WO2017038914A1 - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
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- WO2017038914A1 WO2017038914A1 PCT/JP2016/075601 JP2016075601W WO2017038914A1 WO 2017038914 A1 WO2017038914 A1 WO 2017038914A1 JP 2016075601 W JP2016075601 W JP 2016075601W WO 2017038914 A1 WO2017038914 A1 WO 2017038914A1
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- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- sheet
- mass
- Prior art date
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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
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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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 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.
- a silicone type adhesive after peeling a mask sheet, low molecular weight siloxane may remain on a to-be-adhered body surface, and there exists a possibility of producing an electrical contact failure.
- the residue of a silicone type adhesive is water-repellent and oil-repellent.
- the plating suitability of the electrical connection portion may be reduced, or the adhesive strength of the protective material on the circuit surface may be reduced, resulting in a decrease in package reliability such as an increase in electrical resistance and a failure due to the occurrence of cracks.
- various studies have been made on adhesives with little adhesive residue, but the adhesive strength becomes excessively high after a process in which high temperature conditions are imposed, which may make it difficult to peel off the adhesive sheet.
- An object of the present invention is to provide a pressure-sensitive adhesive sheet that is easy to peel off from an adherend and has little adhesive residue even after a process subject to high temperature conditions.
- a pressure-sensitive adhesive sheet used for sealing a semiconductor element on a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is an acrylic sheet.
- a pressure-sensitive adhesive sheet containing an acrylic copolymer containing 2-ethylhexyl acid as a main monomer is provided.
- the pressure-sensitive adhesive force at room temperature with respect to the copper foil of the pressure-sensitive adhesive layer is 0.7N / 25mm or more and 2.0N / 25mm or less is preferable.
- the pressure-sensitive adhesive layer is obtained by crosslinking a composition containing at least the acrylic copolymer and a crosslinking agent containing a compound having an isocyanate group as a main component.
- the adhesive preferably contains at least an adhesive, and the cross-linking agent mainly composed of the compound having an isocyanate group preferably has an isocyanurate ring.
- 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.
- the acrylic copolymer further includes a copolymer component derived from acrylic acid, and the copolymer component derived from the acrylic acid in the acrylic copolymer.
- the ratio is preferably 1% by mass or less.
- the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m or more and 60 ⁇ m or less.
- 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.
- a release sheet RL is laminated as shown in FIG.
- the shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a sheet shape, a tape shape, and a label shape.
- the pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive composition.
- This pressure-sensitive adhesive composition contains an acrylic copolymer having 2-ethylhexyl acrylate as a main monomer.
- 2-ethylhexyl acrylate is the main monomer, and the ratio of the mass of the copolymer component derived from 2-ethylhexyl acrylate to the total mass of the acrylic copolymer is 50% by mass or more. Means.
- the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, and 60% by mass or more and 95% by mass or less. It is more preferable that it is 80 mass% or more and 95 mass% or less, and it is still more preferable that it is 85 mass% or more and 93 mass% or less. 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.
- 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, preferably an acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer,
- the carboxyl group-containing monomer is preferably acrylic acid
- 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 at least 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.
- the crosslinking agent containing a compound having an isocyanate group as a main component means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. means.
- the content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If content of the crosslinking agent in an adhesive composition is in such a range, the adhesiveness of the 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 contains a reactive pressure-sensitive adhesive aid.
- 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.
- 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.
- pressure-sensitive adhesive composition includes the following pressure-sensitive adhesive compositions, but the present invention is not limited to such examples.
- An example of the pressure-sensitive adhesive composition according to this embodiment includes an acrylic copolymer and a crosslinking agent, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a hydroxyl group-containing monomer, and a carboxyl group-containing monomer.
- a pressure-sensitive adhesive composition in which the crosslinking agent is an isocyanate-based crosslinking agent.
- an acrylic copolymer and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and acrylic.
- a pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing an acid, and the crosslinking agent is an isocyanate crosslinking agent.
- 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 isocyanate-based crosslinking agent is preferably a compound having an isocyanurate ring, and more preferably an isocyanurate-type modified product of hexamethylene diisocyanate. .
- 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 to 60 ⁇ m, and more preferably 5 ⁇ m to 50 ⁇ m. 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 substrate 11 is a member that supports the pressure-sensitive adhesive layer 12.
- 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
- the first surface 11a may be subjected to at least one surface treatment such as primer treatment, corona treatment, and plasma treatment.
- An adhesive may be applied to the first surface 11a of the substrate 11 to perform an adhesion 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.
- a sheet material such as a synthetic resin film
- 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 oligomers contained in the polyester film are derived from polyester-forming monomers, dimers, trimers, and the like.
- 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 adhesive strength after heating.
- the pressure-sensitive adhesive sheet 10 is attached to an adherend (copper foil), heated under conditions of 100 ° C. and 30 minutes, and subsequently heated under conditions of 180 ° C. and 30 minutes, and then the copper foil of the pressure-sensitive adhesive layer 12
- the adhesive force at room temperature is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less. If the adhesive strength after 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 and the adherend are 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 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.
- another manufacturing method of the adhesive sheet 10 it manufactures through the following processes. First, an adhesive composition is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12, and the first surface 11 a of the substrate 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 10 (peeling step) are carried out after thermosetting.
- bonding step a step of bonding the semiconductor chip CP to the exposed adhesive layer 12
- sealing step a step of covering the semiconductor chip CP with the sealing resin 30
- a step of thermosetting the sealing resin 30 A thermosetting step
- peeling the pressure-sensitive adhesive sheet 10 peeling step
- the frame member 20 is formed in a lattice shape and has a plurality of openings 21.
- the frame member 20 is preferably formed of a material having heat resistance. Examples of the material of the frame member 20 include metals such as copper and stainless steel, and heat resistant resins such as polyimide resin and glass epoxy resin.
- the opening 21 is a hole that penetrates the front and back surfaces of the frame member 20.
- the shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame.
- the depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
- FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
- the semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces.
- a semiconductor chip CP semiconductor element
- the dicing apparatus is not particularly limited, and a known dicing apparatus can be used.
- the dicing conditions are not particularly limited. Note that a laser dicing method or a stealth dicing method may be used instead of the dicing method using a dicing blade.
- an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP.
- the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding process, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
- the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden.
- the energy ray polymerizable compound When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced.
- the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable.
- UV ultraviolet rays
- EB electron beams
- the energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
- the material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin.
- the epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
- the method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited. In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example.
- the sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A.
- the sheet-shaped sealing resin 30 it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being generated between the semiconductor chip CP and the frame member 20.
- the temperature condition range for heating by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
- a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used.
- the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured.
- Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
- a transfer molding method may be employed.
- the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device.
- a fluid resin material is injected into the mold to cure the resin material.
- the heating and pressure conditions are not particularly limited.
- a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds.
- the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
- the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process).
- the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. .
- the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20.
- corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
- the 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 glass epoxy resin.
- the adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50.
- the adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
- the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure.
- the sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time.
- the conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa.
- a metal plate such as stainless steel can be used as the plate-like member.
- FIG. 2E The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
- the adhesive sheet 10 when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent.
- peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree
- the peeling angle ⁇ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A.
- the peeling angle ⁇ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less.
- the reinforcing member 40 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed. Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step).
- a method for dividing the sealing body 50 into individual pieces is not particularly limited.
- the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer.
- the step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like.
- the pressure-sensitive adhesive sheet 10 that is easily peeled off from the adherend and has little adhesive residue even after undergoing a process in which high temperature conditions are imposed.
- 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 high temperature conditions 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 adhesive sheet 10 may be a single wafer or may be provided in a state where a plurality of adhesive sheets 10 are laminated.
- the pressure-sensitive adhesive layer 12 may be covered with the base material 11 of another pressure-sensitive adhesive sheet to be laminated.
- the adhesive sheet 10 may be a long sheet or may be provided in a state of being wound in a roll. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
- the sealing resin 30 is a thermosetting resin
- the present invention is not limited to such a mode.
- the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
- the adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
- the adhesive sheet cut to a width of 25 mm was laminated on a copper foil as an adherend at room temperature to obtain a sheet with a copper foil.
- a copper foil As the copper foil, a C1220R-H standard 0.08 mm thick drawn copper foil was used.
- This sheet with copper foil was heated under conditions of 100 ° C. and 30 minutes, and subsequently heated under conditions of 180 ° C. and 30 minutes. After heating, the peel angle was 180 degrees, the pulling speed (peeling speed) was 300 mm / min, and the adhesive strength when the tape was peeled from the copper foil at room temperature was measured.
- 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.
- 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 ⁇ 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 made 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 form a coating film. It was made to dry and the adhesive layer was produced.
- a comma coater registered trademark
- Example 2 The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
- the polymer used in Example 2 is an acrylate copolymer prepared by copolymerizing 93.0% by mass of 2-ethylhexyl acrylate and 7.0% by mass of 2-hydroxyethyl acrylate.
- 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 polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
- the polymer used in Comparative Example 1 was an acrylic ester prepared by copolymerizing 92.8% by mass of lauryl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid. It is a copolymer.
- Comparative Example 2 The pressure-sensitive adhesive sheet according to Comparative Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
- the polymer used in Comparative Example 2 was an acrylate prepared by copolymerizing 92.8% by weight of butyl acrylate, 7.0% by weight of 2-hydroxyethyl acrylate, and 0.2% by weight of acrylic acid. It is a copolymer.
- Table 1 shows the composition of the adhesive liquid for coating used in Examples 1 and 2 and Comparative Examples 1 and 2.
- HEA 2-hydroxyethyl acrylate
- 2EHA 2-ethylhexyl acrylate
- AAc acrylic acid
- LMA lauryl acrylate
- BA butyl acrylate
- Table 2 shows the evaluation results of the pressure-sensitive adhesive sheets according to Examples 1 and 2 and Comparative Examples 1 and 2.
- the pressure-sensitive adhesive sheets according to Examples 1 and 2 contained an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer, and as a result, adhesive residue on the adherend could be reduced. Furthermore, according to the adhesive sheet which concerns on Example 1 and 2, compared with the adhesive sheet which concerns on Comparative example 1 and 2, the adhesive force after heat processing was able to be reduced. Thus, it turns out that the adhesive sheet which concerns on this invention can be utilized suitably in the semiconductor device manufacturing process including the process in which high temperature conditions are imposed.
Abstract
Description
また、糊残りの少ない粘着剤についても様々な検討が行われているが、高温条件が課される工程を経ると粘着力が大きくなり過ぎて、粘着シートの剥離が困難になる場合もある。 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. Moreover, when using a silicone type adhesive, after peeling a mask sheet, low molecular weight siloxane may remain on a to-be-adhered body surface, and there exists a possibility of producing an electrical contact failure. Furthermore, the residue of a silicone type adhesive is water-repellent and oil-repellent. For this reason, the plating suitability of the electrical connection portion may be reduced, or the adhesive strength of the protective material on the circuit surface may be reduced, resulting in a decrease in package reliability such as an increase in electrical resistance and a failure due to the occurrence of cracks.
In addition, various studies have been made on adhesives with little adhesive residue, but the adhesive strength becomes excessively high after a process in which high temperature conditions are imposed, which may make it difficult to peel off the adhesive sheet.
(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。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
The pressure-sensitive
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。本明細書において、アクリル酸2-エチルヘキシルを主たるモノマーとするとは、アクリル系共重合体全体の質量に占めるアクリル酸2-エチルヘキシル由来の共重合体成分の質量の割合が50質量%以上であることを意味する。本実施形態においては、アクリル系共重合体におけるアクリル酸2-エチルヘキシルに由来する共重合体成分の割合は、50質量%以上95質量%以下であることが好ましく、60質量%以上95質量%以下であることがより好ましく、80質量%以上95質量%以下であることがさらに好ましく、85質量%以上93質量%以下であることがよりさらに好ましい。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。 (Adhesive layer)
The pressure-sensitive
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.
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.
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.
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して含有する架橋剤とは、架橋剤を構成する成分全体の質量に占めるイソシアネート基を有する化合物の質量の割合が50質量%以上であることを意味する。 In the present embodiment, examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These cross-linking agents may be used alone or in combination of two or more.
In the present embodiment, from the viewpoint of improving the heat resistance and adhesive strength of the pressure-
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 this specification, the crosslinking agent containing a compound having an isocyanate group as a main component means that the ratio of the mass of the compound having an isocyanate group to the total mass of the components constituting the crosslinking agent is 50% by mass or more. means.
本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、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、水酸基含有モノマー、及びカルボキシル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、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2-ヒドロキシエチル、及びアクリル酸を共重合して得られるアクリル系共重合体であり、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。
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であることが好ましく、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であることがより好ましい。 More specific examples of the pressure-sensitive adhesive composition according to this embodiment include the following pressure-sensitive adhesive compositions, but the present invention is not limited to such examples.
An example of the pressure-sensitive adhesive composition according to this embodiment includes an acrylic copolymer and a crosslinking agent, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a hydroxyl group-containing monomer, and a carboxyl group-containing monomer. A pressure-sensitive adhesive composition in which the crosslinking agent is an isocyanate-based crosslinking agent.
As an example of the pressure-sensitive adhesive composition according to this embodiment, an acrylic copolymer and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and acrylic. A pressure-sensitive adhesive composition, which is an acrylic copolymer obtained by copolymerizing an acid, and the crosslinking agent is an isocyanate crosslinking agent.
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.
In these examples of the pressure-sensitive adhesive composition according to this embodiment, the isocyanate-based crosslinking agent is preferably a compound having an isocyanurate ring, and more preferably an isocyanurate-type modified product of hexamethylene diisocyanate. .
基材11は、粘着剤層12を支持する部材である。
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が積層されている。基材11と粘着剤層12との密着性を高めるために、第一面11aは、プライマー処理、コロナ処理、及びプラズマ処理等の少なくともいずれかの表面処理が施されてもよい。基材11の第一面11aには、粘着剤が塗布されて粘着処理が施されていてもよい。基材の粘着処理に用いられる粘着剤としては、例えば、アクリル系、ゴム系、シリコーン系、及びウレタン系等の粘着剤が挙げられる。 (Base material)
The
The
ポリエステル系樹脂としては、例えば、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリブチレンナフタレート樹脂、及びこれらの樹脂の共重合樹脂からなる群から選択されるいずれかの樹脂であることが好ましく、ポリエチレンテレフタレート樹脂がより好ましい。
基材11としては、ポリエチレンテレフタレートフィルム、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、及びトリマーなどに由来する。 The
The polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins. Is preferred, and polyethylene terephthalate resin is more preferred.
As the
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.
剥離剤層の厚みは、特に限定されない。剥離剤を含む溶液を塗布して剥離剤層を形成する場合、剥離剤層の厚みは、0.01μm以上2.0μm以下であることが好ましく、0.03μm以上1.0μm以下であることがより好ましい。
剥離基材としてプラスチックフィルムを用いる場合、当該プラスチックフィルムの厚みは、3μm以上50μm以下であることが好ましく、5μm以上40μm以下であることがより好ましい。 The thickness of the release sheet RL is not particularly limited. The thickness of the release sheet RL is usually 20 μm or more and 200 μm or less, and preferably 25 μm or more and 150 μm or less.
The thickness of the release agent layer is not particularly limited. When a release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 μm or more and 2.0 μm or less, and preferably 0.03 μm or more and 1.0 μm or less. More preferred.
When a plastic film is used as the peeling substrate, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 40 μm or less.
粘着シート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の第一面11aの上に粘着剤組成物を塗布し、塗膜を形成する。次に、この塗膜を乾燥させて、粘着剤層12を形成する。その後、粘着剤層12を覆うように剥離シートRLを貼着する。
また、粘着シート10の別の製造方法としては、次のような工程を経て製造される。まず、剥離シートRLの上に粘着剤組成物を塗布し、塗膜を形成する。次に、塗膜を乾燥させて、粘着剤層12を形成し、この粘着剤層12に基材11の第一面11aを貼り合わせる。 (Method for producing adhesive sheet)
The manufacturing method of the
For example, the
Moreover, as another manufacturing method of the
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又は剥離シート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-
In order to prevent the organic solvent and the low-boiling component from remaining in the pressure-
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-
The pressure-
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-
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
図2Aには、粘着シート10の粘着剤層12に枠部材20を貼着させる工程を説明する概略図が示されている。なお、粘着シート10に剥離シートRLが貼着されている場合には、予め剥離シートRLを剥離する。
本実施形態に係る枠部材20は、格子状に形成され、複数の開口部21を有する。枠部材20は、耐熱性を有する材質で形成されていることが好ましい。枠部材20の材質としては、例えば、銅及びステンレス等の金属、並びにポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂などが挙げられる。
開口部21は、枠部材20の表裏面を貫通する孔である。開口部21の形状は、半導体チップCPを枠内に収容可能であれば、特に限定されない。開口部21の孔の深さも、半導体チップCPを収容可能であれば、特に限定されない。 -Adhesive sheet sticking process The schematic explaining the process of sticking the
The
The
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
When the pressure-
ダイシング装置は、特に限定されず、公知のダイシング装置を用いることができる。また、ダイシングの条件についても、特に限定されない。なお、ダイシングブレードを用いてダイシングする方法に代えて、レーザーダイシング法またはステルスダイシング法などを用いてもよい。 The semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for dividing the semiconductor wafer into individual pieces. In the dicing step, a semiconductor chip CP (semiconductor element) is obtained by sticking the semiconductor wafer to the adhesive layer of the dicing sheet and separating the semiconductor wafer using a cutting means such as a dicing saw.
The dicing apparatus is not particularly limited, and a known dicing apparatus can be used. Also, the dicing conditions are not particularly limited. Note that a laser dicing method or a stealth dicing method may be used instead of the dicing method using a dicing blade.
ダイシング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.
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
The material of the sealing
The method for covering the semiconductor chip CP and the
In the present embodiment, an embodiment using a sheet-
図2Dには、封止体50に補強部材40を貼着させる工程を説明する概略図が示されている。
粘着シート10を剥離した後、露出した半導体チップCPの回路面に対して再配線層を形成する再配線工程及びバンプ付け工程が実施される。このような再配線工程及びバンプ付け工程における封止体50の取り扱い性を向上させるため、必要に応じて、封止体50に補強部材40を貼着させる工程(補強部材貼着工程)を実施してもよい。補強部材貼着工程を実施する場合には、粘着シート10を剥離する前に実施することが好ましい。図2Dに示すように、封止体50は、粘着シート10及び補強部材40によって挟まれた状態で支持されている。 -Reinforcing member sticking process The schematic diagram explaining the process of sticking the reinforcing
After the
図2Eには、粘着シート10を剥離する工程を説明する概略図が示されている。
本実施形態では、粘着シート10の基材11が屈曲可能である場合、粘着シート10を屈曲させながら、枠部材20、半導体チップCP及び封止樹脂層30Aから容易に剥離することができる。剥離角度θは、特に限定されないが、90度以上の剥離角度θで粘着シート10を剥離することが好ましい。剥離角度θが90度以上であれば、粘着シート10を、枠部材20、半導体チップCP及び封止樹脂層30Aから容易に剥離することができる。剥離角度θは、90度以上180度以下が好ましく、135度以上180度以下がより好ましい。このように粘着シート10を屈曲させながら剥離を行うことで、枠部材20、半導体チップCP及び封止樹脂層30Aにかかる負荷を低減しながら剥離することができ、粘着シート10の剥離による、半導体チップCP及び封止樹脂層30Aの損傷を抑制することができる。粘着シート10を剥離した後、前述の再配線工程及びバンプ付け工程等が実施される。粘着シート10の剥離後、再配線工程及びバンプ付け工程等の実施前に、必要に応じて、前述の補強部材貼着工程を実施してもよい。 -Peeling process The schematic explaining the process of peeling the
In this embodiment, when the
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
Thereafter, the sealing
本発明は、前記実施形態に限定されず、本発明の目的を達成できる範囲での変形及び改良等は、本発明に含まれる。なお、以下の説明では、前記実施形態で説明した部材等と同一であれば、同一符号を付してその説明を省略または簡略化する。 [Modification of Embodiment]
The present invention is not limited to the above-described embodiment, but includes modifications and improvements as long as the object of the present invention can be achieved. In the following description, if it is the same as the member described in the above embodiment, the same reference numeral is given and the description is omitted or simplified.
また、粘着シート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。 In the said embodiment, although the aspect in which the
Moreover, the
Moreover, the
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.
25mm幅に切断した粘着シートを室温で被着体としての銅箔にラミネートし、銅箔付きシートを得た。銅箔としては、C1220R-H規格の厚み0.08mmの延伸銅箔を用いた。
この銅箔付きシートを、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た。加熱後、剥離角度を180度とし、引っ張り速度(剥離速度)を300mm/minとし、室温でテープを銅箔から剥離した際の粘着力を測定した。このようにして測定した粘着力が、0.7N/25mm以上2.0N/25mm以下である場合に「A」と判定し、粘着力が0.7N/25mm未満の場合又は2.0N/25mmを超える場合に「B」と判定した。粘着力の測定装置として、(株)オリエンテック製「テンシロン」(製品名)を用いた。 [Adhesive strength evaluation]
The adhesive sheet cut to a width of 25 mm was laminated on a copper foil as an adherend at room temperature to obtain a sheet with a copper foil. As the copper foil, a C1220R-H standard 0.08 mm thick drawn copper foil was used.
This sheet with copper foil was heated under conditions of 100 ° C. and 30 minutes, and subsequently heated under conditions of 180 ° C. and 30 minutes. After heating, the peel angle was 180 degrees, the pulling speed (peeling speed) was 300 mm / min, and the adhesive strength when the tape was peeled from the copper foil at room temperature was measured. When the adhesive strength measured in this way is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less, it is determined as “A”, and the adhesive strength is less than 0.7 N / 25 mm or 2.0 N / 25 mm. When it exceeded, it determined with "B". “Tensilon” (product name) manufactured by Orientec Co., Ltd. was used as an adhesive force measuring device.
上述の粘着力評価における銅箔付きシートを、180℃及び1時間の条件で加熱した。加熱後、剥離角度を180度とし、引っ張り速度(剥離速度)を3mm/minとし、室温で粘着シートを銅箔から剥離した。剥離後の銅箔表面を目視で観察し、被着体表面の残渣の有無を確認した。テープ剥離後に、糊残りなく剥離できた場合を「A」と判定し、糊残りが少なく、テープの貼り跡が確認できる程度である場合を「B」と判定した。 [Adhesive residue evaluation]
The sheet with copper foil in the above-described evaluation of adhesive strength was heated under the conditions of 180 ° C. and 1 hour. After heating, the peeling angle was 180 degrees, the pulling rate (peeling rate) was 3 mm / min, and the adhesive sheet was peeled from the copper foil at room temperature. The surface of the copper foil after peeling was visually observed to confirm the presence or absence of residues on the adherend surface. After the tape was peeled off, it was determined as “A” when the adhesive could be peeled without residue, and “B” was determined when there was little adhesive remaining and the tape sticking could be confirmed.
(実施例1) [Preparation of adhesive sheet]
Example 1
以下の材料(ポリマー、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を調製した。 (1) Preparation of pressure-sensitive adhesive composition The following materials (polymer, cross-linking agent, and dilution solvent) were blended and sufficiently stirred to prepare a pressure-sensitive adhesive liquid for application according to Example 1.
アクリル酸エステル共重合体は、アクリル酸2-エチルヘキシル92.8質量%と、アクリル酸2-ヒドロキシエチル7.0質量%と、アクリル酸0.2質量%とを共重合して調製した。 -Polymer: Acrylic ester copolymer, 40 parts by mass (solid content)
The acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
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)社製;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、粘着剤層を作製した。 (2) Preparation of pressure-sensitive adhesive layer 38 μm transparent polyethylene terephthalate provided with a silicone-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 μm. It is applied to the release layer side of a release film made 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 form a coating film. It was made to dry and the adhesive layer was produced.
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〔東洋紡(株)社製;PET50A-4300〕を用い、基材の易接着面に粘着剤層を貼り合わせた。 (3) Preparation of pressure-sensitive adhesive sheet After the coating film of the pressure-sensitive adhesive liquid for application was dried, the pressure-sensitive adhesive layer and the substrate were bonded together to obtain a pressure-sensitive adhesive sheet according to Example 1. A transparent polyethylene terephthalate film [manufactured by Toyobo Co., Ltd .; PET50A-4300] was used as the base material, and the pressure-sensitive adhesive layer was bonded to the easy adhesion surface of the base material.
実施例2に係る粘着シートは、粘着剤層に含まれるポリマーが実施例1と異なること以外は、実施例1と同様に作製した。
実施例2で用いたポリマーは、アクリル酸2-エチルヘキシル93.0質量%と、アクリル酸2-ヒドロキシエチル7.0質量%とを共重合して調製したアクリル酸エステル共重合体である。 (Example 2)
The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
The polymer used in Example 2 is an acrylate copolymer prepared by copolymerizing 93.0% by mass of 2-ethylhexyl acrylate and 7.0% by mass of 2-hydroxyethyl acrylate.
比較例1に係る粘着シートは、粘着剤層に含まれるポリマーが実施例1と異なること以外は、実施例1と同様に作製した。
比較例1で用いたポリマーは、アクリル酸ラウリル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アクリル酸エステル共重合体である。 (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 polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
The polymer used in Comparative Example 1 was an acrylic ester prepared by copolymerizing 92.8% by mass of lauryl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid. It is a copolymer.
比較例2に係る粘着シートは、粘着剤層に含まれるポリマーが実施例1と異なること以外は、実施例1と同様に作製した。
比較例2で用いたポリマーは、アクリル酸ブチル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アクリル酸エステル共重合体である。 (Comparative Example 2)
The pressure-sensitive adhesive sheet according to Comparative Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
The polymer used in Comparative Example 2 was an acrylate prepared by copolymerizing 92.8% by weight of butyl acrylate, 7.0% by weight of 2-hydroxyethyl acrylate, and 0.2% by weight of acrylic acid. It is a copolymer.
2EHA:アクリル酸2-エチルヘキシル
AAc :アクリル酸
LMA :アクリル酸ラウリル
BA :アクリル酸ブチル HEA: 2-hydroxyethyl acrylate 2EHA: 2-ethylhexyl acrylate AAc: acrylic acid LMA: lauryl acrylate BA: butyl acrylate
Claims (7)
- 粘着シート上の半導体素子を封止する際に使用される粘着シートであって、
基材と、粘着剤層と、を有し、
前記粘着剤層は、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、粘着シート。 A pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet,
A substrate and an adhesive layer;
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet containing an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer. - 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た後、前記粘着剤層の銅箔に対する室温での粘着力が、0.7N/25mm以上2.0N/25mm以下である、請求項1に記載の粘着シート。 After heating at 100 ° C. and 30 minutes, and subsequently heating at 180 ° C. and 30 minutes, the adhesive strength of the adhesive layer to the copper foil at room temperature is 0.7 N / 25 mm to 2.0 N / The pressure sensitive adhesive sheet according to claim 1 which is 25 mm or less.
- 前記粘着剤層は、前記アクリル系共重合体と、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を少なくとも配合した組成物を架橋させて得られる粘着剤を少なくとも含む、請求項1または請求項2に記載の粘着シート。 The said adhesive layer contains at least the adhesive obtained by bridge | crosslinking the composition which mix | blended at least the said acrylic copolymer and the crosslinking agent which has a compound which has an isocyanate group as a main component. Item 3. The pressure-sensitive adhesive sheet according to item 2.
- 前記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は、イソシアヌレート環を有する、請求項3に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 3, wherein the cross-linking agent mainly comprising a compound having an isocyanate group has an isocyanurate ring.
- 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は、50質量%以上95質量%以下である、請求項1から請求項4のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein a ratio of a copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 50% by mass or more and 95% by mass or less. Sheet.
- 前記アクリル系共重合体は、アクリル酸に由来する共重合体成分をさらに含み、
前記アクリル系共重合体における前記アクリル酸に由来する共重合体成分の割合は、1質量%以下である、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 acrylic copolymer further includes a copolymer component derived from acrylic acid,
The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein a ratio of the copolymer component derived from the acrylic acid in the acrylic copolymer is 1% by mass or less. - 前記粘着剤層の厚みは、5μm以上60μm以下である、請求項1から請求項6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 6, wherein the pressure-sensitive adhesive layer has a thickness of 5 µm or more and 60 µm or less.
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