WO2015046341A1 - Adhesive sheet - Google Patents
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- WO2015046341A1 WO2015046341A1 PCT/JP2014/075450 JP2014075450W WO2015046341A1 WO 2015046341 A1 WO2015046341 A1 WO 2015046341A1 JP 2014075450 W JP2014075450 W JP 2014075450W WO 2015046341 A1 WO2015046341 A1 WO 2015046341A1
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- pressure
- sensitive adhesive
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- acrylic acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
Definitions
- the present invention relates to an adhesive sheet having an energy ray-curable adhesive layer.
- an adhesive sheet has been used for the purpose of fixing the semiconductor wafer and protecting the circuit.
- a pressure-sensitive adhesive sheet having an energy ray-curable pressure-sensitive adhesive layer that has a strong pressure-sensitive adhesive force in the processing step after attaching a semiconductor wafer, while the pressure-sensitive adhesive force is reduced by irradiation with energy rays at the time of peeling. May be used.
- the energy ray-curable pressure-sensitive adhesive layer as described above is usually formed from a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive component and, if desired, a crosslinking agent.
- the energy ray curable adhesive component contains an acrylic polymer that does not have energy ray curable and an energy ray curable compound, or an acrylic polymer having an energy ray curable group introduced in the side chain. What is used is generally used.
- Patent Document 1 As the pressure-sensitive adhesive sheet using a pressure-sensitive adhesive containing an acrylic polymer having an energy ray-curable group introduced in the side chain, for example, those described in Patent Documents 1 and 2 are known.
- Patent Document 1 obtained by copolymerizing 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and octadecyl acrylate, and then reacting the copolymer with 2-isocyanatoethyl methacrylate (meth)
- a radiation-curable pressure-sensitive adhesive composition is prepared by mixing an acrylic polymer, a polyisocyanate compound that is a crosslinking agent, and a photopolymerization initiator, and a pressure-sensitive adhesive layer and a substrate made of the radiation-curable pressure-sensitive adhesive composition
- a film is laminated to form a pressure-sensitive adhesive sheet for dicing.
- Patent Document 2 after copolymerization of n-butyl acrylate, ethyl acrylate, acrylic acid and 2-hydroxyethyl acrylate, the copolymer and 2-isocyanatoethyl methacrylate are reacted.
- the releasable pressure-sensitive adhesive is prepared by mixing the obtained polymerizable polymer, the polyfunctional oligomer pentaerythritol triacrylate, the crosslinking agent polyisocyanate compound, and the photopolymerization initiator.
- a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive and a base film are laminated to form a pressure-sensitive adhesive sheet for dicing.
- JP 2010-232629 A Japanese Patent No. 2887274
- the pressure-sensitive adhesive sheet of Patent Document 1 or 2 After sticking the pressure-sensitive adhesive sheet to a semiconductor wafer and dicing, the pressure-sensitive adhesive layer is irradiated with energy rays such as ultraviolet rays to reduce the adhesive strength, The chip is peeled off from the adhesive layer of the adhesive sheet and picked up.
- energy rays such as ultraviolet rays
- the present invention has been made in view of the above situation, and an object thereof is to provide a pressure-sensitive adhesive sheet having excellent adhesion between a pressure-sensitive adhesive layer and a substrate even after irradiation with energy rays.
- the present invention includes a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material, and the pressure-sensitive adhesive layer is energy ray curable.
- the (meth) acrylic acid ester copolymer (A) and the pressure-sensitive adhesive composition containing the epoxy-based crosslinking agent (B), and the (meth) acrylic acid ester copolymer (A ) Is a (meth) acrylic acid alkyl ester monomer (A1), a hydroxyl group-containing monomer (A2) having a hydroxyl group, a functional group-containing monomer (A3) having a functional group capable of reacting with an epoxy group (excluding a hydroxyl group), It is obtained by reacting an acrylic copolymer (AP) copolymerized with a functional group capable of reacting with a hydroxyl group and a curable group-containing compound (A4) having an energy ray-curable carbon-carbon double bond.
- an adhesive layer is formed from the adhesive composition containing the said (meth) acrylic acid ester copolymer (A) and an epoxy type crosslinking agent (B), Even after energy beam irradiation, the adhesiveness between the pressure-sensitive adhesive layer and the substrate is excellent.
- the said (meth) acrylic acid ester copolymer (A) makes the said (meth) acrylic acid ester copolymer the curable group derived from the said sclerosing
- the ratio of the mass of the structural part derived from the (meth) acrylic acid alkyl ester monomer (A1) in the total mass of the (meth) acrylic acid ester copolymer (A) is: It is preferably 50 to 99% by mass (Invention 3).
- the alkyl group of the (meth) acrylic acid alkyl ester monomer (A1) preferably has 6 or more carbon atoms (Invention 4).
- the ratio of the mass of the structural portion derived from the functional group-containing monomer (A3) to the total mass of the (meth) acrylic acid ester copolymer (A) is 0.1 to It is preferably 5% by mass (Invention 5).
- the ratio of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is 1 to 25% by mass.
- the substrate is preferably mainly composed of a polyolefin film (Invention 7).
- the adhesive sheet is preferably an adhesive sheet for semiconductor processing (Invention 8).
- the pressure-sensitive adhesive sheet according to the present invention is excellent in adhesion between the pressure-sensitive adhesive layer and the substrate even after irradiation with energy rays.
- FIG. 1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention.
- the pressure-sensitive adhesive sheet 1 according to this embodiment includes a base material 2 and a pressure-sensitive adhesive layer 3 laminated on one surface (the upper surface in FIG. 1) of the base material 2.
- the pressure-sensitive adhesive sheet 1 according to the present embodiment can be used as a pressure-sensitive adhesive sheet for semiconductor processing such as a dicing sheet or a back grind sheet having an adherend as a semiconductor wafer, but is not limited thereto. Absent.
- the case where it is used as a dicing sheet or a back grinding sheet will be mainly described.
- Base material The base material 2 of the pressure-sensitive adhesive sheet 1 according to the present embodiment has a configuration as long as it exhibits a desired function in the use process of the pressure-sensitive adhesive sheet 1, for example, unless it breaks in a back grinding process, a dicing process, an expanding process, and the like.
- the material is not particularly limited, and is usually composed mainly of a film (resin film) mainly composed of a resin-based material, preferably composed of a resin film.
- the resin film include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid ester copolymer films; Polyethylene film such as density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film Polyolefin films using only olefinic hydrocarbons as polymerization monomers, such as norbornene resin films; Polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; Chi terephthalate film, polyester films such as polyethylene terephthalate and polybutylene terephthalate film; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluor
- modified films such as these crosslinked films and ionomer films are also used.
- the substrate 2 may be a resin film made of one of these, or may be a laminated film in which two or more of these are combined.
- (meth) acrylic acid in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.
- polyolefin film is preferable, polyethylene film and polypropylene film are particularly preferable, and polypropylene film is more preferable. These polyolefin films are excellent in heat resistance and solvent resistance.
- various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers and the like may be included in the resin film.
- the pigment include titanium dioxide and carbon black.
- the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such additives is not particularly limited, but should be limited to a range in which the substrate 2 exhibits a desired function and does not lose smoothness and flexibility.
- the base material 2 preferably has transparency to the ultraviolet rays.
- the base material 2 has the transparency of an electron beam.
- the thickness of the substrate 2 is not limited as long as it can function properly in the process in which the pressure-sensitive adhesive sheet 1 is used, but it is usually preferably 20 to 450 ⁇ m, particularly preferably 25 to 300 m, and more preferably 50 It is preferable that the thickness is ⁇ 200 ⁇ m.
- the breaking elongation of the substrate 2 in this embodiment is preferably 100% or more as a value measured at 23 ° C. and a relative humidity of 50%, particularly preferably 200 to 1000%.
- the elongation at break is the elongation relative to the original length of the test piece at the time of breaking the test piece in a tensile test according to JIS K7161: 1994 (ISO 527-1 1993).
- the base material 2 having a breaking elongation of 100% or more is not easily broken during the expanding process, and the chips formed by cutting the workpiece are easily separated.
- the tensile stress at 25% strain of the base material 2 in this embodiment is preferably 5 to 15 N / 10 mm, and the maximum tensile stress is preferably 15 to 50 MPa.
- the tensile stress at 25% strain and the maximum tensile stress are measured by a test based on JIS K7161: 1994.
- the base material 2 is loosened when it is fixed to a frame such as a ring frame after a workpiece is adhered to the pressure-sensitive adhesive sheet 1. Generation
- production is suppressed and it can prevent that a conveyance error arises.
- the adhesive sheet 1 itself is prevented from peeling off from the ring frame during the expanding process.
- the elongation at break, the tensile stress at 25% strain, and the maximum tensile stress are values measured in the longitudinal direction of the original fabric in the substrate 2.
- the pressure-sensitive adhesive layer 3 is formed of a pressure-sensitive adhesive composition containing an energy ray-curable (meth) acrylic acid ester copolymer (A) and an epoxy-based crosslinking agent (B).
- the energy ray-curable (meth) acrylic acid ester copolymer (A) is a functional group capable of reacting with a (meth) acrylic acid alkyl ester monomer (A1), a hydroxyl group-containing monomer (A2) having a hydroxyl group, and an epoxy group.
- the (meth) acrylic acid ester copolymer (A) contains the (meth) acrylic acid alkyl ester monomer (A1) as a monomer unit that constitutes the copolymer, so that preferable adhesiveness can be expressed. it can.
- the (meth) acrylic acid alkyl ester monomer (A1) those having an alkyl group having 6 or more carbon atoms are preferred, those having 8 to 18 are particularly preferred, and those having 10 to 14 are more preferred.
- the carbon number of the alkyl group of the (meth) acrylic acid alkyl ester monomer (A1) is 6 or more, the resulting pressure-sensitive adhesive layer 3 has excellent solvent resistance.
- the adhesive is applied to the support substrate when removing the pressure-sensitive adhesive remaining on the semiconductor wafer after peeling the back grind sheet from the semiconductor wafer or for processing such as grinding.
- the adhesive is applied to the support substrate when removing the semiconductor wafer fixed in step by dissolving the adhesive with a solvent, or when removing the adhesive remaining on the semiconductor wafer by washing with a solvent after the separation, etc.
- the affixed dicing sheet may also come into contact with the solvent. Even in such a case, the pressure-sensitive adhesive layer 3 does not swell, dissolve, etc., and maintains a good layer state and an adhesive state to the adherend.
- the adhesive force to the adherend tends to be low after irradiation with energy rays.
- the content of the (meth) acrylic acid alkyl ester monomer having a long side chain in the (meth) acrylic acid ester copolymer is increased, a crosslinking agent that binds to a small amount of carboxyl groups on the surface of the substrate.
- the reaction efficiency with the functional group of the (meth) acrylic acid ester copolymer is deteriorated, the adhesiveness between the pressure-sensitive adhesive layer and the substrate tends to be lowered.
- an excellent effect that the adhesiveness between the pressure-sensitive adhesive layer 3 and the substrate 2 is maintained can be obtained.
- the solvent is preferably a solvent having a relatively high polarity.
- a solvent having a solubility parameter (SP value) of 9 to 12, particularly 10 to 12 (cal / cm 3 ) 1/2 is preferable. It becomes a target.
- SP value solubility parameter
- examples of such a solvent include N-methylpyrrolidone (NMP), ethyl acetate, acetone, methyl ethyl ketone and the like, and among them, N-methylpyrrolidone (NMP) is particularly preferable.
- Examples of the (meth) acrylic acid alkyl ester monomer (A1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic.
- N-pentyl acid N-pentyl acid, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic
- acrylic examples include acid myristyl, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
- the (meth) acrylic acid alkyl ester monomer (A1) having an alkyl group having 6 or more carbon atoms those having an alkyl group having 6 to 18 carbon atoms are preferable.
- acrylic examples include acid stearyl.
- lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like are preferable.
- a (meth) acrylic-acid alkylester monomer (A1) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the proportion of the mass of the structural portion derived from the (meth) acrylic acid alkyl ester monomer (A1) in the total mass of the (meth) acrylic acid ester copolymer (A) is preferably 50 to 97% by mass, particularly It is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass.
- the proportion of the mass of the structural portion derived from the (meth) acrylic acid alkyl ester monomer (A1) is in the above range, the solvent resistance of the pressure-sensitive adhesive layer 3 is further improved.
- the acrylic copolymer (AP), which is a precursor of the (meth) acrylic acid ester copolymer (A), has, as monomer units constituting the copolymer, a hydroxyl group-containing monomer (A2) and a functional group-containing monomer ( By having both of A3), the reaction point (hydroxyl group of the hydroxyl group-containing monomer (A2)) reacting with the curable group-containing compound (A4) and the reaction point (functional group-containing) reacting with the epoxy-based crosslinking agent (B). Monomer (A3) functional group).
- the amount of introduction of the curable group by the curable group-containing compound (A4) and the reaction amount with the epoxy-based crosslinking agent (B) are adjusted to desired amounts, and the energy ray curable property of the pressure-sensitive adhesive layer 3 obtained is adjusted.
- the degree of crosslinking can be controlled within a preferable range. Therefore, as a result of trying to increase the addition ratio of the curable group-containing compound (A4) to the hydroxyl group of the acrylic copolymer (AP), crosslinking can be performed effectively even when the residual hydroxyl group is reduced.
- the pressure-sensitive adhesive layer 3 is excellent in adhesion with the base material 2 even after irradiation with energy rays. Therefore, when the adherend and the pressure-sensitive adhesive sheet 1 are separated after irradiation with energy rays, it is possible to effectively prevent the base material 2 and the pressure-sensitive adhesive layer 3 from being peeled off by the pressure-sensitive adhesive sheet 1. Moreover, the said adhesive layer 3 becomes a thing with the preferable adhesive force before and behind energy-beam irradiation. That is, the adhesive force to the adherend is sufficiently high before the energy beam irradiation, and the adhesive force to the adherend is sufficiently low after the energy beam irradiation. In addition, said adhesive effect is exhibited especially effectively when the adhesive layer 3 and the base material 2 made of a resin film, particularly the base material 2 made of a polyolefin film, are directly laminated.
- Examples of the hydroxyl group-containing monomer (A2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
- (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 3-hydroxybutyl and (meth) acrylic acid 4-hydroxybutyl.
- 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of reactivity with the curable group-containing compound (A4). These may be used alone or in combination of two or more.
- the ratio of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is preferably 1 to 25% by mass, particularly 5 to 25% by mass. It is preferably 7 to 15% by mass.
- the proportion of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) is in the above range, the amount of the curable group introduced by the curable group-containing compound (A4) and the amount of the remaining hydroxyl group can be controlled within a preferable range. it can. Thereby, the adhesive force of the adhesive layer 3 after energy beam irradiation can be made sufficiently small.
- Examples of the functional group of the functional group-containing monomer (A3) having a functional group capable of reacting with an epoxy group (excluding a hydroxyl group) include a carboxyl group, an amino group, and an aziridinyl group. A carboxyl group having high reactivity is preferable.
- Examples of the monomer containing a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
- Examples of the monomer containing an amino group include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like.
- a functional group containing monomer (A3) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the ratio of the mass of the structural portion derived from the functional group-containing monomer (A3) to the total mass of the (meth) acrylic acid ester copolymer (A) is preferably 0.1 to 5% by mass, particularly preferably The content is preferably 3 to 3% by mass, and more preferably 0.3 to 2% by mass.
- the (meth) acrylic acid ester copolymer (A) may contain other monomers as desired in addition to the above monomers as monomer units constituting the copolymer.
- examples of other monomers include (meth) acrylic acid containing alkoxyalkyl groups such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
- Ester (meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate, non-crosslinkable acrylamide such as acrylamide, methacrylamide, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) Examples thereof include (meth) acrylic acid ester having a non-crosslinking tertiary amino group such as acrylic acid and N, N-dimethylaminopropyl, vinyl acetate, styrene and the like. These may be used alone or in combination of two or more.
- the acrylic copolymer (AP) can be obtained by copolymerizing the above monomers by a conventional method.
- the polymerization mode of the acrylic copolymer (AP) may be a random copolymer or a block copolymer.
- the curable group-containing compound (A4) is for imparting energy beam curability to the (meth) acrylic acid ester copolymer (A).
- a functional group which can react with the hydroxyl group which a curable group containing compound (A4) has an isocyanate group, an epoxy group, a carboxyl group etc. are mentioned, for example, Among them, an isocyanate group with high reactivity with a hydroxyl group is preferable.
- the curable group-containing compound (A4) contains an energy ray-curable carbon-carbon double bond.
- This energy ray-curable carbon-carbon double bond is preferably contained in 1 to 5 molecules per molecule of the curable group-containing compound (A4), and more preferably 1 to 2 in particular. preferable.
- curable group-containing compound (A4) examples include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxy).
- Methyl) ethyl isocyanate acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth) acrylate
- Examples include acryloyl monoisocyanate compounds obtained by the reaction. Among these, 2-methacryloyloxyethyl isocyanate is particularly preferable.
- hardenable group containing compound (A4) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the (meth) acrylic acid ester copolymer (A) has a curable group derived from the curable group-containing compound (A4) with respect to the hydroxyl group of the (meth) acrylic acid ester copolymer (A). It is preferably contained in an amount of 50 mol% or more, particularly preferably 70 to 400 mol%, more preferably 90 to 200 mol%. In addition, when a curable group containing compound (A4) is monofunctional, an upper limit will be 100 mol%, but when a curable group containing compound (A4) is polyfunctional, it may exceed 100 mol%.
- the ratio of the curable group to the hydroxyl group is 50 mol% or more, the introduction amount of the curable group becomes sufficient and the residual hydroxyl group in the (meth) acrylic acid ester copolymer (A) decreases. Thereby, the adhesive force of the adhesive layer 3 after energy beam irradiation can be made sufficiently small. Further, when the ratio of the curable group to the hydroxyl group is 70 mol% or more, there is a high possibility that the adhesive strength after irradiation with energy rays can be reduced to about 115 mN / 25 mm or less, and the area is large when used as a dicing sheet. Even a chip can be easily picked up.
- the ratio of the curable group to the hydroxyl group is too large, the adhesive strength of the pressure-sensitive adhesive layer 3 after energy beam irradiation is excessively lowered, and there is a concern that the chip may fall off the dicing sheet before picking up.
- the reaction between the acrylic copolymer (AP) and the curable group-containing compound (A4) may be performed by a conventional method.
- the hydroxyl group in the acrylic copolymer (AP) reacts with the functional group in the curable group-containing compound (A4) (functional group capable of reacting with the hydroxyl group, for example, an isocyanate group) to cure.
- the functional group is introduced into the side chain of the acrylic copolymer (AP) to obtain the energy ray-curable (meth) acrylic acid ester copolymer (A).
- the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 150,000 to 2,000,000, particularly preferably 200,000 to 1,500,000, and more preferably 250,000 to 1,200,000. Is preferred.
- the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is 150,000 or more, a decrease in cohesiveness before curing of the pressure-sensitive adhesive layer 3 can be suppressed. For example, when used as a dicing sheet In addition, the possibility of chipping (chipping) at the end of the chip can be reduced. Further, when the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is 2 million or less, when the pressure-sensitive adhesive layer 3 is formed by coating the coating composition, A situation in which the viscosity becomes excessively high and coating becomes difficult can be avoided.
- the (meth) acrylic acid ester polymer (A) may be used alone or in combination of two or more.
- the adhesive composition P may further contain a (meth) acrylic acid ester polymer different from the (meth) acrylic acid ester polymer (A).
- Examples of the energy rays for curing the (meth) acrylic acid ester polymer (A) include ionizing radiation, that is, X-rays, ultraviolet rays, electron beams, and the like. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.
- near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling.
- the amount of light may be appropriately selected according to the type of (meth) acrylic acid ester polymer (A) and the thickness of the pressure-sensitive adhesive layer 3, and is usually about 50 to 500 mJ / cm 2 , and is 100 to 450 mJ / cm 2. 2 is preferable, and 200 to 400 mJ / cm 2 is more preferable.
- the ultraviolet illumination is usually 50 ⁇ 500mW / cm 2 or so, preferably 100 ⁇ 450mW / cm 2, more preferably 200 ⁇ 400mW / cm 2.
- the ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
- the acceleration voltage may be appropriately selected according to the type of (meth) acrylic acid ester polymer (A) and the thickness of the pressure-sensitive adhesive layer 3. It is preferably about 10 to 1000 kV.
- the irradiation dose may be set in a range where the (meth) acrylic acid ester polymer (A) is appropriately cured, and is usually selected in the range of 10 to 1000 krad.
- the electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
- Epoxy crosslinking agent (B) The epoxy-based crosslinking agent (B) reacts with a functional group capable of reacting with an epoxy group in the (meth) acrylic acid ester copolymer (A) to crosslink the (meth) acrylic acid ester copolymer (A).
- the functional group capable of reacting with the epoxy group in the (meth) acrylic acid ester copolymer (A) is derived from the functional group-containing monomer (A3), and in the (meth) acrylic acid ester copolymer (A). Therefore, the degree of crosslinking can be controlled within a preferable range.
- the cohesiveness of the pressure-sensitive adhesive layer 3 can be maintained satisfactorily before irradiation with energy rays, and the adhesiveness with the substrate 2 can be sufficiently increased after irradiation with energy rays. .
- Examples of the epoxy crosslinking agent (B) include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, and ethylene glycol. Examples include diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, and diglycidyl amine.
- An epoxy type crosslinking agent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of the epoxy-based crosslinking agent (B) in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 3 is 0.01 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A).
- the amount is preferably 0.05 to 3 parts by mass, more preferably 0.08 to 2 parts by mass.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 3 in the present embodiment is a photopolymerization initiator, an antistatic agent, a coloring material such as a dye or a pigment, a flame retardant, You may contain various additives, such as a filler.
- photopolymerization initiators examples include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones.
- 1-hydroxycyclohexyl phenyl ketone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- ultraviolet rays When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.
- the thickness of the pressure-sensitive adhesive layer 3 is not limited as long as it can function properly in the process in which the pressure-sensitive adhesive sheet 1 is used.
- the thickness of the pressure-sensitive adhesive layer 3 is preferably 1 to 80 ⁇ m, particularly preferably 3 to 60 ⁇ m, and more preferably 5 to 35 ⁇ m. It is preferable that When the thickness of the pressure-sensitive adhesive layer 3 is 1 ⁇ m or more, variations in the adhesive strength of the pressure-sensitive adhesive sheet 1 can be reduced. Moreover, when the thickness of the adhesive layer 3 is 80 ⁇ m or less, it can be avoided that drying takes too much time when the adhesive layer 3 is formed by applying the coating composition.
- the pressure-sensitive adhesive sheet 1 is opposite to the surface of the pressure-sensitive adhesive layer 3 on the substrate 2 side for the purpose of protecting the pressure-sensitive adhesive layer 3 until the pressure-sensitive adhesive layer 3 is applied to the adherend.
- a release sheet may be laminated on the side surface.
- the configuration of the release sheet is arbitrary, and examples thereof include a plastic film having peelability with respect to the protective film-forming film 1 and a release film obtained by peeling the plastic film with a release agent or the like.
- Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
- silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable.
- the thickness of the release sheet is not particularly limited, but is usually about 20 to 250 ⁇ m.
- the adhesive strength of the pressure-sensitive adhesive sheet 1 before and after energy beam irradiation varies depending on the application of the pressure-sensitive adhesive sheet 1. For example, when the pressure-sensitive adhesive sheet 1 is used as a dicing sheet or a back grind sheet, the energy rays of the pressure-sensitive adhesive sheet 1 are used.
- the adhesive strength before irradiation is preferably 500 to 30000 mN / 25 mm, particularly preferably 750 to 22000 mN / 25 mm, and more preferably 1000 to 18000 mN / 25 mm. Since the adhesive force before energy beam irradiation is within the above range, the workpiece being processed can be firmly held, and the occurrence of chip scattering can be suppressed.
- the adhesive strength of the pressure-sensitive adhesive sheet 1 after irradiation with energy rays is preferably 10 to 400 mN / 25 mm, particularly preferably 20 to 115 mN / 25 mm, and more preferably 30 to 80 mN / 25 mm. . Since the adhesive force after energy beam irradiation is within the above range, the workpiece after processing and the chip obtained by processing the workpiece can be easily separated from the adhesive sheet 1.
- the adhesive strength before irradiation with energy rays was determined by applying a silicon mirror wafer as an adherend, applying a 1 kg weight, sticking an adhesive sheet, and leaving it in an atmosphere of 23 ° C. and 50% RH for 20 minutes. Let it be the adhesive strength (mN / 25 mm) measured by 180 ° peeling method according to Z0237: 2000.
- the adhesive strength after irradiation with energy rays was determined by applying the adhesive sheet to the adherend under the same conditions as described above, and then leaving it in an atmosphere of 23 ° C. and 50% RH for 20 minutes. After the ultraviolet irradiation (illuminance 230 mW / cm 2 , light quantity 190 mJ / cm 2 ) from the base material side of the pressure-sensitive adhesive sheet, the adhesive strength measured in the same manner as described above is used.
- the ratio of the adhesive strength after irradiation with energy rays to the adhesive strength before irradiation with energy rays of the adhesive sheet 1 is preferably 0.001 to 0.3, and more preferably 0.01 to 0.2.
- the ratio of the adhesive strength is within the above range, the balance between the adhesive strength before energy beam irradiation and the adhesive strength after energy beam irradiation becomes good, and the high adhesive strength before energy beam irradiation and after energy beam irradiation. It is easy to achieve a low adhesive strength.
- the pressure-sensitive adhesive sheet 1 in this embodiment is formed from the pressure-sensitive adhesive composition described above, the pressure-sensitive adhesive force before energy beam irradiation, the pressure-sensitive adhesive force after energy beam irradiation, and the ratio thereof are within the above range. Easy to control.
- the manufacturing method of the adhesive sheet 1 will not be specifically limited if the adhesive layer 3 formed from the above-mentioned adhesive composition can be laminated
- FIG. For example, a coating composition containing the aforementioned pressure-sensitive adhesive composition and, if desired, further containing a solvent or a dispersion medium is prepared, and a die coater, curtain coater, spray coater is formed on one surface of the substrate 1.
- the pressure-sensitive adhesive layer 3 can be formed by applying the coating composition with a slit coater, knife coater or the like to form a coating film and drying the coating film.
- the properties of the coating composition are not particularly limited as long as it can be applied.
- the composition for forming the pressure-sensitive adhesive layer 3 may be contained as a solute, or may be contained as a dispersoid. There is also.
- the crosslinking reaction of the (meth) acrylic acid ester polymer (A) in the coating film and the epoxy crosslinking agent (B) proceeds, A crosslinked structure is formed, and the pressure-sensitive adhesive layer 3 is formed.
- the obtained semiconductor processing sheet 1 is, for example, 23 ° C. and relative humidity 50%. Carry out curing such as leaving it in the environment for several days.
- a coating film is formed on the release surface of the above-described release sheet to form a coating film, which is dried to form the pressure-sensitive adhesive layer 3 and the release sheet.
- a surface of the pressure-sensitive adhesive layer 3 opposite to the surface on the side of the release sheet is attached to the substrate 1 to obtain a layered product of the pressure-sensitive adhesive sheet 1 and the release sheet.
- the release sheet in the laminate may be peeled off as a process material, or the pressure-sensitive adhesive layer 3 may be protected until being attached to an adherend such as a semiconductor package.
- the pressure-sensitive adhesive sheet 1 is attached to a semiconductor wafer such that the surface on the pressure-sensitive adhesive layer 3 side (that is, the surface opposite to the base material 2 of the pressure-sensitive adhesive layer 3) is in contact with the semiconductor wafer.
- the surface on the pressure-sensitive adhesive layer 3 side that is, the surface opposite to the base material 2 of the pressure-sensitive adhesive layer 3
- the surface of the pressure-sensitive adhesive layer 3 is exposed by peeling off the release sheet, and the surface is affixed to the semiconductor wafer. do it.
- the semiconductor wafer with the adhesive sheet 1 may be immersed in a solvent.
- the (meth) acrylic acid ester copolymer (A) constituting the pressure-sensitive adhesive layer 3 contains a (meth) acrylic acid alkyl ester monomer (A1) having 6 or more alkyl groups as a constituent monomer unit.
- the pressure-sensitive adhesive layer 3 since the pressure-sensitive adhesive layer 3 is excellent in solvent resistance, the pressure-sensitive adhesive layer 3 maintains a good layer state and an adhesion state to the semiconductor wafer without swelling and dissolution.
- a dicing process is performed to obtain a plurality of chips from the semiconductor wafer. Since the pressure-sensitive adhesive layer 3 in the present embodiment has a sufficient adhesive strength for the dicing process before irradiation with energy rays, the chip to be formed is firmly fixed to the pressure-sensitive adhesive sheet 1 and chipping occurs during the dicing process. hard.
- an expanding process for extending the adhesive sheet 1 in the plane direction is performed so that a plurality of chips arranged close to the adhesive sheet 1 can be easily picked up.
- the chip on the adhesive layer 3 is picked up.
- the pickup can be performed by general means such as a suction collet. Since the pressure-sensitive adhesive layer 3 in the present embodiment has a sufficiently low adhesive strength after irradiation with energy rays, the above pickup can be easily performed. Moreover, since the adhesive layer 3 in this embodiment is excellent in adhesiveness with the base material 2 even after energy beam irradiation, the base material 2 and the adhesive layer 3 are peeled off at the time of the pick-up, and the adhesive layer 3 Can be effectively suppressed from adhering to the chip side.
- the picked-up chip is used for the next process such as a transport process.
- another layer may be laminated on the surface of the adhesive sheet 1 opposite to the adhesive layer 3 side of the base material 2.
- Example 1 89.5 parts by mass of lauryl acrylate, 10 parts by mass of 2-hydroxyethyl acrylate, and 0.5 parts by mass of acrylic acid were copolymerized to obtain an acrylic copolymer.
- the acrylic copolymer and methacryloyloxyethyl isocyanate (MOI) were mixed at a MOI reaction amount of 12.1 g per 100 g of the acrylic copolymer (100 mol of 2-hydroxyethyl acrylate units in the acrylic copolymer). It was made to react so that it might become 95 mol (95 mol%) per weight, and the energy-beam curable (meth) acrylic acid ester copolymer (weight average molecular weight: 600,000) was obtained.
- the thickness after drying the coating composition is 10 ⁇ m. It was applied and dried (drying conditions: 100 ° C., 1 minute) to form an adhesive layer.
- a polypropylene film (thickness 80 ⁇ m) having a corona-treated one side is prepared as a base material, and the base material and the pressure-sensitive adhesive layer are placed so that the corona-treated surface of the polypropylene film is in contact with the pressure-sensitive adhesive layer.
- the adhesive sheet which consists of a base material, an adhesive layer, and a peeling film was bonded together.
- Table 1 shows the composition of the pressure-sensitive adhesive composition. Details of the abbreviations and the like described in Table 1 are as follows.
- LA lauryl acrylate
- HEA 2-hydroxyethyl acrylate
- AAc acrylic acid
- BA n-butyl acrylate
- 2-EHA 2-ethylhexyl acrylate
- iOA isooctyl acrylate
- epoxy polyglycidylamine compound (manufactured by Mitsubishi Gas Chemical Company, TETRAD-C)
- TDI-TMP adduct of tolylene diisocyanate and trimethylolpropane triacrylate (Toyochem, BHS8515)
- HDI-TMP Addition product of hexamethylene diisocyanate and trimethylolpropane triacrylate (Toyochem, Bxx4773)
- Example 1 except that the ratio of each monomer constituting the (meth) acrylic acid ester copolymer, the reaction amount of methacryloyloxyethyl isocyanate (MOI), and the type and amount of the crosslinking agent were changed as shown in Table 1.
- a pressure-sensitive adhesive sheet was produced in the same manner as described above.
- the crosslinking agent used in Comparative Examples 1 to 3 was an isocyanate crosslinking agent (TDI-TMP or HDI-TMP).
- an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) was pasted on the above board using a squeegee in an environment of 23 ° C. and 50% RH. After sticking, the adhesive tape was rubbed with a metal plate for about 1 minute, and after the adhesive tape was sufficiently adhered to the grid, it was allowed to stand for 20 minutes. Then, the pressure-sensitive adhesive tape was peeled off, and the number of grids (number of squares; number of NG) where peeling occurred between the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the substrate was counted. The results are shown in Table 2.
- UV irradiation (illuminance 230 mW / cm 2 , light amount 190 mJ / cm 2 ) was performed from the base material side of the adhesive sheet.
- adhesive force was measured like the above, and it was set as the adhesive force (mN / 25mm) after energy ray irradiation. The results are shown in Table 2.
- the evaluation sample was immersed in N-methylpyrrolidone (SP value: 11.2 (cal / cm 3 ) 1/2 ) as a solvent at 80 ° C. for 1 minute. Thereafter, the width of the solvent soaked between the silicon mirror wafer and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (soaking width) was measured. The results are shown in Table 2.
- the pressure-sensitive adhesive sheets produced in the examples were excellent in adhesion between the pressure-sensitive adhesive layer and the substrate even after irradiation with energy rays.
- the pressure-sensitive adhesive sheets produced in Examples 1 to 3 and 7 to 9 were excellent in solvent resistance.
- the pressure-sensitive adhesive sheets produced in the comparative examples were all inferior in adhesiveness between the pressure-sensitive adhesive layer and the substrate after irradiation with energy rays.
- the pressure-sensitive adhesive sheet according to the present invention is suitably used as a dicing sheet for semiconductor wafer processing, a back grind sheet, or the like.
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Abstract
An adhesive sheet (1) comprising a base material (2) and an adhesive agent layer (3) that is laminated on at least one surface of the base material (2), wherein the adhesive agent layer (3) is formed from an adhesive agent composition comprising an energy-ray-curable (meth)acrylic acid ester copolymer (A) and an epoxy-type cross-linking agent (B), and the (meth)acrylic acid ester copolymer (A) is produced by reacting an acrylic copolymer (AP) with a curable-group-containing compound (A4), the acrylic copolymer (AP) is produced by copolymerizing a (meth)acrylic acid alkyl ester monomer (A1), a hydroxyl-group-containing monomer (A2) that has a hydroxy group and a functional-group-containing monomer (A3) that has a functional group capable of reacting with an epoxy group (which is different from a hydroxy group), and the curable-group-containing compound (A4) has a functional group capable of reacting with a hydroxy group and also has an energy-ray-curable carbon-carbon double bond. In the adhesive sheet (1), the adhesion between the adhesive agent layer (3) and the base material (2) is excellent even after the irradiation of the adhesive sheet (1) with energy ray.
Description
本発明は、エネルギー線硬化性の粘着剤層を有する粘着シートに関するものである。
The present invention relates to an adhesive sheet having an energy ray-curable adhesive layer.
従来より、例えば半導体ウエハを研削、切断する工程においては、半導体ウエハの固定や回路などの保護を目的として、粘着シートが用いられている。この粘着シートとして、半導体ウエハを貼付した後の処理工程においては強い粘着力を有し、一方剥離時にはエネルギー線の照射により粘着力が低下する、エネルギー線硬化性の粘着剤層を備えた粘着シートが用いられることがある。
Conventionally, for example, in the process of grinding and cutting a semiconductor wafer, an adhesive sheet has been used for the purpose of fixing the semiconductor wafer and protecting the circuit. As the pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet having an energy ray-curable pressure-sensitive adhesive layer that has a strong pressure-sensitive adhesive force in the processing step after attaching a semiconductor wafer, while the pressure-sensitive adhesive force is reduced by irradiation with energy rays at the time of peeling. May be used.
上記のようなエネルギー線硬化性の粘着剤層は、通常、エネルギー線硬化性粘着成分と、所望により架橋剤とを含有する粘着剤組成物から形成される。エネルギー線硬化性粘着成分としては、エネルギー線硬化性を有しないアクリル系重合体およびエネルギー線硬化性化合物を含有するもの、あるいは側鎖にエネルギー線硬化性基が導入されたアクリル系重合体を含有するものが一般的に使用される。
The energy ray-curable pressure-sensitive adhesive layer as described above is usually formed from a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive component and, if desired, a crosslinking agent. The energy ray curable adhesive component contains an acrylic polymer that does not have energy ray curable and an energy ray curable compound, or an acrylic polymer having an energy ray curable group introduced in the side chain. What is used is generally used.
側鎖にエネルギー線硬化性基が導入されたアクリル系重合体を含有する粘着剤を使用した粘着シートとしては、例えば、特許文献1及び2に記載のものが知られている。特許文献1の実施例では、アクリル酸2-エチルヘキシル、アクリル酸2-ヒドロキシエチルおよびアクリル酸オクタデシルを共重合した後、当該共重合体および2-イソシアネートエチルメタクリレートを反応させて得られた(メタ)アクリル系ポリマーと、架橋剤であるポリイソシアネート化合物と、光重合開始剤とを混合して放射線硬化性粘着剤組成物を調製し、当該放射線硬化性粘着剤組成物からなる粘着剤層と基材フィルムとを積層し、ダイシング用の粘着シートとしている。
As the pressure-sensitive adhesive sheet using a pressure-sensitive adhesive containing an acrylic polymer having an energy ray-curable group introduced in the side chain, for example, those described in Patent Documents 1 and 2 are known. In Examples of Patent Document 1, obtained by copolymerizing 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and octadecyl acrylate, and then reacting the copolymer with 2-isocyanatoethyl methacrylate (meth) A radiation-curable pressure-sensitive adhesive composition is prepared by mixing an acrylic polymer, a polyisocyanate compound that is a crosslinking agent, and a photopolymerization initiator, and a pressure-sensitive adhesive layer and a substrate made of the radiation-curable pressure-sensitive adhesive composition A film is laminated to form a pressure-sensitive adhesive sheet for dicing.
また、特許文献2の実施例では、アクリル酸n-ブチル、アクリル酸エチル、アクリル酸およびアクリル酸2-ヒドロキシエチルを共重合した後、当該共重合体およびメタクリル酸2-イソシアネートエチルを反応させて得られた重合性ポリマーと、多官能オリゴマーであるペンタエリスリトールトリアクリレートと、架橋剤であるポリイソシアネート化合物と、光重合開始剤とを混合して再剥離型粘着剤を調製し、当該再剥離型粘着剤からなる粘着剤層と基材フィルムとを積層し、ダイシング用の粘着シートとしている。
In Examples of Patent Document 2, after copolymerization of n-butyl acrylate, ethyl acrylate, acrylic acid and 2-hydroxyethyl acrylate, the copolymer and 2-isocyanatoethyl methacrylate are reacted. The releasable pressure-sensitive adhesive is prepared by mixing the obtained polymerizable polymer, the polyfunctional oligomer pentaerythritol triacrylate, the crosslinking agent polyisocyanate compound, and the photopolymerization initiator. A pressure-sensitive adhesive layer made of a pressure-sensitive adhesive and a base film are laminated to form a pressure-sensitive adhesive sheet for dicing.
特許文献1又は2の粘着シートを使用する場合、当該粘着シートを半導体ウエハに貼付し、ダイシングを行った後、粘着剤層に対して紫外線等のエネルギー線を照射して粘着力を低下させ、チップを粘着シートの粘着剤層から剥離してピックアップする。
When using the pressure-sensitive adhesive sheet of Patent Document 1 or 2, after sticking the pressure-sensitive adhesive sheet to a semiconductor wafer and dicing, the pressure-sensitive adhesive layer is irradiated with energy rays such as ultraviolet rays to reduce the adhesive strength, The chip is peeled off from the adhesive layer of the adhesive sheet and picked up.
しかしながら、特許文献1及び2の粘着シートでは、エネルギー線照射後に基材フィルムと粘着剤層との密着性が低くなるため、上記のようにピックアップしたときに、基材フィルムと粘着剤層との間で剥離が生じ、チップを粘着剤層から良好にピックアップすることができないことがあった。
However, in the pressure-sensitive adhesive sheets of Patent Documents 1 and 2, the adhesion between the base film and the pressure-sensitive adhesive layer is reduced after irradiation with energy rays. In some cases, the chip was peeled off, and the chip could not be picked up well from the pressure-sensitive adhesive layer.
本発明は、上記のような実状に鑑みてなされたものであり、エネルギー線照射後にも粘着剤層と基材との密着性に優れた粘着シートを提供することを目的とする。
The present invention has been made in view of the above situation, and an object thereof is to provide a pressure-sensitive adhesive sheet having excellent adhesion between a pressure-sensitive adhesive layer and a substrate even after irradiation with energy rays.
上記目的を達成するために、第1に本発明は、基材と、前記基材の少なくとも一方の面に積層された粘着剤層とを備えており、前記粘着剤層は、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)と、エポキシ系架橋剤(B)とを含有する粘着剤組成物から形成されたものであり、前記(メタ)アクリル酸エステル共重合体(A)は、(メタ)アクリル酸アルキルエステルモノマー(A1)と、水酸基を有する水酸基含有モノマー(A2)と、エポキシ基と反応可能な官能基(水酸基を除く)を有する官能基含有モノマー(A3)とを共重合したアクリル系共重合体(AP)と、水酸基と反応可能な官能基およびエネルギー線硬化性の炭素-炭素二重結合を有する硬化性基含有化合物(A4)とを反応させて得られるものであることを特徴とする粘着シートを提供する(発明1)。
In order to achieve the above object, first, the present invention includes a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material, and the pressure-sensitive adhesive layer is energy ray curable. The (meth) acrylic acid ester copolymer (A) and the pressure-sensitive adhesive composition containing the epoxy-based crosslinking agent (B), and the (meth) acrylic acid ester copolymer (A ) Is a (meth) acrylic acid alkyl ester monomer (A1), a hydroxyl group-containing monomer (A2) having a hydroxyl group, a functional group-containing monomer (A3) having a functional group capable of reacting with an epoxy group (excluding a hydroxyl group), It is obtained by reacting an acrylic copolymer (AP) copolymerized with a functional group capable of reacting with a hydroxyl group and a curable group-containing compound (A4) having an energy ray-curable carbon-carbon double bond. With things Providing a pressure-sensitive adhesive sheet characterized by Rukoto (invention 1).
上記発明(発明1)によれば、粘着剤層が、上記(メタ)アクリル酸エステル共重合体(A)およびエポキシ系架橋剤(B)を含有する粘着剤組成物から形成されることにより、エネルギー線照射後にも粘着剤層と基材との密着性が優れたものとなる。
According to the said invention (invention 1), an adhesive layer is formed from the adhesive composition containing the said (meth) acrylic acid ester copolymer (A) and an epoxy type crosslinking agent (B), Even after energy beam irradiation, the adhesiveness between the pressure-sensitive adhesive layer and the substrate is excellent.
上記発明(発明1)において、前記(メタ)アクリル酸エステル共重合体(A)は、前記硬化性基含有化合物(A4)に由来する硬化性基を、当該(メタ)アクリル酸エステル共重合体(A)が有する水酸基に対して、50モル%以上含有することが好ましい(発明2)。
In the said invention (invention 1), the said (meth) acrylic acid ester copolymer (A) makes the said (meth) acrylic acid ester copolymer the curable group derived from the said sclerosing | hardenable group containing compound (A4). It is preferable to contain 50 mol% or more with respect to the hydroxyl group which (A) has (Invention 2).
上記発明(発明1,2)において、前記(メタ)アクリル酸エステル共重合体(A)全体の質量に占める前記(メタ)アクリル酸アルキルエステルモノマー(A1)由来の構造部分の質量の割合は、50~99質量%であることが好ましい(発明3)。
In the said invention (invention 1 and 2), the ratio of the mass of the structural part derived from the (meth) acrylic acid alkyl ester monomer (A1) in the total mass of the (meth) acrylic acid ester copolymer (A) is: It is preferably 50 to 99% by mass (Invention 3).
上記発明(発明1~3)において、前記(メタ)アクリル酸アルキルエステルモノマー(A1)のアルキル基の炭素数は、6以上であることが好ましい(発明4)。
In the above inventions (Inventions 1 to 3), the alkyl group of the (meth) acrylic acid alkyl ester monomer (A1) preferably has 6 or more carbon atoms (Invention 4).
上記発明(発明1~4)において、前記(メタ)アクリル酸エステル共重合体(A)全体の質量に占める前記官能基含有モノマー(A3)由来の構造部分の質量の割合は、0.1~5質量%であることが好ましい(発明5)。
In the above inventions (Inventions 1 to 4), the ratio of the mass of the structural portion derived from the functional group-containing monomer (A3) to the total mass of the (meth) acrylic acid ester copolymer (A) is 0.1 to It is preferably 5% by mass (Invention 5).
上記発明(発明1~5)において、前記アクリル系共重合体(AP)全体の質量に占める前記水酸基含有モノマー(A2)由来の構造部分の質量の割合は、1~25質量%であることが好ましい(発明6)。
In the above inventions (Inventions 1 to 5), the ratio of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is 1 to 25% by mass. Preferred (Invention 6).
上記発明(発明1~6)において、前記基材は、ポリオレフィン系フィルムを主体とするものであることが好ましい(発明7)。
In the above inventions (Inventions 1 to 6), the substrate is preferably mainly composed of a polyolefin film (Invention 7).
上記発明(発明1~7)において、前記粘着シートは、半導体加工用の粘着シートであることが好ましい(発明8)。
In the above inventions (Inventions 1 to 7), the adhesive sheet is preferably an adhesive sheet for semiconductor processing (Invention 8).
本発明に係る粘着シートは、エネルギー線照射後にも粘着剤層と基材との密着性に優れる。
The pressure-sensitive adhesive sheet according to the present invention is excellent in adhesion between the pressure-sensitive adhesive layer and the substrate even after irradiation with energy rays.
以下、本発明の実施形態について説明する。
図1は本発明の一実施形態に係る粘着シートの断面図である。本実施形態に係る粘着シート1は、基材2と、基材2の一方の面(図1では上側の面)に積層された粘着剤層3とを備えて構成される。本実施形態に係る粘着シート1は、例えば、被着体を半導体ウエハ等とするダイシングシート、バックグラインドシートなどの半導体加工用の粘着シートとして使用することができるが、これに限定されるものではない。以下、ダイシングシートまたはバックグラインドシートとして使用される場合を中心に説明する。 Hereinafter, embodiments of the present invention will be described.
FIG. 1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention. The pressure-sensitive adhesive sheet 1 according to this embodiment includes abase material 2 and a pressure-sensitive adhesive layer 3 laminated on one surface (the upper surface in FIG. 1) of the base material 2. The pressure-sensitive adhesive sheet 1 according to the present embodiment can be used as a pressure-sensitive adhesive sheet for semiconductor processing such as a dicing sheet or a back grind sheet having an adherend as a semiconductor wafer, but is not limited thereto. Absent. Hereinafter, the case where it is used as a dicing sheet or a back grinding sheet will be mainly described.
図1は本発明の一実施形態に係る粘着シートの断面図である。本実施形態に係る粘着シート1は、基材2と、基材2の一方の面(図1では上側の面)に積層された粘着剤層3とを備えて構成される。本実施形態に係る粘着シート1は、例えば、被着体を半導体ウエハ等とするダイシングシート、バックグラインドシートなどの半導体加工用の粘着シートとして使用することができるが、これに限定されるものではない。以下、ダイシングシートまたはバックグラインドシートとして使用される場合を中心に説明する。 Hereinafter, embodiments of the present invention will be described.
FIG. 1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention. The pressure-sensitive adhesive sheet 1 according to this embodiment includes a
1.基材
本実施形態に係る粘着シート1の基材2は、粘着シート1の使用工程で所望の機能を発揮する限り、例えば、バックグラインド工程、ダイシング工程、エキスパンド工程などにおいて破断しない限り、その構成材料は特に限定されず、通常は樹脂系の材料を主材とするフィルム(樹脂フィルム)を主体として構成され、好ましくは樹脂フィルムから構成される。その樹脂フィルムの具体例として、エチレン-酢酸ビニル共重合体フィルム、エチレン-(メタ)アクリル酸共重合体フィルム、エチレン-(メタ)アクリル酸エステル共重合体フィルム等のエチレン系共重合フィルム;低密度ポリエチレン(LDPE)フィルム、直鎖低密度ポリエチレン(LLDPE)フィルム、高密度ポリエチレン(HDPE)フィルム等のポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、エチレン-ノルボルネン共重合体フィルム、ノルボルネン樹脂フィルム等の、オレフィン系炭化水素のみを重合単量体としたポリオレフィン系フィルム;ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム等のポリ塩化ビニル系フィルム;ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステル系フィルム;ポリウレタンフィルム;ポリイミドフィルム;ポリスチレンフィルム;ポリカーボネートフィルム;フッ素樹脂フィルムなどが挙げられる。またこれらの架橋フィルム、アイオノマーフィルムのような変性フィルムも用いられる。上記の基材2はこれらの1種からなる樹脂フィルムでもよいし、さらにこれらを2種類以上組み合わせた積層フィルムであってもよい。なお、本明細書における「(メタ)アクリル酸」は、アクリル酸およびメタクリル酸の両方を意味する。他の類似用語についても同様である。 1. Base material Thebase material 2 of the pressure-sensitive adhesive sheet 1 according to the present embodiment has a configuration as long as it exhibits a desired function in the use process of the pressure-sensitive adhesive sheet 1, for example, unless it breaks in a back grinding process, a dicing process, an expanding process, and the like. The material is not particularly limited, and is usually composed mainly of a film (resin film) mainly composed of a resin-based material, preferably composed of a resin film. Specific examples of the resin film include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid ester copolymer films; Polyethylene film such as density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film Polyolefin films using only olefinic hydrocarbons as polymerization monomers, such as norbornene resin films; Polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; Chi terephthalate film, polyester films such as polyethylene terephthalate and polybutylene terephthalate film; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used. The substrate 2 may be a resin film made of one of these, or may be a laminated film in which two or more of these are combined. In addition, “(meth) acrylic acid” in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.
本実施形態に係る粘着シート1の基材2は、粘着シート1の使用工程で所望の機能を発揮する限り、例えば、バックグラインド工程、ダイシング工程、エキスパンド工程などにおいて破断しない限り、その構成材料は特に限定されず、通常は樹脂系の材料を主材とするフィルム(樹脂フィルム)を主体として構成され、好ましくは樹脂フィルムから構成される。その樹脂フィルムの具体例として、エチレン-酢酸ビニル共重合体フィルム、エチレン-(メタ)アクリル酸共重合体フィルム、エチレン-(メタ)アクリル酸エステル共重合体フィルム等のエチレン系共重合フィルム;低密度ポリエチレン(LDPE)フィルム、直鎖低密度ポリエチレン(LLDPE)フィルム、高密度ポリエチレン(HDPE)フィルム等のポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、エチレン-ノルボルネン共重合体フィルム、ノルボルネン樹脂フィルム等の、オレフィン系炭化水素のみを重合単量体としたポリオレフィン系フィルム;ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム等のポリ塩化ビニル系フィルム;ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステル系フィルム;ポリウレタンフィルム;ポリイミドフィルム;ポリスチレンフィルム;ポリカーボネートフィルム;フッ素樹脂フィルムなどが挙げられる。またこれらの架橋フィルム、アイオノマーフィルムのような変性フィルムも用いられる。上記の基材2はこれらの1種からなる樹脂フィルムでもよいし、さらにこれらを2種類以上組み合わせた積層フィルムであってもよい。なお、本明細書における「(メタ)アクリル酸」は、アクリル酸およびメタクリル酸の両方を意味する。他の類似用語についても同様である。 1. Base material The
上記の中でも、ポリオレフィン系フィルムが好ましく、特にポリエチレンフィルムおよびポリプロピレンフィルムが好ましく、さらにはポリプロピレンフィルムが好ましい。これらのポリオレフィン系フィルムは、耐熱性および耐溶剤性に優れる。
Among the above, polyolefin film is preferable, polyethylene film and polypropylene film are particularly preferable, and polypropylene film is more preferable. These polyolefin films are excellent in heat resistance and solvent resistance.
基材2においては、上記の樹脂フィルム内に、顔料、染料、難燃剤、可塑剤、帯電防止剤、滑剤、フィラー等の各種添加剤が含まれていてもよい。顔料としては、例えば、二酸化チタン、カーボンブラック等が挙げられる。また、フィラーとしては、メラミン樹脂のような有機系材料、ヒュームドシリカのような無機系材料およびニッケル粒子のような金属系材料が例示される。こうした添加剤の含有量は特に限定されないが、基材2が所望の機能を発揮し、平滑性や柔軟性を失わない範囲に留めるべきである。
In the base material 2, various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers and the like may be included in the resin film. Examples of the pigment include titanium dioxide and carbon black. Examples of the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such additives is not particularly limited, but should be limited to a range in which the substrate 2 exhibits a desired function and does not lose smoothness and flexibility.
粘着剤層3を硬化させるために照射するエネルギー線として紫外線を用いる場合には、基材2は紫外線に対して透過性を有することが好ましい。なお、エネルギー線として電子線を用いる場合には、基材2は電子線の透過性を有していることが好ましい。
In the case where ultraviolet rays are used as the energy rays to be irradiated to cure the pressure-sensitive adhesive layer 3, the base material 2 preferably has transparency to the ultraviolet rays. In addition, when using an electron beam as an energy beam, it is preferable that the base material 2 has the transparency of an electron beam.
ここで、本技術分野においては、他の層との密着性向上のために、樹脂フィルムの表面にプライマー層を設けることが知られているが、その場合には塗工等の製膜工程が必要となり、コスト増大の要因となり望ましくない。本実施形態の粘着剤層3であれば、プライマー層がなくても、樹脂フィルムとの密着性に優れる。
Here, in this technical field, it is known to provide a primer layer on the surface of the resin film in order to improve adhesion with other layers. In that case, a film forming process such as coating is performed. This is necessary and causes an increase in cost, which is undesirable. If it is the adhesive layer 3 of this embodiment, even if there is no primer layer, it is excellent in adhesiveness with a resin film.
基材2の厚さは、粘着シート1が使用される工程において適切に機能できる限り限定されないが、通常、20~450μmであることが好ましく、特に25~300mであることが好ましく、さらには50~200μmであることが好ましい。
The thickness of the substrate 2 is not limited as long as it can function properly in the process in which the pressure-sensitive adhesive sheet 1 is used, but it is usually preferably 20 to 450 μm, particularly preferably 25 to 300 m, and more preferably 50 It is preferable that the thickness is ˜200 μm.
本実施形態における基材2の破断伸度は、23℃、相対湿度50%のときに測定した値として100%以上であることが好ましく、特に200~1000%であることが好ましい。ここで、破断伸度はJIS K7161:1994(ISO 527-1 1993)に準拠した引張り試験における、試験片破壊時の試験片の長さの元の長さに対する伸び率である。上記の破断伸度が100%以上である基材2は、エキスパンド工程の際に破断し難く、ワークを切断して形成したチップを離間し易いものとなる。
The breaking elongation of the substrate 2 in this embodiment is preferably 100% or more as a value measured at 23 ° C. and a relative humidity of 50%, particularly preferably 200 to 1000%. Here, the elongation at break is the elongation relative to the original length of the test piece at the time of breaking the test piece in a tensile test according to JIS K7161: 1994 (ISO 527-1 1993). The base material 2 having a breaking elongation of 100% or more is not easily broken during the expanding process, and the chips formed by cutting the workpiece are easily separated.
また、本実施形態における基材2の25%ひずみ時引張応力は5~15N/10mmであることが好ましく、最大引張応力は15~50MPaであることが好ましい。ここで25%ひずみ時引張応力および最大引張応力はJIS K7161:1994に準拠した試験により測定される。25%ひずみ時引張応力が5N/10mm以上、最大引張応力が15MPa以上であると、粘着シート1にワークを貼着した後、リングフレームなどの枠体に固定した際、基材2に弛みが発生することが抑制され、搬送エラーが生じることを防止することができる。一方、25%ひずみ時引張応力が15N/10mm以下、最大引張応力が50MPa以下であると、エキスパンド工程時にリングフレームから粘着シート1自体が剥がれたりすることが抑制される。なお、上記の破断伸度、25%ひずみ時引張応力、最大引張応力は基材2における原反の長尺方向について測定した値を指す。
Further, the tensile stress at 25% strain of the base material 2 in this embodiment is preferably 5 to 15 N / 10 mm, and the maximum tensile stress is preferably 15 to 50 MPa. Here, the tensile stress at 25% strain and the maximum tensile stress are measured by a test based on JIS K7161: 1994. When the tensile stress at 25% strain is 5 N / 10 mm or more and the maximum tensile stress is 15 MPa or more, the base material 2 is loosened when it is fixed to a frame such as a ring frame after a workpiece is adhered to the pressure-sensitive adhesive sheet 1. Generation | occurrence | production is suppressed and it can prevent that a conveyance error arises. On the other hand, when the tensile stress at 25% strain is 15 N / 10 mm or less and the maximum tensile stress is 50 MPa or less, the adhesive sheet 1 itself is prevented from peeling off from the ring frame during the expanding process. The elongation at break, the tensile stress at 25% strain, and the maximum tensile stress are values measured in the longitudinal direction of the original fabric in the substrate 2.
2.粘着剤層
粘着剤層3は、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)と、エポキシ系架橋剤(B)とを含有する粘着剤組成物から形成される。 2. Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer 3 is formed of a pressure-sensitive adhesive composition containing an energy ray-curable (meth) acrylic acid ester copolymer (A) and an epoxy-based crosslinking agent (B).
粘着剤層3は、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)と、エポキシ系架橋剤(B)とを含有する粘着剤組成物から形成される。 2. Pressure-sensitive adhesive layer The pressure-
(1)(メタ)アクリル酸エステル共重合体(A)
エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)は、(メタ)アクリル酸アルキルエステルモノマー(A1)と、水酸基を有する水酸基含有モノマー(A2)と、エポキシ基と反応可能な官能基(水酸基を除く)を有する官能基含有モノマー(A3)とを共重合したアクリル系共重合体(AP)と、水酸基と反応可能な官能基およびエネルギー線硬化性の炭素-炭素二重結合を有する硬化性基含有化合物(A4)とを反応させて得られるものである。 (1) (Meth) acrylic acid ester copolymer (A)
The energy ray-curable (meth) acrylic acid ester copolymer (A) is a functional group capable of reacting with a (meth) acrylic acid alkyl ester monomer (A1), a hydroxyl group-containing monomer (A2) having a hydroxyl group, and an epoxy group. An acrylic copolymer (AP) copolymerized with a functional group-containing monomer (A3) having a group (excluding a hydroxyl group), a functional group capable of reacting with a hydroxyl group, and an energy ray-curable carbon-carbon double bond It is obtained by reacting the curable group-containing compound (A4).
エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)は、(メタ)アクリル酸アルキルエステルモノマー(A1)と、水酸基を有する水酸基含有モノマー(A2)と、エポキシ基と反応可能な官能基(水酸基を除く)を有する官能基含有モノマー(A3)とを共重合したアクリル系共重合体(AP)と、水酸基と反応可能な官能基およびエネルギー線硬化性の炭素-炭素二重結合を有する硬化性基含有化合物(A4)とを反応させて得られるものである。 (1) (Meth) acrylic acid ester copolymer (A)
The energy ray-curable (meth) acrylic acid ester copolymer (A) is a functional group capable of reacting with a (meth) acrylic acid alkyl ester monomer (A1), a hydroxyl group-containing monomer (A2) having a hydroxyl group, and an epoxy group. An acrylic copolymer (AP) copolymerized with a functional group-containing monomer (A3) having a group (excluding a hydroxyl group), a functional group capable of reacting with a hydroxyl group, and an energy ray-curable carbon-carbon double bond It is obtained by reacting the curable group-containing compound (A4).
(メタ)アクリル酸エステル共重合体(A)は、当該共重合体を構成するモノマー単位として、(メタ)アクリル酸アルキルエステルモノマー(A1)を含有することで、好ましい粘着性を発現することができる。(メタ)アクリル酸アルキルエステルモノマー(A1)としては、アルキル基の炭素数が6以上であるものが好ましく、特に8~18であるものが好ましく、さらには10~14であるものが好ましい。(メタ)アクリル酸アルキルエステルモノマー(A1)のアルキル基の炭素数が6以上であることにより、得られる粘着剤層3は、耐溶剤性に優れたものとなる。例えば、粘着シート1がダイシングシートとして使用される場合、半導体ウエハからバックグラインドシートを剥がした後、半導体ウエハに残存した粘着剤を除去するときや、研削等の加工のために支持基板に接着剤で固定されている半導体ウエハを、接着剤を溶剤により溶かすことで剥離するときや、その剥離後に、半導体ウエハ上に残った接着剤を溶剤で洗浄することにより除去するときなどに、半導体ウエハに貼付されたダイシングシートも溶剤に接触することがある。このような場合においても粘着剤層3は膨潤、溶解等することなく、良好な層状態および被着体に対する接着状態を保持する。
The (meth) acrylic acid ester copolymer (A) contains the (meth) acrylic acid alkyl ester monomer (A1) as a monomer unit that constitutes the copolymer, so that preferable adhesiveness can be expressed. it can. As the (meth) acrylic acid alkyl ester monomer (A1), those having an alkyl group having 6 or more carbon atoms are preferred, those having 8 to 18 are particularly preferred, and those having 10 to 14 are more preferred. When the carbon number of the alkyl group of the (meth) acrylic acid alkyl ester monomer (A1) is 6 or more, the resulting pressure-sensitive adhesive layer 3 has excellent solvent resistance. For example, when the pressure-sensitive adhesive sheet 1 is used as a dicing sheet, the adhesive is applied to the support substrate when removing the pressure-sensitive adhesive remaining on the semiconductor wafer after peeling the back grind sheet from the semiconductor wafer or for processing such as grinding. When removing the semiconductor wafer fixed in step by dissolving the adhesive with a solvent, or when removing the adhesive remaining on the semiconductor wafer by washing with a solvent after the separation, etc. The affixed dicing sheet may also come into contact with the solvent. Even in such a case, the pressure-sensitive adhesive layer 3 does not swell, dissolve, etc., and maintains a good layer state and an adhesive state to the adherend.
また、(メタ)アクリル酸アルキルエステルモノマー(A1)のアルキル基の炭素数が6以上になると、エネルギー線照射後に被着体に対する粘着力が低くなり易くなる。ここで、一般的に、(メタ)アクリル酸エステル共重合体において側鎖の長い(メタ)アクリル酸アルキルエステルモノマーの含有量が多くなると、基材表面の微量のカルボキシル基等に結合する架橋剤と、(メタ)アクリル酸エステル共重合体が有する官能基との反応効率が悪くなるため、粘着剤層と基材との密着性が低下する傾向がある。しかし、本実施形態によれば、このような場合でも、粘着剤層3と基材2との密着性が維持されるという優れた効果が得られる。
Moreover, when the carbon number of the alkyl group of the (meth) acrylic acid alkyl ester monomer (A1) is 6 or more, the adhesive force to the adherend tends to be low after irradiation with energy rays. Here, generally, when the content of the (meth) acrylic acid alkyl ester monomer having a long side chain in the (meth) acrylic acid ester copolymer is increased, a crosslinking agent that binds to a small amount of carboxyl groups on the surface of the substrate. And, since the reaction efficiency with the functional group of the (meth) acrylic acid ester copolymer is deteriorated, the adhesiveness between the pressure-sensitive adhesive layer and the substrate tends to be lowered. However, according to the present embodiment, even in such a case, an excellent effect that the adhesiveness between the pressure-sensitive adhesive layer 3 and the substrate 2 is maintained can be obtained.
上記溶剤としては、好ましくは極性の比較的高い溶剤が対象となり、具体的には溶解パラメーター(SP値)が9~12、特に10~12(cal/cm3)1/2である溶剤が好ましい対象となる。かかる溶剤としては、例えば、N-メチルピロリドン(NMP)、酢酸エチル、アセトン、メチルエチルケトン等が挙げられ、中でも特にN-メチルピロリドン(NMP)が好ましい。
The solvent is preferably a solvent having a relatively high polarity. Specifically, a solvent having a solubility parameter (SP value) of 9 to 12, particularly 10 to 12 (cal / cm 3 ) 1/2 is preferable. It becomes a target. Examples of such a solvent include N-methylpyrrolidone (NMP), ethyl acetate, acetone, methyl ethyl ketone and the like, and among them, N-methylpyrrolidone (NMP) is particularly preferable.
(メタ)アクリル酸アルキルエステルモノマー(A1)としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリル等が挙げられる。
Examples of the (meth) acrylic acid alkyl ester monomer (A1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. N-pentyl acid, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Examples include acid myristyl, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
また、アルキル基の炭素数が6以上の(メタ)アクリル酸アルキルエステルモノマー(A1)としては、アルキル基の炭素数が6~18のものが好ましく、例えば、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリル等が挙げられる。これらの中でも(メタ)アクリル酸ラウリル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリル等が好ましい。なお、(メタ)アクリル酸アルキルエステルモノマー(A1)は、1種を単独で使用することもできるし、2種以上を組み合わせて使用することもできる。
Further, as the (meth) acrylic acid alkyl ester monomer (A1) having an alkyl group having 6 or more carbon atoms, those having an alkyl group having 6 to 18 carbon atoms are preferable. For example, n-hexyl (meth) acrylate, 2-Methylhexyl acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, (meth) acrylic Examples include acid stearyl. Among these, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like are preferable. In addition, a (meth) acrylic-acid alkylester monomer (A1) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
(メタ)アクリル酸エステル共重合体(A)全体の質量に占める(メタ)アクリル酸アルキルエステルモノマー(A1)由来の構造部分の質量の割合は、50~97質量%であることが好ましく、特に60~95質量%であることが好ましく、さらには70~90質量%であることが好ましい。(メタ)アクリル酸アルキルエステルモノマー(A1)由来の構造部分の質量の割合が上記の範囲にあることにより、粘着剤層3の耐溶剤性がより向上する。
The proportion of the mass of the structural portion derived from the (meth) acrylic acid alkyl ester monomer (A1) in the total mass of the (meth) acrylic acid ester copolymer (A) is preferably 50 to 97% by mass, particularly It is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass. When the proportion of the mass of the structural portion derived from the (meth) acrylic acid alkyl ester monomer (A1) is in the above range, the solvent resistance of the pressure-sensitive adhesive layer 3 is further improved.
(メタ)アクリル酸エステル共重合体(A)の前駆体であるアクリル系共重合体(AP)は、当該共重合体を構成するモノマー単位として、水酸基含有モノマー(A2)および官能基含有モノマー(A3)の両者を有することにより、硬化性基含有化合物(A4)と反応する反応点(水酸基含有モノマー(A2)の水酸基)と、エポキシ系架橋剤(B)と反応する反応点(官能基含有モノマー(A3)の官能基)とを有することとなる。これにより、硬化性基含有化合物(A4)による硬化性基の導入量およびエポキシ系架橋剤(B)との反応量を所望の量に調整して、得られる粘着剤層3のエネルギー線硬化性および架橋の程度を好ましい範囲に制御することができる。したがって、アクリル系共重合体(AP)の水酸基に対する硬化性基含有化合物(A4)の付加率を高めようとした結果、残存水酸基が減少した場合でも、有効に架橋を行うことができる。
The acrylic copolymer (AP), which is a precursor of the (meth) acrylic acid ester copolymer (A), has, as monomer units constituting the copolymer, a hydroxyl group-containing monomer (A2) and a functional group-containing monomer ( By having both of A3), the reaction point (hydroxyl group of the hydroxyl group-containing monomer (A2)) reacting with the curable group-containing compound (A4) and the reaction point (functional group-containing) reacting with the epoxy-based crosslinking agent (B). Monomer (A3) functional group). Thereby, the amount of introduction of the curable group by the curable group-containing compound (A4) and the reaction amount with the epoxy-based crosslinking agent (B) are adjusted to desired amounts, and the energy ray curable property of the pressure-sensitive adhesive layer 3 obtained is adjusted. In addition, the degree of crosslinking can be controlled within a preferable range. Therefore, as a result of trying to increase the addition ratio of the curable group-containing compound (A4) to the hydroxyl group of the acrylic copolymer (AP), crosslinking can be performed effectively even when the residual hydroxyl group is reduced.
かかる粘着剤層3は、エネルギー線照射後にも基材2との密着性に優れる。したがって、エネルギー線照射後に被着体と粘着シート1とを分離させるときに、粘着シート1にて基材2と粘着剤層3とが剥離してしまうことを効果的に抑制することができる。また、上記粘着剤層3は、エネルギー線照射前後における粘着力が好ましいものとなる。すなわち、エネルギー線照射前には、被着体に対する粘着力が十分に高く、エネルギー線照射後には、被着体に対する粘着力が十分に低いものとなる。なお、上記の密着性の効果は、粘着剤層3と、樹脂フィルムからなる基材2、特にポリオレフィン系フィルムからなる基材2とが直接積層された場合に、特に効果的に発揮される。
The pressure-sensitive adhesive layer 3 is excellent in adhesion with the base material 2 even after irradiation with energy rays. Therefore, when the adherend and the pressure-sensitive adhesive sheet 1 are separated after irradiation with energy rays, it is possible to effectively prevent the base material 2 and the pressure-sensitive adhesive layer 3 from being peeled off by the pressure-sensitive adhesive sheet 1. Moreover, the said adhesive layer 3 becomes a thing with the preferable adhesive force before and behind energy-beam irradiation. That is, the adhesive force to the adherend is sufficiently high before the energy beam irradiation, and the adhesive force to the adherend is sufficiently low after the energy beam irradiation. In addition, said adhesive effect is exhibited especially effectively when the adhesive layer 3 and the base material 2 made of a resin film, particularly the base material 2 made of a polyolefin film, are directly laminated.
水酸基含有モノマー(A2)としては、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシブチル、(メタ)アクリル酸4-ヒドロキシブチルなどの(メタ)アクリル酸ヒドロキシアルキルエステル等が挙げられる。これらの中でも、硬化性基含有化合物(A4)との反応性の点から(メタ)アクリル酸2-ヒドロキシエチルおよび(メタ)アクリル酸4-ヒドロキシブチルが好ましい。これらは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
Examples of the hydroxyl group-containing monomer (A2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. And (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 3-hydroxybutyl and (meth) acrylic acid 4-hydroxybutyl. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of reactivity with the curable group-containing compound (A4). These may be used alone or in combination of two or more.
アクリル系共重合体(AP)全体の質量に占める水酸基含有モノマー(A2)由来の構造部分の質量の割合は、1~25質量%であることが好ましく、特に5~25質量%であることが好ましく、さらには7~15質量%であることが好ましい。水酸基含有モノマー(A2)由来の構造部分の質量の割合が上記範囲にあることにより、硬化性基含有化合物(A4)による硬化性基の導入量および残存水酸基の量を好ましい範囲に制御することができる。これによって、エネルギー線照射後における粘着剤層3の粘着力を十分に小さくすることができる。
The ratio of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is preferably 1 to 25% by mass, particularly 5 to 25% by mass. It is preferably 7 to 15% by mass. When the proportion of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) is in the above range, the amount of the curable group introduced by the curable group-containing compound (A4) and the amount of the remaining hydroxyl group can be controlled within a preferable range. it can. Thereby, the adhesive force of the adhesive layer 3 after energy beam irradiation can be made sufficiently small.
エポキシ基と反応可能な官能基(水酸基を除く)を有する官能基含有モノマー(A3)の官能基としては、例えば、カルボキシル基、アミノ基、アジリジニル基等が挙げられ、中でも水酸基よりもエポキシ基との反応性が高いカルボキシル基が好ましい。官能基含有モノマー(A3)の官能基をカルボキシル基とすることにより、エポキシ系架橋剤(B)のエポキシ基と選択的に反応が起こり、本実施形態の効果に優れた粘着剤を得ることができる。
Examples of the functional group of the functional group-containing monomer (A3) having a functional group capable of reacting with an epoxy group (excluding a hydroxyl group) include a carboxyl group, an amino group, and an aziridinyl group. A carboxyl group having high reactivity is preferable. By making the functional group of the functional group-containing monomer (A3) a carboxyl group, a reaction occurs selectively with the epoxy group of the epoxy-based crosslinking agent (B), and an adhesive having excellent effects of the present embodiment can be obtained. it can.
カルボキシル基を含有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸等のエチレン性不飽和カルボン酸が挙げられる。アミノ基を含有するモノマーとしては、例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸n-ブチルアミノエチル等が挙げられる。官能基含有モノマー(A3)は、1種を単独で使用することもできるし、2種以上を組み合わせて使用することもできる。
Examples of the monomer containing a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Examples of the monomer containing an amino group include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like. A functional group containing monomer (A3) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
(メタ)アクリル酸エステル共重合体(A)全体の質量に占める官能基含有モノマー(A3)由来の構造部分の質量の割合は、0.1~5質量%であることが好ましく、特に0.3~3質量%であることが好ましく、さらには0.3~2質量%であることが好ましい。官能基含有モノマー(A3)由来の構造部分の質量の割合が上記範囲にあることにより、エポキシ系架橋剤(B)との反応量を好ましい範囲に制御して、架橋の程度を良好にすることができる。これによって、エネルギー線照射後における粘着剤層3の基材2との密着性を向上させることができる。
The ratio of the mass of the structural portion derived from the functional group-containing monomer (A3) to the total mass of the (meth) acrylic acid ester copolymer (A) is preferably 0.1 to 5% by mass, particularly preferably The content is preferably 3 to 3% by mass, and more preferably 0.3 to 2% by mass. By controlling the amount of reaction with the epoxy-based cross-linking agent (B) to a preferable range and improving the degree of cross-linking by having the mass ratio of the structural portion derived from the functional group-containing monomer (A3) within the above range. Can do. Thereby, the adhesiveness with the base material 2 of the adhesive layer 3 after energy-beam irradiation can be improved.
(メタ)アクリル酸エステル共重合体(A)は、当該共重合体を構成するモノマー単位として、上記のモノマー以外に、所望により、他のモノマーを含有してもよい。他のモノマーとしては、例えば、(メタ)アクリル酸メトキシメチル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシメチル、(メタ)アクリル酸エトキシエチル等のアルコキシアルキル基含有(メタ)アクリル酸エステル、(メタ)アクリル酸フェニル等の芳香族環を有する(メタ)アクリル酸エステル、アクリルアミド、メタクリルアミド等の非架橋性のアクリルアミド、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸、N,N-ジメチルアミノプロピル等の非架橋性の3級アミノ基を有する(メタ)アクリル酸エステル、酢酸ビニル、スチレンなどが挙げられる。これらは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
The (meth) acrylic acid ester copolymer (A) may contain other monomers as desired in addition to the above monomers as monomer units constituting the copolymer. Examples of other monomers include (meth) acrylic acid containing alkoxyalkyl groups such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Ester, (meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate, non-crosslinkable acrylamide such as acrylamide, methacrylamide, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) Examples thereof include (meth) acrylic acid ester having a non-crosslinking tertiary amino group such as acrylic acid and N, N-dimethylaminopropyl, vinyl acetate, styrene and the like. These may be used alone or in combination of two or more.
アクリル系共重合体(AP)は、上記各モノマーを常法によって共重合することにより得られる。アクリル系共重合体(AP)の重合態様は、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。
The acrylic copolymer (AP) can be obtained by copolymerizing the above monomers by a conventional method. The polymerization mode of the acrylic copolymer (AP) may be a random copolymer or a block copolymer.
硬化性基含有化合物(A4)は、(メタ)アクリル酸エステル共重合体(A)にエネルギー線硬化性を付与するためのものである。硬化性基含有化合物(A4)が有する水酸基と反応可能な官能基としては、例えば、イソシアネート基、エポキシ基、カルボキシル基等が挙げられ、中でも水酸基との反応性の高いイソシアネート基が好ましい。
The curable group-containing compound (A4) is for imparting energy beam curability to the (meth) acrylic acid ester copolymer (A). As a functional group which can react with the hydroxyl group which a curable group containing compound (A4) has, an isocyanate group, an epoxy group, a carboxyl group etc. are mentioned, for example, Among them, an isocyanate group with high reactivity with a hydroxyl group is preferable.
硬化性基含有化合物(A4)には、エネルギー線硬化性の炭素-炭素二重結合が含まれている。このエネルギー線硬化性の炭素-炭素二重結合は、硬化性基含有化合物(A4)の1分子毎に1~5個含まれていることが好ましく、特に1~2個含まれていることが好ましい。
The curable group-containing compound (A4) contains an energy ray-curable carbon-carbon double bond. This energy ray-curable carbon-carbon double bond is preferably contained in 1 to 5 molecules per molecule of the curable group-containing compound (A4), and more preferably 1 to 2 in particular. preferable.
このような硬化性基含有化合物(A4)としては、例えば、2-メタクリロイルオキシエチルイソシアネート、メタ-イソプロペニル-α,α-ジメチルベンジルイソシアネート、メタクリロイルイソシアネート、アリルイソシアネート、1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート;ジイソシアネート化合物またはポリイソシアネート化合物と、ヒドロキシエチル(メタ)アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物;ジイソシアネート化合物またはポリイソシアネート化合物と、ポリオール化合物と、ヒドロキシエチル(メタ)アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物などが挙げられる。これらの中でも、特に2-メタクリロイルオキシエチルイソシアネートが好ましい。硬化性基含有化合物(A4)は、1種を単独で使用することもできるし、2種以上を組み合わせて使用することもできる。
Examples of such a curable group-containing compound (A4) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxy). Methyl) ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth) acrylate Examples include acryloyl monoisocyanate compounds obtained by the reaction. Among these, 2-methacryloyloxyethyl isocyanate is particularly preferable. A sclerosing | hardenable group containing compound (A4) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
(メタ)アクリル酸エステル共重合体(A)は、硬化性基含有化合物(A4)に由来する硬化性基を、当該(メタ)アクリル酸エステル共重合体(A)が有する水酸基に対して、50モル%以上含有することが好ましく、特に70~400モル%含有することが好ましく、さらには90~200モル%含有することが好ましい。なお、硬化性基含有化合物(A4)が一官能の場合は、上限は100モル%となるが、硬化性基含有化合物(A4)が多官能の場合は、100モル%を超えることがある。水酸基に対する硬化性基の比率が50モル%以上であることにより、硬化性基の導入量が十分になるとともに、(メタ)アクリル酸エステル共重合体(A)中における残存水酸基が少なくなる。これによって、エネルギー線照射後における粘着剤層3の粘着力を十分に小さくすることができる。また、水酸基に対する硬化性基の比率が70モル%以上であると、エネルギー線照射後の粘着力を115mN/25mm以下程度に低減できる可能性が高まり、ダイシングシートとして使用した場合に、面積の大きいチップであっても容易にピックアップが可能となる。なお、水酸基に対する硬化性基の比率が大き過ぎると、エネルギー線照射後における粘着剤層3の粘着力が過度に低下して、チップがピックアップ前にダイシングシートから脱落等する懸念がある。
The (meth) acrylic acid ester copolymer (A) has a curable group derived from the curable group-containing compound (A4) with respect to the hydroxyl group of the (meth) acrylic acid ester copolymer (A). It is preferably contained in an amount of 50 mol% or more, particularly preferably 70 to 400 mol%, more preferably 90 to 200 mol%. In addition, when a curable group containing compound (A4) is monofunctional, an upper limit will be 100 mol%, but when a curable group containing compound (A4) is polyfunctional, it may exceed 100 mol%. When the ratio of the curable group to the hydroxyl group is 50 mol% or more, the introduction amount of the curable group becomes sufficient and the residual hydroxyl group in the (meth) acrylic acid ester copolymer (A) decreases. Thereby, the adhesive force of the adhesive layer 3 after energy beam irradiation can be made sufficiently small. Further, when the ratio of the curable group to the hydroxyl group is 70 mol% or more, there is a high possibility that the adhesive strength after irradiation with energy rays can be reduced to about 115 mN / 25 mm or less, and the area is large when used as a dicing sheet. Even a chip can be easily picked up. If the ratio of the curable group to the hydroxyl group is too large, the adhesive strength of the pressure-sensitive adhesive layer 3 after energy beam irradiation is excessively lowered, and there is a concern that the chip may fall off the dicing sheet before picking up.
アクリル系共重合体(AP)と硬化性基含有化合物(A4)との反応は、常法によって行えばよい。この反応工程により、アクリル系共重合体(AP)中の水酸基と、硬化性基含有化合物(A4)中の官能基(水酸基と反応可能な官能基、例えばイソシアネート基)とが反応して、硬化性基がアクリル系共重合体(AP)の側鎖に導入され、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)が得られる。
The reaction between the acrylic copolymer (AP) and the curable group-containing compound (A4) may be performed by a conventional method. By this reaction step, the hydroxyl group in the acrylic copolymer (AP) reacts with the functional group in the curable group-containing compound (A4) (functional group capable of reacting with the hydroxyl group, for example, an isocyanate group) to cure. The functional group is introduced into the side chain of the acrylic copolymer (AP) to obtain the energy ray-curable (meth) acrylic acid ester copolymer (A).
(メタ)アクリル酸エステル重合体(A)の重量平均分子量は、15万~200万であることが好ましく、特に20万~150万であることが好ましく、さらには25万~120万であることが好ましい。なお、本明細書における重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定した標準ポリスチレン換算の値である。
The weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 150,000 to 2,000,000, particularly preferably 200,000 to 1,500,000, and more preferably 250,000 to 1,200,000. Is preferred. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
(メタ)アクリル酸エステル重合体(A)の重量平均分子量が15万以上であると、粘着剤層3の硬化前における凝集性の低下を抑制することができ、例えば、ダイシングシートとして使用した場合に、チップの端部の欠け(チッピング)が発生する可能性を低減することができる。また、(メタ)アクリル酸エステル重合体(A)の重量平均分子量が200万以下であると、粘着剤層3を塗工用組成物の塗工により形成するときに、塗工用組成物の粘度が過剰に高くなって塗工が困難となる事態を回避することができる。
When the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is 150,000 or more, a decrease in cohesiveness before curing of the pressure-sensitive adhesive layer 3 can be suppressed. For example, when used as a dicing sheet In addition, the possibility of chipping (chipping) at the end of the chip can be reduced. Further, when the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is 2 million or less, when the pressure-sensitive adhesive layer 3 is formed by coating the coating composition, A situation in which the viscosity becomes excessively high and coating becomes difficult can be avoided.
なお、粘着性組成物Pにおいて、(メタ)アクリル酸エステル重合体(A)は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。また、粘着性組成物Pは、上記(メタ)アクリル酸エステル重合体(A)とは別の(メタ)アクリル酸エステル重合体をさらに含有してもよい。
In addition, in the adhesive composition P, the (meth) acrylic acid ester polymer (A) may be used alone or in combination of two or more. Moreover, the adhesive composition P may further contain a (meth) acrylic acid ester polymer different from the (meth) acrylic acid ester polymer (A).
(メタ)アクリル酸エステル重合体(A)を硬化させるためのエネルギー線としては、電離放射線、すなわち、X線、紫外線、電子線などが挙げられる。これらのうちでも、比較的照射設備の導入の容易な紫外線が好ましい。
Examples of the energy rays for curing the (meth) acrylic acid ester polymer (A) include ionizing radiation, that is, X-rays, ultraviolet rays, electron beams, and the like. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.
電離放射線として紫外線を用いる場合には、取り扱いの容易さから波長200~380nm程度の紫外線を含む近紫外線を用いればよい。光量としては、(メタ)アクリル酸エステル重合体(A)の種類や粘着剤層3の厚さに応じて適宜選択すればよく、通常50~500mJ/cm2程度であり、100~450mJ/cm2が好ましく、200~400mJ/cm2がより好ましい。また、紫外線照度は、通常50~500mW/cm2程度であり、100~450mW/cm2が好ましく、200~400mW/cm2がより好ましい。紫外線源としては特に制限はなく、例えば高圧水銀ランプ、メタルハライドランプ、UV-LEDなどが用いられる。
When ultraviolet rays are used as the ionizing radiation, near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling. The amount of light may be appropriately selected according to the type of (meth) acrylic acid ester polymer (A) and the thickness of the pressure-sensitive adhesive layer 3, and is usually about 50 to 500 mJ / cm 2 , and is 100 to 450 mJ / cm 2. 2 is preferable, and 200 to 400 mJ / cm 2 is more preferable. The ultraviolet illumination is usually 50 ~ 500mW / cm 2 or so, preferably 100 ~ 450mW / cm 2, more preferably 200 ~ 400mW / cm 2. The ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
電離放射線として電子線を用いる場合には、その加速電圧については、(メタ)アクリル酸エステル重合体(A)の種類や粘着剤層3の厚さに応じて適宜選定すればよく、通常加速電圧10~1000kV程度であることが好ましい。また、照射線量は、(メタ)アクリル酸エステル重合体(A)が適切に硬化する範囲に設定すればよく、通常10~1000kradの範囲で選定される。電子線源としては、特に制限はなく、例えばコックロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、あるいは直線型、ダイナミトロン型、高周波型などの各種電子線加速器を用いることができる。
When an electron beam is used as the ionizing radiation, the acceleration voltage may be appropriately selected according to the type of (meth) acrylic acid ester polymer (A) and the thickness of the pressure-sensitive adhesive layer 3. It is preferably about 10 to 1000 kV. The irradiation dose may be set in a range where the (meth) acrylic acid ester polymer (A) is appropriately cured, and is usually selected in the range of 10 to 1000 krad. The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
(2)エポキシ系架橋剤(B)
エポキシ系架橋剤(B)は、(メタ)アクリル酸エステル共重合体(A)中のエポキシ基と反応可能な官能基と反応して、(メタ)アクリル酸エステル共重合体(A)を架橋する。(メタ)アクリル酸エステル共重合体(A)中のエポキシ基と反応可能な官能基は、官能基含有モノマー(A3)由来のものであり、(メタ)アクリル酸エステル共重合体(A)中に適量存在するため、架橋の程度を好ましい範囲に制御することができる。これにより、得られる粘着剤層3において、エネルギー線照射前には粘着剤層3の凝集性を良好に維持し、エネルギー線照射後には基材2との密着性を十分に高くすることができる。 (2) Epoxy crosslinking agent (B)
The epoxy-based crosslinking agent (B) reacts with a functional group capable of reacting with an epoxy group in the (meth) acrylic acid ester copolymer (A) to crosslink the (meth) acrylic acid ester copolymer (A). To do. The functional group capable of reacting with the epoxy group in the (meth) acrylic acid ester copolymer (A) is derived from the functional group-containing monomer (A3), and in the (meth) acrylic acid ester copolymer (A). Therefore, the degree of crosslinking can be controlled within a preferable range. Thereby, in the pressure-sensitive adhesive layer 3 to be obtained, the cohesiveness of the pressure-sensitive adhesive layer 3 can be maintained satisfactorily before irradiation with energy rays, and the adhesiveness with the substrate 2 can be sufficiently increased after irradiation with energy rays. .
エポキシ系架橋剤(B)は、(メタ)アクリル酸エステル共重合体(A)中のエポキシ基と反応可能な官能基と反応して、(メタ)アクリル酸エステル共重合体(A)を架橋する。(メタ)アクリル酸エステル共重合体(A)中のエポキシ基と反応可能な官能基は、官能基含有モノマー(A3)由来のものであり、(メタ)アクリル酸エステル共重合体(A)中に適量存在するため、架橋の程度を好ましい範囲に制御することができる。これにより、得られる粘着剤層3において、エネルギー線照射前には粘着剤層3の凝集性を良好に維持し、エネルギー線照射後には基材2との密着性を十分に高くすることができる。 (2) Epoxy crosslinking agent (B)
The epoxy-based crosslinking agent (B) reacts with a functional group capable of reacting with an epoxy group in the (meth) acrylic acid ester copolymer (A) to crosslink the (meth) acrylic acid ester copolymer (A). To do. The functional group capable of reacting with the epoxy group in the (meth) acrylic acid ester copolymer (A) is derived from the functional group-containing monomer (A3), and in the (meth) acrylic acid ester copolymer (A). Therefore, the degree of crosslinking can be controlled within a preferable range. Thereby, in the pressure-
エポキシ系架橋剤(B)としては、例えば、1,3-ビス(N,N’-ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン、エチレングリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン等が挙げられる。エポキシ系架橋剤(B)は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
Examples of the epoxy crosslinking agent (B) include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, and ethylene glycol. Examples include diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, and diglycidyl amine. An epoxy type crosslinking agent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
粘着剤層3を形成する粘着剤組成物のエポキシ系架橋剤(B)の含有量は、(メタ)アクリル酸エステル共重合体(A)100質量部に対して0.01~5質量部であることが好ましく、特に0.05~3質量部であることが好ましく、さらには0.08~2質量部であることが好ましい。エポキシ系架橋剤(B)の含有量が上記の範囲にあることにより、得られる粘着剤層3において、エネルギー線照射前には粘着剤層3の凝集性を良好に維持し、エネルギー線照射後には基材2との密着性を十分に高くすることができる。
The content of the epoxy-based crosslinking agent (B) in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 3 is 0.01 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). The amount is preferably 0.05 to 3 parts by mass, more preferably 0.08 to 2 parts by mass. When the content of the epoxy-based crosslinking agent (B) is in the above range, in the resulting pressure-sensitive adhesive layer 3, the cohesiveness of the pressure-sensitive adhesive layer 3 is favorably maintained before irradiation with energy rays, and after irradiation with energy rays. Can sufficiently increase the adhesion to the substrate 2.
(3)その他の成分
本実施形態における粘着剤層3を形成する粘着剤組成物は、上記の成分に加えて、光重合開始剤、帯電防止剤、染料や顔料などの着色材料、難燃剤、フィラー等の各種添加剤を含有してもよい。 (3) Other components In addition to the above components, the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 3 in the present embodiment is a photopolymerization initiator, an antistatic agent, a coloring material such as a dye or a pigment, a flame retardant, You may contain various additives, such as a filler.
本実施形態における粘着剤層3を形成する粘着剤組成物は、上記の成分に加えて、光重合開始剤、帯電防止剤、染料や顔料などの着色材料、難燃剤、フィラー等の各種添加剤を含有してもよい。 (3) Other components In addition to the above components, the pressure-sensitive adhesive composition forming the pressure-
光重合開始剤としては、ベンゾイン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、チオキサントン化合物、パーオキサイド化合物等の光開始剤、アミンやキノン等の光増感剤などが挙げられ、具体的には、1-ヒドロキシシクロヘキシルフェニルケトン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジフェニルサルファイド、テトラメチルチウラムモノサルファイド、アゾビスイソブチロニトリル、ジベンジル、ジアセチル、β-クロールアンスラキノン、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイドなどが例示される。エネルギー線として紫外線を用いる場合には、光重合開始剤を配合することにより照射時間、照射量を少なくすることができる。
Examples of photopolymerization initiators include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones. 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, β-chloranthraquinone Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.
(4)厚さ
粘着剤層3の厚さは、粘着シート1が使用される工程において適切に機能できる限り、限定されない。例えば粘着シート1がダイシングシートやバックグラインドシートとして使用される場合、粘着剤層3の厚さは、1~80μmであることが好ましく、特に3~60μmであることが好ましく、さらには5~35μmであることが好ましい。粘着剤層3の厚さが1μm以上であると、粘着シート1の粘着力のばらつきを小さく抑えることができる。また、粘着剤層3の厚さが80μm以下であると、粘着剤層3を塗工用組成物の塗工により形成するときに、乾燥に時間がかかり過ぎることを回避することができる。 (4) Thickness The thickness of the pressure-sensitive adhesive layer 3 is not limited as long as it can function properly in the process in which the pressure-sensitive adhesive sheet 1 is used. For example, when the pressure-sensitive adhesive sheet 1 is used as a dicing sheet or a back grind sheet, the thickness of the pressure-sensitive adhesive layer 3 is preferably 1 to 80 μm, particularly preferably 3 to 60 μm, and more preferably 5 to 35 μm. It is preferable that When the thickness of the pressure-sensitive adhesive layer 3 is 1 μm or more, variations in the adhesive strength of the pressure-sensitive adhesive sheet 1 can be reduced. Moreover, when the thickness of the adhesive layer 3 is 80 μm or less, it can be avoided that drying takes too much time when the adhesive layer 3 is formed by applying the coating composition.
粘着剤層3の厚さは、粘着シート1が使用される工程において適切に機能できる限り、限定されない。例えば粘着シート1がダイシングシートやバックグラインドシートとして使用される場合、粘着剤層3の厚さは、1~80μmであることが好ましく、特に3~60μmであることが好ましく、さらには5~35μmであることが好ましい。粘着剤層3の厚さが1μm以上であると、粘着シート1の粘着力のばらつきを小さく抑えることができる。また、粘着剤層3の厚さが80μm以下であると、粘着剤層3を塗工用組成物の塗工により形成するときに、乾燥に時間がかかり過ぎることを回避することができる。 (4) Thickness The thickness of the pressure-
3.剥離シート
本実施形態に係る粘着シート1は、被着体に粘着剤層3を貼付するまでの間、粘着剤層3を保護する目的で、粘着剤層3の基材2側の面と反対側の面に、剥離シートが積層されていてもよい。剥離シートの構成は任意であり、フィルム自体が保護膜形成フィルム1に対し剥離性を有するプラスチックフィルム、およびプラスチックフィルムを剥離剤等により剥離処理したものが例示される。プラスチックフィルムの具体例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、およびポリプロピレンやポリエチレン等のポリオレフィンフィルムが挙げられる。剥離剤としては、シリコーン系、フッ素系、長鎖アルキル系等を用いることができるが、これらの中で、安価で安定した性能が得られるシリコーン系が好ましい。剥離シートの厚さについては特に制限はないが、通常20~250μm程度である。 3. Release Sheet The pressure-sensitive adhesive sheet 1 according to the present embodiment is opposite to the surface of the pressure-sensitive adhesive layer 3 on the substrate 2 side for the purpose of protecting the pressure-sensitive adhesive layer 3 until the pressure-sensitive adhesive layer 3 is applied to the adherend. A release sheet may be laminated on the side surface. The configuration of the release sheet is arbitrary, and examples thereof include a plastic film having peelability with respect to the protective film-forming film 1 and a release film obtained by peeling the plastic film with a release agent or the like. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable. The thickness of the release sheet is not particularly limited, but is usually about 20 to 250 μm.
本実施形態に係る粘着シート1は、被着体に粘着剤層3を貼付するまでの間、粘着剤層3を保護する目的で、粘着剤層3の基材2側の面と反対側の面に、剥離シートが積層されていてもよい。剥離シートの構成は任意であり、フィルム自体が保護膜形成フィルム1に対し剥離性を有するプラスチックフィルム、およびプラスチックフィルムを剥離剤等により剥離処理したものが例示される。プラスチックフィルムの具体例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、およびポリプロピレンやポリエチレン等のポリオレフィンフィルムが挙げられる。剥離剤としては、シリコーン系、フッ素系、長鎖アルキル系等を用いることができるが、これらの中で、安価で安定した性能が得られるシリコーン系が好ましい。剥離シートの厚さについては特に制限はないが、通常20~250μm程度である。 3. Release Sheet The pressure-sensitive adhesive sheet 1 according to the present embodiment is opposite to the surface of the pressure-
4.物性(粘着力)
粘着シート1のエネルギー線照射前およびエネルギー線照射後の粘着力は、粘着シート1の用途によって異なるが、例えば粘着シート1がダイシングシートやバックグラインドシートとして使用される場合、粘着シート1のエネルギー線照射前の粘着力は、500~30000mN/25mmであることが好ましく、特に750~22000mN/25mmであることが好ましく、さらには1000~18000mN/25mmであることが好ましい。エネルギー線照射前の粘着力が上記の範囲内にあることで、加工中のワークを強固に保持することができ、また、チップ飛散の発生を抑制することができる。 4). Physical properties (adhesive strength)
The adhesive strength of the pressure-sensitive adhesive sheet 1 before and after energy beam irradiation varies depending on the application of the pressure-sensitive adhesive sheet 1. For example, when the pressure-sensitive adhesive sheet 1 is used as a dicing sheet or a back grind sheet, the energy rays of the pressure-sensitive adhesive sheet 1 are used. The adhesive strength before irradiation is preferably 500 to 30000 mN / 25 mm, particularly preferably 750 to 22000 mN / 25 mm, and more preferably 1000 to 18000 mN / 25 mm. Since the adhesive force before energy beam irradiation is within the above range, the workpiece being processed can be firmly held, and the occurrence of chip scattering can be suppressed.
粘着シート1のエネルギー線照射前およびエネルギー線照射後の粘着力は、粘着シート1の用途によって異なるが、例えば粘着シート1がダイシングシートやバックグラインドシートとして使用される場合、粘着シート1のエネルギー線照射前の粘着力は、500~30000mN/25mmであることが好ましく、特に750~22000mN/25mmであることが好ましく、さらには1000~18000mN/25mmであることが好ましい。エネルギー線照射前の粘着力が上記の範囲内にあることで、加工中のワークを強固に保持することができ、また、チップ飛散の発生を抑制することができる。 4). Physical properties (adhesive strength)
The adhesive strength of the pressure-sensitive adhesive sheet 1 before and after energy beam irradiation varies depending on the application of the pressure-sensitive adhesive sheet 1. For example, when the pressure-sensitive adhesive sheet 1 is used as a dicing sheet or a back grind sheet, the energy rays of the pressure-sensitive adhesive sheet 1 are used. The adhesive strength before irradiation is preferably 500 to 30000 mN / 25 mm, particularly preferably 750 to 22000 mN / 25 mm, and more preferably 1000 to 18000 mN / 25 mm. Since the adhesive force before energy beam irradiation is within the above range, the workpiece being processed can be firmly held, and the occurrence of chip scattering can be suppressed.
一方、粘着シート1のエネルギー線照射後の粘着力は、10~400mN/25mmであることが好ましく、特に20~115mN/25mmであることが好ましく、さらには30~80mN/25mmであることが好ましい。エネルギー線照射後の粘着力が上記の範囲内にあることで、加工後のワークや、ワークを加工して得られたチップを、粘着シート1から分離し易い。
On the other hand, the adhesive strength of the pressure-sensitive adhesive sheet 1 after irradiation with energy rays is preferably 10 to 400 mN / 25 mm, particularly preferably 20 to 115 mN / 25 mm, and more preferably 30 to 80 mN / 25 mm. . Since the adhesive force after energy beam irradiation is within the above range, the workpiece after processing and the chip obtained by processing the workpiece can be easily separated from the adhesive sheet 1.
なお、エネルギー線照射前の粘着力は、シリコンミラーウエハを被着体とし、1kg重の荷重を加えて粘着シートを貼付し、23℃、50%RHの雰囲気下に20分間放置した後、JIS Z0237:2000に準じた180°引き剥がし法により測定した粘着力(mN/25mm)とする。また、エネルギー線照射後の粘着力は、粘着シートを上記被着体に上記と同じ条件で貼付してから、23℃、50%RHの雰囲気下に20分間放置し、窒素雰囲気下にて、粘着シートの基材側より紫外線照射(照度230mW/cm2,光量190mJ/cm2)した後、上記と同様にして測定した粘着力とする。
Note that the adhesive strength before irradiation with energy rays was determined by applying a silicon mirror wafer as an adherend, applying a 1 kg weight, sticking an adhesive sheet, and leaving it in an atmosphere of 23 ° C. and 50% RH for 20 minutes. Let it be the adhesive strength (mN / 25 mm) measured by 180 ° peeling method according to Z0237: 2000. In addition, the adhesive strength after irradiation with energy rays was determined by applying the adhesive sheet to the adherend under the same conditions as described above, and then leaving it in an atmosphere of 23 ° C. and 50% RH for 20 minutes. After the ultraviolet irradiation (illuminance 230 mW / cm 2 , light quantity 190 mJ / cm 2 ) from the base material side of the pressure-sensitive adhesive sheet, the adhesive strength measured in the same manner as described above is used.
粘着シート1のエネルギー線照射前の粘着力に対するエネルギー線照射後の粘着力の比は、0.001~0.3であることが好ましく、0.01~0.2であることがより好ましい。上記粘着力の比が上記の範囲内にあると、エネルギー線照射前の粘着力とエネルギー線照射後の粘着力とのバランスが良好になり、エネルギー線照射前の高い粘着力とエネルギー線照射後の低い粘着力とを達成し易くなる。
The ratio of the adhesive strength after irradiation with energy rays to the adhesive strength before irradiation with energy rays of the adhesive sheet 1 is preferably 0.001 to 0.3, and more preferably 0.01 to 0.2. When the ratio of the adhesive strength is within the above range, the balance between the adhesive strength before energy beam irradiation and the adhesive strength after energy beam irradiation becomes good, and the high adhesive strength before energy beam irradiation and after energy beam irradiation. It is easy to achieve a low adhesive strength.
本実施形態における粘着シート1は、粘着剤層3が前述した粘着剤組成物から形成されるため、エネルギー線照射前の粘着力、エネルギー線照射後の粘着力およびそれらの比を上記の範囲内に制御し易い。
Since the pressure-sensitive adhesive sheet 1 in this embodiment is formed from the pressure-sensitive adhesive composition described above, the pressure-sensitive adhesive force before energy beam irradiation, the pressure-sensitive adhesive force after energy beam irradiation, and the ratio thereof are within the above range. Easy to control.
5.粘着シートの製造方法
粘着シート1の製造方法は、前述の粘着剤組成物から形成される粘着剤層3を基材2の一の面に積層できれば、詳細な方法は特に限定されない。一例を挙げれば、前述の粘着剤組成物、および所望によりさらに溶媒または分散媒を含有する塗工用組成物を調製し、基材1の一の面上に、ダイコーター、カーテンコーター、スプレーコーター、スリットコーター、ナイフコーター等によりその塗工用組成物を塗布して塗膜を形成し、当該塗膜を乾燥させることにより、粘着剤層3を形成することができる。塗工用組成物は、塗布を行うことが可能であればその性状は特に限定されず、粘着剤層3を形成するための成分を溶質として含有する場合もあれば、分散質として含有する場合もある。 5. Manufacturing method of adhesive sheet The manufacturing method of the adhesive sheet 1 will not be specifically limited if theadhesive layer 3 formed from the above-mentioned adhesive composition can be laminated | stacked on one surface of the base material 2. FIG. For example, a coating composition containing the aforementioned pressure-sensitive adhesive composition and, if desired, further containing a solvent or a dispersion medium is prepared, and a die coater, curtain coater, spray coater is formed on one surface of the substrate 1. The pressure-sensitive adhesive layer 3 can be formed by applying the coating composition with a slit coater, knife coater or the like to form a coating film and drying the coating film. The properties of the coating composition are not particularly limited as long as it can be applied. The composition for forming the pressure-sensitive adhesive layer 3 may be contained as a solute, or may be contained as a dispersoid. There is also.
粘着シート1の製造方法は、前述の粘着剤組成物から形成される粘着剤層3を基材2の一の面に積層できれば、詳細な方法は特に限定されない。一例を挙げれば、前述の粘着剤組成物、および所望によりさらに溶媒または分散媒を含有する塗工用組成物を調製し、基材1の一の面上に、ダイコーター、カーテンコーター、スプレーコーター、スリットコーター、ナイフコーター等によりその塗工用組成物を塗布して塗膜を形成し、当該塗膜を乾燥させることにより、粘着剤層3を形成することができる。塗工用組成物は、塗布を行うことが可能であればその性状は特に限定されず、粘着剤層3を形成するための成分を溶質として含有する場合もあれば、分散質として含有する場合もある。 5. Manufacturing method of adhesive sheet The manufacturing method of the adhesive sheet 1 will not be specifically limited if the
上記の乾燥処理により、または加熱処理を別途行うことにより、塗膜内の(メタ)アクリル酸エステル重合体(A)とエポキシ系架橋剤(B)との架橋反応が進行し、塗膜内に架橋構造が形成され、粘着剤層3が形成される。この架橋反応を十分に進行させるために、通常は、上記の方法などによって基材2に粘着剤層3を形成した後、得られた半導体加工用シート1を、例えば23℃、相対湿度50%の環境に数日間静置するといった養生を行う。
By performing the above drying treatment or separately performing the heat treatment, the crosslinking reaction of the (meth) acrylic acid ester polymer (A) in the coating film and the epoxy crosslinking agent (B) proceeds, A crosslinked structure is formed, and the pressure-sensitive adhesive layer 3 is formed. In order to sufficiently advance the crosslinking reaction, usually, after the pressure-sensitive adhesive layer 3 is formed on the base material 2 by the above-described method or the like, the obtained semiconductor processing sheet 1 is, for example, 23 ° C. and relative humidity 50%. Carry out curing such as leaving it in the environment for several days.
粘着シート1の製造方法の別の一例として、前述の剥離シートの剥離面上に塗工用組成物を塗布して塗膜を形成し、これを乾燥させて粘着剤層3と剥離シートとからなる積層体を形成し、この積層体の粘着剤層3における剥離シート側の面と反対側の面を基材1に貼付して、粘着シート1と剥離シートとの積層体を得てもよい。この積層体における剥離シートは工程材料として剥離してもよいし、半導体パッケージ等の被着体に貼付するまでの間、粘着剤層3を保護してもよい。
As another example of the production method of the pressure-sensitive adhesive sheet 1, a coating film is formed on the release surface of the above-described release sheet to form a coating film, which is dried to form the pressure-sensitive adhesive layer 3 and the release sheet. And a surface of the pressure-sensitive adhesive layer 3 opposite to the surface on the side of the release sheet is attached to the substrate 1 to obtain a layered product of the pressure-sensitive adhesive sheet 1 and the release sheet. . The release sheet in the laminate may be peeled off as a process material, or the pressure-sensitive adhesive layer 3 may be protected until being attached to an adherend such as a semiconductor package.
6.粘着シートの使用方法
本実施形態に係る粘着シート1をダイシングシートとして使用する場合の使用方法を以下に説明する。 6). Usage method of an adhesive sheet The usage method in the case of using the adhesive sheet 1 which concerns on this embodiment as a dicing sheet is demonstrated below.
本実施形態に係る粘着シート1をダイシングシートとして使用する場合の使用方法を以下に説明する。 6). Usage method of an adhesive sheet The usage method in the case of using the adhesive sheet 1 which concerns on this embodiment as a dicing sheet is demonstrated below.
まず、本実施形態に係る粘着シート1を、粘着剤層3側の面(すなわち、粘着剤層3の基材2と反対側の面)が半導体ウエハに接触するように、半導体ウエハに貼付する。粘着シート1の粘着剤層3側の面に剥離シートが積層されている場合には、その剥離シートを剥離して粘着剤層3側の面を表出させて、半導体ウエハにその面を貼付すればよい。
First, the pressure-sensitive adhesive sheet 1 according to this embodiment is attached to a semiconductor wafer such that the surface on the pressure-sensitive adhesive layer 3 side (that is, the surface opposite to the base material 2 of the pressure-sensitive adhesive layer 3) is in contact with the semiconductor wafer. . When a release sheet is laminated on the surface of the pressure-sensitive adhesive sheet 1 on the pressure-sensitive adhesive layer 3 side, the surface of the pressure-sensitive adhesive layer 3 is exposed by peeling off the release sheet, and the surface is affixed to the semiconductor wafer. do it.
ここで、粘着シート1付きの半導体ウエハは、溶剤に浸漬されることがある。このとき、粘着剤層3を構成する(メタ)アクリル酸エステル共重合体(A)が、構成モノマー単位としてアルキル基の炭素数が6以上の(メタ)アクリル酸アルキルエステルモノマー(A1)を含有する場合には、粘着剤層3は耐溶剤性に優れるため、粘着剤層3は膨潤、溶解等することなく、良好な層状態および半導体ウエハに対する接着状態を保持する。
Here, the semiconductor wafer with the adhesive sheet 1 may be immersed in a solvent. At this time, the (meth) acrylic acid ester copolymer (A) constituting the pressure-sensitive adhesive layer 3 contains a (meth) acrylic acid alkyl ester monomer (A1) having 6 or more alkyl groups as a constituent monomer unit. In this case, since the pressure-sensitive adhesive layer 3 is excellent in solvent resistance, the pressure-sensitive adhesive layer 3 maintains a good layer state and an adhesion state to the semiconductor wafer without swelling and dissolution.
次いで、ダイシング工程を実施し、半導体ウエハから複数のチップを得る。本実施形態における粘着剤層3は、エネルギー線照射前にはダイシング工程に十分な程度の粘着力を有するため、形成されるチップは粘着シート1に強固に固定され、ダイシング工程中にチッピングが生じ難い。
Next, a dicing process is performed to obtain a plurality of chips from the semiconductor wafer. Since the pressure-sensitive adhesive layer 3 in the present embodiment has a sufficient adhesive strength for the dicing process before irradiation with energy rays, the chip to be formed is firmly fixed to the pressure-sensitive adhesive sheet 1 and chipping occurs during the dicing process. hard.
ダイシング工程終了後、粘着シート1の基材2側からエネルギー線照射を行う。これにより、粘着剤層3に含まれる(メタ)アクリル酸エステル重合体(A)が有する硬化性基の重合反応が進行して粘着性が低下し、チップのピックアップが可能となる。
After completion of the dicing process, energy beam irradiation is performed from the base material 2 side of the pressure-sensitive adhesive sheet 1. As a result, the polymerization reaction of the curable group of the (meth) acrylic acid ester polymer (A) contained in the pressure-sensitive adhesive layer 3 proceeds, the pressure-sensitive adhesiveness is lowered, and the chip can be picked up.
一例としてエネルギー線照射の後、粘着シート1上に近接配置されている複数のチップをピックアップし易いように、粘着シート1を平面方向に伸長するエキスパンド工程を行う。なお、エキスパンド工程は、エネルギー線照射の前に行ってもよい。
As an example, after the energy ray irradiation, an expanding process for extending the adhesive sheet 1 in the plane direction is performed so that a plurality of chips arranged close to the adhesive sheet 1 can be easily picked up. In addition, you may perform an expanding process before energy beam irradiation.
エキスパンド工程の後、粘着剤層3上のチップのピックアップを行う。ピックアップは、吸引コレット等の汎用手段により行うことができる。本実施形態における粘着剤層3は、エネルギー線照射後には粘着力が十分に低くなるため、上記ピックアップは容易に行うことができる。また、本実施形態における粘着剤層3は、エネルギー線照射後にも基材2との密着性に優れるため、上記ピックアップ時に、基材2と粘着剤層3とが剥離して、粘着剤層3がチップ側に付いてしまうことを効果的に抑制することができる。なお、ピックアップされたチップは、搬送工程など次の工程へと供される。
After the expanding process, the chip on the adhesive layer 3 is picked up. The pickup can be performed by general means such as a suction collet. Since the pressure-sensitive adhesive layer 3 in the present embodiment has a sufficiently low adhesive strength after irradiation with energy rays, the above pickup can be easily performed. Moreover, since the adhesive layer 3 in this embodiment is excellent in adhesiveness with the base material 2 even after energy beam irradiation, the base material 2 and the adhesive layer 3 are peeled off at the time of the pick-up, and the adhesive layer 3 Can be effectively suppressed from adhering to the chip side. The picked-up chip is used for the next process such as a transport process.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。
The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
例えば、上記粘着シート1における基材2の粘着剤層3側とは反対側の面には、他の層が積層されていてもよい。
For example, another layer may be laminated on the surface of the adhesive sheet 1 opposite to the adhesive layer 3 side of the base material 2.
以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔実施例1〕
アクリル酸ラウリル89.5質量部と、アクリル酸2-ヒドロキシエチル10質量部と、アクリル酸0.5質量部とを共重合し、アクリル系共重合体を得た。このアクリル系共重合体と、メタクリロイルオキシエチルイソシアネート(MOI)とを、MOIの反応量がアクリル系共重合体100g当たり12.1g(アクリル系共重合体中のアクリル酸2-ヒドロキシエチル単位100モル当たり95モル(95モル%))となるように反応させて、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(重量平均分子量:60万)を得た。 [Example 1]
89.5 parts by mass of lauryl acrylate, 10 parts by mass of 2-hydroxyethyl acrylate, and 0.5 parts by mass of acrylic acid were copolymerized to obtain an acrylic copolymer. The acrylic copolymer and methacryloyloxyethyl isocyanate (MOI) were mixed at a MOI reaction amount of 12.1 g per 100 g of the acrylic copolymer (100 mol of 2-hydroxyethyl acrylate units in the acrylic copolymer). It was made to react so that it might become 95 mol (95 mol%) per weight, and the energy-beam curable (meth) acrylic acid ester copolymer (weight average molecular weight: 600,000) was obtained.
アクリル酸ラウリル89.5質量部と、アクリル酸2-ヒドロキシエチル10質量部と、アクリル酸0.5質量部とを共重合し、アクリル系共重合体を得た。このアクリル系共重合体と、メタクリロイルオキシエチルイソシアネート(MOI)とを、MOIの反応量がアクリル系共重合体100g当たり12.1g(アクリル系共重合体中のアクリル酸2-ヒドロキシエチル単位100モル当たり95モル(95モル%))となるように反応させて、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(重量平均分子量:60万)を得た。 [Example 1]
89.5 parts by mass of lauryl acrylate, 10 parts by mass of 2-hydroxyethyl acrylate, and 0.5 parts by mass of acrylic acid were copolymerized to obtain an acrylic copolymer. The acrylic copolymer and methacryloyloxyethyl isocyanate (MOI) were mixed at a MOI reaction amount of 12.1 g per 100 g of the acrylic copolymer (100 mol of 2-hydroxyethyl acrylate units in the acrylic copolymer). It was made to react so that it might become 95 mol (95 mol%) per weight, and the energy-beam curable (meth) acrylic acid ester copolymer (weight average molecular weight: 600,000) was obtained.
得られたエネルギー線硬化性の(メタ)アクリル酸エステル共重合体100質量部(固形分換算;以下同じ)と、光重合開始剤としての1-ヒドロキシシクロヘキシルフェニルケトン(チバ・スペシャリティ・ケミカルズ社製,イルガキュア184)3質量部と、エポキシ系架橋剤としてのポリグリシジルアミン系化合物(三菱ガス化学社製,TETRAD-C)0.1質量部とを溶媒中で混合し、粘着剤組成物(塗工用組成物)を得た。
100 parts by mass of the resulting energy ray-curable (meth) acrylic acid ester copolymer (in terms of solid content; the same applies hereinafter) and 1-hydroxycyclohexyl phenyl ketone (produced by Ciba Specialty Chemicals) as a photopolymerization initiator , Irgacure 184) 3 parts by mass and 0.1 part by mass of a polyglycidylamine compound (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-C) as an epoxy-based crosslinking agent are mixed in a solvent to produce an adhesive composition (coating A working composition) was obtained.
ポリエチレンテレフタレートフィルムの片面がシリコーン系剥離剤で剥離処理された剥離フィルム(リンテック社製,SP-PET3811)の剥離処理面に、上記塗工用組成物を乾燥後の厚さが10μmとなるように塗布し、乾燥(乾燥条件:100℃,1分間)して、粘着剤層を形成した。
On the release-treated surface of a release film (SP-PET3811, manufactured by Lintec Corporation) where one side of the polyethylene terephthalate film is release-treated with a silicone-based release agent, the thickness after drying the coating composition is 10 μm. It was applied and dried (drying conditions: 100 ° C., 1 minute) to form an adhesive layer.
次いで、基材として、片面がコロナ処理されたポリプロピレンフィルム(厚さ80μm)を用意し、このポリプロピレンフィルムのコロナ処理面が上記粘着剤層と接するように、当該基材と上記粘着剤層とを貼り合わせて、基材と粘着剤層と剥離フィルムとからなる粘着シートを得た。
Next, a polypropylene film (thickness 80 μm) having a corona-treated one side is prepared as a base material, and the base material and the pressure-sensitive adhesive layer are placed so that the corona-treated surface of the polypropylene film is in contact with the pressure-sensitive adhesive layer. The adhesive sheet which consists of a base material, an adhesive layer, and a peeling film was bonded together.
ここで、上記粘着剤組成物の配合を表1に示す。なお、表1に記載の略号等の詳細は以下の通りである。
[(メタ)アクリル酸エステル共重合体]
LA:アクリル酸ラウリル
HEA:アクリル酸2-ヒドロキシエチル
AAc:アクリル酸
BA:アクリル酸n-ブチル
2-EHA:アクリル酸2-エチルヘキシル
iOA:アクリル酸イソオクチル
[架橋剤]
epoxy:ポリグリシジルアミン系化合物(三菱ガス化学社製,TETRAD-C)
TDI-TMP:トリレンジイソシアネートとトリメチロールプロパントリアクリレートとの付加物(トーヨーケム社製,BHS8515)
HDI-TMP:ヘキサメチレンジイソシアネートとトリメチロールプロパントリアクリレートとの付加物(トーヨーケム社製,Bxx4773) Here, Table 1 shows the composition of the pressure-sensitive adhesive composition. Details of the abbreviations and the like described in Table 1 are as follows.
[(Meth) acrylic acid ester copolymer]
LA: lauryl acrylate HEA: 2-hydroxyethyl acrylate AAc: acrylic acid BA: n-butyl acrylate 2-EHA: 2-ethylhexyl acrylate iOA: isooctyl acrylate
[Crosslinking agent]
epoxy: polyglycidylamine compound (manufactured by Mitsubishi Gas Chemical Company, TETRAD-C)
TDI-TMP: adduct of tolylene diisocyanate and trimethylolpropane triacrylate (Toyochem, BHS8515)
HDI-TMP: Addition product of hexamethylene diisocyanate and trimethylolpropane triacrylate (Toyochem, Bxx4773)
[(メタ)アクリル酸エステル共重合体]
LA:アクリル酸ラウリル
HEA:アクリル酸2-ヒドロキシエチル
AAc:アクリル酸
BA:アクリル酸n-ブチル
2-EHA:アクリル酸2-エチルヘキシル
iOA:アクリル酸イソオクチル
[架橋剤]
epoxy:ポリグリシジルアミン系化合物(三菱ガス化学社製,TETRAD-C)
TDI-TMP:トリレンジイソシアネートとトリメチロールプロパントリアクリレートとの付加物(トーヨーケム社製,BHS8515)
HDI-TMP:ヘキサメチレンジイソシアネートとトリメチロールプロパントリアクリレートとの付加物(トーヨーケム社製,Bxx4773) Here, Table 1 shows the composition of the pressure-sensitive adhesive composition. Details of the abbreviations and the like described in Table 1 are as follows.
[(Meth) acrylic acid ester copolymer]
LA: lauryl acrylate HEA: 2-hydroxyethyl acrylate AAc: acrylic acid BA: n-butyl acrylate 2-EHA: 2-ethylhexyl acrylate iOA: isooctyl acrylate
[Crosslinking agent]
epoxy: polyglycidylamine compound (manufactured by Mitsubishi Gas Chemical Company, TETRAD-C)
TDI-TMP: adduct of tolylene diisocyanate and trimethylolpropane triacrylate (Toyochem, BHS8515)
HDI-TMP: Addition product of hexamethylene diisocyanate and trimethylolpropane triacrylate (Toyochem, Bxx4773)
〔実施例2~12,比較例1~3〕
(メタ)アクリル酸エステル共重合体を構成する各モノマーの割合、メタクリロイルオキシエチルイソシアネート(MOI)の反応量、ならびに架橋剤の種類および配合量を表1に示すように変更する以外、実施例1と同様にして粘着シートを製造した。なお、比較例1~3で使用した架橋剤は、イソシアネート系架橋剤(TDI-TMPまたはHDI-TMP)であった。 [Examples 2 to 12, Comparative Examples 1 to 3]
Example 1 except that the ratio of each monomer constituting the (meth) acrylic acid ester copolymer, the reaction amount of methacryloyloxyethyl isocyanate (MOI), and the type and amount of the crosslinking agent were changed as shown in Table 1. A pressure-sensitive adhesive sheet was produced in the same manner as described above. The crosslinking agent used in Comparative Examples 1 to 3 was an isocyanate crosslinking agent (TDI-TMP or HDI-TMP).
(メタ)アクリル酸エステル共重合体を構成する各モノマーの割合、メタクリロイルオキシエチルイソシアネート(MOI)の反応量、ならびに架橋剤の種類および配合量を表1に示すように変更する以外、実施例1と同様にして粘着シートを製造した。なお、比較例1~3で使用した架橋剤は、イソシアネート系架橋剤(TDI-TMPまたはHDI-TMP)であった。 [Examples 2 to 12, Comparative Examples 1 to 3]
Example 1 except that the ratio of each monomer constituting the (meth) acrylic acid ester copolymer, the reaction amount of methacryloyloxyethyl isocyanate (MOI), and the type and amount of the crosslinking agent were changed as shown in Table 1. A pressure-sensitive adhesive sheet was produced in the same manner as described above. The crosslinking agent used in Comparative Examples 1 to 3 was an isocyanate crosslinking agent (TDI-TMP or HDI-TMP).
〔試験例1〕<密着性試験>
実施例および比較例にて製造した粘着シートに対し、紫外線照射装置(リンテック社製:RAD-2000m/12)を用い、窒素雰囲気下にて粘着シートの基材側から紫外線(UV)照射(照度230mW/cm2,光量190mJ/cm2)を行った。その後、硬化した粘着剤層に対し、カッターナイフで縦横5mm角の碁盤目を400マス形成した。 [Test Example 1] <Adhesion test>
The pressure-sensitive adhesive sheets produced in Examples and Comparative Examples were irradiated with ultraviolet rays (UV) from the substrate side of the pressure-sensitive adhesive sheet in a nitrogen atmosphere using an ultraviolet irradiation device (Rintec Corporation: RAD-2000m / 12). 230 mW / cm 2 , light quantity 190 mJ / cm 2 ). Thereafter, 400 squares of 5 mm squares were formed with a cutter knife on the cured adhesive layer.
実施例および比較例にて製造した粘着シートに対し、紫外線照射装置(リンテック社製:RAD-2000m/12)を用い、窒素雰囲気下にて粘着シートの基材側から紫外線(UV)照射(照度230mW/cm2,光量190mJ/cm2)を行った。その後、硬化した粘着剤層に対し、カッターナイフで縦横5mm角の碁盤目を400マス形成した。 [Test Example 1] <Adhesion test>
The pressure-sensitive adhesive sheets produced in Examples and Comparative Examples were irradiated with ultraviolet rays (UV) from the substrate side of the pressure-sensitive adhesive sheet in a nitrogen atmosphere using an ultraviolet irradiation device (Rintec Corporation: RAD-2000m / 12). 230 mW / cm 2 , light quantity 190 mJ / cm 2 ). Thereafter, 400 squares of 5 mm squares were formed with a cutter knife on the cured adhesive layer.
次いで、23℃、50%RHの環境下で、スキージを用いて粘着テープ(ニチバン社製セロハンテープ)を上記碁盤目に貼付した。貼付後、金属板で1分ほど粘着テープを擦り、粘着テープを上記碁盤目に十分に密着させてから、20分間静置した。そして、粘着テープを剥離し、粘着シートの粘着剤層と基材との間で剥離が生じた碁盤目の個数(マスの数;NG数)をカウントした。結果を表2に示す。
Next, an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) was pasted on the above board using a squeegee in an environment of 23 ° C. and 50% RH. After sticking, the adhesive tape was rubbed with a metal plate for about 1 minute, and after the adhesive tape was sufficiently adhered to the grid, it was allowed to stand for 20 minutes. Then, the pressure-sensitive adhesive tape was peeled off, and the number of grids (number of squares; number of NG) where peeling occurred between the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the substrate was counted. The results are shown in Table 2.
〔試験例2〕<粘着力の測定>
実施例および比較例にて製造した粘着シートを幅25mm×長さ200mmに裁断し、これを試験片とした。シリコンミラーウエハ(直径8インチ,厚さ50μm)のミラー面に、1kg重の荷重を加えて粘着シートを貼付し、23℃、50%RHの雰囲気下に20分間放置した。その後、JIS Z0237;2000に準じ、万能型引張試験機(オリエンテック社製,TENSILON/UTM-4-100)を用いて、剥離速度300mm/分、剥離角度180°にて粘着シートの粘着力を測定し、エネルギー線照射前の粘着力(mN/25mm)とした。結果を表2に示す。 [Test Example 2] <Measurement of adhesive strength>
The pressure-sensitive adhesive sheets produced in the examples and comparative examples were cut into a width of 25 mm and a length of 200 mm, and this was used as a test piece. A 1 kg weight load was applied to the mirror surface of a silicon mirror wafer (diameter 8 inches, thickness 50 μm), and an adhesive sheet was affixed and left in an atmosphere of 23 ° C. and 50% RH for 20 minutes. Then, according to JIS Z0237; 2000, the adhesive strength of the pressure-sensitive adhesive sheet was measured at a peeling speed of 300 mm / min and a peeling angle of 180 ° using a universal tensile tester (Orientec Co., Ltd., TENSILON / UTM-4-100). It measured and it was set as the adhesive force (mN / 25mm) before energy ray irradiation. The results are shown in Table 2.
実施例および比較例にて製造した粘着シートを幅25mm×長さ200mmに裁断し、これを試験片とした。シリコンミラーウエハ(直径8インチ,厚さ50μm)のミラー面に、1kg重の荷重を加えて粘着シートを貼付し、23℃、50%RHの雰囲気下に20分間放置した。その後、JIS Z0237;2000に準じ、万能型引張試験機(オリエンテック社製,TENSILON/UTM-4-100)を用いて、剥離速度300mm/分、剥離角度180°にて粘着シートの粘着力を測定し、エネルギー線照射前の粘着力(mN/25mm)とした。結果を表2に示す。 [Test Example 2] <Measurement of adhesive strength>
The pressure-sensitive adhesive sheets produced in the examples and comparative examples were cut into a width of 25 mm and a length of 200 mm, and this was used as a test piece. A 1 kg weight load was applied to the mirror surface of a silicon mirror wafer (diameter 8 inches, thickness 50 μm), and an adhesive sheet was affixed and left in an atmosphere of 23 ° C. and 50% RH for 20 minutes. Then, according to JIS Z0237; 2000, the adhesive strength of the pressure-sensitive adhesive sheet was measured at a peeling speed of 300 mm / min and a peeling angle of 180 ° using a universal tensile tester (Orientec Co., Ltd., TENSILON / UTM-4-100). It measured and it was set as the adhesive force (mN / 25mm) before energy ray irradiation. The results are shown in Table 2.
また、粘着シートをシリコンミラーウエハに貼付してから、23℃、50%RHの雰囲気下に20分間放置した後、紫外線照射装置(リンテック社製:RAD-2000m/12)を用い、窒素雰囲気下にて粘着シートの基材側から紫外線(UV)照射(照度230mW/cm2,光量190mJ/cm2)を行った。紫外線照射後の粘着シートにつき、上記と同様にして粘着力を測定し、エネルギー線照射後の粘着力(mN/25mm)とした。結果を表2に示す。
Also, after sticking the adhesive sheet on the silicon mirror wafer, it was allowed to stand in an atmosphere of 23 ° C. and 50% RH for 20 minutes, and then an ultraviolet irradiation device (Rintec Co., Ltd .: RAD-2000m / 12) was used in a nitrogen atmosphere. Then, ultraviolet (UV) irradiation (illuminance 230 mW / cm 2 , light amount 190 mJ / cm 2 ) was performed from the base material side of the adhesive sheet. About the adhesive sheet after ultraviolet irradiation, adhesive force was measured like the above, and it was set as the adhesive force (mN / 25mm) after energy ray irradiation. The results are shown in Table 2.
〔試験例3〕<耐溶剤性試験>
実施例および比較例にて製造した粘着シートを、23℃、50%RHの雰囲気下、シリコンミラーウエハ(直径8インチ,厚さ50μm)のミラー面に、貼付圧0.3MPa、貼付速度5mm/秒で粘着シートを貼付した。また、同じ貼付条件にて、上記粘着シートの周縁部にリングフレームを貼付した。そして、当該粘着シートを、リングフレームの外周に沿った形状に裁断し、これを評価サンプルとした。 [Test Example 3] <Solvent resistance test>
The pressure-sensitive adhesive sheets produced in the examples and comparative examples were applied to a mirror surface of a silicon mirror wafer (diameter 8 inches, thickness 50 μm) in an atmosphere of 23 ° C. and 50% RH with a pressure of 0.3 MPa and a speed of 5 mm / second. An adhesive sheet was attached in seconds. Moreover, the ring frame was stuck on the peripheral part of the said adhesive sheet on the same sticking conditions. And the said adhesive sheet was cut | judged to the shape along the outer periphery of a ring frame, and this was made into the evaluation sample.
実施例および比較例にて製造した粘着シートを、23℃、50%RHの雰囲気下、シリコンミラーウエハ(直径8インチ,厚さ50μm)のミラー面に、貼付圧0.3MPa、貼付速度5mm/秒で粘着シートを貼付した。また、同じ貼付条件にて、上記粘着シートの周縁部にリングフレームを貼付した。そして、当該粘着シートを、リングフレームの外周に沿った形状に裁断し、これを評価サンプルとした。 [Test Example 3] <Solvent resistance test>
The pressure-sensitive adhesive sheets produced in the examples and comparative examples were applied to a mirror surface of a silicon mirror wafer (diameter 8 inches, thickness 50 μm) in an atmosphere of 23 ° C. and 50% RH with a pressure of 0.3 MPa and a speed of 5 mm / second. An adhesive sheet was attached in seconds. Moreover, the ring frame was stuck on the peripheral part of the said adhesive sheet on the same sticking conditions. And the said adhesive sheet was cut | judged to the shape along the outer periphery of a ring frame, and this was made into the evaluation sample.
上記の評価サンプルを、溶剤であるN-メチルピロリドン(SP値:11.2(cal/cm3)1/2)に、80℃、1分間の条件で浸漬した。その後、シリコンミラーウエハと粘着シートの粘着剤層との間に浸み込んだ溶剤の幅(浸み込み幅)を測定した。結果を表2に示す。
The evaluation sample was immersed in N-methylpyrrolidone (SP value: 11.2 (cal / cm 3 ) 1/2 ) as a solvent at 80 ° C. for 1 minute. Thereafter, the width of the solvent soaked between the silicon mirror wafer and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (soaking width) was measured. The results are shown in Table 2.
表2から明らかなように、実施例で製造した粘着シートは、エネルギー線照射後にも粘着剤層と基材との密着性に優れるものであった。また、特に実施例1~3および7~9で製造した粘着シートは、耐溶剤性にも優れるものであった。一方、比較例で製造した粘着シートは、いずれもエネルギー線照射後に粘着剤層と基材との密着性に劣るものであった。
As is clear from Table 2, the pressure-sensitive adhesive sheets produced in the examples were excellent in adhesion between the pressure-sensitive adhesive layer and the substrate even after irradiation with energy rays. In particular, the pressure-sensitive adhesive sheets produced in Examples 1 to 3 and 7 to 9 were excellent in solvent resistance. On the other hand, the pressure-sensitive adhesive sheets produced in the comparative examples were all inferior in adhesiveness between the pressure-sensitive adhesive layer and the substrate after irradiation with energy rays.
本発明に係る粘着シートは、半導体ウエハ加工用のダイシングシートまたはバックグラインドシート等として好適に用いられる。
The pressure-sensitive adhesive sheet according to the present invention is suitably used as a dicing sheet for semiconductor wafer processing, a back grind sheet, or the like.
1…粘着シート
2…基材
3…粘着剤層 DESCRIPTION OF SYMBOLS 1 ...Adhesive sheet 2 ... Base material 3 ... Adhesive layer
2…基材
3…粘着剤層 DESCRIPTION OF SYMBOLS 1 ...
Claims (8)
- 基材と、前記基材の少なくとも一方の面に積層された粘着剤層とを備えており、
前記粘着剤層は、エネルギー線硬化性の(メタ)アクリル酸エステル共重合体(A)と、エポキシ系架橋剤(B)とを含有する粘着剤組成物から形成されたものであり、
前記(メタ)アクリル酸エステル共重合体(A)は、
(メタ)アクリル酸アルキルエステルモノマー(A1)と、水酸基を有する水酸基含有モノマー(A2)と、エポキシ基と反応可能な官能基(水酸基を除く)を有する官能基含有モノマー(A3)とを共重合したアクリル系共重合体(AP)と、
水酸基と反応可能な官能基およびエネルギー線硬化性の炭素-炭素二重結合を有する硬化性基含有化合物(A4)と
を反応させて得られるものである
ことを特徴とする粘着シート。 A base material, and an adhesive layer laminated on at least one surface of the base material,
The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an energy ray-curable (meth) acrylic acid ester copolymer (A) and an epoxy-based crosslinking agent (B),
The (meth) acrylic acid ester copolymer (A) is
Copolymerized (meth) acrylic acid alkyl ester monomer (A1), a hydroxyl group-containing monomer (A2) having a hydroxyl group, and a functional group-containing monomer (A3) having a functional group capable of reacting with an epoxy group (excluding the hydroxyl group) An acrylic copolymer (AP),
A pressure-sensitive adhesive sheet obtained by reacting a functional group capable of reacting with a hydroxyl group and a curable group-containing compound (A4) having an energy ray-curable carbon-carbon double bond. - 前記(メタ)アクリル酸エステル共重合体(A)は、前記硬化性基含有化合物(A4)に由来する硬化性基を、当該(メタ)アクリル酸エステル共重合体(A)が有する水酸基に対して、50モル%以上含有することを特徴とする請求項1に記載の粘着シート。 The (meth) acrylic acid ester copolymer (A) has a curable group derived from the curable group-containing compound (A4) with respect to the hydroxyl group of the (meth) acrylic acid ester copolymer (A). The pressure-sensitive adhesive sheet according to claim 1, comprising 50 mol% or more.
- 前記(メタ)アクリル酸エステル共重合体(A)全体の質量に占める前記(メタ)アクリル酸アルキルエステルモノマー(A1)由来の構造部分の質量の割合は、50~99質量%であることを特徴とする請求項1または2に記載の粘着シート。 The ratio of the mass of the structural portion derived from the (meth) acrylic acid alkyl ester monomer (A1) to the total mass of the (meth) acrylic acid ester copolymer (A) is 50 to 99% by mass. The pressure-sensitive adhesive sheet according to claim 1 or 2.
- 前記(メタ)アクリル酸アルキルエステルモノマー(A1)のアルキル基の炭素数は、6以上であることを特徴とする請求項1~3のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the alkyl group of the (meth) acrylic acid alkyl ester monomer (A1) has 6 or more carbon atoms.
- 前記(メタ)アクリル酸エステル共重合体(A)全体の質量に占める前記官能基含有モノマー(A3)由来の構造部分の質量の割合は、0.1~5質量%であることを特徴とする請求項1~4のいずれか一項に記載の粘着シート。 A ratio of the mass of the structural portion derived from the functional group-containing monomer (A3) to the total mass of the (meth) acrylic acid ester copolymer (A) is 0.1 to 5% by mass. The pressure-sensitive adhesive sheet according to any one of claims 1 to 4.
- 前記アクリル系共重合体(AP)全体の質量に占める前記水酸基含有モノマー(A2)由来の構造部分の質量の割合は、1~25質量%であることを特徴とする請求項1~5のいずれか一項に記載の粘着シート。 6. The ratio of the mass of the structural portion derived from the hydroxyl group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is 1 to 25% by mass. The pressure-sensitive adhesive sheet according to claim 1.
- 前記基材は、オレフィン系炭化水素のみを重合単量体としたポリオレフィン系フィルムを主体とするものであることを特徴とする請求項1~6のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the base material is mainly composed of a polyolefin-based film containing only an olefinic hydrocarbon as a polymerization monomer.
- 前記粘着シートは、半導体加工用の粘着シートであることを特徴とする請求項1~7のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet for semiconductor processing.
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JP2015539338A JP6412873B2 (en) | 2013-09-27 | 2014-09-25 | Adhesive sheet |
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Cited By (4)
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JP2017008255A (en) * | 2015-06-25 | 2017-01-12 | リンテック株式会社 | Composite sheet for forming protective film, tip with protective film and manufacturing method of tip with protective film |
JP2018083917A (en) * | 2016-11-25 | 2018-05-31 | Dic株式会社 | Adhesive tape |
JP2018195705A (en) * | 2017-05-17 | 2018-12-06 | グンゼ株式会社 | Base film for backside grinding |
CN112552839A (en) * | 2019-09-25 | 2021-03-26 | 麦克赛尔控股株式会社 | Adhesive tape |
Families Citing this family (2)
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CN110408334B (en) * | 2018-04-27 | 2023-04-07 | 东丽先端材料研究开发(中国)有限公司 | Adhesive film |
CN111693368A (en) * | 2020-06-15 | 2020-09-22 | 苏州高泰电子技术股份有限公司 | Test method for microscopic characterization performance of wafer cutting adhesive tape |
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JP2008143924A (en) * | 2006-12-06 | 2008-06-26 | Nitto Denko Corp | Repeelable adhesive composition, and adhesive tape or sheet |
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JP5702912B2 (en) * | 2008-11-21 | 2015-04-15 | 積水化学工業株式会社 | Double-sided adhesive tape for fixing adhesive and abrasive cloth |
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JPH11335655A (en) * | 1998-05-22 | 1999-12-07 | Lintec Corp | Energy ray-curable hydrophilic adhesive composition and its utilization |
JP2004256793A (en) * | 2003-02-05 | 2004-09-16 | Furukawa Electric Co Ltd:The | Adhesive tape for sticking wafer |
JP2008143924A (en) * | 2006-12-06 | 2008-06-26 | Nitto Denko Corp | Repeelable adhesive composition, and adhesive tape or sheet |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017008255A (en) * | 2015-06-25 | 2017-01-12 | リンテック株式会社 | Composite sheet for forming protective film, tip with protective film and manufacturing method of tip with protective film |
JP2018083917A (en) * | 2016-11-25 | 2018-05-31 | Dic株式会社 | Adhesive tape |
JP6992250B2 (en) | 2016-11-25 | 2022-01-13 | Dic株式会社 | Adhesive tape |
JP2018195705A (en) * | 2017-05-17 | 2018-12-06 | グンゼ株式会社 | Base film for backside grinding |
CN112552839A (en) * | 2019-09-25 | 2021-03-26 | 麦克赛尔控股株式会社 | Adhesive tape |
CN112552839B (en) * | 2019-09-25 | 2024-03-15 | 麦克赛尔株式会社 | Adhesive tape |
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TWI625376B (en) | 2018-06-01 |
TW201522563A (en) | 2015-06-16 |
JP6412873B2 (en) | 2018-10-24 |
JPWO2015046341A1 (en) | 2017-03-09 |
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