WO2022185611A1 - Adhesive sheet - Google Patents

Adhesive sheet Download PDF

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Publication number
WO2022185611A1
WO2022185611A1 PCT/JP2021/040263 JP2021040263W WO2022185611A1 WO 2022185611 A1 WO2022185611 A1 WO 2022185611A1 JP 2021040263 W JP2021040263 W JP 2021040263W WO 2022185611 A1 WO2022185611 A1 WO 2022185611A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
liner
adhesive sheet
adhesive layer
Prior art date
Application number
PCT/JP2021/040263
Other languages
French (fr)
Japanese (ja)
Inventor
高正 平山
昭徳 西尾
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2023503373A priority Critical patent/JP7568825B2/en
Priority to KR1020237029743A priority patent/KR20230141837A/en
Priority to CN202180095230.9A priority patent/CN116917432A/en
Publication of WO2022185611A1 publication Critical patent/WO2022185611A1/en

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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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to an adhesive sheet.
  • the semiconductor chips are often sealed with resin in order to prevent damage to the semiconductor chips and expand metal wiring.
  • the semiconductor chip is sometimes resin-sealed on the adhesive sheet from the viewpoint of workability.
  • a plurality of semiconductor chips are placed on an adhesive sheet as a predetermined temporary fixing material, and the semiconductor chips are collectively sealed on the adhesive sheet.
  • a sealing resin precursor having fluidity is applied to cover the semiconductor chip, and then the fluidity of the precursor is reduced to seal the semiconductor chip.
  • the fluidity of the precursor at this time is one factor that affects sealing quality (particularly working time and sealing uniformity).
  • the fluidity of the precursor depends on the affinity between the surface to be coated with the sealing resin (that is, the surface of the adhesive layer of the adhesive sheet) and the sealing resin.
  • the fluidity of the precursor may not be constant.
  • the present invention has been made to solve the above-mentioned conventional problems, and its object is to provide an adhesive layer on the surface of which a sealing resin for sealing a semiconductor chip or the like can flow with little variation. To provide an adhesive sheet.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer disposed on at least one side of the base material, wherein the pressure-sensitive adhesive layer adheres to polyethylene terephthalate at 23°C.
  • the force is 0.1 N/20 mm to 8 N/20 mm
  • the adhesive layer is composed of an adhesive containing a base polymer
  • the sp value of the base polymer is 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2
  • the water content of the adhesive sheet is 0.05% by weight to 6% by weight.
  • the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 60°C to 450°C.
  • the base material is composed of an aromatic polyimide resin.
  • the pressure-sensitive adhesive layer has a thickness of 2 ⁇ m to 15 ⁇ m.
  • the adhesive layer has a gel fraction of 60% to 100%.
  • the base polymer is an acrylic polymer, the acrylic polymer contains a structural unit derived from a hydroxyl group-containing monomer, and the content of the structural unit derived from the hydroxyl group-containing monomer is the acrylic polymer It is 0.1 to 20 parts by weight per 100 parts by weight of all structural units constituting the polymer.
  • the pressure-sensitive adhesive sheet further comprises a second pressure-sensitive adhesive layer on the opposite side of the base material to the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet is used as a sheet for temporarily fixing a semiconductor chip when manufacturing a CSP (Chip Size/Scale Package) or a WLP (Wafer Level Package).
  • the semiconductor chip is sealed with a sealing resin, and the processing temperature during the resin sealing is 100° C. or higher. According to another aspect of the present invention, there is provided a method for producing the pressure-sensitive adhesive sheet.
  • This manufacturing method comprises the steps of: forming a coating layer of a composition containing an adhesive on a substrate; placing a liner on the surface of the coating layer to form a laminate; Humidification heat time (for example, 2 hours to 7 days), and a heat humidification step in an environment where temperature and humidity are controlled, and the product of the heat humidification time, temperature and humidity in the heat humidification step is 100 ⁇ 300000°C.RH%.h.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on the surface of which a sealing resin for sealing semiconductor chips or the like can flow with little variation.
  • FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention
  • FIG. 4 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to another embodiment of the invention
  • FIG. 1 is a schematic cross-sectional view of a liner-attached double-sided pressure-sensitive adhesive sheet according to one embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention.
  • the adhesive sheet 100 includes a substrate 10 and an adhesive layer (first adhesive layer) 20 arranged on at least one side of the substrate 10 .
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive strength of 0.1 N/20 mm to 8 N/20 mm at 23° C. when the pressure-sensitive adhesive layer is adhered to polyethylene terephthalate.
  • the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive containing a base polymer, and the base polymer has an sp value of 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 . Further, the pressure-sensitive adhesive sheet has a moisture content of 0.05% to 6% by weight.
  • the adhesive sheet of the present invention can be suitably used as a temporary fixing material when sealing semiconductor chips with resin. More specifically, the pressure-sensitive adhesive sheet of the present invention is obtained by arranging semiconductor chips on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, covering the semiconductor chips with a sealing resin (usually epoxy resin) precursor, and It can be used as a temporary fixing material for the semiconductor chip when the semiconductor chip is resin-sealed by curing the precursor. After the semiconductor chip is resin-encapsulated, in the case of predetermined post-processes (for example, back grinding of the encapsulation resin, pattern formation, bump formation, chip formation (cutting)), the adhesive sheet is used to separate the encapsulation resin and the semiconductor. It can be peeled off from the structure composed of the chip.
  • the epoxy equivalent of the sealing resin is, for example, 50 g/eq to 500 g/eq.
  • the sealing resin Precursors can preferably flow.
  • the time required for the sealing process can be shortened in the mass production process of semiconductor chips, and resin sealing with excellent uniformity can be stably performed.
  • the pressure-sensitive adhesive sheet of the present invention is characterized in that it has an excellent balance of adhesiveness and peelability (that is, excellent temporary fixability) and can contribute to improvement in sealing quality.
  • the pressure-sensitive adhesive sheet of the present invention is particularly useful in that it can contribute to improvement in sealing quality even at high temperatures.
  • FIG. 2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the invention.
  • the pressure-sensitive adhesive sheet 200 is a double-sided pressure-sensitive adhesive sheet, and further includes a second pressure-sensitive adhesive layer 30 on the opposite side of the base material 10 to the pressure-sensitive adhesive layer 20 . That is, the adhesive sheet 200 includes the adhesive layer 20, the base material 10, and the second adhesive layer 30 in this order.
  • the adhesive sheet 200 can be used with good fixability by sticking the second adhesive layer 30 side to the pedestal when resin sealing is performed on the pedestal. can be done.
  • the second adhesive layer contains thermally expandable microspheres.
  • the heat-expandable microspheres can expand at a given temperature.
  • the pressure-sensitive adhesive layer containing such heat-expandable microspheres is heated to a predetermined temperature or higher, the heat-expandable microspheres expand and irregularities occur on the pressure-sensitive adhesive surface (that is, the surface of the second pressure-sensitive adhesive layer). Adhesion is reduced or lost.
  • the necessary pressure-sensitive adhesiveness is exhibited when the pressure-sensitive adhesive sheet is fixed (for example, when fixed to a pedestal), and when the pressure-sensitive adhesive sheet is peeled off ( For example, when peeling from the pedestal), the adhesive strength is reduced or lost by heating, and good peelability is exhibited.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive strength at 23° C. when the pressure-sensitive adhesive layer is adhered to polyethylene terephthalate, as described above, from 0.1 N/20 mm to 8 N/20 mm, preferably from 0.2 N/20 mm. 7.5 N/20 mm, more preferably 0.5 N/20 mm to 6 N/20 mm, still more preferably 0.8 N/20 mm to 5 N/20 mm, most preferably 0.8 N/20 mm to 3 N/20 mm is. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet that can preferably fix an adherend (for example, a semiconductor chip) and leaves little adhesive residue when peeled off. In this specification, the “adhesive strength at 23° C.
  • the moisture content of the adhesive sheet is 0.05% to 6% by weight.
  • the moisture content of the adhesive sheet is preferably 0.1% to 5% by weight, more preferably 0.5% to 4% by weight, and still more preferably 1% to 3% by weight.
  • the affinity with the encapsulating resin precursor is appropriately adjusted, and a pressure-sensitive adhesive layer that can contribute to the improvement of resin encapsulation quality can be formed. Also, deterioration of the sealing resin can be prevented.
  • the water content can be measured by Karl Fischer titration.
  • the moisture content of the PSA sheet can be adjusted by any appropriate method. For example, it can be adjusted by adjusting the water content of the adhesive during the formation of the adhesive layer (during the coating of the adhesive), the composition of the base polymer contained in the adhesive, and the implementation of the moistening and heating process (described later).
  • the thickness of the adhesive sheet of the present invention is preferably 3 ⁇ m to 300 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m, still more preferably 10 ⁇ m to 100 ⁇ m.
  • Adhesive layer The adhesive layer is composed of an adhesive containing a base polymer.
  • a “base polymer” means the main component of the polymer contained in an adhesive.
  • main component refers to a component contained in an amount exceeding 50% by weight unless otherwise specified.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, still more preferably 5 ⁇ m to 20 ⁇ m. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet that is difficult for the semiconductor chip to be embedded in the resin even when pressurized during the sealing process.
  • the pressure-sensitive adhesive layer has a thickness of 2 ⁇ m to 15 ⁇ m. Within such a range, the diffusion of moisture from the pressure-sensitive adhesive layer can be appropriately adjusted, and the fluidity of the sealing resin precursor can be made preferable.
  • the sp value of the base polymer is 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2
  • the sp value of the base polymer is preferably 7.5 ( cal/cm 3 ) 1/2 to 9.5 (cal/cm 3 ) 1/2 , more preferably 8 (cal/cm 3 ) 1/2 to 9 (cal/cm 3 ) 1/2 .
  • a pressure-sensitive adhesive layer whose affinity for the encapsulating resin is appropriately adjusted and which can contribute to the improvement of resin encapsulation quality.
  • the sp value is determined by the method of Fedors (Hideki Yamamoto, "Sp Value: Fundamentals, Applications and Calculation Methods", Joho Kyoukai Publishing Co., Ltd., published on April 3, 2006, pp. 66-67). Specifically, the sp value is the evaporation energy ⁇ e (cal) of each atom or atomic group forming the polymer at 25° C. and the molar volume ⁇ V (cm 3 ) of each atom or atomic group forming the polymer at 25° C. is calculated by the following formula.
  • the water contact angle of the pressure-sensitive adhesive layer is preferably 70° to 120°, more preferably 80° to 110°, still more preferably 90° to 105°. Within such a range, the affinity with the encapsulating resin precursor is appropriately adjusted, and a pressure-sensitive adhesive layer that can contribute to the improvement of resin encapsulation quality can be formed.
  • the contact angle of water is determined by dropping 2 ⁇ l of pure water onto the adhesive layer surface in a 23° C./50% RH environment using a contact angle meter (for example, Kyowa Interface Co., Ltd., trade name “CX-A”). , the measurement of the contact angle of the droplet five seconds after the droplet is dropped is repeated five times, and the average value can be obtained.
  • the gel fraction of the adhesive layer is preferably 60% to 100%, more preferably 70% to 99%, still more preferably 75% to 98%, and particularly preferably 80% to 95%. is. Within such a range, the diffusion of moisture from the pressure-sensitive adhesive layer can be appropriately adjusted, and the fluidity of the sealing resin precursor can be made preferable. In addition, it is possible to form a pressure-sensitive adhesive layer that has appropriate adhesiveness and does not leave adhesive residue, etc., when peeled off, and does not easily stain the adherend. A method for measuring the gel fraction will be described later.
  • the elastic modulus of the pressure-sensitive adhesive layer measured by the nanoindentation method at 25°C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and still more preferably 0.1 MPa to 10 MPa. If it is such a range, the adhesive sheet which has suitable adhesive force can be obtained.
  • the elastic modulus by the nanoindentation method is obtained by continuously measuring the load applied to the indenter and the indentation depth during loading and unloading when the indenter is pushed into the sample. It refers to the elastic modulus obtained from the curve.
  • the elastic modulus by the nanoindentation method refers to the elastic modulus measured as described above under the measurement conditions of load: 1 mN, loading/unloading rate: 0.1 mN/s, and holding time: 1 s.
  • the adhesive constituting the adhesive layer is an acrylic adhesive.
  • the acrylic pressure-sensitive adhesive for example, an acrylic polymer (homopolymer or copolymer) using one or more of (meth)acrylic acid alkyl esters as a monomer component is used as a prepolymer, and the prepolymer Examples include acrylic pressure-sensitive adhesives using a crosslinked product as a base polymer.
  • the "base polymer" contained in the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer means a polymer formed by cross-linking a prepolymer (uncross-linked polymer).
  • the base polymer has a crosslinked structure of an acrylic polymer and an epoxy crosslinking agent.
  • (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, ( isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic undecyl acid, dodecyl (meth)acrylate,
  • (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 4 to 20 carbon atoms (more preferably 6 to 20, particularly preferably 8 to 18 carbon atoms) are more preferable.
  • 2-ethylhexyl (meth)acrylate is 2-ethylhexyl (meth)acrylate.
  • (meth)acryl means acryl and/or methacryl.
  • the acrylic polymer (prepolymer), for the purpose of modifying cohesive strength, heat resistance, crosslinkability, etc., if necessary, other monomer components copolymerizable with the (meth)acrylic acid alkyl ester may include units corresponding to Examples of such monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic anhydride; Acid anhydride monomers such as; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, (meth)acrylate Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxyllauryl (meth)
  • cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, (meth)acrylic acid Glycol-based acrylic ester monomers such as methoxyethylene glycol and methoxypolypropylene glycol (meth)acrylate; heterocycles such as tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, and silicone (meth)acrylate, halogen atoms, silicon atoms Acrylic acid ester-based monomers having, etc.; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol Polyfunctional mono
  • the acrylic polymer (prepolymer) further contains a structural unit derived from a hydroxyl group-containing monomer.
  • the content of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.1 part by weight, with respect to 100 parts by weight of all the structural units constituting the acrylic polymer. ⁇ 10 parts by weight. It is more preferably 0.5 to 10 parts by weight. Within such a range, it is possible to form a pressure-sensitive adhesive layer in which the diffusion of water from the pressure-sensitive adhesive layer is appropriately adjusted and the water content is preferably adjusted. Moreover, it has moderate cohesiveness and can form a pressure-sensitive adhesive layer with little adhesive residue.
  • the hydroxyl group may be an alcoholic hydroxyl group or an acidic hydroxyl group such as a carboxyl group.
  • the acrylic pressure-sensitive adhesive may contain any suitable additive as necessary.
  • the additives include, for example, cross-linking agents, tackifiers, plasticizers (e.g., trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, etc.), pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, and the like.
  • cross-linking agent contained in the acrylic pressure-sensitive adhesive examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide cross-linking agents, Examples include metal chelate cross-linking agents, metal salt cross-linking agents, carbodiimide cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, and amine cross-linking agents.
  • the amount of the cross-linking agent to be added to the carboxyl groups of the acrylic polymer (prepolymer) is preferably 0.08 molar equivalents to 2 molar equivalents, more preferably 0.1 molar equivalents to 1 molar equivalent. molar equivalents. Within such a range, an acrylic pressure-sensitive adhesive having a high cross-linking density can be formed, and component migration between the pressure-sensitive adhesive layer and the encapsulating resin is preferably prevented.
  • the blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
  • the isocyanate-based cross-linking agent contained in the acrylic pressure-sensitive adhesive include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; group isocyanates; 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate and other aromatic isocyanates; name "Coronate L”), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product isocyanate adducts such as the name "Coronate HX");
  • the amount of the isocyanate-based cross-linking agent can be set to any appropriate amount depending on the
  • the blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
  • epoxy-based cross-linking agent contained in the acrylic pressure-sensitive adhesive examples include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N- glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C”), 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 1600"), neopentyl glycol diglycidyl ether ( Kyoeisha Chemical Co., Ltd., trade name "Epolite 1500NP”), ethylene glycol diglycidyl ether (Kyoeisha Chemical Co., Ltd., trade name "Epolite 40E”), propylene glycol diglycidyl ether (Kyoeisha Chemical Co., Ltd., trade
  • the amount of the epoxy-based cross-linking agent can be set to any appropriate amount depending on the desired adhesive strength. parts, more preferably 0.6 to 15 parts by weight, still more preferably 2 to 13 parts by weight, and particularly preferably 3 to 10 parts by weight. With such a range, it is possible to obtain a pressure-sensitive adhesive sheet with few residual carboxyl groups in the components of the pressure-sensitive adhesive layer.
  • the blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
  • Substrates of the substrate include resin sheets, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foam sheets, laminates thereof (especially laminates containing resin sheets), and the like.
  • the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene- Vinyl acetate copolymer (EVA), polyamide (nylon), wholly aromatic polyamide (aramid), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine resin, polyether ether ketone (PEEK) ) and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • EVA ethylene-propylene
  • nonwoven fabrics include nonwoven fabrics made of heat-resistant natural fibers such as nonwoven fabrics containing manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics and ester resin nonwoven fabrics.
  • metal foil include copper foil, stainless steel foil, and aluminum foil.
  • paper include Japanese paper and kraft paper.
  • the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 60° C. to 450° C. (preferably 65° C. to 430° C., more preferably 80° C. to 420° C.).
  • Tg glass transition temperature
  • the molecular motion of the molecules constituting the base material does not become too vigorous, and the diffusion of moisture can be moderately suppressed.
  • a pressure-sensitive adhesive sheet having excellent flexibility can be obtained.
  • resins forming such a resin sheet include polyethylene terephthalate, polyimide, and polyethylene naphthalate.
  • the base material is composed of an aromatic polyimide resin.
  • Aromatic polyimide resins have a polar functional imide group, and the electron-donating properties of the amino group and the electron-withdrawing property of the carbonyl group make it easy to adjust the moisture content, and the high degree of processing required in the resin encapsulation process. It is preferable because it can maintain the vapor dissipation ability over a wide temperature range.
  • aromatic functional groups phenyl group, phenylene group, naphthyl group, naphthylene group, etc.
  • the molecular mobility of the polymer molecules is low, and the surface shape of the tape is maintained smooth.
  • aromatic polyimides examples include ether-based polyphthalimides having an ether bond in the main chain skeleton, ketone-based polyphthalimides having a ketone bond in the main chain skeleton, and bisphenol-based polyphthalimides having a skeleton derived from the same bisphenol.
  • Commercially available products such as “Upilex” manufactured by Ube Industries, “LARC-TPI” manufactured by Mitsui Chemicals, Inc., and “Ultem” manufactured by GE may also be used.
  • ether-based pyromellitimides having an ether bond in the main chain skeleton can be preferably used because the number of imide groups present per weight of repeating monomer residues increases.
  • a resin commercially available products such as "Kapton” manufactured by DuPont, "Apical” manufactured by Kaneka, and “Aurum” manufactured by Mitsui Chemicals, Inc. may be used.
  • the thickness of the base material can be set to any appropriate thickness depending on the desired strength or flexibility, purpose of use, and the like.
  • the thickness of the substrate is preferably 1000 ⁇ m or less, more preferably 25 ⁇ m to 1000 ⁇ m, still more preferably 40 ⁇ m to 500 ⁇ m.
  • the base material may be surface-treated.
  • surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, and coating treatment with a primer.
  • the organic coating material examples include materials described in Plastic Hard Coat Materials II (CMC Publishing, (2004)). Urethane-based polymers are preferably used, more preferably polyacrylurethane, polyesterurethane, or precursors thereof. This is because coating and applying to the base material is simple, and industrially, a wide variety of materials can be selected and are available at low cost.
  • the urethane-based polymer is, for example, a polymer composed of a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound).
  • the organic coating material may contain optional additives such as chain extenders such as polyamines, anti-aging agents, oxidation stabilizers, and the like.
  • the thickness of the organic coating layer is not particularly limited.
  • the second adhesive layer may be an adhesive layer composed of any appropriate adhesive.
  • the second pressure-sensitive adhesive layer further contains thermally expandable microspheres, as described above.
  • the adhesive contained in the second adhesive layer may be a curable adhesive (for example, an active energy ray-curable adhesive) or a pressure-sensitive adhesive.
  • pressure-sensitive adhesives include acrylic adhesives and rubber adhesives. Details of the adhesive contained in the second adhesive layer can be referred to, for example, the description of JP-A-2018-009050. The publication is incorporated herein by reference in its entirety.
  • the adhesive contained in the second adhesive layer may be the acrylic adhesive described in section B above.
  • the acrylic polymer (prepolymer) contained in the acrylic pressure-sensitive adhesive contains a structural unit derived from a hydroxyl group-containing monomer.
  • the content of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.1 part by weight, with respect to 100 parts by weight of all the structural units constituting the acrylic polymer. ⁇ 10 parts by weight. It is more preferably 0.5 to 10 parts by weight.
  • heat-expandable microspheres can be used as the heat-expandable microspheres as long as they are microspheres that can be expanded or foamed by heating.
  • the heat-expandable microspheres for example, microspheres in which a substance (a volatile substance such as an organic solvent) that is easily expanded by heating is encapsulated in an elastic shell can be used.
  • Such heat-expandable microspheres can be produced by any appropriate method such as coacervation, interfacial polymerization, and the like.
  • Substances that easily expand when heated include, for example, propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, normal hexane, isohexane, heptane, octane, petroleum ether, methane halides, and tetraalkylsilanes.
  • low boiling point liquid such as; azodicarbonamide gasified by thermal decomposition; and the like.
  • substances constituting the shell include nitrile monomers such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Carboxylic acid monomers such as citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (Meth)acrylic acid esters such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, ⁇ -carboxyethyl acrylate; styrene monomers such as styrene, ⁇ -methyl
  • copolymer examples include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, acrylonitrile-methacrylonitrile-itaconic acid copolymer, A polymer etc. are mentioned.
  • the structural unit derived from the carboxyl group-containing monomer is preferably 80 parts by weight or less, more preferably 70 parts by weight or less, relative to 100 parts by weight of the polymer constituting the shell. Within such a range, it is possible to form a second pressure-sensitive adhesive layer with a moderately adjusted water content.
  • An inorganic foaming agent or an organic foaming agent may be used as the thermally expandable microspheres.
  • inorganic foaming agents include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, and various azides.
  • organic foaming agents include chlorofluoroalkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; and azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate.
  • hydrazine compounds such as paratoluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide, 4,4′-oxybis(benzenesulfonyl hydrazide), and allylbis(sulfonyl hydrazide); p-toluylenesulfonyl semicarbazide, 4, Semicarbazide compounds such as 4'-oxybis(benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; N,N'-dinitrosopentamethylenetetramine, N,N' -dimethyl-N,N'-dinitrosoterephthalamide; and other N-nitroso compounds.
  • thermally expandable microspheres Commercially available products may be used as the thermally expandable microspheres.
  • specific examples of commercially available heat-expandable microspheres include Matsumoto Yushi Seiyaku's trade name "Matsumoto Microspheres" (grades: F-30, F-30D, F-36D, F-36LV, F-50 , F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), a product name manufactured by Nippon Philite Co., Ltd.
  • the average particle size (number basis) of the heat-expandable microspheres before heating is preferably 1 ⁇ m to 40 ⁇ m, more preferably 5 ⁇ m to 40 ⁇ m, still more preferably 10 ⁇ m to 40 ⁇ m.
  • the above particle size and average particle size are values determined by a particle size distribution measurement method in a laser scattering method.
  • the thermally expandable microspheres have an appropriate strength such that they do not burst until the volume expansion coefficient is preferably 5 times or more, more preferably 7 times or more, and still more preferably 10 times or more.
  • the adhesive strength can be efficiently reduced by heat treatment.
  • the content ratio of the heat-expandable microspheres in the second adhesive layer can be appropriately set according to the desired decrease in adhesive force.
  • the content of the heat-expandable microspheres is, for example, 1 to 150 parts by weight, preferably 10 to 130 parts by weight, with respect to 100 parts by weight of the base polymer forming the second pressure-sensitive adhesive layer. , more preferably 25 to 100 parts by weight.
  • the arithmetic surface roughness Ra of the second adhesive layer before the thermally expandable microspheres are expanded is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. is. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet having excellent adhesion to an adherend.
  • an undercoat layer may be provided between the substrate and the second pressure-sensitive adhesive layer.
  • the undercoat layer contains any suitable adhesive.
  • the adhesive that constitutes the undercoat layer include acrylic adhesives, rubber adhesives, silicone adhesives, and the like. Among them, an acrylic pressure-sensitive adhesive can be preferably used.
  • an active energy ray-curable acrylic adhesive (hereinafter referred to as an active energy ray-curable adhesive) may be used.
  • the same pressure-sensitive adhesive as the pressure-sensitive adhesive forming the second pressure-sensitive adhesive layer is used as the pressure-sensitive adhesive forming the undercoat layer.
  • the thickness of the undercoat layer is preferably 1 ⁇ m to 40 ⁇ m, more preferably 5 ⁇ m to 35 ⁇ m, still more preferably 10 ⁇ m to 30 ⁇ m.
  • the adhesive sheet of the present invention can be produced by any appropriate method.
  • Methods for obtaining the pressure-sensitive adhesive sheet of the present invention include, for example, a method of directly coating a substrate with a composition containing a pressure-sensitive adhesive (for example, an acrylic pressure-sensitive adhesive), or a method of applying a pressure-sensitive adhesive onto any appropriate substrate. Examples include a method of transferring a coating layer formed by coating a composition containing the composition to a substrate.
  • a composition containing an acrylic pressure-sensitive adhesive may contain any suitable solvent.
  • composition containing the adhesive contains any suitable solvent.
  • the water content in the solvent is preferably 0.003% to 0.3% by weight.
  • a pressure-sensitive adhesive layer (second pressure-sensitive adhesive layer) containing heat-expandable microspheres
  • a composition containing heat-expandable microspheres, a pressure-sensitive adhesive, and any appropriate solvent is applied to a substrate.
  • the pressure-sensitive adhesive layer can be formed.
  • the heat-expandable microspheres are embedded in the adhesive using a laminator or the like to form an adhesive layer containing the heat-expandable microspheres. may be formed.
  • each layer can be formed by coating and then drying.
  • the coating method include coating methods using a multi-coater, die coater, gravure coater, applicator, and the like. Drying methods include, for example, natural drying and heat drying.
  • the heating temperature for drying by heating can be set to any suitable temperature depending on the properties of the substance to be dried.
  • a liner is placed on the surface of the coating layer to obtain a laminate (liner-attached pressure-sensitive adhesive sheet precursor),
  • the laminate (liner-attached pressure-sensitive adhesive sheet precursor) is subjected to a step of placing the laminate (liner-attached pressure-sensitive adhesive sheet precursor) in an environment in which the temperature and humidity are controlled for a predetermined moist heat time (for example, 2 hours to 7 days) (humidification heat step), and the pressure-sensitive adhesive sheet is removed.
  • a predetermined moist heat time for example, 2 hours to 7 days
  • the moisture content of the pressure-sensitive adhesive sheet can be preferably adjusted by performing the moist heat step.
  • the temperature in this step is, for example, 40°C to 120°C.
  • the humidity is, for example, 1% RH to 100% RH.
  • the adhesive sheet is a double-sided adhesive sheet, both sides of the adhesive coating layer surface (that is, the adhesive coating layer surface forming the adhesive layer and the adhesive coating layer forming the second adhesive layer)
  • a laminate obtained by arranging the liners (the first liner and the second liner) on the layer surface) can be subjected to the humidification heat step. Details of the liner will be described later.
  • the product of the heat humidification time, the temperature and the humidity is preferably 100 to 300000°C.RH%h, more preferably 180 to 265000°C.RH%h. Within such a range, the moisture content of the pressure-sensitive adhesive sheet can be preferably adjusted.
  • FIG. 3 is a schematic cross-sectional view of a liner-attached double-sided pressure-sensitive adhesive sheet according to one embodiment of the present invention.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet 110 comprises a double-sided pressure-sensitive adhesive sheet 200, a first liner 40 releasably arranged directly on one side of the pressure-sensitive adhesive sheet 200, and a releasable first liner 40 on the other side of the double-sided pressure-sensitive adhesive sheet 200. and a directly disposed second liner 50 .
  • the first liner 40 and the second liner 50 By arranging the first liner 40 and the second liner 50, it is possible to protect the pressure-sensitive adhesive layer from contamination and prevent blocking of the double-sided pressure-sensitive adhesive sheet of the roll or sheet.
  • the first liner and the second liner comprise a liner substrate and a release treatment layer disposed on at least one side of the liner substrate. The first liner and the second liner are arranged so that the release treated layer is on the double-sided pressure-sensitive adhesive sheet side.
  • the double-sided pressure-sensitive adhesive sheet 200 may be the pressure-sensitive adhesive sheet described above, that is, a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer 20, the base material 10, and the second pressure-sensitive adhesive layer 30.
  • the first liner 20 and the second liner 30 may be heterogeneous. “Heterogeneous” means, for example, different thicknesses (for example, the absolute value of the difference in thickness is 1 ⁇ m or more (preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more)), different colors, different constituent materials, etc. can be
  • the difference in thickness between the first liner 20 and the second liner 30 is preferably 70 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 25 ⁇ m or less.
  • the first liner when using the liner-attached double-sided pressure-sensitive adhesive sheet, the first liner is removed first. More specifically, the liner-attached double-sided pressure-sensitive adhesive sheet is prepared by first peeling off the first liner and attaching an adherend (for example, an electronic component) to the exposed pressure-sensitive adhesive surface (for example, the surface of the first pressure-sensitive adhesive layer). It can be used by sticking, then peeling off the second liner, and sticking the surface of the second pressure-sensitive adhesive layer on another adherend (for example, a pedestal).
  • adherend for example, an electronic component
  • the adherend e.g., electronic component
  • the adherend is temporarily fixed to the pedestal via the adhesive sheet; the adherend is subjected to a predetermined process; By reducing the adhesive strength of the adhesive layer, the adhesive sheet with the adherend is peeled off from the base. As described above, if the first liner and the second liner are different, it becomes easy to identify the liner to be peeled off at a predetermined timing.
  • the peel force of the first liner to the double-sided pressure-sensitive adhesive sheet is preferably 0.001N/50mm to 2N/50mm, more preferably 0.01N/50mm to 1.5N/50mm, and still more preferably 0.05N. /50 mm to 1 N/50 mm, particularly preferably 0.1 N/50 mm to 0.8 N/50 mm.
  • the release force of the first liner to the double-sided PSA sheet (and the release force of the second liner to the double-sided PSA sheet) was determined by peeling the liner from the double-sided PSA sheet of the liner-attached double-sided PSA sheet in an environment of 23°C. angle: 180°, peeling speed (tensile speed): 300 mm/min.
  • the release force of the liner to the double-sided PSA sheet can be adjusted by any appropriate method, such as the composition of the PSA layer, the type of liner, and the surface treatment applied to the liner.
  • the peel force of the second liner to the double-sided pressure-sensitive adhesive sheet is preferably 0.001N/50mm to 2N/50mm, more preferably 0.01N/50mm to 1.5N/50mm, and still more preferably 0.05N. /50 mm to 1 N/50 mm, particularly preferably 0.1 N/50 mm to 0.8 N/50 mm.
  • the thickness of the first liner is preferably 5 ⁇ m to 250 ⁇ m, more preferably 10 ⁇ m to 200 ⁇ m, even more preferably 20 to 150 ⁇ m, most preferably 30 to 100 ⁇ m.
  • the thickness of the second liner is preferably 5 ⁇ m to 250 ⁇ m, more preferably 10 ⁇ m to 200 ⁇ m, even more preferably 20 to 150 ⁇ m, most preferably 30 to 100 ⁇ m.
  • the liner base material can be composed of any appropriate material.
  • the liner base material for example, in addition to plastic films and plastic sheets, various sheet-like materials such as paper, cloth, nonwoven fabric, metal foil, plastic laminates thereof, and laminates of plastics can be used. .
  • plastic films and plastic sheets are most preferable from the viewpoint of handling and cost.
  • the material for the plastic film can be selected according to need from the viewpoint of strength, heat resistance, and the like.
  • polyethylene polyethylene
  • PP polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • PBT polyethylene terephthalate
  • PET polyethylene
  • Polyesters such as naphthalate (PEN) and polybutylene terephthalate (PBT)
  • PVC polyvinyl chloride
  • PPS polyphenylene sulfide
  • amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); Ketone (PEEK), polyimide, polyetherimide, polystyrene, acrylic resin and the like.
  • any of an unstretched film, a uniaxially oriented film, and a biaxially oriented film may be used.
  • these films may be laminated films composed of two or more film layers, or films to which a lubricant such as inert particles is appropriately added may be used from the viewpoint of handleability.
  • the release treated layer is a silicone treated layer.
  • a reactive silicone compound containing a dimethylpolysiloxane as a main component and having a functional group necessary for cross-linking (curing) can be preferably used. This is because it can be applied to a film in a low-molecular-weight state, and can be cured after application to form a release treated layer that is resistant to rubbing and the like.
  • functional groups of reactive silicone compounds include vinyl groups, epoxy groups, alkoxy groups, isocyanato groups, and the like.
  • the silicone-treated layer is formed, for example, by diluting the above-mentioned reactive silicone compound with a solvent or the like to adjust the concentration, and applying and heating with a gravure coater or the like. Heating accelerates solvent drying and curing reactions.
  • a catalyst that accelerates the curing reaction. Examples of catalysts that can be used include metal complexes such as platinum, palladium, rhodium, zirconium and tin, organic bases such as amines, and organic acids such as acetic acid.
  • the first liner and/or the second liner (substantially the release treatment layer of each liner) has a Si—K ⁇ ray intensity of 0.01 by fluorescent X-ray analysis. ⁇ 500 kcps (preferably 0.5 to 250 kcps, more preferably 1.0 to 150 kcps, still more preferably 1.05 to 100 kcps, particularly preferably 10 to 30 kcps). Within such a range, the liner can be peeled off from the pressure-sensitive adhesive layer with a small force. In addition, the adhesion between the liner and the adhesive layer is sufficient, and unnecessary peeling of the liner can be prevented.
  • the intensity of the Si-K ⁇ ray obtained by the above fluorescent X-ray analysis is obtained by measuring the Si intensity of the release agent layer and the non-release agent layer by the fluorescence X-ray analysis, and calculating the intensity of the release agent layer from the intensity of the non-release agent. It is a value obtained by reducing the strength of the layer.
  • the strength can be adjusted by controlling the release treatment layer forming conditions such as the coating amount, concentration, coating speed and drying of the release treatment agent.
  • the first liner and the second liner are different colors.
  • a liner-equipped double-sided pressure-sensitive adhesive sheet having such a structure can be obtained, for example, by coloring one of the liners (for example, the liner substrate). If both liners are of different colors, the front and back of the liner-attached double-sided pressure-sensitive adhesive sheet can be clearly distinguished, making it easy to identify the liner to be peeled off.
  • the pressure-sensitive adhesive sheet and the liner-attached double-sided pressure-sensitive adhesive sheet can be preferably used as a temporary fixing sheet when processing any appropriate member (for example, electronic parts such as semiconductor chips).
  • the liner-attached double-sided pressure-sensitive adhesive sheet can be used as a sheet for temporarily fixing a semiconductor chip during the manufacture of CSP (Chip Size/Scale Package) or WLP (Wafer Level Package).
  • the liner-attached double-sided pressure-sensitive adhesive sheet is used for processing including the step of peeling off the second liner first.
  • the semiconductor chip is sealed with the sealing resin, and the processing temperature during resin sealing is 100° C. or higher.
  • the liner-attached double-sided pressure-sensitive adhesive sheet is roll-shaped.
  • Example 1 A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ” and 10 parts by weight to prepare an adhesive.
  • the above-mentioned adhesive is applied (applied and dried) to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”), and the adhesive is A layer (thickness: 10 ⁇ m) was formed.
  • the liner with the pressure-sensitive adhesive layer was attached to a base material (polyester film, trade name “Lumirror S10” manufactured by Toray Industries, Inc., thickness: 50 ⁇ m) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
  • the Si—K ⁇ ray intensity of the liner (trade name “MRF-38”) was 18 (kcps).
  • the method for measuring the intensity of the Si—K ⁇ ray is as follows.
  • the liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand for 5 days in an environment with a temperature of 40° C.
  • the intensity (i) of the Si—K ⁇ ray of the surface of the liner in contact with the adhesive layer (the surface coated with the release agent) and the surface not in contact with the adhesive layer (the surface coated with the release agent) Measure the intensity (ii) of the Si-K ⁇ ray of the surface that is not exposed), obtain the absolute value of the value obtained by subtracting the value of (ii) from the value of (i), and calculate the average value of 100 measurements of the value.
  • the Si—K ⁇ ray intensity of the liner was used.
  • the intensity of the Si-K ⁇ ray is the intensity at a wavelength of 7.125 angstroms as measured by the following equipment.
  • Example 2 A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ”) was mixed with 10 parts by weight to prepare an adhesive.
  • the above-mentioned adhesive is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”) to form an adhesive layer (thickness: 10 ⁇ m ) was formed.
  • the liner with the pressure-sensitive adhesive layer was attached to a substrate (polyethylene naphthalate film, manufactured by Teijin DuPont Films Ltd., trade name "Teonex Q51", thickness: 50 ⁇ m) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
  • the liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment of 40° C. and 20% humidity for 5 days to obtain a liner-attached pressure-sensitive adhesive sheet consisting of liner/adhesive layer (first adhesive layer)/substrate. .
  • Example 3 A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ”) was mixed with 10 parts by weight to prepare an adhesive.
  • the above-mentioned adhesive is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”) to form an adhesive layer (thickness: 10 ⁇ m ) was formed.
  • the liner with the pressure-sensitive adhesive layer was attached to a base material (aromatic polyimide film, manufactured by Ube Industries, Ltd., trade name “Upilex-R”, thickness: 50 ⁇ m) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
  • the liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment of 40° C. and 20% humidity for 5 days to obtain a liner-attached pressure-sensitive adhesive sheet consisting of liner/adhesive layer (first adhesive layer)/substrate. .
  • Example 4 A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ”) was mixed with 10 parts by weight to prepare adhesive a1.
  • the pressure-sensitive adhesive a1 is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 ⁇ m) was formed.
  • the liner with the pressure-sensitive adhesive layer was attached to a base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 ⁇ m) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
  • the liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment of 40° C. and 20% humidity for 5 days to obtain a liner-attached pressure-sensitive adhesive sheet consisting of liner/adhesive layer (first adhesive layer)/substrate. .
  • Example 5 A liner-attached pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the pressure-sensitive adhesive layer was 2 ⁇ m.
  • Example 6 A liner-attached pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the pressure-sensitive adhesive layer was 15 ⁇ m.
  • Example 7 (Adhesive sheet with liner a2) A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ”) was mixed with 10 parts by weight to prepare adhesive a1.
  • the pressure-sensitive adhesive a1 is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 ⁇ m) was formed.
  • the base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 ⁇ m) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a2 consisting of the pressure-sensitive adhesive layer)/base material was obtained.
  • Liner-attached adhesive sheet a2/undercoat layer laminate A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L”) were mixed to prepare adhesive b.
  • the base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 ⁇ m).
  • the composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 ⁇ m).
  • the Si—K ⁇ ray intensity of the liner (trade name “MRF-50”) was 28 (kcps).
  • the second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a2 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand for 5 days in an environment with a temperature of 40° C. and a humidity of 20% to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive layer. / A liner-equipped double-sided pressure-sensitive adhesive sheet consisting of a second liner was obtained.
  • Example 8 Adhesive sheet with liner a2
  • liner (first liner)/pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer)/substrate) was obtained in the same manner as in Example 7.
  • Liner-attached adhesive sheet a2/undercoat layer laminate A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b.
  • the base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 ⁇ m).
  • the composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 ⁇ m).
  • the second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a2 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand for 2 hours in an environment with a temperature of 90° C. and a humidity of 1% RH to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive.
  • a lined double-sided PSA sheet consisting of layer/second liner was obtained.
  • Example 9 Adhesive sheet with liner a2
  • liner (first liner)/pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer)/substrate) was obtained in the same manner as in Example 7.
  • Liner-attached adhesive sheet a2/undercoat layer laminate A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b.
  • the base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 ⁇ m).
  • the composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 ⁇ m).
  • the second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a/undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 40° C. and a humidity of 92% RH for 3 days to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive.
  • a lined double-sided PSA sheet consisting of layer/second liner was obtained.
  • Example 10 Adhesive sheet with liner a3 Toluene solution of acrylic polymer 2 (acrylic polymer 2: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, tackifying resin (manufactured by Arakawa Chemical Industries, trade name " Tamanol 200N”) was mixed with 15 parts by weight to prepare an adhesive a'.
  • the adhesive a' is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, product name "MRF-38”) to form an adhesive layer (thickness: : 5 ⁇ m).
  • the base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 ⁇ m) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a3 consisting of the pressure-sensitive adhesive layer)/substrate was obtained.
  • Liner-attached adhesive sheet a3/undercoat layer laminate A toluene solution of acrylic polymer 2 (acrylic polymer 2: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L”) were mixed to prepare adhesive b'.
  • Adhesive b′ was applied to the substrate of the liner-attached adhesive sheet a3 to form a laminate consisting of the liner-attached adhesive sheet a3/undercoat layer (thickness: 13 ⁇ m).
  • the composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 ⁇ m).
  • the second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a3 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 40° C. and a humidity of 20% RH for 5 days to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive.
  • a lined double-sided PSA sheet consisting of layer/second liner was obtained.
  • Example 11 (Adhesive sheet a4 with liner) Toluene solution of acrylic polymer 3 (acrylic polymer 3: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, tackifier resin (manufactured by Arakawa Chemical Industries, trade name " Tamanol 200N”) was mixed with 15 parts by weight to prepare an adhesive a''. The adhesive a' is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, product name "MRF-38”) to form an adhesive layer (thickness: : 5 ⁇ m).
  • PET film thickness: 38 ⁇ m
  • silicone-based release-treated product manufactured by Mitsubishi Plastics, product name "MRF-38
  • the base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 ⁇ m) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a4 consisting of the pressure-sensitive adhesive layer)/substrate was obtained.
  • Liner-attached adhesive sheet a4/undercoat layer laminate A toluene solution of acrylic polymer 3 (acrylic polymer 3: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L”) were mixed to prepare adhesive b''.
  • the base material of the liner-attached adhesive sheet a4 was coated with the adhesive b′′ to form a laminate composed of the liner-attached adhesive sheet a4/undercoat layer (thickness: 13 ⁇ m).
  • the composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 ⁇ m).
  • the second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a4 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 40° C. and a humidity of 20% RH for 5 days to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive.
  • a lined double-sided PSA sheet consisting of layer/second liner was obtained.
  • a toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ”) was mixed with 10 parts by weight to prepare adhesive a1.
  • the adhesive a is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 ⁇ m) was formed.
  • the liner with the pressure-sensitive adhesive layer was attached to a base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 ⁇ m) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
  • the liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 200° C. and a humidity of 0.1% RH for 4 hours to obtain a liner-attached pressure-sensitive adhesive sheet consisting of a liner/adhesive layer (first pressure-sensitive adhesive layer)/substrate. got a sheet.
  • Adhesive sheet with liner a2 A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) 3 parts by weight, a plasticizer (manufactured by DIC, trade name “Monocizer W700”) ”) was mixed with 10 parts by weight to prepare adhesive a1.
  • the adhesive a is applied to the release-treated surface of the liner (PET film, thickness: 38 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 ⁇ m) was formed.
  • the base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 ⁇ m) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a2 consisting of the pressure-sensitive adhesive layer)/base material was obtained.
  • Liner-attached adhesive sheet a2/undercoat layer laminate A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L”) were mixed to prepare adhesive b.
  • the base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 ⁇ m).
  • the composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 ⁇ m, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 ⁇ m).
  • the second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a2 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
  • the liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand for 7 days in an environment with a temperature of 85° C. and a humidity of 92% RH to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive.
  • a lined double-sided PSA sheet consisting of layer/second liner was obtained.
  • a 2-kg roller was reciprocated one time under the pressure and bonded together to prepare an evaluation sample.
  • the evaluation sample was set in a tensile tester with a constant temperature bath set at 23° C. (manufactured by Shimadzu Corporation, trade name “Shimadzu Autograph AG-120 kN”) and left for 30 minutes. After standing, the polyethylene terephthalate was peeled off from the adhesive sheet at a temperature of 23° C. under the conditions of a peeling angle of 180° and a peeling speed (tensile speed) of 300 mm/min. The maximum load (the maximum value of the load excluding the peak top at the initial stage of measurement) was obtained, and this maximum load was defined as the adhesive strength (N/20 mm).
  • a 130 ⁇ m thick polytetrafluoroethylene (PTFE) sheet with 3 mm diameter holes was placed on the first adhesive layer.
  • a sealing resin precursor epoxy resin, manufactured by Nagase ChemteX Corporation, trade name "R4212"
  • R4212 epoxy resin, manufactured by Nagase ChemteX Corporation, trade name "R4212”
  • the PTFE sheet was removed, and the pressure-sensitive adhesive sheet with the pillars of the sealing resin precursor was placed on an optical microscope with a hot stage.
  • the time required for the shortest distance between the outer edge of the columnar body formation position and the outer edge of the sealing resin precursor after flowing to be 30 ⁇ m was measured.
  • the above measurement was performed 10 times, and the difference between the longest time and the shortest time was used to evaluate the variation in fluidity of the sealing resin precursor according to the following criteria.
  • Excellent ⁇ in the table: The above difference is less than 60 seconds Acceptable ( ⁇ in the table): The above difference is 60 seconds to 180 seconds Impossible (X in the table): The above difference exceeds 180 seconds

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Abstract

The present invention provides an adhesive sheet including, on the surface thereof, an adhesive layer on which a sealing resin for sealing a semiconductor chip can evenly flow.　An adhesive sheet according to the present invention includes a substrate and an adhesive layer that is disposed on at least one side of the substrate, wherein the adhesive force at 23°C when the adhesive layer is bonded to polyethylene terephthalate is 0.1N/20mm to 8N/20mm, the adhesive layer is composed of an adhesive that contains a base polymer, the sp value of the base polymer is 7(cal/cm3)1/2 to 10(cal/cm3)1/2, and the water content of the adhesive sheet is 0.05wt% to 6wt%.

Description

粘着シートAdhesive sheet
　本発明は、粘着シートに関する。 The present invention relates to an adhesive sheet.
　近年、半導体チップを含む半導体部品の製造において、半導体チップの傷つき防止、金属配線の拡張等のために、当該半導体チップを樹脂封止することが行われることがある。樹脂封止工程では、作業性等の観点から、粘着シート上で、半導体チップを樹脂封止することが行われることがある。例えば、半導体チップの移動を防止するために、複数の半導体チップを所定の仮固定材としての粘着シート上に配置し、当該粘着シート上で、半導体チップを一括に封止する。 In recent years, in the manufacture of semiconductor parts including semiconductor chips, the semiconductor chips are often sealed with resin in order to prevent damage to the semiconductor chips and expand metal wiring. In the resin sealing process, the semiconductor chip is sometimes resin-sealed on the adhesive sheet from the viewpoint of workability. For example, in order to prevent the semiconductor chips from moving, a plurality of semiconductor chips are placed on an adhesive sheet as a predetermined temporary fixing material, and the semiconductor chips are collectively sealed on the adhesive sheet.
　樹脂封止の工程においては、流動性を有する封止樹脂前駆体を塗布して半導体チップを覆い、その後、当該前駆体の流動性を減ずることにより、半導体チップが封止される。このときの当該前駆体の流動性は、封止品質（特に、作業時間、封止の均一性）に影響する一因である。一般に、上記前駆体の流動性は、封止樹脂が塗工される面（すなわち、粘着シートの粘着剤層表面）と、封止樹脂との親和性に依存する。しかしながら、粘着剤層および封止樹脂の組成に変化がないにもかかわらず、上記前駆体の流動性が一定となはならないことがある。 In the process of resin sealing, a sealing resin precursor having fluidity is applied to cover the semiconductor chip, and then the fluidity of the precursor is reduced to seal the semiconductor chip. The fluidity of the precursor at this time is one factor that affects sealing quality (particularly working time and sealing uniformity). In general, the fluidity of the precursor depends on the affinity between the surface to be coated with the sealing resin (that is, the surface of the adhesive layer of the adhesive sheet) and the sealing resin. However, even though the composition of the pressure-sensitive adhesive layer and the sealing resin does not change, the fluidity of the precursor may not be constant.
特開２００１－３０８１１６号公報Japanese Patent Application Laid-Open No. 2001-308116 特開２００１－３１３３５０号公報Japanese Patent Application Laid-Open No. 2001-313350
　本発明は上記従来の課題を解決するためになされたものであり、その目的とするところは、その表面で、半導体チップ等を封止する封止樹脂がバラツキ少なく流動し得る粘着剤層を備える粘着シートを提供することにある。 The present invention has been made to solve the above-mentioned conventional problems, and its object is to provide an adhesive layer on the surface of which a sealing resin for sealing a semiconductor chip or the like can flow with little variation. To provide an adhesive sheet.
　本発明の粘着シートは、基材と、該基材の少なくとも片側に配置された粘着剤層とを備える粘着シートであって、該粘着剤層をポリエチレンテレフタレートに貼着した際の２３℃における粘着力が、０．１Ｎ／２０ｍｍ～８Ｎ／２０ｍｍであり、該粘着剤層が、ベースポリマーを含む粘着剤から構成され、該ベースポリマーのｓｐ値が７（ｃａｌ／ｃｍ３）１／２～１０（ｃａｌ／ｃｍ３）１／２であり、該粘着シートの含水率が、０．０５重量％～６重量％である。
　１つの実施形態においては、上記基材が、ガラス転移温度（Ｔｇ）が６０℃～４５０℃の樹脂から構成される樹脂シートである。
　１つの実施形態においては、上記基材が、芳香族性ポリイミド系樹脂から構成される。
　１つの実施形態においては、上記粘着剤層の厚みが、２μｍ～１５μｍである。
　１つの実施形態においては、上記粘着剤層のゲル分率が、６０％～１００％である。
　１つの実施形態においては、上記ベースポリマーが、アクリル系ポリマーであり、該アクリル系ポリマーが、水酸基含有モノマー由来の構成単位を含み、該水酸基含有モノマー由来の構成単位の含有量が、該アクリル系ポリマーを構成する全構成単位１００重量部に対して、０．１重量部～２０重量部である。
　１つの実施形態においては、上記粘着シートは、上記基材の前記粘着剤層とは反対側に、第２の粘着剤層をさらに備える。
　１つの実施形態においては、上記粘着シートは、ＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ／Ｓｃａｌｅ　Ｐａｃｋａｇｅ）またはＷＬＰ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ）の製造の際に、半導体チップを仮固定するシートとして用いられる。
　１つの実施形態においては、上記半導体チップは、封止樹脂により封止され、該樹脂封止の際の加工温度が１００℃以上である。
　本発明の別の局面よれば、上記粘着シートの製造方法が提供される。この製造方法は、　基材上に粘着剤を含む組成物の塗工層を形成する工程と、該塗工層面上にライナーを配置して積層体を形成する工程と、該積層体を、所定の加湿熱時間（例えば、２時間～７日）、温度および湿度が管理された環境下に置く加湿熱工程とを含み、加湿熱工程における、加湿熱時間と温度と湿度との積が、１００～３０００００℃・ＲＨ％・ｈである。 The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer disposed on at least one side of the base material, wherein the pressure-sensitive adhesive layer adheres to polyethylene terephthalate at 23°C. The force is 0.1 N/20 mm to 8 N/20 mm, the adhesive layer is composed of an adhesive containing a base polymer, and the sp value of the base polymer is 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 , and the water content of the adhesive sheet is 0.05% by weight to 6% by weight.
In one embodiment, the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 60°C to 450°C.
In one embodiment, the base material is composed of an aromatic polyimide resin.
In one embodiment, the pressure-sensitive adhesive layer has a thickness of 2 μm to 15 μm.
In one embodiment, the adhesive layer has a gel fraction of 60% to 100%.
In one embodiment, the base polymer is an acrylic polymer, the acrylic polymer contains a structural unit derived from a hydroxyl group-containing monomer, and the content of the structural unit derived from the hydroxyl group-containing monomer is the acrylic polymer It is 0.1 to 20 parts by weight per 100 parts by weight of all structural units constituting the polymer.
In one embodiment, the pressure-sensitive adhesive sheet further comprises a second pressure-sensitive adhesive layer on the opposite side of the base material to the pressure-sensitive adhesive layer.
In one embodiment, the pressure-sensitive adhesive sheet is used as a sheet for temporarily fixing a semiconductor chip when manufacturing a CSP (Chip Size/Scale Package) or a WLP (Wafer Level Package).
In one embodiment, the semiconductor chip is sealed with a sealing resin, and the processing temperature during the resin sealing is 100° C. or higher.
According to another aspect of the present invention, there is provided a method for producing the pressure-sensitive adhesive sheet. This manufacturing method comprises the steps of: forming a coating layer of a composition containing an adhesive on a substrate; placing a liner on the surface of the coating layer to form a laminate; Humidification heat time (for example, 2 hours to 7 days), and a heat humidification step in an environment where temperature and humidity are controlled, and the product of the heat humidification time, temperature and humidity in the heat humidification step is 100 ~300000°C.RH%.h.
　本発明によれば、その表面で、半導体チップ等を封止する封止樹脂がバラツキ少なく流動し得る粘着剤層を備える粘着シートを提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on the surface of which a sealing resin for sealing semiconductor chips or the like can flow with little variation.
本発明の１つの実施形態による粘着シートの概略断面図である。1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention; FIG. 本発明の別の実施形態による粘着シートの概略断面図である。4 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet according to another embodiment of the invention; FIG. 本発明の１つの実施形態によるライナー付両面粘着シートの概略断面図である。1 is a schematic cross-sectional view of a liner-attached double-sided pressure-sensitive adhesive sheet according to one embodiment of the present invention; FIG.
Ａ．粘着シートの概要
　図１は、本発明の１つの実施形態による粘着シートの概略断面図である。粘着シート１００は、基材１０と、基材１０の少なくとも片側に配置された粘着剤層（第１の粘着剤層）２０とを備える。 A. Outline of Adhesive Sheet FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention. The adhesive sheet 100 includes a substrate 10 and an adhesive layer (first adhesive layer) 20 arranged on at least one side of the substrate 10 .
　本発明の粘着シートは、粘着剤層をポリエチレンテレフタレートに貼着した際の２３℃における粘着力が、０．１Ｎ／２０ｍｍ～８Ｎ／２０ｍｍである。また、上記粘着剤層は、ベースポリマーを含む粘着剤から構成され、当該ベースポリマーのｓｐ値が７（ｃａｌ／ｃｍ３）１／２～１０（ｃａｌ／ｃｍ３）１／２である。また、上記粘着シートは、含水率が、０．０５重量％～６重量％である。 The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive strength of 0.1 N/20 mm to 8 N/20 mm at 23° C. when the pressure-sensitive adhesive layer is adhered to polyethylene terephthalate. The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive containing a base polymer, and the base polymer has an sp value of 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 . Further, the pressure-sensitive adhesive sheet has a moisture content of 0.05% to 6% by weight.
　本発明の粘着シートは、半導体チップを樹脂封止する際の仮固定材として、好適に用いられ得る。より詳細には、本発明の粘着シートは、当該粘着シートの粘着剤層上に半導体チップを配列し、当該半導体チップを封止樹脂（通常、エポキシ系樹脂）前駆体で覆い、当該封止樹脂前駆体を硬化することによって半導体チップを樹脂封止する際の、当該半導体チップの仮固定材として用いられ得る。半導体チップを樹脂封止した後、所定の後工程（例えば、封止樹脂の裏面研削、パターン形成、バンプ形成、チップ化（切断））の際には、上記粘着シートは、封止樹脂と半導体チップとから構成される構造体から剥離され得る。封止樹脂のエポキシ当量は、例えば、５０ｇ／ｅｑ～５００ｇ／ｅｑである。 The adhesive sheet of the present invention can be suitably used as a temporary fixing material when sealing semiconductor chips with resin. More specifically, the pressure-sensitive adhesive sheet of the present invention is obtained by arranging semiconductor chips on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, covering the semiconductor chips with a sealing resin (usually epoxy resin) precursor, and It can be used as a temporary fixing material for the semiconductor chip when the semiconductor chip is resin-sealed by curing the precursor. After the semiconductor chip is resin-encapsulated, in the case of predetermined post-processes (for example, back grinding of the encapsulation resin, pattern formation, bump formation, chip formation (cutting)), the adhesive sheet is used to separate the encapsulation resin and the semiconductor. It can be peeled off from the structure composed of the chip. The epoxy equivalent of the sealing resin is, for example, 50 g/eq to 500 g/eq.
　本発明の粘着シートにおいては、上記のように、粘着剤層が含有するベースポリマーのｓｐ値を特定し、かつ、粘着シート含水率を特定することにより、上記粘着剤層上で、封止樹脂前駆体が好ましく流動し得る。また、封止樹脂前駆体の流動性のバラツキが抑制されるため、半導体チップの量産工程において、封止工程の時間を短縮でき、均一性に優れた樹脂封止を安定的に行うことができる。このように、本発明の粘着シートは、粘着性と剥離性のバランスに優れ（すなわち、仮固定性に優れ）、かつ、封止品質向上に寄与し得ることを特徴とする。また、本発明の粘着シートは、高温下においても、封止品質向上に寄与し得る点で特に有用である。 In the adhesive sheet of the present invention, as described above, by specifying the sp value of the base polymer contained in the adhesive layer and specifying the moisture content of the adhesive sheet, on the adhesive layer, the sealing resin Precursors can preferably flow. In addition, since variations in the fluidity of the sealing resin precursor are suppressed, the time required for the sealing process can be shortened in the mass production process of semiconductor chips, and resin sealing with excellent uniformity can be stably performed. . As described above, the pressure-sensitive adhesive sheet of the present invention is characterized in that it has an excellent balance of adhesiveness and peelability (that is, excellent temporary fixability) and can contribute to improvement in sealing quality. Moreover, the pressure-sensitive adhesive sheet of the present invention is particularly useful in that it can contribute to improvement in sealing quality even at high temperatures.
　図２は、本発明の別の実施形態による粘着シートの概略断面図である。粘着シート２００は、両面粘着シートであり、基材１０の粘着剤層２０と反対側に、第２の粘着剤層３０をさらに備える。すなわち、粘着シート２００は、粘着剤層２０と、基材１０と、第２の粘着剤層３０とをこの順に備える。第２の粘着剤層３０を備えることにより、台座上で樹脂封止をする際に、第２の粘着剤層３０側を当該台座に貼着して、固定性よく粘着シート２００を使用することができる。 FIG. 2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the invention. The pressure-sensitive adhesive sheet 200 is a double-sided pressure-sensitive adhesive sheet, and further includes a second pressure-sensitive adhesive layer 30 on the opposite side of the base material 10 to the pressure-sensitive adhesive layer 20 . That is, the adhesive sheet 200 includes the adhesive layer 20, the base material 10, and the second adhesive layer 30 in this order. By providing the second adhesive layer 30, the adhesive sheet 200 can be used with good fixability by sticking the second adhesive layer 30 side to the pedestal when resin sealing is performed on the pedestal. can be done.
　１つの実施形態においては、第２の粘着剤層は、熱膨張性微小球を含む。該熱膨張性微小球は所定温度で膨張し得る。このような熱膨張性微小球を含む粘着剤層は、所定温度以上に加熱することよって熱膨張性微小球が膨張し、粘着面（すなわち第２の粘着剤層表面）に凹凸が生じて、粘着力が低下または消失する。熱膨張性微小球を含む第２の粘着剤層を形成すれば、粘着シートを固定する際（例えば、台座に固定する際）には必要な粘着性が発現され、粘着シートを剥離する際（例えば、台座から剥離する際）には、加熱により粘着力が低下または消失して、良好な剥離性が発現される。 In one embodiment, the second adhesive layer contains thermally expandable microspheres. The heat-expandable microspheres can expand at a given temperature. When the pressure-sensitive adhesive layer containing such heat-expandable microspheres is heated to a predetermined temperature or higher, the heat-expandable microspheres expand and irregularities occur on the pressure-sensitive adhesive surface (that is, the surface of the second pressure-sensitive adhesive layer). Adhesion is reduced or lost. By forming the second pressure-sensitive adhesive layer containing heat-expandable microspheres, the necessary pressure-sensitive adhesiveness is exhibited when the pressure-sensitive adhesive sheet is fixed (for example, when fixed to a pedestal), and when the pressure-sensitive adhesive sheet is peeled off ( For example, when peeling from the pedestal), the adhesive strength is reduced or lost by heating, and good peelability is exhibited.
　本発明の粘着シートは、粘着剤層をポリエチレンテレフタレートに貼着した際の２３℃における粘着力は、上記のとおり、０．１Ｎ／２０ｍｍ～８Ｎ／２０ｍｍであり、好ましくは０．２Ｎ／２０ｍｍ～７．５Ｎ／２０ｍｍであり、より好ましくは０．５Ｎ／２０ｍｍ～６Ｎ／２０ｍｍであり、さらに好ましくは０．８Ｎ／２０ｍｍ～５Ｎ／２０ｍｍであり、最も好ましくは０．８Ｎ／２０ｍｍ～３Ｎ／２０ｍｍである。このような範囲であれば、被着体（例えば、半導体チップ）を好ましく固定し得、かつ、剥離時の糊残りの少ない粘着シートを得ることができる。なお、本明細書において、「粘着剤層をポリエチレンテレフタレートに貼着した際の２３℃における粘着力」とは、ポリエチレンテレフタレートフィルム（厚み２５μｍ）に、粘着シート（幅２０ｍｍ×長さ１４０ｍｍ）の粘着剤層を貼り合わせ（貼り合わせ条件：２ｋｇローラー１往復）、２３℃の環境温度下で３０分間放置した後、該試料を引っ張り試験（剥離速度：３００ｍｍ／ｍｉｎ、剥離角度１８０°）に供して測定される粘着力をいう。 The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive strength at 23° C. when the pressure-sensitive adhesive layer is adhered to polyethylene terephthalate, as described above, from 0.1 N/20 mm to 8 N/20 mm, preferably from 0.2 N/20 mm. 7.5 N/20 mm, more preferably 0.5 N/20 mm to 6 N/20 mm, still more preferably 0.8 N/20 mm to 5 N/20 mm, most preferably 0.8 N/20 mm to 3 N/20 mm is. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet that can preferably fix an adherend (for example, a semiconductor chip) and leaves little adhesive residue when peeled off. In this specification, the “adhesive strength at 23° C. when the adhesive layer is attached to polyethylene terephthalate” refers to the adhesiveness of the adhesive sheet (width 20 mm × length 140 mm) to the polyethylene terephthalate film (thickness 25 μm). After laminating the agent layers (lamination conditions: 1 reciprocation of a 2-kg roller) and leaving for 30 minutes under an environmental temperature of 23° C., the sample was subjected to a tensile test (peeling speed: 300 mm/min, peeling angle: 180°). Adhesive strength that is measured.
　上記のとおり、粘着シートの含水率は、０．０５重量％～６重量％である。粘着シートの含水率は、好ましくは０．１重量％～５重量％であり、さらに好ましくは０．５重量％～４重量％であり、さらに好ましくは１重量％～３重量％である。このような範囲であれば、封止樹脂前駆体との親和性が適度に調整され、樹脂封止品質の向上に寄与し得る粘着剤層を形成することができる。また、封止樹脂の変質を防止することができる。上記含水率は、カールフィッシャー滴定法で測定され得る。粘着シートの含水率は、任意の適切な方法により調整され得る。例えば、粘着剤層形成時（粘着剤塗工時）の粘着剤の含水率の調整、粘着剤に含まれるベースポリマーの構成、加湿熱工程の実施（後述）等により、調整することができる。 As described above, the moisture content of the adhesive sheet is 0.05% to 6% by weight. The moisture content of the adhesive sheet is preferably 0.1% to 5% by weight, more preferably 0.5% to 4% by weight, and still more preferably 1% to 3% by weight. Within such a range, the affinity with the encapsulating resin precursor is appropriately adjusted, and a pressure-sensitive adhesive layer that can contribute to the improvement of resin encapsulation quality can be formed. Also, deterioration of the sealing resin can be prevented. The water content can be measured by Karl Fischer titration. The moisture content of the PSA sheet can be adjusted by any appropriate method. For example, it can be adjusted by adjusting the water content of the adhesive during the formation of the adhesive layer (during the coating of the adhesive), the composition of the base polymer contained in the adhesive, and the implementation of the moistening and heating process (described later).
　本発明の粘着シートの厚みは、好ましくは３μｍ～３００μｍであり、より好ましくは５μｍ～１５０μｍであり、さらに好ましくは１０μｍ～１００μｍである。 The thickness of the adhesive sheet of the present invention is preferably 3 µm to 300 µm, more preferably 5 µm to 150 µm, still more preferably 10 µm to 100 µm.
Ｂ．粘着剤層
　上記粘着剤層は、ベースポリマーを含む粘着剤から構成される。なお、「ベースポリマー」とは、粘着剤に含まれるポリマーの主成分をいう。また、この明細書において「主成分」とは、特記しない場合、５０重量％を超えて含まれる成分を指す。 B. Adhesive layer The adhesive layer is composed of an adhesive containing a base polymer. In addition, a "base polymer" means the main component of the polymer contained in an adhesive. In this specification, the term "main component" refers to a component contained in an amount exceeding 50% by weight unless otherwise specified.
　上記粘着剤層の厚みは、好ましくは１μｍ～５０μｍであり、より好ましくは３μｍ～３０μｍであり、さらに好ましくは５μｍ～２０μｍである。このような範囲であれば、封止工程時の加圧によっても、半導体チップの樹脂への埋まり込みがたい粘着シートを得ることができる。１つの実施形態においては、上記粘着剤層の厚みは、２μｍ～１５μｍである。このような範囲であれば、粘着剤層からの水分の放散が適度に調整され、封止樹脂前駆体の流動性を好ましいものとすることができる。 The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm, still more preferably 5 μm to 20 μm. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet that is difficult for the semiconductor chip to be embedded in the resin even when pressurized during the sealing process. In one embodiment, the pressure-sensitive adhesive layer has a thickness of 2 μm to 15 μm. Within such a range, the diffusion of moisture from the pressure-sensitive adhesive layer can be appropriately adjusted, and the fluidity of the sealing resin precursor can be made preferable.
　上記のとおり、上記ベースポリマーのｓｐ値は、７（ｃａｌ／ｃｍ３）１／２～１０（ｃａｌ／ｃｍ３）１／２であり、上記ベースポリマーのｓｐ値は、好ましくは７．５（ｃａｌ／ｃｍ３）１／２～９．５（ｃａｌ／ｃｍ３）１／２であり、より好ましくは８（ｃａｌ／ｃｍ３）１／２～９（ｃａｌ／ｃｍ３）１／２である。このような範囲であれば、封止樹脂対する親和性が適度に調整され、樹脂封止品質の向上に寄与し得る粘着剤層を形成することができる。ｓｐ値は、フェドーズ（Ｆｅｄｏｒｓ）の方法（山本秀樹著、「ｓｐ値　基礎・応用と計算方法」、株式会社情報機構出版、２００６年４月３日発行、６６～６７ページ）により、求められる。具体的には、該ｓｐ値は、ポリマーを形成する各原子または原子団の２５℃における蒸発エネルギーΔｅ（ｃａｌ）と、ポリマーを形成する各原子または原子団の２５℃におけるモル容積ΔＶ（ｃｍ３）とから、以下の式により算出される。ポリマーが共重合体である場合、そのｓｐ値は、その共重合体を構成する各構成単位のそれぞれの単独共重合体のｓｐ値を算出し、これらのｓｐ値のそれぞれに各構成単位のモル分率を乗じたものを合算して算出される。
　ｓｐ値＝（ΣΔｅ／ΣΔｖ）１／２ As described above, the sp value of the base polymer is 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 , and the sp value of the base polymer is preferably 7.5 ( cal/cm 3 ) 1/2 to 9.5 (cal/cm 3 ) 1/2 , more preferably 8 (cal/cm 3 ) 1/2 to 9 (cal/cm 3 ) 1/2 . Within such a range, it is possible to form a pressure-sensitive adhesive layer whose affinity for the encapsulating resin is appropriately adjusted and which can contribute to the improvement of resin encapsulation quality. The sp value is determined by the method of Fedors (Hideki Yamamoto, "Sp Value: Fundamentals, Applications and Calculation Methods", Joho Kyoukai Publishing Co., Ltd., published on April 3, 2006, pp. 66-67). Specifically, the sp value is the evaporation energy Δe (cal) of each atom or atomic group forming the polymer at 25° C. and the molar volume ΔV (cm 3 ) of each atom or atomic group forming the polymer at 25° C. is calculated by the following formula. When the polymer is a copolymer, the sp value is obtained by calculating the sp value of each homopolymer of each structural unit that constitutes the copolymer, and adding the moles of each structural unit to each of these sp values. Calculated by summing the products multiplied by the fractions.
sp value = (ΣΔe/ΣΔv) 1/2
　上記粘着剤層の水の接触角は、好ましくは７０°～１２０°であり、より好ましくは８０°～１１０°であり、さらに好ましくは９０°～１０５°である。このような範囲であれば、封止樹脂前駆体との親和性が適度に調整され、樹脂封止品質の向上に寄与し得る粘着剤層を形成することができる。水の接触角は、接触角計（例えば、協和界面社製、商品名「ＣＸ－Ａ型」）を用いて、２３℃／５０％ＲＨ環境下、純水を粘着剤層表面に２μｌ滴下し、滴下して５秒後に液滴の接触角を測定することを５回繰り返し、その平均値から求めることができる。 The water contact angle of the pressure-sensitive adhesive layer is preferably 70° to 120°, more preferably 80° to 110°, still more preferably 90° to 105°. Within such a range, the affinity with the encapsulating resin precursor is appropriately adjusted, and a pressure-sensitive adhesive layer that can contribute to the improvement of resin encapsulation quality can be formed. The contact angle of water is determined by dropping 2 μl of pure water onto the adhesive layer surface in a 23° C./50% RH environment using a contact angle meter (for example, Kyowa Interface Co., Ltd., trade name “CX-A”). , the measurement of the contact angle of the droplet five seconds after the droplet is dropped is repeated five times, and the average value can be obtained.
　上記粘着剤層のゲル分率は、好ましくは６０％～１００％であり、より好ましくは７０％～９９％であり、さらに好ましくは７５％～９８％であり、特に好ましくは８０％～９５％である。このような範囲であれば、粘着剤層からの水分の放散が適度に調整され、封止樹脂前駆体の流動性を好ましいものとすることができる。また、適度な粘着性を有し、剥離時の糊残り等なく被着体を汚染し難い粘着剤層を形成することができる。ゲル分率の測定方法は、後述する。 The gel fraction of the adhesive layer is preferably 60% to 100%, more preferably 70% to 99%, still more preferably 75% to 98%, and particularly preferably 80% to 95%. is. Within such a range, the diffusion of moisture from the pressure-sensitive adhesive layer can be appropriately adjusted, and the fluidity of the sealing resin precursor can be made preferable. In addition, it is possible to form a pressure-sensitive adhesive layer that has appropriate adhesiveness and does not leave adhesive residue, etc., when peeled off, and does not easily stain the adherend. A method for measuring the gel fraction will be described later.
　上記粘着剤層の２５℃におけるナノインデンテーション法による弾性率は、好ましくは１００ＭＰａ未満であり、より好ましくは０．１ＭＰａ～５０ＭＰａであり、さらに好ましくは０．１ＭＰａ～１０ＭＰａである。このような範囲であれば、適切な粘着力を有する粘着シートを得ることができる。ナノインデンテーション法による弾性率とは、圧子を試料に押し込んだときの、圧子への負荷荷重と押し込み深さとを負荷時、除荷時にわたり連続的に測定し、得られた負荷荷重－押し込み深さ曲線から求められる弾性率をいう。本明細書において、ナノインデンテーション法による弾性率とは、測定条件を荷重：１ｍＮ、負荷・除荷速度：０．１ｍＮ／ｓ、保持時間：１ｓとして上記のように測定した弾性率をいう。 The elastic modulus of the pressure-sensitive adhesive layer measured by the nanoindentation method at 25°C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and still more preferably 0.1 MPa to 10 MPa. If it is such a range, the adhesive sheet which has suitable adhesive force can be obtained. The elastic modulus by the nanoindentation method is obtained by continuously measuring the load applied to the indenter and the indentation depth during loading and unloading when the indenter is pushed into the sample. It refers to the elastic modulus obtained from the curve. As used herein, the elastic modulus by the nanoindentation method refers to the elastic modulus measured as described above under the measurement conditions of load: 1 mN, loading/unloading rate: 0.1 mN/s, and holding time: 1 s.
（アクリル系粘着剤）
　１つの実施形態においては、粘着剤層を構成する粘着剤は、アクリル系粘着剤である。上記アクリル系粘着剤としては、例えば、（メタ）アクリル酸アルキルエステルの１種または２種以上を単量体成分として用いたアクリル系ポリマー（ホモポリマーまたはコポリマー）をプレポリマーとし、該プレポリマーの架橋体をベースポリマーとするアクリル系粘着剤等が挙げられる。なお、本明細書において、粘着剤層中のアクリル系粘着剤に含まれる「ベースポリマー」とは、プレポリマー（未架橋ポリマー）を架橋させて形成されたポリマーを意味する。１つの実施形態においては、上記ベースポリマーは、アクリル系ポリマーとエポキシ架橋剤による架橋体構造を有する。 (Acrylic adhesive)
In one embodiment, the adhesive constituting the adhesive layer is an acrylic adhesive. As the acrylic pressure-sensitive adhesive, for example, an acrylic polymer (homopolymer or copolymer) using one or more of (meth)acrylic acid alkyl esters as a monomer component is used as a prepolymer, and the prepolymer Examples include acrylic pressure-sensitive adhesives using a crosslinked product as a base polymer. In this specification, the "base polymer" contained in the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer means a polymer formed by cross-linking a prepolymer (uncross-linked polymer). In one embodiment, the base polymer has a crosslinked structure of an acrylic polymer and an epoxy crosslinking agent.
　上記（メタ）アクリル酸アルキルエステルの具体例としては、（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）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（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）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシル等の（メタ）アクリル酸Ｃ１－２０アルキルエステルが挙げられる。なかでも好ましくは、炭素数が４～２０（より好ましくは６～２０、特に好ましくは８～１８）の直鎖状もしくは分岐状のアルキル基を有する（メタ）アクリル酸アルキルエステルであり、より好ましくは（メタ）アクリル酸２－エチルヘキシルである。なお、本明細書において、（メタ）アクリルとは、アクリルおよび／またはメタクリルを意味する。 Specific examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, ( isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic undecyl acid, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, (meth)acrylic acid Examples include (meth)acrylic acid C1-20 alkyl esters such as octadecyl, nonadecyl (meth)acrylate and eicosyl (meth)acrylate. Among them, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 4 to 20 carbon atoms (more preferably 6 to 20, particularly preferably 8 to 18 carbon atoms) are more preferable. is 2-ethylhexyl (meth)acrylate. In addition, in this specification, (meth)acryl means acryl and/or methacryl.
　上記アクリル系ポリマー（プレポリマー）は、凝集力、耐熱性、架橋性等の改質を目的として、必要に応じて、上記（メタ）アクリル酸アルキルエステルと共重合可能な他の単量体成分に対応する単位を含んでいてもよい。このような単量体成分として、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸等のカルボキシル基含有モノマー；無水マレイン酸、無水イコタン酸等の酸無水物モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシオクチル、（メタ）アクリル酸ヒドロキシデシル、（メタ）アクリル酸ヒドロキシラウリル、（４－ヒドロキシメチルシクロヘキシル）メチルメタクリレート等のヒドロキシル基含有モノマー；スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸等のスルホン酸基含有モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミド等の（Ｎ－置換）アミド系モノマー；（メタ）アクリル酸アミノエチル、（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ｔ－ブチルアミノエチル等の（メタ）アクリル酸アミノアルキル系モノマー；（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エチル等の（メタ）アクリル酸アルコキシアルキル系モノマー；Ｎ－シクロヘキシルマレイミド、Ｎ－イソプロピルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－フェニルマレイミド等のマレイミド系モノマー；Ｎ－メチルイタコンイミド、Ｎ－エチルイタコンイミド、Ｎ－ブチルイタコンイミド、Ｎ－オクチルイタコンイミド、Ｎ－２－エチルヘキシルイタコンイミド、Ｎ－シクロヘキシルイタコンイミド、Ｎ－ラウリルイタコンイミド等のイタコンイミド系モノマー；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクルロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシオクタメチレンスクシンイミド等のスクシンイミド系モノマー；酢酸ビニル、プロピオン酸ビニル、Ｎ－ビニルピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、Ｎ－ビニルカルボン酸アミド類、スチレン、α－メチルスチレン、Ｎ－ビニルカプロラクタム等のビニル系モノマー；アクリロニトリル、メタクリロニトリル等のシアノアクリレートモノマー；（メタ）アクリル酸グリシジル等のエポキシ基含有アクリル系モノマー；（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコール、（メタ）アクリル酸メトキシエチレングリコール、（メタ）アクリル酸メトキシポリプロピレングリコール等のグリコール系アクリルエステルモノマー；（メタ）アクリル酸テトラヒドロフルフリル、フッ素（メタ）アクリレート、シリコーン（メタ）アクリレート等の複素環、ハロゲン原子、ケイ素原子等を有するアクリル酸エステル系モノマー；ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート等の多官能モノマー；イソプレン、ブタジエン、イソブチレン等のオレフィン系モノマー；ビニルエーテル等のビニルエーテル系モノマー等が挙げられる。これらの単量体成分は、単独で、または２種以上組み合わせて用いてもよい。 The acrylic polymer (prepolymer), for the purpose of modifying cohesive strength, heat resistance, crosslinkability, etc., if necessary, other monomer components copolymerizable with the (meth)acrylic acid alkyl ester may include units corresponding to Examples of such monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic anhydride; Acid anhydride monomers such as; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, (meth)acrylate Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxyllauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate; styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid , (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid and other sulfonic acid group-containing monomers; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-butyl (N-substituted) amide-based monomers such as (meth)acrylamide, N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide; aminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylate Aminoalkyl (meth)acrylate monomers such as aminoethyl and t-butylaminoethyl (meth)acrylate; Alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Monomers: Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N-lauryl itaconimide and other itaconimide monomers; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, Succinimide-based monomers such as N-(meth)acryloyl-8-oxyoctamethylenesuccinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone Vinyls such as lydone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic acid amides, styrene, α-methylstyrene, N-vinylcaprolactam, etc. cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, (meth)acrylic acid Glycol-based acrylic ester monomers such as methoxyethylene glycol and methoxypolypropylene glycol (meth)acrylate; heterocycles such as tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, and silicone (meth)acrylate, halogen atoms, silicon atoms Acrylic acid ester-based monomers having, etc.; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol Polyfunctional monomers such as di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, Olefin monomers such as isobutylene; vinyl ether monomers such as vinyl ether; These monomer components may be used alone or in combination of two or more.
　１つの実施形態においては、上記アクリル系ポリマー（プレポリマー）は、水酸基含有モノマー由来の構成単位をさらに含む。水酸基含有モノマー由来の構成単位の含有量は、アクリル系ポリマーを構成する全構成単位１００重量部に対して、好ましくは０．１重量部～２０重量部であり、より好ましくは０．１重量部～１０重量部である。より好ましくは０．５重量部～１０重量部である。このような範囲であれば、粘着剤層からの水分の放散が適度に調整され、含水率が好ましく調整された粘着剤層を形成することができる。また、適度な凝集性を有して、糊残りの少ない粘着剤層を形成することができる。水酸基は、アルコール性水酸基であってもよく、カルボキシル基等の酸性水酸基であってもよい。 In one embodiment, the acrylic polymer (prepolymer) further contains a structural unit derived from a hydroxyl group-containing monomer. The content of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.1 part by weight, with respect to 100 parts by weight of all the structural units constituting the acrylic polymer. ~10 parts by weight. It is more preferably 0.5 to 10 parts by weight. Within such a range, it is possible to form a pressure-sensitive adhesive layer in which the diffusion of water from the pressure-sensitive adhesive layer is appropriately adjusted and the water content is preferably adjusted. Moreover, it has moderate cohesiveness and can form a pressure-sensitive adhesive layer with little adhesive residue. The hydroxyl group may be an alcoholic hydroxyl group or an acidic hydroxyl group such as a carboxyl group.
　上記アクリル系粘着剤は、必要に応じて、任意の適切な添加剤を含み得る。該添加剤としては、例えば、架橋剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤等）、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 The acrylic pressure-sensitive adhesive may contain any suitable additive as necessary. The additives include, for example, cross-linking agents, tackifiers, plasticizers (e.g., trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, etc.), pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, and the like.
　上記アクリル系粘着剤に含まれる架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などが挙げられる。 Examples of the cross-linking agent contained in the acrylic pressure-sensitive adhesive include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide cross-linking agents, Examples include metal chelate cross-linking agents, metal salt cross-linking agents, carbodiimide cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, and amine cross-linking agents.
　１つの実施形態においては、アクリル系ポリマー（プレポリマー）のカルボキシル基に対する、架橋剤の配合量は、好ましくは０．０８モル当量～２モル当量であり、より好ましくは０．１モル当量～１モル当量である。このような範囲であれば、架橋密度が高いアクリル系粘着剤を形成することができ、粘着剤層／封止樹脂間における成分移行が好ましく防止される。ここでの架橋剤の配合量とは、アクリル系ポリマーが架橋する前の架橋剤の含有量を意味する。 In one embodiment, the amount of the cross-linking agent to be added to the carboxyl groups of the acrylic polymer (prepolymer) is preferably 0.08 molar equivalents to 2 molar equivalents, more preferably 0.1 molar equivalents to 1 molar equivalent. molar equivalents. Within such a range, an acrylic pressure-sensitive adhesive having a high cross-linking density can be formed, and component migration between the pressure-sensitive adhesive layer and the encapsulating resin is preferably prevented. The blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
　上記アクリル系粘着剤に含まれる上記イソシアネート系架橋剤の具体例としては、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類；シクロペンチレンジイソシアネート、シクロへキシレンジイソシアネート、イソホロン　ジイソシアネート等の脂環族イソシアネート類；２，４－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族イソシアネート類；トリメチロールプロパン／トリレンジイソシアネート３量体付加物（日本ポリウレタン工業社製、商品名「コロネートＬ」）、トリメチロールプロパン／へキサメチレンジイソシアネート３量体付加物（日本ポリウレタン工業社製、商品名「コロネートＨＬ」）、ヘキサメチレンジイソシアネートのイソシアヌレート体（日本ポリウレタン工業社製、商品名「コロネートＨＸ」）等のイソシアネート付加物；等が挙げられる。イソシアネート系架橋剤の配合量は、所望とする粘着力に応じて、任意の適切な量に設定され得、アクリル系ポリマー１００重量部に対して、代表的には０．１重量部～２０重量部であり、より好ましくは１重量部～１０重量部である。このような範囲であれば、粘着剤層中の成分の残存カルボキシル基が少ない粘着シートを得ることができる。ここでの架橋剤の配合量とは、アクリル系ポリマーが架橋する前の架橋剤の含有量を意味する。 Specific examples of the isocyanate-based cross-linking agent contained in the acrylic pressure-sensitive adhesive include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; group isocyanates; 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate and other aromatic isocyanates; name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL"), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product isocyanate adducts such as the name "Coronate HX"); The amount of the isocyanate-based cross-linking agent can be set to any appropriate amount depending on the desired adhesive strength. parts, more preferably 1 to 10 parts by weight. With such a range, it is possible to obtain a pressure-sensitive adhesive sheet with few residual carboxyl groups in the components of the pressure-sensitive adhesive layer. The blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
　上記アクリル系粘着剤に含まれる前記エポキシ系架橋剤としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、ジグリシジルアニリン、１，３－ビス（Ｎ，Ｎ－グリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製、商品名「テトラッドＣ」）、１，６－ヘキサンジオールジグリシジルエーテル（共栄社化学社製、商品名「エポライト１６００」）、ネオペンチルグリコールジグリシジルエーテル（共栄社化学社製、商品名「エポライト１５００ＮＰ」）、エチレングリコールジグリシジルエーテル（共栄社化学社製、商品名「エポライト４０Ｅ」）、プロピレングリコールジグリシジルエーテル（共栄社化学社製、商品名「エポライト７０Ｐ」）、ポリエチレングリコールジグリシジルエーテル（日本油脂社製、商品名「エピオールＥ－４００」）、ポリプロピレングリコールジグリシジルエーテル（日本油脂社製、商品名「エピオールＰ－２００」）、ソルビトールポリグリシジルエーテル（ナガセケムテックス社製、商品名「デナコール　ＥＸ－６１１」）、グリセロールポリグリシジルエーテル（ナガセケムテックス社製、商品名「デナコール　ＥＸ－３１４」）、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル（ナガセケムテックス社製、商品名「デナコール　ＥＸ－５１２」）、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、ｏ－フタル酸ジグリシジルエステル、トリグリシジル－トリス（２－ヒドロキシエチル）イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール－Ｓ－ジグリシジルエーテル、分子内にエポキシ基を２つ以上有するエポキシ系樹脂等が挙げられる。エポキシ系架橋剤の配合量は、所望とする粘着力に応じて、任意の適切な量に設定され得、アクリル系ポリマー１００重量部に対して、代表的には０．０１重量部～５０重量部であり、より好ましくは０．６重量部～１５重量部であり、さらに好ましくは２重量部～１３重量部であり、特に好ましくは３重量部～１０重量部である。このような範囲であれば、粘着剤層中の成分の残存カルボキシル基が少ない粘着シートを得ることができる。ここでの架橋剤の配合量とは、アクリル系ポリマーが架橋する前の架橋剤の含有量を意味する。 Examples of the epoxy-based cross-linking agent contained in the acrylic pressure-sensitive adhesive include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N- glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 1600"), neopentyl glycol diglycidyl ether ( Kyoeisha Chemical Co., Ltd., trade name "Epolite 1500NP"), ethylene glycol diglycidyl ether (Kyoeisha Chemical Co., Ltd., trade name "Epolite 40E"), propylene glycol diglycidyl ether (Kyoeisha Chemical Co., Ltd., trade name "Epolite 70P") , polyethylene glycol diglycidyl ether (manufactured by NOF Corporation, trade name "Epiol E-400"), polypropylene glycol diglycidyl ether (manufactured by NOF Corporation, trade name "Epiol P-200"), sorbitol polyglycidyl ether (Nagasechem Tex Corporation, trade name "Denacol EX-611"), glycerol polyglycidyl ether (Nagase ChemteX Corporation, trade name "Denacol EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (Nagase ChemteX Corporation) company, product name "Denacol EX-512"), sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, o-diglycidyl phthalate, triglycidyl-tris(2-hydroxyethyl) isocyanate Examples include nurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. The amount of the epoxy-based cross-linking agent can be set to any appropriate amount depending on the desired adhesive strength. parts, more preferably 0.6 to 15 parts by weight, still more preferably 2 to 13 parts by weight, and particularly preferably 3 to 10 parts by weight. With such a range, it is possible to obtain a pressure-sensitive adhesive sheet with few residual carboxyl groups in the components of the pressure-sensitive adhesive layer. The blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
Ｃ．基材
　上記基材としては、例えば、樹脂シート、不織布、紙、金属箔、織布、ゴムシート、発泡シート、これらの積層体（特に、樹脂シートを含む積層体）等が挙げられる。樹脂シートを構成する樹脂としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体（ＥＶＡ）、ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）、ポリイミド（ＰＩ）、ポリ塩化ビニル（ＰＶＣ）、ポリフェニレンサルファイド（ＰＰＳ）、フッ素系樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）等が挙げられる。不織布としては、マニラ麻を含む不織布等の耐熱性を有する天然繊維による不織布；ポリプロピレン樹脂不織布、ポリエチレン樹脂不織布、エステル系樹脂不織布等の合成樹脂不織布等が挙げられる。金属箔としては、銅箔、ステンレス箔、アルミニウム箔等が挙げられる。紙としては、和紙、クラフト紙等が挙げられる。 C. Substrate Examples of the substrate include resin sheets, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foam sheets, laminates thereof (especially laminates containing resin sheets), and the like. Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene- Vinyl acetate copolymer (EVA), polyamide (nylon), wholly aromatic polyamide (aramid), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine resin, polyether ether ketone (PEEK) ) and the like. Examples of nonwoven fabrics include nonwoven fabrics made of heat-resistant natural fibers such as nonwoven fabrics containing manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics and ester resin nonwoven fabrics. Examples of metal foil include copper foil, stainless steel foil, and aluminum foil. Examples of paper include Japanese paper and kraft paper.
　１つの実施形態においては、ガラス転移温度（Ｔｇ）が６０℃～４５０℃（好ましくは、６５℃～４３０℃、より好ましくは８０℃～４２０℃）の樹脂から構成される樹脂シートが、基材として好ましく用いられる。このような樹脂シートを用いれば、加熱時（例えば、封止工程時の加熱）においても、基材を構成する分子の分子運動が激しくなりすぎず、水分の放散性が適度に抑制され得る。また、柔軟性に優れた粘着シートを得ることができる。このような樹脂シートを構成する樹脂としては、例えば、ポリエチレンテレフタレート、ポリイミド、ポリエチレンナフタレート等が挙げられる。 In one embodiment, the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 60° C. to 450° C. (preferably 65° C. to 430° C., more preferably 80° C. to 420° C.). Preferably used as. When such a resin sheet is used, even during heating (for example, heating during the sealing process), the molecular motion of the molecules constituting the base material does not become too vigorous, and the diffusion of moisture can be moderately suppressed. Also, a pressure-sensitive adhesive sheet having excellent flexibility can be obtained. Examples of resins forming such a resin sheet include polyethylene terephthalate, polyimide, and polyethylene naphthalate.
　１つの実施形態においては、上記基材は、芳香族性ポリイミド系樹脂から構成される。芳香族性ポリイミド系樹脂はイミド基が極性官能基であること、また、アミノ基の電子供与性とカルボニル基の電子吸引性により、水分率を調整しやすく、樹脂封止工程に必要な高い加工温度の幅広い領域で蒸気放散能を維持できるため好ましい。また、芳香族官能基(フェニル基、フェニレン基、ナフチル基、ナフチレン基など)を多く含むためポリマー分子の分子運動性が低く、テープ表面形状が平滑であることを維持する。このことから樹脂流動も一様に起こりやすく、このため本発明の課題解決にとても好ましい。芳香族性ポリイミドとしては、主鎖骨格にエーテル結合を有するエーテル系ポリフタルイミド類、同ケトン結合を有すケトン系ポリフタルイミド類、同ビスフェノール由来の骨格を有するビスフェノール系ポリフタルイミド類等が挙げられる。宇部興産社製「ユーピレックス」、三井化学社製「ＬＡＲＣ－ＴＰＩ」、ＧＥ社製「ウルテム」等の市販品を用いてもよい。特に主鎖骨格にエーテル結合を有するエーテル系ピロメリトイミドは、繰り返しモノマー残基の重量当たりのイミド基存在数が大きくなるので、好ましく用いられ得る。このような樹脂としては、デュポン社製「カプトン」、カネカ社製「アピカル」、三井化学社製「オーラム」等の市販品を用いてもよい。 In one embodiment, the base material is composed of an aromatic polyimide resin. Aromatic polyimide resins have a polar functional imide group, and the electron-donating properties of the amino group and the electron-withdrawing property of the carbonyl group make it easy to adjust the moisture content, and the high degree of processing required in the resin encapsulation process. It is preferable because it can maintain the vapor dissipation ability over a wide temperature range. In addition, since it contains many aromatic functional groups (phenyl group, phenylene group, naphthyl group, naphthylene group, etc.), the molecular mobility of the polymer molecules is low, and the surface shape of the tape is maintained smooth. For this reason, resin flow is likely to occur uniformly, which is very favorable for solving the problems of the present invention. Examples of aromatic polyimides include ether-based polyphthalimides having an ether bond in the main chain skeleton, ketone-based polyphthalimides having a ketone bond in the main chain skeleton, and bisphenol-based polyphthalimides having a skeleton derived from the same bisphenol. Commercially available products such as “Upilex” manufactured by Ube Industries, “LARC-TPI” manufactured by Mitsui Chemicals, Inc., and “Ultem” manufactured by GE may also be used. In particular, ether-based pyromellitimides having an ether bond in the main chain skeleton can be preferably used because the number of imide groups present per weight of repeating monomer residues increases. As such a resin, commercially available products such as "Kapton" manufactured by DuPont, "Apical" manufactured by Kaneka, and "Aurum" manufactured by Mitsui Chemicals, Inc. may be used.
　上記基材の厚さは、所望とする強度または柔軟性、ならびに使用目的等に応じて、任意の適切な厚みに設定され得る。基材の厚みは、好ましくは１０００μｍ以下であり、より好ましくは２５μｍ～１０００μｍであり、さらに好ましくは４０μｍ～５００μｍである。 The thickness of the base material can be set to any appropriate thickness depending on the desired strength or flexibility, purpose of use, and the like. The thickness of the substrate is preferably 1000 μm or less, more preferably 25 μm to 1000 μm, still more preferably 40 μm to 500 μm.
　上記基材は、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理等が挙げられる。 The base material may be surface-treated. Examples of surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, and coating treatment with a primer.
　上記有機コーティング材料としては、例えば、プラスチックハードコート材料ＩＩ（ＣＭＣ出版、（２００４））に記載される材料が挙げられる。好ましくはウレタン系ポリマー、より好ましくはポリアクリルウレタン、ポリエステルウレタンまたはこれらの前駆体が用いられる。基材への塗工・塗布が簡便であり、かつ、工業的に多種のものが選択でき安価に入手できるからである。該ウレタン系ポリマーは、例えば、イソシアナートモノマーとアルコール性水酸基含有モノマー（例えば、水酸基含有アクリル化合物又は水酸基含有エステル化合物）との反応混合物からなるポリマーである。有機コーティング材料は、任意の添加剤として、ポリアミンなどの鎖延長剤、老化防止剤、酸化安定剤等を含んでいてもよい。有機コーティング層の厚みは特に限定されないが、例えば、０．１μｍ～１０μｍ程度が適しており、０．１μｍ～５μｍ程度が好ましく、０．５μｍ～５μｍ程度がより好ましい。 Examples of the organic coating material include materials described in Plastic Hard Coat Materials II (CMC Publishing, (2004)). Urethane-based polymers are preferably used, more preferably polyacrylurethane, polyesterurethane, or precursors thereof. This is because coating and applying to the base material is simple, and industrially, a wide variety of materials can be selected and are available at low cost. The urethane-based polymer is, for example, a polymer composed of a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound). The organic coating material may contain optional additives such as chain extenders such as polyamines, anti-aging agents, oxidation stabilizers, and the like. The thickness of the organic coating layer is not particularly limited.
Ｄ．第２の粘着剤層
　上記第２の粘着剤層は、任意の適切な粘着剤から構成される粘着剤層であり得る。１つの実施形態においては、上記のとおり、第２の粘着剤層は、熱膨張性微小球をさらに含む。 D. Second Adhesive Layer The second adhesive layer may be an adhesive layer composed of any appropriate adhesive. In one embodiment, the second pressure-sensitive adhesive layer further contains thermally expandable microspheres, as described above.
　上記第２の粘着剤層に含まれる粘着剤は、硬化型粘着剤（例えば、活性エネルギー線硬化型粘着剤）であってもよく、感圧型粘着剤であってもよい。感圧型粘着剤としては、例えば、アクリル系粘着剤、ゴム系粘着剤等が挙げられる。第２の粘着剤層に含まれる粘着剤の詳細は、例えば特開２０１８－００９０５０号公報の記載を参照することができる。当該公報は、その全体の記載が本明細書に参考として援用される。１つの実施形態においては、第２の粘着剤層に含まれる粘着剤は、上記Ｂ項で説明したアクリル系粘着剤であり得る。１つの実施形態においては、上記Ｂ項で説明したように、アクリル系粘着剤に含まれるアクリル系ポリマー（プレポリマー）は、水酸基含有モノマー由来の構成単位を含む。水酸基含有モノマー由来の構成単位の含有量は、アクリル系ポリマーを構成する全構成単位１００重量部に対して、好ましくは０．１重量部～２０重量部であり、より好ましくは０．１重量部～１０重量部である。より好ましくは０．５重量部～１０重量部である。 The adhesive contained in the second adhesive layer may be a curable adhesive (for example, an active energy ray-curable adhesive) or a pressure-sensitive adhesive. Examples of pressure-sensitive adhesives include acrylic adhesives and rubber adhesives. Details of the adhesive contained in the second adhesive layer can be referred to, for example, the description of JP-A-2018-009050. The publication is incorporated herein by reference in its entirety. In one embodiment, the adhesive contained in the second adhesive layer may be the acrylic adhesive described in section B above. In one embodiment, as described in section B above, the acrylic polymer (prepolymer) contained in the acrylic pressure-sensitive adhesive contains a structural unit derived from a hydroxyl group-containing monomer. The content of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.1 part by weight, with respect to 100 parts by weight of all the structural units constituting the acrylic polymer. ~10 parts by weight. It is more preferably 0.5 to 10 parts by weight.
　上記熱膨張性微小球としては、加熱により膨張または発泡し得る微小球である限りにおいて、任意の適切な熱膨張性微小球を用いることができる。上記熱膨張性微小球としては、例えば、加熱により容易に膨張する物質（有機溶媒等の揮発性物質）を、弾性を有する殻内に内包させた微小球が用いられ得る。このような熱膨張性微小球は、任意の適切な方法、例えば、コアセルベーション法、界面重合法等により製造できる。 Any appropriate heat-expandable microspheres can be used as the heat-expandable microspheres as long as they are microspheres that can be expanded or foamed by heating. As the heat-expandable microspheres, for example, microspheres in which a substance (a volatile substance such as an organic solvent) that is easily expanded by heating is encapsulated in an elastic shell can be used. Such heat-expandable microspheres can be produced by any appropriate method such as coacervation, interfacial polymerization, and the like.
　加熱により容易に膨張する物質としては、例えば、プロパン、プロピレン、ブテン、ノルマルブタン、イソブタン、イソペンタン、ネオペンタン、ノルマルペンタン、ノルマルヘキサン、イソヘキサン、ヘプタン、オクタン、石油エーテル、メタンのハロゲン化物、テトラアルキルシラン等の低沸点液体；熱分解によりガス化するアゾジカルボンアミド；等が挙げられる。 Substances that easily expand when heated include, for example, propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, normal hexane, isohexane, heptane, octane, petroleum ether, methane halides, and tetraalkylsilanes. low boiling point liquid such as; azodicarbonamide gasified by thermal decomposition; and the like.
　上記殻を構成する物質としては、例えば、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エトキシアクリロニトリル、フマロニトリル等のニトリル単量体；アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、シトラコン酸等のカルボン酸単量体；塩化ビニリデン；酢酸ビニル；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、β－カルボキシエチルアクリレート等の（メタ）アクリル酸エステル；スチレン、α－メチルスチレン、クロロスチレン等のスチレンモノマー；アクリルアミド、置換アクリルアミド、メタクリルアミド、置換メタクリルアミド等のアミド単量体；等から構成されるポリマーが挙げられる。これらの単量体から構成されるポリマーは、ホモポリマーであってもよく、コポリマーであってもよい。該コポリマーとしては、例えば、塩化ビニリデン‐メタクリル酸メチル－アクリロニトリル共重合体、メタクリル酸メチル－アクリロニトリル－メタクリロニトリル共重合体、メタクリル酸メチル－アクリロニトリル共重合体、アクリロニトリル－メタクリロニトリル－イタコン酸共重合体等が挙げられる。 Examples of substances constituting the shell include nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Carboxylic acid monomers such as citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (Meth)acrylic acid esters such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, β-carboxyethyl acrylate; styrene monomers such as styrene, α-methylstyrene, chlorostyrene; acrylamide, substituted acrylamide , methacrylamide, substituted methacrylamide, and other amide monomers; A polymer composed of these monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, acrylonitrile-methacrylonitrile-itaconic acid copolymer, A polymer etc. are mentioned.
　上記殻を構成するポリマー中、カルボキシル基含有モノマー由来の構成単位は、殻を構成するポリマー１００重量部に対して、好ましくは８０重量部以下であり、より好ましくは７０重量部以下である。このような範囲であれば、含水率が適度に調整された第２の粘着剤層を形成することができる。 In the polymer constituting the shell, the structural unit derived from the carboxyl group-containing monomer is preferably 80 parts by weight or less, more preferably 70 parts by weight or less, relative to 100 parts by weight of the polymer constituting the shell. Within such a range, it is possible to form a second pressure-sensitive adhesive layer with a moderately adjusted water content.
　熱膨張性微小球を構成する「加熱により容易に膨張する物質」および「殻」の詳細は、例えば、特開２０１８－１４１０８６号公報にも記載される。当該文献は、本明細書に参考として援用される。 Details of the "substance that easily expands when heated" and the "shell" that constitute the thermally expandable microspheres are also described in, for example, Japanese Patent Application Laid-Open No. 2018-141086. The document is incorporated herein by reference.
　上記熱膨張性微小球として、無機系発泡剤または有機系発泡剤を用いてもよい。無機系発泡剤としては、例えば、炭酸アンモニウム、炭酸水素アンモニウム、炭酸水素ナトリウム、亜硝酸アンモニウム、水酸化ホウ素ナトリウム、各種アジド類等が挙げられる。また、有機系発泡剤としては、例えば、トリクロロモノフルオロメタン、ジクロロモノフルオロメタン等の塩フッ化アルカン系化合物；アゾビスイソブチロニトリル、アゾジカルボンアミド、バリウムアゾジカルボキシレート等のアゾ系化合物；パラトルエンスルホニルヒドラジド、ジフェニルスルホン－３，３´－ジスルホニルヒドラジド、４，４´－オキシビス（ベンゼンスルホニルヒドラジド）、アリルビス（スルホニルヒドラジド）等のヒドラジン系化合物；ｐ－トルイレンスルホニルセミカルバジド、４，４´－オキシビス（ベンゼンスルホニルセミカルバジド）等のセミカルバジド系化合物；５－モルホリル－１，２，３，４－チアトリアゾール等のトリアゾール系化合物；Ｎ，Ｎ´－ジニトロソペンタメチレンテトラミン、Ｎ，Ｎ´－ジメチル－Ｎ，Ｎ´－ジニトロソテレフタルアミド；等のＮ－ニトロソ系化合物などが挙げられる。 An inorganic foaming agent or an organic foaming agent may be used as the thermally expandable microspheres. Examples of inorganic foaming agents include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, and various azides. Examples of organic foaming agents include chlorofluoroalkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; and azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate. hydrazine compounds such as paratoluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide, 4,4′-oxybis(benzenesulfonyl hydrazide), and allylbis(sulfonyl hydrazide); p-toluylenesulfonyl semicarbazide, 4, Semicarbazide compounds such as 4'-oxybis(benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; N,N'-dinitrosopentamethylenetetramine, N,N' -dimethyl-N,N'-dinitrosoterephthalamide; and other N-nitroso compounds.
　上記熱膨張性微小球は市販品を用いてもよい。市販品の熱膨張性微小球の具体例としては、松本油脂製薬社製の商品名「マツモトマイクロスフェアー」（グレード：Ｆ－３０、Ｆ－３０Ｄ、Ｆ－３６Ｄ、Ｆ－３６ＬＶ、Ｆ－５０、Ｆ－５０Ｄ、Ｆ－６５、Ｆ－６５Ｄ、ＦＮ－１００ＳＳ、ＦＮ－１００ＳＳＤ、ＦＮ－１８０ＳＳ、ＦＮ－１８０ＳＳＤ、Ｆ－１９０Ｄ、Ｆ－２６０Ｄ、Ｆ－２８００Ｄ）、日本フィライト社製の商品名「エクスパンセル」（グレード：０５３－４０、０３１－４０、９２０－４０、９０９－８０、９３０－１２０）、呉羽化学工業社製「ダイフォーム」（グレード：Ｈ７５０、Ｈ８５０、Ｈ１１００、Ｓ２３２０Ｄ、Ｓ２６４０Ｄ、Ｍ３３０、Ｍ４３０、Ｍ５２０）、積水化学工業社製「アドバンセル」（グレード：ＥＭＬ１０１、ＥＭＨ２０４、ＥＨＭ３０１、ＥＨＭ３０２、ＥＨＭ３０３、ＥＭ３０４、ＥＨＭ４０１、ＥＭ４０３、ＥＭ５０１）等が挙げられる。 Commercially available products may be used as the thermally expandable microspheres. Specific examples of commercially available heat-expandable microspheres include Matsumoto Yushi Seiyaku's trade name "Matsumoto Microspheres" (grades: F-30, F-30D, F-36D, F-36LV, F-50 , F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), a product name manufactured by Nippon Philite Co., Ltd. " Expancel” (Grade: 053-40, 031-40, 920-40, 909-80, 930-120), Kureha Chemical Industry Co., Ltd. “Daiform” (Grade: H750, H850, H1100, S2320D, S2640D, M330, M430, M520), "Advancel" manufactured by Sekisui Chemical Co., Ltd. (grades: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501).
　上記熱膨張性微小球の加熱前の平均粒子径（数基準）は、好ましくは１μｍ～４０μｍであり、より好ましくは５μｍ～４０μｍであり、さらに好ましくは１０μｍ～４０μｍである。上記の粒子径と平均粒子径はレーザー散乱法における粒度分布測定法によって求められる値である。 The average particle size (number basis) of the heat-expandable microspheres before heating is preferably 1 μm to 40 μm, more preferably 5 μm to 40 μm, still more preferably 10 μm to 40 μm. The above particle size and average particle size are values determined by a particle size distribution measurement method in a laser scattering method.
　上記熱膨張性微小球は、体積膨張率が好ましくは５倍以上、より好ましくは７倍以上、さらに好ましくは１０倍以上となるまで破裂しない適度な強度を有することが好ましい。このような熱膨張性微小球を用いる場合、加熱処理により粘着力を効率よく低下させることができる。 It is preferable that the thermally expandable microspheres have an appropriate strength such that they do not burst until the volume expansion coefficient is preferably 5 times or more, more preferably 7 times or more, and still more preferably 10 times or more. When such heat-expandable microspheres are used, the adhesive strength can be efficiently reduced by heat treatment.
　上記第２の粘着剤層における熱膨張性微小球の含有割合は、所望とする粘着力の低下性等に応じて適切に設定し得る。熱膨張性微小球の含有割合は、第２の粘着剤層を形成するベースポリマー１００重量部に対して、例えば１重量部～１５０重量部であり、好ましくは１０重量部～１３０重量部であり、さらに好ましくは２５重量部～１００重量部である。 The content ratio of the heat-expandable microspheres in the second adhesive layer can be appropriately set according to the desired decrease in adhesive force. The content of the heat-expandable microspheres is, for example, 1 to 150 parts by weight, preferably 10 to 130 parts by weight, with respect to 100 parts by weight of the base polymer forming the second pressure-sensitive adhesive layer. , more preferably 25 to 100 parts by weight.
　熱膨張性微小球が膨張する前（すなわち、加熱前）の第２の粘着剤層の算術表面粗さＲａは、好ましくは５００ｎｍ以下であり、より好ましくは４００ｎｍ以下であり、さらに好ましくは３００ｎｍ以下である。このような範囲であれば、被着体に対する密着性に優れる粘着シートを得ることができる。 The arithmetic surface roughness Ra of the second adhesive layer before the thermally expandable microspheres are expanded (that is, before heating) is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. is. Within such a range, it is possible to obtain a pressure-sensitive adhesive sheet having excellent adhesion to an adherend.
（下塗り層）
　上記粘着シートが、第２の粘着剤層を備える場合、基材と第２の粘着層との間には下塗り層が設けられていてもよい。上記下塗り層は、任意の適切な粘着剤を含む。下塗り層を構成する粘着剤としては、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤等が挙げられる。なかでも、アクリル系粘着剤が好ましく用いられ得る。また、粘着剤として、活性エネルギー線硬化型のアクリル系粘着剤(以下、活性エネルギー線硬化型粘着剤)を用いてもよい。好ましくは、下塗り層を構成する粘着剤として、上記第２の粘着剤層を構成する粘着剤と同様の粘着剤が用いられる。 (Undercoat layer)
When the pressure-sensitive adhesive sheet has a second pressure-sensitive adhesive layer, an undercoat layer may be provided between the substrate and the second pressure-sensitive adhesive layer. The undercoat layer contains any suitable adhesive. Examples of the adhesive that constitutes the undercoat layer include acrylic adhesives, rubber adhesives, silicone adhesives, and the like. Among them, an acrylic pressure-sensitive adhesive can be preferably used. As the adhesive, an active energy ray-curable acrylic adhesive (hereinafter referred to as an active energy ray-curable adhesive) may be used. Preferably, the same pressure-sensitive adhesive as the pressure-sensitive adhesive forming the second pressure-sensitive adhesive layer is used as the pressure-sensitive adhesive forming the undercoat layer.
　上記下塗り層の厚みは、好ましくは１μｍ～４０μｍであり、より好ましくは５μｍ～３５μｍであり、さらに好ましくは１０μｍ～３０μｍである。 The thickness of the undercoat layer is preferably 1 μm to 40 μm, more preferably 5 μm to 35 μm, still more preferably 10 μm to 30 μm.
Ｅ．粘着シートの製造方法
　本発明の粘着シートは、任意の適切な方法により製造することができる。本発明の粘着シートを得る方法としては、例えば、基材上に直接、粘着剤（例えば、アクリル系粘着剤）を含む組成物を塗工する方法、または任意の適切な基体上に粘着剤を含む組成物を塗工し形成された塗工層を基材に転写する方法等が挙げられる。アクリル系粘着剤を含む組成物は、任意の適切な溶媒を含み得る。 E. Production Method of Adhesive Sheet The adhesive sheet of the present invention can be produced by any appropriate method. Methods for obtaining the pressure-sensitive adhesive sheet of the present invention include, for example, a method of directly coating a substrate with a composition containing a pressure-sensitive adhesive (for example, an acrylic pressure-sensitive adhesive), or a method of applying a pressure-sensitive adhesive onto any appropriate substrate. Examples include a method of transferring a coating layer formed by coating a composition containing the composition to a substrate. A composition containing an acrylic pressure-sensitive adhesive may contain any suitable solvent.
　上記粘着剤を含む組成物は、任意の適切な溶剤を含む。当該溶剤中の水分率は、好ましくは０．００３重量％～０．３重量％である。 The composition containing the adhesive contains any suitable solvent. The water content in the solvent is preferably 0.003% to 0.3% by weight.
　熱膨張性微小球を含む粘着剤層（第２の粘着剤層）を形成する場合、熱膨張性微小球と粘着剤と任意の適切な溶媒とを含む組成物を基材に塗工して、該粘着剤層を形成することができる。あるいは、粘着剤塗工層に、熱膨張性微小球を振りかけた後、ラミネーター等を用いて、該熱膨張性微小球を粘着剤中に埋め込んで、熱膨張性微小球を含む粘着剤層を形成してもよい。 When forming a pressure-sensitive adhesive layer (second pressure-sensitive adhesive layer) containing heat-expandable microspheres, a composition containing heat-expandable microspheres, a pressure-sensitive adhesive, and any appropriate solvent is applied to a substrate. , the pressure-sensitive adhesive layer can be formed. Alternatively, after sprinkling heat-expandable microspheres on the adhesive coating layer, the heat-expandable microspheres are embedded in the adhesive using a laminator or the like to form an adhesive layer containing the heat-expandable microspheres. may be formed.
　上記粘着剤および各組成物の塗工方法としては、任意の適切な塗工方法が採用され得る。例えば、塗布した後に乾燥して各層を形成することができる。塗布方法としては、例えば、マルチコーター、ダイコーター、グラビアコーター、アプリケーター等を用いた塗布方法が挙げられる。乾燥方法としては、例えば、自然乾燥、加熱乾燥等が挙げられる。加熱乾燥する場合の加熱温度は、乾燥対象となる物質の特性に応じて、任意の適切な温度に設定され得る。 Any appropriate coating method can be adopted as the coating method for the adhesive and each composition. For example, each layer can be formed by coating and then drying. Examples of the coating method include coating methods using a multi-coater, die coater, gravure coater, applicator, and the like. Drying methods include, for example, natural drying and heat drying. The heating temperature for drying by heating can be set to any suitable temperature depending on the properties of the substance to be dried.
　１つの実施形態においては、基材上に粘着剤を含む組成物の塗工層を形成した後、当該塗工層面上にライナーを配置して積層体（ライナー付粘着シート前駆体）を得、当該積層体（ライナー付粘着シート前駆体）を所定の加湿熱時間（例えば、２時間～７日）、温度および湿度が管理された環境下に置く工程（加湿熱工程）を経て、粘着シートを得ることができる。加湿熱工程を行うことにより、粘着シートの含水率を好ましく調整することができる。当該工程における温度は、例えば、４０℃～１２０℃である。また、湿度は、例えば、１％ＲＨ～１００％ＲＨである。なお、粘着シートが両面粘着シートである場合、粘着剤の塗工層面両面（すなわち、粘着剤層を形成する粘着剤の塗工層面、および、第２の粘着剤層を形成する粘着剤の塗工層面）にライナー（第１のライナーおよび第２のライナー）を配置して得られた積層体が、上記加湿熱工程に供され得る。ライナーの詳細は後述する。 In one embodiment, after forming a coating layer of a composition containing an adhesive on a substrate, a liner is placed on the surface of the coating layer to obtain a laminate (liner-attached pressure-sensitive adhesive sheet precursor), The laminate (liner-attached pressure-sensitive adhesive sheet precursor) is subjected to a step of placing the laminate (liner-attached pressure-sensitive adhesive sheet precursor) in an environment in which the temperature and humidity are controlled for a predetermined moist heat time (for example, 2 hours to 7 days) (humidification heat step), and the pressure-sensitive adhesive sheet is removed. Obtainable. The moisture content of the pressure-sensitive adhesive sheet can be preferably adjusted by performing the moist heat step. The temperature in this step is, for example, 40°C to 120°C. Also, the humidity is, for example, 1% RH to 100% RH. When the adhesive sheet is a double-sided adhesive sheet, both sides of the adhesive coating layer surface (that is, the adhesive coating layer surface forming the adhesive layer and the adhesive coating layer forming the second adhesive layer) A laminate obtained by arranging the liners (the first liner and the second liner) on the layer surface) can be subjected to the humidification heat step. Details of the liner will be described later.
　加湿熱工程における、加湿熱時間と温度と湿度との積は、好ましくは１００～３０００００℃・ＲＨ％・ｈであり、より好ましくは１８０～２６５０００℃・ＲＨ％・ｈである。このような範囲であれば、粘着シートの含水率が好ましく調整することができる。 In the humidification heat step, the product of the heat humidification time, the temperature and the humidity is preferably 100 to 300000°C.RH%h, more preferably 180 to 265000°C.RH%h. Within such a range, the moisture content of the pressure-sensitive adhesive sheet can be preferably adjusted.
Ｆ.ライナー付両面粘着シート
　図３は、本発明の１つの実施形態によるライナー付両面粘着シートの概略断面図である。ライナー付両面粘着シート１１０は、両面粘着シート２００と、粘着シート２００の一方の面に、剥離可能に直接配置された第１のライナー４０と、両面粘着シート２００の他方の面に、剥離可能に直接配置された第２のライナー５０とを備える。第１のライナー４０および第２のライナー５０を配置することにより、粘着剤層を汚染などから保護したり、ロール状またはシート状の両面粘着シートブロッキングを防止することができる。代表的には、上記第１のライナーおよび第２のライナーは、ライナー基材と、ライナー基材の少なくとも片面に配置された剥離処理層とを備える。第１のライナーおよび第２のライナーは、上記剥離処理層が両面粘着シート側となるようにして配置される。 F. Liner-attached double-sided pressure-sensitive adhesive sheet FIG. 3 is a schematic cross-sectional view of a liner-attached double-sided pressure-sensitive adhesive sheet according to one embodiment of the present invention. The liner-equipped double-sided pressure-sensitive adhesive sheet 110 comprises a double-sided pressure-sensitive adhesive sheet 200, a first liner 40 releasably arranged directly on one side of the pressure-sensitive adhesive sheet 200, and a releasable first liner 40 on the other side of the double-sided pressure-sensitive adhesive sheet 200. and a directly disposed second liner 50 . By arranging the first liner 40 and the second liner 50, it is possible to protect the pressure-sensitive adhesive layer from contamination and prevent blocking of the double-sided pressure-sensitive adhesive sheet of the roll or sheet. Typically, the first liner and the second liner comprise a liner substrate and a release treatment layer disposed on at least one side of the liner substrate. The first liner and the second liner are arranged so that the release treated layer is on the double-sided pressure-sensitive adhesive sheet side.
　両面粘着シート２００は、上記の粘着シート、すなわち、粘着剤層２０と、基材１０と、第２の粘着剤層３０とを備える粘着シートであり得る。 The double-sided pressure-sensitive adhesive sheet 200 may be the pressure-sensitive adhesive sheet described above, that is, a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer 20, the base material 10, and the second pressure-sensitive adhesive layer 30.
　第１のライナー２０と第２のライナー３０とは異質であり得る。「異質」であるとは、例えば、厚みが異なる（例えば、厚みの差の絶対値が１μｍ以上（好ましくは５μｍ以上、より好ましくは１０μｍ以上））、色が異なる、構成材料が異なる等の態様であり得る。なお、第１のライナー２０と第２のライナー３０との厚みの差は、７０μｍ以下であることが好ましく、５０μｍ以下であることがより好ましく、２５μｍ以下であることがさらに好ましい。 The first liner 20 and the second liner 30 may be heterogeneous. “Heterogeneous” means, for example, different thicknesses (for example, the absolute value of the difference in thickness is 1 μm or more (preferably 5 μm or more, more preferably 10 μm or more)), different colors, different constituent materials, etc. can be The difference in thickness between the first liner 20 and the second liner 30 is preferably 70 μm or less, more preferably 50 μm or less, even more preferably 25 μm or less.
　１つの実施形態においては、上記ライナー付両面粘着シートを使用する際、第１のライナーが先に剥離される。より詳細には、上記ライナー付両面粘着シートは、第１のライナーを先に剥離して、露出した粘着面（例えば、第１の粘着剤層表面）に被着体（例えば、電子部品）を貼着し、その後、第２のライナーを剥離して、第２の粘着剤層表面を別の被着体（例えば、台座）にて貼着するようにして用いられ得る。このような実施形態においては、粘着シートを介して、台座に被着体（例えば、電子部品）を仮固定し；当該被着体を所定の加工に供し；その後、加熱することにより第２の粘着剤層の粘着力を低下させて、被着体付の粘着シートが台座から剥離される。上記のように、第１のライナーと第２のライナーとが異質であれば、所定のタイミングで剥離すべきライナーの識別が容易となる。 In one embodiment, when using the liner-attached double-sided pressure-sensitive adhesive sheet, the first liner is removed first. More specifically, the liner-attached double-sided pressure-sensitive adhesive sheet is prepared by first peeling off the first liner and attaching an adherend (for example, an electronic component) to the exposed pressure-sensitive adhesive surface (for example, the surface of the first pressure-sensitive adhesive layer). It can be used by sticking, then peeling off the second liner, and sticking the surface of the second pressure-sensitive adhesive layer on another adherend (for example, a pedestal). In such an embodiment, the adherend (e.g., electronic component) is temporarily fixed to the pedestal via the adhesive sheet; the adherend is subjected to a predetermined process; By reducing the adhesive strength of the adhesive layer, the adhesive sheet with the adherend is peeled off from the base. As described above, if the first liner and the second liner are different, it becomes easy to identify the liner to be peeled off at a predetermined timing.
　第１のライナーの両面粘着シートに対する剥離力は、好ましくは０．００１Ｎ／５０ｍｍ～２Ｎ／５０ｍｍであり、より好ましくは０．０１Ｎ／５０ｍｍ～１．５Ｎ／５０ｍｍであり、さらに好ましくは０．０５Ｎ／５０ｍｍ～１Ｎ／５０ｍｍであり、特に好ましくは０．１Ｎ／５０ｍｍ～０．８Ｎ／５０ｍｍである。第１のライナーの両面粘着シートに対する剥離力（および、第２のライナーの両面粘着シートに対する剥離力）は、２３℃の環境下で、ライナー付両面粘着シートの両面粘着シートからライナーを剥離（剥離角度：１８０°、剥離速度（引張速度）：３００ｍｍ／ｍｉｎ）して測定される粘着力を意味する。ライナーの両面粘着シートに対する剥離力は、粘着剤層の組成、ライナーの種類、ライナーに施される表面処理等、任意の適切な方法により調整することができる。 The peel force of the first liner to the double-sided pressure-sensitive adhesive sheet is preferably 0.001N/50mm to 2N/50mm, more preferably 0.01N/50mm to 1.5N/50mm, and still more preferably 0.05N. /50 mm to 1 N/50 mm, particularly preferably 0.1 N/50 mm to 0.8 N/50 mm. The release force of the first liner to the double-sided PSA sheet (and the release force of the second liner to the double-sided PSA sheet) was determined by peeling the liner from the double-sided PSA sheet of the liner-attached double-sided PSA sheet in an environment of 23°C. angle: 180°, peeling speed (tensile speed): 300 mm/min. The release force of the liner to the double-sided PSA sheet can be adjusted by any appropriate method, such as the composition of the PSA layer, the type of liner, and the surface treatment applied to the liner.
　第２のライナーの両面粘着シートに対する剥離力は、好ましくは０．００１Ｎ／５０ｍｍ～２Ｎ／５０ｍｍであり、より好ましくは０．０１Ｎ／５０ｍｍ～１．５Ｎ／５０ｍｍであり、さらに好ましくは０．０５Ｎ／５０ｍｍ～１Ｎ／５０ｍｍであり、特に好ましくは０．１Ｎ／５０ｍｍ～０．８Ｎ／５０ｍｍである。 The peel force of the second liner to the double-sided pressure-sensitive adhesive sheet is preferably 0.001N/50mm to 2N/50mm, more preferably 0.01N/50mm to 1.5N/50mm, and still more preferably 0.05N. /50 mm to 1 N/50 mm, particularly preferably 0.1 N/50 mm to 0.8 N/50 mm.
　上記第１のライナーの厚みは、好ましくは５μｍ～２５０μｍであり、より好ましくは１０μｍ～２００μｍであり、さらに好ましくは、２０～１５０μｍ、最も好ましくは３０～１００μｍである。上記第２のライナーの厚みは、好ましくは５μｍ～２５０μｍであり、より好ましくは１０μｍ～２００μｍであり、さらに好ましくは、２０～１５０μｍ、最も好ましくは３０～１００μｍである。 The thickness of the first liner is preferably 5 μm to 250 μm, more preferably 10 μm to 200 μm, even more preferably 20 to 150 μm, most preferably 30 to 100 μm. The thickness of the second liner is preferably 5 μm to 250 μm, more preferably 10 μm to 200 μm, even more preferably 20 to 150 μm, most preferably 30 to 100 μm.
　上記ライナー基材は、任意の適切な材料から構成され得る。ライナー基材は、例えば、プラスチックフィルム、プラスチックシートの他、紙、布、不織布、金属箔、あるいはそれらのプラスチックラミネート体、プラスチック同士の積層体など、様々なシート状物を用いることが可能である。中でも、取り扱い性やコストの観点から、プラスチックフィルムやプラスチックシート（以下、プラスチックフィルムという）が最も好ましい。プラスチックフィルムの素材としては、強度、耐熱性などの観点から、必要に応じて選択できる。例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体（ＥＶＡ）等のα－オレフィンをモノマー成分とするオレフィン系樹脂；ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル；ポリ塩化ビニル（ＰＶＣ）；ポリフェニレンスルフィド（ＰＰＳ）；ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）等のアミド系樹脂；ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリイミド、ポリエーテルイミド、ポリスチレン、アクリル樹脂などが挙げられる。これらの素材は単独で又は２種以上組み合わせて使用することができる。また、プラスチックフィルムとしては、未延伸フィルム、１軸配向フィルム、２軸配向フィルムのいずれを用いてもよい。また、これらのフィルムは２層以上のフィルム層からなる積層フィルムでもよいし、取り扱い性の観点から、適宜、不活性粒子などの滑剤を添加したフィルムを用いてもよい。 The liner base material can be composed of any appropriate material. As the liner base material, for example, in addition to plastic films and plastic sheets, various sheet-like materials such as paper, cloth, nonwoven fabric, metal foil, plastic laminates thereof, and laminates of plastics can be used. . Among them, plastic films and plastic sheets (hereinafter referred to as plastic films) are most preferable from the viewpoint of handling and cost. The material for the plastic film can be selected according to need from the viewpoint of strength, heat resistance, and the like. For example, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and other α-olefin-based resins as monomer components; polyethylene terephthalate (PET), polyethylene Polyesters such as naphthalate (PEN) and polybutylene terephthalate (PBT); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); Ketone (PEEK), polyimide, polyetherimide, polystyrene, acrylic resin and the like. These materials can be used alone or in combination of two or more. Moreover, as the plastic film, any of an unstretched film, a uniaxially oriented film, and a biaxially oriented film may be used. In addition, these films may be laminated films composed of two or more film layers, or films to which a lubricant such as inert particles is appropriately added may be used from the viewpoint of handleability.
　上記剥離処理層を形成するための処理としては、任意の適切な処理が採用され得る。１つの実施形態においては、剥離処理層は、シリコーン処理層である。シリコーンとしては、主成分がジメチルポリシロキサン類で架橋（硬化）に必要な官能基を有する反応性シリコーン系化合物が好ましく用いられ得る。低分子状態でフィルムへの塗布が可能であり、塗布後に硬化させることで擦過などに強い剥離処理層にできるからである。反応性シリコーン化合物の官能基としては、例えば、ビニル基、エポキシ基、アルコキシ基、イソシアナト基等が挙げられる。 Any appropriate treatment can be adopted as the treatment for forming the release treatment layer. In one embodiment, the release treated layer is a silicone treated layer. As the silicone, a reactive silicone compound containing a dimethylpolysiloxane as a main component and having a functional group necessary for cross-linking (curing) can be preferably used. This is because it can be applied to a film in a low-molecular-weight state, and can be cured after application to form a release treated layer that is resistant to rubbing and the like. Examples of functional groups of reactive silicone compounds include vinyl groups, epoxy groups, alkoxy groups, isocyanato groups, and the like.
　シリコーン処理層は、例えば、上記反応性シリコーン系化合物を溶媒等に希釈して濃度調整を行い、グラビアコーター等で塗布・加熱することで形成される。加熱することにより、溶剤乾燥と硬化反応を促す。ここで硬化反応を促進する触媒を併用することが好ましい。触媒としては、例えば、白金、パラジウム、ロジウム、ジルコニウム、スズ等の金属錯体やアミンなどの有機塩基、酢酸などの有機酸が利用できる。 The silicone-treated layer is formed, for example, by diluting the above-mentioned reactive silicone compound with a solvent or the like to adjust the concentration, and applying and heating with a gravure coater or the like. Heating accelerates solvent drying and curing reactions. Here, it is preferable to use a catalyst that accelerates the curing reaction. Examples of catalysts that can be used include metal complexes such as platinum, palladium, rhodium, zirconium and tin, organic bases such as amines, and organic acids such as acetic acid.
　１つの実施形態においては、上記第１のライナーおよび／または第２のライナー（実質的には、各ライナーの剥離処理層）は、蛍光Ｘ線分析によるＳｉ－Ｋα線の強度が、０．０１～５００ｋｃｐｓ（好ましくは０．５～２５０ｋｃｐｓ、より好ましくは１．０～１５０ｋｃｐｓ、さらに好ましくは、１．０５～１００ｋｃｐｓ、特に好ましくは１０～３０ｋｃｐｓである）である。このような範囲であれば、粘着剤層からライナーを、小さい力で剥離することができる。また、ライナー／粘着剤層間との密着性が十分となり、ライナーの不要な剥離を防止することができる。上記蛍光Ｘ線分析によるＳｉ－Ｋα線の強度は、蛍光Ｘ線分析にて、剥離処理剤層と非剥離処理剤層のＳｉ強度をそれぞれ測定し、剥離処理剤層の強度から非剥離処理剤層の強度を減じて求めた値である。なお、強度は、例えば、剥離処理剤の塗布量、濃度、塗工速度、乾燥など剥離処理層形成条件を制御することで、調整が可能である。 In one embodiment, the first liner and/or the second liner (substantially the release treatment layer of each liner) has a Si—Kα ray intensity of 0.01 by fluorescent X-ray analysis. ~500 kcps (preferably 0.5 to 250 kcps, more preferably 1.0 to 150 kcps, still more preferably 1.05 to 100 kcps, particularly preferably 10 to 30 kcps). Within such a range, the liner can be peeled off from the pressure-sensitive adhesive layer with a small force. In addition, the adhesion between the liner and the adhesive layer is sufficient, and unnecessary peeling of the liner can be prevented. The intensity of the Si-Kα ray obtained by the above fluorescent X-ray analysis is obtained by measuring the Si intensity of the release agent layer and the non-release agent layer by the fluorescence X-ray analysis, and calculating the intensity of the release agent layer from the intensity of the non-release agent. It is a value obtained by reducing the strength of the layer. The strength can be adjusted by controlling the release treatment layer forming conditions such as the coating amount, concentration, coating speed and drying of the release treatment agent.
　１つの実施形態においては、上記第１のライナーと第２のライナーとは異なる色である。このように構成されたライナー付両面粘着シートは、例えば、いずれか一方のライナー（例えば、ライナー基材）を着色することにより、得ることができる。両ライナーを異なる色とすれば、ライナー付両面粘着シートの表裏が明確になり、剥離すべきライナーの識別が容易となる。 In one embodiment, the first liner and the second liner are different colors. A liner-equipped double-sided pressure-sensitive adhesive sheet having such a structure can be obtained, for example, by coloring one of the liners (for example, the liner substrate). If both liners are of different colors, the front and back of the liner-attached double-sided pressure-sensitive adhesive sheet can be clearly distinguished, making it easy to identify the liner to be peeled off.
Ｇ．用途
　上記粘着シートおよび上記ライナー付両面粘着シートは、任意の適切な部材（例えば、半導体チップ等の電子部品）を加工する際の仮固定用シートとして好ましく用いられ得る。１つの実施形態においては、上記ライナー付両面粘着シートは、ＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ／Ｓｃａｌｅ　Ｐａｃｋａｇｅ）またはＷＬＰ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ）の製造の際に、半導体チップを仮固定するシートとして用いられ得る。１つの実施形態においては、上記ライナー付両面粘着シートは、上記第２のライナーが先に剥離される工程を含む加工に用いられる。１つの実施形態においては、上記半導体チップは、上記封止樹脂により封止され、樹脂封止の際の加工温度は１００℃以上である。 G. Applications The pressure-sensitive adhesive sheet and the liner-attached double-sided pressure-sensitive adhesive sheet can be preferably used as a temporary fixing sheet when processing any appropriate member (for example, electronic parts such as semiconductor chips). In one embodiment, the liner-attached double-sided pressure-sensitive adhesive sheet can be used as a sheet for temporarily fixing a semiconductor chip during the manufacture of CSP (Chip Size/Scale Package) or WLP (Wafer Level Package). In one embodiment, the liner-attached double-sided pressure-sensitive adhesive sheet is used for processing including the step of peeling off the second liner first. In one embodiment, the semiconductor chip is sealed with the sealing resin, and the processing temperature during resin sealing is 100° C. or higher.
　１つの実施形態においては、上記ライナー付両面粘着シートは、ロール状である。 In one embodiment, the liner-attached double-sided pressure-sensitive adhesive sheet is roll-shaped.
　以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。実施例において、特に明記しない限り、「部」および「％」は重量基準である。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" are by weight unless otherwise specified.
［製造例１］アクリル系ポリマー１の調製
　トルエン中に、エチルアクリレート７０部と、ブチルアクリレート３部と、２－エチルヘキシルアクリレート３０部と、メチルメタクリレート５部と、２－ヒドロキシエチルアクリレート３．５部と、重合開始剤として過酸化ベンゾイル０．２部とを加えた後、加熱して、アクリル系ポリマー１のトルエン溶液を得た。なお、ここでのアクリル系ポリマー１を構成するモノマー由来の繰り返し単位のうち３．１重量％が活性水素基を有すモノマー由来の繰り返し単位である。 [Production Example 1] Preparation of acrylic polymer 1 In toluene, 70 parts of ethyl acrylate, 3 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 5 parts of methyl methacrylate, and 3.5 parts of 2-hydroxyethyl acrylate were mixed. and 0.2 parts of benzoyl peroxide as a polymerization initiator were added and then heated to obtain a toluene solution of acrylic polymer 1 . In addition, 3.1% by weight of the repeating units derived from the monomers constituting the acrylic polymer 1 here are repeating units derived from the monomer having an active hydrogen group.
［製造例２］アクリル系ポリマー２の調製
　トルエン中に、ブチルアクリレート５０部と、エチルアクリレート５０部と、アクリル酸０．５部と、２－ヒドロキシエチルアクリレート０．１部と、重合開始剤として過酸化ベンゾイル０．２部とを加えた後、加熱して、アクリル系ポリマー２のトルエン溶液を得た。なお、ここでのアクリル系ポリマー２を構成するモノマー由来の繰り返し単位のうち０．６０重量％が活性水素基を有すモノマー由来の繰り返し単位である。 [Production Example 2] Preparation of acrylic polymer 2 In toluene, 50 parts of butyl acrylate, 50 parts of ethyl acrylate, 0.5 parts of acrylic acid, and 0.1 parts of 2-hydroxyethyl acrylate are added as a polymerization initiator. After adding 0.2 part of benzoyl peroxide, the mixture was heated to obtain a toluene solution of acrylic polymer 2. In addition, 0.60% by weight of the repeating units derived from the monomers constituting the acrylic polymer 2 here are the repeating units derived from the monomer having an active hydrogen group.
［製造例３］アクリル系ポリマー３の調製
　酢酸エチル中に、メチルアクリレート７０部と、ブチルアクリレート２部と、２－エチルヘキシルアクリレート３０部と、アクリル酸１０部と、重合開始剤として過酸化ベンゾイル０．２部とを加えた後、加熱して、アクリル系ポリマー３の酢酸エチル溶液を得た。なお、ここでのアクリル系ポリマー３を構成するモノマー由来の繰り返し単位のうち８．９重量％が活性水素基を有すモノマー由来の繰り返し単位である。 [Production Example 3] Preparation of acrylic polymer 3 In ethyl acetate, 70 parts of methyl acrylate, 2 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, and 0 part of benzoyl peroxide as a polymerization initiator were added. .2 parts were added and heated to obtain an ethyl acetate solution of acrylic polymer 3 . In addition, 8.9% by weight of the repeating units derived from the monomers constituting the acrylic polymer 3 here are repeating units derived from the monomer having an active hydrogen group.
［実施例１］
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」１０重量部とを混合して、粘着剤を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤を塗工（塗布・乾燥）して、粘着剤層（厚み：１０μｍ）を形成した。
　基材（ポリエステルフィルム、東レ社製、商品名「ルミラーＳ１０」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー付粘着シート前駆体を得た。なお、ライナー（商品名「ＭＲＦ－３８」）のＳｉ－Ｋα線の強度は１８（ｋｃｐｓ）であった。Ｓｉ－Ｋα線の強度の測定方法は下記のとおりである。
　ライナー付粘着シート前駆体を、温度４０℃、湿度２０％の環境下で５日間放置して（加湿熱工程）、ライナー／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートを得た。
 
・ライナーのＳｉ－Ｋα線強度測定
　ライナー表面（剥離処理面）で無作為に抽出した１００点について、蛍光Ｘ線分析を行った。より詳細には、ライナーの粘接着剤層に接する面（剥離処理剤を塗布した面）のＳｉ－Ｋα線の強度（ｉ）および粘接着剤層と接しない面（剥離処理剤を塗布していない面）のＳｉ－Ｋα線の強度（ｉｉ）を測定し、（ｉ）の値から（ｉｉ）の値を引いた値の絶対値を求め、当該値の１００点測定の平均値をライナーのＳｉ－Ｋα線強度とした。
　なお、Ｓｉ－Ｋα線の強度とは下記装置での測定で波長７．１２５オングストロームにおける強度である。
　装置　　　：　Ｒｉｇａｋｕ製　ＺＳＸ１００ｅ
　分析面積　：　３０ｍｍφ
　分析元素　：　Ｓｉ　
　分析結晶　：　ＲＸ４　
　出力　　　：　５０ｋＶ、７０ｍＡ [Example 1]
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ” and 10 parts by weight to prepare an adhesive.
The above-mentioned adhesive is applied (applied and dried) to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”), and the adhesive is A layer (thickness: 10 μm) was formed.
The liner with the pressure-sensitive adhesive layer was attached to a base material (polyester film, trade name “Lumirror S10” manufactured by Toray Industries, Inc., thickness: 50 μm) to obtain a liner-attached pressure-sensitive adhesive sheet precursor. The Si—Kα ray intensity of the liner (trade name “MRF-38”) was 18 (kcps). The method for measuring the intensity of the Si—Kα ray is as follows.
The liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand for 5 days in an environment with a temperature of 40° C. and a humidity of 20% (humidification heat step) to obtain a liner-attached pressure-sensitive adhesive sheet consisting of a liner/adhesive layer (first pressure-sensitive adhesive layer)/substrate. A sticky sheet was obtained.

Measurement of Si—Kα Ray Intensity of Liner Fluorescent X-ray analysis was performed on 100 randomly selected points on the surface of the liner (release-treated surface). More specifically, the intensity (i) of the Si—Kα ray of the surface of the liner in contact with the adhesive layer (the surface coated with the release agent) and the surface not in contact with the adhesive layer (the surface coated with the release agent) Measure the intensity (ii) of the Si-Kα ray of the surface that is not exposed), obtain the absolute value of the value obtained by subtracting the value of (ii) from the value of (i), and calculate the average value of 100 measurements of the value. The Si—Kα ray intensity of the liner was used.
The intensity of the Si-Kα ray is the intensity at a wavelength of 7.125 angstroms as measured by the following equipment.
Equipment: Rigaku ZSX100e
Analysis area: 30mmφ
Analysis element: Si
Analysis crystal: RX4
Output: 50kV, 70mA
［実施例２］
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」）１０重量部とを混合して、粘着剤を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤を塗工して、粘着剤層（厚み：１０μｍ）を形成した。
　基材（ポリエチレンナフタレートフィルム、帝人デュポンフィルム社製、商品名「テオネックスＱ５１」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー付粘着シート前駆体を得た。
　ライナー付粘着シート前駆体を、温度４０℃、湿度２０％の環境下で５日間放置して、ライナー／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートを得た。 [Example 2]
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ”) was mixed with 10 parts by weight to prepare an adhesive.
The above-mentioned adhesive is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”) to form an adhesive layer (thickness: 10 μm ) was formed.
The liner with the pressure-sensitive adhesive layer was attached to a substrate (polyethylene naphthalate film, manufactured by Teijin DuPont Films Ltd., trade name "Teonex Q51", thickness: 50 µm) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
The liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment of 40° C. and 20% humidity for 5 days to obtain a liner-attached pressure-sensitive adhesive sheet consisting of liner/adhesive layer (first adhesive layer)/substrate. .
［実施例３］
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」）１０重量部とを混合して、粘着剤を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤を塗工して、粘着剤層（厚み：１０μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、宇部興産社製、商品名「ユーピレックス－Ｒ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー付粘着シート前駆体を得た。
　ライナー付粘着シート前駆体を、温度４０℃、湿度２０％の環境下で５日間放置して、ライナー／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートを得た。 [Example 3]
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ”) was mixed with 10 parts by weight to prepare an adhesive.
The above-mentioned adhesive is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., product name “MRF-38”) to form an adhesive layer (thickness: 10 μm ) was formed.
The liner with the pressure-sensitive adhesive layer was attached to a base material (aromatic polyimide film, manufactured by Ube Industries, Ltd., trade name “Upilex-R”, thickness: 50 μm) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
The liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment of 40° C. and 20% humidity for 5 days to obtain a liner-attached pressure-sensitive adhesive sheet consisting of liner/adhesive layer (first adhesive layer)/substrate. .
［実施例４］
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」）１０重量部とを混合して、粘着剤ａ１を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤ａ1を塗工して、粘着剤層（厚み：７μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、デュポン社製、商品名「カプトン２００Ｈ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー付粘着シート前駆体を得た。
　ライナー付粘着シート前駆体を、温度４０℃、湿度２０％の環境下で５日間放置して、ライナー／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートを得た。 [Example 4]
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ”) was mixed with 10 parts by weight to prepare adhesive a1.
The pressure-sensitive adhesive a1 is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 μm) was formed.
The liner with the pressure-sensitive adhesive layer was attached to a base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 µm) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
The liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment of 40° C. and 20% humidity for 5 days to obtain a liner-attached pressure-sensitive adhesive sheet consisting of liner/adhesive layer (first adhesive layer)/substrate. .
［実施例５］
　粘着剤層の厚みを２μｍとしたこと以外は、実施例４と同様にしてライナー付粘着シートを得た。 [Example 5]
A liner-attached pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the pressure-sensitive adhesive layer was 2 μm.
［実施例６］
　粘着剤層の厚みを１５μｍとしたこと以外は、実施例４と同様にしてライナー付粘着シートを得た。 [Example 6]
A liner-attached pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4, except that the thickness of the pressure-sensitive adhesive layer was 15 μm.
［実施例７］
（ライナー付粘着シートａ２）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」）１０重量部とを混合して、粘着剤ａ１を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤ａ1を塗工して、粘着剤層（厚み：７μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、デュポン社製、商品名「カプトン２００Ｈ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー（第１のライナー）／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートａ２を得た。
（ライナー付粘着シートａ２／下塗り層積層体）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部とを混合して、粘着剤ｂを調製した。
　ライナー付粘着シートａ２の基材に、粘着剤ｂを塗工して、ライナー付粘着シートａ２／下塗り層（厚み：１３μｍ）からなる積層体を形成した。
（ライナー付両面粘着シートｂ）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）１．５重量部、粘着付与樹脂（住友ベークライト社製、商品名「スミライトＰＲ１２６０３」）１０重量部、熱膨張性微小球（松本油脂製薬社製、商品名「マツモトマイクロスフェアーＦＮ－１８０ＳＳＤ」）３０重量部、着色剤（大日精化社製、商品名「ＤＹＭＩＣＳ　ＳＺ７５１０　グリーン」）０．５重量部を混合して、第２の粘着剤層形成用組成物を調製した。
　当該第２の粘着剤層形成用組成物を、ライナー（ＰＥＴフィルム、厚み：５０μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－５０」）の剥離処理面に、塗工して、第２の粘着剤層（厚み：３５μｍ）を形成した。なお、ライナー（商品名「ＭＲＦ－５０」）のＳｉ－Ｋα線の強度は２８（ｋｃｐｓ）であった。
　第２の粘着剤層付ライナーと、ライナー付粘着シートａ２／下塗り層からなる積層体とを貼り合わせ、ライナー付両面粘着シート前駆体を得た。
　ライナー付両面粘着シート前駆体を、温度４０℃、湿度２０％の環境下で５日間放置して、第１のライナー／第１の粘着剤層／基材／下塗り層／第２の粘着剤層／第２のライナーからなる、ライナー付両面粘着シートを得た。 [Example 7]
(Adhesive sheet with liner a2)
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ”) was mixed with 10 parts by weight to prepare adhesive a1.
The pressure-sensitive adhesive a1 is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 μm) was formed.
The base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 μm) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a2 consisting of the pressure-sensitive adhesive layer)/base material was obtained.
(Liner-attached adhesive sheet a2/undercoat layer laminate)
A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b.
The base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 μm).
(Double-sided adhesive sheet with liner b)
Toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 1.5 parts by weight, tackifier resin (manufactured by Sumitomo Bakelite Co., trade name) "SUMILITE PR12603") 10 parts by weight, thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD") 30 parts by weight, coloring agent (manufactured by Dainichiseika Co., Ltd., trade name "DYMICS") SZ7510 Green”) was mixed to prepare a composition for forming a second pressure-sensitive adhesive layer.
The composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 μm). The Si—Kα ray intensity of the liner (trade name “MRF-50”) was 28 (kcps).
The second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a2 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
The liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand for 5 days in an environment with a temperature of 40° C. and a humidity of 20% to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive layer. / A liner-equipped double-sided pressure-sensitive adhesive sheet consisting of a second liner was obtained.
［実施例８］
（ライナー付粘着シートａ２）
　実施例７と同様にしてライナー付粘着シートａ２（ライナー（第１のライナー）／粘着剤層（第１の粘着剤層）／基材）を得た。
（ライナー付粘着シートａ２／下塗り層積層体）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部とを混合して、粘着剤ｂを調製した。
　ライナー付粘着シートａ２の基材に、粘着剤ｂを塗工して、ライナー付粘着シートａ２／下塗り層（厚み：１３μｍ）からなる積層体を形成した。
（ライナー付両面粘着シートｂ’）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）１．５重量部、粘着付与樹脂（住友ベークライト社製、商品名「スミライトＰＲ１２６０３」）１０重量部、熱膨張性微小球（松本油脂製薬社製、商品名「マツモトマイクロスフェアーＦＮ－１８０ＳＳＤ」）３０重量部、着色剤（大日精化社製、商品名「ＤＹＭＩＣＳ　ＳＺ７５１０　グリーン」）０．５重量部を混合して、第２の粘着剤層形成用組成物を調製した。
　当該第２の粘着剤層形成用組成物を、ライナー（ＰＥＴフィルム、厚み：５０μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－５０」）の剥離処理面に、塗工して、第２の粘着剤層（厚み：３５μｍ）を形成した。
　第２の粘着剤層付ライナーと、ライナー付粘着シートａ２／下塗り層からなる積層体とを貼り合わせ、ライナー付両面粘着シート前駆体を得た。
　ライナー付両面粘着シート前駆体を、温度９０℃、湿度１％ＲＨの環境下で２時間放置して、第１のライナー／第１の粘着剤層／基材／下塗り層／第２の粘着剤層／第２のライナーからなる、ライナー付両面粘着シートを得た。 [Example 8]
(Adhesive sheet with liner a2)
A liner-attached pressure-sensitive adhesive sheet a2 (liner (first liner)/pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer)/substrate) was obtained in the same manner as in Example 7.
(Liner-attached adhesive sheet a2/undercoat layer laminate)
A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b.
The base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 μm).
(Double-sided adhesive sheet with liner b')
Toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 1.5 parts by weight, tackifier resin (manufactured by Sumitomo Bakelite Co., trade name) "SUMILITE PR12603") 10 parts by weight, thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD") 30 parts by weight, coloring agent (manufactured by Dainichiseika Co., Ltd., trade name "DYMICS") SZ7510 Green”) was mixed to prepare a composition for forming a second pressure-sensitive adhesive layer.
The composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 μm).
The second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a2 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
The liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand for 2 hours in an environment with a temperature of 90° C. and a humidity of 1% RH to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive. A lined double-sided PSA sheet consisting of layer/second liner was obtained.
［実施例９］
（ライナー付粘着シートａ２）
　実施例７と同様にしてライナー付粘着シートａ２（ライナー（第１のライナー）／粘着剤層（第１の粘着剤層）／基材）を得た。
（ライナー付粘着シートａ２／下塗り層積層体）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部とを混合して、粘着剤ｂを調製した。
　ライナー付粘着シートａ２の基材に、粘着剤ｂを塗工して、ライナー付粘着シートａ２／下塗り層（厚み：１３μｍ）からなる積層体を形成した。
（ライナー付両面粘着シートｂ’’）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）１．５重量部、粘着付与樹脂（住友ベークライト社製、商品名「スミライトＰＲ１２６０３」）１０重量部、熱膨張性微小球（松本油脂製薬社製、商品名「マツモトマイクロスフェアーＦＮ－１８０ＳＳＤ」）６０重量部、着色剤（大日精化社製、商品名「ＤＹＭＩＣＳ　ＳＺ７５１０　グリーン」）０．５重量部を混合して、第２の粘着剤層形成用組成物を調製した。
　当該第２の粘着剤層形成用組成物を、ライナー（ＰＥＴフィルム、厚み：５０μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－５０」）の剥離処理面に、塗工して、第２の粘着剤層（厚み：３５μｍ）を形成した。
　第２の粘着剤層付ライナーと、ライナー付粘着シートａ／下塗り層からなる積層体とを貼り合わせ、ライナー付両面粘着シート前駆体を得た。
　ライナー付両面粘着シート前駆体を、温度４０℃、湿度９２％ＲＨの環境下で３日間放置して、第１のライナー／第１の粘着剤層／基材／下塗り層／第２の粘着剤層／第２のライナーからなる、ライナー付両面粘着シートを得た。 [Example 9]
(Adhesive sheet with liner a2)
A liner-attached pressure-sensitive adhesive sheet a2 (liner (first liner)/pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer)/substrate) was obtained in the same manner as in Example 7.
(Liner-attached adhesive sheet a2/undercoat layer laminate)
A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b.
The base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 μm).
(Double-sided adhesive sheet with liner b'')
Toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 1.5 parts by weight, tackifier resin (manufactured by Sumitomo Bakelite Co., trade name) "SUMILITE PR12603") 10 parts by weight, thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD") 60 parts by weight, coloring agent (manufactured by Dainichiseika Co., Ltd., trade name "DYMICS") SZ7510 Green”) was mixed to prepare a composition for forming a second pressure-sensitive adhesive layer.
The composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 μm).
The second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a/undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
The liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 40° C. and a humidity of 92% RH for 3 days to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive. A lined double-sided PSA sheet consisting of layer/second liner was obtained.
［実施例１０］
（ライナー付粘着シートａ３）
　上記アクリル系ポリマー２のトルエン溶液（アクリル系ポリマー２：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、粘着付与樹脂（荒川化学工業社製、商品名「タマノル２００Ｎ」）１５重量部とを混合して、粘着剤ａ’を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤ａ’を塗工して、粘着剤層（厚み：５μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、デュポン社製、商品名「カプトン２００Ｈ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合せ、ライナー（第１のライナー）／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートａ３を得た。
（ライナー付粘着シートａ３／下塗り層積層体）
　上記アクリル系ポリマー２のトルエン溶液（アクリル系ポリマー２：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部を混合して、粘着剤ｂ’を調製した。
　ライナー付粘着シートａ３の基材に、粘着剤ｂ’を塗工して、ライナー付粘着シートａ３／下塗り層（厚み：１３μｍ）からなる積層体を形成した。
（ライナー付両面粘着シートｂ２）
　上記アクリル系ポリマー２のトルエン溶液（アクリル系ポリマー２：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）１．５重量部、粘着付与樹脂（住友ベークライト社製、商品名「スミライトＰＲ１２６０３」）１０重量部、熱膨張性微小球（松本油脂製薬社製、商品名「マツモトマイクロスフェアーＦＮ－１８０ＳＳＤ」）３０重量部、着色剤（大日精化社製、商品名「ＤＹＭＩＣＳ　ＳＺ７５１０　グリーン」）０．５重量部を混合して、第２の粘着剤層形成用組成物を調製した。
　当該第２の粘着剤層形成用組成物を、ライナー（ＰＥＴフィルム、厚み：５０μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－５０」）の剥離処理面に、塗工して、第２の粘着剤層（厚み：３５μｍ）を形成した。
　第２の粘着剤層付ライナーと、ライナー付粘着シートａ３／下塗り層からなる積層体とを貼り合わせ、ライナー付両面粘着シート前駆体を得た。
　ライナー付両面粘着シート前駆体を、温度４０℃、湿度２０％ＲＨの環境下で５日間放置して、第１のライナー／第１の粘着剤層／基材／下塗り層／第２の粘着剤層／第２のライナーからなる、ライナー付両面粘着シートを得た。 [Example 10]
(Adhesive sheet with liner a3)
Toluene solution of acrylic polymer 2 (acrylic polymer 2: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, tackifying resin (manufactured by Arakawa Chemical Industries, trade name " Tamanol 200N") was mixed with 15 parts by weight to prepare an adhesive a'.
The adhesive a' is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, product name "MRF-38") to form an adhesive layer (thickness: : 5 μm).
The base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 μm) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a3 consisting of the pressure-sensitive adhesive layer)/substrate was obtained.
(Liner-attached adhesive sheet a3/undercoat layer laminate)
A toluene solution of acrylic polymer 2 (acrylic polymer 2: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b'.
Adhesive b′ was applied to the substrate of the liner-attached adhesive sheet a3 to form a laminate consisting of the liner-attached adhesive sheet a3/undercoat layer (thickness: 13 μm).
(Double-sided adhesive sheet with liner b2)
Toluene solution of acrylic polymer 2 (acrylic polymer 2: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 1.5 parts by weight, tackifying resin (manufactured by Sumitomo Bakelite Co., trade name) "SUMILITE PR12603") 10 parts by weight, thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD") 30 parts by weight, coloring agent (manufactured by Dainichiseika Co., Ltd., trade name "DYMICS") SZ7510 Green”) was mixed to prepare a composition for forming a second pressure-sensitive adhesive layer.
The composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 μm).
The second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a3 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
The liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 40° C. and a humidity of 20% RH for 5 days to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive. A lined double-sided PSA sheet consisting of layer/second liner was obtained.
［実施例１１］
（ライナー付粘着シートａ４）
　上記アクリル系ポリマー３のトルエン溶液（アクリル系ポリマー３：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、粘着付与樹脂（荒川化学工業社製、商品名「タマノル２００Ｎ」）１５重量部とを混合して、粘着剤ａ’’を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤ａ’を塗工して、粘着剤層（厚み：５μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、デュポン社製、商品名「カプトン２００Ｈ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合せ、ライナー（第１のライナー）／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートａ４を得た。
（ライナー付粘着シートａ４／下塗り層積層体）
　上記アクリル系ポリマー３のトルエン溶液（アクリル系ポリマー３：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部を混合して、粘着剤ｂ’’を調製した。
　ライナー付粘着シートａ４の基材に、粘着剤ｂ’’を塗工して、ライナー付粘着シートａ４／下塗り層（厚み：１３μｍ）からなる積層体を形成した。
（ライナー付両面粘着シートｂ３）
　上記アクリル系ポリマー３のトルエン溶液（アクリル系ポリマー３：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）１．５重量部、粘着付与樹脂（住友ベークライト社製、商品名「スミライトＰＲ１２６０３」）１０重量部、熱膨張性微小球（松本油脂製薬社製、商品名「マツモトマイクロスフェアーＦＮ－１８０ＳＳＤ」）３０重量部、着色剤（大日精化社製、商品名「ＤＹＭＩＣＳ　ＳＺ７５１０　グリーン」）０．５重量部を混合して、第２の粘着剤層形成用組成物を調製した。
　当該第２の粘着剤層形成用組成物を、ライナー（ＰＥＴフィルム、厚み：５０μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－５０」）の剥離処理面に、塗工して、第２の粘着剤層（厚み：３５μｍ）を形成した。
　第２の粘着剤層付ライナーと、ライナー付粘着シートａ４／下塗り層からなる積層体とを貼り合わせ、ライナー付両面粘着シート前駆体を得た。
　ライナー付両面粘着シート前駆体を、温度４０℃、湿度２０％ＲＨの環境下で５日間放置して、第１のライナー／第１の粘着剤層／基材／下塗り層／第２の粘着剤層／第２のライナーからなる、ライナー付両面粘着シートを得た。 [Example 11]
(Adhesive sheet a4 with liner)
Toluene solution of acrylic polymer 3 (acrylic polymer 3: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, tackifier resin (manufactured by Arakawa Chemical Industries, trade name " Tamanol 200N") was mixed with 15 parts by weight to prepare an adhesive a''.
The adhesive a' is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, product name "MRF-38") to form an adhesive layer (thickness: : 5 μm).
The base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 μm) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a4 consisting of the pressure-sensitive adhesive layer)/substrate was obtained.
(Liner-attached adhesive sheet a4/undercoat layer laminate)
A toluene solution of acrylic polymer 3 (acrylic polymer 3: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b''.
The base material of the liner-attached adhesive sheet a4 was coated with the adhesive b″ to form a laminate composed of the liner-attached adhesive sheet a4/undercoat layer (thickness: 13 μm).
(Double-sided adhesive sheet with liner b3)
Toluene solution of acrylic polymer 3 (acrylic polymer 3: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 1.5 parts by weight, tackifying resin (manufactured by Sumitomo Bakelite Co., trade name) "SUMILITE PR12603") 10 parts by weight, thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD") 30 parts by weight, coloring agent (manufactured by Dainichiseika Co., Ltd., trade name "DYMICS") SZ7510 Green”) was mixed to prepare a composition for forming a second pressure-sensitive adhesive layer.
The composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 μm).
The second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a4 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
The liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 40° C. and a humidity of 20% RH for 5 days to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive. A lined double-sided PSA sheet consisting of layer/second liner was obtained.
［比較例１］
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」）１０重量部とを混合して、粘着剤ａ１を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤ａを塗工して、粘着剤層（厚み：７μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、デュポン社製、商品名「カプトン２００Ｈ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー付粘着シート前駆体を得た。
　ライナー付粘着シート前駆体を、温度２００℃、湿度０．１％ＲＨの環境下で４時間間放置して、ライナー／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートを得た。 [Comparative Example 1]
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ”) was mixed with 10 parts by weight to prepare adhesive a1.
The adhesive a is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 μm) was formed.
The liner with the pressure-sensitive adhesive layer was attached to a base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 µm) to obtain a liner-attached pressure-sensitive adhesive sheet precursor.
The liner-attached pressure-sensitive adhesive sheet precursor was allowed to stand in an environment with a temperature of 200° C. and a humidity of 0.1% RH for 4 hours to obtain a liner-attached pressure-sensitive adhesive sheet consisting of a liner/adhesive layer (first pressure-sensitive adhesive layer)/substrate. got a sheet.
［比較例２］
（ライナー付粘着シートａ２）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部、可塑剤（ＤＩＣ社製、商品名「モノサイザーＷ７００」）１０重量部とを混合して、粘着剤ａ１を調製した。
　ライナー（ＰＥＴフィルム、厚み：３８μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－３８」）の剥離処理面に、上記粘着剤ａを塗工して、粘着剤層（厚み：７μｍ）を形成した。
　基材（芳香族性ポリイミドフィルム、デュポン社製、商品名「カプトン２００Ｈ」、厚み：５０μｍ）に、上記粘着剤層付ライナーを貼り合わせ、ライナー（第１のライナー）／粘着剤層（第１の粘着剤層）／基材からなるライナー付粘着シートａ２を得た。
（ライナー付粘着シートａ２／下塗り層積層体）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）３重量部とを混合して、粘着剤ｂを調製した。
　ライナー付粘着シートａ２の基材に、粘着剤ｂを塗工して、ライナー付粘着シートａ２／下塗り層（厚み：１３μｍ）からなる積層体を形成した。
（ライナー付粘着シート）
　上記アクリル系ポリマー１のトルエン溶液（アクリル系ポリマー１：１００重量部）、架橋剤（東ソー社製、商品名「コロネートＬ」）１．５重量部、粘着付与樹脂（住友ベークライト社製、商品名「スミライトＰＲ１２６０３」）１０重量部、熱膨張性微小球（松本油脂製薬社製、商品名「マツモトマイクロスフェアーＦＮ－１８０ＳＳＤ」）３０重量部、着色剤（大日精化社製、商品名「ＤＹＭＩＣＳ　ＳＺ７５１０　グリーン」）０．５重量部を混合して、第２の粘着剤層形成用組成物を調製した。
　当該第２の粘着剤層形成用組成物を、ライナー（ＰＥＴフィルム、厚み：５０μｍ、シリコーン系剥離処理品、三菱樹脂社製、商品名「ＭＲＦ－５０」）の剥離処理面に、塗工して、第２の粘着剤層（厚み：３５μｍ）を形成した。
　第２の粘着剤層付ライナーと、ライナー付粘着シートａ２／下塗り層からなる積層体とを貼り合わせ、ライナー付両面粘着シート前駆体を得た。
　ライナー付両面粘着シート前駆体を、温度８５℃、湿度９２％ＲＨの環境下で７日間放置して、第１のライナー／第１の粘着剤層／基材／下塗り層／第２の粘着剤層／第２のライナーからなる、ライナー付両面粘着シートを得た。 [Comparative Example 2]
(Adhesive sheet with liner a2)
A toluene solution of the acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 3 parts by weight, a plasticizer (manufactured by DIC, trade name "Monocizer W700") ”) was mixed with 10 parts by weight to prepare adhesive a1.
The adhesive a is applied to the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, Inc., trade name “MRF-38”) to form an adhesive layer (thickness: 7 μm) was formed.
The base material (aromatic polyimide film, manufactured by DuPont, trade name “Kapton 200H”, thickness: 50 μm) is laminated with the liner with the adhesive layer, and the liner (first liner)/adhesive layer (first A liner-attached pressure-sensitive adhesive sheet a2 consisting of the pressure-sensitive adhesive layer)/base material was obtained.
(Liner-attached adhesive sheet a2/undercoat layer laminate)
A toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b.
The base material of the liner-attached adhesive sheet a2 was coated with the adhesive b to form a laminate composed of the liner-attached adhesive sheet a2/undercoat layer (thickness: 13 μm).
(Adhesive sheet with liner)
Toluene solution of acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 1.5 parts by weight, tackifier resin (manufactured by Sumitomo Bakelite Co., trade name) "SUMILITE PR12603") 10 parts by weight, thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD") 30 parts by weight, coloring agent (manufactured by Dainichiseika Co., Ltd., trade name "DYMICS") SZ7510 Green”) was mixed to prepare a composition for forming a second pressure-sensitive adhesive layer.
The composition for forming the second pressure-sensitive adhesive layer is applied to the release-treated surface of a liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics, trade name “MRF-50”). to form a second adhesive layer (thickness: 35 μm).
The second pressure-sensitive adhesive layer-bearing liner and a laminate consisting of the liner-bearing pressure-sensitive adhesive sheet a2 and the undercoat layer were laminated together to obtain a liner-bearing double-faced pressure-sensitive adhesive sheet precursor.
The liner-equipped double-sided pressure-sensitive adhesive sheet precursor was allowed to stand for 7 days in an environment with a temperature of 85° C. and a humidity of 92% RH to form a first liner/first pressure-sensitive adhesive layer/substrate/undercoat layer/second pressure-sensitive adhesive. A lined double-sided PSA sheet consisting of layer/second liner was obtained.
［評価］
　実施例および比較例で得られた粘着シートを以下の評価に供した。結果を表１に示す。
（１）粘着力
　実施例および比較例で得られたライナー付粘着シートから第１のライナーを剥離し、粘着シートを幅：２０ｍｍ、長さ：１４０ｍｍのサイズに切断し、第１の粘着剤層に、ポリエチレンテレフタレートフィルム（東レ社製、商品名「ルミラーＳ－１０」、厚さ：２５μｍ、幅：２０ｍｍ）を、ＪＩＳ　Ｚ　０２３７（２０００年）に準じ、温度：２３℃および湿度：６５ＲＨの雰囲気下で、２ｋｇのローラーを１往復させて圧着して貼り合わせて、評価サンプルを作製した。
　当該評価サンプルを、２３℃に設定された恒温槽付き引張試験機（島津製作所社製、商品名「島津オートグラ　フＡＧ－１２０ｋＮ」）にセットし、３０分間放置した。
　放置後、２３℃の温度下で、ポリエチレンテレフタレートを、剥離角度：１８０°、剥離速度（引張速度）：３００ｍｍ／ｍｉｎの条件で、粘着シートから引き剥がした時の荷重を測定し、その際の最大荷重（測定初期のピークトップを除いた荷重の最大値）を求め、この最大荷重を粘着力（Ｎ／２０ｍｍ）とした。
（２）含水率
　実施例および比較例で得られたライナー付粘着シートからライナーを剥離し、粘着シートの含水率をカールフィッシャー滴定法により測定した。測定装置および測定条件の詳細は以下のとおりである。
　測定装置：電量滴定式水分測定装置（三菱化学社製、ＣＡ－０６）、加熱気化装置（三菱化学社製、ＶＡ－０６）
　測定条件：加熱気化法（１５０℃加熱）
　　陽極液：アクアミクロンＡＫＸ（エーピーアイコーポレーション社製）
　　陰極液：アクアミクロンＣＸＵ（エーピーアイコーポレーション社製）
（３）接触角
　実施例および比較例で得られたライナー付粘着シートから第１のライナーを剥離し、第１の粘着剤層における水の接触角を測定した。
　接触角計（協和界面社製、商品名「ＣＸ－Ａ型」）を用いて、２３℃／５０％ＲＨ環境下、純水を第１の粘着剤層の表面に２μｌ滴下し、滴下して５秒後に液滴の接触角を測定することを５回繰り返し、その平均値を求めた。
（４）ゲル分率
　第１の粘着剤層０．１ｇを、メッシュ状シートで包み、トルエン５０ｍｌ中、室温下で１週間静置して、該サンプルにトルエンを浸漬させた。その後、トルエン不溶分を取り出し、７０℃で２時間かけて乾燥させた後、乾燥後のトルエン不溶分を秤量した。
　トルエン浸漬前のサンプル重量とトルエン不溶分の重量とから、次式により樹脂層のゲル分率を算出した。
　ゲル分率（％）＝［（トルエン不溶分の重量）／（トルエン浸漬前のサンプル重量）］×１００
（５）封止樹脂前駆体の流動性評価
　実施例および比較例で得られたライナー付粘着シートからライナーを剥離し、第２の粘着剤層側を板ガラスに貼着した。
　第１の粘着剤層上に、直径３ｍｍの孔をあけた厚み１３０μｍポリテトラフルオロエチレン（ＰＴＦＥ）シートを置いた。このＰＴＦＥシートの孔に封止樹脂前駆体（エポキシ樹脂、ナガセケムテックス社製、商品名「Ｒ４２１２」）を流し込み、直径３ｍｍ、厚み１３０μｍの封止樹脂前駆体の柱状体を形成した。
　ＰＴＦＥシートを取り除き、封止樹脂前駆体の柱状体付の粘着シートを、ホットステージ付き光学顕微鏡に試料を設置し、２３℃で１分間放置後、１３０℃に加熱した。
　加熱により流動する封止樹脂前駆体について、上記柱状体形成位置の外縁と、流動後の封止樹脂前駆体外縁との最短距離が３０μｍとなる時間を計測した。
　上記計測を１０回を行い、最長時間と最短時間との差により、封止樹脂前駆体の流動性のバラツキを以下の基準により評価した。
　優（表中〇）：上記差が６０秒未満
　可（表中△）：上記差が６０秒～１８０秒
　不可（表中×）：上記差が１８０秒を超える [evaluation]
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were subjected to the following evaluations. Table 1 shows the results.
(1) Adhesive strength The first liner was peeled off from the liner-attached adhesive sheets obtained in Examples and Comparative Examples, and the adhesive sheets were cut into pieces having a width of 20 mm and a length of 140 mm to obtain a first adhesive layer. In addition, a polyethylene terephthalate film (manufactured by Toray Industries, product name “Lumirror S-10”, thickness: 25 μm, width: 20 mm) was placed in an atmosphere of 23 ° C. and 65 RH in accordance with JIS Z 0237 (2000). A 2-kg roller was reciprocated one time under the pressure and bonded together to prepare an evaluation sample.
The evaluation sample was set in a tensile tester with a constant temperature bath set at 23° C. (manufactured by Shimadzu Corporation, trade name “Shimadzu Autograph AG-120 kN”) and left for 30 minutes.
After standing, the polyethylene terephthalate was peeled off from the adhesive sheet at a temperature of 23° C. under the conditions of a peeling angle of 180° and a peeling speed (tensile speed) of 300 mm/min. The maximum load (the maximum value of the load excluding the peak top at the initial stage of measurement) was obtained, and this maximum load was defined as the adhesive strength (N/20 mm).
(2) Moisture Content The liner was peeled off from the lined adhesive sheets obtained in Examples and Comparative Examples, and the moisture content of the adhesive sheets was measured by Karl Fischer titration. The details of the measuring apparatus and measuring conditions are as follows.
Measuring device: coulometric titration moisture measuring device (manufactured by Mitsubishi Chemical Corporation, CA-06), heating and vaporization device (manufactured by Mitsubishi Chemical Corporation, VA-06)
Measurement conditions: Heat vaporization method (heated at 150°C)
Anolyte: Aquamicron AKX (manufactured by API Corporation)
Catholyte: Aquamicron CXU (manufactured by API Corporation)
(3) Contact Angle The first liner was peeled off from the liner-attached pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and the contact angle of water on the first pressure-sensitive adhesive layer was measured.
Using a contact angle meter (manufactured by Kyowa Kaimen Co., Ltd., trade name "CX-A type"), 2 μl of pure water is dropped on the surface of the first adhesive layer in a 23 ° C./50% RH environment, and then dropped. Measurement of the contact angle of the droplet after 5 seconds was repeated 5 times, and the average value was obtained.
(4) Gel Fraction 0.1 g of the first pressure-sensitive adhesive layer was wrapped with a mesh sheet and allowed to stand in 50 ml of toluene at room temperature for 1 week to immerse the sample in toluene. After that, the toluene-insoluble matter was taken out and dried at 70° C. for 2 hours, and then the toluene-insoluble matter after drying was weighed.
From the weight of the sample before immersion in toluene and the weight of the toluene-insoluble matter, the gel fraction of the resin layer was calculated by the following formula.
Gel fraction (%) = [(toluene-insoluble weight) / (sample weight before toluene immersion)] × 100
(5) Fluidity Evaluation of Encapsulating Resin Precursor The liner was peeled off from the liner-attached pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and the second pressure-sensitive adhesive layer side was adhered to a plate glass.
A 130 μm thick polytetrafluoroethylene (PTFE) sheet with 3 mm diameter holes was placed on the first adhesive layer. A sealing resin precursor (epoxy resin, manufactured by Nagase ChemteX Corporation, trade name "R4212") was poured into the holes of this PTFE sheet to form a columnar body of the sealing resin precursor having a diameter of 3 mm and a thickness of 130 µm.
The PTFE sheet was removed, and the pressure-sensitive adhesive sheet with the pillars of the sealing resin precursor was placed on an optical microscope with a hot stage.
For the sealing resin precursor flowing by heating, the time required for the shortest distance between the outer edge of the columnar body formation position and the outer edge of the sealing resin precursor after flowing to be 30 μm was measured.
The above measurement was performed 10 times, and the difference between the longest time and the shortest time was used to evaluate the variation in fluidity of the sealing resin precursor according to the following criteria.
Excellent (○ in the table): The above difference is less than 60 seconds Acceptable (△ in the table): The above difference is 60 seconds to 180 seconds Impossible (X in the table): The above difference exceeds 180 seconds
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１０　　　基材
　２０　　　粘着剤層
　３０　　　第２の粘着剤層
　１００、２００　　粘着シート
　 REFERENCE SIGNS LIST 10 base material 20 adhesive layer 30 second adhesive layer 100, 200 adhesive sheet

Claims (10)

  1. 　基材と、該基材の少なくとも片側に配置された粘着剤層とを備える粘着シートであって、
    　該粘着剤層をポリエチレンテレフタレートに貼着した際の２３℃における粘着力が、０．１Ｎ／２０ｍｍ～８Ｎ／２０ｍｍであり、
    　該粘着剤層が、ベースポリマーを含む粘着剤から構成され、該ベースポリマーのｓｐ値が７（ｃａｌ／ｃｍ３）１／２～１０（ｃａｌ／ｃｍ３）１／２であり、
    　該粘着シートの含水率が、０．０５重量％～６重量％である、
    　粘着シート。     A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer disposed on at least one side of the base material,
    The pressure-sensitive adhesive layer has a pressure-sensitive adhesive strength at 23° C. of 0.1 N/20 mm to 8 N/20 mm when adhered to polyethylene terephthalate,
    The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive containing a base polymer, the sp value of the base polymer being 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 ,
    The pressure-sensitive adhesive sheet has a moisture content of 0.05% to 6% by weight.
    adhesive sheet.
  2. 　前記基材が、ガラス転移温度（Ｔｇ）が６０℃～４５０℃の樹脂から構成される樹脂シートである、請求項１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 60°C to 450°C.
  3. 　前記基材が、芳香族性ポリイミド系樹脂から構成される、請求項１または２に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the base material is composed of an aromatic polyimide resin.
  4. 　前記粘着剤層の厚みが、２μｍ～１５μｍである、請求項１から３のいずれか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 pressure-sensitive adhesive layer has a thickness of 2 µm to 15 µm.
  5. 　前記粘着剤層のゲル分率が、６０％～１００％である、請求項１から４のいずれかに記載の粘着シート。 The adhesive sheet according to any one of claims 1 to 4, wherein the adhesive layer has a gel fraction of 60% to 100%.
  6. 　前記ベースポリマーが、アクリル系ポリマーであり、
    　該アクリル系ポリマーが、水酸基含有モノマー由来の構成単位を含み、
    　該水酸基含有モノマー由来の構成単位の含有量が、該アクリル系ポリマーを構成する全構成単位１００重量部に対して、０．１重量部～２０重量部である、請求項１から５のいずれかに記載の粘着シート。     the base polymer is an acrylic polymer,
    The acrylic polymer contains a structural unit derived from a hydroxyl group-containing monomer,
    6. Any one of claims 1 to 5, wherein the content of the structural unit derived from the hydroxyl group-containing monomer is 0.1 to 20 parts by weight with respect to 100 parts by weight of all the structural units constituting the acrylic polymer. The adhesive sheet described in .
  7. 　前記基材の前記粘着剤層とは反対側に、第２の粘着剤層をさらに備える、請求項１から６のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 6, further comprising a second pressure-sensitive adhesive layer on the opposite side of the base material to the pressure-sensitive adhesive layer.
  8. 　ＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ／Ｓｃａｌｅ　Ｐａｃｋａｇｅ）またはＷＬＰ（Ｗａｆｅｒ　Ｌｅｖｅｌ　Ｐａｃｋａｇｅ）の製造の際に、半導体チップを仮固定するシートとして用いられる、請求項１から７のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, which is used as a sheet for temporarily fixing semiconductor chips when manufacturing CSP (Chip Size/Scale Package) or WLP (Wafer Level Package).
  9. 　前記半導体チップは、封止樹脂により封止され、該樹脂封止の際の加工温度が１００℃以上である、請求項８に記載の粘着シート。 The adhesive sheet according to claim 8, wherein the semiconductor chip is sealed with a sealing resin, and the processing temperature during the resin sealing is 100°C or higher.
  10. 　基材上に粘着剤を含む組成物の塗工層を形成する工程と、
    　該塗工層面上にライナーを配置して積層体を形成する工程と、
    　該積層体を、所定の加湿熱時間（例えば、２時間～７日）、温度および湿度が管理された環境下に置く加湿熱工程とを含み、
    　加湿熱工程における、加湿熱時間と温度と湿度との積が、１００～３０００００℃・ＲＨ％・ｈである、
    　請求項１から９のいずれかに記載の粘着シートの製造方法。
     

          A step of forming a coating layer of a composition containing an adhesive on a substrate;
    placing a liner on the surface of the coating layer to form a laminate;
    a humidifying and heating step in which the laminate is placed in an environment where the temperature and humidity are controlled for a predetermined humidifying and heating time (for example, 2 hours to 7 days),
    In the humidifying heat step, the product of the humidifying heat time, the temperature and the humidity is 100 to 300000 ° C. RH% h.
    A method for producing the pressure-sensitive adhesive sheet according to any one of claims 1 to 9.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012102229A (en) * 2010-11-10 2012-05-31 Nitto Denko Corp Insulating tape
JP2015168711A (en) * 2014-03-05 2015-09-28 日東電工株式会社 Pressure sensitive adhesive sheet
WO2016063802A1 (en) * 2014-10-20 2016-04-28 積水化成品工業株式会社 Tacky gel sheet having adhesive applications, method for producing same, method for fixing a pair of objects, and composite material
JP2018016701A (en) * 2016-07-27 2018-02-01 東洋インキＳｃホールディングス株式会社 Adhesive composition, and adhesive sheet
JP2020117677A (en) * 2018-12-07 2020-08-06 長興材料工業股▲ふん▼有限公司Ｅｔｅｒｎａｌ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． Crosslinkable copolymer and use thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4403631B2 (en) 2000-04-24 2010-01-27 ソニー株式会社 Manufacturing method of chip-shaped electronic component and manufacturing method of pseudo wafer used for manufacturing the same
JP2001313350A (en) 2000-04-28 2001-11-09 Sony Corp Chip-shaped electronic component and its manufacturing method, and pseudo-wafer used for manufacture of chip- shaped electronic component and its manufacturing method
WO2014142193A1 (en) 2013-03-15 2014-09-18 日東電工株式会社 Adhesive sheet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012102229A (en) * 2010-11-10 2012-05-31 Nitto Denko Corp Insulating tape
JP2015168711A (en) * 2014-03-05 2015-09-28 日東電工株式会社 Pressure sensitive adhesive sheet
WO2016063802A1 (en) * 2014-10-20 2016-04-28 積水化成品工業株式会社 Tacky gel sheet having adhesive applications, method for producing same, method for fixing a pair of objects, and composite material
JP2018016701A (en) * 2016-07-27 2018-02-01 東洋インキＳｃホールディングス株式会社 Adhesive composition, and adhesive sheet
JP2020117677A (en) * 2018-12-07 2020-08-06 長興材料工業股▲ふん▼有限公司Ｅｔｅｒｎａｌ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． Crosslinkable copolymer and use thereof

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