follows.
-Preheating temperature: 100 ° C for both table and diaphragm
・ Vacuum evacuation: 60 seconds ・ Dynamic press mode: 30 seconds ・ Static press mode: 10 seconds Then, the semiconductor chips on the pressure-sensitive adhesive sheet after the sealing process are observed with a microscope (the entire circumference of each semiconductor chip), and the semiconductor It was confirmed whether or not the sealing resin was embedded in the gap between the step portion of the chip and the adhesive layer. The case where the sealing resin was embedded in the gap was determined as “A”, and the case where the sealing resin was not embedded in the gap or a void was generated in the gap was determined as “B”.
For the pressure-sensitive adhesive sheets prepared in Examples 2 to 5 and Comparative Examples 1 to 3, the filling properties were evaluated in the same manner as described above.
〔粘着シートの作製〕
（実施例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、及び希釈溶剤）を配合し、十分に撹拌して、実施例１に係る塗布用粘着剤液（粘着剤組成物）を調製した。
・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。得られた重合体の重量平均分子量は、８５０，０００であった。
・粘着助剤：両末端水酸基水素化ポリブタジエン〔日本曹達株式会社製；ＧＩ－１０００〕、５質量部（固形分）
・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式会社製；コロネートＨＸ〕、３．５質量部（固形分）
・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。 [Preparation of adhesive sheet]
Example 1
(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 coating according to Example 1 (pressure-sensitive adhesive composition) Prepared).
-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. The weight average molecular weight of the obtained polymer was 850,000.
Adhesion aid: hydroxylated hydrogenated polybutadiene at both ends (Nippon Soda Co., Ltd .; GI-1000), 5 parts by mass (solid content)
Crosslinking agent: Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate) [manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX], 3.5 parts by mass (solid content)
Diluting solvent: Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
（２）粘着剤層の作製
　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〔リンテック株式会社製；ＳＰ－ＰＥＴ３８２１５０〕の剥離層面側に、調製した塗布用粘着剤液を、コンマコーター（登録商標）を用いて塗布し、９０℃及び９０秒間の加熱を行い、続いて１１５℃及び９０秒間の加熱を行い、塗膜を乾燥させて、粘着剤層を作製した。粘着剤層の厚さは５０μｍであった。 (2) Preparation of pressure-sensitive adhesive layer The prepared pressure-sensitive adhesive liquid was applied to the release layer surface side of a release film made of 38 μm transparent polyethylene terephthalate film provided with a silicone release layer [manufactured by Lintec Corporation; SP-PET382150]. Application was performed using a comma coater (registered trademark), heating was performed at 90 ° C. and 90 seconds, followed by heating at 115 ° C. and 90 seconds, and the coating film was dried to prepare an adhesive layer. The thickness of the pressure-sensitive adhesive layer was 50 μm.
（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式会社製；ＰＥＴ５０ＫＦＬ１２Ｄ、厚さ５０μｍ、１００℃における貯蔵弾性率３．１×１０９Ｐａ〕を用い、基材の一方の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. 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 an adhesive is applied to one side of the base material The layers were laminated.
（実施例２）
（１）粘着剤組成物の調製
　実施例２では、シリコーン系粘着剤を用いた。
　実施例２においては、
　　シリコーン系粘着剤Ａ（ＳＤ４５８０ＰＳＡ）１８質量部（固形分）、
　　シリコーン系粘着剤Ｂ（ＳＤ－４５８７Ｌ）４０質量部（固形分）、
　　触媒Ａ（ＮＣ－２５ＣＡＴ）０．３質量部（固形分）、
　　触媒Ｂ（ＣＡＴ－ＳＲＸ－２１２）０．６５質量部（固形分）、及び
　　シリコーンディスパージョン（ＢＹ－２４－７１２）５質量部（固形分）
を配合し、希釈溶剤としてトルエンを用いて固形分が２０質量％となるように希釈し、十分に撹拌して、実施例２に係る塗布用粘着剤液（粘着剤組成物）を調製した。実施例２の粘着剤組成物に用いた材料は、いずれも東レ・ダウコーニング株式会社製である。 (Example 2)
(1) Preparation of pressure-sensitive adhesive composition In Example 2, a silicone-based pressure-sensitive adhesive was used.
In Example 2,
Silicone-based adhesive A (SD4580PSA) 18 parts by mass (solid content)
40 parts by mass (solid content) of silicone-based adhesive B (SD-4487L),
Catalyst A (NC-25CAT) 0.3 parts by mass (solid content)
Catalyst B (CAT-SRX-212) 0.65 parts by mass (solid content) and Silicone dispersion (BY-24-712) 5 parts by mass (solid content)
Was mixed with toluene as a diluent solvent so that the solid content was 20% by mass and stirred sufficiently to prepare a coating pressure-sensitive adhesive liquid (pressure-sensitive adhesive composition) according to Example 2. The materials used for the pressure-sensitive adhesive composition of Example 2 are all manufactured by Toray Dow Corning Co., Ltd.
（２）粘着シートの作製
　基材としてのポリイミドフィルム〔東レ・デュポン株式会社製；カプトン１００Ｈ、厚さ２５μｍ、１００℃における貯蔵弾性率３．１×１０９Ｐａ〕の一方の面側に、実施例２に係る塗布用粘着剤液を、コンマコーター（登録商標）を用いて塗布し、１３０℃及び２分間の加熱を行い、塗膜を乾燥させて、粘着剤層を作製することで、実施例２に係る粘着シートを得た。粘着剤層の厚みは２０μｍであった。 (2) Preparation of pressure-sensitive adhesive sheet Implemented on one side of a polyimide film as a base material [manufactured by Toray DuPont Co., Ltd .; Kapton 100H, thickness 25 μm, storage elastic modulus 3.1 × 10 9 Pa at 100 ° C.] It is carried out by applying the pressure-sensitive adhesive liquid for application according to Example 2 using a comma coater (registered trademark), heating at 130 ° C. for 2 minutes, drying the coating film, and preparing a pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet according to Example 2 was obtained. The thickness of the pressure-sensitive adhesive layer was 20 μm.
（実施例３）
　塗布用粘着剤液を、乾燥後の粘着剤層の厚みを３０μｍとしたこと以外は、実施例２と同様にして、粘着シートを作製した。 (Example 3)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying the pressure-sensitive adhesive liquid for coating was 30 μm.
（実施例４）
　塗布用粘着剤液を、乾燥後の粘着剤層の厚みを４０μｍとしたこと以外は、実施例２と同様にして、粘着シートを作製した。 Example 4
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying of the pressure-sensitive adhesive liquid for coating was 40 μm.
（実施例５）
　塗布用粘着剤液を、乾燥後の粘着剤層の厚みを５０μｍとしたこと以外は、実施例２と同様にして、粘着シートを作製した。 (Example 5)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying the pressure-sensitive adhesive liquid for coating was 50 μm.
（比較例１）
　塗布用粘着剤液を、乾燥後の粘着剤層の厚みを１０μｍとしたこと以外は、実施例２と同様にして、粘着シートを作製した。 (Comparative Example 1)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer after drying the pressure-sensitive adhesive liquid for coating was 10 μm.
（比較例２）
　実施例１のポリマーを下記の配合に変化させた以外は実施例１と同様にして、粘着シートを作製した。
　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８０．８質量％と、アクリロイルモルホリン１２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。得られた重合体の重量平均分子量は、７６０，０００であった。 (Comparative Example 2)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the polymer of Example 1 was changed to the following composition.
The acrylic ester copolymer comprises a copolymer of 80.8% by mass of 2-ethylhexyl acrylate, 12% by mass of acryloylmorpholine, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid. Prepared by polymerization. The weight average molecular weight of the obtained polymer was 760,000.
（比較例３）
　比較例２の粘着剤厚みを２０μｍに変更させた以外は比較例２と同様にして、粘着シートを作製した。 (Comparative Example 3)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Comparative Example 2 except that the thickness of the pressure-sensitive adhesive in Comparative Example 2 was changed to 20 μm.
　表１に、実施例１～５及び比較例１～３に係る粘着シートの評価結果を示す。 Table 1 shows the evaluation results of the pressure-sensitive adhesive sheets according to Examples 1 to 5 and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～５に係る粘着シートは、粘着剤層の表面自由エネルギーが１０ｍJ／ｍ２以上２２ｍJ／ｍ２以下であり、かつ、Ａ×Ｂ２により算出される数値が１．５×１０－５以上であるため、フィリング性が良好であり、かつ樹脂漏れを防止することができることが確認された。
　一方、比較例１に係る粘着シートは、Ａ×Ｂ２により算出される数値が１．５×１０－５未満であるため、樹脂漏れを防止することができなかったと考えられる。また、比較例２～３に係る粘着シートは、粘着剤層の表面自由エネルギーが２２ｍＪ／ｍ２を超えているため、粘着シート上の半導体素子を封止する際のフィリング性に劣ると考えられる。 As shown in Table 1, the pressure-sensitive adhesive sheets according to Examples 1-5, the numerical values surface free energy of the pressure-sensitive adhesive layer is 10 mJ / m 2 or more 22 mJ / m 2 or less, and is calculated by A × B 2 Is 1.5 × 10 −5 or more, it was confirmed that the filling property is good and the resin leakage can be prevented.
On the other hand, the adhesive sheet according to Comparative Example 1 has a numerical value calculated by A × B 2 of less than 1.5 × 10 −5 , so it is considered that resin leakage could not be prevented. In addition, the pressure-sensitive adhesive sheets according to Comparative Examples 2 to 3 are considered to be inferior in filling property when sealing semiconductor elements on the pressure-sensitive adhesive sheet because the surface free energy of the pressure-sensitive adhesive layer exceeds 22 mJ / m 2. .
　１０…粘着シート、１１…基材、１２…粘着剤層、２０…枠部材、２１…開口部。
  DESCRIPTION OF SYMBOLS 10 ... Adhesive sheet, 11 ... Base material, 12 ... Adhesive layer, 20 ... Frame member, 21 ... Opening part.

Claims (14)

  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、
    　当該粘着シートは、基材と、粘着剤組成物を含む粘着剤層とを備え、
    　前記粘着剤層の表面自由エネルギーが１０ｍJ／ｍ２以上２２ｍJ／ｍ２以下であり、かつ、
    　前記粘着剤層の１００℃における貯蔵弾性率をＡ（Ｐａ）、前記粘着剤層の厚みをＢ（ｍ）としたとき、下記関係式（１）により算出される数値が１．５×１０－５以上である、
    　粘着シート。
    　　Ａ×Ｂ２　　　　　（１）     A pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet,
    The pressure-sensitive adhesive sheet comprises a substrate and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition,
    The surface free energy of the pressure-sensitive adhesive layer has a 10 mJ / m 2 or more 22 mJ / m 2 or less, and,
    When the storage elastic modulus at 100 ° C. of the pressure-sensitive adhesive layer is A (Pa) and the thickness of the pressure-sensitive adhesive layer is B (m), the numerical value calculated by the following relational expression (1) is 1.5 × 10 − 5 or more
    Adhesive sheet.
    A × B 2 (1)
  2. 　前記粘着剤層に対する１－ブロモナフタレンの接触角が６５°以上である、
    　請求項１に記載の粘着シート。     The contact angle of 1-bromonaphthalene to the pressure-sensitive adhesive layer is 65 ° or more;
    The pressure-sensitive adhesive sheet according to claim 1.
  3. 　下記関係式（２）により算出される数値が１．５×１０－１０以上である、
    　請求項１または請求項２に記載の粘着シート。
    　　Ａ×Ｂ３　　　　　（２）     The numerical value calculated by the following relational expression (2) is 1.5 × 10 −10 or more,
    The pressure-sensitive adhesive sheet according to claim 1 or claim 2.
    A × B 3 (2)
  4. 　前記基材の１００℃における貯蔵弾性率は、１×１０７Ｐａ以上である、
    　請求項１から請求項３のいずれか一項に記載の粘着シート。     The storage elastic modulus at 100 ° C. of the substrate is 1 × 10 7 Pa or more.
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 3.
  5. 　前記粘着剤層は、アクリル系粘着剤組成物またはシリコーン系粘着剤組成物からなる、
    　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 comprises 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. 　前記粘着剤層は、アクリル系粘着剤組成物からなり、
    　前記アクリル系粘着剤組成物は、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 pressure-sensitive adhesive layer is made of an acrylic pressure-sensitive adhesive composition,
    The acrylic pressure-sensitive adhesive composition contains an acrylic copolymer,
    The pressure-sensitive adhesive sheet according to claim 5.
  7. 　前記アクリル系共重合体全体の質量に占める、（メタ）アクリル酸アルキルエステルに由来する共重合体成分の質量の割合が、９０質量％以上である、
    　請求項６に記載の粘着シート。     The proportion of the mass of the copolymer component derived from the (meth) acrylic acid alkyl ester in the total mass of the acrylic copolymer is 90% by mass or more.
    The pressure-sensitive adhesive sheet according to claim 6.
  8. 　前記（メタ）アクリル酸アルキルエステルにおけるアルキルの炭素数が６～８である、
    　請求項７に記載の粘着シート。     The alkyl in the (meth) acrylic acid alkyl ester has 6 to 8 carbon atoms;
    The pressure-sensitive adhesive sheet according to claim 7.
  9. 　前記アクリル系共重合体は、（メタ）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６から請求項８のいずれか一項に記載の粘着シート。     The acrylic copolymer includes an acrylic copolymer mainly composed of 2-ethylhexyl (meth) acrylate.
    The pressure-sensitive adhesive sheet according to any one of claims 6 to 8.
  10. 　前記アクリル系共重合体は、水酸基を有するモノマーに由来する共重合体成分を含む、
    　請求項６から請求項９のいずれか一項に記載の粘着シート。     The acrylic copolymer includes a copolymer component derived from a monomer having a hydroxyl group.
    The pressure-sensitive adhesive sheet according to any one of claims 6 to 9.
  11. 　前記アクリル系共重合体全体の質量に占める、前記水酸基を有するモノマーに由来する共重合体成分の質量の割合が、３質量％以上である、
    　請求項１０に記載の粘着シート。     The proportion of the mass of the copolymer component derived from the monomer having a hydroxyl group in the total mass of the acrylic copolymer is 3% by mass or more.
    The pressure-sensitive adhesive sheet according to claim 10.
  12. 　前記アクリル系共重合体は、
    　カルボキシル基を有するモノマーに由来する共重合体成分を含まない、または
    　カルボキシル基を有するモノマーに由来する共重合体成分を含み、かつ、前記アクリル系共重合体全体の質量に占める、前記カルボキシル基を有するモノマーに由来する共重合体成分の質量の割合が１質量％以下である、
    　請求項６から請求項１１のいずれか一項に記載の粘着シート。     The acrylic copolymer is
    It does not contain a copolymer component derived from a monomer having a carboxyl group, or contains a copolymer component derived from a monomer having a carboxyl group, and occupies the total mass of the acrylic copolymer. The proportion of the mass of the copolymer component derived from the monomer having is 1% by mass or less,
    The pressure-sensitive adhesive sheet according to any one of claims 6 to 11.
  13. 　前記アクリル系粘着剤組成物は、炭化水素骨格を有するオリゴマーを含む粘着助剤を含有する、
    　請求項６から請求項１２のいずれか一項に記載の粘着シート。     The acrylic pressure-sensitive adhesive composition contains a pressure-sensitive adhesive agent including an oligomer having a hydrocarbon skeleton,
    The pressure-sensitive adhesive sheet according to any one of claims 6 to 12.
  14. 　前記粘着剤層は、シリコーン系粘着剤組成物からなり、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 pressure-sensitive adhesive layer is composed of a silicone-based pressure-sensitive adhesive composition, and the silicone-based pressure-sensitive adhesive composition includes an addition polymerization type silicone resin.
    The pressure-sensitive adhesive sheet according to claim 5.
PCT/JP2017/007979 2017-02-28 2017-02-28 Adhesive sheet WO2018158858A1 (en)

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