WO2015046341A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
acrylic acid
group
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PCT/JP2014/075450
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English (en)
Japanese (ja)
Inventor
朋治 宮永
章生 加太
明徳 佐藤
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リンテック株式会社
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Priority to JP2015539338A priority Critical patent/JP6412873B2/ja
Publication of WO2015046341A1 publication Critical patent/WO2015046341A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Wood Science & Technology (AREA)
  • Adhesive Tapes (AREA)
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  • Dicing (AREA)

Abstract

On décrit une feuille adhésive (1) comprenant un matériau de base (2) et une couche d'agent adhésif (3) stratifiée sur au moins une surface du matériau de base (2). La couche d'agent adhésif (3) est formée à partir d'une composition d'agent adhésif comprenant un copolymère d'ester d'acide (méth)acrylique polymérisable par rayons d'énergie (A) et un agent de réticulation de type époxyde (B). Le copolymère d'ester d'acide (méth)acrylique (A) est produit par réaction d'un copolymère acrylique (AP) avec un composé contenant un groupe polymérisable (A4). Le copolymère acrylique (AP) est produit par copolymérisation d'un monomère d'ester d'alkyle d'acide (méth)acrylique (A1), d'un monomère contenant un groupe hydroxyle (A2) et comportant un groupe hydroxy, et d'un monomère contenant un groupe fonctionnel (A3) et dont le groupe fonctionnel peut réagir avec un groupe époxyde (différent d'un groupe hydroxy). Le composé contenant un groupe polymérisable (A4) comporte un groupe fonctionnel pouvant réagir avec un groupe hydroxy mais comporte aussi une double liaison carbone-carbone polymérisable par rayons d'énergie. La feuille adhésive (1) présente une excellente adhérence entre la couche d'agent adhésif (3) et le matériau de base (2), même après irradiation de la feuille adhésive (1) par rayonnement d'énergie.
PCT/JP2014/075450 2013-09-27 2014-09-25 Feuille adhésive WO2015046341A1 (fr)

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JP2021095449A (ja) * 2019-12-13 2021-06-24 日東電工株式会社 粘着シート剥離方法
CN111693368A (zh) * 2020-06-15 2020-09-22 苏州高泰电子技术股份有限公司 用于晶圆切割胶带微观表征性能的测试方法

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CN112552839B (zh) * 2019-09-25 2024-03-15 麦克赛尔株式会社 粘着带

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