WO2017038916A1 - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
WO2017038916A1
WO2017038916A1 PCT/JP2016/075603 JP2016075603W WO2017038916A1 WO 2017038916 A1 WO2017038916 A1 WO 2017038916A1 JP 2016075603 W JP2016075603 W JP 2016075603W WO 2017038916 A1 WO2017038916 A1 WO 2017038916A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
hard coat
meth
Prior art date
Application number
PCT/JP2016/075603
Other languages
French (fr)
Japanese (ja)
Inventor
高野　健
和浩 菊池
貴志 杉野
Original Assignee
リンテック株式会社
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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 JP2017538095A priority Critical patent/JP6714004B2/en
Publication of WO2017038916A1 publication Critical patent/WO2017038916A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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

Definitions

  • the present invention relates to an adhesive sheet.
  • Patent Document 1 discloses a mask sheet for suppressing adhesive residue of an adhesive and stably producing a QFN (Quad Flat Non-lead) semiconductor package.
  • a mask sheet is prepared using a specific heat-resistant film and a silicone-based pressure-sensitive adhesive to withstand an environment of 150 to 180 ° C. for 1 to 6 hours in a die attach process and a resin sealing process. It is stated that you get.
  • the mask sheet is used for some applications such as a QFN package. Limited.
  • pressure-sensitive adhesive sheets are also used in processes where high temperature conditions such as 180 ° C. or higher and 200 ° C. or lower are imposed.
  • high-temperature process for example, when a low-cost and low-cost film (for example, a film such as polyethylene terephthalate) is used as a base material as compared with a polyimide film or the like, There is a possibility that the oligomer adheres to and contaminates the equipment and members, and the equipment and members and the base material are fused.
  • the base material When the base material is fused to the equipment and members, it becomes difficult to peel off the pressure-sensitive adhesive sheet. Even if the adhesive sheet can be peeled off, the base material oligomer or the like may remain on the equipment and members, and the equipment and members may be contaminated. For example, when a high temperature condition is imposed in the step of resin-sealing a semiconductor element attached to an adhesive layer of an adhesive sheet, the surface of the semiconductor element may be contaminated, causing a problem in the semiconductor device.
  • the objective of this invention is providing the adhesive sheet which can prevent the contamination of an installation and a member, and can prevent a fusion
  • a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet, the first surface and the second surface opposite to the first surface, A base material containing a polyester resin, an adhesive layer laminated on the first surface of the base material, and a hard coat layer laminated on the second surface of the base material, and the hard coat
  • the layer is provided with an adhesive sheet that is a cured film formed by curing an organic-inorganic hybrid material.
  • the shrinkage rate in a direction along any surface of the base material is 1.7% or less after being heated at 190 ° C. for 1 hour.
  • the polyester resin is preferably a resin selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin.
  • the thickness of the hard coat layer is preferably 0.5 ⁇ m or more and 3.0 ⁇ m or less.
  • the pressure-sensitive adhesive layer further includes a second hard coat layer between the pressure-sensitive adhesive layer and the base material, and the second hard coat layer includes a polyfunctional acrylic resin. preferable.
  • the organic-inorganic hybrid material preferably includes a material in which silica fine particles and an organic compound having a polymerizable unsaturated group are bonded, and an active energy ray-curable resin.
  • the adhesive sheet which can prevent the contamination of an installation and a member, and can prevent fusion
  • FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
  • the pressure-sensitive adhesive sheet 10 has a base material 11, a pressure-sensitive adhesive layer 12, and a hard coat layer 13.
  • the base material 11 has a first surface 11a and a second surface 11b opposite to the first surface 11a.
  • the adhesive layer 12 is laminated
  • a release sheet RL is laminated on the pressure-sensitive adhesive layer 12 as shown in FIG.
  • the shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a sheet shape, a tape shape, and a label shape.
  • the substrate 11 includes a polyester resin.
  • the base material 11 is more preferably made of a material mainly composed of a polyester resin.
  • the material having a polyester-based resin as a main component means that the ratio of the mass of the polyester-based resin to the total mass of the material constituting the substrate is 50% by mass or more.
  • the polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins.
  • a resin selected from the group consisting of polyethylene terephthalate resins, polyethylene naphthalate resins, and polybutylene terephthalate resins, and polyethylene terephthalate resins are even more preferred.
  • a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film is more preferable.
  • the oligomers contained in the polyester film are derived from polyester-forming monomers, dimers, trimers, and the like.
  • the first surface 11a and the second surface 11b are subjected to primer treatment, corona treatment, and plasma. At least any surface treatment such as treatment may be performed.
  • the first surface 11a and the second surface 11b of the base material 11 may be applied with an adhesive and subjected to an adhesive treatment.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate include acrylic, rubber-based, silicone-based, and urethane-based pressure-sensitive adhesives.
  • the thickness of the substrate 11 is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 15 ⁇ m or more and 300 ⁇ m or less, and further preferably 20 ⁇ m or more and 250 ⁇ m or less.
  • the shrinkage rate in the direction along any surface of the substrate 11 is preferably 1.7% or less.
  • the pressure-sensitive adhesive sheet 10 is heated under the conditions of 190 ° C. and 1 hour, at least the shrinkage rate in the MD direction of the base material 11 is preferably 1.7% or less.
  • the manufacturing process of the semiconductor device includes a heating process at 180 ° C. to 190 ° C. for about 1 hour. If the shrinkage rate is 1.7% or less, the adhesive sheet 10 is adhered to the adherend due to the shrinkage of the base material 11. Can be prevented from peeling off.
  • the pressure-sensitive adhesive sheet 10 By preventing the pressure-sensitive adhesive sheet 10 from being peeled off from the adherend in the heating step, it is possible to prevent a conveyance failure during the manufacturing process.
  • the surface of the adherend (for example, the circuit surface of the semiconductor chip) may be exposed due to the peeling of the pressure-sensitive adhesive sheet 10, and may be contaminated. Contamination can also be prevented.
  • the MD (MD: Machine Direction) direction of the base material 11 is a direction parallel to the longitudinal direction of the original fabric that gives the base material 11 (the feed direction during production of the original fabric).
  • the hard coat layer 13 is a layer made of a cured film formed by curing an organic-inorganic hybrid material.
  • the hard coat layer 13 includes a cured product of an organic-inorganic hybrid material.
  • the organic-inorganic hybrid material refers to a resin that is cured in a state where the organic component and the inorganic component are mixed closely and dispersed at a molecular level or a particle size close to the molecular level. Specifically, the organic component or the inorganic component is dispersed with a particle size of 100 nm or less, for example.
  • the organic-inorganic hybrid material used in the present embodiment is preferably a material capable of forming a cured film (hard coat film) by reacting and curing the inorganic component and the organic component by irradiation with active energy rays.
  • active energy rays include ultraviolet rays and electron beams.
  • the particle size of the organic component or inorganic component in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring device (Microtrac Bell, Nanotrac Wave-UT151). .
  • an active energy ray-curable composition containing an active energy ray-curable resin and silica fine particles is preferable.
  • the active energy ray-sensitive composition By irradiating the active energy ray-sensitive composition with the active energy ray, the active energy ray-sensitive composition can be crosslinked and cured to obtain an organic-inorganic hybrid cured resin.
  • the organic-inorganic hybrid material in the present embodiment preferably includes a material obtained by binding silica fine particles and an organic compound having a polymerizable unsaturated group, and an active energy ray-curable resin. Since the organic-inorganic hybrid material contains silica fine particles, shrinkage during curing can be reduced, and curling of the pressure-sensitive adhesive sheet 10 can be suppressed.
  • the active energy ray-curable resin is a polymerizable compound that crosslinks and cures when irradiated with active energy rays.
  • the thermal history of the substrate 11 can be reduced.
  • active energy rays include electromagnetic waves such as ultraviolet rays and electron beams, and charged particle beams having energy quanta.
  • the resin used for the hard coat layer 13 of the present embodiment is preferably an ultraviolet curable resin.
  • the active energy ray curable resin preferably contains a polyfunctional acrylic resin.
  • the polyfunctional acrylic resin is preferably at least one resin selected from the group consisting of polyfunctional (meth) acrylate monomers and (meth) acrylate prepolymers, and the polyfunctional (meth) acrylate monomers are More preferred.
  • (meth) acrylate” is a notation used to represent both acrylate and methacrylate, and the same applies to other similar terms.
  • multifunctional (meth) acrylate monomers examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene.
  • Examples of the (meth) acrylate prepolymer include a polyester (meth) acrylate prepolymer, an epoxy (meth) acrylate prepolymer, a urethane (meth) acrylate prepolymer, and a polyol (meth) acrylate prepolymer. Can be mentioned.
  • a polyester (meth) acrylate prepolymer is obtained by, for example, obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, and further esterifying the hydroxyl group with (meth) acrylic acid. Can be obtained.
  • the polyester (meth) acrylate-based prepolymer is obtained, for example, by adding an alkylene oxide to a polyvalent carboxylic acid to obtain an oligomer, and esterifying the terminal hydroxyl group of the oligomer with (meth) acrylic acid. Can do.
  • the epoxy (meth) acrylate-based prepolymer can be obtained, for example, by reacting an oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin with (meth) acrylic acid for esterification.
  • the urethane (meth) acrylate-based prepolymer can be obtained by, for example, obtaining a polyurethane oligomer by a reaction between a polyether polyol or a polyester polyol and a polyisocyanate, and esterifying the polyurethane oligomer with (meth) acrylic acid. it can.
  • the polyol (meth) acrylate-based prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
  • these prepolymers may be used independently, may be used in combination of 2 or more type, and may be used together with the said polyfunctional (meth) acrylate type monomer.
  • the average particle size of the silica fine particles is preferably from 0.5 nm to 500 nm, and more preferably from 1 nm to 100 nm.
  • the average particle diameter of the silica fine particles is a value measured by, for example, the BET method.
  • silica fine particles silica surface-modified with an organic compound having a polymerizable unsaturated group capable of reacting with the active energy ray-curable resin from the viewpoint of forming a strong bond with the active energy ray-curable resin.
  • Fine particles reactive silica fine particles are preferred.
  • Silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group are polymerizable unsaturated groups having a (meth) acryloyl group which is a functional group capable of reacting with the silanol group on the silanol group on the surface of the silica fine particle. It can be obtained by reacting the containing organic compound.
  • the organic compound having a polymerizable unsaturated group that modifies the surface of the silica fine particles may be a compound corresponding to the above-described active energy ray-curable resin.
  • the compound that modifies the surface of the silica fine particles is included as a component of the silica fine particles, and is distinguished from the above active energy ray-curable resin.
  • polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group for example, a compound represented by the following general formula (I) is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is any group selected from the group consisting of a halogen atom or a group represented by the following formula.
  • Examples of the polymerizable unsaturated group-containing organic compound include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanate ethyl, (meth) acrylic acid glycidyl, and (meth) acrylic acid 2 , 3-iminopropyl, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid derivatives such as (meth) acryloyloxypropyltrimethoxysilane.
  • These polymerizable unsaturated group-containing organic compounds may be used alone or in combination of two or more.
  • the content of silica fine particles in the organic-inorganic hybrid material is preferably 80 parts by mass or more and 400 parts by mass or less, and 100 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable resin. It is more preferable that
  • the organic-inorganic hybrid material preferably contains a photopolymerization initiator.
  • the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylamino
  • Examples of commercially available organic-inorganic hybrid materials containing these active energy ray-curable resins, silica fine particles, and photopolymerization initiators include “OPSTAR Z7530”, “OPSTAR Z7524”, and “OPSTAR TU4086” (product). Name, both of which are manufactured by JSR Corporation).
  • an ultraviolet absorber In the active energy ray-sensitive composition, an ultraviolet absorber, a light stabilizer, an antioxidant, an infrared absorber, an antistatic agent, a leveling agent, and an antifoaming agent are added as necessary as long as the effects of the present invention are not impaired.
  • the active energy ray sensitive composition may contain an ultraviolet absorber.
  • the UV absorber include benzotriazole UV absorbers, hindered amine UV absorbers, benzophenone UV absorbers, and triazine UV absorbers. These ultraviolet absorbers may be used alone or in combination of two or more. Among these, a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule is preferable.
  • the content of the ultraviolet absorber is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0 with respect to 100 parts by mass in total of the active energy ray-curable resin, the silica fine particles, and the photopolymerization initiator. .5 parts by mass or more and 7 parts by mass or less.
  • the active energy ray sensitive composition may contain a light stabilizer.
  • the light stabilizer include hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers. These light stabilizers may be used alone or in combination of two or more.
  • the content of the light stabilizer is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0 with respect to 100 parts by mass in total of the active energy ray-curable resin, the silica fine particles, and the photopolymerization initiator. .5 parts by mass or more and 7 parts by mass or less.
  • the thickness of the hard coat layer 13 is preferably 0.5 ⁇ m or more and 3.0 ⁇ m or less. If the thickness of the hard coat layer 13 is 0.5 ⁇ m or more, the heat resistance in the manufacturing process of the semiconductor device can be improved, and if it is 3.0 ⁇ m or less, the pressure-sensitive adhesive sheet 10 can be prevented from curling.
  • the active energy ray-sensitive composition used for forming the hard coat layer 13
  • the active energy ray-sensitive composition includes reactive silica fine particles, a polyfunctional (meth) acrylate monomer, and a (meth) acrylate prepolymer. Mold compositions.
  • the pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various types of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12.
  • Examples of the adhesive contained in the adhesive layer 12 include rubber-based, acrylic-based, silicone-based, polyester-based, and urethane-based.
  • the kind of adhesive is selected in consideration of the use and the kind of adherend to be attached.
  • the pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer 12 preferably contains an acrylic copolymer having 2-ethylhexyl acrylate as a main monomer.
  • 2-ethylhexyl acrylate is the main monomer
  • the ratio of the mass of the copolymer component derived from 2-ethylhexyl acrylate to the total mass of the acrylic copolymer is 50% by mass or more. Means.
  • the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, and 60% by mass or more and 95% by mass or less.
  • the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 50% by mass or more, the adhesive strength does not become too high after heating, and the adhesive sheet is more easily peeled off from the adherend, and 80% by mass or more. If it is, it will become still easier to peel. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, the initial adhesive force is insufficient and the substrate is deformed during heating, or the adhesive sheet is peeled off from the adherend due to the deformation. Can be prevented.
  • the type and number of copolymer components other than 2-ethylhexyl acrylate in the acrylic copolymer are not particularly limited.
  • a functional group-containing monomer having a reactive functional group is preferable.
  • a reactive functional group of a 2nd copolymer component when using the crosslinking agent mentioned later, it is preferable that it is a functional group which can react with the said crosslinking agent.
  • This reactive functional group is preferably at least one substituent selected from the group consisting of, for example, a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. These substituents are more preferable, and a carboxyl group is still more preferable.
  • Examples of the monomer having a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • carboxyl group-containing monomers acrylic acid is preferable from the viewpoint of reactivity and copolymerization.
  • a carboxyl group-containing monomer may be used independently and may be used in combination of 2 or more type.
  • Examples of the monomer having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 And (meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of hydroxyl reactivity and copolymerization.
  • a hydroxyl-containing monomer may be used independently and may be used in combination of 2 or more type.
  • “(meth) acrylic acid” is a notation used to represent both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
  • Examples of other copolymer components in the acrylic copolymer include (meth) acrylic acid alkyl esters having an alkyl group with 2 to 20 carbon atoms.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and (meth) acrylic acid n.
  • Examples of other copolymer components in the acrylic copolymer include, for example, alkoxyalkyl group-containing (meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring, and (meth) acrylic acid having an aromatic ring.
  • alkoxyalkyl group-containing (meth) acrylic acid ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
  • examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate.
  • examples of the (meth) acrylic acid ester having an aromatic ring examples include phenyl (meth) acrylate.
  • non-crosslinkable acrylamides examples include acrylamide and methacrylamide.
  • Examples of the (meth) acrylic acid ester having a non-crosslinkable tertiary amino group include (meth) acrylic acid (N, N-dimethylamino) ethyl and (meth) acrylic acid (N, N-dimethylamino). Propyl. These monomers may be used independently and may be used in combination of 2 or more type.
  • a carboxyl group-containing monomer or a hydroxyl group-containing monomer is preferable as the second copolymer component, and acrylic acid is more preferable.
  • the acrylic copolymer includes a copolymer component derived from 2-ethylhexyl acrylate and a copolymer component derived from acrylic acid
  • the copolymer component derived from acrylic acid occupies the total mass of the acrylic copolymer.
  • the mass ratio is preferably 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. If the ratio of acrylic acid is 1 mass% or less, when an adhesive composition contains a crosslinking agent, crosslinking of the acrylic copolymer can be prevented from proceeding too quickly.
  • the acrylic copolymer may contain a copolymer component derived from two or more kinds of functional group-containing monomers.
  • the acrylic copolymer may be a ternary copolymer.
  • an acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer and a hydroxyl group-containing monomer is preferred, and this carboxyl group-containing monomer is preferred.
  • the hydroxyl group-containing monomer is preferably 2-hydroxyethyl acrylate.
  • the ratio of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less, and the ratio of the mass of the copolymer component derived from acrylic acid is 1% by mass or less.
  • the balance is preferably a copolymer component derived from 2-hydroxyethyl acrylate.
  • the weight average molecular weight (Mw) of the acrylic copolymer is preferably from 300,000 to 2,000,000, more preferably from 600,000 to 1,500,000, and even more preferably from 800,000 to 1,200,000. preferable. If the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, the acrylic copolymer can be peeled without a residue of the adhesive on the adherend. When the weight average molecular weight Mw of the acrylic copolymer is 2 million or less, it can be reliably attached to the adherend.
  • the weight average molecular weight Mw of the acrylic copolymer is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.
  • the acrylic copolymer can be produced according to a conventionally known method using the above-mentioned various raw material monomers.
  • the form of copolymerization of the acrylic copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.
  • the content of the acrylic copolymer in the pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 preferably contains a pressure-sensitive adhesive obtained by crosslinking a composition containing a crosslinking agent in addition to the above-mentioned acrylic copolymer.
  • the pressure-sensitive adhesive composition is also preferably substantially composed of a pressure-sensitive adhesive obtained by cross-linking the above-mentioned acrylic copolymer and the cross-linking agent as described above.
  • substantially means that it is composed only of the pressure-sensitive adhesive except for a small amount of impurities that are inevitably mixed in the pressure-sensitive adhesive.
  • examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent.
  • These cross-linking agents may be used alone or in combination of two or more.
  • a crosslinking agent (isocyanate-based crosslinking agent) containing a compound having an isocyanate group as a main component is preferable.
  • isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
  • Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate,
  • the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product having an isocyanurate ring.
  • crosslinking agent mainly comprising a compound having an isocyanate group means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. To do.
  • the content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If content of the crosslinking agent in an adhesive composition is in such a range, the adhesiveness of the adhesive layer 12 and the base material 11 can be improved, and the adhesive characteristic is stabilized after manufacture of an adhesive sheet. The curing period for making it possible can be shortened.
  • the isocyanate-based crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product).
  • the compound having an isocyanurate ring is preferably blended in an amount of 0.7 to 1.5 equivalents with respect to the hydroxyl equivalent of the acrylic copolymer. If the compounding quantity of the compound which has an isocyanurate ring is 0.7 equivalent or more, the adhesive strength will not become too high after heating, the adhesive sheet will be easily peeled off, and the adhesive residue can be reduced. If the compounding quantity of the compound which has an isocyanurate ring is 1.5 equivalent or less, it can prevent that an initial stage adhesive force becomes low too much, or can prevent a sticking fall.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 in the present embodiment includes a cross-linking agent
  • the pressure-sensitive adhesive composition preferably further includes a cross-linking accelerator.
  • the crosslinking accelerator is preferably selected and used as appropriate according to the type of the crosslinking agent.
  • the pressure-sensitive adhesive composition contains a polyisocyanate compound as a crosslinking agent, it is preferable to further contain an organic metal compound-based crosslinking accelerator such as an organic tin compound.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 preferably includes a reactive pressure-sensitive adhesive aid (hereinafter sometimes simply referred to as “pressure-sensitive adhesive aid”).
  • a reactive pressure-sensitive adhesive aid include a polybutadiene resin having a reactive functional group and a hydrogenated product of a polybutadiene resin having a reactive functional group.
  • the reactive functional group possessed by the reactive adhesive aid is one or more functional groups selected from the group consisting of hydroxyl groups, isocyanate groups, amino groups, oxirane groups, acid anhydride groups, alkoxy groups, acryloyl groups, and methacryloyl groups. It is preferably a group.
  • the pressure-sensitive adhesive composition contains a reactive pressure-sensitive adhesive aid, the adhesive residue when the pressure-sensitive adhesive sheet 10 is peeled off from the adherend can be reduced.
  • a reactive adhesive adjuvant Both terminal hydroxyl group hydrogenated polybutadiene is preferable.
  • the content of the reactive adhesive aid in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content of the reactive adhesive aid in the pressure-sensitive adhesive composition is 3% by mass or more, no adhesive remains, and if it is 50% by mass or less, the adhesive strength does not decrease.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 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, for example, organic solvents, flame retardants, tackifiers, ultraviolet absorbers, antioxidants, antiseptics, antifungal agents, plasticizers, antifoaming agents, and wetting And a sex modifier.
  • the pressure-sensitive adhesive composition according to the present embodiment for example, the following pressure-sensitive adhesive composition examples are given, but the present invention is not limited to such examples.
  • an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer.
  • An adhesive composition is mentioned.
  • an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer.
  • an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and acrylic.
  • a certain adhesive composition is mentioned.
  • an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and acrylic.
  • a pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Is mentioned.
  • the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less.
  • the proportion of the mass of the copolymer component derived from the group-containing monomer is preferably 1% by mass or less, and the remainder is preferably another copolymer component.
  • the other copolymer component is a copolymer derived from a hydroxyl group-containing monomer. It preferably contains a polymer component.
  • the thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the use of the pressure-sensitive adhesive sheet 10.
  • the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 ⁇ m or more and 60 ⁇ m or less, and more preferably 10 ⁇ m or more and 50 ⁇ m or less. If the thickness of the pressure-sensitive adhesive layer 12 is too thin, the pressure-sensitive adhesive layer 12 may not follow the irregularities on the circuit surface of the semiconductor chip, and a gap may be generated. For example, an interlayer insulating material and a sealing resin may enter the gap, and the wiring connection electrode pad on the chip circuit surface may be blocked.
  • the pressure-sensitive adhesive layer 12 When the thickness of the pressure-sensitive adhesive layer 12 is 5 ⁇ m or more, the pressure-sensitive adhesive layer 12 easily follows the unevenness of the chip circuit surface, and the generation of a gap can be prevented. If the thickness of the pressure-sensitive adhesive layer 12 is too thick, the semiconductor chip sinks into the pressure-sensitive adhesive layer, and there is a risk that a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip occurs. If such a step occurs, the wiring may be disconnected during rewiring. If the thickness of the pressure-sensitive adhesive layer 12 is 60 ⁇ m or less, a step is hardly generated.
  • the release sheet RL is not particularly limited.
  • the release sheet RL preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate.
  • the release sheet RL may include a release agent layer only on one side of the release substrate, or may include a release agent layer on both sides of the release substrate.
  • the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
  • the paper substrate include glassine paper, coated paper, and cast coated paper.
  • plastic film examples include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
  • release agent examples include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins.
  • the thickness of the release sheet RL is not particularly limited.
  • the thickness of the release sheet RL is usually 20 ⁇ m or more and 200 ⁇ m or less, and preferably 25 ⁇ m or more and 150 ⁇ m or less.
  • the thickness of the release agent layer is not particularly limited.
  • the thickness of the release agent layer is preferably 0.01 ⁇ m or more and 2.0 ⁇ m or less, and preferably 0.03 ⁇ m or more and 1.0 ⁇ m or less. More preferred.
  • the thickness of the plastic film is preferably 3 ⁇ m or more and 50 ⁇ m or less, and more preferably 5 ⁇ m or more and 40 ⁇ m or less.
  • the pressure-sensitive adhesive sheet 10 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 adherend is deformed by heating. Moreover, if the adhesive force after a heating is 2.0 N / 25mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body.
  • room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower.
  • the adhesive strength is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the adhesive sheet of 25 mm.
  • the manufacturing method of the adhesive sheet 10 is not particularly limited.
  • the adhesive sheet 10 is manufactured through the following processes.
  • a coating agent for a hard coat layer (hereinafter referred to as a hard coat agent) containing the organic-inorganic hybrid material described above is prepared or prepared.
  • the hard coating agent is further added with a solvent to form a coating solution.
  • the solvent used for the hard coating agent include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, cellosolve solvents, and ethers. System solvents and the like.
  • Examples of the aliphatic hydrocarbon solvent include hexane and heptane.
  • Examples of the aromatic hydrocarbon solvent include toluene and xylene.
  • Examples of the halogenated hydrocarbon solvent include methylene chloride and ethylene chloride.
  • Examples of the alcohol solvent include methanol, ethanol, propanol, and butanol.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone.
  • Examples of ester solvents include ethyl acetate and butyl acetate.
  • Examples of the cellosolve solvent include ethyl cellosolve.
  • Examples of the ether solvent include propylene glycol monomethyl ether.
  • the solid content concentration is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 40% or less, from the viewpoint of applicability to a substrate and workability. It is below mass%.
  • this coating film is irradiated with an active energy ray, and this coating film
  • the hard coat layer 13 is formed by curing.
  • the coating method of the hard coating agent include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.
  • active energy rays include ultraviolet rays and electron beams, and ultraviolet rays are preferred. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or a xenon lamp.
  • the dose of ultraviolet rays is not particularly limited, preferably 100 mJ / cm 2 or more 500 mJ / cm 2 or less, more preferably 150 mJ / cm 2 or more 450 mJ / cm 2 or less.
  • the electron beam can be irradiated using an electron beam accelerator or the like.
  • the amount of electron beam irradiation is not particularly limited, but is preferably 150 kV or more and 350 kV or less.
  • a cured film can be obtained, without adding a photoinitiator.
  • the pressure-sensitive adhesive composition is applied on the first surface 11a of the substrate 11 to form a coating film.
  • this coating film is dried to form the pressure-sensitive adhesive layer 12.
  • release sheet RL is stuck so that adhesive layer 12 may be covered.
  • the adhesive sheet 10 As another manufacturing method of the adhesive sheet 10, it is manufactured through the following steps. 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.
  • the pressure-sensitive adhesive sheet 10 can also be manufactured by bonding the release sheet RL having the pressure-sensitive adhesive layer 12 and the base material 11 having the hard coat layer 13 described above. In this case, the pressure-sensitive adhesive layer 12 and the first surface 11a of the substrate 11 are bonded together.
  • the pressure-sensitive adhesive composition 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 by diluting the pressure-sensitive adhesive composition with an organic solvent.
  • 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.
  • a crosslinking agent is mix
  • the pressure-sensitive adhesive sheet 10 is used when sealing a semiconductor element.
  • the pressure-sensitive adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing a semiconductor element that is stuck on the pressure-sensitive adhesive sheet 10.
  • the pressure-sensitive adhesive sheet 10 is not used when sealing a semiconductor element mounted on a metal lead frame, but seals a semiconductor element that is stuck to the pressure-sensitive adhesive layer 12.
  • a panel scale package Panel Scale Package
  • WLP wafer Level Package
  • the pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process having a step of covering the semiconductor chip with a sealing resin and a step of thermosetting the sealing resin.
  • FIGS. 2A to 2E are schematic views illustrating the method for manufacturing the semiconductor device according to the present embodiment.
  • the manufacturing method of the semiconductor device according to the present embodiment includes a step of attaching the frame member 20 in which a plurality of openings 21 are formed on the adhesive sheet 10 (adhesive sheet attaching step), and an opening 21 of the frame member 20.
  • a step of bonding the semiconductor chip CP to the exposed adhesive layer 12 (bonding step), a step of covering the semiconductor chip CP with the sealing resin 30 (sealing step), and a step of thermosetting the sealing resin 30 ( A thermosetting step) and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting.
  • bonding step a step of bonding the semiconductor chip CP to the exposed adhesive layer 12
  • sealing step a step of covering the semiconductor chip CP with the sealing resin 30
  • a step of thermosetting the sealing resin 30 A thermosetting step
  • peeling the pressure-sensitive adhesive sheet 10 peeling step
  • the frame member 20 is formed in a lattice shape and has a plurality of openings 21.
  • the frame member 20 is preferably formed of a heat-resistant material, and examples thereof include metals such as copper and stainless steel, and heat-resistant resins such as polyimide resins and glass epoxy resins.
  • the opening 21 is a hole that penetrates the front and back surfaces of the frame member 20.
  • the shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame.
  • the depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
  • FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
  • the semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces.
  • a semiconductor chip CP semiconductor element
  • the dicing apparatus is not particularly limited, and a known dicing apparatus can be used.
  • the dicing conditions are not particularly limited. Instead of dicing using a dicing blade, a laser dicing method, a stealth dicing method, or the like may be used.
  • an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP.
  • the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding process, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
  • the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden.
  • the energy ray polymerizable compound When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced.
  • the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable.
  • UV ultraviolet rays
  • EB electron beams
  • the energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
  • the material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin.
  • the epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
  • the method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited. In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example.
  • the sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A.
  • the sheet-shaped sealing resin 30 it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being generated between the semiconductor chip CP and the frame member 20.
  • the temperature condition range for heating by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
  • a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used.
  • the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured.
  • Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
  • a transfer molding method may be employed.
  • the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device.
  • a fluid resin material is injected into the mold to cure the resin material.
  • the heating and pressure conditions are not particularly limited.
  • a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds.
  • the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
  • the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process).
  • the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. .
  • the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20.
  • corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
  • the hard coat layer 13 of the pressure-sensitive adhesive sheet 10 comes into contact with the plate-like member, so that contact between the base material 11 and the plate-like member can be prevented.
  • 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 shown in FIG. 2D, the sealing body 50 is supported while being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
  • the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42.
  • the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a glass epoxy resin.
  • the adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50.
  • the adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
  • the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure.
  • the sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time.
  • the conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa. Also in the 2nd heat press process, since the hard-coat layer 13 of the adhesive sheet 10 contacts a plate-shaped member, the contact with the base material 11 and a plate-shaped member can be prevented. Also in the second heat pressing step, as the plate-like member, for example, a metal plate such as stainless steel can be used.
  • FIG. 2E The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
  • the adhesive sheet 10 when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent.
  • peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree
  • the peeling angle ⁇ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less.
  • the reinforcing member 40 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed. Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step).
  • a method for dividing the sealing body 50 into individual pieces is not particularly limited.
  • the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer.
  • the step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like.
  • a pressure-sensitive adhesive sheet 10 capable of preventing contamination of equipment and members and preventing fusion between the equipment and members even after undergoing a process in which high temperature conditions are imposed. Can do. Since the hard coat layer 13 is laminated on the second surface 11b of the base material 11 of the pressure-sensitive adhesive sheet 10, for example, a plate-like member such as a stainless steel plate in the above-described first heat press step and second heat press step Contact with the substrate 11 can be prevented. Therefore, even if the base material 11 contains a polyester-based resin, it is possible to prevent the equipment and members from being contaminated by oligomers resulting from the base material 11, and also to prevent the equipment and members and the base material 11 from being fused.
  • the pressure-sensitive adhesive sheet 10 has a pressure-sensitive adhesive layer 12 containing an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer, the pressure-sensitive adhesive sheet 10 is easily peeled off from the adherend and reduces adhesive residue. Can do.
  • the adherend to which the pressure-sensitive adhesive layer 12 contacts is the semiconductor chip CP and the frame member 20.
  • the pressure-sensitive adhesive layer 12 is exposed to a high temperature condition in contact with the semiconductor chip CP and the frame member 20.
  • the pressure-sensitive adhesive sheet 10 is easy to peel off even after being exposed to high-temperature conditions, and has less adhesive residue on the semiconductor chip CP and the frame member 20. .
  • the pressure-sensitive adhesive sheet according to the second embodiment is different from the pressure-sensitive adhesive sheet according to the first embodiment in that it has two hard coat layers. Since the second embodiment is the same as the first embodiment in other points, the description is omitted or simplified.
  • FIG. 3 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10A of the present embodiment.
  • the pressure-sensitive adhesive sheet 10 ⁇ / b> A includes a base material 11, a pressure-sensitive adhesive layer 12, and a hard coat layer 13.
  • the hard coat layer 13 of the present embodiment includes a first hard coat layer 13a and a second hard coat layer 13b.
  • the base material 11 has the 1st surface 11a and the 2nd surface 11b on the opposite side to the 1st surface 11a similarly to the said embodiment.
  • the second hard coat layer 13b is laminated on the first surface 11a, the first hard coat layer 13a is laminated on the second surface 11b, and the pressure-sensitive adhesive layer is formed on the second hard coat layer 13b. 12 are laminated.
  • the thickness of the second hard coat layer 13b is preferably in the same range as the hard coat layer 13 described in the first embodiment.
  • the second hard coat layer 13b is preferably formed so as to cover the entire first surface 11a of the substrate 11.
  • the first hard coat layer 13a is a cured film formed by curing an organic-inorganic hybrid material, and includes a cured product of the organic-inorganic hybrid material.
  • the second hard coat layer 13b includes a polyfunctional acrylic resin.
  • the second hard coat layer 13b is preferably not a cured film formed by curing an organic-inorganic hybrid material from the viewpoint of adhesion to the pressure-sensitive adhesive layer 12.
  • the active energy ray-sensitive composition used for forming the second hard coat layer 13b can be prepared using the material described in the first embodiment except that it is not an organic-inorganic hybrid material.
  • the layer 13b is preferably a cured film formed by curing the active energy ray sensitive composition.
  • the active energy ray-sensitive composition used for forming the second hard coat layer 13b is also at least selected from the group consisting of a polyfunctional (meth) acrylate monomer and a (meth) acrylate prepolymer, as in the above embodiment.
  • One type of resin is preferably contained, and more preferably a polyfunctional (meth) acrylate monomer is contained.
  • the active energy ray-sensitive composition used for forming the second hard coat layer 13b pentaerythritol tri (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) are used as a multifunctional (meth) acrylate monomer.
  • Active energy ray-sensitive composition containing acrylate As an example of the first hard coat layer 13a according to the present embodiment, an organic-inorganic hybrid material containing reactive silica fine particles, a polyfunctional (meth) acrylate monomer, and a (meth) acrylate prepolymer is cured. The formed first hard coat layer 13a is mentioned.
  • the second hard coat layer 13b in this case, pentaerythritol tri (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate as a polyfunctional (meth) acrylate monomer, photopolymerization initiator
  • examples thereof include a second hard coat layer 13b formed by curing an active energy ray-sensitive composition containing 1-hydroxycyclohexyl phenyl ketone and a siloxane-modified acrylic leveling agent as a leveling agent.
  • the manufacturing method of 10 A of adhesive sheets is not specifically limited.
  • the adhesive sheet 10A is manufactured through the following steps. First, a hard coat agent is prepared or prepared in the same manner as in the above embodiment. Next, a hard coat agent is coated on the second surface 11b of the base material 11 to form a coating film, and after the coating film is dried, the coating film is irradiated with active energy rays, and the coating is performed. The first hard coat layer 13a is formed by curing the film. Next, a hard coat agent is coated on the first surface 11a of the substrate 11, and the coating film is cured in the same manner as described above, whereby the second hard coat layer 13b is formed.
  • an adhesive composition is apply
  • this coating film is dried to form the pressure-sensitive adhesive layer 12.
  • release sheet RL is stuck so that adhesive layer 12 may be covered.
  • another manufacturing method of 10 A of adhesive sheets 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.
  • the adhesive sheet 10A can also be manufactured by bonding the release sheet RL having the adhesive layer 12 and the base material 11 having the first hard coat layer 13a and the second hard coat layer 13b. In this case, the pressure-sensitive adhesive layer 12 and the second hard coat layer 13b of the substrate 11 are bonded together.
  • the pressure-sensitive adhesive sheet 10A can also be used in the same semiconductor device manufacturing process as in the above embodiment.
  • a pressure-sensitive adhesive sheet 10A that can prevent contamination of equipment and members, and can prevent fusion between the equipment and members even after a process in which high temperature conditions are imposed. Can do. Since the pressure-sensitive adhesive sheet 10 ⁇ / b> A further includes the second hard coat layer 13 b between the pressure-sensitive adhesive layer 12 and the base material 11, the oligomer contained in the base material 11 can be prevented from moving to the pressure-sensitive adhesive layer 12. In the pressure-sensitive adhesive sheet 10A, since the hard coat layers are laminated on both surfaces (the first surface 11a and the second surface 11b) of the base material 11, deformation of the base material due to heating can be reduced.
  • the hard coat layer 13 may be formed so as to cover the entire second surface 11b of the substrate 11, or there may be a region where the hard coat layer 13 is not formed. In the latter case, in the process using the pressure-sensitive adhesive sheet 10, the hard coat layer 13 only needs to be formed so that the apparatus and members used during the process do not contact the base material 11.
  • the hard coat layer 13 was formed first as a manufacturing method of an adhesive sheet, and the aspect which forms the adhesive layer 12 after that was mentioned as an example and demonstrated, this invention is limited to such an aspect. Not.
  • the adhesive sheet 10 may be a single wafer or may be provided in a state where a plurality of adhesive sheets 10 are laminated.
  • the pressure-sensitive adhesive layer 12 may be covered with a hard coat layer 13 of another pressure-sensitive adhesive sheet to be laminated.
  • the adhesive sheet 10 may be a long sheet or may be provided in a state of being wound in a roll. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
  • the sealing resin 30 is a thermosetting resin
  • the present invention is not limited to such a mode.
  • the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
  • the adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
  • the pressure-sensitive adhesive sheet laminate was returned to room temperature, and the intervals between the vertices of the square marks were measured again. Based on the initial value and the measured value of the interval after heating, the shrinkage rate of each side was calculated. When the shrinkage rate in the MD direction of the base material was 1.7% or less, it was determined as “A”, and when the shrinkage rate exceeded 1.7%, it was determined as “B”.
  • the pressure-sensitive adhesive sheet was bonded to a copper foil having a thickness of 80 ⁇ m, and a tape with copper foil cut out to a size of 7 cm ⁇ 15 cm was obtained. From the upper surface side and the lower surface side of this tape with copper foil, it was sandwiched up and down using an SUS plate (# 1200 finish) of the same size as the tape with copper foil.
  • the tape with copper foil sandwiched between SUS plates was heated and pressurized under the conditions of 190 ° C., 2.5 MPa, and 90 minutes. After heating and pressurization, the surface state of the SUS plate that was in contact with the pressure-sensitive adhesive sheet was confirmed. When there was no dirt or fusion, it was determined as “A”, and when dirt was generated, it was determined as “B”.
  • Example 1 Preparation of base material 100 parts by mass of a hard coating agent containing an active energy ray-sensitive composition and 83 parts by mass of propylene glycol monomethyl ether as a diluting solvent are uniformly mixed, and the solid content concentration is about 40% by mass.
  • a hard coat agent HC1 was prepared.
  • the hard coating agent HC1 containing the active energy ray-sensitive composition used is a trade name “OPSTAR Z7530” manufactured by JSR Corporation, an active energy ray-sensitive composition (70% by mass), a photopolymerization initiator. (3% by mass) and methyl ethyl ketone (27% by mass), and the solid content concentration is 73% by mass.
  • the composition of the active energy ray-sensitive composition is composed of reactive silica fine particles (42% by mass in the hard coat agent), a polyfunctional (meth) acrylate monomer and a (meth) acrylate prepolymer (in the hard coat agent). 28 mass%).
  • the hard coat agent HC1 was applied to the easy-adhesion surface of a transparent polyethylene terephthalate film [Toyobo Co., Ltd .; PET50A-4300, thickness 50 ⁇ m].
  • the hard coat agent HC1 was applied so that the film thickness after drying and UV curing was 1.5 ⁇ m. Drying conditions were 70 ° C. and 1 minute. UV curing was irradiated with ultraviolet rays of 150 mJ / cm 2 by a high pressure mercury lamp. In this way, a base material HCBS1 having a hard coat layer was produced.
  • Acrylic ester copolymer 100 parts by mass (solid content)
  • the acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
  • Adhesion aid 13-part by mass (solid content) of hydroxylated hydrogenated polybutadiene at both ends (Nippon Soda Co., Ltd .; GI-1000)
  • Crosslinking agent aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate) [manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX], 9.0 parts by mass (solid content)
  • Example 2 The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as Example 1 except that the type of the substrate on which the hard coat layer was formed was different from Example 1.
  • a polyethylene terephthalate film product name: PET50 KFL12D, thickness 50 ⁇ m
  • Teijin DuPont Films Co., Ltd. was used, and the same hard coat agent HC1 as in Example 1 was applied to the easy adhesion surface of this film.
  • a hard coat layer was formed to obtain a base material HCBS2 having a hard coat layer.
  • Example 3 The pressure-sensitive adhesive sheet according to Example 3 was produced in the same manner as Example 2 except that hard coat layers were formed on both surfaces of a polyethylene terephthalate film as a base material.
  • the base material HCBS3 having the hard coat layer of Example 3 is obtained by applying the hard coat agent HC2 according to Example 3 to the surface of the base material HCBS1 opposite to the surface on which the hard coat layer is formed. A layer was formed.
  • the hard coat agent HC2 according to Example 3 was prepared by mixing components (A) to (D) at the following blending amounts (all by weight (solid content ratio)) to prepare a curable resin composition. Thereafter, it was obtained by diluting with propylene glycol monomethyl ether.
  • the solid content concentration of the hard coating agent HC2 was 30% by mass.
  • Component (A) Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMM-3L), 100 parts by mass (solid content).
  • Component (B) Ethylene oxide-modified dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH-12E), 100 parts by mass (solid content).
  • Component (C) 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184, acetophenone photopolymerization initiator), 10 parts by mass (solid content).
  • the prepared hard coat agent HC2 of Example 3 is formed on the easy-adhesion surface opposite to the surface on which the hard coat layer of the base material HCBS1 is formed so that the film thickness after drying using a Meyer bar is 3 ⁇ m. It was applied to.
  • the coating film is dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays at 300 mJ / cm 2 (integrated light amount) using a high-pressure mercury lamp to cure the coating film to have a second hard coat layer having a thickness of 3 ⁇ m.
  • a substrate HCBS3 was produced. When the adhesive layer and the base material HCBS3 are bonded together, the adhesive layer is bonded to the surface opposite to the surface on which the hard coat layer using the hard coat agent HC2 is formed. A sheet was obtained.
  • Comparative Example 1 The pressure-sensitive adhesive sheet according to Comparative Example 1 was the same as Example 1 except that a transparent polyethylene terephthalate film [manufactured by Toyobo Co., Ltd .; PET50A-4300, thickness 50 ⁇ m] was used as a base material without forming a hard coat layer. Produced.
  • Comparative Example 2 The pressure-sensitive adhesive sheet according to Comparative Example 2 was the same as Example 2 except that a polyethylene terephthalate film [manufactured by Teijin DuPont Films; PET50 KFL12D, thickness 50 ⁇ m] was used as a substrate without forming a hard coat layer. Produced.
  • a polyethylene terephthalate film manufactured by Teijin DuPont Films; PET50 KFL12D, thickness 50 ⁇ m
  • Comparative Example 3 The pressure-sensitive adhesive sheet according to Comparative Example 3 was produced in the same manner as in Example 2 except that the hard coat layer of the base material HCBS2 used in Example 2 and the pressure-sensitive adhesive layer were bonded together.
  • Table 1 shows the layer structures of the base material and the hard coat layer of the pressure-sensitive adhesive sheets according to Examples 1 to 3 and Comparative Examples 1 to 3.
  • Table 2 shows the evaluation results of the pressure-sensitive adhesive sheets according to Examples 1 to 3 and Comparative Examples 1 to 3.
  • the pressure-sensitive adhesive sheets of Examples 1 to 3 since they had a hard coat layer, no fusion and contamination to the SUS plate occurred in the heat resistance evaluation.
  • the adhesive sheets of Comparative Examples 1 to 3 do not have a hard coat layer on the second surface of the substrate (the surface opposite to the surface on which the adhesive layer is laminated), the SUS plate and the substrate The surface of the SUS plate was contaminated by being heated in contact with the PET film.
  • the pressure-sensitive adhesive sheets of Examples 1 to 3 since the shrinkage rate was low, it is possible to suppress the occurrence of problems in the process in the semiconductor device manufacturing process, for example.
  • the pressure-sensitive adhesive sheets of Examples 1 to 3 the adhesiveness between the pressure-sensitive adhesive layer and the substrate is excellent.
  • a hard coat layer was provided between the base material and the pressure-sensitive adhesive layer.
  • the hard coat layer was formed using the hard coat agent HC2, the hard coat layer and the pressure-sensitive adhesive were used. It is considered that the adhesion between the substrate and the adhesion between the substrate and the hard coat layer is excellent.
  • Adhesive sheet 11 ... Base material, 11a ... First side, 11b ... Second side, 12 ... Adhesive layer, 13 ... Hard coat layer, 13a ... First hard coat layer, 13b ... Second hard coat Layer, 20 ... frame member, 21 ... opening.

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Abstract

Disclosed is an adhesive sheet (10) that is used at the time of sealing a semiconductor element on the adhesive sheet, the adhesive sheet (10) comprising: a substrate (11) having a first surface (11a) and a second surface (11b) on the opposite side from the first surface (11a), the substrate including a polyester resin; an adhesive agent layer (12) layered on the first surface (11a) of the substrate (11); and a hard coat layer (13) layered on the second surface (11b) of the substrate (11). The hard coat layer (13) is a cured film formed by curing an organic/inorganic hybrid material.

Description

粘着シートAdhesive sheet
　本発明は、粘着シートに関する。 The present invention relates to an adhesive sheet.
　半導体装置の製造工程で使用される粘着シートには、様々な特性が求められる。近年は、粘着シートには、高温条件が課される工程を経ても、製造工程で使用される装置、部材、及び被着体を汚さないことが求められる。さらに、高温条件の工程後、粘着シートを室温で剥離する際に、被着体等への粘着剤が残るという不具合（いわゆる糊残り）が少なく、かつ剥離力が小さいことも求められている。 Various properties are required for adhesive sheets used in the manufacturing process of semiconductor devices. In recent years, pressure-sensitive adhesive sheets are required not to contaminate devices, members, and adherends used in the manufacturing process even after a process in which high temperature conditions are imposed. Furthermore, after peeling off the pressure-sensitive adhesive sheet at room temperature after the process under high temperature conditions, it is also required that there are few problems (so-called adhesive residue) that the pressure-sensitive adhesive remains on the adherend and the like and that the peeling force is small.
　例えば、特許文献１には、粘着剤の糊残りを抑制し、安定してＱＦＮ（Ｑｕａｄ　Ｆｌａｔ　Ｎｏｎ－ｌｅａｄ）の半導体パッケージを生産するためのマスクシートが記載されている。特許文献１には、特定の耐熱フィルム及びシリコーン系粘着剤を用いてマスクシートを作製することによって、ダイアタッチ工程及び樹脂封止工程における１５０℃～１８０℃で１時間～６時間の環境に耐え得ると記載されている。 For example, Patent Document 1 discloses a mask sheet for suppressing adhesive residue of an adhesive and stably producing a QFN (Quad Flat Non-lead) semiconductor package. In Patent Document 1, a mask sheet is prepared using a specific heat-resistant film and a silicone-based pressure-sensitive adhesive to withstand an environment of 150 to 180 ° C. for 1 to 6 hours in a die attach process and a resin sealing process. It is stated that you get.
特開２００２－２７５４３５号公報JP 2002-275435 A
　しかしながら、特許文献１に記載のマスクシートの作製に使用されるポリイミドフィルム等の耐熱性フィルム及びシリコーン系粘着剤は高価であるため、そのマスクシートの用途は、ＱＦＮパッケージ等の一部の用途に限られる。
　近年、１８０℃以上２００℃以下のような高温条件が課される工程でも粘着シートが使用されている。このような高温の工程において、例えば、ポリイミドフィルム等に比べて耐熱性が低く安価なフィルム（例えば、ポリエチレンテレフタレート等のフィルム）を基材として使用すると、加熱及び加圧工程中に基材中のオリゴマーが設備及び部材に付着して汚染したり、設備及び部材と基材とが融着したりするおそれがある。設備及び部材に基材が融着すると、粘着シートを剥がし難くなり、剥がすことができても設備及び部材に基材のオリゴマー等が残留して、設備及び部材が汚染するおそれがある。例えば、粘着シートの粘着剤層に貼着された半導体素子を樹脂封止する工程で高温条件が課されると、半導体素子の表面が汚染され、半導体装置に不具合が生じる可能性がある。 However, since the heat-resistant film such as polyimide film and the silicone-based adhesive used for the production of the mask sheet described in Patent Document 1 are expensive, the mask sheet is used for some applications such as a QFN package. Limited.
In recent years, pressure-sensitive adhesive sheets are also used in processes where high temperature conditions such as 180 ° C. or higher and 200 ° C. or lower are imposed. In such a high-temperature process, for example, when a low-cost and low-cost film (for example, a film such as polyethylene terephthalate) is used as a base material as compared with a polyimide film or the like, There is a possibility that the oligomer adheres to and contaminates the equipment and members, and the equipment and members and the base material are fused. When the base material is fused to the equipment and members, it becomes difficult to peel off the pressure-sensitive adhesive sheet. Even if the adhesive sheet can be peeled off, the base material oligomer or the like may remain on the equipment and members, and the equipment and members may be contaminated. For example, when a high temperature condition is imposed in the step of resin-sealing a semiconductor element attached to an adhesive layer of an adhesive sheet, the surface of the semiconductor element may be contaminated, causing a problem in the semiconductor device.
　本発明の目的は、高温条件が課される工程を経た後でも、設備及び部材の汚染を防止すること、並びに設備及び部材との融着を防止することができる粘着シートを提供することである。 The objective of this invention is providing the adhesive sheet which can prevent the contamination of an installation and a member, and can prevent a fusion | bonding with an installation and a member, even after passing through the process for which high temperature conditions are imposed. .
　本発明の一態様によれば、粘着シート上の半導体素子を封止する際に使用される粘着シートであって、第一面及び前記第一面とは反対側の第二面を有し、ポリエステル系樹脂を含む基材と、前記基材の前記第一面に積層された粘着剤層と、前記基材の前記第二面に積層されたハードコート層と、を有し、前記ハードコート層は、有機無機ハイブリッド材料を硬化させて形成された硬化皮膜である粘着シートが提供される。 According to one aspect of the present invention, a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet, the first surface and the second surface opposite to the first surface, A base material containing a polyester resin, an adhesive layer laminated on the first surface of the base material, and a hard coat layer laminated on the second surface of the base material, and the hard coat The layer is provided with an adhesive sheet that is a cured film formed by curing an organic-inorganic hybrid material.
　本発明の一態様に係る粘着シートにおいて、１９０℃及び１時間の条件で加熱後、前記基材のいずれかの面に沿う方向における収縮率が１．７％以下であることが好ましい。 In the pressure-sensitive adhesive sheet according to one embodiment of the present invention, it is preferable that the shrinkage rate in a direction along any surface of the base material is 1.7% or less after being heated at 190 ° C. for 1 hour.
　本発明の一態様に係る粘着シートにおいて、前記ポリエステル系樹脂は、ポリエ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、及びポリブチレンテレフタレート樹脂からなる群から選択される樹脂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 polyester resin is preferably a resin selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin.
　本発明の一態様に係る粘着シートにおいて、前記ハードコート層の厚みは、０．５μｍ以上３．０μｍ以下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 thickness of the hard coat layer is preferably 0.5 μm or more and 3.0 μm or less.
　本発明の一態様に係る粘着シートにおいて、前記粘着剤層と前記基材との間に第二ハードコート層をさらに有し、前記第二ハードコート層は、多官能アクリル系樹脂を含むことが好ましい。 In the pressure-sensitive adhesive sheet according to an aspect of the present invention, the pressure-sensitive adhesive layer further includes a second hard coat layer between the pressure-sensitive adhesive layer and the base material, and the second hard coat layer includes a polyfunctional acrylic resin. preferable.
　本発明の一態様に係る粘着シートにおいて、前記有機無機ハイブリッド材料は、シリカ微粒子と重合性不飽和基を有する有機化合物とを結合させた材料、並びに活性エネルギー線硬化型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, the organic-inorganic hybrid material preferably includes a material in which silica fine particles and an organic compound having a polymerizable unsaturated group are bonded, and an active energy ray-curable resin.
　本発明によれば、高温条件が課される工程を経た後でも、設備及び部材の汚染を防止すること、並びに設備及び部材との融着を防止することができる粘着シートを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even after passing through the process for which high temperature conditions are imposed, the adhesive sheet which can prevent the contamination of an installation and a member, and can prevent fusion | fusion with an installation and a member can be provided. .
第一実施形態に係る粘着シートの断面概略図である。It is a section schematic diagram of the adhesive sheet concerning a first embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第一実施形態に係る粘着シートを用いた半導体装置の製造工程の一部を説明する図である。It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. 第二実施形態に係る粘着シートの断面概略図である。It is a section schematic diagram of the adhesive sheet concerning a second embodiment.
〔第一実施形態〕
（粘着シート）
　図１には、本実施形態の粘着シート１０の断面概略図が示されている。
　粘着シート１０は、基材１１、粘着剤層１２及びハードコート層１３を有する。
　基材１１は、第一面１１ａ、及び第一面１１ａとは反対側の第二面１１ｂを有する。本実施形態の粘着シート１０においては、第一面１１ａに粘着剤層１２が積層され、第二面１１ｂにハードコート層１３が積層されている。
　本実施形態では、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、シート状、テープ状、ラベル状などあらゆる形状をとり得る。 [First embodiment]
(Adhesive sheet)
FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
The pressure-sensitive adhesive sheet 10 has a base material 11, a pressure-sensitive adhesive layer 12, and a hard coat layer 13.
The base material 11 has a first surface 11a and a second surface 11b opposite to the first surface 11a. In the adhesive sheet 10 of this embodiment, the adhesive layer 12 is laminated | stacked on the 1st surface 11a, and the hard-coat layer 13 is laminated | stacked on the 2nd surface 11b.
In the present embodiment, a release sheet RL is laminated on the pressure-sensitive adhesive layer 12 as shown in FIG. The shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a sheet shape, a tape shape, and a label shape.
（基材）
　基材１１は、ポリエステル系樹脂を含む。基材１１は、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、ポリエチレンナフタレート樹脂、およびポリブチレンテレフタレート樹脂からなる群から選択される樹脂であることがより好ましく、ポリエチレンテレフタレート樹脂がさらに好ましい。
　基材１１としては、ポリエチレンテレフタレートフィルム、またはポリエチレンナフタレートフィルムが好ましく、ポリエチレンテレフタレートフィルムがより好ましい。ポリエステルフィルムに含有するオリゴマーとしては、ポリエステル形成性モノマー、ダイマー、及びトリマーなどに由来する。 (Base material)
The substrate 11 includes a polyester resin. The base material 11 is more preferably made of a material mainly composed of a polyester resin. In this specification, the material having a polyester-based resin as a main component means that the ratio of the mass of the polyester-based resin to the total mass of the material constituting the substrate is 50% by mass or more. The polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins. More preferred is a resin selected from the group consisting of polyethylene terephthalate resins, polyethylene naphthalate resins, and polybutylene terephthalate resins, and polyethylene terephthalate resins are even more preferred.
As the base material 11, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film is more preferable. The oligomers contained in the polyester film are derived from polyester-forming monomers, dimers, trimers, and the like.
　基材１１と粘着剤層１２との密着性、及び基材１１とハードコート層１３との密着性を高めるために、第一面１１ａ及び第二面１１ｂ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もよい。基材１１の第一面１１ａ及び第二面１１ｂには、粘着剤が塗布されて粘着処理が施されていてもよい。基材の粘着処理に用いられる粘着剤としては、例えば、アクリル系、ゴム系、シリコーン系、及びウレタン系等の粘着剤が挙げられる。 In order to improve the adhesion between the substrate 11 and the pressure-sensitive adhesive layer 12 and the adhesion between the substrate 11 and the hard coat layer 13, the first surface 11a and the second surface 11b are subjected to primer treatment, corona treatment, and plasma. At least any surface treatment such as treatment may be performed. The first surface 11a and the second surface 11b of the base material 11 may be applied with an adhesive and subjected to an adhesive treatment. Examples of the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate include acrylic, rubber-based, silicone-based, and urethane-based pressure-sensitive adhesives.
　基材１１の厚みは、１０μｍ以上５００μｍ以下であることが好ましく、１５μｍ以上３００μｍ以下であることがより好ましく、２０μｍ以上２５０μｍ以下であることがさらに好ましい。 The thickness of the substrate 11 is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, and further preferably 20 μm or more and 250 μm or less.
　粘着シート１０を１９０℃及び１時間の条件で加熱後、基材１１のいずれかの面に沿う方向における収縮率が１．７％以下であることが好ましい。
　粘着シート１０を１９０℃及び１時間の条件で加熱後、少なくとも基材１１のＭＤ方向の収縮率が、１．７％以下であることが好ましい。
　半導体装置の製造プロセスには、１８０℃から１９０℃で１時間程度の加熱工程が含まれるところ、収縮率が１．７％以下であれば、基材１１の収縮によって粘着シート１０が被着体から剥離することを防止できる。加熱工程における粘着シート１０の被着体からの剥離を防止することで、製造プロセス中の搬送不具合を防止できる。また、粘着シート１０が剥離することで被着体の面（例えば、半導体チップの回路面）が露出して、汚染されるおそれがあるが、前述の収縮率の条件を満たせば、そのような汚染も防止できる。
　本明細書において基材１１のＭＤ（ＭＤ：Ｍａｃｈｉｎｅ　Ｄｉｒｅｃｔｉｏｎ）方向とは、基材１１を与える原反の長手方向（原反の製造時の送り方向）に平行な方向である。 After the pressure-sensitive adhesive sheet 10 is heated at 190 ° C. and 1 hour, the shrinkage rate in the direction along any surface of the substrate 11 is preferably 1.7% or less.
After the pressure-sensitive adhesive sheet 10 is heated under the conditions of 190 ° C. and 1 hour, at least the shrinkage rate in the MD direction of the base material 11 is preferably 1.7% or less.
The manufacturing process of the semiconductor device includes a heating process at 180 ° C. to 190 ° C. for about 1 hour. If the shrinkage rate is 1.7% or less, the adhesive sheet 10 is adhered to the adherend due to the shrinkage of the base material 11. Can be prevented from peeling off. By preventing the pressure-sensitive adhesive sheet 10 from being peeled off from the adherend in the heating step, it is possible to prevent a conveyance failure during the manufacturing process. In addition, the surface of the adherend (for example, the circuit surface of the semiconductor chip) may be exposed due to the peeling of the pressure-sensitive adhesive sheet 10, and may be contaminated. Contamination can also be prevented.
In this specification, the MD (MD: Machine Direction) direction of the base material 11 is a direction parallel to the longitudinal direction of the original fabric that gives the base material 11 (the feed direction during production of the original fabric).
（ハードコート層）
　ハードコート層１３は、有機無機ハイブリッド材料を硬化させて形成された硬化皮膜からなる層である。ハードコート層１３は、有機無機ハイブリッド材料の硬化物を含む。
　本明細書において、有機無機ハイブリッド材料とは、有機成分と無機成分の混ざり方が緊密であり、分子レベルか分子レベルに近い粒径で分散した状態で硬化した樹脂を指す。具体的には、有機成分又は無機成分は、例えば、粒径１００ｎｍ以下で分散している。本実施形態で使用する有機無機ハイブリッド材料としては、活性エネルギー線の照射により、無機成分と有機成分が反応して硬化し、硬化膜（ハードコート膜）を形成することができる材料が好ましい。活性エネルギー線としては、例えば、紫外線及び電子線等が挙げられる。
　なお、本明細書における有機成分または無機成分の粒径は、粒度分布測定装置（マイクロトラック・ベル社製，ナノトラックＷａｖｅ－ＵＴ１５１）を使用して、動的光散乱法により測定した値とする。 (Hard coat layer)
The hard coat layer 13 is a layer made of a cured film formed by curing an organic-inorganic hybrid material. The hard coat layer 13 includes a cured product of an organic-inorganic hybrid material.
In the present specification, the organic-inorganic hybrid material refers to a resin that is cured in a state where the organic component and the inorganic component are mixed closely and dispersed at a molecular level or a particle size close to the molecular level. Specifically, the organic component or the inorganic component is dispersed with a particle size of 100 nm or less, for example. The organic-inorganic hybrid material used in the present embodiment is preferably a material capable of forming a cured film (hard coat film) by reacting and curing the inorganic component and the organic component by irradiation with active energy rays. Examples of the active energy rays include ultraviolet rays and electron beams.
The particle size of the organic component or inorganic component in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring device (Microtrac Bell, Nanotrac Wave-UT151). .
　有機無機ハイブリッド材料としては、活性エネルギー線硬化型樹脂、及びシリカ微粒子を含む活性エネルギー線感応型組成物が好ましい。活性エネルギー線感応型組成物に対して、上記の活性エネルギー線を照射することで、架橋及び硬化し、有機無機ハイブリッド硬化樹脂を得ることができる。
　本実施形態における有機無機ハイブリッド材料は、シリカ微粒子と重合性不飽和基を有する有機化合物とを結合させた材料、並びに活性エネルギー線硬化型樹脂を含むことが好ましい。有機無機ハイブリッド材料がシリカ微粒子を含むので、硬化時の収縮を低減でき、粘着シート１０がカールすることを抑制できる。 As the organic-inorganic hybrid material, an active energy ray-curable composition containing an active energy ray-curable resin and silica fine particles is preferable. By irradiating the active energy ray-sensitive composition with the active energy ray, the active energy ray-sensitive composition can be crosslinked and cured to obtain an organic-inorganic hybrid cured resin.
The organic-inorganic hybrid material in the present embodiment preferably includes a material obtained by binding silica fine particles and an organic compound having a polymerizable unsaturated group, and an active energy ray-curable resin. Since the organic-inorganic hybrid material contains silica fine particles, shrinkage during curing can be reduced, and curling of the pressure-sensitive adhesive sheet 10 can be suppressed.
（活性エネルギー線硬化型樹脂）
　本実施形態において、活性エネルギー線硬化型樹脂は、活性エネルギー線を照射することにより、架橋及び硬化する重合性化合物である。活性エネルギー線によって硬化する樹脂を用いることにより、基材１１に係る熱履歴を小さくすることができる。活性エネルギー線としては、例えば、紫外線及び電子線等の電磁波、並びにエネルギー量子を有する荷電粒子線等が挙げられる。本実施形態のハードコート層１３に用いる樹脂は、紫外線硬化型樹脂であることが好ましい。 (Active energy ray-curable resin)
In the present embodiment, the active energy ray-curable resin is a polymerizable compound that crosslinks and cures when irradiated with active energy rays. By using a resin that is cured by active energy rays, the thermal history of the substrate 11 can be reduced. Examples of active energy rays include electromagnetic waves such as ultraviolet rays and electron beams, and charged particle beams having energy quanta. The resin used for the hard coat layer 13 of the present embodiment is preferably an ultraviolet curable resin.
　活性エネルギー線硬化型樹脂としては、多官能アクリル系樹脂を含むことが好ましい。多官能アクリル系樹脂としては、多官能性（メタ）アクリレート系モノマー及び（メタ）アクリレート系プレポリマーからなる群から選択される少なくとも１種の樹脂が好ましく、多官能性（メタ）アクリレート系モノマーがより好ましい。
　なお、本明細書において、「（メタ）アクリレート」は、アクリレート及びメタクリレート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。 The active energy ray curable resin preferably contains a polyfunctional acrylic resin. The polyfunctional acrylic resin is preferably at least one resin selected from the group consisting of polyfunctional (meth) acrylate monomers and (meth) acrylate prepolymers, and the polyfunctional (meth) acrylate monomers are More preferred.
In the present specification, “(meth) acrylate” is a notation used to represent both acrylate and methacrylate, and the same applies to other similar terms.
　多官能性（メタ）アクリレート系モノマーとしては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、エチレンオキシド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、及びカプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
　なお、多官能性（メタ）アクリレート系モノマーは、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 multifunctional (meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene. (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified Dipentaerythritol hexa (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di Intererythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propion Examples include acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
In addition, a polyfunctional (meth) acrylate type monomer may be used independently and may be used in combination of 2 or more type.
　（メタ）アクリレート系プレポリマーとしては、例えば、ポリエステル（メタ）アクリレート系プレポリマー、エポキシ（メタ）アクリレート系プレポリマー、ウレタン（メタ）アクリレート系プレポリマー、及びポリオール（メタ）アクリレート系プレポリマー等が挙げられる。 Examples of the (meth) acrylate prepolymer include a polyester (meth) acrylate prepolymer, an epoxy (meth) acrylate prepolymer, a urethane (meth) acrylate prepolymer, and a polyol (meth) acrylate prepolymer. Can be mentioned.
　ポリエステル（メタ）アクリレート系プレポリマーは、例えば、多価カルボン酸と多価アルコールとの縮合によって両末端に水酸基を有するポリエステルオリゴマーを得て、さらにこの水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。また、ポリエステル（メタ）アクリレート系プレポリマーは、例えば、多価カルボン酸にアルキレンオキシドを付加してオリゴマーを得て、このオリゴマーの末端の水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。 A polyester (meth) acrylate prepolymer is obtained by, for example, obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, and further esterifying the hydroxyl group with (meth) acrylic acid. Can be obtained. The polyester (meth) acrylate-based prepolymer is obtained, for example, by adding an alkylene oxide to a polyvalent carboxylic acid to obtain an oligomer, and esterifying the terminal hydroxyl group of the oligomer with (meth) acrylic acid. Can do.
　エポキシ（メタ）アクリレート系プレポリマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂またはノボラック型エポキシ樹脂のオキシラン環に、（メタ）アクリル酸を反応させてエステル化することにより得ることができる。 The epoxy (meth) acrylate-based prepolymer can be obtained, for example, by reacting an oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin with (meth) acrylic acid for esterification.
　ウレタン（メタ）アクリレート系プレポリマーは、例えば、ポリエーテルポリオールまたはポリエステルポリオールと、ポリイソシアネートとの反応によってポリウレタンオリゴマーを得て、このポリウレタンオリゴマーを（メタ）アクリル酸でエステル化することにより得ることができる。 The urethane (meth) acrylate-based prepolymer can be obtained by, for example, obtaining a polyurethane oligomer by a reaction between a polyether polyol or a polyester polyol and a polyisocyanate, and esterifying the polyurethane oligomer with (meth) acrylic acid. it can.
　ポリオール（メタ）アクリレート系プレポリマーは、ポリエーテルポリオールの水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。
　なお、これらのプレポリマーは、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し、前記多官能性（メタ）アクリレート系モノマーと併用してもよい。 The polyol (meth) acrylate-based prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
In addition, these prepolymers may be used independently, may be used in combination of 2 or more type, and may be used together with the said polyfunctional (meth) acrylate type monomer.
（シリカ微粒子）
　シリカ微粒子の平均粒径は０.５ｎｍ以上５００ｎｍ以下であることが好ましく、１ｎｍ以上１００ｎｍ以下であることがより好ましい。なお、シリカ微粒子の平均粒径は、例えば、ＢＥＴ法によって測定された値である。 (Silica fine particles)
The average particle size of the silica fine particles is preferably from 0.5 nm to 500 nm, and more preferably from 1 nm to 100 nm. The average particle diameter of the silica fine particles is a value measured by, for example, the BET method.
　シリカ微粒子の中でも、活性エネルギー線硬化型樹脂と強固な結合を形成する観点から、上記の活性エネルギー線硬化型樹脂と反応することができる重合性不飽和基を有する有機化合物で表面修飾されたシリカ微粒子（反応性シリカ微粒子）が好ましい。 Among silica fine particles, silica surface-modified with an organic compound having a polymerizable unsaturated group capable of reacting with the active energy ray-curable resin from the viewpoint of forming a strong bond with the active energy ray-curable resin. Fine particles (reactive silica fine particles) are preferred.
　重合性不飽和基を有する有機化合物で表面修飾されたシリカ微粒子は、シリカ微粒子の表面のシラノール基に、該シラノール基と反応し得る官能基である（メタ）アクリロイル基を有する重合性不飽和基含有有機化合物を反応させることにより、得ることができる。
　なお、本実施形態において、シリカ微粒子の表面を修飾する重合性不飽和基を有する有機化合物は、上述の活性エネルギー線硬化型樹脂に該当する化合物であってもよい。ただし、シリカ微粒子の表面を修飾する化合物は、シリカ微粒子の構成要素として含まれ、上記の活性エネルギー線硬化型樹脂とは区別される。 Silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group are polymerizable unsaturated groups having a (meth) acryloyl group which is a functional group capable of reacting with the silanol group on the silanol group on the surface of the silica fine particle. It can be obtained by reacting the containing organic compound.
In the present embodiment, the organic compound having a polymerizable unsaturated group that modifies the surface of the silica fine particles may be a compound corresponding to the above-described active energy ray-curable resin. However, the compound that modifies the surface of the silica fine particles is included as a component of the silica fine particles, and is distinguished from the above active energy ray-curable resin.
　前記シラノール基と反応し得る官能基を有する重合性不飽和基含有有機化合物としては、例えば、下記一般式（Ｉ）で表される化合物等が好ましい。 As the polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group, for example, a compound represented by the following general formula (I) is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　前記一般式（Ｉ）中、Ｒ１は、水素原子又はメチル基であり、Ｒ２は、ハロゲン原子又は下記式で示される基からなる群から選択されるいずれかの基である。 In the general formula (I), R 1 is a hydrogen atom or a methyl group, and R 2 is any group selected from the group consisting of a halogen atom or a group represented by the following formula.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　重合性不飽和基含有有機化合物としては、例えば、（メタ）アクリル酸、（メタ）アクリル酸クロリド、（メタ）アクリル酸２－イソシアナートエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２，３－イミノプロピル、（メタ）アクリル酸２－ヒドロキシエチル、及び（メタ）アクリロイルオキシプロピルトリメトキシシラン等の（メタ）アクリル酸誘導体が挙げられる。
　これらの重合性不飽和基含有有機化合物は、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 polymerizable unsaturated group-containing organic compound include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanate ethyl, (meth) acrylic acid glycidyl, and (meth) acrylic acid 2 , 3-iminopropyl, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid derivatives such as (meth) acryloyloxypropyltrimethoxysilane.
These polymerizable unsaturated group-containing organic compounds may be used alone or in combination of two or more.
　有機無機ハイブリッド材料中のシリカ微粒子の含有量としては、上記活性エネルギー線硬化型樹脂１００質量部に対して、８０質量部以上４００質量部以下であることが好ましく、１００質量部以上３００質量部以下であることがより好ましい。 The content of silica fine particles in the organic-inorganic hybrid material is preferably 80 parts by mass or more and 400 parts by mass or less, and 100 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable resin. It is more preferable that
（光重合開始剤）
　有機無機ハイブリッド材料は、光重合開始剤を含有することが好ましい。
　光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－プロパン－１－オン、４－（２－ヒドロキシエトキシ）フェニル－２（ヒドロキシ－２－プロピル）ケトン、ベンゾフェノン、ｐ－フェニルベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、２－メチルアントラキノン、２－エチルアントラキノン、２－ターシャリ－ブチルアントラキノン、２－アミノアントラキノン、２－メチルチオキサントン、２－エチルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、及びｐ－ジメチルアミノ安息香酸エステル等が挙げられる。
　なお、これらの光重合開始剤は、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。 (Photopolymerization initiator)
The organic-inorganic hybrid material preferably contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzene Nzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, and p-dimethylaminobenzoate.
In addition, these photoinitiators may be used independently and may be used in combination of 2 or more type.
　なお、これらの活性エネルギー線硬化型樹脂、シリカ微粒子、及び光重合開始剤を含む有機無機ハイブリッド材料の市販品としては、例えば、「オプスターＺ７５３０」、「オプスターＺ７５２４」、及び「オプスターＴＵ４０８６」（製品名、いずれもＪＳＲ（株）製）等が挙げられる。 Examples of commercially available organic-inorganic hybrid materials containing these active energy ray-curable resins, silica fine particles, and photopolymerization initiators include “OPSTAR Z7530”, “OPSTAR Z7524”, and “OPSTAR TU4086” (product). Name, both of which are manufactured by JSR Corporation).
　活性エネルギー線感応型組成物には、本発明の効果を損なわない範囲で必要に応じて、紫外線吸収剤、光安定剤、酸化防止剤、赤外線吸収剤、帯電防止剤、レベリング剤、消泡剤等からなる群から選択される少なくとも１種の添加剤を含むことができる。これらの添加剤の中でも、耐光性を向上させる観点から、紫外線吸収剤及び光安定剤からなる群から選択される少なくとも１種を含むことが好ましい。 In the active energy ray-sensitive composition, an ultraviolet absorber, a light stabilizer, an antioxidant, an infrared absorber, an antistatic agent, a leveling agent, and an antifoaming agent are added as necessary as long as the effects of the present invention are not impaired. At least one additive selected from the group consisting of and the like. Among these additives, from the viewpoint of improving light resistance, it is preferable to include at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer.
（紫外線吸収剤）
　活性エネルギー線感応型組成物は、紫外線吸収剤を含有してもよい。
　紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ヒンダードアミン系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、及びトリアジン系紫外線吸収剤等が挙げられる。これらの紫外線吸収剤は、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。これらの中でも、分子内にラジカル重合性の二重結合を有するラジカル重合性紫外線吸収剤が好ましい。
　紫外線吸収剤の含有量としては、活性エネルギー線硬化型樹脂、シリカ微粒子、及び光重合開始剤の合計１００質量部に対して、好ましくは０．２質量部以上１０質量部以下、より好ましくは０．５質量部以上７質量部以下である。 (UV absorber)
The active energy ray sensitive composition may contain an ultraviolet absorber.
Examples of the UV absorber include benzotriazole UV absorbers, hindered amine UV absorbers, benzophenone UV absorbers, and triazine UV absorbers. These ultraviolet absorbers may be used alone or in combination of two or more. Among these, a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule is preferable.
The content of the ultraviolet absorber is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0 with respect to 100 parts by mass in total of the active energy ray-curable resin, the silica fine particles, and the photopolymerization initiator. .5 parts by mass or more and 7 parts by mass or less.
（光安定剤）
　活性エネルギー線感応型組成物は、光安定剤を含有してもよい。
　光安定剤としては、ヒンダードアミン系光安定剤、ベンゾフェノン系光安定剤、及びベンゾトリアゾール系光安定剤等が挙げられる。これらの光安定剤は、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。
　光安定剤の含有量としては、活性エネルギー線硬化型樹脂、シリカ微粒子、及び光重合開始剤の合計１００質量部に対して、好ましくは０．２質量部以上１０質量部以下、より好ましくは０．５質量部以上７質量部以下である。 (Light stabilizer)
The active energy ray sensitive composition may contain a light stabilizer.
Examples of the light stabilizer include hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers. These light stabilizers may be used alone or in combination of two or more.
The content of the light stabilizer is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0 with respect to 100 parts by mass in total of the active energy ray-curable resin, the silica fine particles, and the photopolymerization initiator. .5 parts by mass or more and 7 parts by mass or less.
　ハードコート層１３の厚みは、０．５μｍ以上３．０μｍ以下であることが好ましい。ハードコート層１３の厚みが０．５μｍ以上であれば、半導体装置の製造プロセスにおける耐熱性を向上させることができ、３．０μｍ以下であれば、粘着シート１０がカールすることを抑制できる。 The thickness of the hard coat layer 13 is preferably 0.5 μm or more and 3.0 μm or less. If the thickness of the hard coat layer 13 is 0.5 μm or more, the heat resistance in the manufacturing process of the semiconductor device can be improved, and if it is 3.0 μm or less, the pressure-sensitive adhesive sheet 10 can be prevented from curling.
　ハードコート層１３の形成に用いる活性エネルギー線感応型組成物の一例として、反応性シリカ微粒子、多官能性（メタ）アクリレート系モノマー、及び（メタ）アクリレート系プレポリマーを含んでいる活性エネルギー線感応型組成物が挙げられる。 As an example of the active energy ray-sensitive composition used for forming the hard coat layer 13, the active energy ray-sensitive composition includes reactive silica fine particles, a polyfunctional (meth) acrylate monomer, and a (meth) acrylate prepolymer. Mold compositions.
（粘着剤層）
　本実施形態に係る粘着剤層１２は、粘着剤組成物を含んでいる。この粘着剤組成物に含まれる粘着剤としては、特に限定されず、様々な種類の粘着剤を粘着剤層１２に適用できる。粘着剤層１２に含まれる粘着剤としては、例えば、ゴム系、アクリル系、シリコーン系、ポリエステル系、及びウレタン系が挙げられる。なお、粘着剤の種類は、用途及び貼着される被着体の種類等を考慮して選択される。 (Adhesive layer)
The pressure-sensitive adhesive layer 12 according to this embodiment includes a pressure-sensitive adhesive composition. The pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various types of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12. Examples of the adhesive contained in the adhesive layer 12 include rubber-based, acrylic-based, silicone-based, polyester-based, and urethane-based. In addition, the kind of adhesive is selected in consideration of the use and the kind of adherend to be attached.
　粘着剤層１２が含有する粘着剤組成物は、アクリル酸２－エチルヘキシルを主たるモノマーとするアクリル系共重合体を含んでいることが好ましい。本明細書において、アクリル酸２－エチルヘキシルを主たるモノマーとするとは、アクリル系共重合体全体の質量に占めるアクリル酸２－エチルヘキシル由来の共重合体成分の質量の割合が５０質量％以上であることを意味する。本実施形態においては、アクリル系共重合体におけるアクリル酸２－エチルヘキシルに由来する共重合体成分の割合は、５０質量％以上９５質量％以下であることが好ましく、６０質量％以上９５質量％以下であることが好ましく、８０質量％以上９５質量％以下であることがより好ましく、８５質量％以上９３質量％以下であることがさらに好ましい。アクリル酸２－エチルヘキシルに由来する共重合体成分の割合が５０質量％以上であれば、加熱後に粘着力が高くなり過ぎず、被着体から粘着シートをより剥離し易くなり、８０質量％以上であればさらに剥離し易くなる。アクリル酸２－エチルヘキシルに由来する共重合体成分の割合が９５質量％以下であれば、初期密着力が不足して加熱時に基材が変形したり、その変形によって粘着シートが被着体から剥離したりすることを防止できる。 The pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer 12 preferably contains an acrylic copolymer having 2-ethylhexyl acrylate as a main monomer. In this specification, 2-ethylhexyl acrylate is the main monomer, and the ratio of the mass of the copolymer component derived from 2-ethylhexyl acrylate to the total mass of the acrylic copolymer is 50% by mass or more. Means. In the present embodiment, the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, and 60% by mass or more and 95% by mass or less. It is preferable that it is 80 mass% or more and 95 mass% or less, and it is still more preferable that it is 85 mass% or more and 93 mass% or less. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 50% by mass or more, the adhesive strength does not become too high after heating, and the adhesive sheet is more easily peeled off from the adherend, and 80% by mass or more. If it is, it will become still easier to peel. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, the initial adhesive force is insufficient and the substrate is deformed during heating, or the adhesive sheet is peeled off from the adherend due to the deformation. Can be prevented.
　アクリル系共重合体におけるアクリル酸２－エチルヘキシル以外の共重合体成分の種類及び数は、特に限定されない。例えば、第二の共重合体成分としては、反応性の官能基を有する官能基含有モノマーが好ましい。第二の共重合体成分の反応性官能基としては、後述する架橋剤を使用する場合には、当該架橋剤と反応し得る官能基であることが好ましい。この反応性官能基は、例えば、カルボキシル基、水酸基、アミノ基、置換アミノ基、及びエポキシ基からなる群から選択される少なくともいずれかの置換基であることが好ましく、カルボキシル基及び水酸基の少なくともいずれかの置換基であることがより好ましく、カルボキシル基であることが更に好ましい。 The type and number of copolymer components other than 2-ethylhexyl acrylate in the acrylic copolymer are not particularly limited. For example, as the second copolymer component, a functional group-containing monomer having a reactive functional group is preferable. As a reactive functional group of a 2nd copolymer component, when using the crosslinking agent mentioned later, it is preferable that it is a functional group which can react with the said crosslinking agent. This reactive functional group is preferably at least one substituent selected from the group consisting of, for example, a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. These substituents are more preferable, and a carboxyl group is still more preferable.
　カルボキシル基を有するモノマー（カルボキシル基含有モノマー）としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、及びシトラコン酸等のエチレン性不飽和カルボン酸が挙げられる。カルボキシル基含有モノマーの中でも、反応性及び共重合性の点から、アクリル酸が好ましい。カルボキシル基含有モノマーは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the monomer having a carboxyl group (carboxyl group-containing monomer) include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among the carboxyl group-containing monomers, acrylic acid is preferable from the viewpoint of reactivity and copolymerization. A carboxyl group-containing monomer may be used independently and may be used in combination of 2 or more type.
　水酸基を有するモノマー（水酸基含有モノマー）としては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、及び（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキルエステル等が挙げられる。水酸基含有モノマーの中でも、水酸基の反応性及び共重合性の点から、（メタ）アクリル酸２－ヒドロキシエチルが好ましい。水酸基含有モノマーは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。なお、本明細書における「（メタ）アクリル酸」は、「アクリル酸」及び「メタクリル酸」の双方を表す場合に用いる表記であり、他の類似用語についても同様である。 Examples of the monomer having a hydroxyl group (hydroxyl group-containing monomer) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 And (meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of hydroxyl reactivity and copolymerization. A hydroxyl-containing monomer may be used independently and may be used in combination of 2 or more type. In the present specification, “(meth) acrylic acid” is a notation used to represent both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
　エポキシ基を有するアクリル酸エステルとしては、例えば、グリシジルアクリレート、及びグリシジルメタクリレート等が挙げられる。 Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
　アクリル系共重合体におけるその他の共重合体成分としては、アルキル基の炭素数が２～２０の（メタ）アクリル酸アルキルエステルが挙げられる。（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、メタクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチル、及び（メタ）アクリル酸ステアリル等が挙げられる。これらの（メタ）アクリル酸アルキルエステルの中でも、粘着性をより向上させる観点から、アルキル基の炭素数が２～４の（メタ）アクリル酸エステルが好ましく、（メタ）アクリル酸ｎ－ブチルがより好ましい。（メタ）アクリル酸アルキルエステルは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of other copolymer components in the acrylic copolymer include (meth) acrylic acid alkyl esters having an alkyl group with 2 to 20 carbon atoms. Examples of the (meth) acrylic acid alkyl ester include, for example, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and (meth) acrylic acid n. -Hexyl, 2-ethylhexyl methacrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and ( Examples thereof include stearyl methacrylate. Among these (meth) acrylic acid alkyl esters, (meth) acrylic acid esters having an alkyl group with 2 to 4 carbon atoms are preferred, and n-butyl (meth) acrylate is more preferred from the viewpoint of further improving the adhesiveness. preferable. The (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
　アクリル系共重合体におけるその他の共重合体成分としては、例えば、アルコキシアルキル基含有（メタ）アクリル酸エステル、脂肪族環を有する（メタ）アクリル酸エステル、芳香族環を有する（メタ）アクリル酸エステル、非架橋性のアクリルアミド、非架橋性の３級アミノ基を有する（メタ）アクリル酸エステル、酢酸ビニル、及びスチレンからなる群から選択される少なくともいずれかのモノマーに由来する共重合体成分が挙げられる。
　アルコキシアルキル基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メトキシメチル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシメチル、及び（メタ）アクリル酸エトキシエチルが挙げられる。
　脂肪族環を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸シクロヘキシルが挙げられる。
　芳香族環を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸フェニルが挙げられる。
　非架橋性のアクリルアミドとしては、例えば、アクリルアミド、及びメタクリルアミドが挙げられる。
　非架橋性の３級アミノ基を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸（Ｎ，Ｎ－ジメチルアミノ）エチル、及び（メタ）アクリル酸（Ｎ，Ｎ－ジメチルアミノ）プロピルが挙げられる。
　これらのモノマーは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of other copolymer components in the acrylic copolymer include, for example, alkoxyalkyl group-containing (meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring, and (meth) acrylic acid having an aromatic ring. A copolymer component derived from at least one monomer selected from the group consisting of an ester, a non-crosslinkable acrylamide, a (meth) acrylic acid ester having a non-crosslinkable tertiary amino group, vinyl acetate, and styrene; Can be mentioned.
Examples of the alkoxyalkyl group-containing (meth) acrylic acid ester include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. .
Examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate.
Examples of the (meth) acrylic acid ester having an aromatic ring include phenyl (meth) acrylate.
Examples of non-crosslinkable acrylamides include acrylamide and methacrylamide.
Examples of the (meth) acrylic acid ester having a non-crosslinkable tertiary amino group include (meth) acrylic acid (N, N-dimethylamino) ethyl and (meth) acrylic acid (N, N-dimethylamino). Propyl.
These monomers may be used independently and may be used in combination of 2 or more type.
　本実施形態においては、第２の共重合体成分として、カルボキシル基含有モノマーまたは水酸基含有モノマーが好ましく、アクリル酸がより好ましい。アクリル系共重合体が、アクリル酸２－エチルヘキシル由来の共重合体成分、及びアクリル酸由来の共重合体成分を含む場合、アクリル系共重合体全体の質量に占めるアクリル酸由来の共重合体成分の質量の割合が１質量％以下であることが好ましく、０．１質量％以上０．５質量％以下であることがより好ましい。アクリル酸の割合が１質量％以下であれば、粘着剤組成物に架橋剤が含まれる場合にアクリル系共重合体の架橋が早く進行し過ぎることを防止できる。 In the present embodiment, a carboxyl group-containing monomer or a hydroxyl group-containing monomer is preferable as the second copolymer component, and acrylic acid is more preferable. When the acrylic copolymer includes a copolymer component derived from 2-ethylhexyl acrylate and a copolymer component derived from acrylic acid, the copolymer component derived from acrylic acid occupies the total mass of the acrylic copolymer. The mass ratio is preferably 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. If the ratio of acrylic acid is 1 mass% or less, when an adhesive composition contains a crosslinking agent, crosslinking of the acrylic copolymer can be prevented from proceeding too quickly.
　アクリル系共重合体は、２種類以上の官能基含有モノマー由来の共重合体成分を含んでいてもよい。例えば、アクリル系共重合体は、３元系共重合体であってもよい。アクリル系共重合体が３元系共重合体である場合、アクリル酸２－エチルヘキシル、カルボキシル基含有モノマー及び水酸基含有モノマーを共重合して得られるアクリル系共重合体が好ましく、このカルボキシル基含有モノマーは、アクリル酸であることが好ましく、水酸基含有モノマーは、アクリル酸２－ヒドロキシエチルであることが好ましい。アクリル系共重合体におけるアクリル酸２－エチルヘキシルに由来する共重合体成分の割合が８０質量％以上９５質量％以下であり、アクリル酸由来の共重合体成分の質量の割合が１質量％以下であり、残部がアクリル酸２－ヒドロキシエチル由来の共重合体成分であることが好ましい。 The acrylic copolymer may contain a copolymer component derived from two or more kinds of functional group-containing monomers. For example, the acrylic copolymer may be a ternary copolymer. When the acrylic copolymer is a ternary copolymer, an acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer and a hydroxyl group-containing monomer is preferred, and this carboxyl group-containing monomer is preferred. Is preferably acrylic acid, and the hydroxyl group-containing monomer is preferably 2-hydroxyethyl acrylate. The ratio of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less, and the ratio of the mass of the copolymer component derived from acrylic acid is 1% by mass or less. And the balance is preferably a copolymer component derived from 2-hydroxyethyl acrylate.
　アクリル系共重合体の重量平均分子量（Ｍｗ）は、３０万以上２００万以下であることが好ましく、６０万以上１５０万以下であることがより好ましく、８０万以上１２０万以下であることがさらに好ましい。アクリル系共重合体の重量平均分子量Ｍｗが３０万以上であれば、被着体への粘着剤の残渣なく剥離することができる。アクリル系共重合体の重量平均分子量Ｍｗが２００万以下であれば、被着体へ確実に貼り付けることができる。
　アクリル系共重合体の重量平均分子量Ｍｗは、ゲル・パーミエーション・クロマトグラフィー（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ；ＧＰＣ）法により測定される標準ポリスチレン換算値である。 The weight average molecular weight (Mw) of the acrylic copolymer is preferably from 300,000 to 2,000,000, more preferably from 600,000 to 1,500,000, and even more preferably from 800,000 to 1,200,000. preferable. If the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, the acrylic copolymer can be peeled without a residue of the adhesive on the adherend. When the weight average molecular weight Mw of the acrylic copolymer is 2 million or less, it can be reliably attached to the adherend.
The weight average molecular weight Mw of the acrylic copolymer is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.
　アクリル系共重合体は、前述の各種原料モノマーを用いて、従来公知の方法に従って製造することができる。 The acrylic copolymer can be produced according to a conventionally known method using the above-mentioned various raw material monomers.
　アクリル系共重合体の共重合の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、またはグラフト共重合体のいずれでもよい。
　本実施形態において、粘着剤組成物中のアクリル系共重合体の含有率は、４０質量％以上９０質量％以下であることが好ましく、５０質量％以上９０質量％以下であることがより好ましい。 The form of copolymerization of the acrylic copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer may be used.
In the present embodiment, the content of the acrylic copolymer in the pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.
　粘着剤層１２を構成する粘着剤組成物は、前述のアクリル系共重合体の他に、さらに架橋剤を配合した組成物を架橋させて得られる粘着剤を含むことが好ましい。また、粘着剤組成物は、実質的に、前述のように前述のアクリル系共重合体と、架橋剤とを架橋させて得られる粘着剤からなることも好ましい。ここで、実質的にとは、不可避的に粘着剤に混入してしまうような微量な不純物を除いて、当該粘着剤だけからなることを意味する。 The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 preferably contains a pressure-sensitive adhesive obtained by crosslinking a composition containing a crosslinking agent in addition to the above-mentioned acrylic copolymer. The pressure-sensitive adhesive composition is also preferably substantially composed of a pressure-sensitive adhesive obtained by cross-linking the above-mentioned acrylic copolymer and the cross-linking agent as described above. Here, “substantially” means that it is composed only of the pressure-sensitive adhesive except for a small amount of impurities that are inevitably mixed in the pressure-sensitive adhesive.
　本実施形態において、架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤、アミン系架橋剤、及びアミノ樹脂系架橋剤が挙げられる。これらの架橋剤は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
　本実施形態において、粘着剤層１２の耐熱性及び粘着力を向上させる観点から、これら架橋剤の中でも、イソシアネート基を有する化合物を主成分として含有する架橋剤（イソシアネート系架橋剤）が好ましい。イソシアネート系架橋剤としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルメタン－２，４’－ジイソシアネート、３－メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、ジシクロヘキシルメタン－２，４’－ジイソシアネート、及びリジンイソシアネート等の多価イソシアネート化合物が挙げられる。
　また、多価イソシアネート化合物は、上記化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、またはイソシアヌレート環を有するイソシアヌレート型変性体であってもよい。
　本明細書において、イソシアネート基を有する化合物を主成分とする架橋剤とは、架橋剤を構成する成分全体の質量に占めるイソシアネート基を有する化合物の質量の割合が５０質量％以上であることを意味する。 In the present embodiment, examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These cross-linking agents may be used alone or in combination of two or more.
In the present embodiment, from the viewpoint of improving the heat resistance and adhesive strength of the pressure-sensitive adhesive layer 12, among these crosslinking agents, a crosslinking agent (isocyanate-based crosslinking agent) containing a compound having an isocyanate group as a main component is preferable. Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
Further, the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product having an isocyanurate ring.
In the present specification, the term “crosslinking agent mainly comprising a compound having an isocyanate group” means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. To do.
　本実施形態において、粘着剤組成物中の架橋剤の含有量は、アクリル系共重合体１００質量部に対して、好ましくは０．１質量部以上２０質量部以下、より好ましくは１質量部以上１５質量部以下、さらに好ましくは５質量部以上１０質量部以下である。粘着剤組成物中の架橋剤の含有量がこのような範囲内であれば、粘着剤層１２と基材１１との接着性を向上させることができ、粘着シートの製造後に粘着特性を安定化させるための養生期間を短縮できる。 In the present embodiment, the content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If content of the crosslinking agent in an adhesive composition is in such a range, the adhesiveness of the adhesive layer 12 and the base material 11 can be improved, and the adhesive characteristic is stabilized after manufacture of an adhesive sheet. The curing period for making it possible can be shortened.
　本実施形態においては、粘着剤層１２の耐熱性の観点から、イソシアネート系架橋剤は、イソシアヌレート環を有する化合物（イソシアヌレート型変性体）であることがさらに好ましい。イソシアヌレート環を有する化合物は、アクリル系共重合体の水酸基当量に対して、０．７当量以上１．５当量以下配合されていることが好ましい。イソシアヌレート環を有する化合物の配合量が０．７当量以上であれば、加熱後に粘着力が高くなり過ぎず、粘着シートを剥離し易くなり、糊残りを減少させることができる。イソシアヌレート環を有する化合物の配合量が１．５当量以下であれば、初期粘着力が低くなり過ぎることを防止したり、貼付性の低下を防止したりすることができる。 In the present embodiment, from the viewpoint of heat resistance of the pressure-sensitive adhesive layer 12, the isocyanate-based crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product). The compound having an isocyanurate ring is preferably blended in an amount of 0.7 to 1.5 equivalents with respect to the hydroxyl equivalent of the acrylic copolymer. If the compounding quantity of the compound which has an isocyanurate ring is 0.7 equivalent or more, the adhesive strength will not become too high after heating, the adhesive sheet will be easily peeled off, and the adhesive residue can be reduced. If the compounding quantity of the compound which has an isocyanurate ring is 1.5 equivalent or less, it can prevent that an initial stage adhesive force becomes low too much, or can prevent a sticking fall.
　本実施形態における粘着剤層１２を構成する粘着剤組成物が架橋剤を含む場合、粘着剤組成物は、架橋促進剤をさらに含むことが好ましい。架橋促進剤は、架橋剤の種類などに応じて、適宜選択して用いることが好ましい。例えば、粘着剤組成物が、架橋剤としてポリイソシアネート化合物を含む場合には、有機スズ化合物などの有機金属化合物系の架橋促進剤をさらに含むことが好ましい。 When the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 in the present embodiment includes a cross-linking agent, the pressure-sensitive adhesive composition preferably further includes a cross-linking accelerator. The crosslinking accelerator is preferably selected and used as appropriate according to the type of the crosslinking agent. For example, when the pressure-sensitive adhesive composition contains a polyisocyanate compound as a crosslinking agent, it is preferable to further contain an organic metal compound-based crosslinking accelerator such as an organic tin compound.
　本実施形態において、粘着剤層１２を構成する粘着剤組成物は、反応性粘着助剤（以下、単に「粘着助剤」ということもある。）を含むことも好ましい。反応性粘着助剤としては、反応性の官能基を有するポリブタジエン系樹脂、及び反応性の官能基を有するポリブタジエン系樹脂の水素添加物などが挙げられる。反応性粘着助剤が有する反応性の官能基としては、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い。粘着剤組成物が反応性粘着助剤を含んでいると、粘着シート１０を被着体から剥がした際の糊残りを減少させることができる。反応性粘着助剤としては、特に限定されないが、両末端水酸基水素化ポリブタジエンが好ましい。 In the present embodiment, the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 preferably includes a reactive pressure-sensitive adhesive aid (hereinafter sometimes simply referred to as “pressure-sensitive adhesive aid”). Examples of the reactive adhesion assistant include a polybutadiene resin having a reactive functional group and a hydrogenated product of a polybutadiene resin having a reactive functional group. The reactive functional group possessed by the reactive adhesive aid is one or more functional groups selected from the group consisting of hydroxyl groups, isocyanate groups, amino groups, oxirane groups, acid anhydride groups, alkoxy groups, acryloyl groups, and methacryloyl groups. It is preferably a group. When the pressure-sensitive adhesive composition contains a reactive pressure-sensitive adhesive aid, the adhesive residue when the pressure-sensitive adhesive sheet 10 is peeled off from the adherend can be reduced. Although it does not specifically limit as a reactive adhesive adjuvant, Both terminal hydroxyl group hydrogenated polybutadiene is preferable.
　粘着剤組成物中の反応性粘着助剤の含有量は、３質量％以上５０質量％以下であることが好ましく、５質量％以上３０質量％以下であることがより好ましい。粘着剤組成物中の反応性粘着助剤の含有量が３質量％以上であれば、糊残りすることもなく、５０質量％以下であれば粘着力が低下することもない。 The content of the reactive adhesive aid in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content of the reactive adhesive aid in the pressure-sensitive adhesive composition is 3% by mass or more, no adhesive remains, and if it is 50% by mass or less, the adhesive strength does not decrease.
　粘着剤層１２を構成する粘着剤組成物には、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、酸化防止剤、防腐剤、防黴剤、可塑剤、消泡剤、及び濡れ性調整剤などが挙げられる。 The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 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, for example, organic solvents, flame retardants, tackifiers, ultraviolet absorbers, antioxidants, antiseptics, antifungal agents, plasticizers, antifoaming agents, and wetting And a sex modifier.
　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、以下のような粘着材組成物の例が挙げられるが、本発明は、このような例に限定されない。
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、カルボキシル基含有モノマー及び水酸基含有モノマーを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、反応性基を有するゴム系材料を主成分として含み、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、カルボキシル基含有モノマー及び水酸基含有モノマーを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、両末端水酸基水素化ポリブタジエンであり、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、アクリル酸及びアクリル酸２－ヒドロキシエチルを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、反応性基を有するゴム系材料を主成分として含み、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
　本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸２－エチルヘキシル、アクリル酸及びアクリル酸２－ヒドロキシエチルを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、両末端水酸基水素化ポリブタジエンであり、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
　本実施形態に係る粘着剤組成物のこれらの例においては、前記アクリル系共重合体におけるアクリル酸２－エチルヘキシルに由来する共重合体成分の割合が８０質量％以上９５質量％以下であり、カルボキシル基含有モノマー由来の共重合体成分の質量の割合が１質量％以下であり、残部が他の共重合体成分であることが好ましく、他の共重合体成分としては、水酸基含有モノマー由来の共重合体成分を含むことが好ましい。 As a more specific example of the pressure-sensitive adhesive composition according to the present embodiment, for example, the following pressure-sensitive adhesive composition examples are given, but the present invention is not limited to such examples.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer. And an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer, wherein the tackifier includes a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent. An adhesive composition is mentioned.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer. And an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer, the pressure-sensitive adhesive composition in which the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both terminals, and the cross-linking agent is an isocyanate-based cross-linking agent. Can be mentioned.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and acrylic. An acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the tackifier includes a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent. A certain adhesive composition is mentioned.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and acrylic. A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Is mentioned.
In these examples of the pressure-sensitive adhesive composition according to this embodiment, the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less. The proportion of the mass of the copolymer component derived from the group-containing monomer is preferably 1% by mass or less, and the remainder is preferably another copolymer component. The other copolymer component is a copolymer derived from a hydroxyl group-containing monomer. It preferably contains a polymer component.
　粘着剤層１２の厚みは、粘着シート１０の用途に応じて適宜決定される。本実施形態において、粘着剤層１２の厚みは、５μｍ以上６０μｍ以下であることが好ましく、１０μｍ以上５０μｍ以下であることがより好ましい。粘着剤層１２の厚みが薄過ぎると、半導体チップの回路面の凹凸に粘着剤層１２が追従できずに隙間が生じるおそれがある。その隙間に、例えば、層間絶縁材及び封止樹脂等が入り込み、チップ回路面の配線接続用の電極パッドが塞がれるおそれがある。粘着剤層１２の厚みが５μｍ以上であれば、チップ回路面の凹凸に粘着剤層１２が追従し易くなり、隙間の発生を防止できる。また、粘着剤層１２の厚みが厚過ぎると、半導体チップが粘着剤層に沈み込んでしまい、半導体チップ部分と、半導体チップを封止する樹脂部分との段差が生じるおそれがある。このような段差が生じると再配線の際に配線が断線するおそれがある。粘着剤層１２の厚みが６０μｍ以下であれば、段差が生じ難くなる。 The thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the use of the pressure-sensitive adhesive sheet 10. In the present embodiment, the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 μm or more and 60 μm or less, and more preferably 10 μm or more and 50 μm or less. If the thickness of the pressure-sensitive adhesive layer 12 is too thin, the pressure-sensitive adhesive layer 12 may not follow the irregularities on the circuit surface of the semiconductor chip, and a gap may be generated. For example, an interlayer insulating material and a sealing resin may enter the gap, and the wiring connection electrode pad on the chip circuit surface may be blocked. When the thickness of the pressure-sensitive adhesive layer 12 is 5 μm or more, the pressure-sensitive adhesive layer 12 easily follows the unevenness of the chip circuit surface, and the generation of a gap can be prevented. If the thickness of the pressure-sensitive adhesive layer 12 is too thick, the semiconductor chip sinks into the pressure-sensitive adhesive layer, and there is a risk that a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip occurs. If such a step occurs, the wiring may be disconnected during rewiring. If the thickness of the pressure-sensitive adhesive layer 12 is 60 μm or less, a step is hardly generated.
（剥離シート）
　剥離シートＲＬとしては、特に限定されない。例えば、取り扱い易さの観点から、剥離シートＲＬは、剥離基材と、剥離基材の上に剥離剤が塗布されて形成された剥離剤層とを備えることが好ましい。また、剥離シートＲＬは、剥離基材の片面のみに剥離剤層を備えていてもよいし、剥離基材の両面に剥離剤層を備えていてもよい。剥離基材としては、例えば、紙基材、この紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙、並びにプラスチックフィルム等が挙げられる。紙基材としては、グラシン紙、コート紙、及びキャストコート紙等が挙げられる。プラスチックフィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリエチレンナフタレート等のポリエステルフィルム、並びにポリプロピレン及びポリエチレン等のポリオレフィンフィルム等が挙げられる。剥離剤としては、例えば、オレフィン系樹脂、ゴム系エラストマー（例えば、ブタジエン系樹脂、イソプレン系樹脂等）、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂、及びシリコーン系樹脂が挙げられる。 (Peeling sheet)
The release sheet RL is not particularly limited. For example, from the viewpoint of ease of handling, the release sheet RL preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate. Moreover, the release sheet RL may include a release agent layer only on one side of the release substrate, or may include a release agent layer on both sides of the release substrate. Examples of the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film. Examples of the paper substrate include glassine paper, coated paper, and cast coated paper. Examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. Examples of the release agent include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins.
　剥離シートＲＬの厚みは、特に限定されない。剥離シートＲＬの厚みは、通常、２０μｍ以上２００μｍ以下であり、２５μｍ以上１５０μｍ以下であることが好ましい。
　剥離剤層の厚みは、特に限定されない。剥離剤を含む溶液を塗布して剥離剤層を形成する場合、剥離剤層の厚みは、０．０１μｍ以上２．０μｍ以下であることが好ましく、０．０３μｍ以上１．０μｍ以下であることがより好ましい。
　剥離基材としてプラスチックフィルムを用いる場合、当該プラスチックフィルムの厚みは、３μｍ以上５０μｍ以下であることが好ましく、５μｍ以上４０μｍ以下であることがより好ましい。 The thickness of the release sheet RL is not particularly limited. The thickness of the release sheet RL is usually 20 μm or more and 200 μm or less, and preferably 25 μm or more and 150 μm or less.
The thickness of the release agent layer is not particularly limited. When a release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 μm or more and 2.0 μm or less, and preferably 0.03 μm or more and 1.0 μm or less. More preferred.
When a plastic film is used as the peeling substrate, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 40 μm or less.
　本実施形態に係る粘着シート１０は、加熱後に、次のような粘着力を示すことが好ましい。まず、粘着シート１０を被着体（銅箔またはポリイミドフィルム）に貼着させ、１００℃及び３０分間の条件で加熱し、続いて１８０℃及び３０分間の条件で加熱し、さらに１９０℃及び１時間の条件で加熱した後、粘着剤層１２の銅箔に対する室温での粘着力、及び粘着剤層１２のポリイミドフィルムに対する室温での粘着力が、それぞれ０．７Ｎ／２５ｍｍ以上２．０Ｎ／２５ｍｍ以下であることが好ましい。このような加熱を行った後の粘着力が０．７Ｎ／２５ｍｍ以上であれば、加熱によって基材または被着体が変形した場合に粘着シート１０が被着体から剥離することを防止できる。また、加熱後の粘着力が２．０Ｎ／２５ｍｍ以下であれば、剥離力が高くなり過ぎず、粘着シート１０を被着体から剥離し易い。
　なお、本明細書において室温とは、２２℃以上２４℃以下の温度である。
　また、本明細書において、粘着力は、１８０°引き剥がし法により、剥離速度（引っ張り速度）３００ｍｍ／分、粘着シートの幅２５ｍｍにて測定した値である。 The pressure-sensitive adhesive sheet 10 according to 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 performing such heating is 0.7 N / 25 mm or more, the adhesive sheet 10 can be prevented from peeling off from the adherend when the substrate or adherend is deformed by heating. Moreover, if the adhesive force after a heating is 2.0 N / 25mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body.
In this specification, room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower.
In the present specification, the adhesive strength is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the adhesive sheet of 25 mm.
（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、前述の有機無機ハイブリッド材料を含むハードコート層用コーティング剤（以下、ハードコート剤と称する。）を準備または調製する。ハードコート剤を塗布し易くするために、ハードコート剤は、更に溶媒を加えて塗布液の形態とすることが好ましい。ハードコート剤に用いる溶媒としては、例えば、脂肪族炭化水素系溶媒、芳香族炭化水素系溶媒、ハロゲン化炭化水素系溶媒、アルコール系溶媒、ケトン系溶媒、エステル系溶媒、セロソルブ系溶媒、及びエーテル系溶媒等が挙げられる。
　脂肪族炭化水素系溶媒としては、ヘキサン、及びヘプタン等が挙げられる。
　芳香族炭化水素系溶媒としては、トルエン、及びキシレン等が挙げられる。
　ハロゲン化炭化水素系溶媒としては、塩化メチレン、及び塩化エチレン等が挙げられる。
　アルコール系溶媒としては、メタノール、エタノール、プロパノール、及びブタノール等が挙げられる。
　ケトン系溶媒としては、アセトン、メチルエチルケトン、２－ペンタノン、イソホロン、及びシクロヘキサノン等が挙げられる。
　エステル系溶媒としては、酢酸エチル、及び酢酸ブチル等が挙げられる。
　セロソルブ系溶媒としては、エチルセロソルブ等が挙げられる。
　エーテル系溶媒としては、プロピレングリコールモノメチルエーテル等が挙げられる。 (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, a coating agent for a hard coat layer (hereinafter referred to as a hard coat agent) containing the organic-inorganic hybrid material described above is prepared or prepared. In order to make it easy to apply the hard coating agent, it is preferable that the hard coating agent is further added with a solvent to form a coating solution. Examples of the solvent used for the hard coating agent include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, cellosolve solvents, and ethers. System solvents and the like.
Examples of the aliphatic hydrocarbon solvent include hexane and heptane.
Examples of the aromatic hydrocarbon solvent include toluene and xylene.
Examples of the halogenated hydrocarbon solvent include methylene chloride and ethylene chloride.
Examples of the alcohol solvent include methanol, ethanol, propanol, and butanol.
Examples of the ketone solvent include acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone.
Examples of ester solvents include ethyl acetate and butyl acetate.
Examples of the cellosolve solvent include ethyl cellosolve.
Examples of the ether solvent include propylene glycol monomethyl ether.
　溶媒を加えて塗布液としたハードコート剤において、固形分濃度は、基材への塗布性及び作業性の観点から、好ましくは１質量％以上６０質量％以下、より好ましくは５質量％以上４０質量％以下である。 In the hard coating agent to which a solvent is added to form a coating solution, the solid content concentration is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 40% or less, from the viewpoint of applicability to a substrate and workability. It is below mass%.
　そして、ハードコート剤を、基材１１の第二面１１ｂの上にコーティングして塗膜を形成させ、塗膜を乾燥させた後、この塗膜に活性エネルギー線を照射して、該塗膜を硬化させることにより、ハードコート層１３が形成される。ハードコート剤のコーティング方法としては、例えば、バーコート法、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。活性エネルギー線としては、例えば、紫外線及び電子線等が挙げられ、紫外線が好ましい。紫外線は、例えば、高圧水銀ランプ、無電極ランプ、メタルハライドランプ、又はキセノンランプ等を用いて照射させることができる。紫外線の照射量は、特に制限はないが、好ましくは１００ｍＪ／ｃｍ２以上５００ｍＪ／ｃｍ２以下、より好ましくは１５０ｍＪ／ｃｍ２以上４５０ｍＪ／ｃｍ２以下である。一方、電子線は、電子線加速器等を用いて照射させることができる。電子線の照射量は、特に制限はないが、好ましくは１５０ｋＶ以上３５０ｋＶ以下である。なお、電子線を使用する場合は、光重合開始剤を添加することなく、硬化膜を得ることができる。 And after coating a hard-coat agent on the 2nd surface 11b of the base material 11 and forming a coating film and drying a coating film, this coating film is irradiated with an active energy ray, and this coating film The hard coat layer 13 is formed by curing. Examples of the coating method of the hard coating agent include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. Examples of active energy rays include ultraviolet rays and electron beams, and ultraviolet rays are preferred. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or a xenon lamp. The dose of ultraviolet rays is not particularly limited, preferably 100 mJ / cm 2 or more 500 mJ / cm 2 or less, more preferably 150 mJ / cm 2 or more 450 mJ / cm 2 or less. On the other hand, the electron beam can be irradiated using an electron beam accelerator or the like. The amount of electron beam irradiation is not particularly limited, but is preferably 150 kV or more and 350 kV or less. In addition, when using an electron beam, a cured film can be obtained, without adding a photoinitiator.
　次に、基材１１の第一面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。 Next, the pressure-sensitive adhesive composition is applied on the first surface 11a of the substrate 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.
　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を形成する。この粘着剤層１２を有する剥離シートＲＬと、前述のハードコート層１３を有する基材１１とを貼り合わせることによっても、粘着シート１０を製造することができる。この場合、粘着剤層１２と基材１１の第一面１１ａとを貼り合わせる。 Moreover, as another manufacturing method of the adhesive sheet 10, it is manufactured through the following steps. 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. The pressure-sensitive adhesive sheet 10 can also be manufactured by bonding the release sheet RL having the pressure-sensitive adhesive layer 12 and the base material 11 having the hard coat layer 13 described above. In this case, the pressure-sensitive adhesive layer 12 and the first surface 11a of the substrate 11 are bonded together.
　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。また、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 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. Moreover, when a crosslinking agent is mix | blended with the adhesive composition, it is preferable to heat a coating film also in order to advance a crosslinking reaction and to improve cohesion force.
（粘着シートの使用）
　粘着シート１０は、半導体素子を封止する際に使用される。粘着シート１０は、金属製リードフレームに搭載されておらず、粘着シート１０上に貼着された状態の半導体素子を封止する際に使用されることが好ましい。具体的には、粘着シート１０は、金属製リードフレームに搭載された半導体素子を封止する際に使用されるのではなく、粘着剤層１２に貼着された状態の半導体素子を封止する際に使用されることが好ましい。金属製リードフレームを用いずに半導体素子をパッケージングする形態としては、パネルスケールパッケージ（Ｐａｎｅｌ　Ｓｃａｌｅ　Ｐａｃｋａｇｅ；ＰＳＰ）及びウエハレベルパッケージ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ；ＷＬＰ）が挙げられる。
　粘着シート１０は、複数の開口部が形成された枠部材を粘着シート１０に貼着させる工程と、前記枠部材の開口部にて露出する粘着剤層１２に半導体チップを貼着させる工程と、前記半導体チップを封止樹脂で覆う工程と、前記封止樹脂を熱硬化させる工程と、を有するプロセスにおいて使用されることが好ましい。 (Use of adhesive sheet)
The pressure-sensitive adhesive sheet 10 is used when sealing a semiconductor element. The pressure-sensitive adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing a semiconductor element that is stuck on the pressure-sensitive adhesive sheet 10. Specifically, the pressure-sensitive adhesive sheet 10 is not used when sealing a semiconductor element mounted on a metal lead frame, but seals a semiconductor element that is stuck to the pressure-sensitive adhesive layer 12. Preferably used. As a form of packaging a semiconductor element without using a metal lead frame, a panel scale package (Panel Scale Package; PSP) and a wafer level package (Wafer Level Package; WLP) can be cited.
The pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process having a step of covering the semiconductor chip with a sealing resin and a step of thermosetting the sealing resin.
（半導体装置の製造方法）
　本実施形態に係る粘着シート１０を用いて半導体装置を製造する方法を説明する。
　図２Ａ～図２Ｅには、本実施形態に係る半導体装置の製造方法を説明する概略図が示されている。
　本実施形態に係る半導体装置の製造方法は、粘着シート１０に複数の開口部２１が形成された枠部材２０を貼着させる工程（粘着シート貼着工程）と、枠部材２０の開口部２１にて露出する粘着剤層１２に半導体チップＣＰを貼着させる工程（ボンディング工程）と、半導体チップＣＰを封止樹脂３０で覆う工程（封止工程）と、封止樹脂３０を熱硬化させる工程（熱硬化工程）と、熱硬化させた後、粘着シート１０を剥離する工程（剥離工程）と、を実施する。必要に応じて、熱硬化工程の後に、封止樹脂３０で封止された封止体５０に補強部材４０を貼着させる工程（補強部材貼着工程）を実施してもよい。以下に各工程について説明する。 (Method for manufacturing semiconductor device)
A method for manufacturing a semiconductor device using the pressure-sensitive adhesive sheet 10 according to this embodiment will be described.
2A to 2E are schematic views illustrating the method for manufacturing the semiconductor device according to the present embodiment.
The manufacturing method of the semiconductor device according to the present embodiment includes a step of attaching the frame member 20 in which a plurality of openings 21 are formed on the adhesive sheet 10 (adhesive sheet attaching step), and an opening 21 of the frame member 20. A step of bonding the semiconductor chip CP to the exposed adhesive layer 12 (bonding step), a step of covering the semiconductor chip CP with the sealing resin 30 (sealing step), and a step of thermosetting the sealing resin 30 ( A thermosetting step) and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting. As needed, you may implement the process (reinforcing member sticking process) of sticking the reinforcement member 40 to the sealing body 50 sealed with the sealing resin 30 after the thermosetting process. Each step will be described below.
・粘着シート貼着工程
　図２Ａには、粘着シート１０の粘着剤層１２に枠部材２０を貼着させる工程を説明する概略図が示されている。なお、粘着シート１０に剥離シートＲＬが貼着されている場合には、予め剥離シートＲＬを剥離する。
　本実施形態に係る枠部材２０は、格子状に形成され、複数の開口部２１を有する。枠部材２０は、耐熱性を有する材質で形成されていることが好ましく、例えば、銅及びステンレス等の金属、並びにポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂などが挙げられる。
　開口部２１は、枠部材２０の表裏面を貫通する孔である。開口部２１の形状は、半導体チップＣＰを枠内に収容可能であれば、特に限定されない。開口部２１の孔の深さも、半導体チップＣＰを収容可能であれば、特に限定されない。 -Adhesive sheet sticking process The schematic explaining the process of sticking the frame member 20 to the adhesive layer 12 of the adhesive sheet 10 is shown by FIG. 2A. In addition, when peeling sheet RL is affixed on the adhesive sheet 10, peeling sheet RL is peeled previously.
The frame member 20 according to the present embodiment is formed in a lattice shape and has a plurality of openings 21. The frame member 20 is preferably formed of a heat-resistant material, and examples thereof include metals such as copper and stainless steel, and heat-resistant resins such as polyimide resins and glass epoxy resins.
The opening 21 is a hole that penetrates the front and back surfaces of the frame member 20. The shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame. The depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
・ボンディング工程
　図２Ｂには、粘着剤層１２に半導体チップＣＰを貼着させる工程を説明する概略図が示されている。
　枠部材２０に粘着シート１０を貼着させると、それぞれの開口部２１において開口部２１の形状に応じて粘着剤層１２が露出する。各開口部２１の粘着剤層１２に半導体チップＣＰを貼着させる。半導体チップＣＰを、その回路面を粘着剤層１２で覆うように貼着させる。 Bonding Step FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
When the pressure-sensitive adhesive sheet 10 is adhered to the frame member 20, the pressure-sensitive adhesive layer 12 is exposed in each opening 21 according to the shape of the opening 21. The semiconductor chip CP is adhered to the adhesive layer 12 of each opening 21. The semiconductor chip CP is stuck so that its circuit surface is covered with the adhesive layer 12.
　半導体チップＣＰの製造は、例えば、回路が形成された半導体ウエハの裏面を研削するバックグラインド工程、及び半導体ウエハを個片化するダイシング工程を実施することにより製造する。ダイシング工程では、半導体ウエハをダイシングシートの接着剤層に貼着させ、ダイシングソーなどの切断手段を用いて半導体ウエハを個片化することで半導体チップＣＰ（半導体素子）が得られる。
　ダイシング装置は、特に限定されず、公知のダイシング装置を用いることができる。また、ダイシングの条件についても、特に限定されない。なお、ダイシングブレードを用いてダイシングする方法に代えて、レーザーダイシング法及びステルスダイシング法などを用いてもよい。 The semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces. In the dicing step, a semiconductor chip CP (semiconductor element) is obtained by sticking the semiconductor wafer to the adhesive layer of the dicing sheet and separating the semiconductor wafer using a cutting means such as a dicing saw.
The dicing apparatus is not particularly limited, and a known dicing apparatus can be used. Also, the dicing conditions are not particularly limited. Instead of dicing using a dicing blade, a laser dicing method, a stealth dicing method, or the like may be used.
　ダイシング工程の後、ダイシングシートを引き延ばして、複数の半導体チップＣＰ間の間隔を拡げるエキスパンド工程を実施してもよい。エキスパンド工程を実施することで、コレット等の搬送手段を用いて半導体チップＣＰをピックアップすることができる。また、エキスパンド工程を実施することで、ダイシングシートの接着剤層の接着力が減少し、半導体チップＣＰがピックアップし易くなる。
　ダイシングシートの接着剤組成物、または接着剤層にエネルギー線重合性化合物が配合されている場合には、ダイシングシートの基材側から接着剤層にエネルギー線を照射し、エネルギー線重合性化合物を硬化させる。エネルギー線重合性化合物を硬化させると、接着剤層の凝集力が高まり、接着剤層の接着力を低下させることができる。エネルギー線としては、例えば、紫外線（ＵＶ）及び電子線（ＥＢ）等が挙げられ、紫外線が好ましい。エネルギー線の照射は、半導体ウエハの貼付後、半導体チップの剥離（ピックアップ）前のいずれの段階で行ってもよい。例えば、ダイシングの前もしくは後にエネルギー線を照射してもよいし、エキスパンド工程の後にエネルギー線を照射してもよい。 After the dicing process, an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP. By carrying out the expanding step, the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding process, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
When the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden. When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced. Examples of the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable. The energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
・封止工程及び熱硬化工程
　図２Ｃには、粘着シート１０に貼着された半導体チップＣＰ及び枠部材２０を封止する工程を説明する概略図が示されている。
　封止樹脂３０の材質は、熱硬化性樹脂であり、例えば、エポキシ樹脂などが挙げられる。封止樹脂３０として用いられるエポキシ樹脂には、例えば、フェノール樹脂、エラストマー、無機充填材、及び硬化促進剤などが含まれていてもよい。
　封止樹脂３０で半導体チップＣＰ及び枠部材２０を覆う方法は、特に限定されない。
　本実施形態では、シート状の封止樹脂３０を用いた態様を例に挙げて説明する。シート状の封止樹脂３０を半導体チップＣＰ及び枠部材２０を覆うように載置し、封止樹脂３０を加熱硬化させて、封止樹脂層３０Ａを形成する。このようにして、半導体チップＣＰ及び枠部材２０が封止樹脂層３０Ａに埋め込まれる。シート状の封止樹脂３０を用いる場合には、真空ラミネート法により半導体チップＣＰ及び枠部材２０を封止することが好ましい。この真空ラミネート法により、半導体チップＣＰと枠部材２０との間に空隙が生じることを防止できる。真空ラミネート法による加熱の温度条件範囲は、例えば、８０℃以上１２０℃以下である。 -Sealing process and thermosetting process The schematic diagram explaining the process of sealing the semiconductor chip CP and the frame member 20 which were affixed on the adhesive sheet 10 is shown by FIG. 2C.
The material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin. The epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
The method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited.
In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example. The sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A. When the sheet-shaped sealing resin 30 is used, it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being generated between the semiconductor chip CP and the frame member 20. The temperature condition range for heating by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
　封止工程では、シート状の封止樹脂３０がポリエチレンテレフタレート等の樹脂シートに支持された積層シートを用いてもよい。この場合、半導体チップＣＰ及び枠部材２０を覆うように積層シートを載置した後、樹脂シートを封止樹脂３０から剥離して、封止樹脂３０を加熱硬化させてもよい。このような積層シートとしては、例えば、ＡＢＦフィルム（味の素ファインテクノ株式会社製）が挙げられる。 In the sealing step, a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used. In this case, after the laminated sheet is placed so as to cover the semiconductor chip CP and the frame member 20, the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured. Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
　半導体チップＣＰ及び枠部材２０を封止する方法としては、トランスファーモールド法を採用してもよい。この場合、例えば、封止装置の金型の内部に、粘着シート１０に貼着された半導体チップＣＰ及び枠部材２０を収容する。この金型の内部に流動性の樹脂材料を注入し、樹脂材料を硬化させる。トランスファーモールド法の場合、加熱及び圧力の条件は、特に限定されない。トランスファーモールド法における通常の条件の一例として、１５０℃以上の温度と、４ＭＰａ以上１５ＭＰａ以下の圧力を３０秒以上３００秒以下の間維持する。その後、加圧を解除し、封止装置から硬化物を取り出してオーブン内に静置して、１５０℃以上の温度を２時間以上１５時間以下、維持する。このようにして、半導体チップＣＰ及び枠部材２０を封止する。 As a method for sealing the semiconductor chip CP and the frame member 20, a transfer molding method may be employed. In this case, for example, the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device. A fluid resin material is injected into the mold to cure the resin material. In the case of the transfer mold method, the heating and pressure conditions are not particularly limited. As an example of normal conditions in the transfer molding method, a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds. Thereafter, the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
　前述の封止工程においてシート状の封止樹脂３０を用いる場合、封止樹脂３０を熱硬化させる工程（熱硬化工程）の前に、第一加熱プレス工程を実施してもよい。第一加熱プレス工程においては、封止樹脂３０で被覆された半導体チップＣＰ及び枠部材２０付き粘着シート１０を両面から板状部材で挟み込み、所定の温度、時間、及び圧力の条件下でプレスする。第一加熱プレス工程を実施することにより、封止樹脂３０が半導体チップＣＰと枠部材２０との空隙にも充填され易くなる。また、加熱プレス工程を実施することにより、封止樹脂３０により構成される封止樹脂層３０Ａの凹凸を平坦化することもできる。第一加熱プレス工程においては、粘着シート１０のハードコート層１３が板状部材に接触するので、基材１１と板状部材との接触を防止できる。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. In the first heat pressing step, the hard coat layer 13 of the pressure-sensitive adhesive sheet 10 comes into contact with the plate-like member, so that contact between the base material 11 and the plate-like member can be prevented. 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が粘着シート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 shown in FIG. 2D, the sealing body 50 is supported while being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
　本実施形態では、補強部材４０は、耐熱性の補強板４１と、耐熱性の接着層４２とを備える。補強板４１としては、例えば、ガラスエポキシ樹脂等の耐熱性樹脂を含む板状の部材が挙げられる。接着層４２は、補強板４１と封止体５０とを接着させる。接着層４２としては、補強板４１及び封止樹脂層３０Ａの材質に応じて適宜選択される。 In the present embodiment, the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42. Examples of the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a glass epoxy resin. The adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50. The adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
　補強部材貼着工程では、封止体５０の封止樹脂層３０Ａと補強板４１との間に接着層４２を挟み込み、さらに補強板４１側及び粘着シート１０側からそれぞれ板状部材で挟み込み、所定の温度、時間、及び圧力の条件下でプレスする第二加熱プレス工程を実施することが好ましい。第二加熱プレス工程により、封止体５０と補強部材４０とを仮固定する。第二加熱プレス工程の後に、接着層４２を硬化させるために、仮固定された封止体５０と補強部材４０とを所定の温度及び時間の条件下で加熱することが好ましい。加熱硬化の条件は、接着層４２の材質に応じて適宜設定され、例えば、１８５℃、８０分間、及び２．４ＭＰａの条件である。第二加熱プレス工程においても、粘着シート１０のハードコート層１３が板状部材に接触するので、基材１１と板状部材との接触を防止できる。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 2nd heat press process, since the hard-coat layer 13 of the adhesive sheet 10 contacts a plate-shaped member, the contact with the base material 11 and a plate-shaped member can be prevented. Also in the second heat pressing step, as the plate-like member, for example, a metal plate such as stainless steel can be used.
・剥離工程
　図２Ｅには、粘着シート１０を剥離する工程を説明する概略図が示されている。
　本実施形態では、粘着シート１０の基材１１が屈曲可能である場合、粘着シート１０を屈曲させながら、枠部材２０、半導体チップＣＰおよび封止樹脂層３０Ａから容易に剥離することができる。剥離角度θは、特に限定されないが、９０度以上の剥離角度θで粘着シート１０を剥離することが好ましい。剥離角度θが９０度以上であれば、粘着シート１０を、枠部材２０、半導体チップＣＰおよび封止樹脂層３０Ａから容易に剥離することができる。剥離角度θは、９０度以上１８０度以下が好ましく、１３５度以上１８０度以下がより好ましい。このように粘着シート１０を屈曲させながら剥離を行うことで、枠部材２０、半導体チップＣＰおよび封止樹脂層３０Ａにかかる負荷を低減しながら剥離することができ、粘着シート１０の剥離による、半導体チップＣＰおよび封止樹脂層３０Ａの損傷を抑制することができる。粘着シート１０を剥離した後、前述の再配線工程及びバンプ付け工程等が実施される。粘着シート１０の剥離後、再配線工程及びバンプ付け工程等の実施前に、必要に応じて、前述の補強部材貼着工程を実施してもよい。 -Peeling process The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
In this embodiment, when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent. Although peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree | times or more. If the peeling angle θ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A. The peeling angle θ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less. By peeling the adhesive sheet 10 while bending the adhesive sheet 10 in this way, it is possible to peel it while reducing the load applied to the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A. Damage to the chip CP and the sealing resin layer 30A can be suppressed. After the pressure-sensitive adhesive sheet 10 is peeled off, the above-described rewiring process and bumping process are performed. After the pressure-sensitive adhesive sheet 10 is peeled off, before the rewiring step and the bumping step, etc., the aforementioned reinforcing member sticking step may be performed as necessary.
　補強部材４０を貼着させた場合、再配線工程及びバンプ付け工程等が実施された後、補強部材４０による支持が不要になった段階で、補強部材４０を封止体５０から剥離する。
　その後、封止体５０を半導体チップＣＰ単位で個片化する（個片化工程）。封止体５０を個片化させる方法は特に限定されない。例えば、前述の半導体ウエハをダイシングする際に使用した方法と同様の方法で個片化させることができる。封止体５０を個片化させる工程は、封止体５０をダイシングシート等に貼着させた状態で実施してもよい。封止体５０を個片化することで、半導体チップＣＰ単位の半導体パッケージが製造され、この半導体パッケージは、実装工程においてプリント配線基板等に実装される。 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed.
Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step). A method for dividing the sealing body 50 into individual pieces is not particularly limited. For example, the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer. The step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like. By separating the sealing body 50 into individual pieces, a semiconductor package in units of the semiconductor chip CP is manufactured, and this semiconductor package is mounted on a printed wiring board or the like in a mounting process.
　本実施形態によれば、高温条件が課される工程を経た後でも、設備及び部材の汚染を防止すること、並びに設備及び部材との融着を防止することができる粘着シート１０を提供することができる。粘着シート１０の基材１１の第二面１１ｂには、ハードコート層１３が積層されているので、例えば、前述の第一加熱プレス工程及び第二加熱プレス工程においてステンレス板等の板状部材と基材１１との接触を防止できる。そのため、基材１１がポリエステル系樹脂を含んでいても、基材１１に起因するオリゴマーによる設備及び部材の汚染を防止でき、さらに設備及び部材と基材１１との融着も防止できる。 According to the present embodiment, it is possible to provide a pressure-sensitive adhesive sheet 10 capable of preventing contamination of equipment and members and preventing fusion between the equipment and members even after undergoing a process in which high temperature conditions are imposed. Can do. Since the hard coat layer 13 is laminated on the second surface 11b of the base material 11 of the pressure-sensitive adhesive sheet 10, for example, a plate-like member such as a stainless steel plate in the above-described first heat press step and second heat press step Contact with the substrate 11 can be prevented. Therefore, even if the base material 11 contains a polyester-based resin, it is possible to prevent the equipment and members from being contaminated by oligomers resulting from the base material 11, and also to prevent the equipment and members and the base material 11 from being fused.
　粘着シート１０が、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んだ粘着剤層１２を有する場合、粘着シート１０は、被着体から剥離し易く、糊残りを少なくすることができる。本実施形態では、粘着剤層１２が接する被着体は、半導体チップＣＰ及び枠部材２０である。半導体チップＣＰ及び枠部材２０に接した状態で、粘着剤層１２は、高温条件に曝される。従来の高温プロセスに使用されていた粘着シートに比べると、粘着シート１０によれば、高温条件に曝された後であっても、剥がし易く、半導体チップＣＰ及び枠部材２０への糊残りが少ない。 When the pressure-sensitive adhesive sheet 10 has a pressure-sensitive adhesive layer 12 containing an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer, the pressure-sensitive adhesive sheet 10 is easily peeled off from the adherend and reduces adhesive residue. Can do. In the present embodiment, the adherend to which the pressure-sensitive adhesive layer 12 contacts is the semiconductor chip CP and the frame member 20. The pressure-sensitive adhesive layer 12 is exposed to a high temperature condition in contact with the semiconductor chip CP and the frame member 20. Compared to the pressure-sensitive adhesive sheet used in the conventional high-temperature process, the pressure-sensitive adhesive sheet 10 is easy to peel off even after being exposed to high-temperature conditions, and has less adhesive residue on the semiconductor chip CP and the frame member 20. .
〔第二実施形態〕
　第二実施形態に係る粘着シートは、２つのハードコート層を有する点で、第一実施形態に係る粘着シートと相違する。第二実施形態は、その他の点において第一実施形態と同様であるため、説明を省略または簡略化する。 [Second Embodiment]
The pressure-sensitive adhesive sheet according to the second embodiment is different from the pressure-sensitive adhesive sheet according to the first embodiment in that it has two hard coat layers. Since the second embodiment is the same as the first embodiment in other points, the description is omitted or simplified.
（粘着シート）
　図３には、本実施形態の粘着シート１０Ａの断面概略図が示されている。
　粘着シート１０Ａは、基材１１、粘着剤層１２及びハードコート層１３を有する。
　本実施形態のハードコート層１３は、第一ハードコート層１３ａと第二ハードコート層１３ｂとを含む。基材１１は、前記実施形態と同様に、第一面１１ａ、及び第一面１１ａとは反対側の第二面１１ｂを有する。本実施形態の粘着シート１０Ａにおいては、第一面１１ａに第二ハードコート層１３ｂが積層され、第二面１１ｂに第一ハードコート層１３ａが積層され、第二ハードコート層１３ｂに粘着剤層１２が積層されている。
　第二ハードコート層１３ｂの厚みは、第一実施形態で説明したハードコート層１３と同様の範囲の厚みであることが好ましい。第二ハードコート層１３ｂは、基材１１の第一面１１ａの全体を覆うように形成されていることが好ましい。 (Adhesive sheet)
FIG. 3 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10A of the present embodiment.
The pressure-sensitive adhesive sheet 10 </ b> A includes a base material 11, a pressure-sensitive adhesive layer 12, and a hard coat layer 13.
The hard coat layer 13 of the present embodiment includes a first hard coat layer 13a and a second hard coat layer 13b. The base material 11 has the 1st surface 11a and the 2nd surface 11b on the opposite side to the 1st surface 11a similarly to the said embodiment. In the pressure-sensitive adhesive sheet 10A of the present embodiment, the second hard coat layer 13b is laminated on the first surface 11a, the first hard coat layer 13a is laminated on the second surface 11b, and the pressure-sensitive adhesive layer is formed on the second hard coat layer 13b. 12 are laminated.
The thickness of the second hard coat layer 13b is preferably in the same range as the hard coat layer 13 described in the first embodiment. The second hard coat layer 13b is preferably formed so as to cover the entire first surface 11a of the substrate 11.
　第一ハードコート層１３ａは、有機無機ハイブリッド材料を硬化させて形成された硬化皮膜であり、有機無機ハイブリッド材料の硬化物を含む。第一ハードコート層１３ａの形成には、前記実施形態と同様の有機無機ハイブリッド材料を用いることができる。
　第二ハードコート層１３ｂは、多官能アクリル系樹脂を含む。第二ハードコート層１３ｂは、粘着剤層１２との密着性の観点から、有機無機ハイブリッド材料を硬化させて形成された硬化皮膜ではないことが好ましい。第二ハードコート層１３ｂの形成に用いる活性エネルギー線感応型組成物は、有機無機ハイブリッド材料ではない点を除き、第一実施形態で説明した材料を用いて調製することができ、第二ハードコート層１３ｂは、当該活性エネルギー線感応型組成物を硬化させて形成された硬化皮膜であることが好ましい。第二ハードコート層１３ｂの形成に用いる活性エネルギー線感応型組成物も、前記実施形態と同様、多官能性（メタ）アクリレート系モノマー及び（メタ）アクリレート系プレポリマーからなる群から選択される少なくとも１種の樹脂を含んでいることが好ましく、多官能性（メタ）アクリレート系モノマーを含んでいることがより好ましい。
　第二ハードコート層１３ｂの形成に用いる活性エネルギー線感応型組成物の一例として、多官能性（メタ）アクリレート系モノマーとして、ペンタエリスリトールトリ（メタ）アクリレート、及びエチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレートを含んでいる活性エネルギー線感応型組成物が挙げられる。
　本実施形態に係る第一ハードコート層１３ａの一例として、反応性シリカ微粒子、多官能性（メタ）アクリレート系モノマー、及び（メタ）アクリレート系プレポリマーを含んでいる有機無機ハイブリッド材料を硬化させて形成された第一ハードコート層１３ａが挙げられる。この場合の第二ハードコート層１３ｂの一例として、多官能性（メタ）アクリレート系モノマーとしてのペンタエリスリトールトリ（メタ）アクリレート及びエチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、光重合開始剤としての１－ヒドロキシシクロヘキシルフェニルケトン、並びにレベリング剤としてのシロキサン変性アクリル系レベリング剤を含んでいる活性エネルギー線感応型組成物を硬化させて形成された第二ハードコート層１３ｂが挙げられる。 The first hard coat layer 13a is a cured film formed by curing an organic-inorganic hybrid material, and includes a cured product of the organic-inorganic hybrid material. For the formation of the first hard coat layer 13a, the same organic-inorganic hybrid material as in the above embodiment can be used.
The second hard coat layer 13b includes a polyfunctional acrylic resin. The second hard coat layer 13b is preferably not a cured film formed by curing an organic-inorganic hybrid material from the viewpoint of adhesion to the pressure-sensitive adhesive layer 12. The active energy ray-sensitive composition used for forming the second hard coat layer 13b can be prepared using the material described in the first embodiment except that it is not an organic-inorganic hybrid material. The layer 13b is preferably a cured film formed by curing the active energy ray sensitive composition. The active energy ray-sensitive composition used for forming the second hard coat layer 13b is also at least selected from the group consisting of a polyfunctional (meth) acrylate monomer and a (meth) acrylate prepolymer, as in the above embodiment. One type of resin is preferably contained, and more preferably a polyfunctional (meth) acrylate monomer is contained.
As an example of the active energy ray-sensitive composition used for forming the second hard coat layer 13b, pentaerythritol tri (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) are used as a multifunctional (meth) acrylate monomer. ) Active energy ray-sensitive composition containing acrylate.
As an example of the first hard coat layer 13a according to the present embodiment, an organic-inorganic hybrid material containing reactive silica fine particles, a polyfunctional (meth) acrylate monomer, and a (meth) acrylate prepolymer is cured. The formed first hard coat layer 13a is mentioned. As an example of the second hard coat layer 13b in this case, pentaerythritol tri (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate as a polyfunctional (meth) acrylate monomer, photopolymerization initiator Examples thereof include a second hard coat layer 13b formed by curing an active energy ray-sensitive composition containing 1-hydroxycyclohexyl phenyl ketone and a siloxane-modified acrylic leveling agent as a leveling agent.
　粘着シート１０Ａの製造方法は、特に限定されない。例えば、粘着シート１０Ａは、次のような工程を経て製造される。
　まず、前記実施形態と同様にハードコート剤を準備または調製する。次に、ハードコート剤を、基材１１の第二面１１ｂの上にコーティングして塗膜を形成させ、塗膜を乾燥させた後、この塗膜に活性エネルギー線を照射して、該塗膜を硬化させることにより、第一ハードコート層１３ａが形成される。次に、基材１１の第一面１１ａの上にハードコート剤をコーティングして、前述と同様に塗膜を硬化させることにより、第二ハードコート層１３ｂが形成される。
　次に、基材１１の第二ハードコート層１３ｂ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１０Ａ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を形成する。この粘着剤層１２を有する剥離シートＲＬと、前述の第一ハードコート層１３ａ及び第二ハードコート層１３ｂを有する基材１１とを貼り合わせることによっても、粘着シート１０Ａを製造することができる。この場合、粘着剤層１２と基材１１の第二ハードコート層１３ｂとを貼り合わせる。 The manufacturing method of 10 A of adhesive sheets is not specifically limited. For example, the adhesive sheet 10A is manufactured through the following steps.
First, a hard coat agent is prepared or prepared in the same manner as in the above embodiment. Next, a hard coat agent is coated on the second surface 11b of the base material 11 to form a coating film, and after the coating film is dried, the coating film is irradiated with active energy rays, and the coating is performed. The first hard coat layer 13a is formed by curing the film. Next, a hard coat agent is coated on the first surface 11a of the substrate 11, and the coating film is cured in the same manner as described above, whereby the second hard coat layer 13b is formed.
Next, an adhesive composition is apply | coated on the 2nd hard-coat layer 13b of the base material 11, and a coating film is formed. 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 10 A of adhesive sheets, 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. The adhesive sheet 10A can also be manufactured by bonding the release sheet RL having the adhesive layer 12 and the base material 11 having the first hard coat layer 13a and the second hard coat layer 13b. In this case, the pressure-sensitive adhesive layer 12 and the second hard coat layer 13b of the substrate 11 are bonded together.
　粘着シート１０Ａも前記実施形態と同様の半導体装置の製造プロセスにおいて使用できる。 The pressure-sensitive adhesive sheet 10A can also be used in the same semiconductor device manufacturing process as in the above embodiment.
　本実施形態によれば、高温条件が課される工程を経た後でも、設備及び部材の汚染を防止すること、並びに設備及び部材との融着を防止することができる粘着シート１０Ａを提供することができる。
　粘着シート１０Ａは、粘着剤層１２と基材１１との間にも第二ハードコート層１３ｂをさらに有するので、基材１１に含まれるオリゴマーが粘着剤層１２へと移動することを防止できる。
　粘着シート１０Ａは、基材１１の両面（第一面１１ａ及び第二面１１ｂ）にそれぞれハードコート層が積層されているので、加熱による基材の変形を低減させることができる。 According to the present embodiment, it is possible to provide a pressure-sensitive adhesive sheet 10A that can prevent contamination of equipment and members, and can prevent fusion between the equipment and members even after a process in which high temperature conditions are imposed. Can do.
Since the pressure-sensitive adhesive sheet 10 </ b> A further includes the second hard coat layer 13 b between the pressure-sensitive adhesive layer 12 and the base material 11, the oligomer contained in the base material 11 can be prevented from moving to the pressure-sensitive adhesive layer 12.
In the pressure-sensitive adhesive sheet 10A, since the hard coat layers are laminated on both surfaces (the first surface 11a and the second surface 11b) of the base material 11, deformation of the base material due to heating can be reduced.
〔実施形態の変形〕
　本発明は、前記実施形態に限定されず、本発明の目的を達成できる範囲での変形及び改良等は、本発明に含まれる。なお、以下の説明では、前記実施形態で説明した部材等と同一であれば、同一符号を付してその説明を省略または簡略化する。 [Modification of Embodiment]
The present invention is not limited to the above-described embodiment, but includes modifications and improvements as long as the object of the present invention can be achieved. In the following description, if it is the same as the member described in the above embodiment, the same reference numeral is given and the description is omitted or simplified.
　ハードコート層１３は、基材１１の第二面１１ｂの全体を覆うように形成されていてもよいし、ハードコート層１３が形成されていない領域があってもよい。後者の場合は、粘着シート１０を用いるプロセスにおいて、プロセス中に使用する装置及び部材と基材１１とが接触しないようにハードコート層１３が形成されていればよい。 The hard coat layer 13 may be formed so as to cover the entire second surface 11b of the substrate 11, or there may be a region where the hard coat layer 13 is not formed. In the latter case, in the process using the pressure-sensitive adhesive sheet 10, the hard coat layer 13 only needs to be formed so that the apparatus and members used during the process do not contact the base material 11.
　前記実施形態では、粘着シートの製造方法として、先にハードコート層１３を形成し、その後に粘着剤層１２を形成す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。粘着シートの製造方法の別の一態様としては、例えば、先に粘着剤層１２を基材１１に形成し、粘着剤層１２を剥離シートＲＬで覆った後に、ハードコート層１３を形成する態様であってもよい。 In the said embodiment, although the hard coat layer 13 was formed first as a manufacturing method of an adhesive sheet, and the aspect which forms the adhesive layer 12 after that was mentioned as an example and demonstrated, this invention is limited to such an aspect. Not. As another aspect of the method for producing the pressure-sensitive adhesive sheet, for example, a mode in which the pressure-sensitive adhesive layer 12 is first formed on the substrate 11 and the pressure-sensitive adhesive layer 12 is covered with the release sheet RL, and then the hard coat layer 13 is formed. It may be.
　前記実施形態では、粘着シート１０の粘着剤層１２が剥離シートＲＬによって覆われている態様を例に挙げて説明したが、本発明は、このような態様に限定されない。
　また、粘着シート１０は、枚葉であってもよく、複数枚の粘着シート１０が積層された状態で提供されてもよい。この場合、例えば、粘着剤層１２は、積層される別の粘着シートのハードコート層１３によって覆われていてもよい。
　また、粘着シート１０は、長尺状のシートであってもよく、ロール状に巻き取られた状態で提供されてもよい。ロール状に巻き取られた粘着シート１０は、ロールから繰り出されて所望のサイズに切断するなどして使用することができる。 In the said embodiment, although the aspect in which the adhesive layer 12 of the adhesive sheet 10 was covered with the peeling sheet RL was mentioned as an example, this invention is not limited to such an aspect.
Moreover, the adhesive sheet 10 may be a single wafer or may be provided in a state where a plurality of adhesive sheets 10 are laminated. In this case, for example, the pressure-sensitive adhesive layer 12 may be covered with a hard coat layer 13 of another pressure-sensitive adhesive sheet to be laminated.
Moreover, the adhesive sheet 10 may be a long sheet or may be provided in a state of being wound in a roll. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
　前記実施形態では、封止樹脂３０の材質として熱硬化性樹脂である場合を例に挙げて説明したが、本発明はこのような態様に限定されない。例えば、封止樹脂３０は、紫外線等のエネルギー線で硬化するエネルギー線硬化性樹脂でもよい。 In the above embodiment, the case where the sealing resin 30 is a thermosetting resin has been described as an example, but the present invention is not limited to such a mode. For example, the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
　前記実施形態では、半導体装置の製造方法の説明において、枠部材２０を粘着シート１０に貼着させる態様を例に挙げて説明したが、本発明はこのような態様に限定されない。粘着シート１０は、枠部材を用いずに半導体素子を封止する半導体装置の製造方法において使用されてもよい。 In the above embodiment, in the description of the method for manufacturing a semiconductor device, an example in which the frame member 20 is attached to the adhesive sheet 10 has been described as an example, but the present invention is not limited to such an embodiment. The adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
　以下、実施例を挙げて本発明をさらに詳細に説明する。本発明はこれら実施例に何ら限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.
〔評価方法〕
　粘着シートの評価は、以下に示す方法に従って行った。 〔Evaluation methods〕
Evaluation of the pressure-sensitive adhesive sheet was performed according to the following method.
[粘着シート収縮率評価]
　２枚の粘着シートの粘着剤層同士を貼り合わせ、縦１２ｃｍ×横１２ｃｍの大きさに切り出し、粘着シート積層体を得た。２枚の粘着シートを貼り合わせる際に、それぞれの粘着シートの基材のＭＤ方向を揃えて貼り合わせた。
　この粘着シート積層体の表面に、縦１０ｃｍ×横１０ｃｍの四角形の印を書き込んだ。この四角形の印は、四角形の辺が基材のＭＤ方向に沿うように書き込んだ。電子ノギスを用いて、書き込んだ四角形の各頂点の間隔を計測し、この各頂点の間隔を初期値とした。その後、１９０℃及び１時間の条件で粘着シート積層体を加熱した。加熱後、粘着シート積層体を室温に戻してから再び四角形の印の各頂点の間隔を計測した。初期値及び加熱後の間隔の計測値に基づいて、それぞれの辺の収縮率を算出した。基材のＭＤ方向における収縮率が１．７％以下である場合に「Ａ」と判定し、収縮率が１．７％を超える場合に「Ｂ」と判定した。 [Evaluation of shrinkage rate of adhesive sheet]
The pressure-sensitive adhesive layers of the two pressure-sensitive adhesive sheets were bonded together and cut into a size of 12 cm long × 12 cm wide to obtain a pressure-sensitive adhesive sheet laminate. When two adhesive sheets were bonded together, the MD directions of the substrates of the respective adhesive sheets were aligned and bonded together.
A square mark of 10 cm long × 10 cm wide was written on the surface of the pressure-sensitive adhesive sheet laminate. The square marks were written so that the sides of the square were along the MD direction of the substrate. The distance between the vertices of the written rectangle was measured using an electronic caliper, and the distance between the vertices was set as an initial value. Thereafter, the pressure-sensitive adhesive sheet laminate was heated under the conditions of 190 ° C. and 1 hour. After heating, the pressure-sensitive adhesive sheet laminate was returned to room temperature, and the intervals between the vertices of the square marks were measured again. Based on the initial value and the measured value of the interval after heating, the shrinkage rate of each side was calculated. When the shrinkage rate in the MD direction of the base material was 1.7% or less, it was determined as “A”, and when the shrinkage rate exceeded 1.7%, it was determined as “B”.
[粘着シート耐熱性評価]
　粘着シートを厚み８０μｍの銅箔に貼り合わせ、７ｃｍ×１５ｃｍの大きさに切り出した、銅箔付きテープを得た。この銅箔付きテープの上面側及び下面側から、銅箔付きテープと同じサイズのＳＵＳ板(♯１２００仕上げ)を用いて上下に挟み込んだ。ＳＵＳ板で挟み込まれた銅箔付きテープを、１９０℃、２．５ＭＰａ、及び９０分間の条件で、加熱及び加圧した。加熱及び加圧後、粘着シートに接触していたＳＵＳ板の表面状態を確認し、汚れ及び融着が無い場合に「Ａ」と判定し、汚れが生じた場合に「Ｂ」と判定した。 [Adhesive sheet heat resistance evaluation]
The pressure-sensitive adhesive sheet was bonded to a copper foil having a thickness of 80 μm, and a tape with copper foil cut out to a size of 7 cm × 15 cm was obtained. From the upper surface side and the lower surface side of this tape with copper foil, it was sandwiched up and down using an SUS plate (# 1200 finish) of the same size as the tape with copper foil. The tape with copper foil sandwiched between SUS plates was heated and pressurized under the conditions of 190 ° C., 2.5 MPa, and 90 minutes. After heating and pressurization, the surface state of the SUS plate that was in contact with the pressure-sensitive adhesive sheet was confirmed. When there was no dirt or fusion, it was determined as “A”, and when dirt was generated, it was determined as “B”.
[密着性評価]
　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、次に１９０℃及び１時間の条件で粘着シートを加熱した。その後、１ｍｍ幅の碁盤目状のクロスカットを粘着剤層に施し、その碁盤目状にクロスカットされた粘着剤層の表面に、粘着テープ（ニチバン(株)製、商品名：セロテープ（登録商標））を貼り、「ＪＩＳ　Ｋ５６００－５－６」の碁盤目テープ法（クロスカット法）に準拠して、粘着テープの剥離試験を行い、粘着剤層と基材との密着性を下記の基準に基づいて評価した。碁盤目の１００個のマス目の内、剥離したマス目の数が１０以下であれば「Ａ」と判定し、１０を超えた場合に「Ｂ」と判定した。 [Adhesion evaluation]
Heating was performed at 100 ° C for 30 minutes, followed by heating at 180 ° C for 30 minutes, and then the pressure-sensitive adhesive sheet was heated at 190 ° C for 1 hour. After that, a 1 mm wide grid-like cross cut was applied to the adhesive layer, and an adhesive tape (manufactured by Nichiban Co., Ltd., trade name: cello tape (registered trademark)) was applied to the surface of the adhesive layer cross-cut into the grid pattern. )) Is applied and a peel test of the adhesive tape is performed in accordance with the cross-cut tape method (cross cut method) of “JIS K5600-5-6”, and the adhesion between the adhesive layer and the substrate is as follows: Based on the evaluation. If the number of peeled squares out of 100 squares of the grid is 10 or less, it is determined as “A”, and if it exceeds 10, it is determined as “B”.
〔粘着シートの作製〕
（実施例１）
（１）基材の作製
　活性エネルギー線感応型組成物を含有するハードコート剤１００質量部と、希釈溶剤としてプロピレングリコールモノメチルエーテル８３質量部とを均一に混合し、固形分濃度約４０質量％であるハードコート剤ＨＣ１を調製した。用いた活性エネルギー線感応型組成物を含有するハードコート剤ＨＣ１は、ＪＳＲ(株)製の商品名「オプスターＺ７５３０」であり、活性エネルギー線感応型組成物（７０質量％）、光重合開始剤（３質量％）、及びメチルエチルケトン（２７質量％）を含み、固形分濃度が７３質量％である。活性エネルギー線感応型組成物の組成は、反応性シリカ微粒子（ハードコート剤中の４２質量％）と、多官能性(メタ)アクリレート系モノマー及び(メタ)アクリレート系プレポリマー（ハードコート剤中の２８質量％）とを含む。
　バーコーターを用いて、ハードコート剤ＨＣ１を透明ポリエチレンテレフタレートフィルム〔東洋紡（株）製；ＰＥＴ５０Ａ－４３００、厚み５０μｍ〕の易接着面に塗布した。乾燥及びＵＶ硬化後の膜厚が１．５μｍになるようにハードコート剤ＨＣ１を塗布した。乾燥条件は７０℃及び１分間とした。ＵＶ硬化は、高圧水銀ランプで１５０ｍＪ／ｃｍ２の紫外線を照射した。このようにして、ハードコート層を有する基材ＨＣＢＳ１を作製した。 [Preparation of adhesive sheet]
Example 1
(1) Preparation of base material 100 parts by mass of a hard coating agent containing an active energy ray-sensitive composition and 83 parts by mass of propylene glycol monomethyl ether as a diluting solvent are uniformly mixed, and the solid content concentration is about 40% by mass. A hard coat agent HC1 was prepared. The hard coating agent HC1 containing the active energy ray-sensitive composition used is a trade name “OPSTAR Z7530” manufactured by JSR Corporation, an active energy ray-sensitive composition (70% by mass), a photopolymerization initiator. (3% by mass) and methyl ethyl ketone (27% by mass), and the solid content concentration is 73% by mass. The composition of the active energy ray-sensitive composition is composed of reactive silica fine particles (42% by mass in the hard coat agent), a polyfunctional (meth) acrylate monomer and a (meth) acrylate prepolymer (in the hard coat agent). 28 mass%).
Using a bar coater, the hard coat agent HC1 was applied to the easy-adhesion surface of a transparent polyethylene terephthalate film [Toyobo Co., Ltd .; PET50A-4300, thickness 50 μm]. The hard coat agent HC1 was applied so that the film thickness after drying and UV curing was 1.5 μm. Drying conditions were 70 ° C. and 1 minute. UV curing was irradiated with ultraviolet rays of 150 mJ / cm 2 by a high pressure mercury lamp. In this way, a base material HCBS1 having a hard coat layer was produced.
（２）粘着剤組成物の作製
　以下の材料（ポリマー、粘着助剤、架橋剤、及び希釈溶剤）を配合し、十分に撹拌して、実施例１に係る塗布用粘着剤液（粘着剤組成物）を調製した。 (2) 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).
・ポリマー：アクリル酸エステル共重合体、１００質量部（固形分）
　アクリル酸エステル共重合体は、アクリル酸２－エチルヘキシル９２．８質量％と、アクリル酸２－ヒドロキシエチル７．０質量％と、アクリル酸０．２質量％とを共重合して調製した。 ・ Polymer: Acrylic ester copolymer, 100 parts by mass (solid content)
The acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
・粘着助剤：両末端水酸基水素化ポリブタジエン〔日本曹達（株）製；ＧＩ－１０００〕１３質量部（固形分） Adhesion aid: 13-part by mass (solid content) of hydroxylated hydrogenated polybutadiene at both ends (Nippon Soda Co., Ltd .; GI-1000)
・架橋剤：ヘキサメチレンジイソシアネートを有する脂肪族系イソシアネート（ヘキサメチレンジイソシアネートのイソシアヌレート型変性体）〔日本ポリウレタン工業（株）製；コロネートＨＸ〕、９．０質量部（固形分） Crosslinking agent: aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate) [manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX], 9.0 parts by mass (solid content)
・希釈溶剤：トルエン及びＭＥＫ（メチルエチルケトン）の混合溶媒（体積比でトルエン：ＭＥＫ＝２：１）を用い、塗布用粘着剤液の固形分濃度は、３０質量％に調製した。 Diluting solvent: A mixed solvent of toluene and MEK (methyl ethyl ketone) (toluene: MEK = 2: 1 by volume) was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
（３）粘着剤層の作製
　調製した塗布用粘着剤液を、コンマコーター（登録商標）を用いて乾燥後の膜厚が５０μｍになるように、シリコーン系剥離層を設けた透明ポリエチレンテレフタレートフィルムからなる剥離フィルム〔リンテック（株）製；ＳＰ－ＰＥＴ３８２１５０、厚み３８μｍ〕の剥離層面側に塗布し、９０℃及び９０秒間の加熱を行った。続いて１１５℃及び９０秒間の加熱を行い、塗膜を乾燥させた。 (3) Production of pressure-sensitive adhesive layer From the transparent polyethylene terephthalate film provided with a silicone-based release layer, the prepared pressure-sensitive adhesive liquid for coating was dried using a comma coater (registered trademark) so that the film thickness after drying was 50 μm. The resulting release film [manufactured by Lintec Corporation; SP-PET 382150, thickness 38 μm] was applied to the release layer surface side and heated at 90 ° C. for 90 seconds. Subsequently, heating was performed at 115 ° C. for 90 seconds to dry the coating film.
（４）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ＨＣＢＳ１とを貼り合わせて実施例１に係る粘着シートを得た。基材のハードコート層が形成されている面とは反対側の面に粘着剤層を貼り合わせて、粘着シートを得た。 (4) Production 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 HCBS1 were bonded together to obtain a pressure-sensitive adhesive sheet according to Example 1. The pressure-sensitive adhesive layer was bonded to the surface of the substrate opposite to the surface on which the hard coat layer was formed to obtain a pressure-sensitive adhesive sheet.
（実施例２）
　実施例２に係る粘着シートは、ハードコート層が形成される基材の種類が実施例１とは異なること以外、実施例１と同様に作製した。実施例２では、帝人デュポンフィルム（株）製のポリエチレンテレフタレートフィルム（製品名：ＰＥＴ５０　ＫＦＬ１２Ｄ、厚み５０μｍ）を用い、このフィルムの易接着面に実施例１と同じハードコート剤ＨＣ１を塗布して、ハードコート層を形成し、ハードコート層を有する基材ＨＣＢＳ２を得た。 (Example 2)
The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as Example 1 except that the type of the substrate on which the hard coat layer was formed was different from Example 1. In Example 2, a polyethylene terephthalate film (product name: PET50 KFL12D, thickness 50 μm) manufactured by Teijin DuPont Films Co., Ltd. was used, and the same hard coat agent HC1 as in Example 1 was applied to the easy adhesion surface of this film. A hard coat layer was formed to obtain a base material HCBS2 having a hard coat layer.
（実施例３）
　実施例３に係る粘着シートは、基材のポリエチレンテレフタレートフィルムの両面にハードコート層が形成されていること以外、実施例２と同様に作製した。実施例３のハードコート層を有する基材ＨＣＢＳ３は、基材ＨＣＢＳ１のハードコート層が形成されている面とは反対側の面に実施例３に係るハードコート剤ＨＣ２を塗布して、ハードコート層を形成した。
　実施例３に係るハードコート剤ＨＣ２は、以下に示す配合量（いずれも質量部（固形分比））で、（Ａ）～（Ｄ）成分を混合して、硬化性樹脂組成物を調製した後、プロピレングリコールモノメチルエーテルで希釈して得た。ハードコート剤ＨＣ２の固形分濃度は３０質量％とした。 (Example 3)
The pressure-sensitive adhesive sheet according to Example 3 was produced in the same manner as Example 2 except that hard coat layers were formed on both surfaces of a polyethylene terephthalate film as a base material. The base material HCBS3 having the hard coat layer of Example 3 is obtained by applying the hard coat agent HC2 according to Example 3 to the surface of the base material HCBS1 opposite to the surface on which the hard coat layer is formed. A layer was formed.
The hard coat agent HC2 according to Example 3 was prepared by mixing components (A) to (D) at the following blending amounts (all by weight (solid content ratio)) to prepare a curable resin composition. Thereafter, it was obtained by diluting with propylene glycol monomethyl ether. The solid content concentration of the hard coating agent HC2 was 30% by mass.
（Ａ）成分
　ペンタエリスリトールトリアクリレート（新中村化学工業（株）製、商品名：Ａ－ＴＭＭ－３Ｌ）、１００質量部（固形分）。 Component (A) Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMM-3L), 100 parts by mass (solid content).
（Ｂ）成分
　エチレンオキサイド変性ジペンタエリスリトールヘキサアクリレート（新中村化学工業（株）製、商品名：Ａ－ＤＰＨ－１２Ｅ）、１００質量部（固形分）。 Component (B) Ethylene oxide-modified dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH-12E), 100 parts by mass (solid content).
（Ｃ）成分
　１－ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製、商品名：イルガキュア１８４、アセトフェノン系光重合開始剤）、１０質量部（固形分）。 Component (C) 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184, acetophenone photopolymerization initiator), 10 parts by mass (solid content).
（Ｄ）成分
　シロキサン変性アクリル系レベリング剤（ビックケミー・ジャパン（株）製、商品名：ＢＹＫ－３５５０）、０．２質量部（固形分）。 Component (D): Siloxane-modified acrylic leveling agent (manufactured by BYK Japan Japan, trade name: BYK-3550), 0.2 part by mass (solid content).
　調製した実施例３のハードコート剤ＨＣ２を、基材ＨＣＢＳ１のハードコート層が形成されている面とは反対側の易接着面に、マイヤーバーを用いて乾燥後の膜厚が３μｍとなるように塗布した。塗膜を８０℃で１分間乾燥後、高圧水銀ランプを用いて、紫外線を３００ｍＪ／ｃｍ２（積算光量）照射して、塗布膜を硬化させて、膜厚３μｍの第二ハードコート層を有する基材ＨＣＢＳ３を作製した。
　なお、粘着剤層と、基材ＨＣＢＳ３とを貼り合わせる際には、ハードコート剤ＨＣ２を用いたハードコート層が形成されている面とは反対の面に、粘着剤層を貼り合わせて、粘着シートを得た。 The prepared hard coat agent HC2 of Example 3 is formed on the easy-adhesion surface opposite to the surface on which the hard coat layer of the base material HCBS1 is formed so that the film thickness after drying using a Meyer bar is 3 μm. It was applied to. The coating film is dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays at 300 mJ / cm 2 (integrated light amount) using a high-pressure mercury lamp to cure the coating film to have a second hard coat layer having a thickness of 3 μm. A substrate HCBS3 was produced.
When the adhesive layer and the base material HCBS3 are bonded together, the adhesive layer is bonded to the surface opposite to the surface on which the hard coat layer using the hard coat agent HC2 is formed. A sheet was obtained.
（比較例１）
　比較例１に係る粘着シートは、ハードコート層を形成せずに基材として透明ポリエチレンテレフタレートフィルム〔東洋紡（株）製；ＰＥＴ５０Ａ－４３００、厚み５０μｍ〕を用いたこと以外、実施例１と同様に作製した。 (Comparative Example 1)
The pressure-sensitive adhesive sheet according to Comparative Example 1 was the same as Example 1 except that a transparent polyethylene terephthalate film [manufactured by Toyobo Co., Ltd .; PET50A-4300, thickness 50 μm] was used as a base material without forming a hard coat layer. Produced.
（比較例２）
　比較例２に係る粘着シートは、ハードコート層を形成せずに基材としてポリエチレンテレフタレートフィルム〔帝人デュポンフィルム（株）製；ＰＥＴ５０　ＫＦＬ１２Ｄ、厚み５０μｍ〕を用いたこと以外、実施例２と同様に作製した。 (Comparative Example 2)
The pressure-sensitive adhesive sheet according to Comparative Example 2 was the same as Example 2 except that a polyethylene terephthalate film [manufactured by Teijin DuPont Films; PET50 KFL12D, thickness 50 μm] was used as a substrate without forming a hard coat layer. Produced.
（比較例３）
　比較例３に係る粘着シートは、実施例２で用いた基材ＨＣＢＳ２のハードコート層と、粘着剤層とを貼り合わせたこと以外、実施例２と同様に作製した。 (Comparative Example 3)
The pressure-sensitive adhesive sheet according to Comparative Example 3 was produced in the same manner as in Example 2 except that the hard coat layer of the base material HCBS2 used in Example 2 and the pressure-sensitive adhesive layer were bonded together.
　表１に実施例１～３及び比較例１～３に係る粘着シートの基材及びハードコート層の層構成を示す。 Table 1 shows the layer structures of the base material and the hard coat layer of the pressure-sensitive adhesive sheets according to Examples 1 to 3 and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に実施例１～３及び比較例１～３に係る粘着シートの評価結果を示す。 Table 2 shows the evaluation results of the pressure-sensitive adhesive sheets according to Examples 1 to 3 and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例１～３の粘着シートによれば、ハードコート層を有するので、耐熱性評価においてＳＵＳ板への融着及び汚染が生じなかった。一方で、比較例１～３の粘着シートでは、基材の第二面（粘着剤層が積層された面とは反対の面）にハードコート層を有していないため、ＳＵＳ板と基材のＰＥＴフィルムとが接触した状態で加熱されたことにより、ＳＵＳ板の表面が汚染された。
　実施例１～３の粘着シートによれば、収縮率が低かったため、例えば、半導体装置の製造プロセス等において工程上の不具合発生を抑制できる。
　実施例１～３の粘着シートによれば、粘着剤層と基材との密着性に優れる。実施例３の粘着シートは、基材と粘着剤層との間にハードコート層が設けられていたが、前述のハードコート剤ＨＣ２を用いてハードコート層を形成したため、ハードコート層と粘着剤層との密着力、及び基材とハードコート層との密着力が優れていると考えられる。 According to the pressure-sensitive adhesive sheets of Examples 1 to 3, since they had a hard coat layer, no fusion and contamination to the SUS plate occurred in the heat resistance evaluation. On the other hand, since the adhesive sheets of Comparative Examples 1 to 3 do not have a hard coat layer on the second surface of the substrate (the surface opposite to the surface on which the adhesive layer is laminated), the SUS plate and the substrate The surface of the SUS plate was contaminated by being heated in contact with the PET film.
According to the pressure-sensitive adhesive sheets of Examples 1 to 3, since the shrinkage rate was low, it is possible to suppress the occurrence of problems in the process in the semiconductor device manufacturing process, for example.
According to the pressure-sensitive adhesive sheets of Examples 1 to 3, the adhesiveness between the pressure-sensitive adhesive layer and the substrate is excellent. In the pressure-sensitive adhesive sheet of Example 3, a hard coat layer was provided between the base material and the pressure-sensitive adhesive layer. However, since the hard coat layer was formed using the hard coat agent HC2, the hard coat layer and the pressure-sensitive adhesive were used. It is considered that the adhesion between the substrate and the adhesion between the substrate and the hard coat layer is excellent.
　１０，１０Ａ…粘着シート、１１…基材、１１ａ…第一面、１１ｂ…第二面、１２…粘着剤層、１３…ハードコート層、１３ａ…第一ハードコート層、１３ｂ…第二ハードコート層、２０…枠部材、２１…開口部。 DESCRIPTION OF SYMBOLS 10,10A ... Adhesive sheet, 11 ... Base material, 11a ... First side, 11b ... Second side, 12 ... Adhesive layer, 13 ... Hard coat layer, 13a ... First hard coat layer, 13b ... Second hard coat Layer, 20 ... frame member, 21 ... opening.

Claims (6)

  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、
    　第一面及び前記第一面とは反対側の第二面を有し、ポリエステル系樹脂を含む基材と、
    　前記基材の前記第一面に積層された粘着剤層と、
    　前記基材の前記第二面に積層されたハードコート層と、を有し、
    　前記ハードコート層は、有機無機ハイブリッド材料を硬化させて形成された硬化皮膜である、粘着シート。     A pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet,
    A first surface and a second surface opposite to the first surface, and a base material containing a polyester resin;
    An adhesive layer laminated on the first surface of the substrate;
    A hard coat layer laminated on the second surface of the substrate,
    The hard coat layer is a pressure-sensitive adhesive sheet that is a cured film formed by curing an organic-inorganic hybrid material.
  2. 　１９０℃及び１時間の条件で加熱後、前記基材のいずれかの面に沿う方向における収縮率が１．７％以下である、
    　請求項１に記載の粘着シート。     After heating at 190 ° C. and 1 hour, the shrinkage rate in the direction along any surface of the substrate is 1.7% or less.
    The pressure-sensitive adhesive sheet according to claim 1.
  3. 　前記ポリエステル系樹脂は、ポリエ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、及びポリブチレンテレフタレート樹脂からなる群から選択される樹脂である、請求項１または請求項２に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the polyester resin is a resin selected from the group consisting of a polyethylene terephthalate resin, a polyethylene naphthalate resin, and a polybutylene terephthalate resin.
  4. 　前記ハードコート層の厚みは、０．５μｍ以上３．０μｍ以下である、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 pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the hard coat layer has a thickness of 0.5 µm or more and 3.0 µm or less.
  5. 　前記粘着剤層と前記基材との間に第二ハードコート層をさらに有し、
    　前記第二ハードコート層は、多官能アクリル系樹脂を含む、請求項１から請求項４のいずれか一項に記載の粘着シート。     Further having a second hard coat layer between the pressure-sensitive adhesive layer and the substrate,
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the second hard coat layer contains a polyfunctional acrylic resin.
  6. 　前記有機無機ハイブリッド材料は、
    　シリカ微粒子と重合性不飽和基を有する有機化合物とを結合させた材料、並びに
    　活性エネルギー線硬化型樹脂を含む、請求項１から請求項５のいずれか一項に記載の粘着シート。     The organic-inorganic hybrid material is
    The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, comprising a material obtained by bonding silica fine particles and an organic compound having a polymerizable unsaturated group, and an active energy ray-curable resin.
PCT/JP2016/075603 2015-09-01 2016-09-01 Adhesive sheet WO2017038916A1 (en)

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