WO2023105906A1 - Film de renforcement - Google Patents

Film de renforcement Download PDF

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Publication number
WO2023105906A1
WO2023105906A1 PCT/JP2022/037493 JP2022037493W WO2023105906A1 WO 2023105906 A1 WO2023105906 A1 WO 2023105906A1 JP 2022037493 W JP2022037493 W JP 2022037493W WO 2023105906 A1 WO2023105906 A1 WO 2023105906A1
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Prior art keywords
weight
meth
acrylate
sensitive adhesive
alkyl
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PCT/JP2022/037493
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English (en)
Japanese (ja)
Inventor
翔悟 佐々木
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202280075294.7A priority Critical patent/CN118234819A/zh
Priority to KR1020247021738A priority patent/KR20240115299A/ko
Priority to JP2023566107A priority patent/JPWO2023105906A1/ja
Publication of WO2023105906A1 publication Critical patent/WO2023105906A1/fr

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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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to reinforcing films.
  • Adhesive films are used to reinforce members of various shapes.
  • an adhesive film has been reported as a reinforcing film that is used in a state of being adhered to the surface of the device when the device is used, in addition to assembly, processing, transportation, etc. of the device (for example, Patent Document 1). .
  • an adhesive film has a function of reinforcing the device by dispersing the impact on the device and imparting rigidity to the flexible device.
  • thermocompression bonding is usually performed using an anisotropic conductive film (ACF).
  • ACF anisotropic conductive film
  • an adhesive film may be adhered to the back side of the substrate of the semiconductor element in advance to reinforce the substrate (for example, Patent Document 2).
  • a release layer and a flexible film substrate are formed on a support substrate such as glass, A TFT substrate is formed on the film substrate, and an organic EL layer is formed thereon. Then, the support substrate is peeled off to manufacture the flexible device.
  • the flexible display layer is very thin, the device may be defective due to handling or the like. Therefore, in some cases, an adhesive film is adhered to the back side for reinforcement (for example, Patent Document 3).
  • Semiconductor element substrates and flexible devices may be repeatedly bent, and if the adhesive film laminated to the substrate, etc., has poor bending properties, the recovery after bending will deteriorate, and in the worst case, it will break due to repeated bending. It can be chilling.
  • a bent portion for example, a movable bent portion of a folding member
  • a compressive stress acts on the bent inner diameter side
  • Tensile stress acts on the bent outer diameter side
  • stress distortion occurs in the bent portion and its surroundings, which poses a problem of damage to the substrate of the semiconductor element and the flexible device.
  • the storage elastic modulus G' is known as an index indicating the softness of the adhesive, and the elastic modulus change based on the storage elastic modulus G' (-20) at -20°C and the storage elastic modulus G' (40) at 40°C.
  • the adhesive when the adhesive is softened to have low elasticity, the creep value generally increases. For this reason, in adhesive tapes using a conventional low-elasticity adhesive, the fluidity of the adhesive increases due to heat, and for example, the adhesive is greatly distorted when bumping an integrated circuit (IC). There is a problem that the substrate of the semiconductor element is also distorted, resulting in poor connection.
  • IC integrated circuit
  • An object of the present invention is to provide a reinforcing film including a substrate layer and a pressure-sensitive adhesive layer, which has both excellent low elasticity and excellent heat resistance, and which, for example, is unlikely to cause IC connection failure. be.
  • a reinforcing film according to an embodiment of the present invention comprises: A reinforcing film comprising a substrate layer and an adhesive layer,
  • the adhesive layer is composed of an acrylic adhesive
  • the pressure-sensitive adhesive layer has a surface elastic modulus of 50 kPa to 1000 kPa at 25°C,
  • the heat shrinkage rate in the MD direction when the reinforcing film is heated at 180° C. for 5 minutes is 1.0% or less.
  • the reinforcing film according to the embodiment of the present invention has an adhesive strength of 5.0 N/25 mm or more to the polyimide film at 25°C.
  • the reinforcing film according to the embodiment of the present invention has a transmittance of 80% or more at a wavelength of 550 nm.
  • the acrylic pressure-sensitive adhesive is a photocurable acrylic pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer has a storage modulus G' at -20°C of 80 kPa to 300 kPa.
  • An optical member according to an embodiment of the invention includes a reinforcing film according to an embodiment of the invention.
  • An electronic member according to an embodiment of the invention includes a reinforcing film according to an embodiment of the invention.
  • a reinforcing film that includes a substrate layer and an adhesive layer, has both excellent low elasticity and excellent heat resistance, and is resistant to, for example, poor IC connection.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of the reinforcing film of the present invention.
  • (meth) acrylic when used in this specification, it means “acrylic and/or methacrylic", and when the expression “(meth) acrylate” is used, “acrylate and/or methacrylate ", and the expression “(meth)allyl” means “allyl and/or methallyl”, and the expression “(meth)acrolein” means “acrolein and/or methacrolein”. means rain.
  • the expression “acid (salt)” in this specification means “acid and/or its salt”. Examples of salts include alkali metal salts and alkaline earth metal salts, and specific examples include sodium salts and potassium salts.
  • a reinforcing film according to an embodiment of the present invention includes a base layer and an adhesive layer.
  • the base material layer may be one layer, or may be two or more layers.
  • the substrate layer is preferably a single layer in that the effect of the present invention can be exhibited more effectively.
  • the adhesive layer may be one layer, or two or more layers.
  • the pressure-sensitive adhesive layer is preferably a single layer in that the effects of the present invention can be exhibited more effectively.
  • the reinforcing film according to the embodiment of the present invention contains the base material layer and the pressure-sensitive adhesive layer, it may contain any appropriate other layers depending on the purpose within a range that does not impair the effects of the present invention.
  • a reinforcing film according to an embodiment of the present invention includes a structure in which a substrate layer and an adhesive layer are directly laminated, in that the effects of the present invention can be further expressed.
  • a reinforcing film 100 consists of a base layer 10 and an adhesive layer 20, as shown in FIG.
  • the reinforcing film according to the embodiment of the present invention may be provided with any appropriate release liner on the surface of the pressure-sensitive adhesive layer opposite to the base layer for protection before use.
  • the release liner includes, for example, a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, or a base material (liner base material) such as paper or plastic film whose surface is coated with a polyolefin resin.
  • a base material such as paper or plastic film
  • a base material such as paper or plastic film whose surface is coated with a polyolefin resin.
  • Examples include laminated release liners.
  • plastic films as liner substrates include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Polyurethane films, ethylene-vinyl acetate copolymer films and the like are included.
  • the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, even more preferably 5 ⁇ m to 400 ⁇ m, particularly preferably 10 ⁇ m to 300 ⁇ m.
  • the thickness of the reinforcing film according to embodiments of the present invention is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 200 ⁇ m, even more preferably 10 ⁇ m to 150 ⁇ m, particularly preferably 20 ⁇ m to 100 ⁇ m, most preferably 30 ⁇ m to 80 ⁇ m. If the thickness of the reinforcing film according to the embodiment of the present invention is within the above range, the effects of the present invention can be exhibited more effectively.
  • the reinforcing film according to the embodiment of the present invention has a heat shrinkage rate in the MD direction of 1.0% or less, preferably 0.8% or less, more preferably 0.8% or less when the reinforcing film is heated at 180 ° C. for 5 minutes. It is 0.6% or less, more preferably 0.5% or less, and particularly preferably 0.4% or less.
  • the heat shrinkage rate in the MD direction is an index that can appropriately evaluate the heat resistance of the reinforcing film. can exhibit excellent heat resistance. If the heat shrinkage ratio in the MD direction is out of the above range and becomes large, it may become difficult to develop excellent heat resistance. A method for measuring the heat shrinkage rate in the MD direction will be described in detail later.
  • the pressure-sensitive adhesive layer has a surface elastic modulus of 50 kPa to 1000 kPa, preferably 100 kPa to 900 kPa, more preferably 120 kPa to 800 kPa, and still more preferably 140 kPa to 700 kPa at 25°C. , more preferably 160 kPa to 600 kPa, particularly preferably 180 kPa to 500 kPa, and most preferably 200 kPa to 400 kPa.
  • the surface elastic modulus is an index that can appropriately evaluate the degree of low elasticity of the pressure-sensitive adhesive layer.
  • the reinforcing film according to the embodiment of the present invention can , can develop excellent low elasticity. If the surface elastic modulus is out of the specific range, it may be difficult to achieve excellent low elasticity. A method for measuring the surface elastic modulus will be described in detail later.
  • the reinforcing film according to the embodiment of the present invention has an adhesive strength to the polyimide film at 25° C. of preferably 5.0 N/25 mm or more, more preferably 5.0 N/25 mm to 30 N/25 mm, and still more preferably 5.0 N/25 mm to 20 N/25 mm, particularly preferably 5.0 N/25 mm to 10 N/25 mm.
  • Adhesion to the polyimide film at 25 ° C. is an index that can appropriately evaluate the adhesion as a reinforcing film to the substrate of the semiconductor element, flexible device, etc., and this adhesion is adjusted within the above specific range.
  • the reinforcing film according to the embodiment of the present invention can be properly adhered to a substrate of a semiconductor element, a flexible device, or the like. If the adhesive strength is out of the specific range, it may become difficult to properly adhere the reinforcing film to substrates of semiconductor elements, flexible devices, and the like. A method for measuring the adhesive strength at 25° C. to the polyimide film will be described in detail later.
  • the reinforcing film according to the embodiment of the present invention has an adhesive strength to the polyimide film at ⁇ 20° C. of preferably 10 N/25 mm or more, more preferably 10 N/25 mm to 40 N/25 mm, and still more preferably 12 N/25 mm. to 35 N/25 mm, particularly preferably 13 N/25 mm to 30 N/25 mm.
  • the adhesive strength at ⁇ 20° C. to the above-mentioned polyimide film is an index that can appropriately evaluate the adhesive strength (especially the adhesive strength in a relatively low temperature range) as a reinforcing film for semiconductor element substrates, flexible devices, etc.
  • the reinforcing film according to the embodiment of the present invention can be appropriately adhered to a substrate of a semiconductor element, a flexible device, etc. even in a relatively low temperature range. can. If the adhesive strength deviates from the above specified range, it may become difficult to properly adhere the reinforcing film to substrates of semiconductor elements, flexible devices, etc. in a relatively low temperature region. A method for measuring the adhesive strength at ⁇ 20° C. to the polyimide film will be described in detail later.
  • the reinforcing film according to the embodiment of the present invention has an adhesive force to the polyimide film at 180° C. of preferably 0.1 N/25 mm or more, more preferably 0.1 N/25 mm to 5 N/25 mm, and still more preferably 0.1 N/25 mm to 1.0 N/25 mm, particularly preferably 0.1 N/25 mm to 0.6 N/25 mm.
  • the adhesive strength to the polyimide film at 180° C. is an index that can appropriately evaluate the adhesive strength (particularly, the adhesive strength in a relatively high temperature range) as a reinforcing film for semiconductor element substrates, flexible devices, and the like.
  • the reinforcing film according to the embodiment of the present invention can be properly adhered to a substrate of a semiconductor element, a flexible device, or the like even in a relatively high-temperature region. obtain. If the adhesive strength is out of the specific range, it may become difficult to properly adhere the reinforcing film to substrates of semiconductor elements, flexible devices, etc. in a relatively high-temperature region. A method for measuring the adhesive force at 180° C. to the polyimide film will be described in detail later.
  • the reinforcing film according to the embodiment of the present invention preferably has a transmittance at a wavelength of 550 nm of 80% or more, preferably 84% or more, more preferably 86% or more, and still more preferably 88% or more. , particularly preferably 90% or more.
  • the transmittance is an index that can appropriately evaluate the inspectability of the reinforcing film, and by adjusting the transmittance to a very large value as described above, the reinforcing film according to the embodiment of the present invention exhibits excellent inspectability. can be expressed. If the transmittance falls outside the above range and becomes small, it may become difficult to achieve excellent testability. A method for measuring the transmittance will be described in detail later.
  • the storage elastic modulus G′ of the pressure-sensitive adhesive layer at ⁇ 20° C. is preferably 80 kPa to 300 kPa, more preferably 100 kPa to 250 kPa, and still more preferably 130 kPa to 220 kPa. , particularly preferably 150 kPa to 200 kPa.
  • the storage elastic modulus G' at -20°C is an index that can appropriately evaluate the stress relaxation property of the pressure-sensitive adhesive layer (especially the stress relaxation property in a relatively low temperature region), and this storage elasticity at -20°C.
  • the reinforcing film according to the embodiment of the present invention can exhibit excellent stress relaxation properties even in a relatively low temperature region, and in turn, can exhibit excellent stress relaxation properties. It can express low elasticity. If the storage elastic modulus G' at -20°C is out of the specific range, it may be difficult to exhibit excellent stress relaxation properties. The method for measuring the storage modulus G' at -20°C will be described in detail later.
  • the storage elastic modulus G' of the pressure-sensitive adhesive layer at 25°C is preferably 20 kPa to 200 kPa, more preferably 25 kPa to 150 kPa, still more preferably 27 kPa to 100 kPa, Particularly preferably, it is 30 kPa to 60 kPa.
  • the storage elastic modulus G' at 25°C is an index that can appropriately evaluate the stress relaxation property of the pressure-sensitive adhesive layer (especially the stress relaxation property at room temperature), and the storage elastic modulus G' at 25°C
  • the reinforcing film according to the embodiment of the present invention can exhibit excellent stress relaxation properties in the normal temperature range, and can exhibit excellent low elasticity. If the storage elastic modulus G' at 25°C is out of the specific range, it may be difficult to develop excellent stress relaxation properties. A method for measuring the storage elastic modulus G' at 25°C will be described in detail later.
  • the storage elastic modulus G' of the pressure-sensitive adhesive layer at 180°C is preferably 1 kPa to 100 kPa, more preferably 5 kPa to 50 kPa, still more preferably 8 kPa to 30 kPa, Particularly preferably, it is 10 kPa to 20 kPa.
  • the storage elastic modulus G' at 180°C is an index that can appropriately evaluate the stress relaxation property of the pressure-sensitive adhesive layer (especially the stress relaxation property in a high temperature region), and the storage elastic modulus G' at 180°C By adjusting within the above specific range, the reinforcing film according to the embodiment of the present invention can exhibit excellent stress relaxation properties in a high-temperature region and, in turn, exhibit excellent low elasticity. If the storage elastic modulus G' at 180°C is out of the specific range, it may be difficult to develop excellent stress relaxation properties. A method for measuring the storage elastic modulus G' at 180°C will be described in detail later.
  • the thickness of the substrate layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, still more preferably 10 ⁇ m to 100 ⁇ m, particularly preferably 15 ⁇ m to 80 ⁇ m, most preferably 20 ⁇ m to 60 ⁇ m. . If the thickness of the base material layer is within the above range, the effects of the present invention can be exhibited more effectively.
  • any appropriate material can be adopted as the material of the base material layer as long as it does not impair the effects of the present invention.
  • a typical example of the material for such a base material layer is a resin material.
  • resin materials for the substrate layer include polyimide (PI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polymethyl methacrylate.
  • PI polyimide
  • PEEK polyetheretherketone
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • polymethyl methacrylate examples include polymethyl methacrylate.
  • PMMA polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) , polyamide (nylon), wholly aromatic polyamide (aramid), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluorine resin, and cyclic olefin polymer. Only one kind of resin material may be used as the material of the base material layer, or two or more kinds thereof may be used.
  • the base layer preferably has a tensile elastic modulus of 1.0 GPa to 10 GPa, more preferably 2.0 GPa to 9.0 GPa, and still more preferably 3.0 GPa in a peel test at 25° C. at 200 mm/min. 8.0 GPa, particularly preferably 4.0 GPa to 7.0 GPa.
  • the tensile elastic modulus in the peel test at 200 mm / min at 25 ° C. is an index that can appropriately evaluate both the heat resistance and flexibility of the base material layer, and the peel test at 200 mm / min at 25 ° C.
  • the reinforcing film according to the embodiment of the present invention may have difficulty in achieving both excellent low elasticity and excellent heat resistance. .
  • the method for measuring the tensile modulus by the peel test at 25° C. and 200 mm/min will be described in detail later.
  • Examples of the resin material for the substrate layer that can adjust the tensile modulus in the above-mentioned preferable range in the above-mentioned peel test at 25° C. at 200 mm/min include polyimide (PI), which has been annealed. polyethylene terephthalate (annealed PET).
  • Adhesive layer is composed of an acrylic adhesive.
  • An acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
  • the thickness of the adhesive layer is preferably 1 ⁇ m to 250 ⁇ m, more preferably 2 ⁇ m to 150 ⁇ m, still more preferably 3 ⁇ m to 100 ⁇ m, particularly preferably 5 ⁇ m to 50 ⁇ m, most preferably 10 ⁇ m to 35 ⁇ m. . If the thickness of the pressure-sensitive adhesive layer is within the above range, the effects of the present invention can be exhibited more effectively.
  • the acrylic pressure-sensitive adhesive can thus be defined as being formed from an acrylic pressure-sensitive adhesive composition. This is because the acrylic pressure-sensitive adhesive becomes an acrylic pressure-sensitive adhesive when the acrylic pressure-sensitive adhesive composition causes a cross-linking reaction or the like by heating or ultraviolet irradiation, so that the acrylic pressure-sensitive adhesive can be directly specified by its structure. Due to the fact that it is impossible and almost impractical (“impossible / impractical circumstances”), the definition of “things formed from acrylic pressure-sensitive adhesive compositions” does not apply to acrylic It is a valid specification of the system adhesive as a "thing”.
  • any appropriate method can be adopted as the method for forming the acrylic pressure-sensitive adhesive within the range that does not impair the effects of the present invention.
  • a method for forming such an acrylic pressure-sensitive adhesive for example, an acrylic pressure-sensitive adhesive composition is applied onto any appropriate base material, heated and dried as necessary, and cured as necessary. and a method of forming an acrylic pressure-sensitive adhesive into a sheet on the base material.
  • any appropriate means can be adopted as the means for applying the acrylic pressure-sensitive adhesive composition, as long as the effects of the present invention are not impaired.
  • coating means include roll coating, gravure roll coating, reverse roll coating, kiss roll coating, dip roll coating, bar coating, roll brush coating, spray coating, and knife coating. method, air knife coating method, comma coating method, direct coating method and die coating method.
  • heating or drying the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
  • heating/drying means include heating to 60° C. to 180° C., and aging treatment at a temperature of about room temperature, for example.
  • any appropriate means can be adopted for curing the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
  • curing means include ultraviolet irradiation, laser irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, X-ray irradiation, and electron beam irradiation.
  • a representative method for forming an acrylic pressure-sensitive adhesive from an acrylic pressure-sensitive adhesive composition is an acrylic polymer prepared by polymerization (typically, partial polymerization) using a photopolymerization initiator (typically, A method of forming a photocurable acrylic pressure-sensitive adhesive by a photocuring reaction of a photocurable acrylic pressure-sensitive adhesive composition containing an acrylic partial polymer), and an acrylic polymer prepared by solution polymerization using a thermal polymerization initiator.
  • the acrylic pressure-sensitive adhesive typically includes an acrylic polymer (typically, an acrylic partial polymer) prepared by polymerization (typically, partial polymerization) using a photopolymerization initiator (A photocurable acrylic pressure-sensitive adhesive formed by a photocuring reaction of a photocurable acrylic pressure-sensitive adhesive composition containing P1), a heat containing an acrylic polymer (P2) prepared by solution polymerization using a thermal polymerization initiator (A thermosetting acrylic pressure-sensitive adhesive formed by a cross-linking reaction of a curable acrylic pressure-sensitive adhesive composition is exemplified.
  • an acrylic polymer typically, an acrylic partial polymer
  • P2 a heat containing an acrylic polymer
  • thermosetting acrylic pressure-sensitive adhesive formed by a cross-linking reaction of a curable acrylic pressure-sensitive adhesive composition is exemplified.
  • a photopolymerization initiator any appropriate method, such as a conventionally known method, can be adopted as long as the effects of the present invention are not impaired.
  • Polymerization using a photopolymerization initiator is typically carried out by irradiation with light such as UV.
  • the acrylic polymer (P1) is preferably an acrylic partial polymer (sometimes referred to as an acrylic prepolymer).
  • the acrylic partial polymer is different from that obtained as a complete polymer of the monomer components (preferably, a polymer with a polymerization conversion rate of more than 95% by weight), and the monomer component is preferably obtained with a polymerization conversion rate of 95% by weight. % or less.
  • the polymerization conversion rate of the acrylic partial polymer is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less, Most preferably it is 35% by weight or less.
  • the lower limit of the polymerization conversion rate of the acrylic partial polymer is preferably 1% by weight or more, more preferably 5% by weight or more.
  • the acrylic polymer (P1) is obtained by polymerizing the monomer component (M1).
  • the monomer component (M1) as used herein does not include a cross-linking agent that can be contained in the acrylic pressure-sensitive adhesive composition and will be described later.
  • any appropriate additive may be used in addition to the monomer component (M1) and the photopolymerization initiator within a range that does not impair the effects of the present invention.
  • the acrylic polymer (P1) can thus be defined as one obtained by polymerizing the monomer component (M1). This is because the acrylic polymer (P1) becomes the acrylic polymer (P1) by causing a polymerization reaction of the monomer component (M1), and it is impossible to directly specify the acrylic polymer (P1) by its structure. , Also, due to the fact that there are circumstances that are almost impractical ("impossible / impractical circumstances"), the acrylic polymer (P1) is defined as "obtained by polymerizing the monomer component (M1)" is properly identified as a "thing".
  • the acrylic polymer (P1) preferably has a Tg of ⁇ 80° C. to ⁇ 15° C., more preferably ⁇ 70° C. to ⁇ 25° C., in that the effects of the present invention can be exhibited more. It is preferably -65°C to -30°C, particularly preferably -60°C to -35°C.
  • the Tg of the acrylic polymer (P1) is based on the Tg of a homopolymer (homopolymer) of each monomer constituting the acrylic polymer (P1) and the weight fraction of the monomer (copolymerization ratio based on weight). , a value obtained from the Fox formula.
  • Tg is the glass transition temperature of the copolymer (unit: K)
  • Wi is the weight fraction of the monomer i in the copolymer (weight-based copolymerization ratio)
  • Tgi is the homopolymer of the monomer i. represents the glass transition temperature (unit: K).
  • Tg of the homopolymer the values described in known documents shall be adopted.
  • Tg of the homopolymer for example, the following values can be specifically used.
  • BA -55°C
  • LA Lauryl acrylate
  • EHA 2-ethylhexyl acrylate
  • HPA 2-hydroxyethyl acrylate
  • NDP N-vinyl-2-pyrrolidone
  • the monomer component (M1) preferably contains an alkyl (meth)acrylate (a1) and a polar group-containing monomer (b1).
  • Alkyl (meth)acrylates (a1) may be used alone or in combination of two or more.
  • the number of polar group-containing monomers (b1) may be one, or two or more.
  • Alkyl (meth)acrylate (a1) The alkyl group in the ester moiety of the alkyl (meth)acrylate (a1) (hereinafter sometimes referred to as "the alkyl group in the ester moiety") includes an alkyl group containing a hydroxyl group and an alkyl group containing a polar group other than the hydroxyl group. Not included. Therefore, the alkyl (meth)acrylate (a1) is clearly distinguished from the polar group-containing monomer (b1).
  • the content of the alkyl (meth)acrylate (a1) in the monomer component (M1) is preferably 50% by weight to 99% by weight, more preferably 70% by weight, from the viewpoint that the effects of the present invention can be further expressed. to 99% by weight, more preferably 80% to 99% by weight, particularly preferably 82% to 99% by weight, and most preferably 85% to 99% by weight.
  • the alkyl group of the ester moiety is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, and still more preferably, from the viewpoint that the effects of the present invention can be exhibited more effectively.
  • the alkyl group of the ester moiety is preferably a chain alkyl group in that the effects of the present invention can be exhibited more effectively.
  • chain as used herein means a straight-chain or branched chain.
  • alkyl (meth)acrylate (a1) in which the alkyl group of the ester moiety is a chain alkyl group having 1 to 20 carbon atoms examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodec
  • the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) has a homopolymer glass transition temperature Tg of preferably ⁇ 10 from the point of view that the effects of the present invention can be more expressed. ° C. or lower, more preferably -12 °C or lower, still more preferably -15 °C or lower, particularly preferably -18 °C or lower, and most preferably -20 °C or lower.
  • the lower limit of the glass transition temperature Tg is preferably -80°C or higher.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) can affect the adhesion properties and low elasticity of the acrylic polymer (P1).
  • an alkyl (meth)acrylate whose homopolymer (homopolymer) has a glass transition temperature Tg within the above range as the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) acrylic Adhesiveness and low elasticity of the system polymer (P1) can be appropriately adjusted, and the effects of the present invention can be exhibited more.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) a value described in a known document can be adopted.
  • Polymer Handbook (3rd edition, John Wiley & Sons, Inc., 1989).
  • the conventional value is adopted.
  • alkyl (meth)acrylates not listed in the above “Polymer Handbook” the catalog values of monomer manufacturing companies are used.
  • the Tg of the alkyl (meth)acrylate homopolymer which is not described in the above "Polymer Handbook” and is not provided with the catalog value of the monomer manufacturing company, is the value obtained by the measurement method described in JP-A-2007-51271. shall be used.
  • the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) preferably has a homopolymer (homopolymer) glass transition temperature Tg of ⁇ It contains an alkyl (meth)acrylate (a1-1) within the range of 40°C to -10°C (preferably -35°C to -15°C, more preferably -30°C to -20°C).
  • Tg homopolymer glass transition temperature
  • LA lauryl acrylate
  • the content of the alkyl (meth)acrylate (a1-1) in the total amount of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) is preferably 10 from the viewpoint that the effects of the present invention can be exhibited more. % to 80% by weight, more preferably 20% to 70% by weight, still more preferably 25% to 60% by weight, particularly preferably 30% to 55% by weight, most preferably is 35% to 50% by weight.
  • the content of the alkyl (meth)acrylate (a1-1) in the total amount of the monomer component (M1) is preferably 10% by weight to 80% by weight, and more preferably 15% to 70% by weight, more preferably 20% to 60% by weight, particularly preferably 25% to 50% by weight, and most preferably 30% to 45% by weight.
  • the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) preferably has a homopolymer (homopolymer) glass transition temperature Tg of ⁇ It contains an alkyl (meth)acrylate (a1-2) within the range of 80°C to -60°C (preferably -75°C to -60°C, more preferably -75°C to -65°C).
  • Tg homopolymer glass transition temperature
  • the content of the alkyl (meth)acrylate (a1-2) in the total amount of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) is preferably 20 from the viewpoint that the effects of the present invention can be exhibited more. % to 90% by weight, more preferably 30% to 80% by weight, still more preferably 40% to 75% by weight, particularly preferably 45% to 70% by weight, most preferably is 50% to 65% by weight.
  • the content of the alkyl (meth)acrylate (a1-2) in the total amount of the monomer component (M1) is preferably 10% by weight to 80% by weight, and more preferably 20% to 75% by weight, more preferably 30% to 70% by weight, particularly preferably 35% to 65% by weight, and most preferably 40% to 60% by weight.
  • the monomer component (M1) is an alkyl (meth)acrylate having a glass transition temperature Tg of more than -60°C and less than -40°C as an alkyl (meth)acrylate within a range that does not impair the effects of the present invention. may contain alkyl (meth)acrylates (a1-3) within.
  • the content of the alkyl (meth)acrylate (a1-3) in the total amount of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) is preferably 40 from the viewpoint that the effects of the present invention can be exhibited more. % by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, particularly preferably 10% by weight or less, and most preferably 5% by weight or less.
  • the content of the alkyl (meth)acrylate (a1-3) in the total amount of the monomer component (M1) is preferably 40% by weight or less, and more preferably 30% by weight, from the viewpoint that the effects of the present invention can be further expressed. or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less, and most preferably 5% by weight or less.
  • the content of the polar group-containing monomer (b1) in the monomer component (M1) is preferably from 1% by weight to 50% by weight, more preferably from 1% by weight to 1% by weight, from the viewpoint that the effects of the present invention can be further exhibited. 30% by weight, more preferably 1% to 20% by weight, particularly preferably 1% to 18% by weight, and most preferably 1% to 15% by weight.
  • the polar group-containing monomer (b1) is preferably selected from the group consisting of a hydroxyl group-containing monomer (b1-1) and a monomer (b1-2) having a polar group other than a hydroxyl group, in order to further express the effects of the present invention. It contains at least one selected, and more preferably contains both a hydroxyl group-containing monomer (b1-1) and a monomer having a polar group other than a hydroxyl group (b1-2).
  • the number of hydroxyl group-containing monomers (b1-1) may be one, or two or more.
  • hydroxyl group-containing monomers (b1-1) examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4 - hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate; polypropylene glycol mono(meth)acrylate; N-hydroxyethyl (meth)acrylamide;
  • the hydroxyl group-containing monomer (b1-1) preferably has a glass transition temperature Tg of its homopolymer (homopolymer) of -60°C to -10°C. It is preferably -55°C to -10°C, more preferably -45°C to -10°C.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (b1-1) can affect the adhesion properties and low elasticity of the acrylic polymer (P1).
  • the acrylic polymer (b1-1) that can be contained in the monomer component (M1), by adopting a hydroxyl group-containing monomer whose homopolymer (homopolymer) has a glass transition temperature Tg within the above range, the acrylic polymer
  • Tg glass transition temperature
  • glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (b1-1) see [1-2-1-1.
  • Alkyl (meth)acrylate (a1)) the description of the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) can be used.
  • the hydroxyl group-containing monomer (b1-1) is preferably a hydroxyalkyl (meth)acrylate, more preferably a hydroxyalkyl group in which the alkyl group portion of the hydroxyalkyl group is carbon.
  • the content ratio of the hydroxyl group-containing monomer (b1-1) in the polar group-containing monomer (b1) is preferably 20% by weight to 100% by weight, more preferably 25% by weight, from the viewpoint that the effects of the present invention can be further expressed. % to 95% by weight, more preferably 30% to 90% by weight, particularly preferably 35% to 85% by weight, and most preferably 40% to 80% by weight.
  • the content of the hydroxyl group-containing monomer (b1-1) in the monomer component (M1) is preferably 0.05% by weight to 30% by weight, more preferably 0% by weight, from the viewpoint that the effects of the present invention can be further expressed. .1 wt % to 20 wt %, more preferably 1 wt % to 15 wt %, particularly preferably 2 wt % to 10 wt %, most preferably 4 wt % to 9 wt %.
  • the monomer (b1-2) having a polar group other than a hydroxyl group may be of only one type, or may be of two or more types.
  • the monomer (b1-2) having a polar group other than a hydroxyl group includes, for example, N-vinyl-2-pyrrolidone, nitrogen-containing monomers other than N-vinyl-2-pyrrolidone, carboxyl group-containing monomers, sulfonic acid group-containing monomers, Phosphate group-containing monomers, cyano group-containing monomers, acid anhydride group-containing monomers, vinyl esters (e.g., vinyl acetate (VAc), vinyl propionate, vinyl laurate), aromatic vinyl compounds, amide group-containing monomers, epoxies group-containing monomers, (meth)acryloylmorpholine, and vinyl ethers;
  • N-vinyl-2-pyrrolidone nitrogen-containing monomers other than N-vinyl-2-pyrrolidone
  • carboxyl group-containing monomers e.g., sulfonic acid group-containing monomers, Phosphate group-containing monomers, cyano
  • carboxy group-containing monomers examples include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. mentioned.
  • Nitrogen-containing monomers other than N-vinyl-2-pyrrolidone include, for example, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, (meth) Nitrogen-containing vinyl monomers such as acryloylmorpholine, N-vinylcarboxylic acid amides and N-vinylcaprolactam; cyano group-containing acrylic monomers such as acrylonitrile and methacrylonitrile;
  • the monomer (b1-2) having a polar group other than a hydroxyl group preferably has a homopolymer glass transition temperature Tg of -30°C to 100°C. , more preferably -20°C to 95°C, still more preferably -10°C to 90°C.
  • the glass transition temperature Tg of a homopolymer (homopolymer) of the monomer (b1-2) having a polar group other than a hydroxyl group can affect the adhesion properties and low elasticity of the acrylic polymer (P1).
  • the glass transition temperature Tg of its homopolymer (homopolymer) is within the above range and has a polar group other than a hydroxyl group.
  • the homopolymer preferably has a glass transition temperature Tg of 50° C. to 100° C., in terms of allowing the effect of the present invention to be exhibited more. and a monomer having a polar group other than the hydroxyl group.
  • the glass transition temperature Tg of a homopolymer (homopolymer) of this monomer is preferably 60°C to 95°C, more preferably 70°C to 90°C.
  • glass transition temperature Tg of the homopolymer (homopolymer) of the monomer (b1-2) having a polar group other than a hydroxyl group see [1-2-1-1.
  • Alkyl (meth)acrylate (a1)) the description of the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) can be used.
  • the content of the monomer (b1-2) having a polar group other than a hydroxyl group in the polar group-containing monomer (b1) is preferably 1% by weight to 80% by weight from the viewpoint that the effects of the present invention can be further exhibited. , more preferably 5 wt% to 75 wt%, more preferably 10 wt% to 70 wt%, particularly preferably 15 wt% to 65 wt%, most preferably 20 wt% to 60 wt% is.
  • the content of the monomer (b1-2) having a polar group other than a hydroxyl group in the monomer component (M1) is preferably 0.01% by weight to 20% by weight from the viewpoint that the effects of the present invention can be further exhibited. , more preferably 0.05 wt% to 15 wt%, still more preferably 0.1 wt% to 12 wt%, particularly preferably 0.3 wt% to 10 wt%, most preferably 0 .5% to 9% by weight.
  • the monomer component (M1) preferably comprises an alkyl (meth)acrylate (a1), a hydroxyl group-containing monomer (b1-1), and a monomer having a polar group other than a hydroxyl group, in order to further develop the effects of the present invention.
  • the homopolymer (homopolymer) has a glass transition temperature Tg of -40°C to -10°C (preferably -35°C to -15°C, more preferably -30°C to -20 ° C.), the glass transition temperature Tg of the alkyl (meth) acrylate (a1-1) in the range of -80 ° C. to -60 ° C. (preferably -75 ° C. to -60 ° C., more preferably -75 ° C. to -65 ° C.) alkyl (meth) acrylate (a1-2), a hydroxyl group-containing monomer (b1-1), and a monomer having a polar group other than a hydroxyl group (b1- 2).
  • the glass transition temperature Tg of the homopolymer (homopolymer) in the monomer component (M1) is -40 ° C. to -10 ° C. (preferably -35 ° C. to - 15 ° C., more preferably -30 ° C. to -20 ° C.), the glass transition temperature Tg of the alkyl (meth) acrylate (a1-1) in the range of -80 ° C. to -60 ° C. ° C. (preferably ⁇ 75° C. to ⁇ 60° C., more preferably ⁇ 75° C.
  • alkyl (meth)acrylate (a1-2), hydroxyl group-containing monomer (b1-1), and hydroxyl group The content ratio of the total amount of the monomer (b1-2) having a polar group other than the % to 100% by weight, particularly preferably 90% to 100% by weight, most preferably 95% to 100% by weight.
  • the monomer component (M1) preferably includes lauryl acrylate, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, and N-vinyl-2-pyrrolidone, in order to further develop the effects of the present invention. include.
  • the monomer component (M1) may contain other monomers (c1) that are neither alkyl (meth)acrylates (a1) nor polar group-containing monomers (b1).
  • Other monomers (c1) can be used, for example, for the purpose of adjusting the glass transition temperature (Tg) of the acrylic polymer (P1), adjusting adhesive performance, and the like. Only one kind of other monomer may be used, or two or more kinds thereof may be used.
  • the content of the other monomer (c1) in the monomer component (M1) is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, and particularly preferably 3% by weight. % by weight or less, and most preferably 1% by weight or less.
  • the photopolymerization initiator can be appropriately selected from any appropriate photopolymerization initiators depending on the type of polymerization method. Only one type of photopolymerization initiator may be used, or two or more types may be used.
  • photopolymerization initiators include, for example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, ⁇ -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators.
  • Polymerization initiators benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, etc. mentioned.
  • benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- 1-one (commercially available, for example, trade name "OMNIRAD651", manufactured by IGM Resins B.V.), anisole methyl ether, and the like.
  • acetophenone-based photopolymerization initiator examples include 1-hydroxycyclohexylphenyl ketone (commercially available products, such as the trade name "OMNIRAD184", manufactured by IGM Resins B.V.), 4-phenoxydichloroacetophenone. , 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (commercially available products such as "OMNIRAD2959", manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methoxyacetophenone and the like.
  • ⁇ -ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2- and methylpropan-1-one.
  • aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride.
  • photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
  • Benzoin-based photopolymerization initiators specifically include, for example, benzoin.
  • benzyl-based photopolymerization initiators include benzyl and the like.
  • benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and ⁇ -hydroxycyclohexylphenyl ketone.
  • ketal-based photopolymerization initiators include benzyl dimethyl ketal.
  • thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, and 2,4-diethyl thioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like.
  • acylphosphine-based photopolymerization initiators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl).
  • Phosphine oxide bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl) )-(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6- dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2 ,6-diethoxybenzoyl)(2-methylpropan-1-yl)pho
  • the amount of the photopolymerization initiator used can be set to any suitable amount within a range that does not impair the effects of the present invention.
  • the amount of the photopolymerization initiator used is preferably 0.001 parts by weight to 10 parts by weight, more preferably 0.001 part by weight to 10 parts by weight with respect to 100 parts by weight of the monomer component (M1), in order to further express the effects of the present invention. 0.005 to 5 parts by weight, more preferably 0.007 to 3 parts by weight, particularly preferably 0.01 to 1 part by weight.
  • a thermal polymerization initiator any appropriate method, such as a conventionally known method, can be adopted as long as the effects of the present invention are not impaired.
  • the acrylic polymer (P2) is obtained by polymerizing the monomer component (M2).
  • the monomer component (M2) as used herein does not include a cross-linking agent that can be contained in the acrylic pressure-sensitive adhesive composition and will be described later.
  • any appropriate additive may be used in addition to the monomer component (M2) and the thermal polymerization initiator within a range that does not impair the effects of the present invention.
  • the acrylic polymer (P2) can thus be defined as one obtained by polymerizing the monomer component (M2). This is because the acrylic polymer (P2) becomes the acrylic polymer (P2) by causing a polymerization reaction of the monomer component (M2), and it is impossible to directly specify the acrylic polymer (P2) by its structure. , Also, due to the fact that there are circumstances that are almost impractical ("impossible / impractical circumstances"), the acrylic polymer (P2) is defined as "obtained by polymerizing the monomer component (M2)" is properly identified as a "thing".
  • the acrylic polymer (P2) preferably has a Tg of ⁇ 85° C. to ⁇ 30° C., more preferably ⁇ 80° C. to ⁇ 40° C., in that the effects of the present invention can be exhibited more. It is preferably -75°C to -50°C, particularly preferably -70°C to -60°C.
  • the Tg of the acrylic polymer (P2) is based on the Tg of a homopolymer (homopolymer) of each monomer constituting the acrylic polymer (P2) and the weight fraction of the monomer (copolymerization ratio based on weight). , a value obtained from the Fox formula. For the Fox formula and the Tg of various homopolymers, see ⁇ 1-2-1.
  • the description in the section of Acrylic Polymer (P1)> can be used.
  • the monomer component (M2) preferably contains an alkyl (meth)acrylate (a2) and a polar group-containing monomer (b2).
  • Alkyl (meth)acrylates (a2) may be used alone or in combination of two or more.
  • the number of polar group-containing monomers (b2) may be one, or two or more.
  • Alkyl (meth)acrylate (a2) The alkyl group in the ester portion of the alkyl (meth)acrylate (a2) (hereinafter sometimes referred to as "the alkyl group in the ester portion") includes an alkyl group containing a hydroxyl group and an alkyl group containing a polar group other than a hydroxyl group. Not included. Therefore, the alkyl (meth)acrylate (a2) is clearly distinguished from the polar group-containing monomer (b2).
  • the content of the alkyl (meth)acrylate (a2) in the monomer component (M2) is preferably 70% by weight to 99.9% by weight, more preferably 80% by weight, from the viewpoint that the effects of the present invention can be further expressed. % to 99.5% by weight, more preferably 90% to 99.2% by weight, more preferably 93% to 99.2% by weight, particularly preferably 95% to 99% by weight %, most preferably 97% to 99% by weight.
  • the alkyl group of the ester moiety is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, and still more preferably, from the viewpoint that the effects of the present invention can be exhibited more effectively.
  • the alkyl group of the ester moiety is preferably a chain alkyl group in that the effects of the present invention can be exhibited more effectively.
  • chain as used herein means a straight-chain or branched chain.
  • alkyl (meth)acrylate (a2) in which the alkyl group of the ester portion is a chain alkyl group having 1 to 20 carbon atoms see [1-2-1-1.
  • the description of the alkyl (meth)acrylate (a1) in which the alkyl group of the ester moiety is a chain alkyl group having 1 to 20 carbon atoms in the section of "Alkyl (meth)acrylate (a1)" can be referred to.
  • the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) has a homopolymer glass transition temperature Tg of preferably ⁇ 10 from the point of view that the effects of the present invention can be more expressed. ° C. or lower, more preferably -12 °C or lower, still more preferably -15 °C or lower, particularly preferably -18 °C or lower, and most preferably -20 °C or lower.
  • the lower limit of the glass transition temperature Tg is preferably -80°C or higher.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) can affect the adhesion properties and low elasticity of the acrylic polymer (P2).
  • an alkyl (meth)acrylate whose homopolymer (homopolymer) has a glass transition temperature Tg within the above range as the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) acrylic Adhesiveness and low elasticity of the system polymer (P2) can be appropriately adjusted, and the effects of the present invention can be exhibited more.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) is described in [1-2-1-1.
  • Alkyl (meth)acrylate (a1)] the description of the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) can be used.
  • the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) preferably has a homopolymer glass transition temperature Tg of ⁇ It contains an alkyl (meth)acrylate (a2-1) within the range of 40°C to -10°C (preferably -35°C to -15°C, more preferably -30°C to -20°C).
  • Tg homopolymer glass transition temperature
  • the alkyl (meth)acrylate (a2-1) within the range of 40°C to -10°C (preferably -35°C to -15°C, more preferably -30°C to -20°C).
  • LA lauryl acrylate
  • the content of the alkyl (meth)acrylate (a2-1) in the total amount of the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) is preferably 1 from the viewpoint that the effect of the present invention can be exhibited more. % to 30% by weight, more preferably 2% to 20% by weight, still more preferably 4% to 15% by weight, particularly preferably 5% to 12% by weight, most preferably is 6% to 10% by weight.
  • the content of the alkyl (meth)acrylate (a2-1) in the total amount of the monomer component (M2) is preferably 1% by weight to 30% by weight, and more preferably 2% to 20% by weight, more preferably 4% to 15% by weight, particularly preferably 5% to 12% by weight, and most preferably 6% to 10% by weight.
  • the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) preferably has a homopolymer glass transition temperature Tg of ⁇ It contains an alkyl (meth)acrylate (a2-2) within the range of 80°C to -60°C (preferably -75°C to -60°C, more preferably -75°C to -65°C).
  • Tg homopolymer glass transition temperature
  • the alkyl (meth)acrylate (a2-2) within the range of 80°C to -60°C (preferably -75°C to -60°C, more preferably -75°C to -65°C).
  • the content of the alkyl (meth)acrylate (a2-2) in the total amount of the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) is preferably 40 from the viewpoint that the effects of the present invention can be exhibited more.
  • % to 95% by weight more preferably 50% to 90% by weight, still more preferably 55% to 85% by weight, particularly preferably 60% to 80% by weight, and most preferably is 65% to 75% by weight.
  • the content of the alkyl (meth)acrylate (a2-2) in the total amount of the monomer component (M2) is preferably 40% by weight to 95% by weight, and more preferably 50% to 90% by weight, more preferably 55% to 85% by weight, particularly preferably 60% to 80% by weight, and most preferably 65% to 75% by weight.
  • the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) preferably has a homopolymer glass transition temperature Tg of ⁇ Including alkyl (meth)acrylates (a2-3) in the range above 60°C and below -40°C.
  • the content ratio of the alkyl (meth)acrylate (a2-3) in the total amount of the alkyl (meth)acrylate (a2) that can be contained in the monomer component (M2) is preferably 1 in that the effects of the present invention can be exhibited more. % to 50% by weight, more preferably 5% to 35% by weight, still more preferably 10% to 30% by weight, particularly preferably 13% to 28% by weight, most preferably is between 15% and 25% by weight.
  • the content of the alkyl (meth)acrylate (a2-3) in the total amount of the monomer component (M2) is preferably 1% by weight to 50% by weight, and more preferably 5% to 35% by weight, more preferably 10% to 30% by weight, particularly preferably 13% to 28% by weight, and most preferably 15% to 25% by weight.
  • the content of the polar group-containing monomer (b2) in the monomer component (M2) is preferably 0.1% by weight to 30% by weight, and more preferably 0.1% by weight to 30% by weight, from the viewpoint that the effects of the present invention can be further exhibited.
  • the polar group-containing monomer (b2) is preferably selected from the group consisting of a hydroxyl group-containing monomer (b2-1) and a monomer (b2-2) having a polar group other than a hydroxyl group, in order to further express the effects of the present invention. It contains at least one selected, and more preferably contains both a hydroxyl-containing monomer (b2-1) and a monomer having a polar group other than a hydroxyl group (b2-2).
  • the number of hydroxyl group-containing monomers (b2-1) may be one, or two or more.
  • hydroxyl group-containing monomer (b2-1) see [1-2-1-2.
  • the description of the hydroxyl group-containing monomer (b1-1) in the section of Polar Group-Containing Monomer (b1)] may be used.
  • the hydroxyl group-containing monomer (b2-1) preferably has a glass transition temperature Tg of its homopolymer (homopolymer) of -60°C to -10°C. It is preferably -55°C to -10°C, more preferably -45°C to -10°C.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (b2-1) can affect the adhesion properties and low elasticity of the acrylic polymer (P2).
  • the acrylic polymer (b2-1) that can be contained in the monomer component (M2), by adopting a hydroxyl group-containing monomer whose homopolymer has a glass transition temperature Tg within the above range, the acrylic polymer
  • Tg glass transition temperature
  • glass transition temperature Tg of the homopolymer (homopolymer) of the hydroxyl group-containing monomer (b2-1) see [1-2-1-1.
  • Alkyl (meth)acrylate (a1)) the description of the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) can be used.
  • the hydroxyl group-containing monomer (b2-1) is preferably a hydroxyalkyl (meth)acrylate, more preferably a hydroxyalkyl group in which the alkyl group portion of the hydroxyalkyl group is carbon.
  • HOA 2-hydroxyethyl acrylate
  • the content ratio of the hydroxyl group-containing monomer (b2-1) in the polar group-containing monomer (b2) is preferably 1% by weight to 99% by weight, more preferably 20% by weight, from the viewpoint that the effects of the present invention can be further expressed.
  • % to 90% by weight more preferably 40% to 80% by weight, particularly preferably 45% to 75% by weight, and most preferably 50% to 70% by weight.
  • the content ratio of the hydroxyl group-containing monomer (b2-1) in the monomer component (M2) is preferably 0.001% by weight to 10% by weight, more preferably 0, in terms of allowing the effect of the present invention to be exhibited more. 0.01 wt % to 5 wt %, more preferably 0.05 wt % to 3 wt %, particularly preferably 0.1 wt % to 2 wt %, most preferably 0.5 wt % to 1.5% by weight.
  • the monomer (b2-2) having a polar group other than a hydroxyl group preferably has a homopolymer glass transition temperature Tg of -30°C to 100°C. , more preferably -20°C to 95°C, still more preferably -10°C to 90°C.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the monomer (b2-2) having a polar group other than a hydroxyl group can affect the adhesion properties and low elasticity of the acrylic polymer (P2).
  • the glass transition temperature Tg of the homopolymer thereof is within the above range and has a polar group other than a hydroxyl group.
  • the homopolymer preferably has a glass transition temperature Tg of 50° C. to 100° C., in that the effect of the present invention can be exhibited more. and a monomer having a polar group other than the hydroxyl group.
  • the glass transition temperature Tg of a homopolymer (homopolymer) of this monomer is preferably 60°C to 95°C, more preferably 70°C to 90°C.
  • the glass transition temperature Tg of the homopolymer (homopolymer) of the monomer (b2-2) having a polar group other than a hydroxyl group see [1-2-1-1.
  • Alkyl (meth)acrylate (a1)) the description of the glass transition temperature Tg of the homopolymer of the alkyl (meth)acrylate (a1) that can be contained in the monomer component (M1) can be used.
  • the content of the monomer (b2-2) having a polar group other than a hydroxyl group in the polar group-containing monomer (b2) is preferably 1% by weight to 99% by weight from the viewpoint that the effects of the present invention can be further exhibited. , more preferably 10 wt% to 80 wt%, more preferably 20 wt% to 60 wt%, particularly preferably 25 wt% to 55 wt%, most preferably 30 wt% to 50 wt% is.
  • the content of the monomer (b2-2) having a polar group other than a hydroxyl group in the monomer component (M2) is preferably 0.0001% by weight to 10% by weight from the viewpoint that the effects of the present invention can be further exhibited. , more preferably 0.005 wt% to 5 wt%, still more preferably 0.01 wt% to 3 wt%, particularly preferably 0.05 wt% to 2 wt%, most preferably 0 .1% to 1% by weight.
  • the monomer component (M2) preferably comprises an alkyl (meth)acrylate (a2), a hydroxyl group-containing monomer (b2-1), and a monomer having a polar group other than a hydroxyl group, in order to further develop the effects of the present invention.
  • the homopolymer (homopolymer) has a glass transition temperature Tg of -40°C to -10°C (preferably -35°C to -15°C, more preferably -30°C to -20 ° C.), the glass transition temperature Tg of the alkyl (meth) acrylate (a2-1) in the range of -80 ° C. to -60 ° C. (preferably -75 ° C. to -60 ° C., more preferably -75 ° C.
  • the glass transition temperature Tg of the homopolymer (homopolymer) thereof exceeds -60 ° C.
  • Alkyl (meth)acrylate (a2-3) having a temperature of less than 40° C., hydroxyl group-containing monomer (b2-1), and monomer (b2-2) having a polar group other than hydroxyl group are included.
  • the glass transition temperature Tg of the homopolymer (homopolymer) in the monomer component (M2) is -40 ° C. to -10 ° C. (preferably -35 ° C. to - 15 ° C., more preferably -30 ° C. to -20 ° C.), the glass transition temperature Tg of the alkyl (meth) acrylate (a2-1) in the range of -80 ° C. to -60 ° C. ° C. (preferably -75 ° C. to -60 ° C., more preferably -75 ° C.
  • the content of the total amount of 2) is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, still more preferably 80% to 100% by weight, and particularly preferably is between 90% and 100% by weight, most preferably between 95% and 100% by weight.
  • the monomer component (M2) is preferably lauryl acrylate, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, N-vinyl acrylate, or -2-pyrrolidone.
  • the monomer component (M2) may contain other monomers (c2) that are neither alkyl (meth)acrylates (a2) nor polar group-containing monomers (b2).
  • Other monomers (c2) can be used, for example, for the purpose of adjusting the glass transition temperature (Tg) of the acrylic polymer (P2), adjusting adhesive performance, and the like. Only one kind of other monomer may be used, or two or more kinds thereof may be used.
  • the content of the other monomer (c2) in the monomer component (M2) is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, and particularly preferably 3% by weight. % by weight or less, and most preferably 1% by weight or less.
  • the thermal polymerization initiator can be appropriately selected from any suitable thermal polymerization initiator depending on the type of polymerization method.
  • the thermal polymerization initiator may be used alone or in combination of two or more.
  • thermal polymerization initiators examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis(2-methylpropionic acid ) dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis[2-(5-methyl -2-imidazolin-2-yl)propane]dihydrochloride, 2,2′-azobis(2-methylpropionamidine) disulfate, 2,2′-azobis(N,N′-dimethyleneisobutyramidine), 2 , 2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) and other azo initiators; potassium persulfate, ammonium persulfate persul
  • redox initiators in combination with a peroxide and a reducing agent such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate; substitutions such as phenyl-substituted ethane ethane-based initiators; aromatic carbonyl compounds;
  • the amount of the thermal polymerization initiator used can be set to any suitable amount as long as it does not impair the effects of the present invention.
  • the amount of the thermal polymerization initiator to be used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 10 parts by weight, relative to 100 parts by weight of the monomer component (M2), from the point of view that the effect of the present invention can be more expressed. 0.005 to 5 parts by weight, more preferably 0.007 to 3 parts by weight, particularly preferably 0.01 to 1 part by weight.
  • Photocurable acrylic pressure-sensitive adhesive composition and photocurable acrylic pressure-sensitive adhesive are a photocurable acrylic pressure-sensitive adhesive, and the photocurable acrylic pressure-sensitive adhesive is typically a photocurable acrylic pressure-sensitive adhesive containing an acrylic polymer (P1). It is formed by a photo-curing reaction of the composition.
  • a photocurable acrylic pressure-sensitive adhesive is formed from a photocurable acrylic pressure-sensitive adhesive composition by any appropriate method.
  • a photocurable acrylic pressure-sensitive adhesive composition is applied onto any appropriate base material, and then a separate adhesive layer is coated on the surface of the pressure-sensitive adhesive layer formed by A method of placing any appropriate base material and curing it by irradiating with ultraviolet rays.
  • the substrate include the aforementioned release liner.
  • any appropriate method of application can be used as long as the effects of the present invention are not impaired. Examples of such coating methods include roll coating, gravure roll coating, reverse roll coating, kiss roll coating, dip roll coating, bar coating, roll brush coating, spray coating, and knife coating. method, air knife coating method, comma coating method, direct coating method and die coating method.
  • heating may be performed as necessary.
  • aging may be performed for the purpose of adjusting the migration of components in the formed photocurable acrylic pressure-sensitive adhesive, progressing the cross-linking reaction, relaxing strain that may exist in the photocurable acrylic pressure-sensitive adhesive, and the like. .
  • the photocurable acrylic pressure-sensitive adhesive composition preferably contains a cross-linking agent (L1).
  • the cross-linking agent (L1) may be of only one type, or may be of two or more types.
  • the content of the cross-linking agent (L1) in the photocurable acrylic pressure-sensitive adhesive composition can be set to any appropriate content within a range that does not impair the effects of the present invention.
  • the content of the cross-linking agent (L1) in the photocurable acrylic pressure-sensitive adhesive composition is preferably 0.00 to 100 parts by weight of the acrylic polymer (P1), in order to achieve the effects of the present invention. 001 parts by weight to 0.5 parts by weight, more preferably 0.005 parts by weight to 0.3 parts by weight, still more preferably 0.01 parts by weight to 0.2 parts by weight, particularly preferably 0 0.05 parts by weight to 0.1 parts by weight.
  • cross-linking agent (L1) Any appropriate cross-linking agent can be employed as the cross-linking agent (L1) as long as it does not impair the effects of the present invention.
  • a cross-linking agent (L1) preferably includes polyfunctional (meth)acrylates.
  • any appropriate polyfunctional (meth)acrylate can be adopted as the polyfunctional (meth)acrylate as long as it does not impair the effects of the present invention. Only one kind of polyfunctional (meth)acrylate may be used, or two or more kinds thereof may be used.
  • polyfunctional (meth)acrylates include, for example, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6- Polyhydric alcohol such as hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate and (meth)acrylic acid vinyl (meth)acrylate; divinylbenzene; epoxy
  • the photocurable acrylic pressure-sensitive adhesive composition may contain an acrylic oligomer. Only one type of acrylic oligomer may be used, or two or more types may be used.
  • the content of the acrylic oligomer in the photocurable acrylic pressure-sensitive adhesive composition can be set to any appropriate content within a range that does not impair the effects of the present invention.
  • the content of the acrylic oligomer in the photocurable acrylic pressure-sensitive adhesive composition is preferably 0.1 parts by weight with respect to 100 parts by weight of the acrylic polymer (P1) in that the effects of the present invention can be exhibited more. parts to 20 parts by weight, more preferably 1 part to 15 parts by weight, still more preferably 3 parts to 10 parts by weight, and particularly preferably 5 parts to 8 parts by weight.
  • the weight average molecular weight of the acrylic oligomer is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, even more preferably 1,500 to 10,000, and particularly preferably 2,000 to 8,000.
  • the weight-average molecular weight (Mw) can be obtained by converting to polystyrene using the GPC method. For example, it can be measured under the following conditions using a high-speed GPC apparatus "HPLC-8120GPC" manufactured by Tosoh Corporation. Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6 ml/min
  • the glass transition temperature (Tg) of the acrylic oligomer is preferably 20°C to 300°C, more preferably 30°C to 300°C, and more preferably 40°C to 300°C.
  • the Tg of an acrylic oligomer is defined by Fox based on the Tg of a homopolymer (homopolymer) of each monomer constituting the acrylic oligomer and the weight fraction (copolymerization ratio on a weight basis) of the monomer. A value obtained from a formula. For the Fox formula and the Tg of various homopolymers, see ⁇ 1-2-1. The description in the section of Acrylic Polymer (P1)> can be used.
  • the acrylic oligomer is preferably an acrylic oligomer obtained from a monomer composition containing a (meth)acrylic ester having a cyclic structure in the molecule as an essential component, and a (meth)acrylic ester having a cyclic structure in the molecule and An acrylic oligomer obtained from a monomer composition containing a (meth)acrylic acid alkyl ester having a linear or branched alkyl group as an essential component is more preferable.
  • Only one type of (meth)acrylic acid ester having a cyclic structure in the molecule may be used, or two or more types may be used.
  • Only one type of (meth)acrylic acid alkyl ester having a linear or branched alkyl group may be used, or two or more types may be used.
  • the cyclic structure in the (meth)acrylic acid ester having a cyclic structure in the molecule may be either an aromatic ring or a non-aromatic ring.
  • aromatic rings include aromatic carbocyclic rings (eg, monocyclic carbocyclic rings such as benzene ring, condensed carbocyclic rings such as naphthalene ring, etc.), various aromatic heterocyclic rings, and the like.
  • Non-aromatic rings include, for example, non-aromatic aliphatic rings (non-aromatic alicyclic rings) (e.g., cyclopentane rings, cyclohexane rings, cycloheptane rings, cycloalkane rings such as cyclooctane rings; Cycloalkene rings such as cyclohexene rings), non-aromatic bridging rings (e.g., bicyclic hydrocarbon rings in pinane, pinene, bornane, norbornane, norbornene, etc.; tricyclic or higher aliphatic hydrocarbon rings in adamantane, etc.) (bridged hydrocarbon ring), etc.), non-aromatic heterocyclic rings (eg, epoxy ring, oxolane ring, oxetane ring, etc.), and the like.
  • non-aromatic aliphatic rings e.g., cyclopentane rings, cyclo
  • Tricyclic or higher aliphatic hydrocarbon rings include, for example, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a tricyclopentanyl group, and a tricyclopentenyl group. etc.
  • (meth)acrylic acid ester having a cyclic structure in the molecule include, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and (meth)acrylic acid.
  • (meth)acrylic acid cycloalkyl esters such as cyclooctyl; (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate, dicyclo pentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc.
  • (Meth)acrylic acid esters having a tricyclic or higher aliphatic hydrocarbon ring (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; aryl (meth)acrylates such as phenoxyethyl (meth)acrylate oxyalkyl esters, (meth)acrylic acid esters having an aromatic ring such as arylalkyl (meth)acrylates such as benzyl (meth)acrylate; and the like.
  • the (meth)acrylic acid ester having a cyclic structure in the molecule preferably includes a non-aromatic ring-containing (meth)acrylic acid ester, more preferably , cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), dicyclopentanyl acrylate (DCPA), dicyclopentanyl methacrylate (DCPMA), more preferably dicyclopentanyl acrylate (DCPA ), and dicyclopentanyl methacrylate (DCPMA).
  • a non-aromatic ring-containing (meth)acrylic acid ester more preferably , cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), dicyclopentanyl acrylate (DCPA), dicyclopentanyl methacrylate (DCPMA), more preferably dicyclopentanyl acrylate (DCPA ), and dicyclopentanyl methacrylate (DCPMA
  • the content ratio of the (meth)acrylic acid ester having a cyclic structure in the molecule in all the monomers that can be used to constitute the acrylic oligomer is 100 parts by weight of the total monomers in that the effects of the present invention can be further expressed. On the other hand, it is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight.
  • Examples of (meth)acrylic acid alkyl esters having a linear or branched alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid.
  • the content ratio of the (meth)acrylic acid alkyl ester having a linear or branched alkyl group in all the monomers that can be used to constitute the acrylic oligomer can further express the effects of the present invention. It is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, still more preferably 20 to 60 parts by weight, based on 100 parts by weight of the total monomers.
  • All monomers (monomer composition) that can be used to constitute the acrylic oligomer include (meth)acrylic acid esters having a cyclic structure in the molecule, (meth)acrylic acid having a linear or branched alkyl group, In addition to alkyl esters, other monomers (copolymerizable monomers) that can be copolymerized with these monomers may be included.
  • the content of other monomers (copolymerizable monomers) in all the monomers (monomer composition) that can be used to constitute the acrylic oligomer is preferably less than 50 parts by weight with respect to 100 parts by weight of all the monomers. , more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, and particularly preferably 20 parts by weight or less.
  • Such other monomers include, for example, (meth)acrylic acid alkoxyalkyl esters (e.g., 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth) ) methoxytriethylene glycol acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, etc.), Carboxyl group-containing monomers (e.g., (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, acid anhydride group-containing monomers such as maleic anhydride), hydroxyl group-containing monomers (e.g., (meth) ) hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acryl
  • All monomers (monomer composition) that can be used to constitute acrylic oligomers are particularly preferably selected from (1) dicyclopentanyl acrylate, dicyclopentanyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. and (2) methyl methacrylate.
  • the content of the monomer (1) is preferably 30 to 70 parts by weight with respect to 100 parts by weight of all the monomers (monomer composition) that can be used to constitute the acrylic oligomer, and ( The content of the monomer 2) is preferably 30 to 70 parts by weight.
  • the acrylic oligomer can be produced by any appropriate polymerization as long as the effects of the present invention are not impaired.
  • a polymerization method include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
  • active energy ray polymerization method active energy ray polymerization method
  • bulk polymerization method and solution polymerization method are preferred, and solution polymerization method is more preferred.
  • solvents examples include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and organic solvents. Only one kind of solvent may be used, or two or more kinds thereof may be used.
  • Any appropriate polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, etc.
  • a thermal polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, etc.
  • Only one polymerization initiator may be used, or two or more polymerization initiators may be used.
  • an oil-soluble polymerization initiator when performing solution polymerization, it is preferable to use an oil-soluble polymerization initiator.
  • thermal polymerization initiator Any appropriate thermal polymerization initiator can be used as the thermal polymerization initiator as long as it does not impair the effects of the present invention.
  • the thermal polymerization initiator may be used alone or in combination of two or more. Specific examples of such thermal polymerization initiators are described in [1-2-2-4. Thermal polymerization initiator] can be referred to.
  • the content of the thermal polymerization initiator is, for example, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of all the monomers (monomer composition) that can be used to form the acrylic oligomer.
  • photopolymerization initiator Any appropriate photopolymerization initiator can be employed as the photopolymerization initiator as long as it does not impair the effects of the present invention. Only one type of photopolymerization initiator may be used, or two or more types may be used. Specific examples of such photopolymerization initiators are described in [1-2-1-4. Photopolymerization initiator] can be referred to.
  • the content of the photopolymerization initiator is, for example, preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of all the monomers (monomer composition) that can be used to form the acrylic oligomer. be.
  • a chain transfer agent may be used in the polymerization of the acrylic oligomer to adjust the molecular weight (preferably to adjust the weight average molecular weight to 1000 to 30000).
  • chain transfer agents include 2-mercaptoethanol, ⁇ -thioglycerol, 2,3-dimercapto-1-propanol, octyl mercaptan, t-nonyl mercaptan, dodecyl mercaptan (lauryl mercaptan), t-dodecyl mercaptan, glycidyl mercaptan.
  • thioglycolic acid methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, thio Examples include decyl glycolate, dodecyl thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate, and ⁇ -methylstyrene dimer.
  • ⁇ -thioglycerol and methyl thioglycolate are preferred, and ⁇ -thioglycerol is particularly preferred, from the viewpoint of suppressing whitening of the double-sided pressure-sensitive adhesive tape of the present invention.
  • Only one type of chain transfer agent may be used, or two or more types may be used.
  • the content of the chain transfer agent is, for example, preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the total monomers (monomer composition) that can be used to form the acrylic oligomer. is 0.2 to 15 parts by weight, more preferably 0.3 to 10 parts by weight.
  • the photocurable acrylic pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention.
  • Such other components include, for example, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, colorants, foils, softeners, anti-aging agents, conductive agents, UV absorbers, oxidation Inhibitors, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, other cross-linking agents, solvents, catalysts, cross-linking catalysts, cross-linking retarders and the like.
  • One embodiment of the acrylic pressure-sensitive adhesive is a thermosetting acrylic pressure-sensitive adhesive, and the thermosetting acrylic pressure-sensitive adhesive is typically a thermosetting acrylic pressure-sensitive adhesive containing an acrylic polymer (P2). It is formed by the cross-linking reaction of the composition.
  • thermosetting acrylic pressure-sensitive adhesive is formed from a thermosetting acrylic pressure-sensitive adhesive composition by any appropriate method.
  • a thermosetting acrylic pressure-sensitive adhesive composition is applied onto any appropriate base material, heated and dried as necessary, and cured as necessary.
  • a method of forming a thermosetting acrylic pressure-sensitive adhesive into a sheet on the base material may be mentioned.
  • any coating method can be adopted as long as the effects of the present invention are not impaired. Examples of such coating methods include roll coating, gravure roll coating, reverse roll coating, kiss roll coating, dip roll coating, bar coating, roll brush coating, spray coating, and knife coating. method, air knife coating method, comma coating method, direct coating method and die coating method.
  • thermosetting acrylic pressure-sensitive adhesive composition Any appropriate means can be employed for heating and drying the thermosetting acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired.
  • heating/drying means for example, heating at about 60° C. to 180° C. can be mentioned.
  • Any appropriate means can be employed for curing the thermosetting acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. Examples of such curing means include ultraviolet irradiation, laser irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, ⁇ -ray irradiation, X-ray irradiation, and electron beam irradiation.
  • thermosetting acrylic pressure-sensitive adhesive When forming a thermosetting acrylic pressure-sensitive adhesive, it is necessary to adjust the migration of components in the formed thermosetting acrylic pressure-sensitive adhesive, progress the cross-linking reaction, and Aging may be performed for the purpose of relaxing any strain that may exist.
  • thermosetting acrylic pressure-sensitive adhesive composition preferably contains a cross-linking agent (L2).
  • the cross-linking agent (L2) may be of only one type, or may be of two or more types.
  • the cross-linking agent (L2) By using the cross-linking agent (L2), it is possible to impart appropriate cohesion to the thermosetting acrylic pressure-sensitive adhesive.
  • the cross-linking agent (L2) may be included in the thermosetting acrylic pressure-sensitive adhesive in the form after the cross-linking reaction, the form before the cross-linking reaction, the form in which the cross-linking reaction is partially performed, or an intermediate or composite form thereof.
  • the cross-linking agent (L2) is typically contained in the thermosetting acrylic pressure-sensitive adhesive in the form after the cross-linking reaction.
  • the content of the cross-linking agent (L2) in the thermosetting acrylic pressure-sensitive adhesive composition is preferably 0.00 to 100 parts by weight of the acrylic polymer (P2), in order to achieve the effects of the present invention.
  • 005 parts by weight to 10 parts by weight more preferably 0.01 parts by weight to 5 parts by weight, still more preferably 0.01 parts by weight to 3 parts by weight, still more preferably 0.01 parts by weight to 1 part by weight parts by weight, more preferably 0.01 to 0.7 parts by weight, still more preferably 0.01 to 0.5 parts by weight, and particularly preferably 0.01 to 0.5 parts by weight. 4 parts by weight, most preferably 0.01 to 0.1 parts by weight.
  • cross-linking agents examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, silicone-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl-etherified melamine-based cross-linking agents, and metal chelate-based cross-linking agents.
  • Peroxides and other cross-linking agents preferably isocyanate-based cross-linking agents, epoxy-based cross-linking agents, or peroxides, more preferably isocyanate-based cross-linking agents, in that the effects of the present invention can be more expressed. agent, peroxide.
  • isocyanate-based cross-linking agent a compound having two or more isocyanate groups (including an isocyanate-regenerating polar group temporarily protected by a blocking agent or by quantification of the isocyanate group) in one molecule can be used.
  • isocyanate-based cross-linking agents include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.
  • isocyanate-based cross-linking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate , 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, aromatic diisocyanates such as polymethylene polyphenyl isocyanate; trimethylolpropane/tolylene diisocyanate trimer adduct (for example, manufactured by Tosoh Corporation, trade name Coronate L), Trimethylolpropane/hexamethylene diisocyanate trimer adduct (for example, manufactured by Tosoh Corporation, trade name: Coronate HL), isocyanate adduct of hexamethylene diisocyanate
  • trimethylolpropane adduct of xylylene diisocyanate e.g., Mitsui Chemicals, trade name: Takenate D110N
  • hexamethylene diisocyanate trimethylolpropane adduct e.g., Mitsui Chemicals, trade name: Takenate D160N
  • polyisocyanates polyfunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds, and the like.
  • epoxy-based cross-linking agent a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used.
  • epoxy-based cross-linking agents include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta erythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyg
  • peroxides examples include dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxine)hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5 -dimethyl-2,5-mono(t-butylperoxy)-hexane, ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, di(2-ethylhexyl)peroxydicarbonate, di( 4-t-butyl cyclohexyl)peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl per
  • thermosetting acrylic pressure-sensitive adhesive composition may contain an acrylic oligomer. Only one type of acrylic oligomer may be used, or two or more types may be used. For acrylic oligomers, see [1-2-3-2. Acrylic Oligomer] can be referred to.
  • thermosetting acrylic pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention.
  • Such other components include, for example, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, colorants, foils, softeners, anti-aging agents, conductive agents, UV absorbers, oxidation Inhibitors, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, other cross-linking agents, solvents, catalysts, cross-linking catalysts, cross-linking retarders and the like.
  • Reinforcement films according to embodiments of the present invention may be used in any suitable application.
  • the surface protective film of the present invention is preferably used for reinforcing optical members and electronic members, for example.
  • optical members include LCDs, touch panels using LCDs, color filters used in LCDs, and polarizing plates.
  • the optical member according to the embodiment of the present invention is attached with the reinforcing film of the present invention.
  • an electronic member according to an embodiment of the present invention has the reinforcing film of the present invention adhered thereto.
  • optical members and electronic members are flexible devices such as bendable devices (devices that can be bent), foldable devices (devices that can be folded), and rollable devices (devices that can be rolled). It can be a device.
  • ⁇ Surface elastic modulus of adhesive layer at 25°C> The release liner was peeled off from the obtained reinforcing film, and the strength was determined by the following method using AFM. 1) A sample of about 5 mm x 10 mm was cut out and fixed on a predetermined sample table. 2) The value described by the manufacturer was adopted as the spring constant used for calculating the surface elastic modulus. 3) A sensitivity coefficient was obtained using a silicon wafer. 4) Static electricity was removed before measurement, and 16 ⁇ 16 points of force curve mapping were measured in an area of 50 ⁇ m square (a square of 50 ⁇ m long ⁇ 50 ⁇ m wide) using an AFM.
  • the heat shrinkage ratio of the reinforcing film in the MD direction was calculated as follows. Specifically, the reinforcing film to which the release liner is adhered is cut into a size of 100 mm in width and 100 mm in length to form a test piece, and an image measuring machine Quick vision (manufactured by Mitsutoyo) equipped with a non-contact displacement sensor is used to measure MD. The directional length (mm) was measured. Then, after peeling off the release liner, the test piece was placed with the pressure-sensitive adhesive layer facing upward, and heat treatment (180° C., 5 minutes) was performed.
  • MD direction heat shrinkage rate (%) [(length before heating (mm) - length after heating (mm)) / length before heating (mm)] ⁇ 100
  • a polyimide film (manufactured by Ube Industries, "Upilex S”) having a thickness of 25 ⁇ m was attached to a glass plate via a double-sided adhesive tape (manufactured by Nitto Denko, "No. 531”) to obtain a polyimide film substrate for measurement.
  • the release liner was peeled off from the surface of the reinforcing film cut into a size of 25 mm in width and 100 mm in length, and the film was attached to a polyimide film substrate for measurement using a hand roller to prepare a sample for adhesion measurement.
  • the edge of the base layer of the reinforcing film is held with a chuck, and the reinforcing film is subjected to a 180° peel test at a tensile speed of 300 mm/min in an environment of 25°C. , the peel strength was measured, and the obtained peel strength was taken as the adhesive strength at 25°C to the polyimide film.
  • a polyimide film (manufactured by Ube Industries, "Upilex S”) having a thickness of 25 ⁇ m was attached to a glass plate via a double-sided adhesive tape (manufactured by Nitto Denko, "No. 531”) to obtain a polyimide film substrate for measurement.
  • the release liner was peeled off from the surface of the reinforcing film cut into a size of 25 mm in width and 100 mm in length, and the film was attached to a polyimide film substrate for measurement using a hand roller to prepare a sample for adhesion measurement. After being left at 25° C.
  • the edge of the base layer of the reinforcing film is held with a chuck, and the reinforcing film is subjected to a 180° peel test at a tensile speed of 300 mm/min in a ⁇ 20° C. environment.
  • the obtained peel strength was taken as the adhesive strength at -20°C to the polyimide film.
  • a polyimide film (manufactured by Ube Industries, "Upilex S”) having a thickness of 25 ⁇ m was attached to a glass plate via a double-sided adhesive tape (manufactured by Nitto Denko, "No. 531”) to obtain a polyimide film substrate for measurement.
  • the release liner was peeled off from the surface of the reinforcing film cut into a size of 25 mm in width and 100 mm in length, and the film was attached to a polyimide film substrate for measurement using a hand roller to prepare a sample for adhesion measurement.
  • the end of the base layer of the reinforcing film is held with a chuck, and the reinforcing film is subjected to a 180° peel test at a tensile speed of 300 mm/min in an environment of 180°C. , the peel strength was measured, and the obtained peel strength was taken as the adhesive strength at 180°C to the polyimide film.
  • ⁇ Storage elastic modulus G′ at ⁇ 20° C. of pressure-sensitive adhesive layer> [Sample preparation method 1 (Examples 3-5, 7-8, 11-13, 15-16, Comparative Examples 3-5, 7-12)]
  • the pressure-sensitive adhesive composition was applied to the release-treated surface of a 75 ⁇ m-thick polyester film (trade name “Diafoil MRF75”, manufactured by Mitsubishi Chemical Corporation) whose one side was release-treated with silicone so that the thickness after drying with a fountain roll was 25 ⁇ m. It was applied and dried by curing under the conditions of a drying temperature of 130° C. and a drying time of 1 minute. Thus, a pressure-sensitive adhesive layer was produced on the substrate.
  • a polyester film having a thickness of 75 ⁇ m (trade name “Diafoil MRF75”, manufactured by Mitsubishi Chemical Corporation) with one side treated with silicone for release is applied, and the release-treated surface of the polyester film is the adhesive layer side. and aged at 50° C. for 1 day to prepare a pressure-sensitive adhesive sheet with a thickness of 25 ⁇ m as a sample.
  • Example preparation method 2 (Examples 1, 2, 6, 9 to 10, 14, Comparative Examples 1, 2, 6)]
  • a 75 ⁇ m-thick polyester film (trade name “Diafoil MRF75”, manufactured by Mitsubishi Chemical Corporation) with one side treated with silicone for release is used as a substrate (double release film), and a pressure-sensitive adhesive composition is applied to a thickness of 25 ⁇ m on the substrate. to form a coating layer.
  • a 75 ⁇ m-thick polyester film (trade name “Diafoil MRF75”, manufactured by Mitsubishi Chemical Corporation) whose one side was treated with silicone for release was laminated as a cover sheet (which also serves as a light release film) on the coating layer.
  • this laminate was irradiated with ultraviolet rays by a black light whose position was adjusted so that the irradiation intensity on the irradiation surface directly below the lamp was 5 mW/cm 2 , and photocuring was performed.
  • An adhesive sheet was produced.
  • ⁇ Measuring method ⁇ It was obtained by the following method using a dynamic viscoelasticity measuring device (manufactured by Rheometrics, ARES). Only the pressure-sensitive adhesive layer was taken out from the obtained pressure-sensitive adhesive sheet as a sample, laminated to a thickness of about 1 mm, and punched out to a diameter of 8 mm to prepare a cylindrical pellet, which was used as a measurement sample.
  • the obtained measurement sample was fixed to a ⁇ 8 mm parallel plate jig, and the storage elastic modulus G′ was calculated by the dynamic viscoelasticity measuring device.
  • the measurement conditions are as follows. Measurement: Shear mode Temperature range: -70°C to 200°C Heating rate: 5°C/min Frequency: 1Hz
  • Example 1 Preparation of annealed polyethylene terephthalate film
  • An annealed polyethylene terephthalate film (hereinafter sometimes referred to as an annealed PET film) was obtained by heat-treating a polyethylene terephthalate film having a thickness of 50 ⁇ m (trade name “T100C50” manufactured by Mitsubishi Chemical) at 200° C. for 5 minutes without surface treatment. was made.
  • a coating layer was formed by applying the agent composition (1) to a thickness of 15 ⁇ m.
  • a 75 ⁇ m thick PET film manufactured by Mitsubishi Chemical, trade name “Diafoil MRE75” having one side subjected to silicone release treatment was laminated as a cover sheet (also a light release film) onto this coating layer.
  • the obtained laminate was irradiated with ultraviolet rays from the cover sheet side by a black light whose position was adjusted so that the irradiation intensity on the irradiation surface directly below the lamp was 5 mW/cm 2 , and photocuring was performed to form an adhesive layer having a thickness of 15 ⁇ m.
  • a sheet was produced. (Preparation of reinforcing film (1))
  • the light release film of the obtained pressure-sensitive adhesive sheet was peeled off and laminated on an annealed PET film as a substrate to prepare a reinforcing film (1).
  • Various results are shown in Table 1.
  • Example 2 A reinforcing film (2) was produced in the same manner as in Example 1, except that the thickness of the adhesive composition after drying was changed to 25 ⁇ m. Various results are shown in Table 1.
  • Example 3 (Preparation of annealed polyethylene terephthalate film) An annealed PET film was produced in the same manner as in Example 1.
  • adhesive composition (3) Acrylic polymer B: 100 parts by weight, acrylic oligomer A: 6 parts by weight, NOF's "Nyper BW” (BPO) as a cross-linking agent: 0.38 parts by weight, and pressure-sensitive adhesive composition (3) was prepared.
  • BPO Noper BW
  • the pressure-sensitive adhesive composition (3) was applied onto the annealed PET using a fountain roll so that the thickness after drying was 15 ⁇ m. After drying at 130° C.
  • Example 4 A reinforcing film (4) was produced in the same manner as in Example 3, except that the thickness of the adhesive composition after drying was changed to 25 ⁇ m. Various results are shown in Table 1.
  • Example 5 (Preparation of annealed polyethylene terephthalate film) An annealed PET film was produced in the same manner as in Example 1.
  • adhesive composition (5) Acrylic polymer B: 100 parts by weight, acrylic oligomer B: 1.5 parts by weight, and NOF's "Nyper BW" (BPO) as a cross-linking agent: 0.28 parts by weight to prepare a pressure-sensitive adhesive composition ( 5) was prepared.
  • Example 6 (Preparation of annealed polyethylene terephthalate film) An annealed PET film was produced in the same manner as in Example 1. (Preparation of adhesive composition (6)) Acrylic polymer C: 100 parts by weight, 1,6-hexanediol diacrylate (HDDA) (trade name “A-HD-N”, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a post-addition component: 0.08 weight and acrylic oligomer A: 2 parts by weight were added and uniformly mixed to prepare a pressure-sensitive adhesive composition (6).
  • HDDA 1,6-hexanediol diacrylate
  • A-HD-N 1,6-hexanediol diacrylate
  • acrylic oligomer A 2 parts by weight were added and uniformly mixed to prepare a pressure-sensitive adhesive composition (6).
  • Example 7 (Preparation of annealed polyethylene terephthalate film) An annealed PET film was produced in the same manner as in Example 1.
  • adhesive composition (7) Acrylic polymer E: 100 parts by weight, acrylic oligomer A: 1.5 parts by weight, NOF's "Niper BW” (BPO) as a cross-linking agent: 0.3 parts by weight and a trifunctional isocyanate compound (manufactured by Mitsui Chemicals "Takenate D-110N”): 0.1 part by weight was added to prepare an adhesive composition (7).
  • the pressure-sensitive adhesive composition (7) was applied onto the annealed PET using a fountain roll so that the thickness after drying was 25 ⁇ m. After drying at 130° C. for 1 minute to remove the solvent, a release-treated surface of a release liner (polyethylene terephthalate film having a thickness of 25 ⁇ m and having a silicone release treatment on the surface) was adhered to the coated surface. After that, aging treatment was performed for 4 days in an atmosphere of 25° C. to promote cross-linking, and a reinforcing film (7) was produced. Various results are shown in Table 1.
  • Example 8 (Preparation of annealed polyethylene terephthalate film) An annealed PET film was produced in the same manner as in Example 1. (Preparation of adhesive composition (8)) Acrylic polymer F: 100 parts by weight, acrylic oligomer B: 25 parts by weight, and an epoxy compound ("TETRAD-C" manufactured by Mitsubishi Gas Chemical Co., Ltd.): 0.08 parts by weight as a cross-linking agent are added to prepare an adhesive composition. Item (8) was prepared. (Preparation of reinforcing film (8)) The pressure-sensitive adhesive composition (8) was applied onto the annealed PET using a fountain roll so that the thickness after drying was 15 ⁇ m. After drying at 130° C.
  • Example 9 to 16 Except for using a 50 ⁇ m thick polyimide (PI) film (manufactured by Toray DuPont, trade name “Kapton 200H”) as the base material, the same procedures as in Examples 1 to 8 were performed, and reinforcing films (9) to (16) were prepared. made. Various results are shown in Table 1.
  • PI polyimide
  • Comparative Example 8 A reinforcing film (C8) was produced in the same manner as in Comparative Example 7, except that the thickness of the adhesive composition after drying was changed to 25 ⁇ m. Various results are shown in Table 1.
  • Comparative Example 10 A reinforcing film (C10) was produced in the same manner as in Comparative Example 8, except that an annealed PET film was used as the base material. Various results are shown in Table 1.
  • Comparative Example 11 A reinforcing film (C11) was produced in the same manner as in Comparative Example 7, except that a 50 ⁇ m thick polyimide (PI) film (manufactured by Toray DuPont, trade name “Kapton 200H”) was used as the base material. Various results are shown in Table 1.
  • PI polyimide
  • Comparative Example 12 A reinforcing film (C12) was produced in the same manner as in Comparative Example 8 except that a 50 ⁇ m thick polyimide (PI) film (manufactured by Toray DuPont, trade name “Kapton 200H”) was used as the base material. Various results are shown in Table 1.
  • PI polyimide
  • the reinforcing film according to the embodiment of the present invention is preferably used for reinforcing optical members and electronic members, for example.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film de renforcement comprenant une couche de base et une couche adhésive autocollante, le film de renforcement ayant à la fois une excellente faible élasticité et une excellente résistance à la chaleur et une mauvaise connexion de CI, par exemple, n'étant pas susceptible de se produire.　Un film de renforcement selon un mode de réalisation de la présente invention comprend une couche de base et une couche adhésive autocollante, la couche adhésive autocollante étant formée à partir d'un adhésif acrylique autocollant ; l'élasticité de surface de la couche adhésive autocollante étant de 50 kPa à 1 000 kPa à 25 °C ; et le retrait thermique dans la direction MD lorsque le film de renforcement est chauffé pendant 5 minutes à 180 °C étant inférieur ou égal à 1,0 %.
PCT/JP2022/037493 2021-12-07 2022-10-06 Film de renforcement WO2023105906A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169458A (ja) * 2005-12-22 2007-07-05 Fujimori Kogyo Co Ltd 保護フィルム
JP2008169307A (ja) * 2007-01-12 2008-07-24 Toyo Ink Mfg Co Ltd 粘着剤組成物及びこれを用いた粘着シート
WO2018043155A1 (fr) * 2016-08-30 2018-03-08 東レフィルム加工株式会社 Film protecteur et film stratifié
JP2020050792A (ja) * 2018-09-27 2020-04-02 日東電工株式会社 補強フィルム
JP2020132851A (ja) * 2019-02-12 2020-08-31 日東電工株式会社 補強フィルム、デバイスの製造方法および補強方法
JP2020183502A (ja) * 2019-05-09 2020-11-12 Dic株式会社 粘着フィルム
JP2021521034A (ja) * 2018-11-22 2021-08-26 エルジー・ケム・リミテッド フォルダブルバックプレート、フォルダブルバックプレートの製造方法およびこれを含むフォルダブルディスプレイ装置
JP2021169554A (ja) * 2020-04-15 2021-10-28 星光Pmc株式会社 耐熱性粘着テープ
WO2022030307A1 (fr) * 2020-08-06 2022-02-10 日東電工株式会社 Film de renforcement, élément optique et élément électronique

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169458A (ja) * 2005-12-22 2007-07-05 Fujimori Kogyo Co Ltd 保護フィルム
JP2008169307A (ja) * 2007-01-12 2008-07-24 Toyo Ink Mfg Co Ltd 粘着剤組成物及びこれを用いた粘着シート
WO2018043155A1 (fr) * 2016-08-30 2018-03-08 東レフィルム加工株式会社 Film protecteur et film stratifié
JP2020050792A (ja) * 2018-09-27 2020-04-02 日東電工株式会社 補強フィルム
JP2021521034A (ja) * 2018-11-22 2021-08-26 エルジー・ケム・リミテッド フォルダブルバックプレート、フォルダブルバックプレートの製造方法およびこれを含むフォルダブルディスプレイ装置
JP2020132851A (ja) * 2019-02-12 2020-08-31 日東電工株式会社 補強フィルム、デバイスの製造方法および補強方法
JP2020183502A (ja) * 2019-05-09 2020-11-12 Dic株式会社 粘着フィルム
JP2021169554A (ja) * 2020-04-15 2021-10-28 星光Pmc株式会社 耐熱性粘着テープ
WO2022030307A1 (fr) * 2020-08-06 2022-02-10 日東電工株式会社 Film de renforcement, élément optique et élément électronique

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