WO2017038918A1 - 粘着シート - Google Patents
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- WO2017038918A1 WO2017038918A1 PCT/JP2016/075605 JP2016075605W WO2017038918A1 WO 2017038918 A1 WO2017038918 A1 WO 2017038918A1 JP 2016075605 W JP2016075605 W JP 2016075605W WO 2017038918 A1 WO2017038918 A1 WO 2017038918A1
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- pressure
- sensitive adhesive
- adhesive sheet
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to an adhesive sheet.
- Patent Document 1 describes an adhesive tape that is used by being attached when a substrate-less semiconductor chip that does not use a metal lead frame is resin-sealed.
- Patent Document 1 discloses a pressure-sensitive adhesive tape in which an adhesive layer having an elastic modulus at 180 ° C. of 1.0 ⁇ 10 5 Pa or more is provided on one side or both sides of a base material layer having a glass transition temperature exceeding 180 ° C. Is described.
- An object of the present invention is to provide a pressure-sensitive adhesive sheet that can prevent a semiconductor element from moving and being displaced when sealing a semiconductor element on a pressure-sensitive adhesive sheet.
- a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer, A pressure-sensitive adhesive sheet having a value obtained by a die pull test for silicon in an atmosphere of 100 ° C. of 3.0 N / die or more is provided.
- the storage elastic modulus of the substrate at 100 ° C. is preferably 1 ⁇ 10 7 Pa or more.
- the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
- the acrylic pressure-sensitive adhesive composition preferably includes an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer.
- the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
- a pressure-sensitive adhesive sheet that can prevent a semiconductor element from moving and being displaced when sealing a semiconductor element on the pressure-sensitive adhesive sheet.
- FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
- the pressure-sensitive adhesive sheet 10 has a base material 11 and a pressure-sensitive adhesive layer 12. On the pressure-sensitive adhesive layer 12, a release sheet RL is laminated as shown in FIG.
- the base material 11 has a first base material surface 11a and a second base material surface 11b opposite to the first base material surface 11a.
- the shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a sheet shape, a tape shape, and a label shape.
- the substrate 11 is a member that supports the pressure-sensitive adhesive layer 12.
- a sheet material such as a synthetic resin film can be used.
- synthetic resin films include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film.
- examples of the substrate 11 include these cross-linked films and laminated films.
- the base material 11 preferably includes a polyester-based resin, and more preferably includes a material having a polyester-based resin as a main component.
- the material having a polyester-based resin as a main component means that the ratio of the mass of the polyester-based resin to the total mass of the material constituting the substrate is 50% by mass or more.
- the polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins. Is preferred, and polyethylene terephthalate resin is more preferred.
- a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a polyethylene terephthalate film is more preferable.
- the oligomer contained in the polyester film is derived from a polyester-forming monomer, dimer, trimer or the like.
- the lower limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 ⁇ 10 7 Pa or more, and more preferably 1 ⁇ 10 8 Pa or more, from the viewpoint of dimensional stability during processing.
- the upper limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 ⁇ 10 12 Pa or less from the viewpoint of workability.
- the storage elastic modulus is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring apparatus.
- the substrate to be measured is cut into a width of 5 mm and a length of 20 mm, and a viscoelasticity measuring device (manufactured by TA Instruments, DMAQ800) is used, and the storage viscoelasticity at 100 ° C. is measured at a frequency of 1 Hz and a tensile mode. taking measurement.
- a viscoelasticity measuring device manufactured by TA Instruments, DMAQ800
- the first substrate surface 11a may be subjected to at least one surface treatment such as a primer treatment, a corona treatment, a plasma treatment or the like in order to enhance the adhesion with the pressure-sensitive adhesive layer 12.
- the first base material surface 11a of the base material 11 may be subjected to an adhesive treatment by applying an adhesive.
- the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate include acrylic, rubber-based, silicone-based, and urethane-based pressure-sensitive adhesives.
- the thickness of the substrate 11 is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 15 ⁇ m or more and 300 ⁇ m or less, and further preferably 20 ⁇ m or more and 250 ⁇ m or less.
- required by the die pull test with respect to the silicon in the 100 degreeC atmosphere of the adhesive layer 12 needs to be 3.0 N / die or more. If the value obtained in the die pull test is 3.0 N / die or more, when the semiconductor element on the pressure-sensitive adhesive sheet is sealed, the semiconductor element moves and is displaced (hereinafter sometimes referred to as die shift). Can be prevented.
- die shift is presumed that the semiconductor element does not slide sideways on the pressure-sensitive adhesive layer 12 but is once again peeled off from the pressure-sensitive adhesive layer 12 and moved again after moving.
- the value obtained by this die pull test is preferably 4.0 N / die or more, and preferably 5.0 N / die or more and 15 N / die or less. Is more preferable. If the value obtained by the die pull test is less than 3.0 N / die, there is a possibility of die shifting, and if it exceeds 15 N / die, the circuit surface of the semiconductor element is destroyed when the semiconductor element is peeled from the adhesive sheet. there is a possibility.
- silicone in the 100 degreeC atmosphere of the adhesive layer 12 can be measured by the method as described in the Example mentioned later.
- required by this die pull test the following methods are mentioned.
- required by this die pull test can be adjusted by changing the composition of the adhesive composition used with the adhesive layer 12.
- the pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various types of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12.
- Examples of the adhesive contained in the adhesive layer 12 include rubber-based, acrylic-based, silicone-based, polyester-based, and urethane-based.
- the kind of adhesive is selected in consideration of the use and the kind of adherend to be attached.
- the pressure-sensitive adhesive layer 12 preferably contains an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
- the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer. . Moreover, when the adhesive layer 12 contains an acrylic adhesive composition, it is preferable that the acrylic copolymer and the adhesion promoter are included.
- the acrylic copolymer is preferably a copolymer having 2-ethylhexyl acrylate as a main monomer.
- the adhesive aid preferably contains a rubber-based material having a reactive group as a main component.
- 2-ethylhexyl acrylate is the main monomer, and the ratio of the mass of the copolymer component derived from 2-ethylhexyl acrylate to the total mass of the acrylic copolymer is 50% by mass or more. Means.
- the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, and 60% by mass or more and 95% by mass or less. It is preferable that it is 80 mass% or more and 95 mass% or less, and it is still more preferable that it is 85 mass% or more and 93 mass% or less.
- the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 60% by mass or more, the adhesive strength does not become too high after heating, and the adhesive sheet is more easily peeled off from the adherend, and 80% by mass or more. If it is, it will become still easier to peel. If the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, the initial adhesive force is insufficient and the substrate is deformed during heating, or the adhesive sheet is peeled off from the adherend due to the deformation. Can be prevented.
- the type and number of copolymer components other than 2-ethylhexyl acrylate in the acrylic copolymer are not particularly limited.
- a functional group-containing monomer having a reactive functional group is preferable.
- a reactive functional group of a 2nd copolymer component when using the crosslinking agent mentioned later, it is preferable that it is a functional group which can react with the said crosslinking agent.
- This reactive functional group is preferably at least one substituent selected from the group consisting of, for example, a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. These substituents are more preferable, and a carboxyl group is still more preferable.
- Examples of the monomer having a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
- carboxyl group-containing monomers acrylic acid is preferable from the viewpoint of reactivity and copolymerization.
- a carboxyl group-containing monomer may be used independently and may be used in combination of 2 or more type.
- Examples of the monomer having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 And (meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of hydroxyl reactivity and copolymerization.
- a hydroxyl-containing monomer may be used independently and may be used in combination of 2 or more type.
- “(meth) acrylic acid” is a notation used to represent both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
- Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
- Examples of other copolymer components in the acrylic copolymer include (meth) acrylic acid alkyl esters having an alkyl group with 2 to 20 carbon atoms.
- Examples of the (meth) acrylic acid alkyl ester include, for example, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and (meth) acrylic acid n.
- Examples of other copolymer components in the acrylic copolymer include, for example, alkoxyalkyl group-containing (meth) acrylic acid ester, (meth) acrylic acid ester having an aliphatic ring, and (meth) acrylic acid having an aromatic ring.
- alkoxyalkyl group-containing (meth) acrylic acid ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
- examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate.
- examples of the (meth) acrylic acid ester having an aromatic ring examples include phenyl (meth) acrylate.
- non-crosslinkable acrylamides examples include acrylamide and methacrylamide.
- Examples of the (meth) acrylic acid ester having a non-crosslinkable tertiary amino group include (meth) acrylic acid (N, N-dimethylamino) ethyl and (meth) acrylic acid (N, N-dimethylamino). Propyl.
- a copolymer component derived from a monomer having a nitrogen atom-containing ring is also preferable from the viewpoint of improving the polarity of the pressure-sensitive adhesive and improving the adhesion and the adhesive strength.
- Monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Examples include vinyl morpholine, N-vinyl caprolactam, and N- (meth) acryloyl morpholine. Of these, N- (meth) acryloylmorpholine is preferred. 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 adhesion promoter contains a rubber-based material having a reactive group as a main component.
- the pressure-sensitive adhesive composition contains a reactive pressure-sensitive adhesive aid, the adhesive residue can be reduced.
- the content of the adhesion assistant in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content of the adhesion assistant in the pressure-sensitive adhesive composition is 3% by mass or less, there is a possibility that adhesive residue may remain, and if it exceeds 50% by mass, the adhesive strength may be reduced.
- including a rubber-based material having a reactive group as a main component means that the proportion of the mass of the rubber-based material having a reactive group in the total mass of the adhesive aid exceeds 50% by mass.
- the ratio of the rubber-based material having a reactive group in the adhesion assistant is preferably more than 50% by mass, and more preferably 80% by mass or more. It is also preferable that the adhesion assistant is made of a rubber-based material having a substantially reactive group.
- the reactive group is preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group.
- the reactive group possessed by the rubber material may be one type or two or more types.
- the rubber-based material having a hydroxyl group may further have the aforementioned reactive group.
- the number of reactive groups may be one per molecule constituting the rubber-based material, or two or more.
- the rubber-based material is not particularly limited, but a polybutadiene-based resin and a hydrogenated product of a polybutadiene-based resin are preferable, and a hydrogenated product of a polybutadiene-based resin is more preferable.
- the polybutadiene-based resin include resins having 1,4-repeating units, resins having 1,2-repeating units, and resins having both 1,4-repeating units and 1,2-repeating units.
- the hydrogenated product of the polybutadiene resin of the present embodiment includes a hydride of a resin having these repeating units.
- the polybutadiene resin and the hydrogenated product of the polybutadiene resin preferably have reactive groups at both ends.
- the reactive groups at both ends may be the same or different.
- the reactive groups at both ends are preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group.
- a hydroxyl group is preferred.
- both ends are hydroxyl groups.
- the pressure-sensitive adhesive composition according to the present embodiment preferably contains a cross-linked product obtained by cross-linking a composition containing a cross-linking agent in addition to the acrylic copolymer and the pressure-sensitive adhesive aid.
- the solid content of the pressure-sensitive adhesive composition substantially consists of a cross-linked product obtained by cross-linking the above-mentioned acrylic copolymer, the pressure-sensitive adhesive aid, and the cross-linking agent as described above.
- “substantially” means that the solid content of the pressure-sensitive adhesive composition is composed only of the cross-linked product, excluding trace amounts of impurities that are inevitably mixed in the pressure-sensitive adhesive.
- examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent.
- These cross-linking agents may be used alone or in combination of two or more.
- a cross-linking agent isocyanate-based cross-linking agent whose main component is a compound having an isocyanate group is preferable.
- isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
- Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate,
- the polyisocyanate compound may be a trimethylolpropane adduct-type modified product of the above-described compound, a burette-type modified product reacted with water, or an isocyanurate-type modified product having an isocyanurate ring.
- crosslinking agent mainly comprising a compound having an isocyanate group means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. To do.
- the content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If content of the crosslinking agent in an adhesive composition is in such a range, the adhesiveness of the layer (adhesive layer) containing an adhesive composition and a to-be-adhered body (for example, base material) will be improved. It is possible to shorten the curing period for stabilizing the adhesive property after the production of the adhesive sheet.
- the isocyanate-based crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product).
- the compound having an isocyanurate ring is preferably blended in an amount of 0.7 to 1.5 equivalents with respect to the hydroxyl equivalent of the acrylic copolymer. If the compounding quantity of the compound which has an isocyanurate ring is 0.7 equivalent or more, the adhesive strength will not become too high after heating, the adhesive sheet will be easily peeled off, and the adhesive residue can be reduced. If the compounding quantity of the compound which has an isocyanurate ring is 1.5 equivalent or less, it can prevent that an initial stage adhesive force becomes low too much, or can prevent the adhesiveness fall.
- the pressure-sensitive adhesive composition in this embodiment contains a crosslinking agent
- the pressure-sensitive adhesive composition preferably further contains a crosslinking accelerator.
- the crosslinking accelerator is preferably selected and used as appropriate according to the type of the crosslinking agent.
- the pressure-sensitive adhesive composition contains a polyisocyanate compound as a crosslinking agent
- a silicone-type adhesive composition contains an addition polymerization type silicone resin.
- a silicone pressure-sensitive adhesive composition containing an addition polymerization type silicone resin is referred to as an addition reaction type silicone pressure-sensitive adhesive composition.
- the addition reaction type silicone pressure-sensitive adhesive composition contains a main agent and a crosslinking agent.
- the addition reaction type silicone pressure-sensitive adhesive composition has an advantage that it can be used only by primary curing at a low temperature and does not require secondary curing at a high temperature.
- the conventional peroxide-curing silicone pressure-sensitive adhesive requires secondary curing at a high temperature such as 150 ° C. or higher. Therefore, by using the addition reaction type silicone pressure-sensitive adhesive composition, it is possible to produce a pressure-sensitive adhesive sheet at a relatively low temperature, use the base material 11 having excellent energy economy and relatively low heat resistance. Thus, the pressure-sensitive adhesive sheet 10 can be manufactured. Further, since no by-product is produced during curing unlike the peroxide-curing silicone pressure-sensitive adhesive, there are no problems such as odor and corrosion.
- the addition-reaction type silicone pressure-sensitive adhesive composition is generally composed of a main agent composed of a mixture of a silicone resin component and a silicone rubber component, a hydrosilyl group (SiH group) -containing crosslinking agent, and a curing catalyst used as necessary. Consists of.
- the silicone resin component is a network-structured organopolysiloxane obtained by hydrolyzing organochlorosilane and organoalkoxysilane and then performing a dehydration condensation reaction.
- the silicone rubber component is a diorganopolysiloxane having a linear structure.
- both the silicone resin component and the silicone rubber component are a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like.
- the aforementioned organo groups are partially vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth) acryloyl, (meth) acryloylmethyl, (meth) acryloylpropyl, and cyclohexenyl.
- Substituting with an unsaturated group such as a group.
- An organo group having a vinyl group that is easily available industrially is preferred.
- crosslinking proceeds by an addition reaction between an unsaturated group and a hydrosilyl group to form a network structure, thereby exhibiting adhesiveness.
- the number of unsaturated groups such as vinyl groups is usually from 0.05 to 3.0, preferably from 0.1 to 2.5, per 100 organo groups.
- organopolysiloxane described above examples include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 per 100 methyl groups), Toray Dow Corning BY23-753 manufactured by the company (the number of vinyl groups is 0.1 per 100 methyl groups) and BY24-162 (the number of vinyl groups is 1.4 per 100 methyl groups) Things).
- SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Toray Dow Corning can also be used.
- organopolysiloxane which is a silicone resin component
- silicone rubber component KS-3800 (manufactured by Shin-Etsu Chemical Co., Ltd.) 7.6 for 100 methyl groups), BY24-162 made by Toray Dow Corning (number of vinyl groups is 1.4 for 100 methyl groups), BY24- 843 (having no unsaturated group) and SD-7292 (the number of vinyl groups is 5.0 with respect to 100 methyl groups).
- Specific examples of the addition reaction type silicone as described above are described in, for example, JP-A-10-219229.
- the crosslinking agent is usually 0.5 to 10 hydrogen atoms bonded to silicon atoms, preferably 1 or more to one unsaturated group such as a vinyl group of the silicone resin component and the silicone rubber component. It mix
- the number By setting the number to 0.5 or more, the reaction between the unsaturated group such as a vinyl group and the hydrosilyl group does not proceed completely, thereby preventing poor curing.
- the addition reaction type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst together with the aforementioned addition reaction type silicone component (main agent comprising a silicone resin component and a silicone rubber component) and a crosslinking agent.
- This curing catalyst is used to accelerate the hydrosilylation reaction between the unsaturated group in the silicone resin component and the silicone rubber component and the Si—H group in the crosslinking agent.
- the curing catalyst is a platinum-based catalyst, that is, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol solution, a reaction product of chloroplatinic acid and an olefin compound, chloroplatinic acid and vinyl Examples thereof include a reaction product with a group-containing siloxane compound, a platinum-olefin complex, a platinum-vinyl group-containing siloxane complex, and a platinum-phosphorus complex.
- Specific examples of the curing catalyst as described above are described in, for example, JP-A-2006-28311 and JP-A-10-147758. More specifically, commercially available products include SRX-212 manufactured by Toray Dow Corning and PL-50T manufactured by Shin-Etsu Chemical.
- the blending amount of the curing catalyst is usually 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass ppm or more and 500 mass ppm or less with respect to the total amount of the silicone resin component and the silicone rubber component as platinum content.
- curability is lowered and the crosslinking density is reduced, that is, the adhesive force and the cohesive force (holding force) are prevented from being reduced. While preventing, the stability of an adhesive layer can be hold
- addition reaction type silicone pressure-sensitive adhesive composition adhesive force is exhibited even at room temperature by blending the above-mentioned components, but the addition reaction type silicone pressure-sensitive adhesive composition is applied to the substrate 11 or a release sheet described later. From the standpoint of stability of adhesive strength, the base material 11 and the release sheet are bonded together, and then a heating or active energy ray is irradiated to promote the crosslinking reaction of the silicone resin component and the silicone rubber component by the crosslinking agent. preferable.
- the heating temperature is usually 60 ° C. or higher and 140 ° C. or lower, preferably 80 ° C. or higher and 130 ° C. or lower.
- the crosslinking between the silicone resin component and the silicone rubber component is insufficient and the adhesive strength is prevented from becoming insufficient.
- heating at 140 ° C. or lower the base sheet is thermally contracted and wrinkled. Occurrence, deterioration, or discoloration can be prevented.
- active energy rays having energy quanta in electromagnetic waves or charged particle beams that is, activities such as ultraviolet rays or electron beams can be used.
- a photopolymerization initiator is not required.
- a photopolymerization initiator is present.
- the photopolymerization initiator in the case of irradiation with ultraviolet rays is not particularly limited, and any photopolymerization initiator that has been conventionally used in ultraviolet curable resins can be appropriately selected and used. it can.
- photopolymerization initiator examples include benzoins, benzophenones, acetophenones, ⁇ -hydroxy ketones, ⁇ -amino ketones, ⁇ -diketones, ⁇ -diketone dialkyl acetals, anthraquinones, thioxanthones, and other compounds. Is mentioned. These photopolymerization initiators may be used alone or in combination of two or more. Further, the amount used is usually 0.01 parts by mass or more and 30 parts by mass or less, preferably 0.05 parts by mass with respect to 100 parts by mass of the total amount of the addition reaction type silicone component and the crosslinking agent used as the main agent. It is selected in the range of 20 parts by mass or less.
- a pressure-sensitive adhesive sheet having a stable adhesive force can be obtained by crosslinking by irradiation with heat or active energy rays.
- the acceleration voltage of the electron beam is generally 130 kV or more and 300 kV or less, preferably 150 kV or more and 250 kV or less. Irradiation at an acceleration voltage of 130 kV or more can prevent the silicone resin component and the silicone rubber component from being insufficiently crosslinked and prevent the adhesive force from becoming insufficient. By irradiation at an acceleration voltage of 300 kV or less, the adhesive It can prevent that a layer and a base material sheet deteriorate or discolor. A preferable range of the beam current is 1 mA or more and 100 mA or less.
- the dose of the irradiated electron beam is preferably 1 Mrad to 70 Mrad, and more preferably 2 Mrad to 20 Mrad. Irradiation with a dose of 1 Mrad or more can prevent the pressure-sensitive adhesive layer and the base sheet from being deteriorated or discolored, and can prevent the adhesiveness from becoming insufficient due to insufficient crosslinking. By irradiating with a dose of 70 Mrad or less, it is possible to prevent the cohesive force from being reduced due to deterioration or discoloration of the pressure-sensitive adhesive layer, and it is possible to prevent the base sheet from being deteriorated or contracted. The irradiation amount in the case of ultraviolet irradiation is appropriately selected.
- the light amount is from 100 mJ / cm 2 to 500 mJ / cm 2 and the illuminance is from 10 mW / cm 2 to 500 mW / cm 2 .
- Heating and irradiation with active energy rays are preferably performed in a nitrogen atmosphere in order to prevent reaction inhibition by oxygen.
- the thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the use of the pressure-sensitive adhesive sheet 10.
- the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 ⁇ m or more and 60 ⁇ m or less, and more preferably 10 ⁇ m or more and 50 ⁇ m or less. If the thickness of the pressure-sensitive adhesive layer 12 is too thin, the pressure-sensitive adhesive layer 12 may not follow the irregularities on the circuit surface of the semiconductor chip, and a gap may be generated. For example, an interlayer insulating material and a sealing resin may enter the gap, and the wiring connection electrode pad on the chip circuit surface may be blocked.
- the pressure-sensitive adhesive layer 12 When the thickness of the pressure-sensitive adhesive layer 12 is 5 ⁇ m or more, the pressure-sensitive adhesive layer 12 easily follows the unevenness of the chip circuit surface, and the generation of a gap can be prevented. If the thickness of the pressure-sensitive adhesive layer 12 is too thick, the semiconductor chip sinks into the pressure-sensitive adhesive layer, and there is a risk that a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip occurs. If such a step occurs, the wiring may be disconnected during rewiring. If the thickness of the pressure-sensitive adhesive layer 12 is 60 ⁇ m or less, a step is hardly generated.
- the pressure-sensitive adhesive composition may contain other components as long as the effects of the present invention are not impaired.
- other components that can be included in the pressure-sensitive adhesive composition include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, antiseptics, antifungal agents, and plastics. Agents, antifoaming agents, colorants, fillers, wettability adjusting agents and the like.
- the addition reaction type silicone pressure-sensitive adhesive composition may contain a non-reactive polyorganosiloxane such as dimethylsiloxane and dimethyldiphenylsiloxane as an additive.
- 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 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 attached to an adherend (copper foil or polyimide film), heated at 100 ° C. and 30 minutes, and further heated at 190 ° C. and 1 hour.
- the adhesive force at room temperature with respect to the copper foil and the adhesive force at room temperature with respect to the polyimide film of the adhesive layer 12 are 0.7 N / 25 mm or more and 2.0 N / 25 mm or less, respectively. 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.
- the adhesive force after a heating is 2.0 N / 25mm or less, peeling force will not become high too much and it will be easy to peel the adhesive sheet 10 from a to-be-adhered body.
- room temperature is a temperature of 22 ° C. or higher and 24 ° C. or lower.
- the adhesive strength is a value measured by a 180 ° peeling method at a pulling speed of 300 mm / min and a width of 25 mm of the adhesive sheet.
- the manufacturing method of the adhesive sheet 10 is not particularly limited.
- the adhesive sheet 10 is manufactured through the following processes. First, an adhesive is applied on the first substrate 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.
- another manufacturing method of the adhesive sheet 10 it manufactures through the following processes. First, an adhesive is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12, and the first base material surface 11 a of the base material 11 is bonded to the pressure-sensitive adhesive layer 12.
- 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 (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) and a step of peeling the pressure-sensitive adhesive sheet (peeling step) are carried out after thermosetting.
- the frame member 20 is formed in a lattice shape and has a plurality of openings 21.
- the frame member 20 is preferably formed of a material having heat resistance. Examples of the material of the frame member 20 include metals such as copper and stainless steel, and heat resistant resins such as polyimide resin and glass epoxy resin.
- the opening 21 is a hole that penetrates the front and back surfaces of the frame member 20.
- the shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame.
- the depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
- FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
- the semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces.
- a semiconductor chip CP semiconductor element
- the dicing apparatus is not particularly limited, and a known dicing apparatus can be used.
- the dicing conditions are not particularly limited. Note that a laser dicing method or a stealth dicing method may be used instead of the dicing method using a dicing blade.
- an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP.
- the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding process, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
- the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden.
- the energy ray polymerizable compound When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced.
- the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable.
- UV ultraviolet rays
- EB electron beams
- the energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
- the material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin.
- the epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
- the method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited. In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example.
- the sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A.
- the temperature condition range for heat curing by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
- a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used.
- the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be 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.
- heating and pressure 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 pressurization is released, the pressure is removed from the sealing device, and left in the oven, and the temperature is maintained at 150 ° C. or higher for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
- the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process).
- the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. .
- the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20.
- corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
- the plate member for example, a metal plate such as stainless steel can be used.
- the sealing body 50 When the pressure-sensitive adhesive sheet 10 is peeled after the thermosetting step, the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained. Hereinafter, this may be referred to as a sealing body 50.
- FIG. 2D The schematic diagram explaining the process of sticking the reinforcing member 40 to the sealing body 50 is shown by FIG. 2D.
- a rewiring process and a bumping process for forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed.
- a process (reinforcing member attaching process) of attaching the reinforcing member 40 to the sealing body 50 is performed as necessary. May be.
- FIG. As illustrated in FIG. 2D, the sealing body 50 is supported in a state of being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
- the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42.
- the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a polyimide resin and a glass epoxy resin.
- the adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50.
- the adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
- the adhesive layer 42 is preferably a glass cloth including a thermoplastic resin.
- the thermoplastic resin contained bismaleimide triazine resin (BT resin) is preferable.
- the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure.
- the sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time.
- the conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa.
- a metal plate such as stainless steel can be used as the plate-like member.
- FIG. 2E The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
- the adhesive sheet 10 when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent.
- peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree
- the peeling angle ⁇ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less.
- the reinforcing member 40 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed. Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step).
- a method for dividing the sealing body 50 into individual pieces is not particularly limited.
- the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer.
- the step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like.
- the semiconductor chip CP it is possible to prevent the semiconductor chip CP from moving and being displaced in the sealing process.
- the value obtained by the die pull test for silicon in the atmosphere of 100 ° C. of the pressure-sensitive adhesive layer 12 is 3.0 N / die or more, and the semiconductor chip CP is relatively peeled from the pressure-sensitive adhesive layer 12. It becomes difficult. Therefore, in the sealing process, the semiconductor chip CP can be prevented from peeling from the adhesive layer 12, and the semiconductor chip CP can be prevented from moving and being displaced.
- the adhesive sheet 10 may be a single wafer or may be provided in a state where a plurality of adhesive sheets 10 are laminated.
- the pressure-sensitive adhesive layer 12 may be covered with the base material 11 of another pressure-sensitive adhesive sheet to be laminated.
- the adhesive sheet 10 may be a long sheet or may be provided in a state of being wound in a roll. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
- the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
- the aspect which sticks the frame member 20 to the adhesive sheet 10 was mentioned as an example, However, This invention is not limited to such an aspect.
- the pressure-sensitive adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using the frame member 20.
- D As shown in FIG. 3D, semiconductor chips CP (eight) are placed at 2.5 cm intervals on the adhesive layer 12 using tweezers so that the circuit surface CPA is in contact with the adhesive layer 12. did. At that time, the semiconductor chip CP was gently and vertically installed so that the corner of the semiconductor chip CP was not applied to the adhesive layer 12.
- Atmosphere temperature 100 °C Test speed: 200 ⁇ m / s (H)
- a die pull test is performed on another semiconductor chip CP as in (g) above until the number of valid data becomes six. The force on one die was determined. And the average value of the obtained effective data was made into the value (unit: N / die) calculated
- Example 1 Preparation of pressure-sensitive adhesive composition The following materials (polymer, pressure-sensitive adhesive, cross-linking agent, and diluting solvent) were blended and sufficiently stirred, and the pressure-sensitive adhesive liquid for application according to Example 1 (pressure-sensitive adhesive composition) Prepared).
- Acrylic ester copolymer 40 parts by mass (solid content)
- the acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
- Adhesion aid hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000), 5 parts by mass (solid content)
- Adhesion aid polyetheramine derivative [manufactured by NOF Corporation; DT-203], 1.5 parts by mass (solid content)
- Crosslinking agent Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate; manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX), 3.5 parts by mass (solid content)
- Diluting solvent Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
- pressure-sensitive adhesive layer 38 Preparation of pressure-sensitive adhesive layer 38 ⁇ m transparent polyethylene terephthalate provided with a silicone-based release layer so that the thickness of the prepared pressure-sensitive adhesive solution for coating after drying using a comma coater (registered trademark) is 50 ⁇ m. It is applied to the release layer side of a release film consisting of a film [manufactured by Lintec Corporation; SP-PET382150], heated at 90 ° C. for 90 seconds, and then heated at 115 ° C. for 90 seconds to dry the coating film. I let you.
- Example 2 The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer was different from that in Example 1.
- the adhesion promoter used in Example 2 was 5 parts by mass (solid content) of hydroxylated hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd .; GI-1000).
- Example 3 In Example 3, a silicone-based adhesive was used.
- Silicone-based adhesive A (SD4580PSA) 18 parts by mass (solid content) 40 parts by mass (solid content) of silicone-based adhesive B (SD4587L), Catalyst A (NC-25 CAT) 0.3 parts by mass (solid content)
- Catalyst B (CAT-SRX-212) 0.65 parts by mass (solid content)
- primer (BY24-712) 5 parts by mass (solid content) was prepared.
- the materials used for the pressure-sensitive adhesive composition of Example 3 are all manufactured by Toray Dow Corning Co., Ltd.
- the pressure-sensitive adhesive liquid for application according to Example 3 was applied to a substrate and dried so that the thickness after drying was 20 ⁇ m, thereby preparing a pressure-sensitive adhesive layer. Drying conditions were 100 ° C. and 1 minute.
- the base material used in Example 3 was a polyimide film [manufactured by Toray DuPont Co., Ltd .; Kapton 100H, thickness 25 ⁇ m, storage elastic modulus at 100 ° C. 3.1 ⁇ 10 9 Pa].
- the pressure-sensitive adhesive layer produced on the surface of the release film was bonded to the base material to obtain a pressure-sensitive adhesive sheet according to Example 3.
- Example 4 The pressure-sensitive adhesive sheet according to Example 4 was produced in the same manner as in Example 2 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 2.
- the polymer used in Example 4 was composed of 80.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, 12% by mass of 4-acryloylmorpholine, and 0.2% by mass of acrylic acid. Prepared by copolymerization.
- Comparative Example 1 The pressure-sensitive adhesive sheet according to Comparative Example 1 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer was different from that in Example 1.
- the adhesion promoter used in Comparative Example 1 was 5 parts by mass (solid content) of tributyl acetylcitrate (manufactured by Taoka Chemical Co., Ltd.).
- Table 1 shows the evaluation results of the adhesive sheets according to Examples 1 to 4 and Comparative Example 1.
- the pressure-sensitive adhesives used in Examples 1 to 4 and Comparative Example 1 are shown in Table 1.
- Adhesive sheet 11 ... Base material, 12 ... Adhesive layer.
Abstract
Description
このようなWLPの製造方法においては、従来、基板上に固定するチップを、別の支持体上に固定することが必要となる。そこで、例えば、特許文献1には、金属製のリードフレームを用いない基板レス半導体チップを樹脂封止する際に、貼着して使用される粘着テープが記載されている。特許文献1には、ガラス転移温度が180℃を超える基材層の片面、または、両面に、180℃での弾性率が1.0×105Pa以上の粘着剤層を設けてなる粘着テープが記載されている。
(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及び粘着剤層12を有する。粘着剤層12の上には、図1に示されているように、剥離シートRLが積層されている。
基材11は、第一基材面11a、及び第一基材面11aとは反対側の第二基材面11bを有する。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。
基材11は、粘着剤層12を支持する部材である。
基材11としては、例えば、合成樹脂フィルムなどのシート材料などを用いることができる。合成樹脂フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニル共重合体フィルム、アイオノマー樹脂フィルム、エチレン・(メタ)アクリル酸共重合体フィルム、エチレン・(メタ)アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、及びポリイミドフィルム等が挙げられる。その他、基材11としては、これらの架橋フィルム及び積層フィルム等が挙げられる。
基材11としては、ポリエチレンテレフタレートフィルム、及び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、トリマーなどに由来する。
本実施形態においては、粘着剤層12の100℃の雰囲気におけるシリコンに対するダイプル試験で求められる値が3.0N/ダイ以上であることが必要である。ダイプル試験で求められる値が3.0N/ダイ以上であれば、粘着シート上の半導体素子を封止する際に、半導体素子が移動して位置がずれること(以下ダイシフトと称する場合がある)を防止できる。このような理由は、必ずしも明らかではないが、次のようなメカニズムによると推定する。すなわち、ダイシフトは、半導体素子が粘着剤層12上を横滑りしているわけではなく、粘着剤層12から一度半導体素子が剥離し、移動した後に再び粘着していると推定する。そして、ダイプル試験で求められる値が高いほど、半導体素子が粘着剤層12から剥離することが困難となることを示す。そのため、ダイプル試験で求められる値とダイシフトとの間に相関関係があると推定する。
また、半導体素子の位置ずれをより確実に防止する観点から、このダイプル試験で求められる値は、4.0N/ダイ以上であることが好ましく、5.0N/ダイ以上15N/ダイ以下であることがより好ましい。ダイプル試験で求められる値が、3.0N/ダイ未満であると、ダイシフトする可能性があり、15N/ダイを超えると粘着シートから半導体素子を剥離するときに、半導体素子の回路面を破壊する可能性がある。
なお、このダイプル試験で求められる値を調整する方法としては、以下のような方法が挙げられる。例えば、粘着剤層12で用いる粘着剤組成物の組成を変更することで、このダイプル試験で求められる値を調整できる。
粘着剤層12がアクリル系粘着剤組成物を含む場合、アクリル系粘着剤組成物は、アクリル酸2-エチルヘキシルを主たるモノマーとするアクリル系共重合体を含むことが好ましい。
また、粘着剤層12がアクリル系粘着剤組成物を含む場合、アクリル系共重合体と、粘着助剤と、を含んでいることが好ましい。アクリル系共重合体は、アクリル酸2-エチルヘキシルを主たるモノマーとする共重合体であることが好ましい。粘着助剤は、反応性基を有するゴム系材料を主成分として含むことが好ましい。
アルコキシアルキル基含有(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸メトキシメチル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシメチル、及び(メタ)アクリル酸エトキシエチルが挙げられる。
脂肪族環を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸シクロヘキシルが挙げられる。
芳香族環を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸フェニルが挙げられる。
非架橋性のアクリルアミドとしては、例えば、アクリルアミド、及びメタクリルアミドが挙げられる。
非架橋性の3級アミノ基を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸(N,N-ジメチルアミノ)エチル、及び(メタ)アクリル酸(N,N-ジメチルアミノ)プロピルが挙げられる。
アクリル系共重合体におけるその他の共重合体成分として、粘着剤の極性を向上させ、密着性及び粘着力を向上させる観点から、窒素原子含有環を有するモノマーに由来する共重合体成分も好ましい。
窒素原子含有環を有するモノマーとしては、N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピペリドン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルモルホリン、N-ビニルカプロラクタム、及びN-(メタ)アクリロイルモルホリン等が挙げられる。これらの中でも、N-(メタ)アクリロイルモルホリンが好ましい。
これらのモノマーは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
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。
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。
本明細書において、反応性基を有するゴム系材料を主成分として含むとは、粘着助剤全体の質量に占める反応性基を有するゴム系材料の質量の割合が50質量%を超えることを意味する。本実施形態においては、粘着助剤における反応性基を有するゴム系材料の割合は、50質量%超であることが好ましく、80質量%以上であることがより好ましい。粘着助剤が実質的に反応性基を有するゴム系材料からなることも好ましい。
ポリブタジエン系樹脂としては、1,4-繰り返し単位を有する樹脂、1,2-繰り返し単位を有する樹脂、並びに1,4-繰り返し単位及び1,2-繰り返し単位の両方を有する樹脂が挙げられる。本実施形態のポリブタジエン系樹脂の水素添加物は、これらの繰り返し単位を有する樹脂の水素化物も含む。
本実施形態において、粘着剤組成物の耐熱性及び粘着力を向上させる観点から、これら架橋剤の中でも、イソシアネート基を有する化合物を主成分とする架橋剤(イソシアネート系架橋剤)が好ましい。イソシアネート系架橋剤としては、例えば、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、1,3-キシリレンジイソシアネート、1,4-キシリレンジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、ジフェニルメタン-2,4’-ジイソシアネート、3-メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン-4,4’-ジイソシアネート、ジシクロヘキシルメタン-2,4’-ジイソシアネート、及びリジンイソシアネート等の多価イソシアネート化合物が挙げられる。
また、多価イソシアネート化合物は、前述の化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、またはイソシアヌレート環を有するイソシアヌレート型変性体であってもよい。
本明細書において、イソシアネート基を有する化合物を主成分とする架橋剤とは、架橋剤を構成する成分全体の質量に占めるイソシアネート基を有する化合物の質量の割合が50質量%以上であることを意味する。
粘着剤層12がシリコーン系粘着剤組成物を含む場合、シリコーン系粘着剤組成物は、付加重合型シリコーン樹脂を含むことが好ましい。本明細書において、付加重合型シリコーン樹脂を含むシリコーン系粘着剤組成物を付加反応型シリコーン系粘着剤組成物と称する。
したがって、付加反応型シリコーン系粘着剤組成物を用いることにより、比較的低温での粘着シートの製造が可能となり、エネルギー経済性に優れており、かつ、比較的耐熱性の低い基材11を用いて粘着シート10を製造することも可能となる。また、過酸化物硬化型シリコーン系粘着剤のように硬化時に副生物を生じないので、臭気及び腐食などの問題もない。
シリコーン樹脂成分は、オルガノクロルシラン及びオルガノアルコキシシランを加水分解した後、脱水縮合反応を行うことにより得られる網状構造のオルガノポリシロキサンである。
シリコーンゴム成分は、直鎖構造を有するジオルガノポリシロキサンである。
オルガノ基としては、シリコーン樹脂成分、及びシリコーンゴム成分ともに、メチル基、エチル基、プロピル基、ブチル基、フェニル基等である。前述のオルガノ基は、一部、ビニル基、ヘキセニル基、アリル基、ブテニル基、ペンテニル基、オクテニル基、(メタ)アクリロイル基、(メタ)アクリロイルメチル基、(メタ)アクリロイルプロピル基、及びシクロヘキセニル基のような不飽和基に置換されている。工業的に入手が容易なビニル基を有するオルガノ基が好ましい。付加反応型シリコーン系粘着剤組成物においては、不飽和基とヒドロシリル基との付加反応によって架橋が進行して網状の構造が形成され、粘着性が発現する。
ビニル基のような不飽和基の数は、オルガノ基100個に対して、通常0.05個以上3.0個以下、好ましくは、0.1個以上2.5個以下である。オルガノ基100個に対する不飽和基の数を0.05個以上とすることにより、ヒドロシリル基との反応性が低下して硬化しにくくなるのを防止して適度な粘着力を付与することができる。オルガノ基100個に対する不飽和基の数を3.0個以下とすることにより、粘着剤の架橋密度が高くなり粘着力及び凝集力が大きくなって被着面に悪影響を与えるのを防止する。
前述のように、シリコーン樹脂成分であるオルガノポリシロキサンは、通常、シリコーンゴム成分と混合して使用されるが、シリコーンゴム成分としては、信越化学工業社製のKS-3800(ビニル基の数がメチル基100個に対して7.6個であるもの)、東レ・ダウコーニング社製のBY24-162(ビニル基の数がメチル基100個に対して1.4個であるもの)、BY24-843(不飽和基を有していない)及びSD-7292(ビニル基の数がメチル基100個に対して5.0個であるもの)などが挙げられる。
前述のような付加反応型シリコーンの具体例は、例えば、特開平10-219229号公報に記載されている。
この硬化触媒は、シリコーン樹脂成分及びシリコーンゴム成分中の不飽和基と架橋剤中のSi-H基とのヒドロシリル化反応を促進させるために使用される。
硬化触媒としては、白金系の触媒、すなわち、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコール溶液との反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサン化合物との反応物、白金-オレフィン錯体、白金-ビニル基含有シロキサン錯体、及び白金-リン錯体等が挙げられる。前述のような硬化触媒の具体例は、例えば、特開2006-28311号公報及び特開平10-147758号公報に記載されている。
より具体的には、市販品として東レ・ダウコーニング社製のSRX-212、及び信越化学工業製のPL-50Tなどが挙げられる。
紫外線照射させる場合の光重合開始剤としては、特に制限はなく、従来、紫外線硬化型樹脂に慣用されている光重合開始剤の中から、任意の光重合開始剤を適宜選択して用いることができる。この光重合開始剤としては、例えばベンゾイン類、ベンゾフェノン類、アセトフェノン類、α-ヒドロキシケトン類、α-アミノケトン類、α-ジケトン類、α-ジケトンジアルキルアセタール類、アントラキノン類、チオキサントン類、その他化合物などが挙げられる。
これらの光重合開始剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、その使用量は、主剤として用いられる前記付加反応型シリコーン成分と架橋剤との合計量100質量部に対し、通常、0.01質量部以上30質量部以下、好ましくは0.05質量部以上20質量部以下の範囲で選定される。
加熱または活性エネルギー線を照射して架橋することにより、安定した粘着力を有する粘着シートが得られる。
照射される電子線の線量は1Mrad以上70Mrad以下が好ましく、2Mrad以上20Mrad以下がより好ましい。1Mrad以上の線量で照射することにより粘着剤層及び基材シートが劣化したり変色したりするのを防止し、架橋不足により粘着性が不十分になるのを防止することができる。70Mrad以下の線量で照射することにより、粘着剤層が劣化したり変色することによる凝集力の低下を防止し、基材シートが劣化したり収縮したりするのを防止することができる。
紫外線照射の場合の照射量としては、適宜選択されるが、光量は、100mJ/cm2以上500mJ/cm2以下、照度は、10mW/cm2以上500mW/cm2以下である。
加熱及び活性エネルギー線の照射は酸素による反応阻害を防止するため、窒素雰囲気下で行うのが好ましい。
付加反応型シリコーン系粘着剤組成物には、添加剤として、ジメチルシロキサン及びジメチルジフェニルシロキサンのような非反応性のポリオルガノシロキサンが含まれていてもよい。
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。
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。
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。
なお、本明細書において室温とは、22℃以上24℃以下の温度である。本明細書において、粘着力は、180°引き剥がし法により、引っ張り速度300mm/分、粘着シートの幅25mmにて測定した値である。
粘着シート10の製造方法は、特に限定されない。
例えば、粘着シート10は、次のような工程を経て製造される。まず、基材11の第一基材面11aの上に粘着剤を塗布し、塗膜を形成する。次に、この塗膜を乾燥させて、粘着剤層12を形成する。その後、粘着剤層12を覆うように剥離シートRLを貼着する。
また、粘着シート10の別の製造方法としては、次のような工程を経て製造される。まず、剥離シートRLの上に粘着剤を塗布し、塗膜を形成する。次に、塗膜を乾燥させて、粘着剤層12を形成し、この粘着剤層12に基材11の第一基材面11aを貼り合わせる。
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。
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。
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。
図2Aには、粘着シート10の粘着剤層12に枠部材20を貼着させる工程を説明する概略図が示されている。
本実施形態に係る枠部材20は、格子状に形成され、複数の開口部21を有する。枠部材20は、耐熱性を有する材質で形成されていることが好ましい。枠部材20の材質としては、例えば、銅及びステンレス等の金属、並びに、ポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂などが挙げられる。
開口部21は、枠部材20の表裏面を貫通する孔である。開口部21の形状は、半導体チップCPを枠内に収容可能であれば、特に限定されない。開口部21の孔の深さも、半導体チップCPを収容可能であれば、特に限定されない。
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。
ダイシング装置は、特に限定されず、公知のダイシング装置を用いることができる。また、ダイシングの条件についても、特に限定されない。なお、ダイシングブレードを用いてダイシングする方法に代えて、レーザーダイシング法またはステルスダイシング法などを用いてもよい。
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。
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硬化の温度条件範囲は、例えば、80℃以上120℃以下である。
図2Dには、封止体50に補強部材40を貼着させる工程を説明する概略図が示されている。
粘着シート10を剥離した後、露出した半導体チップCPの回路面に対して再配線層を形成する再配線工程及びバンプ付け工程が実施される。このような再配線工程及びバンプ付け工程における封止体50の取り扱い性を向上させるため、必要に応じて、封止体50に補強部材40を貼着させる工程(補強部材貼着工程)を実施してもよい。補強部材貼着工程を実施する場合には、粘着シート10を剥離する前に実施することが好ましい。図2Dに示すように、封止体50は、粘着シート10及び補強部材40によって挟まれた状態で支持されている。
補強板41としては、例えば、ポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂を含む板状の部材が挙げられる。
接着層42は、補強板41と封止体50とを接着させる。接着層42としては、補強板41及び封止樹脂層30Aの材質に応じて適宜選択される。例えば、封止樹脂層30Aがエポキシ系樹脂を含み、補強板41がガラスエポキシ樹脂を含んでいる場合には、接着層42としては、熱可塑性樹脂を含んだガラスクロスが好ましく、接着層42に含まれる熱可塑性樹脂としては、ビスマレイミドトリアジン樹脂(BTレジン)が好ましい。
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。
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。
本発明は、前記実施形態に限定されず、本発明の目的を達成できる範囲での変形及び改良等は、本発明に含まれる。なお、以下の説明では、前記実施形態で説明した部材等と同一であれば、同一符号を付してその説明を省略または簡略する。
また、粘着シート10は、枚葉であってもよく、複数枚の粘着シート10が積層された状態で提供されてもよい。この場合、例えば、粘着剤層12は、積層される別の粘着シートの基材11によって覆われていてもよい。
また、粘着シート10は、長尺状のシートであってもよく、ロール状に巻き取られた状態で提供されてもよい。ロール状に巻き取られた粘着シート10は、ロールから繰り出されて所望のサイズに切断するなどして使用することができる。
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20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。
粘着シートの評価は、以下に示す方法に従って行った。
粘着剤層の100℃の雰囲気におけるシリコンに対するダイプル試験で求められる値を測定した。具体的には、下記の(a)~(h)の手順に沿って測定した。
(a)測定対象の半導体チップ(シリコン)を、下記の条件にて作製した。
・バックグラインドテープ:E-8180HR(リンテック(株)製)、ダイシングテープ:D-174A(リンテック(株)製)
・ダイシング装置:(株)ディスコ製の「DFD651」
・標準ダイシング条件:ブレード=27HECC、35,000rpm、カットモードA、50mm/s
・チップ厚み:200μm(♯2000)、チップサイズ:6.4mm×6.4mm(6.435mmステップ)
(b)図3Aに示す裏打ち用のベーク板BBに、図3Bに示すように、両面テープDF(TL-6177-12-LNテスト、リンテック(株)製)を全面に貼り付け、その後、両面テープDFの剥離フィルムを剥離した。
(c)実施例および比較例で作製した粘着剤層12を試料フィルムとし、図3Cに示すように、両面テープDFに、粘着剤層12を貼り付け、その後、粘着剤層12の剥離フィルムを剥離した。
(d)図3Dに示すように、半導体チップCP(8個)を、回路面CPAが粘着剤層12に接するようにして、粘着剤層12上にピンセットを用いて、2.5cm間隔で設置した。その際に、粘着剤層12に半導体チップCPの角を当てないように、半導体チップCPを優しく垂直に設置した。
(e)上記の(d)で作製したサンプルを、真空ラミネーターを用いて、下記の条件にて、真空ラミネートした。なお、真空ラミネートをする際には、図3Eに示すように、上下に剥離フィルムLF(厚み:38μm)を2枚配置し、真空ラミネートをした。
・真空ラミネーター:NISSINBO社製
・温度:100℃
・圧力:100Pa、真空度:設定なし(全引き)、プレス:設定なし(大気圧との差圧)
・ラミネート速度:高速モード
・プログラム:真空引き60秒間後に、高速ラミネートで40秒間
・温度設定後、1時間後以降にラミネートを行い、実際のサンプルラミネートの前には、一度空運転する。
(f)上記の(e)で真空ラミネートしたサンプルを、プル試験機(ノードソン・アドバンスト・テクノロジー(株)製の「Dage4000」)に載せて、100℃に予熱する。
(g)図3Fに示すように、両面テープDF2(リンテック(株)製の「A208」)が貼り付けられたプルブロックPBを、図3Gに示すように、半導体チップCP上に置き、5秒間指圧した。1分間経過後に、下記の条件にて、図3Hに示すようにして、ダイプル試験を行い、ロードセルの変位および力を測定し、力のピーク値を、1つのダイ(半導体チップCP)にかかる力(単位:N/ダイ)とした。
・雰囲気の温度:100℃
・試験速度:200μm/s
(h)その後、半導体チップCPをプルブロックPBから取り外した後に、上記の(g)のようにして、別の半導体チップCPにて、ダイプル試験を行い、有効データの数が6個になるまで、1つのダイにかかる力を求めた。そして、得られた有効データの平均値を、ダイプル試験で求められる値(単位:N/ダイ)とした。
粘着シートの粘着面に半導体チップ(シリコンミラーチップ、チップサイズ:2.3mm×1.7mm、チップ厚み:0.2mm)8000個を、粘着シートの粘着面と半導体チップの回路面とが接するように、必要な間隔で設置する。その後、封止樹脂(味の素ファインテクノ(株)製ABFフィルム、GX T-31)で粘着シート上の半導体チップを、真空加熱加圧ラミネーター(ROHM and HAAS社製の「7024HP5」)を用いて封止した。封止条件は、下記の通りである。
・予熱温度:テーブルおよびダイアフラムとも100℃
・真空引き:60秒間
・ダイナミックプレスモード:30秒間
・スタティックプレスモード:10秒間
そして、埋め込み後の粘着シート上の半導体チップを目視および顕微鏡にて観察し、半導体チップの位置ずれの有無を確認した。半導体チップの位置ずれがない場合を「A」と判定し、半導体チップの位置ずれがある場合を「B」と判定した。なお、埋め込みを行う前後で半導体チップが20μm以上移動した場合に、「位置ずれがある」と判定した。
(1)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。
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。
・粘着助剤:ポリエーテルアミン誘導体〔日油(株)製;DT-203〕、1.5質量部(固形分)
調製した塗布用粘着剤液を、コンマコーター(登録商標)を用いて乾燥後の膜厚が50μmになるように、シリコーン系剥離層を設けた38μmの透明ポリエチレンテレフタレートフィルムからなる剥離フィルム〔リンテック(株)製;SP-PET382150〕の剥離層面側に塗布し、90℃及び90秒間の加熱を行い、続いて115℃及び90秒間の加熱を行い、塗膜を乾燥させた。
塗布用粘着剤液の塗膜を乾燥させた後、粘着剤層と、基材とを貼り合わせて実施例1に係る粘着シートを得た。なお、基材として、透明ポリエチレンテレフタレートフィルム〔帝人デュポンフィルム(株)製;PET50KFL12D、厚さ50μm、100℃における貯蔵弾性率3.1×109Pa〕を用い、基材の易接着面に粘着剤層を貼り合わせた。
実施例2に係る粘着シートは、粘着剤層に含まれる粘着助剤が実施例1と異なること以外は、実施例1と同様に作製した。
実施例2で用いた粘着助剤は、両末端水酸基水素化ポリブタジエン〔日本曹達(株)製;GI-1000〕、5質量部(固形分)である。
実施例3では、シリコーン系粘着剤を用いた。
実施例3においては、
シリコーン系粘着剤A(SD4580PSA)18質量部(固形分)、
シリコーン系粘着剤B(SD4587L)40質量部(固形分)、
触媒A(NC-25 CAT)0.3質量部(固形分)、
触媒B(CAT-SRX-212)0.65質量部(固形分)、及び
プライマー(BY24-712)5質量部(固形分)を配合し、十分に撹拌して、塗布用粘着剤液(粘着剤組成物)を調製した。実施例3の粘着剤組成物に用いた材料は、いずれも東レ・ダウコーニング(株)製である。
実施例3に係る塗布用粘着剤液を、乾燥後の厚みが20μmとなるように基材に塗布及び乾燥して粘着剤層を作製した。乾燥条件は、100℃及び1分間とした。実施例3で用いた基材は、ポリイミドフィルム〔東レ・デュポン(株)製;カプトン100H、厚さ25μm、100℃における貯蔵弾性率3.1×109Pa〕を用いた。剥離フィルムの表面上に作製された粘着剤層と、基材とを貼り合わせて実施例3に係る粘着シートを得た。
実施例4に係る粘着シートは、粘着剤層に含まれるポリマーが実施例2と異なること以外は、実施例2と同様に作製した。
実施例4で用いたポリマーは、アクリル酸2-エチルヘキシル80.8質量%と、アクリル酸2-ヒドロキシエチル7質量%と、4-アクリロイルモルホリン12質量%と、アクリル酸0.2質量%とを共重合して調製した。
比較例1に係る粘着シートは、粘着剤層に含まれる粘着助剤が実施例1と異なること以外は、実施例1と同様に作製した。
比較例1で用いた粘着助剤は、アセチルクエン酸トリブチル〔田岡化学工業(株)製〕、5質量部(固形分)である。
Claims (5)
- 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、
前記粘着シートは、基材と粘着剤層とを備え、前記粘着剤層の100℃の雰囲気におけるシリコンに対するダイプル試験で求められる値が3.0N/ダイ以上である、
粘着シート。 - 前記基材の100℃における貯蔵弾性率が1×107Pa以上である、
請求項1に記載の粘着シート。 - 前記粘着剤層が、アクリル系粘着剤組成物またはシリコーン系粘着剤組成物を含有する、
請求項1または請求項2に記載の粘着シート。 - 前記アクリル系粘着剤組成物は、アクリル酸2-エチルヘキシルを主たるモノマーとするアクリル系共重合体を含む、
請求項3に記載の粘着シート。 - 前記シリコーン系粘着剤組成物は、付加重合型シリコーン樹脂を含む、
請求項3に記載の粘着シート。
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