WO2017168825A1 - 電子デバイスパッケージ用テープ - Google Patents
電子デバイスパッケージ用テープ Download PDFInfo
- Publication number
- WO2017168825A1 WO2017168825A1 PCT/JP2016/084563 JP2016084563W WO2017168825A1 WO 2017168825 A1 WO2017168825 A1 WO 2017168825A1 JP 2016084563 W JP2016084563 W JP 2016084563W WO 2017168825 A1 WO2017168825 A1 WO 2017168825A1
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- WIPO (PCT)
- Prior art keywords
- tape
- adhesive
- metal layer
- adhesive layer
- base tape
- Prior art date
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Classifications
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- 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
Definitions
- the present invention relates to an electronic device package tape, and more particularly to an electronic device package tape having a metal layer.
- Such an electronic device package includes, for example, a flip chip (FC) package.
- the linear expansion coefficient of the electronic device and the linear expansion coefficient of the circuit board may be greatly different.
- the intermediate product is heated and cooled in the manufacturing process of the electronic device package, there is a difference in the amount of expansion and contraction between the electronic device and the circuit board. This difference causes warpage in the electronic device package.
- a spacer includes a step of bonding a spacer adhesive sheet having a metal layer provided with an adhesive layer on at least one surface to a dicing sheet using the adhesive layer as a bonding surface, and a spacer adhesive sheet.
- the metal layer with the adhesive layer is useful for various electronic device packages, but as disclosed in Patent Document 4, it is picked up using an existing apparatus and fixed to the adherend. It is convenient if possible.
- a ring frame R which is a ring-shaped holding member, is bonded to the peripheral portion of the adhesive surface of a dicing tape D that adhesively holds a wafer W or a wafer with a die bond layer.
- the wafer W is set in the pickup apparatus (see FIG. 5C). Therefore, the dicing tape D needs to be cut into a shape corresponding to the ring frame R in use.
- a metal layer, an adhesive layer, and an adhesive tape are provided in this order on the base tape, and the adhesive tape is cut into a shape corresponding to the ring frame, and the metal layer and the adhesive layer are also this.
- Prepare an electronic device package tape (see Figs. 1 and 2) that has been cut into a predetermined shape (ie pre-cut) according to If the frame can be pasted, it is very convenient.
- the electronic device package tape having such a configuration is not disclosed in the above-mentioned patent document.
- the metal layer and the adhesive layer need to be cut into a shape smaller than the pressure-sensitive adhesive tape so that the ring frame can be bonded to the peripheral edge of the pressure-sensitive adhesive tape.
- a long metal foil and an adhesive film are provided in this order on a long film-like base tape, and the metal foil and the adhesive film are cut into a predetermined shape.
- a long film adhesive tape is bonded to the adhesive layer side, and the adhesive tape corresponds to the ring frame
- the metal layer and the adhesive layer may be cut in alignment, and unnecessary portions may be removed.
- the surface in contact with the metal layer of the base tape needs to have a certain degree of adhesive strength.
- the pressure-sensitive adhesive tape is larger than the metal layer and the adhesive layer, there is a portion where the pressure-sensitive adhesive surface of the pressure-sensitive adhesive tape and the surface having the adhesive strength of the base tape are bonded. To do. For this reason, at the time of use, even if it is going to peel a base tape, there exists a possibility that it cannot peel well.
- the present invention has an object to provide an electronic device package tape that can hold a metal layer on a base tape at the time of pre-cut processing and can peel the base tape satisfactorily at the time of use. .
- an electronic device package tape includes a base tape having an adhesive surface, and a metal layer provided on the adhesive surface of the base tape and having a predetermined planar shape.
- the pressure-sensitive adhesive tape includes a label portion having a predetermined planar shape so as to cover the adhesive layer and to be in contact with the base tape around the adhesive layer;
- the adhesive force P1 between the tape and the metal layer is 0.01 to 0.5 N / 25 mm
- the adhesive force P2 between the base tape and the adhesive tape is 0.01 to 0.5 N / 25 mm
- Adhesive force P1 between the base tape and the metal layer The ratio P1 / P2 between the adhesive force P2 between the adhesive tape and the base tape, characterized in that 0.1 to 10.
- the metal layer preferably contains copper or aluminum.
- the base tape has a resin film and a base tape adhesive layer provided on one side of the resin film.
- the adhesive layer contains (A) an epoxy resin, (B) a curing agent, (C) an acrylic resin or a phenoxy resin, and (D) a surface-treated inorganic filler. It is preferable to do.
- the pressure-sensitive adhesive layer contains an acrylic ester represented by CH 2 ⁇ CHCOOR (wherein R is an alkyl group having 4 to 18 carbon atoms) and a hydroxyl group-containing It is preferable to contain an acrylic polymer comprising a monomer and an isocyanate compound having a radical-reactive carbon-carbon double bond in the molecule.
- the metal layer can be held on the base tape at the time of pre-cut processing, and the base tape can be favorably peeled at the time of use.
- (A) is a top view which shows typically the structure of the tape for electronic device packages which concerns on embodiment of this invention
- (b) is the same sectional drawing. It is a perspective view which shows typically the structure of the tape for electronic device packages which concerns on embodiment of this invention. It is explanatory drawing which shows typically the manufacturing method of the tape for electronic device packages which concerns on embodiment of this invention
- (A) is a longitudinal cross-sectional view which shows the bonding process of a metal layer
- (B) is an adhesive agent
- (C) is a transversal direction sectional view which shows a precut process
- (D) is a perspective view which shows the removal process of an unnecessary part.
- FIG. 1 is a cross-sectional view showing an electronic device package tape 1 according to an embodiment of the present invention.
- the electronic device package tape 1 has a base tape 2 having an adhesive surface.
- a metal layer 3 having a predetermined planar shape, and a metal layer 3 Provided by laminating the metal layer 3 on the side opposite to the base tape 2 side, covering the adhesive layer 4 having a predetermined planar shape, and covering the adhesive layer 4 and surrounding the adhesive layer 4
- a pressure-sensitive adhesive tape 5 having a label portion 5a having a predetermined planar shape provided so as to come into contact with the tape 2 and a peripheral portion 5b surrounding the outside of the label portion 5a is provided.
- the label portion 5a has a shape corresponding to the ring frame R for dicing.
- the shape corresponding to the shape of the ring frame R for dicing is preferably similar in shape to the inside of the ring frame R and larger than the size inside the ring frame R.
- similar to circle is preferable and it is more preferable that it is circular.
- the peripheral part 5b includes a form that completely surrounds the outside of the label part 5a and a form that is not completely enclosed as shown. Note that the peripheral portion 5b may not be provided.
- the adhesive layer 4 has a predetermined planar shape, and this planar shape allows the ring frame R to be bonded to the peripheral edge of the label portion 5a of the adhesive tape 5 so that it can be pushed up by the push-up member of the pickup device. (See FIG. 6C), the shape is smaller than the label portion 5a.
- the adhesive layer 4 is preferably similar in shape to the label portion 5a and smaller in size than the label portion 5a.
- the adhesive layer 4 is not necessarily circular, but a shape close to a circle is preferable, and a circular shape is more preferable.
- the metal layer 3 has the same shape as the adhesive layer 4, and the adhesive layer 4 is laminated on the metal layer 3. In this case, it is sufficient that the main portions are laminated, and the metal layer 3 and the adhesive layer 4 do not necessarily have the same size, but they may have substantially the same shape for convenience of manufacturing. preferable.
- the lamination referred to here is indirectly provided through the case where the adhesive layer 4 is provided directly on the metal layer 3 and the primer layer for improving the adhesion between the two. Including cases.
- An electronic device package tape 1 of the present invention is a roll of a long base tape 2 in which a plurality of laminated bodies in which a metal layer 3, an adhesive layer 4, and a label portion 5a of an adhesive tape 5 are laminated are formed.
- the form wound up may be sufficient and the laminated body provided in the base tape 2 may be the form cut
- the base tape 2 has an adhesive surface, the adhesive force P1 between the base tape 2 and the metal layer 3 is 0.01 to 0.5 N / 25 mm, and the adhesive force between the base tape 2 and the adhesive tape 5 P2 is 0.01 to 0.5 N / 25 mm, and the ratio P1 / P2 between the adhesive force P1 between the base tape 2 and the metal layer 3 and the adhesive force P2 between the base tape 2 and the adhesive tape 5 is 0 As long as it is 1 to 10, there is no particular limitation.
- a base tape 2 for example, a tape having a resin film and a base tape adhesive layer provided on one side of the resin film can be suitably used.
- polyester PET, PBT, PEN, PBN, PTT
- polyolefin PP, PE
- films obtained by partially replacing these materials copolymers (EVA, EEA, EBA), and further improving adhesion and mechanical strength.
- the laminated body of these films may be sufficient. From the viewpoint of heat resistance, smoothness, and availability, it is preferably selected from polyethylene terephthalate, polypropylene, and high-density polyethylene.
- the thickness of the resin film constituting the base tape 2 is not particularly limited and may be appropriately set, but is preferably 10 to 150 ⁇ m.
- the resin used for the adhesive layer for the base tape constituting the base tape 2 has an adhesive force P1 between the base tape 2 and the metal layer 3 of 0.01 to 0.5 N / 25 mm.
- the adhesive strength P2 between the tape 2 and the adhesive tape 5 is 0.01 to 0.5 N / 25 mm, the adhesive strength P1 between the base tape 2 and the metal layer 3, and the adhesive strength between the base tape 2 and the adhesive tape 5.
- the ratio P1 / P2 with P2 is not particularly limited as long as the ratio P1 / P2 is 0.1 to 10.
- Known chlorinated polypropylene resins, acrylic resins, polyester resins, polyurethane resins, epoxy resins used for adhesives Etc. can be used, but an acrylic adhesive having an acrylic polymer as a base polymer is preferred.
- acrylic polymer examples include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, A linear or branched alkyl ester of an alkyl group such as octadecyl ester or eicosyl ester having 1 to 30 carbon atoms,
- the acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. May be.
- Such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Styrene Contains sulfonic acid groups such as phonic acid, allyl sulf
- a polyfunctional monomer or the like can be included as a monomer component for copolymerization as necessary.
- examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably
- the acrylic polymer can be prepared, for example, by applying an appropriate method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a suspension polymerization method to a mixture of one or more component monomers.
- the adhesive layer for the base tape preferably has a composition that suppresses the inclusion of a low molecular weight substance.
- the main component is preferably an acrylic polymer having a weight average molecular weight of 300,000 or more, particularly 400,000 to 3,000,000. Therefore, the pressure-sensitive adhesive can also be of an appropriate crosslinking type by an internal crosslinking method, an external crosslinking method, or the like.
- a polyfunctional isocyanate compound for example, a polyfunctional epoxy compound, a melamine compound, a metal salt compound, An energy beam obtained by mixing a low-molecular compound having two or more carbon-carbon double bonds with a method of crosslinking using an appropriate external crosslinking agent such as a metal chelate compound, an amino resin compound, or a peroxide.
- Appropriate methods such as a method of crosslinking by irradiation or the like can be employed.
- the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. Generally, it is preferable to add about 10 parts by weight or less, and further 0.1 to 10 parts by weight with respect to 100 parts by weight of the base polymer.
- acrylic polymers described above in particular, an acrylic ester represented by CH 2 ⁇ CHCOOR (wherein R is an alkyl group having 4 to 18 carbon atoms), a hydroxyl group-containing monomer, an isocyanate compound, Acrylic polymer P composed of is preferable.
- the carbon number of the alkyl group of the acrylic acid alkyl ester is less than 4, the polarity is so high that the peel force becomes too large, and the metal layer 3 and the adhesive layer 4 or the pressure-sensitive adhesive tape in the manufacturing process of the electronic device package tape 1 After cutting 5 into a predetermined shape, it may be difficult to peel off unnecessary portions around the predetermined shape from the base tape 2.
- the number of carbon atoms of the alkyl group of the acrylic acid alkyl ester exceeds 18, the glass transition temperature of the pressure-sensitive adhesive layer for the base tape becomes too high, and the adhesive properties at room temperature deteriorate, resulting in an electronic device package.
- the metal layer 3 may not be sufficiently held by the base tape 2, or the metal layer 3 and the adhesive layer 4 may be wrinkled when the ring frame is bonded.
- the acrylic polymer P may contain units corresponding to other monomer components as necessary.
- the acrylic polymer P it is preferable to use an isocyanate compound having no radical reactive carbon-carbon double bond, but an isocyanate compound having a radical reactive carbon-carbon double bond may be used.
- an isocyanate compound having a radical-reactive carbon-carbon double bond is used, the acrylic polymer is obtained by adding a double bond-containing isocyanate compound to the polymer based on the monomer composition such as the acrylate ester or the hydroxyl group-containing monomer. It will have the structure. Thereby, it can be set as the active energy ray hardening-type adhesive layer (UV cure adhesive layer etc.) hardened
- the adhesive tape layer for the base tape bites into the irregularities on the surface of the metal layer 3 due to curing shrinkage of the adhesive layer for the base tape due to energy ray irradiation,
- the peeling force between the base tape 2 and the metal layer 3 may increase.
- it since it will fall to the adhesive force of the adhesive tape 5, if it irradiates an energy ray after bonding with the adhesive tape 5, it is necessary to irradiate before bonding of the adhesive tape 5, and a process becomes complicated. Therefore, in the acrylic polymer P, it is preferable to use an isocyanate compound having no radical reactive carbon-carbon double bond.
- the thickness of the pressure-sensitive adhesive layer for the base tape constituting the base tape 2 is not particularly limited and can be appropriately determined, but is generally about 3 to 200 ⁇ m. Moreover, the adhesive layer for base tapes may be composed of a single layer or a plurality of layers.
- the adhesive force P2 between the base tape 2 and the adhesive tape 5 is 0.01 to 0.5 N / 25 mm, and the adhesive force P1 between the base tape 2 and the metal layer 3 and the base tape 2 If the ratio P1 / P2 of the adhesive strength P2 to the adhesive tape 5 is 0.1 to 10, there is no particular limitation, and the conventional adhesive tape 5 can be used.
- the adhesive tape 5 for example, a base film provided with an adhesive layer can be suitably used.
- the base film can be used without particular limitation as long as it is a conventionally known base film.
- a radiation curable material is used as an adhesive layer described later, a base film having radiation transparency is used. It is preferable to use it.
- the materials include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic.
- Homopolymers or copolymers of ⁇ -olefins such as methyl acid copolymers, ethylene-acrylic acid copolymers, ionomers or mixtures thereof, polyurethane, styrene-ethylene-butene or pentene copolymers, polyamide-polyols Listed are thermoplastic elastomers such as copolymers, and mixtures thereof.
- the base film may be a mixture of two or more materials selected from these groups, or may be a single layer or a multilayer.
- the thickness of the base film is not particularly limited and may be set as appropriate, but is preferably 50 to 200 ⁇ m.
- Chemical or physical surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, etc. on the surface of the base film in order to improve the adhesion between the base film and the adhesive layer May be applied.
- the pressure-sensitive adhesive layer is provided directly on the base film, but a primer layer for increasing adhesion, an anchor layer for improving machinability during dicing, and a stress relaxation layer Alternatively, it may be provided indirectly via an antistatic layer or the like.
- the resin used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape 5 is not particularly limited, and a known chlorinated polypropylene resin, acrylic resin, polyester resin, polyurethane resin, epoxy resin or the like used for the pressure-sensitive adhesive is used. However, an acrylic adhesive having an acrylic polymer as a base polymer is preferred.
- acrylic polymer examples include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, A linear or branched alkyl ester of an alkyl group such as octadecyl ester or eicosyl ester having 1 to 30 carbon atoms,
- the acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. May be.
- Such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Styrene Contains sulfonic acid groups such as phonic acid, allyl sulf
- a polyfunctional monomer or the like can be included as a monomer component for copolymerization as necessary.
- examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably
- the acrylic polymer can be prepared, for example, by applying an appropriate method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a suspension polymerization method to a mixture of one or more component monomers.
- the pressure-sensitive adhesive layer preferably has a composition that suppresses the inclusion of a low molecular weight substance from the viewpoint of preventing contamination of the wafer. From this point, an acrylic polymer having a weight average molecular weight of 300,000 or more, particularly 400,000 to 3,000,000 is a main component. Therefore, the pressure-sensitive adhesive can be of an appropriate crosslinking type by an internal crosslinking method, an external crosslinking method, or the like.
- polyfunctional isocyanate compounds for example, polyfunctional epoxy compounds, melamine compounds, metal salt compounds, metal chelate compounds, amino resin compounds
- a method of crosslinking using an appropriate external crosslinking agent such as peroxide, a method of mixing low molecular weight compounds having two or more carbon-carbon double bonds, and crosslinking by irradiation with energy rays, etc. Any suitable method can be adopted.
- an external cross-linking agent the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive.
- additives such as various tackifiers and anti-aging agents may be used for the pressure-sensitive adhesive in addition to the above components.
- a radiation curable pressure-sensitive adhesive As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, a radiation curable pressure-sensitive adhesive is suitable.
- the radiation-curable pressure-sensitive adhesive include additive-type radiation-curable pressure-sensitive adhesives in which a radiation-curable monomer component or a radiation-curable oligomer component is blended with the above-mentioned pressure-sensitive adhesive.
- Examples of the radiation curable monomer component to be blended include urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( And (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. These monomer components can be used alone or in combination of two or more.
- the radiation curable oligomer component includes various oligomers such as urethane, polyether, polyester, polycarbonate, and polybutadiene, and those having a molecular weight in the range of about 100 to 30000 are suitable.
- the compounding amount of the radiation-curable monomer component or oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the adhesive strength of the pressure-sensitive adhesive layer. Generally, the amount is, for example, about 5 to 500 parts by weight, preferably about 70 to 150 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.
- the radiation curable pressure-sensitive adhesive in addition to the additive-type radiation curable pressure-sensitive adhesive, a base polymer having a carbon-carbon double bond in the polymer side chain or in the main chain or at the main chain terminal was used.
- An internal radiation-curable pressure-sensitive adhesive is also included.
- Intrinsic radiation curable adhesives do not need to contain oligomer components, which are low molecular components, or do not contain much, so they are stable without the oligomer components moving through the adhesive over time. This is preferable because an adhesive layer having a layered structure can be formed.
- the base polymer having a carbon-carbon double bond a polymer having a carbon-carbon double bond and having adhesiveness can be used without particular limitation.
- a base polymer those having an acrylic polymer as a basic skeleton are preferable.
- the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.
- the method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. However, it is easy to introduce the carbon-carbon double bond into the polymer side chain in terms of molecular design. is there. For example, after a monomer having a functional group is copolymerized in advance with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into a radiation-curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.
- combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups, and the like.
- a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction.
- the functional group may be on either side of the acrylic polymer and the compound as long as the combination of these functional groups generates an acrylic polymer having the carbon-carbon double bond.
- it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group.
- examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, and the like.
- the acrylic polymer a copolymer obtained by copolymerizing the above-exemplified hydroxy group-containing monomer, an ether compound such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like is used.
- the base polymer having carbon-carbon double bonds can be used alone, but the radiation-curable monomer component does not deteriorate the properties.
- photopolymerizable compounds such as oligomer components can also be blended.
- the amount of the photopolymerizable compound is usually 30 parts by weight or less, preferably 0 to 10 parts by weight, based on 100 parts by weight of the base polymer.
- the radiation curable pressure-sensitive adhesive preferably contains a photopolymerization initiator when cured by ultraviolet rays or the like.
- Acrylic polymer A comprising an isocyanate compound having a radical reactive carbon-carbon double bond is preferred.
- the number of carbon atoms in the alkyl group of the acrylic acid alkyl ester is less than 4, the polarity is high and the peel force becomes too large, so that the pickup property may be lowered.
- the number of carbon atoms of the alkyl group of the acrylic acid alkyl ester exceeds 18, the glass transition temperature of the pressure-sensitive adhesive layer becomes too high, and the adhesive properties at room temperature are deteriorated. As a result, the adhesive is used during dicing or expanding. Separation of the layer 4 and the metal layer 3 may occur.
- the acrylic polymer A may contain units corresponding to other monomer components as necessary.
- the acrylic polymer A an isocyanate compound having a radical reactive carbon-carbon double bond is used. That is, it is preferable that the acrylic polymer has a configuration in which a double bond-containing isocyanate compound is subjected to an addition reaction with a polymer based on a monomer composition such as an acrylic ester or a hydroxyl group-containing monomer. Accordingly, the acrylic polymer preferably has a radical reactive carbon-carbon double bond in its molecular structure.
- the active energy ray hardening type adhesive layer (ultraviolet ray hardening type adhesive layer etc.) hardened
- double bond-containing isocyanate compound examples include methacryloyl isocyanate, acryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, and the like.
- a double bond containing isocyanate compound can be used individually or in combination of 2 or more types.
- an external cross-linking agent can be appropriately used for the active energy ray-curable adhesive in order to adjust the adhesive strength before irradiation with active energy rays and the adhesive strength after irradiation with active energy rays.
- Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them.
- a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them.
- the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive.
- the amount of the external crosslinking agent used is generally 20 parts by weight or less (preferably 0.1 to 10 parts by weight) with respect to 100 parts by weight of the base polymer.
- the active energy ray-curable pressure-sensitive adhesive may contain various conventionally known additives such as tackifiers, anti-aging agents, and foaming agents in addition to the above components, if necessary.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately determined, but is generally about 5 to 200 ⁇ m.
- the pressure-sensitive adhesive layer may be composed of a single layer or a plurality of layers.
- the metal constituting the metal layer 3 is not particularly limited.
- the metal layer 3 has at least one selected from the group consisting of stainless steel, aluminum, iron, titanium, tin, nickel, and copper, and has a heat dissipation and electronic device package 8. It is preferable from the point of prevention of warpage. Among these, it is particularly preferable to contain copper from the viewpoint of high thermal conductivity and obtaining a heat dissipation effect. In addition, from the viewpoint of preventing warpage of the electronic device package 8, it is particularly preferable to include aluminum.
- the thickness of the metal layer 3 can be appropriately determined in consideration of heat dissipation, warpage prevention of the electronic device package 8, workability, etc., and is usually in the range of 2 to 200 ⁇ m.
- the metal layer 3 is 200 ⁇ m or less, the winding process is easy, and when the metal layer 3 is 50 ⁇ m or less, it is preferable in that it can contribute to thinning of the semiconductor package.
- at least 2 ⁇ m is necessary from the viewpoint of heat dissipation.
- a metal foil can be used, and the metal foil may be an electrolytic foil or a rolled foil.
- the adhesive layer 4 is a film obtained by previously forming an adhesive.
- the adhesive layer 4 is formed of at least a thermosetting resin, and is preferably formed of at least a thermosetting resin and a thermoplastic resin.
- thermoplastic resin examples include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, Thermoplastic polyimide resin, polyamide resin such as 6-nylon and 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET (polyethylene terephthalate) and PBT (polybutylene terephthalate), polyamideimide resin, or fluorine resin Etc.
- a thermoplastic resin can be used individually or in combination of 2 or more types. Among these thermoplastic resins, acrylic resins are less ionic impurities and have excellent stress relaxation properties, phenoxy resins are both high flexibility and strength and high toughness. This is particularly preferable because reliability can be easily secured.
- the acrylic resin is not particularly limited, and is a straight chain or branched chain having 30 or less carbon atoms (preferably 1 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 8 or 9 carbon atoms).
- Examples thereof include a polymer containing one or more esters of acrylic acid or methacrylic acid having an alkyl group as components. That is, in the present invention, acrylic resin has a broad meaning including methacrylic resin.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a 2-ethylhexyl group.
- Octyl group isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group, stearyl group, octadecyl group and the like.
- the other monomer for forming the acrylic resin is not particularly limited.
- acrylic acid Carboxyl group-containing monomers such as methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid, acid anhydride monomers such as maleic anhydride or itaconic anhydride, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meth) Acrylic acid 10-hydroxydec , Hydroxyl group-containing monomers such as 12-hydroxylauryl (meth) acrylic acid or (4-hydroxymethylcyclohexyl)
- thermosetting resin examples include an epoxy resin, a phenol resin, an amino resin, an unsaturated polyester resin, a polyurethane resin, a silicone resin, a thermosetting polyimide resin, and the like.
- a thermosetting resin can be used individually or in combination of 2 or more types.
- an epoxy resin containing a small amount of ionic impurities that corrode semiconductor elements is particularly suitable.
- a phenol resin can be used suitably as a hardening
- the epoxy resin is not particularly limited.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol AF type epoxy.
- Bifunctional epoxy such as resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylolethane type epoxy resin
- Epoxy such as resin, polyfunctional epoxy resin, hydantoin type epoxy resin, trisglycidyl isocyanurate type epoxy resin or glycidylamine type epoxy resin Resin can be used.
- epoxy resin among the examples, novolak type epoxy resin, biphenyl type epoxy resin, trishydroxyphenylmethane type epoxy resin, and tetraphenylolethane type epoxy resin are particularly preferable. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance and the like.
- the phenol resin acts as a curing agent for the epoxy resin.
- a novolak type phenol resin such as a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tert-butylphenol novolak resin, a nonylphenol novolak resin, or a resol type.
- examples thereof include phenol resins and polyoxystyrene such as polyparaoxystyrene.
- a phenol resin can be used individually or in combination of 2 or more types. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.
- the mixing ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 equivalent to 2.0 equivalents per equivalent of epoxy group in the epoxy resin component. More preferred is 0.8 equivalents to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.
- thermosetting acceleration catalyst is not particularly limited, and can be appropriately selected from known thermosetting acceleration catalysts.
- stimulation catalyst can be used individually or in combination of 2 or more types.
- thermosetting acceleration catalyst for example, an amine-based curing accelerator, a phosphorus-based curing accelerator, an imidazole-based curing accelerator, a boron-based curing accelerator, a phosphorus-boron-based curing accelerator, or the like can be used.
- epoxy resin curing agent a phenol resin is preferably used as described above, but known curing agents such as imidazoles, amines, and acid anhydrides can also be used.
- the adhesive layer 4 has adhesiveness (adhesiveness) to the adherend 9 such as an electronic device. Therefore, in order to crosslink the adhesive layer 4 to some extent in advance, a polyfunctional compound that reacts with the functional group at the end of the molecular chain of the polymer may be added as a crosslinking agent. Thereby, the adhesive property under high temperature can be improved and heat resistance can be improved.
- the crosslinking agent is not particularly limited, and a known crosslinking agent can be used. Specifically, for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt Examples thereof include a system crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and an amine crosslinking agent.
- the crosslinking agent an isocyanate crosslinking agent or an epoxy crosslinking agent is suitable.
- the said crosslinking agent can be used individually or in combination of 2 or more types.
- additives can be appropriately blended in the adhesive layer 4 as necessary.
- additives include fillers (fillers), flame retardants, silane coupling agents, ion trapping agents, bulking agents, antioxidants, antioxidants, and surfactants.
- the soot filler may be either an inorganic filler or an organic filler, but an inorganic filler is preferred.
- a filler such as an inorganic filler
- the adhesive layer 4 can be improved in thermal conductivity, adjusted in elastic modulus, and the like.
- the inorganic filler include silica, clay, gypsum, calcium carbonate, barium sulfate, alumina, beryllium oxide, silicon carbide, silicon nitride, aluminum nitride, and other ceramics, aluminum, copper, silver, gold, nickel, chromium,
- examples include various inorganic powders made of metals such as lead, tin, zinc, palladium, solder, alloys, and other carbon.
- a filler can be used individually or in combination of 2 or more types. Among these, silica or alumina is particularly suitable as the filler, and fused silica is particularly suitable as the silica.
- the average particle size of the inorganic filler is preferably in the range of 0.001 ⁇ m to 80 ⁇ m. The average particle diameter of the inorganic filler can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus.
- the blending amount of the filler is preferably 98% by weight or less (0% by weight to 98% by weight) with respect to the organic resin component, and particularly in the case of silica, 0% by weight to 70% by weight.
- the content is preferably 10% by weight to 98% by weight.
- examples of the flame retardant include antimony trioxide, antimony pentoxide, brominated epoxy resin, and the like.
- a flame retardant can be used individually or in combination of 2 or more types.
- examples of the silane coupling agent include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and the like.
- a silane coupling agent can be used individually or in combination of 2 or more types.
- examples of the ion trapping agent include hydrotalcites and bismuth hydroxide. An ion trap agent can be used individually or in combination of 2 or more types.
- the adhesive layer 4 contains, in particular, (A) an epoxy resin, (B) a curing agent, (C) an acrylic resin or a phenoxy resin, and (D) a surface-treated inorganic filler from the viewpoints of adhesiveness and reliability. It is preferable to do.
- epoxy resin By using an epoxy resin, high adhesiveness, water resistance, and heat resistance can be obtained.
- epoxy resin the above-described known epoxy resins can be used.
- curing agent The above-mentioned well-known hardening
- Acrylic resin has both high flexibility and strength and high toughness.
- a preferred acrylic resin has a Tg (glass transition temperature) of ⁇ 50 ° C. to 50 ° C., and is obtained by polymerizing a monomer having an epoxy group, glycidyl group, alcoholic hydroxyl group, phenolic hydroxyl group or carboxyl group as a crosslinkable functional group. It is a crosslinkable functional group-containing (meth) acrylic copolymer.
- higher toughness can be obtained by containing acrylonitrile or the like and exhibiting rubber properties.
- phenoxy resin has high strength because phenoxy resin has a long molecular chain and is similar in structure to epoxy resin, acts as a flexible material in a composition with high crosslink density, and imparts high toughness.
- a tough composition can be obtained.
- Preferable phenoxy resins are those having a main skeleton of bisphenol A type, and other preferable examples include commercially available phenoxy resins such as bisphenol F type phenoxy resin, bisphenol A / F mixed type phenoxy resin and brominated phenoxy resin.
- the surface-treated inorganic filler includes inorganic filler surface-treated with a coupling agent.
- the inorganic filler the above-mentioned known inorganic fillers can be used, for example, silica and alumina. Due to the surface treatment with the coupling agent, the dispersibility of the inorganic filler is improved. For this reason, since the adhesive layer 4 excellent in fluidity
- the surface treatment of the inorganic filler with the silane coupling agent is performed by dispersing the inorganic filler in the silane coupling agent solution by a known method, so that the hydroxyl group and the silane coupling agent present on the surface of the inorganic filler are mixed.
- This is performed by reacting a hydrolyzable group such as an alkoxy group with a hydrolyzed silanol group to form a Si—O—Si bond on the surface of the inorganic filler.
- the thickness of the adhesive layer 4 is not particularly limited, it is usually preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more from the viewpoint of easy handling, and preferably 100 ⁇ m or less in order to contribute to thinning of the semiconductor package, More preferably, it is 50 ⁇ m or less.
- the adhesive layer 4 may be composed of a single layer or a plurality of layers.
- the adhesive layer 4 has a peeling force (23 ° C., peeling angle of 180 degrees, linear speed of 300 mm / min) with the metal layer 3 in the B stage (uncured state or semi-cured state) of 0.3 N or more. Is preferred. If the peeling force is less than 0.3 N, peeling may occur between the adhesive layer 4 and the metal layer 3 during singulation (dicing).
- the water absorption rate of the adhesive layer 4 is preferably 1.5 vol% or less.
- the method for measuring the water absorption rate is as follows. That is, using a 50 ⁇ 50 mm adhesive layer 4 (film adhesive) as a sample, the sample was dried in a vacuum dryer at 120 ° C. for 3 hours, allowed to cool in a desiccator, and then measured for dry mass. M1. The sample is immersed in distilled water at room temperature for 24 hours and then taken out. The surface of the sample is wiped off with a filter paper and quickly weighed to obtain M2.
- the water absorption rate is calculated by the following equation (1).
- d is the density of the film. If the water absorption exceeds 1.5 vol%, package cracks may occur during solder reflow due to the absorbed water.
- the saturated moisture absorption rate of the adhesive layer 4 is preferably 1.0 vol% or less.
- the method for measuring the saturated moisture absorption rate is as follows. That is, a circular adhesive layer 4 (film adhesive) having a diameter of 100 mm was used as a sample, the sample was dried in a vacuum dryer at 120 ° C. for 3 hours, allowed to cool in a desiccator, and then the dry mass was measured. To do. The sample is absorbed in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 168 hours, then taken out, and weighed quickly to obtain M2.
- the saturated moisture absorption rate is calculated by the following equation (2). When the saturated moisture absorption rate exceeds 1.0 vol%, the value of vapor pressure increases due to moisture absorption during reflow, and good reflow characteristics may not be obtained.
- the residual volatile content of the adhesive layer 4 is preferably 3.0 wt% or less.
- the method for measuring the remaining volatile components is as follows. That is, using an adhesive layer 4 (film adhesive) having a size of 50 ⁇ 50 mm as a sample, measuring the initial mass of the sample as M1, and heating the sample at 200 ° C. for 2 hours in a hot air circulating thermostat, Weigh to M2.
- the remaining volatile content is calculated by the following equation (3).
- Residual volatile matter (wt%) [(M2-M1) / M1] ⁇ 100 (3) If the residual volatile content exceeds 3.0 wt%, the solvent is volatilized by heating during packaging, and voids are generated inside the adhesive layer 4, which may cause package cracks.
- the ratio of the linear expansion coefficient of the metal layer 3 to the linear expansion coefficient of the adhesive layer 4 is preferably 0.2 or more. If the ratio is less than 0.2, peeling between the metal layer 3 and the adhesive layer 4 is likely to occur, and package cracking may occur during packaging, which may reduce reliability.
- the adhesive force P1 between the base tape 2 and the metal layer 3 is 0.01 to 0.5 N / 25 mm.
- the adhesive force P2 is 0.01 to 0.5 N / 25 mm, and the ratio P1 / P2 of the adhesive force P1 between the base tape 2 and the metal layer 3 and the adhesive force P2 between the base tape 2 and the adhesive tape 5 is 0.1 to 10.
- Adhesive strength is based on JIS Z0237, a base tape 2 cut to a size of width 25 mm x length 300 mm is bonded to an adherend in an environment of 23 ° C. and 50% RH. Is measured at a peeling angle of 180 ° and a peeling speed of 300 mm / min.
- the adherend is the surface of the metal layer 3 of the laminate of the metal layer 3, the adhesive layer 4, and the adhesive tape 5 when measuring the adhesive strength P1, and when measuring the adhesive strength P2, the adhesive tape 5 is used.
- the pressure-sensitive adhesive layer surface is based on JIS Z0237, a base tape 2 cut to a size of width 25 mm x length 300 mm is bonded to an adherend in an environment of 23 ° C. and 50% RH. Is measured at a peeling angle of 180 ° and a peeling speed of 300 mm / min.
- the adherend is the surface of the metal layer 3 of the laminate of the metal layer 3, the adhesive layer 4, and the adhesive tape 5
- the adhesive force P1 between the base tape 2 and the metal layer 3 is 0.01 N / 25 mm or more, the metal layer 3 is sufficiently held by the base tape 2 in the manufacturing process of the electronic device package tape 1 and good. Precut processing or the like can be performed. If the adhesive force P1 is 0.5 N / 25 mm or less, after the metal layer 3 and the adhesive layer 4 are cut into a predetermined shape in the manufacturing process of the electronic device package tape 1, unnecessary portions around the predetermined shape Can be easily peeled off and removed from the base tape 2 (see FIG. 3D).
- the adhesive force P1 when the adhesive force P1 is too high, when the electronic device package tape 1 is used, when the base tape 2 is peeled off, a strong force is applied in the peeling direction, and the metal layer 3 and the adhesive layer 4 Wrinkles will occur in the laminate. If the adhesive force P1 is 0.5 N / 25 mm or less, the metal layer 3 can be favorably peeled from the base tape 2 when the electronic device package tape 1 is used.
- the adhesive tape 5 is sufficiently held by the base tape 2 in the manufacturing process of the electronic device package tape 1 and is good. Precut processing or the like can be performed.
- the base tape 2 is gradually peeled off from one end of the adhesive tape 5, and the tension applied to the electronic device package tape 1 is controlled by peeling the base tape 2.
- the adhesive tape 5 is bonded to the ring frame R at any time. If the adhesive force P2 is too low, the adhesive tape 5 is peeled off from the base tape 2 before the base tape 2 is peeled off. May end up.
- the tension applied to the electronic device package tape 1 cannot be controlled due to the peeling of the base tape 2.
- wrinkles approach the adhesive tape 5, the adhesive layer 4 and the metal layer 3 laminated thereon.
- the adhesive force P2 is 0.01 N / 25 mm or more, the adhesive tape 5 can be prevented from peeling off from the base tape 2 before the base tape 2 is peeled off, and air can be prevented from entering.
- the adhesive tape 5 can be bonded.
- the following is mentioned as a factor in which the adhesive tape 5 peels from the base tape 2 and air enters before peeling the base tape 2, for example.
- the pre-cut laminate of the adhesive tape 5, the adhesive layer 4 and the metal layer 3 is sequentially unwound to mount the ring frame R.
- the adhesive tape 5 is squeezed over the base tape 2 by the conveyance auxiliary roller arranged in the path for conveyance to the pasting table, and at this time, if the peeling force P2 is too low, the end of the adhesive tape 5 Air floats off the base tape 2 and air enters.
- the adhesive force P2 is 0.5 N / 25 mm or less, in the manufacturing process of the electronic device package tape 1, after cutting the adhesive tape 5 into a predetermined shape, unnecessary portions around the predetermined shape are removed from the base tape 2. Can be easily peeled off and removed (see FIG. 3D).
- the adhesive force P2 is too high, when the electronic device package tape 1 is used, when the base tape 2 is peeled off, a strong force is applied in the peeling direction, and the metal layer 3 and the adhesive layer 4 Wrinkles will occur in the laminate. If the adhesive force P2 is 0.5 N / 25 mm or less, the adhesive tape 5 can be favorably peeled from the base tape 2 when the electronic device package tape 1 is used.
- the viscoelasticity and thickness of the base tape 2 and the adhesive tape 5 may be adjusted, or the surface roughness of the metal layer 3 may be adjusted.
- silane coupling agent treatment, plasma treatment, ozone water treatment, ultraviolet ozone treatment, ion beam treatment, etc. on the surface of the metal layer 3 on the side in contact with the base tape 2 Surface treatment can be performed.
- electrolytic foil as the metal layer 3, the surface roughness of the mat
- a method for manufacturing the electronic device package tape 1 according to the present embodiment will be described.
- a long metal layer 3 is prepared.
- the metal layer 3 a commercially available metal foil may be used.
- the metal layer 3 is bonded to the adhesive surface of the long base tape 2 using a bonding roller r or the like.
- a long film adhesive layer 4 is formed.
- the adhesive layer 4 can be formed using a conventional method of preparing a resin composition and forming it into a film-like layer. Specifically, for example, the resin composition is applied on a suitable separator (such as a release paper) and dried (when heat curing is necessary, heat treatment is performed as necessary to dry), Examples include a method of forming the adhesive layer 4.
- the resin composition may be a solution or a dispersion.
- the adhesive layer 4 peeled from the separator is bonded onto the metal layer 3 bonded to the base tape 2 using a bonding roller r or the like.
- the adhesive layer 4 was bonded onto the metal layer 3, but the metal layer 3 and the adhesive layer 4 were bonded together. Then, the surface on the metal layer 3 side may be bonded to the base tape 2.
- the adhesive layer 4 and the metal layer 3 are pre-cut into a predetermined shape (here circular shape) using a press cutting blade or the like, and as shown in FIG.
- the unnecessary portion 6 is peeled off from the base tape 2 and removed.
- the adhesive force P1 between the base tape 2 and the metal layer 3 is 0.01 N / 25 mm or more and 0.5 N / 25 mm or less, the metal layer 3 is sufficiently adhered and fixed to the base tape 2, Since the unnecessary part 6 can be easily peeled off from the base tape 2, the pre-cut process can be performed satisfactorily.
- the precut is not limited to the above, and the adhesive layer 4 and the metal layer 3 are preliminarily set to a predetermined size such as a size corresponding to the semiconductor chip C by using grid-shaped pressing teeth having a circular outer edge. It may be separated into pieces.
- the method for forming the metal layer 3 and the adhesive layer 4 having a predetermined shape on the base tape 2 is not limited to the above, and the long metal layer 3 is formed on the long base tape 2.
- the adhesive layer 4 formed in a predetermined shape may be bonded onto the metal layer 3 having a predetermined shape
- the metal layer 3 and the adhesive layer 4 formed on the substrate may be bonded to the base tape 2, but from the simplicity of the manufacturing process, the metal layer 3 and the adhesive layer 4 are manufactured by the steps shown in FIGS. It is preferable.
- the base film can be formed by a conventionally known film forming method.
- the film forming method include a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method.
- an adhesive layer composition is apply
- the coating method include roll coating, screen coating, and gravure coating.
- the adhesive layer may be transferred to a substrate film. Thereby, the adhesive tape 5 in which the adhesive layer was formed on the base film is produced.
- the adhesive layer side of the adhesive tape 5 is placed on the surface of the adhesive layer 4 side of the metal layer 3 and the adhesive layer 4 having a predetermined shape provided on the base tape 2.
- the pressure-sensitive adhesive tape 5 is laminated so that the surface is in contact.
- the adhesive force P2 between the base tape 2 and the adhesive tape 5 is 0.01 N / 25 mm or more, the adhesive tape 5 is sufficiently adhered and fixed to the base tape 2 and can be laminated satisfactorily. .
- the adhesive tape 5 is pre-cut into a predetermined shape using a press cutting blade or the like, and the surrounding unnecessary portion 7 is removed from the base tape 2 as shown in FIG. 4 (C).
- the tape 1 for electronic device package is made by peeling and removing.
- the adhesive force P2 is 0.5 N / 25 mm or less, the unnecessary portion 7 can be easily peeled off and removed from the base tape 2.
- a separate dicing tape D similar to the adhesive tape 5 of the electronic device package tape 1 of the present invention is prepared, and a semiconductor as shown in FIG.
- the wafer W is adhered and held and fixed by adhering (mounting process of the semiconductor wafer W), and the ring frame R is adhered to the peripheral portion of the dicing tape D.
- the dicing tape D is attached to the back surface of the semiconductor wafer W.
- the back surface of the semiconductor wafer W means a surface opposite to the circuit surface (also referred to as a non-circuit surface or a non-electrode forming surface).
- the sticking method is not specifically limited, the method by thermocompression bonding is preferable.
- the crimping is usually performed while pressing with a pressing means such as a crimping roll.
- the semiconductor wafer W is diced.
- the semiconductor wafer W is cut into a predetermined size and divided into pieces (small pieces), whereby the semiconductor chip C is manufactured.
- the dicing is performed from the circuit surface side of the semiconductor wafer W according to a conventional method.
- a cutting method called full cut in which cutting is performed up to the dicing tape D can be employed. It does not specifically limit as a dicing apparatus used at this process, A conventionally well-known thing can be used.
- the expanding can be performed using a conventionally known expanding apparatus.
- the pickup method is not particularly limited, and various conventionally known methods can be employed.
- a dicing tape D to which a semiconductor chip C and a ring frame R are bonded is placed on a stage S of a pickup device with the base film side down, and the ring frame R is fixed in a hollow cylindrical shape.
- the push-up member T is raised and the dicing tape D is expanded. In this state, a method of pushing up the individual semiconductor chips C from the base film side of the dicing tape D with the needles N and picking up the pushed-up semiconductor chips C with a pickup device can be mentioned.
- the picked-up semiconductor chip C is fixed to an adherend 9 such as a substrate by a flip chip bonding method (flip chip mounting method).
- the semiconductor chip C is always placed on the adherend 9 such that the circuit surface (also referred to as a surface, a circuit pattern formation surface, an electrode formation surface, etc.) of the semiconductor chip C faces the adherend 9.
- the circuit surface also referred to as a surface, a circuit pattern formation surface, an electrode formation surface, etc.
- flux is attached to the bumps 10 as connection portions formed on the circuit surface side of the semiconductor chip C.
- the bump 10 and the conductive material 11 are melted while bringing the bump 10 of the semiconductor chip C into contact with the bonding conductive material 11 (solder or the like) attached to the connection pad of the adherend 9 and pressing it.
- the electrical conduction between the semiconductor chip C and the adherend 9 can be ensured, and the semiconductor chip C can be fixed to the adherend 9 (flip chip bonding step).
- a gap is formed between the semiconductor chip C and the adherend 9, and the gap distance is generally about 30 ⁇ m to 300 ⁇ m.
- the flux remaining on the opposing surface or gap between the semiconductor chip C and the adherend 9 is removed by washing.
- various substrates such as a lead frame and a circuit substrate (such as a wiring circuit substrate) can be used.
- the material of such a substrate is not particularly limited, and examples thereof include a ceramic substrate and a plastic substrate.
- the plastic substrate include an epoxy substrate, a bismaleimide triazine substrate, and a polyimide substrate.
- a chip-on-chip structure can be obtained by using another semiconductor chip as the adherend 9 and flip-chip connection of the semiconductor chip C.
- the base tape 2 of the electronic device package tape 1 according to the present embodiment is peeled off to expose the adhesive layer of the metal layer 3 and the adhesive tape 5, and the adhesive The peripheral part of the agent layer is fixed to the ring frame R.
- the adhesive force P1 between the base tape 2 and the metal layer 3 is 0.5 N / 25 mm or less
- the adhesive force P2 between the base tape 2 and the adhesive tape 5 is 0.01 N / 25 mm or more and 0.5 N / Since the ratio P1 / P2 of the adhesive strength P1 between the base tape 2 and the metal layer 3 and the adhesive strength P2 between the base tape 2 and the adhesive tape 5 is 0.1-10,
- the material tape 2 can be satisfactorily peeled, and the laminate of the metal layer 3, the adhesive layer 4 and the pressure-sensitive adhesive tape 5 can be bonded to the ring frame R without causing wrinkles.
- the metal layer 3 and the adhesive layer 4 are cut into pieces corresponding to the semiconductor chip C and separated into pieces.
- the cutting can be performed in the same process as the dicing process of the semiconductor wafer W described above. In addition, this process is not performed when the pre-cut process which separates the metal layer 3 and the adhesive bond layer 4 previously is performed.
- the separated metal layer 3 and adhesive layer 4 are picked up and peeled off from the adhesive tape 5.
- the pickup can be performed in the same process as the semiconductor chip C pickup process described above.
- the picked up metal layer 3 and the adhesive layer 4 side of the adhesive layer 4 are bonded to the back surface of the flip chip connected semiconductor chip C as shown in FIG. Thereafter, the periphery of the semiconductor chip C with the metal layer 3 and the gap between the semiconductor chip C and the adherend 9 are filled with a sealing material (such as a sealing resin) and sealed. Sealing is performed according to a conventional method.
- a sealing material such as a sealing resin
- Sealing is performed according to a conventional method.
- the metal layer 3 is provided on the back surface of the semiconductor chip C, warping caused by a difference in thermal expansion coefficient between the semiconductor chip C and the adherend 9 in the flip chip bonding process is caused. 3 is offset by the difference in coefficient of thermal expansion from 3.
- the metal layer 3 is provided on the back surface of the semiconductor chip C, heat generated during use as an electronic device is dissipated by the metal layer 3.
- the package structure in which the metal layer 3 is directly provided on the back surface of the semiconductor chip C via the adhesive layer 4 and the metal layer 3 is also sealed together with the semiconductor chip C has been described.
- the semiconductor chip C is sealed.
- the metal layer 3 may be provided on the upper surface of the sealing body via the adhesive layer 4. Since the electronic device package 8 warps during sealing, the warping during sealing can be offset by providing the metal layer 3 on the upper surface of the sealing body.
- the semiconductor chip C flip-chip connected on the adherend 9 is described as an example of the electronic device package 8, but the present invention is not limited to this, and for example, the same size on the semiconductor chip.
- the lower semiconductor chip is interposed via an adhesive layer 4 in order to use the metal layer 3 of the electronic device package tape 1 of the present invention as a spacer between the two chips.
- the metal layer 3 may be provided thereon.
- Base film a-1 Zinc ionomer a (density 0.96 g / cm 3 , zinc ion content 4 mass) of ethylene-methacrylic acid-ethyl methacrylate (mass ratio 8: 1: 1) terpolymer synthesized by radical polymerization method %, Chlorine content of less than 1% by mass, Vicat softening point 56 ° C., melting point 86 ° C.) are melted at 140 ° C. and formed into a long film of 100 ⁇ m thickness using an extruder. A material film a-1 was produced.
- Base film a-2 (Base film a-2) Novatec PP FW4B (polypropylene) manufactured by Nippon Polychem Co., Ltd. (density: 0.90 g / cm 3 , Vicat softening point 96 ° C., melting point: 140 ° C.) was melted at 180 ° C., and the thickness was 100 ⁇ m using an extruder.
- a base film a-2 was produced by molding into a long film.
- Adhesive layer composition b-1 As the acrylic copolymer (A1) having a functional group, a copolymer comprising 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methacrylic acid, the ratio of 2-ethylhexyl acrylate being 55 mol%, and the weight average molecular weight being 750,000 Was prepared. Next, 2-isocyanatoethyl methacrylate was added so that the iodine value would be 25, and an acrylic copolymer (a1) having a glass transition temperature of ⁇ 50 ° C., a hydroxyl value of 10 gKOH / g, and an acid value of 5 mgKOH / g Was prepared.
- Adhesive layer composition b-2 As the acrylic copolymer (A2) having a functional group, a copolymer comprising 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methacrylic acid, the ratio of 2-ethylhexyl acrylate being 70 mol%, and the mass average molecular weight of 750,000 Was prepared. Next, 2-isocyanatoethyl methacrylate is added so that the iodine value becomes 20, and the acrylic copolymer (a2) having a glass transition temperature of ⁇ 50 ° C., a hydroxyl value of 15 gKOH / g, and an acid value of 5 mgKOH / g Was prepared.
- the prepared pressure-sensitive adhesive layer composition b-1 was applied to a release liner made of a release-treated polyethylene-terephthalate film so that the thickness after drying was 10 ⁇ m, and dried at 110 ° C. for 3 minutes.
- the pressure-sensitive adhesive tape (1) having the pressure-sensitive adhesive layer formed on the base film was prepared by bonding to the base film a-1.
- ⁇ Adhesive tape (2)> The prepared pressure-sensitive adhesive layer composition b-2 was applied to a release liner made of a polyethylene-terephthalate film subjected to a release treatment so that the thickness after drying was 10 ⁇ m, and dried at 110 ° C. for 3 minutes.
- the pressure-sensitive adhesive tape (2) having the pressure-sensitive adhesive layer formed on the base film was prepared by bonding to the base film a-1.
- ⁇ Adhesive tape (3)> The prepared pressure-sensitive adhesive layer composition b-2 was applied to a release liner made of a polyethylene-terephthalate film subjected to a release treatment so that the thickness after drying was 10 ⁇ m, and dried at 110 ° C. for 3 minutes.
- the pressure-sensitive adhesive tape (3) was prepared by laminating with the base film a-2 to form a pressure-sensitive adhesive layer on the base film.
- Epoxy resin “1002” (Mitsubishi Chemical Corporation, trade name, solid bisphenol A type epoxy resin, epoxy equivalent 600) 50 parts by mass, Epoxy resin “806” (Mitsubishi Chemical Corporation, trade name, bisphenol F type epoxy resin) , Epoxy equivalent 160, specific gravity 1.20) 100 parts by mass, curing agent “Dyhard (registered trademark) 100SF” (trade name, dicyandiamide, manufactured by Evonik Degussa), silica filler “SO-C2” (Admafine ( Co., Ltd., trade name, average particle size 0.5 ⁇ m) 150 parts by mass, and “Aerosil R972” which is a silica filler (manufactured by Nippon Aerosil Co., Ltd., trade name, average particle size 0.016 ⁇ m of primary particle size) 5 mass MEK was added to the composition consisting of parts and mixed by stirring to obtain a uniform composition.
- phenoxy resin “PKHH” (trade name, mass average molecular weight 52,000, glass transition temperature 92 ° C., manufactured by INCEM), “KBM-802” (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) as a coupling agent , Mercaptopropyltrimethoxysilane) 0.4 parts by mass
- “Cureazole 2PHZ-PW” (trade name, 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator 0.5 parts by mass of (temperature 230 ° C.) was added and mixed with stirring until uniform. Further, this was filtered through a 100-mesh filter and vacuum degassed to obtain an adhesive layer composition c-1 varnish.
- Adhesive layer composition c-1 was applied to a separator made of a polyethylene-terephthalate film after the release treatment so that the thickness after drying was 5 ⁇ m, and dried at 110 ° C. for 5 minutes. An adhesive film on which the adhesive layer (1) was formed was produced.
- Metal layer The following were prepared as a metal layer.
- GTS-MP trade name, manufactured by Furukawa Electric Co., Ltd., copper foil, thickness 35 ⁇ m, surface roughness Rz 11.0 ⁇ m
- Resin film d-1 Styrene-hydrogenated isoprene-styrene block copolymer (SEPS) (Kuraray Co., Ltd., trade name “Septon KF-2104”) and homopropylene (PP) (Ube Industries, Ltd., trade name “J-105G”)
- SEPS Styrene-hydrogenated isoprene-styrene block copolymer
- PP homopropylene
- J-105G homopropylene
- Resin film d-2 Resin beads of polyethylene terephthalate (PET) (trade name “Cosmo Shine (registered trademark) A4100” manufactured by Toyobo Co., Ltd.) are melted at 260 ° C. and formed into a long film having a thickness of 50 ⁇ m using an extruder. Thus, a resin film d-2 was produced.
- PET polyethylene terephthalate
- the acrylic copolymer (A3) having a functional group is composed of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methacrylic acid, the ratio of 2-ethylhexyl acrylate is 70 mol%, the weight average molecular weight is 500,000, and the glass transition temperature.
- the acrylic copolymer (A4) having a functional group is composed of lauryl acrylate, 2-hydroxyethyl acrylate and methacrylic acid, the ratio of lauryl acrylate is 80 mol%, the weight average molecular weight is 500,000, the glass transition temperature is 10 ° C., the hydroxyl group
- ⁇ Base tape (2)> The prepared pressure-sensitive adhesive layer composition for base tape e-2 was applied to a release liner made of a release-treated polyethylene-terephthalate film so as to have a thickness after drying of 10 ⁇ m, and at 110 ° C. for 3 minutes. After drying, it was bonded to the resin film d-1 to prepare a base tape (2) in which a base tape pressure-sensitive adhesive layer was formed on the resin film.
- the separator is peeled off from the adhesive layer, and the adhesive layer and the metal layer are pre-cut into a circular shape with a diameter of 320 mm using a pressing blade so as to reach the base tape from the surface of the adhesive layer, and unnecessary peripheral portions are removed. It peeled and removed from the base tape (primary precut process).
- the adhesive tape (1) was laminated so that the surface on the adhesive layer side of the metal layer and adhesive layer provided on the base tape was in contact with the surface on the adhesive layer side (adhesive tape laminating step).
- the pressure-sensitive adhesive tape (1) is pre-cut into a circular shape with a diameter of 370 mm so as to be concentric with the metal layer and the adhesive layer, and peripheral unnecessary portions are peeled off and removed from the base tape (secondary pre-cut process).
- a roll of the electronic device package tape according to Example 1 as shown in FIGS. 1 and 2 was produced by winding 100 laminates of the metal layer, the adhesive layer, and the pressure-sensitive adhesive tape.
- the adhesive strength was measured according to the following procedure in accordance with JIS Z0237. (Adhesive force P1 between base tape and metal layer) Three test pieces having a width of 25 mm and a length of 300 mm were collected from the base sheet according to each of the examples and comparative examples, and these were laminated to the metal layer, the adhesive layer, and the pressure-sensitive adhesive tape according to each of the examples and comparative examples. After being adhered to the surface of the metal layer, a 2 kg rubber roller was pressure-bonded over 3 reciprocations and left for 1 hour as a sample. The adhesive strength was measured using a tensile tester conforming to JIS B 7721 whose measured value was in the range of 15 to 85% of its capacity. The measurement was performed by a 180 ° peeling method, and the tensile speed at this time was 300 mm / min. The measurement temperature was 23 ° C. and the measurement humidity was 50%. Tables 1 and 2 show the average values of the three points.
- Adhesive strength P2 between base tape and adhesive tape After collecting three test pieces having a width of 25 mm ⁇ a length of 300 mm from the base sheet according to each example and comparative example, and pasting them on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive tape according to each example and comparative example, A 2 kg rubber roller was pressure-bonded over 3 reciprocations and left for 1 hour as a sample.
- the adhesive strength was measured using a tensile tester conforming to JIS B 7721 whose measured value was in the range of 15 to 85% of its capacity. The measurement was performed by a 180 ° peeling method, and the tensile speed at this time was 300 mm / min.
- the measurement temperature was 23 ° C. and the measurement humidity was 50%. Tables 1 and 2 show the average values of the three points.
- a product having a defect rate of less than 5% of the whole is considered as a good product, and a product having a defect rate of 5% or more and less than 10% in a dicing process and a die bonding process is accepted as a acceptable product, a dicing process and a die bonding. Those having a defect rate of 10% or more due to wrinkles in the process were evaluated as x as defective products.
- the adhesive strength P1 between the base tape and the metal layer is 0.01 to 0.3 N / 25 mm, and the 0.
- the adhesive strength P2 between the base tape and the adhesive tape is 0.01 to 0.5 N / 25 mm as defined in the claims, and the adhesive strength P1 between the base tape and the metal layer is 01 to 0.5 N / 25 mm.
- the ratio P1 / P2 of the adhesive strength P2 between the base tape and the adhesive tape is 0.1 to 8 and 0.1 to 10 as defined in the claims. Good results.
- the electronic device package tape according to Comparative Example 1 has an adhesive force P1 between the base tape and the metal layer of more than 0.5 N / 25 mm, and the base tape and the adhesive tape.
- Adhesive strength P2 exceeds 0.5N / 25mm, so after punching the metal layer and adhesive layer into a circular shape, and after punching the adhesive tape into a circular shape, remove unnecessary peripheral parts from the base tape It was difficult to peel off, resulting in poor pre-cut processability.
- too strong force is applied in the peeling direction of the base tape, wrinkles occur in the laminate of the metal layer and the adhesive layer, resulting in poor ring frame bonding properties. It was.
- the adhesive force P1 between the base tape and the metal layer is less than 0.01 N / 25 mm, so that the metal layer is peeled off during precut processing, resulting in poor precut workability. Since the ratio P1 / P2 of the adhesive strength P1 between the base tape and the metal layer and the adhesive strength P2 between the base tape and the adhesive tape is less than 0.1, the result is inferior in ring frame bonding properties. It became.
- the tapes for electronic device packages according to Comparative Examples 5 and 7 resulted in inferior pre-cut processability because the adhesive force P1 between the base tape and the metal layer exceeded 0.5 N / 25 mm.
- the tape for an electronic device package according to Comparative Example 6 had inferior pre-cut processability because the adhesive force P1 between the base tape and the metal layer was less than 0.01 N / 25 mm.
- the tape for an electronic device package according to Comparative Example 9 has an adhesive force P2 between the base tape and the adhesive tape of less than 0.01 N / 25 mm, so that air enters between the adhesive tape and the base tape, and the ring frame At the time of bonding, the tension applied to the electronic device package tape could not be controlled due to the peeling of the base tape, and wrinkles were generated, resulting in poor ring frame bonding properties.
- the tape for an electronic device package according to Comparative Example 8 has an adhesive force P2 between the base tape and the adhesive tape of less than 0.01 N / 25 mm, and an adhesive force P1 between the base tape and the metal layer, and the base tape and adhesive. Since ratio P1 / P2 with respect to adhesive force P2 with a tape exceeded 10, it became a result inferior to ring frame bonding property.
- the tape for an electronic device package according to Comparative Example 10 resulted in inferior pre-cut processability because the adhesive force P1 between the base tape and the metal layer was less than 0.01 N / 25 mm. Moreover, since the adhesive force P2 of a base tape and an adhesive tape is less than 0.01 N / 25mm, it resulted in being inferior to ring frame bondability.
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- Physics & Mathematics (AREA)
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Abstract
Description
接着剤層4は、所定の平面形状を有しており、この平面形状は、粘着テープ5のラベル部5aの周縁部にリングフレームRを貼合し、ピックアップ装置の突き上げ部材で突き上げ可能なように(図6(C)参照)ラベル部5aよりも小さい形状となっている。接着剤層4は、ラベル部5aと略同じ形状でラベル部5aの大きさより小さい相似形であることが好ましい。接着剤層4は、必ずしも円形でなくてもよいが、円形に近い形状が好ましく、円形であることがさらに好ましい。
基材テープ2は、粘着面を有し、基材テープ2と金属層3との粘着力P1が0.01~0.5N/25mmであり、基材テープ2と粘着テープ5との粘着力P2が0.01~0.5N/25mmであり、基材テープ2と金属層3との粘着力P1と基材テープ2と粘着テープ5との粘着力P2との比P1/P2が、0.1~10であれば、特に限定されるものではない。このような基材テープ2として、例えば、樹脂フィルムと樹脂フィルムの片面に設けられた基材テープ用粘着剤層とを有するテープを好適に使用することができる。
粘着テープ5としては、基材テープ2と粘着テープ5との粘着力P2が0.01~0.5N/25mmであり、基材テープ2と金属層3との粘着力P1と基材テープ2と粘着テープ5との粘着力P2との比P1/P2が、0.1~10であれば、特に制限はなく、従来の粘着テープ5を使用することができる。粘着テープ5として、例えば、基材フィルムに粘着剤層を設けたものを好適に使用できる。
金属層3を構成する金属としては特に限定されず、例えば、ステンレス、アルミニウム、鉄、チタン、スズ、ニッケル及び銅からなる群より選択される少なくとも1種であることが放熱性、電子デバイスパッケージ8の反り防止の点から好ましい。これらの中でも、熱伝導性が高く放熱の効果が得られる観点から、銅を含むことが特に好ましい。また、電子デバイスパッケージ8の反り防止の観点からは、アルミニウムを含むことが特に好ましい。
接着剤層4は、接着剤を予めフィルム化したものである。
また、(C)フェノキシ樹脂は、フェノキシ樹脂は分子鎖が長くエポキシ樹脂と構造が似ており、高架橋密度の組成物中で可とう性材料として作用し、高靭性を付与するので高強度でありながらタフネスな組成物が得られる。好ましいフェノキシ樹脂は、主骨格がビスフェノールA型のものであるが、その他にビスフェノールF型フェノキシ樹脂、ビスフェノールA/F混合型フェノキシ樹脂や臭素化フェノキシ樹脂等市販のフェノキシ樹脂が好ましいものとして挙げられる。
ここで、dはフィルムの密度である。
吸水率が1.5vol%を超えると、吸水した水分によりはんだリフロー時にパッケージクラックを生じるおそれがある。
飽和吸湿率が1.0vol%を超えると、リフロー時の吸湿により蒸気圧の値が高くなり、良好なリフロー特性が得られないおそれがある。
残存揮発分(wt%)=[(M2-M1)/M1]×100 (3)
残存揮発分が3.0wt%を超えると、パッケージングの際の加熱により溶媒が揮発し、接着剤層4の内部にボイドが発生して、パッケージクラックが発生するおそれがある。
次に、本実施形態の電子デバイスパッケージ用テープ1を使用して電子デバイスパッケージ8を製造する方法について、図5~図7を参照しながら説明する。なお、本実施形態においては、電子デバイスパッケージ8として、被着体9上にフリップチップ接続された半導体チップCを例にして説明する。
先ず、本発明の電子デバイスパッケージ用テープ1の粘着テープ5と同様の別体のダイシングテープDを用意し、該ダイシングテープD上の中央部に、図5(A)で示されるように、半導体ウエハWを貼着して、これを粘着保持させ固定する(半導体ウエハWのマウント工程)とともに、ダイシングテープDの周縁部にリングフレームRを貼合する。このとき、ダイシングテープDは、半導体ウエハWの裏面に貼着される。半導体ウエハWの裏面とは、回路面とは反対側の面(非回路面、非電極形成面などとも称される)を意味する。貼着方法は特に限定されないが、加熱圧着による方法が好ましい。圧着は、通常、圧着ロール等の押圧手段により押圧しながら行われる。
次に、図5(B)で示されるように、半導体ウエハWのダイシングを行う。これにより、半導体ウエハWを所定のサイズに切断して個片化(小片化)し、半導体チップCを製造する。ダイシングは、例えば、半導体ウエハWの回路面側から常法に従い行われる。また、本工程では、例えば、ダイシングテープDまで切り込みを行うフルカットと呼ばれる切断方式等を採用できる。本工程で用いるダイシング装置としては特に限定されず、従来公知のものを用いることができる。なお、ダイシングテープDのエキスパンドを行う場合、該エキスパンドは従来公知のエキスパンド装置を用いて行うことができる。
図5(C)で示されるように、半導体チップCのピックアップを行って、半導体チップCをダイシングテープDより剥離させる。ピックアップの方法としては特に限定されず、従来公知の種々の方法を採用できる。例えば、半導体チップCおよびリングフレームRが貼り合わされたダイシングテープDを、基材フィルム側を下にして、ピックアップ装置のステージS上に載置し、リングフレームRを固定した状態で、中空円柱形状の突き上げ部材Tを上昇させ、ダイシングテープDを拡張する。この状態で、個々の半導体チップCをダイシングテープDの基材フィルム側からニードルNによって突き上げ、突き上げられた半導体チップCをピックアップ装置によってピックアップする方法等が挙げられる。
ピックアップした半導体チップCは、図5(D)で示されるように、基板等の被着体9に、フリップチップボンディング方式(フリップチップ実装方式)により固定させる。具体的には、半導体チップCを、半導体チップCの回路面(表面、回路パターン形成面、電極形成面などとも称される)が被着体9と対向する形態で、被着体9に常法に従い固定させる。例えば、まず半導体チップCの回路面側に形成されている接続部としてのバンプ10にフラックスを付着させる。次いで、半導体チップCのバンプ10を被着体9の接続パッドに被着された接合用の導電材11(半田など)に接触させて押圧しながらバンプ10及び導電材11を溶融させることにより、半導体チップCと被着体9との電気的導通を確保し、半導体チップCを被着体9に固定させることができる(フリップチップボンディング工程)。このとき、半導体チップCと被着体9との間には空隙が形成されており、その空隙間距離は、一般的に30μm~300μm程度である。半導体チップCと被着体9との対向面や間隙に残存するフラックスは洗浄除去する。
次に、本発明の効果をさらに明確にするために、実施例および比較例について詳細に説明するが、本発明はこれら実施例に限定されるものではない。
(基材フィルムa-1)
ラジカル重合法によって合成されたエチレン-メタアクリル酸-メタアクリル酸エチル(質量比8:1:1)3元共重合体の亜鉛アイオノマーa(密度0.96g/cm3、亜鉛イオン含有量4質量%、塩素含有量1質量%未満、ビカット軟化点56℃、融点86℃)の樹脂ビーズを140℃で溶融し、押出機を用いて厚さ100μmの長尺フィルム状に成形することにより、基材フィルムa-1を作製した。
日本ポリケム社製 ノバテックPP FW4B(ポリプロピレン)(密度:0.90g/cm3、ビカット軟化点96℃、融点:140℃)の樹脂ビーズを180℃で溶融し、押出機を用いて厚さ100μmの長尺フィルム状に成形することにより、基材フィルムa-2を作製した。
官能基を有するアクリル系共重合体(A1)として、2-エチルヘキシルアクリレート、2-ヒドロキシエチルアクリレートおよびメタクリル酸からなり、2-エチルヘキシルアクリレートの比率が55モル%、質量平均分子量75万の共重合体を調製した。次に、ヨウ素価が25となるように、2-イソシアナトエチルメタクリレートを添加して、ガラス転移温度-50℃、水酸基価10gKOH/g、酸価5mgKOH/gのアクリル系共重合体(a1)を調製した。
アクリル系共重合体(a1)100質量部に対して、ポリイソシアネートとしてコロネートL(東ソー株式会社製、商品名)を3質量部加え、光重合開始剤としてEsacure KIP 150(Lamberti社製、商品名)を3質量部加えた混合物を、酢酸エチルに溶解させ、攪拌して、粘着剤層組成物b-1を得た。
官能基を有するアクリル系共重合体(A2)として、2-エチルヘキシルアクリレート、2-ヒドロキシエチルアクリレートおよびメタクリル酸からなり、2-エチルヘキシルアクリレートの比率が70モル%、質量平均分子量75万の共重合体を調製した。次に、ヨウ素価が20となるように、2-イソシアナトエチルメタクリレートを添加して、ガラス転移温度-50℃、水酸基価15gKOH/g、酸価5mgKOH/gのアクリル系共重合体(a2)を調製した。
アクリル系共重合体(a2)100質量部に対して、ポリイソシアネートとしてコロネートL(日東ソー株式会社製、商品名)を3質量部加え、光重合開始剤としてEsacure KIP 150(Lamberti社製、商品名)を5質量部加えた混合物を、酢酸エチルに溶解させ、攪拌して、粘着剤層組成物b-2を得た。
<粘着テープ(1)>
調製した粘着剤層組成物b-2を、離型処理したポリエチレン-テレフタレートフィルムよりなる剥離ライナーに、乾燥後の厚さが10μmになるように塗工し、110℃で3分間乾燥させた後、上記基材フィルムa-1と貼り合わせ、基材フィルム上に粘着剤層が形成された粘着テープ(2)を作製した。
調製した粘着剤層組成物b-2を、離型処理したポリエチレン-テレフタレートフィルムよりなる剥離ライナーに、乾燥後の厚さが10μmになるように塗工し、110℃で3分間乾燥させた後、上記基材フィルムa-2と貼り合わせ、基材フィルム上に粘着剤層が形成された粘着テープ(3)を作製した。
エポキシ樹脂「1002」(三菱化学株式会社製、商品名、固形ビスフェノールA型エポキシ樹脂、エポキシ当量600)50質量部、エポキシ樹脂「806」(三菱化学株式会社製、商品名、ビスフェノールF型エポキシ樹脂、エポキシ当量160、比重1.20)100質量部、硬化剤「Dyhard(登録商標)100SF」(エボニック デグサ社製、商品名、ジシアンジアミド)5質量部、シリカフィラー「SO-C2」(アドマファイン(株)製商品名、平均粒径0.5μm)150質量部、及び、シリカフィラーである「アエロジルR972」(日本アエロジル株式会社製、商品名、一次粒径の平均粒径0.016μm)5質量部からなる組成物にMEKを加え、攪拌混合し、均一な組成物とした。
これに、フェノキシ樹脂「PKHH」(INCHEM製、商品名、質量平均分子量52,000、ガラス転移温度92℃)100質量部、カップリング剤として「KBM-802」(信越シリコーン株式会社製、商品名、メルカプトプロピルトリメトキシシラン)0.4質量部、並びに、硬化促進剤としての「キュアゾール2PHZ-PW」(四国化成工業株式会社製、商品名、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、分解温度230℃)0.5質量部を加え、均一になるまで攪拌混合した。更にこれを100メッシュのフィルターでろ過し、真空脱泡することにより、接着剤層組成物c-1のワニスを得た。
離型処理したポリエチレン-テレフタレートフィルムよりなるセパレーターに、接着剤層組成物c-1を、乾燥後の厚さが5μmになるように塗工し、110℃で5分間乾燥させて、セパレーター上に接着剤層(1)が形成された接着フィルムを作製した。
金属層として以下のものを準備した。
<金属層(1)>
TQ-M4-VSP(商品名、三井金属鉱業株式会社製、厚さ12μm、表面粗さRz0.6μm)
<金属層(2)>
F0-WS(商品名、古河電気工業株式会社製、銅箔、厚さ12μm、表面粗さRz1.3μm)
<金属層(3)>
GTS-MP(商品名、古河電気工業株式会社製、銅箔、厚さ35μm、表面粗さRz11.0μm)
(4)基材テープの作製
(樹脂フィルムd-1)
スチレン-水添イソプレン-スチレンブロック共重合体(SEPS)(株式会社クラレ社製、商品名「セプトンKF-2104」)とホモプロピレン(PP)(宇部興産株式会社製、商品名「J-105G」)を40:60で示す配合比で混合した樹脂ビーズを200℃で溶融し、押出機を用いて厚さ90μmの長尺フィルム状に成形することにより、樹脂フィルムd-1を作製した。
ポリエチレンテレフタラート(PET)(東洋紡株式会社製、商品名「コスモシャイン(登録商標)A4100」)の樹脂ビーズを260℃で溶融し、押出機を用いて厚さ50μmの長尺フィルム状に成形することにより、樹脂フィルムd-2を作製した。
官能基を有するアクリル系共重合体(A3)として、2-エチルヘキシルアクリレート、2-ヒドロキシエチルアクリレートおよびメタクリル酸からなり、2-エチルヘキシルアクリレートの比率が70モル%、質量平均分子量50万、ガラス転移温度-50℃、水酸基価30gKOH/g、酸価5mgKOH/gのアクリル系共重合体(a3)を調製した。
アクリル系共重合体(a3)100質量部に対して、ポリイソシアネート系化合物(商品名「コロネートL」、東ソー株式会社製)を8質量部加え、酢酸エチルに溶解させ、攪拌して、基材テープ用粘着剤層組成物e-1を得た。
官能基を有するアクリル系共重合体(A4)として、ラウリルアクリレート、2-ヒドロキシエチルアクリレートおよびメタクリル酸からなり、ラウリルアクリレートの比率が80モル%、質量平均分子量50万、ガラス転移温度10℃、水酸基価40gKOH/g、酸価5mgKOH/gのアクリル系共重合体(a4)を調製した。
アクリル系共重合体(a4)100質量部に対して、ポリイソシアネート系化合物(商品名「コロネートL」、東ソー株式会社製)を10質量部加え、酢酸エチルに溶解させ、攪拌して、基材テープ用粘着剤層組成物e-2を得た。
調製した基材テープ用粘着剤層組成物e-1を、離型処理したポリエチレン-テレフタレートフィルムよりなる剥離ライナーに、乾燥後の厚さが10μmになるように塗工し、110℃で3分間乾燥させた後、上記樹脂フィルムd-1と貼り合わせ、樹脂フィルム上に基材テープ用粘着剤層が形成された基材テープ(1)を作製した。
調製した基材テープ用粘着剤層組成物e-2を、離型処理したポリエチレン-テレフタレートフィルムよりなる剥離ライナーに、乾燥後の厚さが10μmになるように塗工し、110℃で3分間乾燥させた後、上記樹脂フィルムd-1と貼り合わせ、樹脂フィルム上に基材テープ用粘着剤層が形成された基材テープ(2)を作製した。
調製した基材テープ用粘着剤層組成物e-2を、離型処理したポリエチレン-テレフタレートフィルムよりなる剥離ライナーに、乾燥後の厚さが10μmになるように塗工し、110℃で3分間乾燥させた後、上記樹脂フィルムd-2と貼り合わせ、樹脂フィルム上に基材テープ用粘着剤層が形成された基材テープ(3)を作製した。
<実施例1>
以上のようにして得られた金属層(1)とセパレーター付き接着剤層(1)の接着剤層(1)側とを貼り合わせ角度120°、圧力0.2MPa、速度10mm/sの条件で貼り合わせた後、金属層上に基材テープ(1)を貼り合わせ角度120°、圧力0.2MPa、速度10mm/sの条件で貼り合わせた(貼合工程)。次いで、セパレーターを接着剤層から剥離し、接着剤層及び金属層を接着剤層の表面から基材テープへ達するように押切刃を用いて直径320mmの円形形状にプリカットし、周辺の不要部分を基材テープから剥離して除去した(1次プリカット工程)。
粘着テープ、接着剤層組成物、金属層、基材テープの組合せを表1,2に記載の組合せにした以外は、実施例1と同様の手法により、実施例2~17、比較例1~10の電子デバイスパッケージ用テープのロール体を作製した。
(基材テープと金属層との粘着力P1)
各実施例及び比較例に係る基材シートから幅25mm×長さ300mmの試験片を3点採取し、それらを各実施例及び比較例に係る金属層、接着剤層、および粘着テープの積層体の金属層表面に貼着した後、2kgのゴムローラを3往復かけて圧着し、1時間放置したものをサンプルとした。測定値がその容量の15~85%の範囲に入るJIS B 7721に適合する引張試験機を用いて粘着力を測定した。測定は、180°引き剥がし法によるものとし、この時の引張速さは300mm/minとした。測定温度は23℃、測定湿度は50%であった。3点の平均値を表1,2に示す。
各実施例及び比較例に係る基材シートから幅25mm×長さ300mmの試験片を3点採取し、それらを各実施例及び比較例に係る粘着テープの粘着剤層表面に貼着した後、2kgのゴムローラを3往復かけて圧着し、1時間放置したものをサンプルとした。測定値がその容量の15~85%の範囲に入るJIS B 7721に適合する引張試験機を用いて粘着力を測定した。測定は、180°引き剥がし法によるものとし、この時の引張速さは300mm/minとした。測定温度は23℃、測定湿度は50%であった。3点の平均値を表1,2に示す。
各実施例及び比較例に係る電子デバイスパッケージ用テープの作製過程において、金属層の基材テープへの積層状態を目視で観察した。金属層が基材テープから全面的に剥離してしまったり、部分的に剥離して捲れ上がってしまったりすることなく、基材テープ上に所定の位置に円形の金属層、接着剤層、および粘着テープの積層体が形成されたものを優良品として◎で評価し、部分的な剥離の最大幅が、0.5mm未満のものを良品として○、0.5mm以上1mm未満のものを許容品として△、1mm以上のものを不良品として×で評価した。また、金属層および接着剤層を円形形状に打ち抜いた後、周辺の不要な部分を基材テープから剥離する際、および/または粘着テープを円形形状に打ち抜いた後、周辺の不要な部分を基材テープから剥離する際に、プリカット装置で自動で剥離することができなかったものも不良品として×で評価した。
金属層、接着剤層、および粘着テープの積層体が良好に形成された実施例及び比較例に係る電子デバイスパッケージ用テープについて、貼合装置(株式会社ディスコ社製:DFM2700)を用いて、50枚の積層体を基材テープから剥離してリングフレームへの貼合を試行した。50枚の積層体全てについてシワが寄ることなくリングフレームに貼合出来たものを優良品として◎で評価し、若干のシワが発生したものの、その後のダイシングプロセスおよびダイボンディングプロセスにおいてシワに起因する不良率が全体の5%未満であったものを良品として○、ダイシングプロセスおよびダイボンディングプロセスにおいてシワに起因する不良率が5%以上10%未満のものを許容品として△、ダイシングプロセスおよびダイボンディングプロセスにおいてシワに起因する不良率が10%以上のものを不良品として×で評価した。
2:基材テープ
3:金属層
4:接着剤層
5:粘着テープ
5a:ラベル部
5b:周辺部
Claims (6)
- 粘着面を有する基材テープと、
前記基材テープの前記粘着面上に設けられ、所定の平面形状を有する金属層と、
前記金属層の前記基材テープ側とは反対側に前記金属層と積層して設けられ、所定の平面形状を有する接着剤層と、
基材フィルムと粘着剤層とを有する粘着テープとを有し、
前記粘着テープは、前記接着剤層を覆い、且つ、前記接着剤層の周囲で前記基材テープに接触するように設けられた所定の平面形状のラベル部を有し、
前記基材テープと前記金属層との粘着力P1が0.01~0.5N/25mmであり、 前記基材テープと前記粘着テープとの粘着力P2が0.01~0.5N/25mmであり、 前記基材テープと前記金属層との粘着力P1と前記基材テープと前記粘着テープとの粘着力P2との比P1/P2が、0.1~10であることを特徴とする電子デバイスパッケージ用テープ。 - 前記金属層が銅またはアルミニウムを含むことを特徴とする請求項1に記載の電子デバイスパッケージ用テープ。
- 前記基材テープは、樹脂フィルムと前記樹脂フィルムの片面に設けられた基材テープ用粘着剤層とを有することを特徴とする請求項1または請求項2に記載の電子デバイスパッケージ用テープ。
- 前記基材テープ用粘着剤層が、CH2=CHCOOR(式中、Rは炭素数が4~18のアルキル基である。)で表されるアクリル酸エステルと、ヒドロキシル基含有モノマーと、イソシアネート化合物とを含んで構成されるアクリル系ポリマーを含有することを特徴とする請求項3に記載の電子デバイスパッケージ用テープ。
- 前記接着剤層が、(A)エポキシ樹脂、(B)硬化剤、(C)アクリル樹脂またはフェノキシ樹脂、および(D)表面処理された無機充填材を含有することを特徴とする請求項1から請求項4のいずれか一項に記載の電子デバイスパッケージ用テープ。
- 前記粘着剤層が、CH2=CHCOOR(式中、Rは炭素数が4~18のアルキル基である。)で表されるアクリル酸エステルと、ヒドロキシル基含有モノマーと、分子内にラジカル反応性炭素-炭素二重結合を有するイソシアネート化合物とを含んで構成されるアクリル系ポリマーを含有することを特徴とする請求項1から請求項5のいずれか一項に記載の電子デバイスパッケージ用テープ。
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- 2016-11-22 KR KR1020187027611A patent/KR102165006B1/ko active IP Right Grant
- 2016-11-22 SG SG11201807410SA patent/SG11201807410SA/en unknown
- 2016-11-22 CN CN201680083857.1A patent/CN108779375B/zh active Active
- 2016-11-22 WO PCT/JP2016/084563 patent/WO2017168825A1/ja active Application Filing
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WO2019146605A1 (ja) * | 2018-01-24 | 2019-08-01 | リンテック株式会社 | 長尺積層シートおよびその巻収体 |
WO2019146604A1 (ja) * | 2018-01-24 | 2019-08-01 | リンテック株式会社 | 長尺積層シートの巻収体 |
JPWO2019146604A1 (ja) * | 2018-01-24 | 2021-02-04 | リンテック株式会社 | 長尺積層シートの巻収体 |
JPWO2019146605A1 (ja) * | 2018-01-24 | 2021-02-04 | リンテック株式会社 | 長尺積層シートおよびその巻収体 |
JP7153034B2 (ja) | 2018-01-24 | 2022-10-13 | リンテック株式会社 | 長尺積層シートおよびその巻収体 |
CN109720623A (zh) * | 2018-12-30 | 2019-05-07 | 上海仪电智能电子有限公司 | 一种轮胎植入式rfid电子标签压合设备及其压合方法 |
CN109720623B (zh) * | 2018-12-30 | 2024-05-14 | 上海仪电智能电子有限公司 | 一种轮胎植入式rfid电子标签压合设备及其压合方法 |
Also Published As
Publication number | Publication date |
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TWI632625B (zh) | 2018-08-11 |
TW201737370A (zh) | 2017-10-16 |
SG11201807410SA (en) | 2018-09-27 |
KR102165006B1 (ko) | 2020-10-13 |
JP2017179262A (ja) | 2017-10-05 |
MY190282A (en) | 2022-04-12 |
KR20180127361A (ko) | 2018-11-28 |
CN108779375B (zh) | 2020-11-10 |
CN108779375A (zh) | 2018-11-09 |
JP6422462B2 (ja) | 2018-11-14 |
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