WO2021106271A1 - Reinforcing film - Google Patents

Reinforcing film Download PDF

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Publication number
WO2021106271A1
WO2021106271A1 PCT/JP2020/028706 JP2020028706W WO2021106271A1 WO 2021106271 A1 WO2021106271 A1 WO 2021106271A1 JP 2020028706 W JP2020028706 W JP 2020028706W WO 2021106271 A1 WO2021106271 A1 WO 2021106271A1
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WO
WIPO (PCT)
Prior art keywords
meth
reinforcing film
film
acrylate
weight
Prior art date
Application number
PCT/JP2020/028706
Other languages
French (fr)
Japanese (ja)
Inventor
翔悟 佐々木
圭太 小川
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2021561156A priority Critical patent/JP7511578B2/en
Priority to KR1020227017230A priority patent/KR20220103958A/en
Priority to CN202080081630.XA priority patent/CN114729241A/en
Publication of WO2021106271A1 publication Critical patent/WO2021106271A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B7/023—Optical properties
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/29—Laminated material
    • 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]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED

Definitions

  • the present invention relates to a reinforcing film.
  • a reinforcing film is previously attached to the exposed surface side of the optical members and electronic members. It may be reinforced (Patent Document 1).
  • the surface protective film may be attached to the exposed surface of the reinforcing film in advance. Such a surface protective film is peeled off from the reinforcing film when the need for surface protection is eliminated (Patent Document 2).
  • a reinforcing film it may be attached to an optical member or an electronic member, and the optical member or the electronic member may be inspected through the reinforcing film.
  • the reinforcing film when the reinforcing film is attached to an optical member or an electronic member and stored for a long period of time in a harsh environment, the reflectance of the reinforcing film changes, which may reduce the inspectability.
  • the point to be improved that is, the optical member or the electronic member When attached and stored for a long time in a harsh environment, it is important that the change in reflectance of the reinforcing film is suppressed.
  • An object of the present invention is a reinforcing film that can be attached to an optical member or an electronic member, and a change in reflectance is suppressed when the optical member or the electronic member is inspected through the reinforcing film. It is an object of the present invention to provide a reinforcing film that does not deteriorate inspectability. Another object of the present invention is to provide an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Further, it is an object of the present invention to provide a reinforcing film with a surface protective film provided with a surface protective film on such a reinforcing film, and to provide a method of using such a reinforcing film with a surface protective film.
  • the reinforcing film according to the embodiment of the present invention A reinforcing film containing a base material layer A1 and an adhesive layer A2.
  • the rate of change in light reflectance at 580 nm after storing the reinforcing film in an environment of 60 ° C. and 90% RH for one week is 2.0% or less.
  • the haze change rate after storing the reinforcing film in an environment of 60 ° C. and 90% RH for one week is 10.0% or less.
  • the total light transmittance of the base material layer A1 is 90% or more.
  • the reinforcing film according to the embodiment of the present invention has a peeling angle of 180 degrees and a peeling speed of 300 mm / min after the pressure-sensitive adhesive layer A2 is attached to the PET film and left at 23 ° C. for 30 minutes.
  • the adhesive strength against PET film is 0.30 N / 25 mm or more.
  • the reinforcing film according to the embodiment of the present invention is attached to an adherend which is an optical member or an electronic member.
  • the optical member with a reinforcing film or the electronic member with a reinforcing film according to the embodiment of the present invention includes the reinforcing film according to the embodiment of the present invention.
  • the reinforcing film with a surface protective film according to the embodiment of the present invention includes a surface protective film on the base material layer A1 side of the reinforcing film according to the embodiment of the present invention.
  • the reinforcing film with a surface protective film according to the embodiment of the present invention is the above-mentioned surface after the reinforcing film with a surface protective film is stored in an environment of 60 ° C. and 90% RH for one week. After peeling off the protective film, the rate of change in light reflectance of the reinforcing film at 580 nm is 5.0% or less.
  • the pressure-sensitive adhesive layer A2 included in the reinforcing film with a surface protective film according to the embodiment of the present invention is exposed and the pressure-sensitive adhesive layer A2 is attached to an adherend. Then, the surface protective film is peeled off.
  • the present invention is a reinforcing film that can be attached to an optical member or an electronic member, and a change in reflectance is suppressed when the optical member or the electronic member is inspected through the reinforcing film. It is possible to provide a reinforcing film that does not deteriorate inspectability. Further, it is possible to provide an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Further, it is possible to provide a reinforcing film with a surface protective film provided with a surface protective film on such a reinforcing film, and to provide a method of using such a reinforcing film with a surface protective film.
  • FIG. 3 is a schematic cross-sectional view of another embodiment of the surface protective film. It is the schematic sectional drawing of one Embodiment of the reinforcing film with a surface protection film of this invention.
  • weight which is generally used as a unit of weight in the past, and conversely, the expression “weight” in the present specification. If there is, it may be read as “mass” which is commonly used as an SI system unit indicating weight.
  • the expression “(meth) acrylic” means “acrylic and / or methacrolein”
  • the expression “(meth) acrylate” means “acrylate and / or methacrylate”.
  • the expression “(meth) allyl” is used, it means “allyl and / or methacrolein”
  • the expression “(meth) acrolein” is used, “acrolein and / or methacrolein” is used. It means “rain”.
  • the reinforcing film of the present invention includes a base material layer A1 and an adhesive layer A2.
  • the reinforcing film of the present invention may have any suitable other layer as long as it has the base material layer A1 and the pressure-sensitive adhesive layer A2, as long as the effects of the present invention are not impaired.
  • a release sheet which will be described later, may be provided on the surface of the pressure-sensitive adhesive layer A2 for protection.
  • the surface of the base material layer A1 may be provided with a functional layer A3, which will be described later, in order to impart various functions.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • Such a thickness is preferably 5 ⁇ m to 800 ⁇ m, more preferably 10 ⁇ m to 650 ⁇ m, further preferably 20 ⁇ m to 550 ⁇ m, and particularly preferably 25 ⁇ m to 450 ⁇ m.
  • one embodiment of the reinforcing film comprises a base material layer A1 (10) and an adhesive layer A2 (20).
  • the reinforcing film of the present invention has a light reflectance change rate of 2.0% or less at 580 nm after the reinforcing film is stored in an environment of 60 ° C. and 90% RH for one week, and is preferably 1. It is 9% or less, more preferably 1.8% or less, further preferably 1.7% or less, and particularly preferably 1.6% or less.
  • the light reflectance change rate is within the above range, it is possible to provide a reinforcing film that does not deteriorate inspectability when an optical member or an electronic member is inspected through the reinforcing film.
  • the reinforcing film of the present invention has a haze change rate of preferably 10.0% or less, more preferably 7.0, after the reinforcing film is stored in an environment of 60 ° C. and 90% RH for 1 week. % Or less, more preferably 6.0% or less, further preferably 5.0% or less, particularly preferably 4.0% or less, and most preferably 3.5% or less.
  • % Or less more preferably 6.0% or less, further preferably 5.0% or less, particularly preferably 4.0% or less, and most preferably 3.5% or less.
  • Base material layer A1 As the base material layer A1, a base material formed from any suitable material can be adopted depending on the intended purpose, as long as the effects of the present invention are not impaired. Examples of such materials include resin sheets, non-woven fabrics, papers, metal foils, woven fabrics, rubber sheets, foam sheets, and laminates thereof (particularly, laminates including resin sheets).
  • the resin constituting the resin sheet examples include acrylic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polymethyl methacrylate (PMMA), polycarbonate, and triacetyl cellulose (TAC).
  • acrylic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polymethyl methacrylate (PMMA), polycarbonate, and triacetyl cellulose (TAC).
  • Polysulfone polyallylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), total aromatic polyamide (aramid), polyimide ( PI), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluororesin, polyether ether ketone (PEEK), cyclic olefin polymer and the like.
  • PE polyethylene
  • PP polypropylene
  • EVA ethylene-propylene copolymer
  • EVA ethylene-vinyl acetate copolymer
  • PI polyamide
  • PVC polyvinyl chloride
  • PPS polyvinyl acetate
  • PES polyphenylene sulfide
  • PEEK polyether ether ketone
  • non-woven fabric examples include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics containing Manila hemp; synthetic resin non-woven fabrics such as polypropylene resin non-woven fabrics, polyethylene resin non-woven fabrics, and ester resin non-woven fabrics.
  • the base material layer A1 may be only one layer or two or more layers.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • a thickness is preferably 4 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 400 ⁇ m, further preferably 15 ⁇ m to 350 ⁇ m, and particularly preferably 20 ⁇ m to 300 ⁇ m.
  • the total light transmittance of the base material layer A1 is preferably 90% or more, more preferably 91% or more, further preferably 92% or more, and particularly preferably 93% or more.
  • the total light transmittance of the base material layer A1 is within the above range, it is possible to provide a reinforcing film in which the inspectability is not further deteriorated when the optical member or the electronic member is inspected through the reinforcing film. it can.
  • the base material layer A1 may contain an antistatic agent.
  • an antistatic agent for example, a resin sheet in which the antistatic agent is kneaded can be used. Such a resin sheet can be formed from a composition for forming a base material layer A1 containing a resin and an antistatic agent.
  • the base material layer A1 itself may act as an antistatic agent.
  • the base material layer A1 itself can act as an antistatic agent.
  • the base material layer A1 may be surface-treated.
  • the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
  • organic coating material examples include the materials described in Plastic Hard Coat Material II (CMC Publishing, (2004)). Such organic coating materials preferably include urethane-based polymers, and more preferably polyacrylic urethane, polyester urethane, or precursors thereof. This is because coating / coating on the base material layer A1 is easy, and various types can be industrially selected and can be obtained at low cost.
  • a urethane polymer examples include a polymer composed of a reaction mixture of an isocyanato monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound).
  • the organic coating material may contain, as an optional additive, a chain extender such as polyamine, an antiaging agent, an oxidation stabilizer and the like.
  • the base material layer A1 may contain any other suitable additive, depending on the intended purpose, as long as the effects of the present invention are not impaired.
  • the pressure-sensitive adhesive layer A2 may be only one layer or two or more layers.
  • the pressure-sensitive adhesive layer A2 may contain a conductive component.
  • the conductive component may be only one kind or two or more kinds.
  • the adhesive strength to the PET film at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is preferably 0.30 N / 25 mm or more. It is more preferably 1N / 25mm to 40N / 25mm, further preferably 5N / 25mm to 35N / 25mm, and particularly preferably 10N / 25mm to 30N / 25mm.
  • the adhesive strength to the PET film at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is preferably 10 N / 25 mm or more, more preferably. Is 10N / 25mm to 40N / 25mm, more preferably 15N / 25mm to 35N / 25mm, and particularly preferably 20N / 25mm to 30N / 25mm.
  • the pressure-sensitive adhesive layer A2 is formed from the pressure-sensitive adhesive composition a2.
  • the pressure-sensitive adhesive layer A2 can be formed by any suitable method as long as the pressure-sensitive adhesive composition a2 can be formed in layers.
  • the pressure-sensitive adhesive composition a2 is applied onto an arbitrary suitable base material, and if necessary, heating or the like, irradiation with active energy rays (ultraviolet rays, etc.), drying, or the like is performed, and if necessary.
  • a method of forming a pressure-sensitive adhesive layer on the substrate by curing accordingly can be mentioned.
  • Examples of such an application method include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, and a roll brush coater. Method can be mentioned.
  • the pressure-sensitive adhesive composition a2 preferably contains a polymer component in that the effects of the present invention can be more exhibited.
  • the polymer component is preferably at least one selected from an acrylic polymer, a urethane polymer, and a silicone polymer.
  • an acrylic polymer will be described as a typical example.
  • Acrylic polymers can be called so-called base polymers in the field of acrylic pressure-sensitive adhesives.
  • the acrylic polymer may be only one kind or two or more kinds.
  • the content ratio of the acrylic polymer in the pressure-sensitive adhesive composition a2 is preferably 60% by weight to 99.999% by weight, more preferably 65% by weight to 99.99% by weight, and further, in terms of solid content. It is preferably 70% by weight to 99.9% by weight, particularly preferably 75% by weight to 99.9% by weight, and most preferably 80% by weight to 99.9% by weight.
  • acrylic polymer any suitable acrylic polymer can be adopted as long as the effect of the present invention is not impaired.
  • the weight average molecular weight of the acrylic polymer is preferably 300,000 to 2.5 million, more preferably 350,000 to 2 million, and further preferably 400,000 to 1.8 million in that the effects of the present invention can be more exhibited. It is particularly preferably 500,000 to 1,500,000.
  • an acrylic polymer formed by polymerization from the composition (A) containing at least one selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid.
  • Each of (component a) and (component b) may be independently of only one type or of two or more types.
  • Examples of the (meth) acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms are n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, and (meth).
  • n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl acrylate and acrylic are more preferable in that the effects of the present invention can be more exhibited.
  • 2-Ethylhexyl acid 2-Ethylhexyl acid.
  • At least one (b component) selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like.
  • examples thereof include (meth) acrylic acid ester having an OH group such as hydroxybutyl (meth) acrylic acid, and (meth) acrylic acid.
  • hydroxyethyl (meth) acrylate and (meth) acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, in that the effects of the present invention can be more exhibited.
  • the composition (A) may contain a copolymerizable monomer other than the components (a) and (b).
  • the copolymerizable monomer may be only one kind or two or more kinds.
  • a copolymerizable monomer for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like, the alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms.
  • carboxyl such as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and their acid anhydrides (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride).
  • Group-containing monomers (excluding (meth) acrylic acid); (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxy Amid group-containing monomers such as methyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate.
  • Amino group-containing monomer Epoxy group-containing monomer such as (meth) glycidyl acrylate, (meth) methyl glycidyl acrylate; Cyan group-containing monomer such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth) acryloyl Heterocyclic-containing vinyl-based monomers such as morpholin, N-vinylpiperidone, N-vinylpiperazin, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; Phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate; imide group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomer such as 2-methacryloy
  • a polyfunctional monomer can also be adopted.
  • the polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule.
  • any suitable ethylenically unsaturated group can be adopted as long as the effect of the present invention is not impaired.
  • examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group) and an allyl ether group (allyloxy group).
  • polyfunctional monomer examples include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol.
  • examples thereof include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate.
  • Such a polyfunctional monomer may be only one kind or two or more kinds.
  • (meth) acrylic acid alkoxyalkyl ester can also be adopted.
  • the (meth) acrylate alkoxyalkyl ester include (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-ethoxyethyl, (meth) acrylate methoxytriethylene glycol, and (meth) acrylate 3-. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • the (meth) acrylic acid alkoxyalkyl ester may be only one kind or two or more kinds.
  • the content of the (meth) acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer constituting the acrylic polymer in that the effects of the present invention can be more exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, still more preferably 40% by weight to 98% by weight, and particularly preferably 50% by weight, based on the total amount of the components (100% by weight). It is from% by weight to 96% by weight.
  • the content of at least one (component b) selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid makes the acrylic polymer more effective in terms of exhibiting the effects of the present invention. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, still more preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 15% by weight.
  • composition (A) may contain any suitable other component as long as the effect of the present invention is not impaired.
  • suitable other components include polymerization initiators, chain transfer agents, solvents and the like.
  • any appropriate content may be adopted as long as the effect of the present invention is not impaired.
  • the polymerization initiator a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like can be adopted depending on the type of polymerization reaction.
  • the polymerization initiator may be only one kind or two or more kinds.
  • the thermal polymerization initiator can be preferably used when obtaining an acrylic polymer by solution polymerization.
  • a thermal polymerization initiator examples include an azo-based polymerization initiator, a peroxide-based polymerization initiator (for example, dibenzoyl peroxide, tert-butyl permalate, etc.), a redox-based polymerization initiator, and the like. ..
  • the azo-based initiator disclosed in JP-A-2002-69411 is particularly preferable.
  • Such an azo-based polymerization initiator is preferable because the decomposition product of the polymerization initiator does not easily remain in the acrylic polymer as a portion that causes the generation of heating generated gas (out gas).
  • azo-based polymerization initiator examples include 2,2'-azobisisobutyronitrile (hereinafter, may be referred to as AIBN) and 2,2'-azobis-2-methylbutyronitrile (hereinafter, referred to as AMBN). , 2,2'-azobis (2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid and the like.
  • the photopolymerization initiator can preferably be used when obtaining an acrylic polymer by active energy ray polymerization.
  • the photopolymerization initiator include a benzoin ether type photopolymerization initiator, an acetophenone type photopolymerization initiator, an ⁇ -ketol type photopolymerization initiator, an aromatic sulfonyl chloride type photopolymerization initiator, and a photoactive oxime type photopolymerization initiator.
  • Examples thereof include benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.
  • benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisole.
  • examples include methyl ether.
  • examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone.
  • Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. ..
  • Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride.
  • Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
  • Examples of the benzoin-based photopolymerization initiator include benzoin and the like.
  • Examples of the benzyl-based photopolymerization initiator include benzyl and the like.
  • Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone and the like.
  • Examples of the ketal-based photopolymerization initiator include benzyldimethyl ketal and the like.
  • thioxanthone-based photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
  • the pressure-sensitive adhesive composition a2 may contain a cross-linking agent.
  • a cross-linking agent By using a cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited.
  • the cross-linking agent may be only one kind or two or more kinds.
  • cross-linking agent examples include polyfunctional isocyanate-based cross-linking agent, epoxy-based cross-linking agent, melamine-based cross-linking agent, peroxide-based cross-linking agent, urea-based cross-linking agent, metal alkoxide-based cross-linking agent, metal chelate-based cross-linking agent, and metal salt.
  • examples thereof include a system cross-linking agent, a carbodiimide-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, and an amine-based cross-linking agent.
  • at least one (c component) selected from the group consisting of a polyfunctional isocyanate-based cross-linking agent and an epoxy-based cross-linking agent is preferable in that the effects of the present invention can be more exhibited.
  • polyfunctional isocyanate-based cross-linking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and the like.
  • Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.
  • Aromatic polyisocyanates and the like examples include trimethylolpropane / tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L”) and trimethylolpropane / hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd.).
  • epoxy-based cross-linking agent examples include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-diglycidylamino).
  • any appropriate content can be adopted as long as the effect of the present invention is not impaired.
  • a content is preferably 0.005 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer, for example, in that the effect of the present invention can be more exhibited.
  • the pressure-sensitive adhesive composition a2 may contain any suitable other component as long as the effect of the present invention is not impaired.
  • suitable other components include polymer components other than acrylic polymers, cross-linking accelerators, cross-linking catalysts, silane coupling agents, tackifier resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.).
  • Anti-aging agents inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, Examples thereof include surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
  • the pressure-sensitive adhesive composition a2 preferably does not contain an oligomer (X) obtained from a monomer composition containing an acrylic monomer having a cyclic structure of three or more rings as a main component.
  • the content ratio of the acrylic monomer having a cyclic structure of three or more rings to 100 parts by weight of all the monomer components contained in the monomer composition used to obtain the oligomer (X) is preferably 50 parts by weight or more. It is more preferably 60 parts by weight to 99 parts by weight, further preferably 70 parts by weight to 98 parts by weight, and particularly preferably 80 parts by weight to 96 parts by weight.
  • the pressure-sensitive adhesive composition a2 does not contain an oligomer (X) obtained from a monomer composition containing an acrylic monomer having a ring structure of three or more rings as a main component, an optical member or an electronic member is formed through a reinforcing film. It is possible to provide a reinforcing film that does not further deteriorate the inspectability when the inspection is performed.
  • Examples of the acrylic monomer having a cyclic structure of three or more rings include dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, and dicyclo. Pentanyloxyethyl acrylate, tricyclopentanyl methacrylate, tricyclopentanyl acrylate, 1-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, Examples thereof include 2-ethyl-2-adamantyl acrylate.
  • the acrylic monomer having a cyclic structure of three or more rings may be only one kind or two or more kinds.
  • the monomer composition used to obtain the oligomer (X) may contain other monomers in addition to the acrylic monomer having a cyclic structure of three or more rings. Such other monomers may be only one kind or two or more kinds.
  • Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
  • Acrylic monomer containing epoxy groups such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; vinyl ester-based monomers such as vinyl acetate and vinyl propionate; hydroxyethyl (meth)
  • Other monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di.
  • Other monomers also include (meth) nitrogen atom-containing monomers (eg, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like.
  • nitrogen atom-containing monomers eg, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like.
  • Aminoalkyl acrylate monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxy (meth) acrylamide; acrylonitrile , Cyanoacrylate-based monomers such as methacrylonitrile; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate).
  • the pressure-sensitive adhesive composition a2 may contain an oligomer (Y) other than the oligomer (X). However, it is preferable that the content of the oligomer (Y) is small in that the effects of the present invention can be more exhibited.
  • the content ratio of the oligomer (Y) in the pressure-sensitive adhesive composition a2 is preferably 50% by weight with respect to 100 parts by weight of the acrylic polymer contained in the pressure-sensitive adhesive composition a2 in that the effects of the present invention can be more exhibited. It is less than or equal to parts, more preferably 40 parts by weight or less, further preferably 30 parts by weight or less, and particularly preferably 25 parts by weight or less.
  • the oligomer (Y) preferably contains an acrylic monomer having a cyclic structure of two rings or less as a main component, and contains 1 part by weight to 10 parts by weight of a carboxyl group-containing monomer with respect to 100 parts by weight of the total amount of the monomer components. It is an oligomer obtained from the monomer composition.
  • the cyclic structure having two or less rings may be either an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferable.
  • the aromatic ring include an aromatic hydrocarbon ring (for example, a benzene ring, a condensed carbon ring in naphthalene and the like), and various aromatic heterocycles.
  • non-aromatic ring examples include a non-aromatic alicyclic ring (cycloalkane ring such as cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring; cycloalkene ring such as cyclohexene ring) and non-aromatic ring.
  • cycloalkane ring such as cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring
  • cycloalkene ring such as cyclohexene ring
  • non-aromatic ring e.g, bicyclic hydrocarbon rings in pinan, pinen, bornan, norbornene, norbornene, etc.
  • acrylic monomer having a cyclic structure of two or less rings examples include (meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylic acid, and (meth) acrylic acid aryl esters such as phenyl (meth) acrylic acid.
  • Molecules such as (meth) acrylic acid aryloxyalkyl ester such as (meth) phenoxyethyl acrylate, (meth) acrylic acid arylalkyl ester such as (meth) benzyl acrylate, and styrene-based monomers such as styrene and ⁇ -methylstyrene. Examples thereof include an ethylenically unsaturated monomer having a cyclic structure inside.
  • acrylic monomer having a cyclic structure of two or less rings examples include a (meth) acrylic acid ester having a non-aromatic ring such as cyclohexyl methacrylate and isobornyl (meth) acrylate, which are transparent. From the viewpoint, cyclohexyl methacrylate is more preferable.
  • the acrylic monomer having a cyclic structure of two or less rings may be only one kind or two or more kinds.
  • the content ratio of the acrylic monomer having a cyclic structure of two rings or less with respect to 100 parts by weight of all the monomer components contained in the monomer composition used for obtaining the oligomer (Y) is preferably 50 parts by weight to 99 parts by weight. It is more preferably 70 parts by weight to 99 parts by weight, further preferably 80 parts by weight to 98 parts by weight, particularly preferably 90 parts by weight to 97 parts by weight, and most preferably 92 parts by weight to 96 parts by weight. It is a part by weight.
  • the oligomer (Y) may contain a carboxyl group-containing monomer as a monomer component.
  • a carboxyl group-containing monomer examples include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, as in the case of the carboxyl group-containing monomer that can form an acrylic polymer.
  • acid anhydrides of these carboxyl group-containing monomers for example, acid anhydride group-containing monomers such as maleic anhydride and icotanic anhydride
  • carboxyl group-containing monomers for example, acid anhydride group-containing monomers such as maleic anhydride and icotanic anhydride
  • the content ratio of the carboxyl group-containing monomer to 100 parts by weight of all the monomer components contained in the monomer composition used for obtaining the oligomer (Y) is preferably 1 part by weight to 10 parts by weight, preferably 2 parts by weight. It is ⁇ 9 parts by weight, more preferably 3 parts by weight to 8 parts by weight, and particularly preferably 4 parts by weight to 7 parts by weight.
  • the monomer composition used to obtain the oligomer (Y) may contain other monomers in addition to the acrylic monomer having a cyclic structure of two or less rings. Such other monomers may be only one kind or two or more kinds.
  • Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
  • Acrylic monomer containing epoxy groups such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; vinyl ester-based monomers such as vinyl acetate and vinyl propionate; hydroxyethyl (meth)
  • Examples of other monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol di.
  • Other monomers include nitrogen atom-containing monomers (eg, (meth) acrylics such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate.
  • nitrogen atom-containing monomers eg, (meth) acrylics such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate.
  • Aminoalkyl acid-based monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-hydroxy (meth) acrylamide; acrylonitrile, methacryl
  • cyanoacrylate-based monomers such as lonitrile; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate).
  • nitrogen atom-containing monomer can cause yellowing of the pressure-sensitive adhesive under heating, it is preferable not to use it when it is not necessary to use it.
  • the oligomer (X) and the oligomer (Y) can be prepared by any suitable polymerization method as long as the effects of the present invention are not impaired.
  • the polymerization method of the acrylic polymer include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method by irradiation with ultraviolet rays, and the like, and the solution polymerization method is preferable in terms of transparency, water resistance, cost, and the like. ..
  • polymerization initiator chain transfer agent, etc. that can be used in the polymerization
  • any appropriate one can be adopted as long as the effect of the present invention is not impaired.
  • any appropriate amount can be adopted as long as the effect of the present invention is not impaired.
  • an amount to be used for example, 0.1% by weight to 15% by weight is preferable with respect to the total amount of the monomer components.
  • the amount of the chain transfer agent used may be any appropriate amount as long as the effect of the present invention is not impaired.
  • amount to be used for example, 0.01% by weight to 15% by weight is preferable with respect to the total amount of the monomer components.
  • various general solvents can be used.
  • a solvent 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; cyclohexane and methyl.
  • organic solvents such as alicyclic hydrocarbons such as cyclohexane; and ketones such as methyl ethyl ketone and methyl isobutyl ketone;
  • the solvent may be only one type or two or more types.
  • the oligomers (X) and (Y) have a weight average molecular weight of preferably 3000 to 6000, more preferably 3300 to 5500, and even more preferably 3500 to 5000.
  • the weight average molecular weight of the oligomers (X) and (Y) can be controlled by the type and amount of the polymerization initiator and chain transfer agent, the temperature and time during polymerization, the monomer concentration, the monomer dropping rate, and the like. it can.
  • the ratio of the acrylic polymer to the oligomer is such that the oligomer is preferably 10 parts by weight to 35 parts by weight with respect to 100 parts by weight of the acrylic polymer. It is a part, more preferably 15 parts by weight to 30 parts by weight.
  • the pressure-sensitive adhesive composition a2 contains an acrylic polymer and an oligomer, the effect of the present invention can be further exhibited if the ratio of the acrylic polymer and the oligomer is within the above range.
  • the pressure-sensitive adhesive composition a2 contains, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, an anti-aging agent, a tackifier, a plasticizer, a softener, a filler, a colorant (pigment, dye, etc.). , Known additives such as surfactants and antistatic agents may be included.
  • a release sheet may be provided on the surface of the pressure-sensitive adhesive layer A2 for protection.
  • the release sheet may have one layer or two or more layers.
  • the thickness of the release sheet is preferably 5 ⁇ m to 300 ⁇ m, more preferably 10 ⁇ m to 200 ⁇ m, still more preferably 10 ⁇ m to 150 ⁇ m, and particularly preferably 10 ⁇ m to 10 ⁇ m in that the effects of the present invention can be more exhibited. It is 130 ⁇ m, most preferably 20 ⁇ m to 120 ⁇ m.
  • the release sheet contains a resin base film.
  • the resin base film examples include plastic films composed of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); polyethylene (PE), polypropylene (PP), and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • a plastic film composed of an olefin resin containing ⁇ -olefin such as polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) as
  • the resin base film may have only one layer or two or more layers.
  • the resin base film may be a stretched one.
  • the resin base film may be surface-treated.
  • the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
  • the resin base film may contain any suitable additive as long as the effects of the present invention are not impaired.
  • the release sheet may have a release layer in order to improve the release property from the pressure-sensitive adhesive layer A2.
  • the release sheet has a release layer, the release layer side is directly laminated on the pressure-sensitive adhesive layer A2.
  • any suitable forming material can be adopted as long as the effect of the present invention is not impaired.
  • a forming material include a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, and a fatty acid amide-based release agent.
  • a silicone-based release agent is preferable.
  • the release layer can be formed as a coating layer.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • a thickness is preferably 10 nm to 2000 nm, more preferably 10 nm to 1500 nm, further preferably 10 nm to 1000 nm, and particularly preferably 10 nm to 500 nm.
  • the release layer may be only one layer or two or more layers.
  • silicone-based release layer examples include an addition reaction type silicone resin.
  • the addition reaction type silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, and KS-847T manufactured by Shin-Etsu Chemical Co., Ltd .; TPR-made by Toshiba Silicone. 6700, TPR-6710, TPR-6721; SD7220, SD7226 manufactured by Toray Dow Corning; and the like.
  • the coating amount (after drying) of the silicone-based release layer is preferably 0.01 g / m 2 to 2 g / m 2 , more preferably 0.01 g / m 2 to 1 g / m 2, and even more preferably 0.01 g / m 2 to 1 g / m 2. It is 0.01 g / m 2 to 0.5 g / m 2 .
  • the release layer is formed, for example, by applying the above-mentioned forming material on any suitable layer by a conventionally known coating method such as reverse gravure coat, bar coat, die coat, etc., and then usually about 120 to 200 ° C. It can be carried out by curing by applying heat treatment in. Further, if necessary, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination.
  • a conventionally known coating method such as reverse gravure coat, bar coat, die coat, etc.
  • the release sheet may have an antistatic layer.
  • any appropriate thickness can be adopted as long as the effect of the present invention is not impaired.
  • Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
  • the antistatic layer may be only one layer or two or more layers.
  • any appropriate antistatic layer can be adopted as long as it can exert an antistatic effect, as long as the effect of the present invention is not impaired.
  • Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on an arbitrary suitable base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a resin base film. Specific coating methods include a roll coating method, a bar coating method, and a gravure coating method.
  • any suitable conductive polymer can be adopted as long as the effects of the present invention are not impaired.
  • a conductive polymer include a conductive polymer in which a ⁇ -conjugated conductive polymer is doped with a polyanion.
  • examples of the ⁇ -conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
  • polyanion examples include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, ethyl acrylate sulfonic acid, polymethacrylcarboxylic acid and the like.
  • the conductive polymer may be only one kind or two or more kinds.
  • the reinforcing film may include the functional layer A3, the base material layer A1, and the pressure-sensitive adhesive layer A2 in this order. That is, another embodiment of the reinforcing film comprises a functional layer A3 (30), a base material layer A1 (10), and an adhesive layer A2 (20), as shown in FIG.
  • the functional layer A3 is a layer that may be arbitrarily provided, and is a layer that can impart various functions to the reinforcing film.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • a thickness is preferably 1 nm to 1000 nm, more preferably 2 nm to 800 nm, further preferably 5 nm to 400 nm, and particularly preferably 10 nm to 200 nm.
  • the functional layer A3 may be only one layer or two or more layers.
  • any appropriate functional layer can be adopted as long as the effect of the present invention is not impaired.
  • a functional layer include an antistatic layer, an antireflection layer, an antiglare layer, a hard coat layer, and the like, and an antireflection layer can be selected in that the effects of the present invention can be more exhibited.
  • any appropriate antireflection layer can be adopted as long as the effect of the present invention is not impaired.
  • Examples of such an antireflection layer include the antireflection layer described in JP-A-2019-144557.
  • an antistatic layer may also be preferably selected in order to exhibit an antistatic effect.
  • both the antireflection layer and the antistatic layer are selected as the functional layer A3, it is preferable to arrange the antistatic layer on the base material layer A1 side in that the function of the antireflection layer can be more exhibited.
  • any appropriate antistatic layer can be adopted as long as it can exert an antistatic effect, as long as the effect of the present invention is not impaired.
  • Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on an arbitrary suitable base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a base material layer A1. Specific coating methods include a roll coating method, a bar coating method, and a gravure coating method.
  • any suitable conductive polymer can be adopted as long as the effects of the present invention are not impaired.
  • a conductive polymer include a conductive polymer in which a ⁇ -conjugated conductive polymer is doped with a polyanion.
  • examples of the ⁇ -conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene.
  • polyanion examples include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, ethyl acrylate sulfonic acid, polymethacrylcarboxylic acid and the like.
  • the reinforcing film of the present invention is attached to an adherend, which is an arbitrary suitable member.
  • the reinforcing film of the present invention is attached to an adherend which is an optical member or an electronic member.
  • the exposed surface side of the pressure-sensitive adhesive layer A2 of the reinforcing film of the present invention is attached to an adherend which is an optical member or an electronic member.
  • the optical member with a reinforcing film or the electronic member with a reinforcing film of the present invention can be obtained. That is, the optical member with a reinforcing film or the electronic member with a reinforcing film of the present invention includes the reinforcing film of the present invention.
  • the surface protective film is arranged on the base material layer A1 side of the reinforcing film.
  • the surface protective film is arranged on the side of the functional layer A3.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • a thickness is preferably 4 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 400 ⁇ m, further preferably 15 ⁇ m to 350 ⁇ m, and particularly preferably 20 ⁇ m to 300 ⁇ m.
  • the surface protective film includes a base material layer B1 and an adhesive layer B2.
  • the surface protective film may have any other suitable layer as long as it has the base material layer B1 and the pressure-sensitive adhesive layer B2, as long as the effects of the present invention are not impaired.
  • a release sheet may be provided on the surface of the adhesive layer B2 for protection.
  • a functional layer B3 may be provided on the surface of the base material layer B1 in order to impart various functions.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • Such a thickness is preferably 5 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 450 ⁇ m, further preferably 15 ⁇ m to 400 ⁇ m, and particularly preferably 20 ⁇ m to 300 ⁇ m.
  • one embodiment of the surface protective film comprises a base material layer B1 (40), an adhesive layer B2 (50), and a release sheet (60).
  • one embodiment of the surface protective film comprises a functional layer B3 (70), a base material layer B1 (40), an adhesive layer B2 (50), and a release sheet (60).
  • Base material layer B1> As the base material layer B1, a base material formed from any suitable material can be adopted depending on the intended purpose, as long as the effects of the present invention are not impaired. Examples of such a material include ⁇ 1-1. Examples thereof include those exemplified in the item of base material layer A1>.
  • the base material layer B1 may be only one layer or two or more layers.
  • any appropriate thickness can be adopted according to the purpose as long as the effects of the present invention are not impaired.
  • Such a thickness is preferably 4 ⁇ m to 350 ⁇ m, more preferably 8 ⁇ m to 325 ⁇ m, further preferably 12 ⁇ m to 290 ⁇ m, and particularly preferably 15 ⁇ m to 205 ⁇ m.
  • the base material layer B1 may contain an antistatic agent.
  • an antistatic agent for example, a resin sheet in which the antistatic agent is kneaded can be used. Such a resin sheet can be formed from a composition for forming a base material layer B1 containing a resin and an antistatic agent.
  • the base material layer B1 itself may act as an antistatic agent.
  • the base material layer B1 itself can act as an antistatic agent.
  • the base material layer B1 may be surface-treated.
  • the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
  • organic coating material for example, ⁇ 1-1.
  • examples thereof include those exemplified in the item of base material layer A1>.
  • the base material layer B1 may contain any other suitable additive, depending on the intended purpose, as long as the effects of the present invention are not impaired.
  • Adhesive layer B2 As the thickness of the pressure-sensitive adhesive layer B2, any appropriate thickness can be adopted depending on the intended purpose as long as the effects of the present invention are not impaired. Such a thickness is preferably 1 ⁇ m to 150 ⁇ m, more preferably 2 ⁇ m to 125 ⁇ m, further preferably 3 ⁇ m to 110 ⁇ m, and particularly preferably 5 ⁇ m to 95 ⁇ m.
  • a pressure-sensitive adhesive layer composed of any suitable pressure-sensitive adhesive can be adopted as long as the effects of the present invention are not impaired.
  • a pressure-sensitive adhesive include the pressure-sensitive adhesives constituting the pressure-sensitive adhesive layer described in JP-A-2019-127526, preferably the acrylic pressure-sensitive adhesive and the urethane-based pressure-sensitive adhesive described in the publication. , At least one selected from the group consisting of silicone-based pressure-sensitive adhesives.
  • a release sheet may be provided on the surface of the pressure-sensitive adhesive layer B2 for protection.
  • the release sheet may have one layer or two or more layers.
  • release sheet that the surface protective film can have, ⁇ 1-3.
  • the explanation in the item of release sheet> can be used.
  • the surface protective film may include the functional layer B3, the base material layer B1 and the adhesive layer B2 in this order.
  • the functional layer B3 is a layer that may be provided arbitrarily, and is a layer that can impart various functions to the reinforcing film.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • a thickness is preferably 1 nm to 1000 nm, more preferably 2 nm to 800 nm, further preferably 5 nm to 400 nm, and particularly preferably 10 nm to 200 nm.
  • the functional layer B3 may be only one layer or two or more layers.
  • the reinforcing film with a surface protective film of the present invention includes a surface protective film on the base material layer A1 side of the reinforcing film of the present invention.
  • a surface protective film is provided on the surface of the functional layer A3.
  • the reinforcing film with a surface protective film of the present invention has a reinforcing film and a surface protective film.
  • the reinforcing film with a surface protective film of the present invention may have any suitable other layer as long as it has the reinforcing film and the surface protective film, as long as the effects of the present invention are not impaired. ..
  • the reinforcing film with a surface protective film of the present invention includes a base material layer A1 and an adhesive layer A2, and the surface protective film includes a base material layer B1 and an adhesive layer B2.
  • any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired.
  • a thickness is preferably 9 ⁇ m to 1300 ⁇ m, more preferably 20 ⁇ m to 1050 ⁇ m, further preferably 35 ⁇ m to 900 ⁇ m, and particularly preferably 45 ⁇ m to 750 ⁇ m.
  • the reinforcing film and the surface protective film are combined with the base material layer A1 (if the base material layer A1 further has the functional layer A3, the functional layer A3) and the surface protective film. (If a release sheet is provided on the pressure-sensitive adhesive layer B2, the pressure-sensitive adhesive layer B2 exposed by peeling off the release sheet) is directly laminated and laminated. Obtainable.
  • one embodiment of the reinforcing film with a surface protective film of the present invention includes a reinforcing film composed of a base material layer A1 (10) and an adhesive layer A2 (20), and a base material layer.
  • the surface protective film composed of B1 (40) and the pressure-sensitive adhesive layer B2 (50) is laminated so that the base material layer A1 (10) and the pressure-sensitive adhesive layer B2 (50) are directly laminated. ..
  • the reinforcing film with a surface protective film of the present invention is the reinforcing film after the surface protective film is peeled off after the reinforcing film with the surface protective film is stored in an environment of 60 ° C. and 90% RH for one week.
  • the rate of change in light reflectance at 580 nm is preferably 5.0% or less, more preferably 4.8%, still more preferably 4.5%, still more preferably 4.2%. It is more preferably 4.0%, particularly preferably 3.7%, and most preferably 3.5%.
  • the light reflectance change rate is within the above range, it is possible to provide a reinforcing film that does not deteriorate inspectability when an optical member or an electronic member is inspected through the reinforcing film.
  • the reinforcing film of the present invention is typically attached to an adherend which is an optical member or an electronic member.
  • the exposed surface of the pressure-sensitive adhesive layer A2 of the reinforcing film of the present invention is attached to an adherend which is an optical member or an electronic member.
  • a release sheet is provided on the surface of the pressure-sensitive adhesive layer A2, the pressure-sensitive adhesive layer A2 exposed by peeling the release sheet is attached to an adherend which is an optical member or an electronic member.
  • Examples of the adherend which is the optical member or the electronic member include LEDs, micro LEDs, mini LEDs, and OLEDs.
  • a typical such adherend is an OLED.
  • the OLED is preferably at least one selected from the group consisting of foldable members, flexible members, and rollable members, in that the effect of the reinforcing film of the present invention can be further utilized.
  • the foldable member is a member having a movable bending portion (foldable), the flexible member is a bendable member, and the rollable member is a rollable member.
  • the pressure-sensitive adhesive layer A2 provided in the reinforcing film with a surface protection film of the present invention is exposed, the pressure-sensitive adhesive layer A2 is attached to an adherend, and then the surface is used. Peel off the protective film.
  • the reinforcing film with a surface protective film of the present invention when a release sheet is provided on the surface of the pressure-sensitive adhesive layer A2, first, the release sheet is peeled off to expose the surface of one of the pressure-sensitive adhesive layers A2. , The surface of the pressure-sensitive adhesive layer is attached to the adherend. Then, the surface protective film is peeled off.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) method. Specifically, it was measured under the following conditions using the trade name "HLC-8120 GPC" (manufactured by Tosoh Corporation) as a GPC measuring device, and calculated by a standard polystyrene conversion value.
  • GPC gel permeation chromatography
  • the release sheet is peeled off from the reinforcing film obtained in Examples or Comparative Examples, and the adhesive surface of the reinforcing film is attached to a black acrylic plate having a thickness of 1 mm, and then the light reflectance from the base material side at 580 nm.
  • a spectrophotometer manufactured by Hitachi, Ltd., model: U-4100
  • the light reflectance R1 (%) was determined.
  • the reinforcing film obtained in Example or Comparative Example was stored for 1 week in an environment of 60 ° C. and 90% RH, left at 23 ° C. for 30 minutes to return to room temperature, and then the release sheet was peeled off.
  • ⁇ Light reflectance change rate (with surface protective film)> The release sheet is peeled off from the reinforcing film obtained in Examples or Comparative Examples, and the adhesive surface of the reinforcing film is attached to a black acrylic plate having a thickness of 1 mm, and then the light reflectance from the base material side at 580 nm. was measured with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100), and the light reflectance R1 (%) was determined. Then, after storing the laminate (reinforcing film with surface protective film) of the reinforcing film and the surface protective film obtained in the corresponding Example or Comparative Example in an environment of 60 ° C. and 90% RH for one week.
  • the adhesive surface of the reinforcing film was similarly attached to a black acrylic plate having a thickness of 1 mm.
  • the light reflectance from the base material side at 580 nm was measured, and the light reflectance R2 (%) was determined.
  • ⁇ Haze change rate> The release sheet was peeled off from the reinforcing film obtained in Examples or Comparative Examples, and haze was measured with a haze meter (manufactured by Murakami Color Co., Ltd., model: HM-150) to determine haze H1 (%).
  • ⁇ Total light transmittance> The transmittance of the base material layer used in Examples or Comparative Examples at 580 nm was measured using a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100).
  • a reinforcing film (width 25 mm x length 140 mm) from which the release sheet had been peeled off was attached to a PET film "Lumirror S10 # 25" (manufactured by Toray Industries, Inc.) lined with glass by one reciprocating 2 kg hand roller. Then, it was left for 30 minutes at an environmental temperature of 23 ° C.
  • the evaluation sample obtained as described above was measured with a tensile tester. As the tensile tester, a trade name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used.
  • the tensile test was started.
  • the conditions of the tensile test were a peeling angle: 180 degrees and a peeling speed (pulling speed): 300 mm / min.
  • the load when the reinforcing film was peeled off from the PET film was measured, and the average load at that time was taken as the adhesive strength of the reinforcing film to the PET film.
  • the tensile test was started.
  • the conditions of the tensile test were a peeling angle: 180 degrees and a peeling speed (pulling speed): 300 mm / min.
  • the load when the reinforcing film was peeled off from the PET film was measured, and the average load at that time was taken as the adhesive strength of the reinforcing film to the PET film.
  • Acrylic acid manufactured by Toa Synthetic Co., Ltd.
  • 2,2'-azobisisobutyronitrile manufactured by Wako Pure Chemical Industries, Ltd.
  • ethyl acetate 156 weight
  • (meth) acrylic pressure-sensitive adhesive composition (1) Production of (meth) acrylic pressure-sensitive adhesive composition (1) The (meth) acrylic polymer (1) was added to the solution of the (meth) acrylic polymer (1) obtained in Production Example 1. ), 1.0 part by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent was added to 100 parts by weight of the solid content of the solution to make the total solid content 25% by weight.
  • the (meth) acrylic pressure-sensitive adhesive composition (1) was prepared by diluting with ethyl acetate and stirring with a disper.
  • a strong acid cation exchange resin (total exchange capacity: 2.0 meq / mL or more) was added, and the mixture was stirred for 1 hour to a pH of 4, and then filtered.
  • the strong acid cation exchange resin was removed to obtain a dispersion of spherical hollow fine particles made of SiO 2.
  • the obtained dispersion was concentrated to a solid content concentration of 20% by weight by ultrafiltration.
  • the spherical hollow fine particles were secondary aggregated.
  • the thickness of the outer shell of the spherical hollow fine particles was 5 nm, which was 1/6 of the average primary particle diameter.
  • the average agglomerated particle size of the spherical hollow fine particles was 40 nm, and the aspect ratio was 1.0.
  • the obtained dispersion of spherical hollow fine particles solid content concentration: 20% by weight: 2 g
  • dispersion of fibrous solid fine particles manufactured by Nissan Chemical Industries, Ltd., IPA-ST-UP, average
  • Aggregated particle size aggregate primary particle size: 90 nm, aspect ratio: 7.0, solid content concentration: 15% by weight): 2 g
  • silicic acid oligomer solution solid content concentration: 5% by weight
  • TAC film base material (A) having an antireflection layer The coating composition for forming an antireflection layer obtained in Production Example 15 may be referred to as cellulose triacetate (hereinafter, "TAC").
  • TAC cellulose triacetate
  • the film (TG60UL, manufactured by FUJIFILM Corporation) was applied to one side, spin-coated at a rotation speed of 200 rpm for 60 seconds to homogenize, and then dried at 200 ° C. for 30 minutes to form an antireflection layer having a film thickness of 100 nm. In this way, a cellulose triacetate film base material having an antireflection layer was obtained.
  • PET film base material (B) having an antireflection layer The coating composition for forming an antireflection layer obtained in Production Example 15 may be referred to as polyethylene terephthalate (hereinafter, “PET”).
  • PET polyethylene terephthalate
  • a film Limirror U48, manufactured by Toray Co., Ltd. was applied to one side, spin-coated at a rotation speed of 200 rpm for 60 seconds to homogenize, and then dried at 200 ° C. for 30 minutes to form an antireflection layer having a film thickness of 100 nm. In this way, a polyethylene terephthalate film base material having an antireflection layer was obtained.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with silicone on one surface of a release sheet made of a polyester resin having a thickness of 25 ⁇ m (trade name “MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation).
  • the surfaces were bonded together to obtain a surface protective film (C).
  • the obtained surface protective film (C) was aged at room temperature for 7 days.
  • Example 1 A release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) made of a polyester resin having a thickness of 25 ⁇ m in which one surface of the (meth) acrylic pressure-sensitive adhesive composition (1) is treated with silicone. It was applied to the silicone-treated surface so that the thickness after drying was 25 ⁇ m, cured under the conditions of a drying temperature of 130 ° C. and a drying time of 3 minutes, and dried. In this way, the pressure-sensitive adhesive layer formed from the (meth) acrylic pressure-sensitive adhesive composition (1) was provided on the silicone-treated surface.
  • MRF25 thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • Example 2 As shown in Table 1, a reinforcing film (2) was obtained in the same manner as in Example 1 except that the base material was changed to a PET film base material (B) having an antireflection layer. The results are shown in Table 1.
  • Example 3 As shown in Table 1, a reinforcing film (3) was obtained in the same manner as in Example 1 except that the base material was changed to a TAC film (TG60UL, manufactured by FUJIFILM Corporation). The results are shown in Table 1.
  • Example 4 As shown in Table 1, a reinforcing film (4) was obtained in the same manner as in Example 1 except that the base material was changed to a PET film (Lumilar U48, manufactured by Toray Industries, Inc.). The results are shown in Table 1.
  • Example 5 As shown in Table 1, the same procedure as in Example 1 was carried out except that the base material was changed to a polyimide (hereinafter sometimes referred to as “PI”) film (Neoprim S-100, manufactured by Mitsubishi Gas Chemical Company, Inc.). , A reinforcing film (5) was obtained. The results are shown in Table 1.
  • PI polyimide
  • Example 6 As shown in Table 1, the same procedure as in Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (6) was obtained. The results are shown in Table 1.
  • Example 7 As shown in Table 1, the same procedure as in Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (7) was obtained. The results are shown in Table 1.
  • Example 8 As shown in Table 1, the same procedure as in Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (8) was obtained. The results are shown in Table 1.
  • Example 9 As shown in Table 1, the same procedure as in Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (9) was obtained. The results are shown in Table 1.
  • Example 10 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (1) obtained in Example 1 to obtain a reinforcing film (10) with a surface protective film. .. The results are shown in Table 1.
  • Example 11 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (2) obtained in Example 2 to obtain a reinforcing film (11) with a surface protective film. .. The results are shown in Table 1.
  • Example 12 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (3) obtained in Example 3 to obtain a reinforcing film (12) with a surface protective film. .. The results are shown in Table 1.
  • Example 13 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (4) obtained in Example 4 to obtain a reinforcing film (13) with a surface protective film. .. The results are shown in Table 1.
  • Example 14 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (5) obtained in Example 5 to obtain a reinforcing film (14) with a surface protective film. .. The results are shown in Table 1.
  • Example 15 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (6) obtained in Example 6 to obtain a reinforcing film (15) with a surface protective film. .. The results are shown in Table 1.
  • Example 16 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (7) obtained in Example 7 to obtain a reinforcing film (16) with a surface protective film. .. The results are shown in Table 1.
  • Example 17 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (8) obtained in Example 8 to obtain a reinforcing film (17) with a surface protective film. .. The results are shown in Table 1.
  • Example 18 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (9) obtained in Example 9 to obtain a reinforcing film (18) with a surface protective film. .. The results are shown in Table 1.
  • Example 19 As shown in Table 1, the same procedure as in Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (19) was obtained. The results are shown in Table 1.
  • Example 20 As shown in Table 1, the same procedure as in Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (20) was obtained. The results are shown in Table 1.
  • Example 21 As shown in Table 1, the same procedure as in Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (21) was obtained. The results are shown in Table 1.
  • Example 22 As shown in Table 1, the same procedure as in Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (22) was obtained. The results are shown in Table 1.
  • Example 23 As shown in Table 1, the same procedure as in Example 5 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (23) was obtained. The results are shown in Table 1.
  • Example 24 As shown in Table 1, the same procedure as in Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (24) was obtained. The results are shown in Table 1.
  • Example 25 As shown in Table 1, the same procedure as in Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (25) was obtained. The results are shown in Table 1.
  • Example 26 As shown in Table 1, the same procedure as in Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (26) was obtained. The results are shown in Table 1.
  • Example 27 As shown in Table 1, the same procedure as in Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (27) was obtained. The results are shown in Table 1.
  • Example 28 As shown in Table 1, the same procedure as in Example 5 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (28) was obtained. The results are shown in Table 1.
  • Example 29 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (19) obtained in Example 19 to obtain a reinforcing film (29) with a surface protective film. .. The results are shown in Table 1.
  • Example 30 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (20) obtained in Example 20 to obtain a reinforcing film (30) with a surface protective film. .. The results are shown in Table 1.
  • Example 31 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (21) obtained in Example 21 to obtain a reinforcing film (31) with a surface protective film. .. The results are shown in Table 1.
  • Example 32 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (22) obtained in Example 22 to obtain a reinforcing film (32) with a surface protective film. .. The results are shown in Table 1.
  • Example 33 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (23) obtained in Example 23 to obtain a reinforcing film (33) with a surface protective film. .. The results are shown in Table 1.
  • Example 34 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (24) obtained in Example 24 to obtain a reinforcing film (34) with a surface protective film. .. The results are shown in Table 1.
  • Example 35 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (25) obtained in Example 25 to obtain a reinforcing film (35) with a surface protective film. .. The results are shown in Table 1.
  • Example 36 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (26) obtained in Example 26 to obtain a reinforcing film (36) with a surface protective film. .. The results are shown in Table 1.
  • Example 37 The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (27) obtained in Example 27 to obtain a reinforcing film (37) with a surface protective film. .. The results are shown in Table 1.
  • Example 38 The surface protective film (C) obtained in Production Example 18 was laminated on the base material of the reinforcing film (28) obtained in Example 28 to obtain a reinforcing film (38) with a surface protective film. .. The results are shown in Table 1.
  • a release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) made of a polyester resin having a thickness of 25 ⁇ m in which one surface of the (meth) acrylic pressure-sensitive adhesive composition (3) is treated with silicone. It was applied to the silicone-treated surface so that the thickness after drying was 25 ⁇ m, cured under the conditions of a drying temperature of 130 ° C. and a drying time of 3 minutes, and dried. In this way, the pressure-sensitive adhesive layer formed from the (meth) acrylic pressure-sensitive adhesive composition (3) was provided on the silicone-treated surface.
  • Comparative Example 5 As shown in Table 2, the same procedure as in Comparative Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C5) was obtained. The results are shown in Table 2.
  • Comparative Example 6 As shown in Table 2, the same procedure as in Comparative Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C6) was obtained. The results are shown in Table 2.
  • Comparative Example 7 As shown in Table 2, the same procedure as in Comparative Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C7) was obtained. The results are shown in Table 2.
  • Comparative Example 8 As shown in Table 2, the same procedure as in Comparative Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C8) was obtained. The results are shown in Table 2.
  • Comparative Example 9 As shown in Table 2, the same procedure as in Comparative Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C9) was obtained. The results are shown in Table 2.
  • Comparative Example 10 As shown in Table 2, the same procedure as in Comparative Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C10) was obtained. The results are shown in Table 2.
  • Comparative Example 11 As shown in Table 2, the same procedure as in Comparative Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C11) was obtained. The results are shown in Table 2.
  • Comparative Example 12 As shown in Table 2, the same procedure as in Comparative Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C12) was obtained. The results are shown in Table 2.
  • the reinforcing film of the present invention and the reinforcing film with a surface protective film can be typically used in the fields of optical members and electronic members.

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  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is a reinforcing film capable of adhering to an optical member and an electronic member, wherein when the optical member or the electronic member is inspected through the reinforcing film, changes in reflectivity are suppressed and inspectability is not reduced. Also provided are a reinforcing film-included optical member and a reinforcing film-included electronic member that include said reinforcing film. Further provided are a surface protection film-included reinforcing film, which is said reinforcing film with a surface protection film provided thereon, and a method for using such surface protection film-included reinforcing film.　A reinforcing film according to an embodiment includes a substrate layer A1 and an adhesive agent layer A2, wherein the percentage of change in the light reflectance of the reinforcing film at 580 nm after the film is stored in an environment of 60°C and 90% RH for a week is no more than 2.0%.

Description

補強用フィルムReinforcing film
　本発明は補強用フィルムに関する。 The present invention relates to a reinforcing film.
　有機ＥＬパネル、ＬＣＤパネル、タッチパネル等に代表される光学部材や電子部材などに剛性や耐衝撃性を付与するために、光学部材や電子部材などの露出面側に予め補強用フィルムを貼り合せて補強しておく場合がある（特許文献１）。 In order to impart rigidity and impact resistance to optical members and electronic members such as organic EL panels, LCD panels, and touch panels, a reinforcing film is previously attached to the exposed surface side of the optical members and electronic members. It may be reinforced (Patent Document 1).
　さらに、加工、組立、検査、輸送などの際の表面の傷付き防止のために、予め補強用フィルムの露出面に表面保護フィルムが貼着された状態で使用される場合がある。このような表面保護フィルムは、表面保護の必要がなくなった時点で、補強用フィルムから剥離される（特許文献２）。 Furthermore, in order to prevent scratches on the surface during processing, assembly, inspection, transportation, etc., the surface protective film may be attached to the exposed surface of the reinforcing film in advance. Such a surface protective film is peeled off from the reinforcing film when the need for surface protection is eliminated (Patent Document 2).
　このような補強用フィルムにおいては、光学部材や電子部材に貼り付けられて、補強用フィルム越しに光学部材や電子部材の検査がされる場合がある。 In such a reinforcing film, it may be attached to an optical member or an electronic member, and the optical member or the electronic member may be inspected through the reinforcing film.
　しかしながら、補強用フィルムが光学部材や電子部材に貼り付けられて過酷な環境に長期保管される場合、補強用フィルムの反射率が変化することで、検査性が低下してしまうことがある。 However, when the reinforcing film is attached to an optical member or an electronic member and stored for a long period of time in a harsh environment, the reflectance of the reinforcing film changes, which may reduce the inspectability.
　以上のように、光学部材や電子部材に貼り付けられて、補強用フィルム越しに光学部材や電子部材の検査がされる補強用フィルムにおいては、改良すべき点、すなわち、光学部材や電子部材に貼り付けられて過酷な環境に長期保管される場合、補強用フィルムの反射率の変化が抑制されることが重要である。 As described above, in the reinforcing film which is attached to the optical member or the electronic member and the optical member or the electronic member is inspected through the reinforcing film, the point to be improved, that is, the optical member or the electronic member When attached and stored for a long time in a harsh environment, it is important that the change in reflectance of the reinforcing film is suppressed.
特許第６３６６１９９号公報Japanese Patent No. 6366199 特開２０１６－１７１０９号公報Japanese Unexamined Patent Publication No. 2016-17109
　本発明の課題は、光学部材や電子部材に貼り付けることが可能な補強用フィルムであって、補強用フィルム越しに光学部材や電子部材の検査がされる際に、反射率の変化が抑制され、検査性が低下しない、補強用フィルムを提供することにある。また、そのような補強用フィルムを備えた補強用フィルム付光学部材または補強用フィルム付電子部材を提供することにある。さらに、そのような補強用フィルムに表面保護フィルムが備えられた表面保護フィルム付補強用フィルムを提供すること、および、そのような表面保護フィルム付補強用フィルムの使用方法を提供することにある。 An object of the present invention is a reinforcing film that can be attached to an optical member or an electronic member, and a change in reflectance is suppressed when the optical member or the electronic member is inspected through the reinforcing film. It is an object of the present invention to provide a reinforcing film that does not deteriorate inspectability. Another object of the present invention is to provide an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Further, it is an object of the present invention to provide a reinforcing film with a surface protective film provided with a surface protective film on such a reinforcing film, and to provide a method of using such a reinforcing film with a surface protective film.
　本発明の実施形態による補強用フィルムは、
　基材層Ａ１と粘着剤層Ａ２を含む補強用フィルムであって、
　該補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後の５８０ｎｍでの光反射率変化率が２．０％以下である。 The reinforcing film according to the embodiment of the present invention
A reinforcing film containing a base material layer A1 and an adhesive layer A2.
The rate of change in light reflectance at 580 nm after storing the reinforcing film in an environment of 60 ° C. and 90% RH for one week is 2.0% or less.
　一つの実施形態においては、上記補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後のヘイズ変化率が１０．０％以下である。 In one embodiment, the haze change rate after storing the reinforcing film in an environment of 60 ° C. and 90% RH for one week is 10.0% or less.
　一つの実施形態においては、上記基材層Ａ１の全光線透過率が９０％以上である。 In one embodiment, the total light transmittance of the base material layer A1 is 90% or more.
　一つの実施形態においては、本発明の実施形態による補強用フィルムは、上記粘着剤層Ａ２をＰＥＴフィルムに貼り付けて２３℃で３０分間放置した後の、剥離角度１８０度、剥離速度３００ｍｍ／ｍｉｎにおける対ＰＥＴフィルム粘着力が０．３０Ｎ／２５ｍｍ以上である。 In one embodiment, the reinforcing film according to the embodiment of the present invention has a peeling angle of 180 degrees and a peeling speed of 300 mm / min after the pressure-sensitive adhesive layer A2 is attached to the PET film and left at 23 ° C. for 30 minutes. The adhesive strength against PET film is 0.30 N / 25 mm or more.
　一つの実施形態においては、本発明の実施形態による補強用フィルムは、光学部材または電子部材である被着体に貼り付けられる。 In one embodiment, the reinforcing film according to the embodiment of the present invention is attached to an adherend which is an optical member or an electronic member.
　本発明の実施形態による補強用フィルム付光学部材または補強用フィルム付電子部材は、本発明の実施形態による補強用フィルムを備える。 The optical member with a reinforcing film or the electronic member with a reinforcing film according to the embodiment of the present invention includes the reinforcing film according to the embodiment of the present invention.
　本発明の実施形態による表面保護フィルム付補強用フィルムは、本発明の実施形態による補強用フィルムの上記基材層Ａ１側に表面保護フィルムを備える。 The reinforcing film with a surface protective film according to the embodiment of the present invention includes a surface protective film on the base material layer A1 side of the reinforcing film according to the embodiment of the present invention.
　一つの実施形態においては、本発明の実施形態による表面保護フィルム付補強用フィルムは、該表面保護フィルム付補強用フィルムを、６０℃、９０％ＲＨの環境下で１週間保管した後に、上記表面保護フィルムを剥離した後の、上記補強用フィルムの５８０ｎｍでの光反射率変化率が５．０％以下である。 In one embodiment, the reinforcing film with a surface protective film according to the embodiment of the present invention is the above-mentioned surface after the reinforcing film with a surface protective film is stored in an environment of 60 ° C. and 90% RH for one week. After peeling off the protective film, the rate of change in light reflectance of the reinforcing film at 580 nm is 5.0% or less.
　本発明の表面保護フィルム付補強用フィルムの使用方法は、本発明の実施形態による表面保護フィルム付補強用フィルムが備える粘着剤層Ａ２を露出させて該粘着剤層Ａ２を被着体に貼り付け、次いで、上記表面保護フィルムを剥離する。 In the method of using the reinforcing film with a surface protective film of the present invention, the pressure-sensitive adhesive layer A2 included in the reinforcing film with a surface protective film according to the embodiment of the present invention is exposed and the pressure-sensitive adhesive layer A2 is attached to an adherend. Then, the surface protective film is peeled off.
　本発明によれば、光学部材や電子部材に貼り付けることが可能な補強用フィルムであって、補強用フィルム越しに光学部材や電子部材の検査がされる際に、反射率の変化が抑制され、検査性が低下しない、補強用フィルムを提供することができる。また、そのような補強用フィルムを備えた補強用フィルム付光学部材または補強用フィルム付電子部材を提供することができる。さらに、そのような補強用フィルムに表面保護フィルムが備えられた表面保護フィルム付補強用フィルムを提供すること、および、そのような表面保護フィルム付補強用フィルムの使用方法を提供することができる。 According to the present invention, it is a reinforcing film that can be attached to an optical member or an electronic member, and a change in reflectance is suppressed when the optical member or the electronic member is inspected through the reinforcing film. It is possible to provide a reinforcing film that does not deteriorate inspectability. Further, it is possible to provide an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Further, it is possible to provide a reinforcing film with a surface protective film provided with a surface protective film on such a reinforcing film, and to provide a method of using such a reinforcing film with a surface protective film.
本発明の実施形態における補強用フィルムの一つの実施形態の概略断面図である。It is schematic sectional drawing of one Embodiment of the reinforcing film in Embodiment of this invention. 本発明の実施形態における補強用フィルムの別の一つの実施形態の概略断面図である。It is the schematic sectional drawing of another embodiment of the reinforcing film in the embodiment of the present invention. 表面保護フィルムの一つの実施形態の概略断面図である。It is the schematic sectional drawing of one Embodiment of a surface protection film. 表面保護フィルムの別の一つの実施形態の概略断面図である。FIG. 3 is a schematic cross-sectional view of another embodiment of the surface protective film. 本発明の表面保護フィルム付補強用フィルムの一つの実施形態の概略断面図である。It is the schematic sectional drawing of one Embodiment of the reinforcing film with a surface protection film of this invention.
　本明細書中で「質量」との表現がある場合は、従来一般に重さの単位として慣用されている「重量」と読み替えてもよく、逆に、本明細書中で「重量」との表現がある場合は、重さを示すＳＩ系単位として慣用されている「質量」と読み替えてもよい。 When the expression "mass" is used in the present specification, it may be read as "weight" which is generally used as a unit of weight in the past, and conversely, the expression "weight" in the present specification. If there is, it may be read as "mass" which is commonly used as an SI system unit indicating weight.
　本明細書中で「（メタ）アクリル」との表現がある場合は、「アクリルおよび／またはメタクリル」を意味し、「（メタ）アクリレート」との表現がある場合は、「アクリレートおよび／またはメタクリレート」を意味し、「（メタ）アリル」との表現がある場合は、「アリルおよび／またはメタリル」を意味し、「（メタ）アクロレイン」との表現がある場合は、「アクロレインおよび／またはメタクロレイン」を意味する。 In the present specification, the expression "(meth) acrylic" means "acrylic and / or methacrolein", and the expression "(meth) acrylate" means "acrylate and / or methacrylate". When the expression "(meth) allyl" is used, it means "allyl and / or methacrolein", and when the expression "(meth) acrolein" is used, "acrolein and / or methacrolein" is used. It means "rain".
≪１．補強用フィルム≫
　本発明の補強用フィルムは、基材層Ａ１と粘着剤層Ａ２を含む。本発明の補強用フィルムは、基材層Ａ１と粘着剤層Ａ２を有していれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していてもよい。 ≪1. Reinforcing film ≫
The reinforcing film of the present invention includes a base material layer A1 and an adhesive layer A2. The reinforcing film of the present invention may have any suitable other layer as long as it has the base material layer A1 and the pressure-sensitive adhesive layer A2, as long as the effects of the present invention are not impaired.
　粘着剤層Ａ２の表面には、保護のために、後述する剥離シートが設けられていてもよい。 A release sheet, which will be described later, may be provided on the surface of the pressure-sensitive adhesive layer A2 for protection.
　基材層Ａ１の表面には、各種機能を付与するために、後述する機能層Ａ３が設けられていてもよい。 The surface of the base material layer A1 may be provided with a functional layer A3, which will be described later, in order to impart various functions.
　補強用フィルムの厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは５μｍ～８００μｍであり、より好ましくは１０μｍ～６５０μｍであり、さらに好ましくは２０μｍ～５５０μｍであり、特に好ましくは２５μｍ～４５０μｍである。 As the thickness of the reinforcing film, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 5 μm to 800 μm, more preferably 10 μm to 650 μm, further preferably 20 μm to 550 μm, and particularly preferably 25 μm to 450 μm.
　補強用フィルムの一つの実施形態は、図１に示すように、基材層Ａ１（１０）と粘着剤層Ａ２（２０）とからなる。 As shown in FIG. 1, one embodiment of the reinforcing film comprises a base material layer A1 (10) and an adhesive layer A2 (20).
　本発明の補強用フィルムは、該補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後の５８０ｎｍでの光反射率変化率が２．０％以下であり、好ましくは１．９％以下であり、より好ましくは１．８％以下であり、さらに好ましくは１．７％以下であり、特に好ましくは１．６％以下である。上記光反射率変化率が上記範囲内にあれば、補強用フィルム越しに光学部材や電子部材の検査がされる際に、検査性が低下しない、補強用フィルムを提供することができる。 The reinforcing film of the present invention has a light reflectance change rate of 2.0% or less at 580 nm after the reinforcing film is stored in an environment of 60 ° C. and 90% RH for one week, and is preferably 1. It is 9% or less, more preferably 1.8% or less, further preferably 1.7% or less, and particularly preferably 1.6% or less. When the light reflectance change rate is within the above range, it is possible to provide a reinforcing film that does not deteriorate inspectability when an optical member or an electronic member is inspected through the reinforcing film.
　本発明の補強用フィルムは、該補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後のヘイズ変化率が、好ましくは１０．０％以下であり、より好ましくは７．０％以下であり、さらに好ましくは６．０％以下であり、さらに好ましくは５．０％以下であり、特に好ましくは４．０％以下であり、最も好ましくは３．５％以下である。上記ヘイズ変化率が上記範囲内にあれば、補強用フィルム越しに光学部材や電子部材の検査がされる際に、検査性がより低下しない、補強用フィルムを提供することができる。 The reinforcing film of the present invention has a haze change rate of preferably 10.0% or less, more preferably 7.0, after the reinforcing film is stored in an environment of 60 ° C. and 90% RH for 1 week. % Or less, more preferably 6.0% or less, further preferably 5.0% or less, particularly preferably 4.0% or less, and most preferably 3.5% or less. When the haze change rate is within the above range, it is possible to provide a reinforcing film in which the inspectability is not further deteriorated when the optical member or the electronic member is inspected through the reinforcing film.
＜１－１．基材層Ａ１＞
　基材層Ａ１としては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な材料から形成される基材を採用し得る。このような材料としては、例えば、樹脂シート、不織布、紙、金属箔、織布、ゴムシート、発泡シート、これらの積層体（特に、樹脂シートを含む積層体）などが挙げられる。 <1-1. Base material layer A1>
As the base material layer A1, a base material formed from any suitable material can be adopted depending on the intended purpose, as long as the effects of the present invention are not impaired. Examples of such materials include resin sheets, non-woven fabrics, papers, metal foils, woven fabrics, rubber sheets, foam sheets, and laminates thereof (particularly, laminates including resin sheets).
　樹脂シートを構成する樹脂としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリメチルメタクリレート（ＰＭＭＡ）等のアクリル系樹脂、ポリカーボネート、トリアセチルセルロース（ＴＡＣ）、ポリサルフォン、ポリアリレート、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体（ＥＶＡ）、ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）、ポリイミド（ＰＩ）、ポリ塩化ビニル（ＰＶＣ）、ポリ酢酸ビニル、ポリフェニレンサルファイド（ＰＰＳ）、フッ素系樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）、環状オレフィン系ポリマーなどが挙げられる。 Examples of the resin constituting the resin sheet include acrylic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polymethyl methacrylate (PMMA), polycarbonate, and triacetyl cellulose (TAC). ), Polysulfone, polyallylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), total aromatic polyamide (aramid), polyimide ( PI), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluororesin, polyether ether ketone (PEEK), cyclic olefin polymer and the like.
　不織布としては、マニラ麻を含む不織布等の耐熱性を有する天然繊維による不織布；ポリプロピレン樹脂不織布、ポリエチレン樹脂不織布、エステル系樹脂不織布等の合成樹脂不織布；などが挙げられる。 Examples of the non-woven fabric include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics containing Manila hemp; synthetic resin non-woven fabrics such as polypropylene resin non-woven fabrics, polyethylene resin non-woven fabrics, and ester resin non-woven fabrics.
　基材層Ａ１は、１層のみであってもよいし、２層以上であってもよい。 The base material layer A1 may be only one layer or two or more layers.
　基材層Ａ１の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは４μｍ～５００μｍであり、より好ましくは１０μｍ～４００μｍであり、さらに好ましくは１５μｍ～３５０μｍであり、特に好ましくは２０μｍ～３００μｍである。 As the thickness of the base material layer A1, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 4 μm to 500 μm, more preferably 10 μm to 400 μm, further preferably 15 μm to 350 μm, and particularly preferably 20 μm to 300 μm.
　基材層Ａ１の全光線透過率は、好ましくは９０％以上であり、より好ましくは９１％以上であり、さらに好ましくは９２％以上であり、特に好ましくは９３％以上である。基材層Ａ１の全光線透過率が上記範囲内にあれば、補強用フィルム越しに光学部材や電子部材の検査がされる際に、検査性がより低下しない、補強用フィルムを提供することができる。 The total light transmittance of the base material layer A1 is preferably 90% or more, more preferably 91% or more, further preferably 92% or more, and particularly preferably 93% or more. When the total light transmittance of the base material layer A1 is within the above range, it is possible to provide a reinforcing film in which the inspectability is not further deteriorated when the optical member or the electronic member is inspected through the reinforcing film. it can.
　基材層Ａ１は、帯電防止剤を含んでいてもよい。帯電防止剤を含む基材層Ａ１としては、例えば、帯電防止剤が練り込まれた樹脂シートが用いられ得る。このような樹脂シートは、樹脂と帯電防止剤とを含む基材層Ａ１形成用組成物から形成され得る。 The base material layer A1 may contain an antistatic agent. As the base material layer A1 containing the antistatic agent, for example, a resin sheet in which the antistatic agent is kneaded can be used. Such a resin sheet can be formed from a composition for forming a base material layer A1 containing a resin and an antistatic agent.
　基材層Ａ１そのものが帯電防止剤として作用してもよい。例えば、基材層Ａ１の材料として金属箔を採用する場合は、基材層Ａ１そのものが帯電防止剤として作用し得る。 The base material layer A1 itself may act as an antistatic agent. For example, when a metal foil is used as the material of the base material layer A1, the base material layer A1 itself can act as an antistatic agent.
　基材層Ａ１は、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理などが挙げられる。 The base material layer A1 may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
　有機コーティング材料としては、例えば、プラスチックハードコート材料ＩＩ（ＣＭＣ出版、（２００４））に記載される材料が挙げられる。このような有機コーティング材料としては、好ましくは、ウレタン系ポリマーが挙げられ、より好ましくは、ポリアクリルウレタン、ポリエステルウレタン、またはこれらの前駆体が挙げられる。基材層Ａ１への塗工・塗布が簡便であり、かつ、工業的に多種のものが選択でき安価に入手できるからである。このようなウレタン系ポリマーは、例えば、イソシアナートモノマーとアルコール性水酸基含有モノマー（例えば、水酸基含有アクリル化合物または水酸基含有エステル化合物）との反応混合物からなるポリマーが挙げられる。有機コーティング材料は、任意の添加剤として、ポリアミンなどの鎖延長剤、老化防止剤、酸化安定剤などを含んでいてもよい。 Examples of the organic coating material include the materials described in Plastic Hard Coat Material II (CMC Publishing, (2004)). Such organic coating materials preferably include urethane-based polymers, and more preferably polyacrylic urethane, polyester urethane, or precursors thereof. This is because coating / coating on the base material layer A1 is easy, and various types can be industrially selected and can be obtained at low cost. Examples of such a urethane polymer include a polymer composed of a reaction mixture of an isocyanato monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound). The organic coating material may contain, as an optional additive, a chain extender such as polyamine, an antiaging agent, an oxidation stabilizer and the like.
　基材層Ａ１には、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な他の添加剤が含まれていてもよい。 The base material layer A1 may contain any other suitable additive, depending on the intended purpose, as long as the effects of the present invention are not impaired.
＜１－２．粘着剤層Ａ２＞
　粘着剤層Ａ２の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは１μｍ～３００μｍであり、より好ましくは２μｍ～２５０μｍであり、さらに好ましくは４μｍ～２００μｍであり、特に好ましくは５μｍ～１５０μｍである。 <1-2. Adhesive layer A2>
As the thickness of the pressure-sensitive adhesive layer A2, any appropriate thickness can be adopted depending on the intended purpose as long as the effects of the present invention are not impaired. Such a thickness is preferably 1 μm to 300 μm, more preferably 2 μm to 250 μm, further preferably 4 μm to 200 μm, and particularly preferably 5 μm to 150 μm.
　粘着剤層Ａ２は、１層のみであってもよいし、２層以上であってもよい。 The pressure-sensitive adhesive layer A2 may be only one layer or two or more layers.
　粘着剤層Ａ２は、導電成分を含んでいてもよい。導電成分は、１種のみであってもよいし、２種以上であってもよい。 The pressure-sensitive adhesive layer A2 may contain a conductive component. The conductive component may be only one kind or two or more kinds.
　粘着剤層Ａ２をＰＥＴフィルムに貼り付けて２３℃で３０分間放置した後の、剥離角度１８０度、剥離速度３００ｍｍ／ｍｉｎにおける対ＰＥＴフィルム粘着力は、好ましくは０．３０Ｎ／２５ｍｍ以上であり、より好ましくは１Ｎ／２５ｍｍ～４０Ｎ／２５ｍｍであり、さらに好ましくは５Ｎ／２５ｍｍ～３５Ｎ／２５ｍｍであり、特に好ましくは１０Ｎ／２５ｍｍ～３０Ｎ／２５ｍｍである。 After the pressure-sensitive adhesive layer A2 is attached to the PET film and left at 23 ° C. for 30 minutes, the adhesive strength to the PET film at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is preferably 0.30 N / 25 mm or more. It is more preferably 1N / 25mm to 40N / 25mm, further preferably 5N / 25mm to 35N / 25mm, and particularly preferably 10N / 25mm to 30N / 25mm.
　粘着剤層Ａ２をＰＥＴフィルムに貼り付けて６０℃で６０分間放置した後の、剥離角度１８０度、剥離速度３００ｍｍ／ｍｉｎにおける対ＰＥＴフィルム粘着力は、好ましくは１０Ｎ／２５ｍｍ以上であり、より好ましくは１０Ｎ／２５ｍｍ～４０Ｎ／２５ｍｍであり、さらに好ましくは１５Ｎ／２５ｍｍ～３５Ｎ／２５ｍｍであり、特に好ましくは２０Ｎ／２５ｍｍ～３０Ｎ／２５ｍｍである。 After the pressure-sensitive adhesive layer A2 is attached to the PET film and left at 60 ° C. for 60 minutes, the adhesive strength to the PET film at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is preferably 10 N / 25 mm or more, more preferably. Is 10N / 25mm to 40N / 25mm, more preferably 15N / 25mm to 35N / 25mm, and particularly preferably 20N / 25mm to 30N / 25mm.
　粘着剤層Ａ２は、粘着剤組成物ａ２から形成される。粘着剤層Ａ２は、粘着剤組成物ａ２を層状に形成できる方法であれば、任意の適切な方法によって形成され得る。例えば、粘着剤層Ａ２は、粘着剤組成物ａ２を、任意の適切な基材上に塗布して、必要に応じて加熱等や活性エネルギー線（紫外線など）照射や乾燥等を行い、必要に応じて硬化させて、該基材上において粘着剤層を形成する方法が挙げられる。このような塗布の方法としては、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、エアーナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーター、ロールブラッシュコーターなどの方法が挙げられる。 The pressure-sensitive adhesive layer A2 is formed from the pressure-sensitive adhesive composition a2. The pressure-sensitive adhesive layer A2 can be formed by any suitable method as long as the pressure-sensitive adhesive composition a2 can be formed in layers. For example, in the pressure-sensitive adhesive layer A2, the pressure-sensitive adhesive composition a2 is applied onto an arbitrary suitable base material, and if necessary, heating or the like, irradiation with active energy rays (ultraviolet rays, etc.), drying, or the like is performed, and if necessary. A method of forming a pressure-sensitive adhesive layer on the substrate by curing accordingly can be mentioned. Examples of such an application method include a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, and a roll brush coater. Method can be mentioned.
　粘着剤組成物ａ２は、本発明の効果をより発現させ得る点で、好ましくは、ポリマー成分を含む。 The pressure-sensitive adhesive composition a2 preferably contains a polymer component in that the effects of the present invention can be more exhibited.
　ポリマー成分としては、好ましくは、アクリル系ポリマー、ウレタン系ポリマー、シリコーン系ポリマーから選ばれる少なくとも１種である。以下、アクリル系ポリマーを代表例として説明する。 The polymer component is preferably at least one selected from an acrylic polymer, a urethane polymer, and a silicone polymer. Hereinafter, an acrylic polymer will be described as a typical example.
　アクリル系ポリマーは、アクリル系粘着剤の分野においていわゆるベースポリマーと称され得るものである。アクリル系ポリマーは、１種のみであってもよいし、２種以上であってもよい。 Acrylic polymers can be called so-called base polymers in the field of acrylic pressure-sensitive adhesives. The acrylic polymer may be only one kind or two or more kinds.
　粘着剤組成物ａ２中のアクリル系ポリマーの含有割合は、固形分換算で、好ましくは６０重量％～９９．９９９重量％であり、より好ましくは６５重量％～９９．９９重量％であり、さらに好ましくは７０重量％～９９．９重量％であり、特に好ましくは７５重量％～９９．９重量％であり、最も好ましくは８０重量％～９９．９重量％である。 The content ratio of the acrylic polymer in the pressure-sensitive adhesive composition a2 is preferably 60% by weight to 99.999% by weight, more preferably 65% by weight to 99.99% by weight, and further, in terms of solid content. It is preferably 70% by weight to 99.9% by weight, particularly preferably 75% by weight to 99.9% by weight, and most preferably 80% by weight to 99.9% by weight.
　アクリル系ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切なアクリル系ポリマーを採用し得る。 As the acrylic polymer, any suitable acrylic polymer can be adopted as long as the effect of the present invention is not impaired.
　アクリル系ポリマーの重量平均分子量は、本発明の効果をより発現させ得る点で、好ましくは３０万～２５０万であり、より好ましくは３５万～２００万であり、さらに好ましくは４０万～１８０万であり、特に好ましくは５０万～１５０万である。 The weight average molecular weight of the acrylic polymer is preferably 300,000 to 2.5 million, more preferably 350,000 to 2 million, and further preferably 400,000 to 1.8 million in that the effects of the present invention can be more exhibited. It is particularly preferably 500,000 to 1,500,000.
　アクリル系ポリマーとしては、本発明の効果をより発現させ得る点で、好ましくは、（ａ成分）アルキルエステル部分のアルキル基の炭素数が４～１２である（メタ）アクリル酸アルキルエステル、（ｂ成分）ＯＨ基を有する（メタ）アクリル酸エステルおよび（メタ）アクリル酸からなる群から選ばれる少なくとも１種、を含む組成物（Ａ）から重合によって形成されるアクリル系ポリマーである。 As the acrylic polymer, a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the (component a) alkyl ester moiety is preferable in that the effects of the present invention can be more exhibited. Ingredient) An acrylic polymer formed by polymerization from the composition (A) containing at least one selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid.
　（ａ成分）、（ｂ成分）は、それぞれ、独立に、１種のみであってもよいし、２種以上であってもよい。 Each of (component a) and (component b) may be independently of only one type or of two or more types.
　アルキルエステル部分のアルキル基の炭素数が４～１２である（メタ）アクリル酸アルキルエステル（ａ成分）としては、例えば、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシルなどが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－エチルヘキシルであり、より好ましくは、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシルである。 Examples of the (meth) acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms are n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, and (meth). S-butyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2--butyl (meth) acrylate Ethylhexyl, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate And so on. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl acrylate and acrylic are more preferable in that the effects of the present invention can be more exhibited. 2-Ethylhexyl acid.
　ＯＨ基を有する（メタ）アクリル酸エステルおよび（メタ）アクリル酸からなる群から選ばれる少なくとも１種（ｂ成分）としては、例えば、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチルなどのＯＨ基を有する（メタ）アクリル酸エステル、（メタ）アクリル酸などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸であり、より好ましくは、アクリル酸ヒドロキシエチル、アクリル酸である。 As at least one (b component) selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. Examples thereof include (meth) acrylic acid ester having an OH group such as hydroxybutyl (meth) acrylic acid, and (meth) acrylic acid. Among these, hydroxyethyl (meth) acrylate and (meth) acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, in that the effects of the present invention can be more exhibited.
　組成物（Ａ）は、（ａ）成分および（ｂ）成分以外の、共重合性モノマーを含んでいてもよい。共重合性モノマーは、１種のみであってもよいし、２種以上であってもよい。このような共重合性モノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピルなどの、アルキルエステル部分のアルキル基の炭素数が１～３である（メタ）アクリル酸アルキルエステル；イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸、これらの酸無水物（例えば、無水マレイン酸、無水イタコン酸などの酸無水物基含有モノマー）などのカルボキシル基含有モノマー（ただし、（メタ）アクリル酸を除く）；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミドなどのアミド基含有モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチルなどのアミノ基含有モノマー；（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジルなどのエポキシ基含有モノマー；アクリロニトリルやメタクリロニトリルなどのシアノ基含有モノマー；Ｎ－ビニル－２－ピロリドン、（メタ）アクリロイルモルホリン、Ｎ－ビニルピペリドン、Ｎ－ビニルピペラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、ビニルピリジン、ビニルピリミジン、ビニルオキサゾールなどの複素環含有ビニル系モノマー；ビニルスルホン酸ナトリウムなどのスルホン酸基含有モノマー；２－ヒドロキシエチルアクリロイルフォスフェートなどのリン酸基含有モノマー；シクロヘキシルマレイミド、イソプロピルマレイミドなどのイミド基含有モノマー；２－メタクリロイルオキシエチルイソシアネートなどのイソシアネート基含有モノマー；シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等の脂環式炭化水素基を有する（メタ）アクリル酸エステル；フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートなどの芳香族炭化水素基を有する（メタ）アクリル酸エステル；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル；スチレン、ビニルトルエンなどの芳香族ビニル化合物；エチレン、ブタジエン、イソプレン、イソブチレンなどのオレフィン類やジエン類；ビニルアルキルエーテルなどのビニルエーテル類；塩化ビニル；などが挙げられる。 The composition (A) may contain a copolymerizable monomer other than the components (a) and (b). The copolymerizable monomer may be only one kind or two or more kinds. As such a copolymerizable monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like, the alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms. (Meta) acrylic acid alkyl ester; carboxyl such as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and their acid anhydrides (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). Group-containing monomers (excluding (meth) acrylic acid); (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxy Amid group-containing monomers such as methyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate. Amino group-containing monomer; Epoxy group-containing monomer such as (meth) glycidyl acrylate, (meth) methyl glycidyl acrylate; Cyan group-containing monomer such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth) acryloyl Heterocyclic-containing vinyl-based monomers such as morpholin, N-vinylpiperidone, N-vinylpiperazin, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; Phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate; imide group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomer such as 2-methacryloyloxyethyl isocyanate; cyclopentyl (meth) acrylate and cyclohexyl (meth) (Meta) acrylic acid ester having an alicyclic hydrocarbon group such as acrylate and isobornyl (meth) acrylate; aromatic hydrocarbon group such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and benzyl (meth) acrylate Has (meth) acrylic acid ester; vinyl ester such as vinyl acetate and vinyl propionate; aromatic vinyl compound such as styrene and vinyl toluene; olefins such as ethylene, butadiene, isoprene and isobutylene and die Vinyl ethers such as vinyl alkyl ethers; vinyl chloride; and the like.
　共重合性モノマーとしては、多官能性モノマーも採用し得る。多官能性モノマーとは、１分子中に２以上のエチレン性不飽和基を有するモノマーをいう。エチレン性不飽和基としては、本発明の効果を損なわない範囲で、任意の適切なエチレン性不飽和基を採用し得る。このようなエチレン性不飽和基としては、例えば、ビニル基、プロペニル基、イソプロペニル基、ビニルエーテル基（ビニルオキシ基）、アリルエーテル基（アリルオキシ基）などのラジカル重合性官能基が挙げられる。多官能性モノマーとしては、例えば、ヘキサンジオールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどが挙げられる。このような多官能性モノマーは、１種のみであってもよいし、２種以上であってもよい。 As the copolymerizable monomer, a polyfunctional monomer can also be adopted. The polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group can be adopted as long as the effect of the present invention is not impaired. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group) and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol. Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropanthry (meth) acrylate, tetramethylolmethanetri (meth) acrylate, allyl Examples thereof include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Such a polyfunctional monomer may be only one kind or two or more kinds.
　共重合性モノマーとしては、（メタ）アクリル酸アルコキシアルキルエステルも採用し得る。（メタ）アクリル酸アルコキシアルキルエステルとしては、例えば、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸メトキシトリエチレングリコール、（メタ）アクリル酸３－メトキシプロピル、（メタ）アクリル酸３－エトキシプロピル、（メタ）アクリル酸４－メトキシブチル、（メタ）アクリル酸４－エトキシブチルなどが挙げられる。（メタ）アクリル酸アルコキシアルキルエステルは、１種のみであってもよいし、２種以上であってもよい。 As the copolymerizable monomer, (meth) acrylic acid alkoxyalkyl ester can also be adopted. Examples of the (meth) acrylate alkoxyalkyl ester include (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-ethoxyethyl, (meth) acrylate methoxytriethylene glycol, and (meth) acrylate 3-. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The (meth) acrylic acid alkoxyalkyl ester may be only one kind or two or more kinds.
　アルキルエステル部分のアルキル基の炭素数が４～１２である（メタ）アクリル酸アルキルエステル（ａ成分）の含有量は、本発明の効果をより発現させ得る点で、アクリル系ポリマーを構成するモノマー成分全量（１００重量％）に対して、好ましくは３０重量％以上であり、より好ましくは３５重量％～９９重量％であり、さらに好ましくは４０重量％～９８重量％であり、特に好ましくは５０重量％～９６重量％である。 The content of the (meth) acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer constituting the acrylic polymer in that the effects of the present invention can be more exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, still more preferably 40% by weight to 98% by weight, and particularly preferably 50% by weight, based on the total amount of the components (100% by weight). It is from% by weight to 96% by weight.
　ＯＨ基を有する（メタ）アクリル酸エステルおよび（メタ）アクリル酸からなる群から選ばれる少なくとも１種（ｂ成分）の含有量は、本発明の効果をより発現させ得る点で、アクリル系ポリマーを構成するモノマー成分全量（１００重量％）に対して、好ましくは１重量％以上であり、より好ましくは１重量％～３０重量％であり、さらに好ましくは２重量％～２０重量％であり、特に好ましくは３重量％～１５重量％である。 The content of at least one (component b) selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid makes the acrylic polymer more effective in terms of exhibiting the effects of the present invention. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, still more preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 15% by weight.
　組成物（Ａ）は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、重合開始剤、連鎖移動剤、溶剤などが挙げられる。これらの他の成分の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。 The composition (A) may contain any suitable other component as long as the effect of the present invention is not impaired. Examples of such other components include polymerization initiators, chain transfer agents, solvents and the like. As the content of these other components, any appropriate content may be adopted as long as the effect of the present invention is not impaired.
　重合開始剤は、重合反応の種類に応じて、熱重合開始剤や光重合開始剤（光開始剤）などを採用し得る。重合開始剤は、１種のみであってもよいし、２種以上であってもよい。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like can be adopted depending on the type of polymerization reaction. The polymerization initiator may be only one kind or two or more kinds.
　熱重合開始剤は、好ましくは、アクリル系ポリマーを溶液重合によって得る際に採用され得る。このような熱重合開始剤としては、例えば、アゾ系重合開始剤、過酸化物系重合開始剤（例えば、ジベンゾイルペルオキシド、ｔｅｒｔ－ブチルペルマレエートなど）、レドックス系重合開始剤などが挙げられる。これらの熱重合開始剤の中でも、特開２００２－６９４１１号公報に開示されたアゾ系開始剤が特に好ましい。このようなアゾ系重合開始剤は、重合開始剤の分解物が加熱発生ガス（アウトガス）の発生原因となる部分としてアクリル系ポリマー中に残留しにくい点で好ましい。アゾ系重合開始剤としては、２，２’－アゾビスイソブチロニトリル（以下、ＡＩＢＮと称する場合がある）、２，２’－アゾビス－２－メチルブチロニトリル（以下、ＡＭＢＮと称する場合がある）、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、４，４’－アゾビス－４－シアノバレリアン酸などが挙げられる。 The thermal polymerization initiator can be preferably used when obtaining an acrylic polymer by solution polymerization. Examples of such a thermal polymerization initiator include an azo-based polymerization initiator, a peroxide-based polymerization initiator (for example, dibenzoyl peroxide, tert-butyl permalate, etc.), a redox-based polymerization initiator, and the like. .. Among these thermal polymerization initiators, the azo-based initiator disclosed in JP-A-2002-69411 is particularly preferable. Such an azo-based polymerization initiator is preferable because the decomposition product of the polymerization initiator does not easily remain in the acrylic polymer as a portion that causes the generation of heating generated gas (out gas). Examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter, may be referred to as AIBN) and 2,2'-azobis-2-methylbutyronitrile (hereinafter, referred to as AMBN). , 2,2'-azobis (2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid and the like.
　光重合開始剤は、好ましくは、アクリル系ポリマーを活性エネルギー線重合によって得る際に採用され得る。光重合開始剤としては、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α－ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤等などが挙げられる。 The photopolymerization initiator can preferably be used when obtaining an acrylic polymer by active energy ray polymerization. Examples of the photopolymerization initiator include a benzoin ether type photopolymerization initiator, an acetophenone type photopolymerization initiator, an α-ketol type photopolymerization initiator, an aromatic sulfonyl chloride type photopolymerization initiator, and a photoactive oxime type photopolymerization initiator. Examples thereof include benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.
　ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、アニソールメチルエーテルなどが挙げられる。アセトフェノン系光重合開始剤としては、例えば、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－（ｔ－ブチル）ジクロロアセトフェノンなどが挙げられる。α－ケトール系光重合開始剤としては、例えば、２－メチル－２－ヒドロキシプロピオフェノン、１－［４－（２－ヒドロキシエチル）フェニル］－２－メチルプロパン－１－オンなどが挙げられる。芳香族スルホニルクロリド系光重合開始剤としては、例えば、２－ナフタレンスルホニルクロライドなどが挙げられる。光活性オキシム系光重合開始剤としては、例えば、１－フェニル－１，１－プロパンジオン－２－（ｏ－エトキシカルボニル）－オキシムなどが挙げられる。ベンゾイン系光重合開始剤としては、例えば、ベンゾインなどが挙げられる。ベンジル系光重合開始剤としては、例えば、ベンジルなどが挙げられる。ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、ベンゾイル安息香酸、３，３'－ジメチル－４－メトキシベンゾフェノン、ポリビニルベンゾフェノン、α－ヒドロキシシクロヘキシルフェニルケトンなどが挙げられる。ケタール系光重合開始剤としては、例えば、ベンジルジメチルケタールなどが挙げられる。チオキサントン系光重合開始剤としては、例えば、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンなどが挙げられる。 Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisole. Examples include methyl ether. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. .. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzyl-based photopolymerization initiator include benzyl and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenyl ketone and the like. Examples of the ketal-based photopolymerization initiator include benzyldimethyl ketal and the like. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
　粘着剤組成物ａ２は、架橋剤を含んでいてもよい。架橋剤を用いることにより、アクリル系粘着剤の凝集力を向上でき、本発明の効果をより発現させ得る。架橋剤は、１種のみであってもよいし、２種以上であってもよい。 The pressure-sensitive adhesive composition a2 may contain a cross-linking agent. By using a cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited. The cross-linking agent may be only one kind or two or more kinds.
　架橋剤としては、多官能イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤の他、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、好ましくは、多官能イソシアネート系架橋剤およびエポキシ系架橋剤からなる群から選ばれる少なくとも１種（ｃ成分）である。 Examples of the cross-linking agent include polyfunctional isocyanate-based cross-linking agent, epoxy-based cross-linking agent, melamine-based cross-linking agent, peroxide-based cross-linking agent, urea-based cross-linking agent, metal alkoxide-based cross-linking agent, metal chelate-based cross-linking agent, and metal salt. Examples thereof include a system cross-linking agent, a carbodiimide-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, and an amine-based cross-linking agent. Among these, at least one (c component) selected from the group consisting of a polyfunctional isocyanate-based cross-linking agent and an epoxy-based cross-linking agent is preferable in that the effects of the present invention can be more exhibited.
　多官能イソシアネート系架橋剤としては、例えば、１，２－エチレンジイソシアネート、１，４－ブチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネートなどの低級脂肪族ポリイソシアネート類；シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネートなどの脂環族ポリイソシアネート類；２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４'－ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート類などが挙げられる。多官能イソシアネート系架橋剤としては、例えば、トリメチロールプロパン／トリレンジイソシアネート付加物（日本ポリウレタン工業株式会社製、商品名「コロネートＬ」）、トリメチロールプロパン／ヘキサメチレンジイソシアネート付加物（日本ポリウレタン工業株式会社製、商品名「コロネートＨＬ」）、商品名「コロネートＨＸ」（日本ポリウレタン工業株式会社）、トリメチロールプロパン／キシリレンジイソシアネート付加物（三井化学株式会社製、商品名「タケネート１１０Ｎ」）などの市販品も挙げられる。 Examples of the polyfunctional isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and the like. Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Aromatic polyisocyanates and the like. Examples of the polyfunctional isocyanate-based cross-linking agent include trimethylolpropane / tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L") and trimethylolpropane / hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd.). Company-made, product name "Coronate HL"), product name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / xylylene diisocyanate adduct (manufactured by Mitsui Chemicals Co., Ltd., product name "Takenate 110N"), etc. Commercial products are also included.
　エポキシ系架橋剤（多官能エポキシ化合物）としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、ジグリシジルアニリン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、ｏ－フタル酸ジグリシジルエステル、トリグリシジル－トリス（２－ヒドロキシエチル）イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール－Ｓ－ジグリシジルエーテルの他、分子内にエポキシ基を２つ以上有するエポキシ系樹脂などが挙げられる。エポキシ系架橋剤としては、商品名「テトラッドＣ」（三菱ガス化学株式会社製）などの市販品も挙げられる。 Examples of the epoxy-based cross-linking agent (polyfunctional epoxy compound) include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-diglycidylamino). Methyl) 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, Gglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylpropan polyglycidyl ether, adipate diglycidyl ester, o-phthalate diglycidyl ester, triglycidyl-tris (2- In addition to hydroxyethyl) isocyanurate, resorcin diglycidyl ether, and bisphenol-S-diglycidyl ether, epoxy-based resins having two or more epoxy groups in the molecule can be mentioned. Examples of the epoxy-based cross-linking agent include commercially available products such as the trade name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Company, Inc.).
　粘着剤組成物ａ２中の架橋剤の含有量は、本発明の効果を損なわない範囲で、任意の適切な含有量を採用し得る。このような含有量としては、例えば、本発明の効果をより発現させ得る点で、アクリル系ポリマーの固形分（１００重量部）に対して、好ましくは０．００５重量部～２０重量部であり、より好ましくは０．０５重量部～１８重量部であり、さらに好ましくは０．０１重量部～１５重量部であり、特に好ましくは０．１重量部～１０重量部である。 As the content of the cross-linking agent in the pressure-sensitive adhesive composition a2, any appropriate content can be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.005 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer, for example, in that the effect of the present invention can be more exhibited. , More preferably 0.05 parts by weight to 18 parts by weight, further preferably 0.01 parts by weight to 15 parts by weight, and particularly preferably 0.1 parts by weight to 10 parts by weight.
　粘着剤組成物ａ２は、本発明の効果を損なわない範囲で、任意の適切な他の成分を含有し得る。このような他の成分としては、例えば、アクリル系ポリマー以外のポリマー成分、架橋促進剤、架橋触媒、シランカップリング剤、粘着付与樹脂（ロジン誘導体、ポリテルペン樹脂、石油樹脂、油溶性フェノールなど）、老化防止剤、無機充填剤、有機充填剤、金属粉、着色剤（顔料や染料など）、箔状物、紫外線吸収剤、酸化防止剤、光安定剤、連鎖移動剤、可塑剤、軟化剤、界面活性剤、帯電防止剤、導電剤、安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒などが挙げられる。 The pressure-sensitive adhesive composition a2 may contain any suitable other component as long as the effect of the present invention is not impaired. Examples of such other components include polymer components other than acrylic polymers, cross-linking accelerators, cross-linking catalysts, silane coupling agents, tackifier resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.). Anti-aging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, Examples thereof include surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
　粘着剤組成物ａ２は、三環以上の環式構造を有するアクリル系モノマーを主成分として含むモノマー組成物から得られるオリゴマー（Ｘ）を含まないことが好ましい。この場合、オリゴマー（Ｘ）を得るために用いられるモノマー組成物に含まれる全モノマー成分１００重量部に対する、三環以上の環式構造を有するアクリル系モノマーの含有割合は、好ましくは５０重量部以上であり、より好ましくは６０重量部～９９重量部であり、さらに好ましくは７０重量部～９８重量部であり、特に好ましくは８０重量部～９６重量部である。粘着剤組成物ａ２が、三環以上の環式構造を有するアクリル系モノマーを主成分として含むモノマー組成物から得られるオリゴマー（Ｘ）を含まないことにより、補強用フィルム越しに光学部材や電子部材の検査がされる際に、検査性がより低下しない、補強用フィルムを提供することができる。 The pressure-sensitive adhesive composition a2 preferably does not contain an oligomer (X) obtained from a monomer composition containing an acrylic monomer having a cyclic structure of three or more rings as a main component. In this case, the content ratio of the acrylic monomer having a cyclic structure of three or more rings to 100 parts by weight of all the monomer components contained in the monomer composition used to obtain the oligomer (X) is preferably 50 parts by weight or more. It is more preferably 60 parts by weight to 99 parts by weight, further preferably 70 parts by weight to 98 parts by weight, and particularly preferably 80 parts by weight to 96 parts by weight. Since the pressure-sensitive adhesive composition a2 does not contain an oligomer (X) obtained from a monomer composition containing an acrylic monomer having a ring structure of three or more rings as a main component, an optical member or an electronic member is formed through a reinforcing film. It is possible to provide a reinforcing film that does not further deteriorate the inspectability when the inspection is performed.
　三環以上の環式構造を有するアクリル系モノマーとしては、例えば、ジシクロペンタニル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、ジシクロペンタニルメタクリレート、ジシクロペンタニルオキシエチルメタクリレート、ジシクロペンタニルオキシエチルアクリレート、トリシクロペンタニルメタクリレート、トリシクロペンタニルアクリレート、１－アダマンチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、２－メチル－２－アダマンチルアクリレート、２－エチル－２－アダマンチルメタクリレート、２－エチル－２－アダマンチルアクリレートなどが挙げられる。 Examples of the acrylic monomer having a cyclic structure of three or more rings include dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, and dicyclo. Pentanyloxyethyl acrylate, tricyclopentanyl methacrylate, tricyclopentanyl acrylate, 1-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, Examples thereof include 2-ethyl-2-adamantyl acrylate.
　三環以上の環式構造を有するアクリル系モノマーは、１種のみであってもよいし、２種以上であってもよい。 The acrylic monomer having a cyclic structure of three or more rings may be only one kind or two or more kinds.
　オリゴマー（Ｘ）を得るために用いられるモノマー組成物には、三環以上の環式構造を有するアクリル系モノマー以外に、他のモノマーが含まれていてもよい。このような他のモノマーは、１種のみであってもよいし、２種以上であってもよい。 The monomer composition used to obtain the oligomer (X) may contain other monomers in addition to the acrylic monomer having a cyclic structure of three or more rings. Such other monomers may be only one kind or two or more kinds.
　他のモノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシルなどの（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジルなどのエポキシ基含有アクリル系モノマー；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル系モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチルなどのヒドロキシル基含有モノマー；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチルなどの（メタ）アクリル酸アルコキシアルキル系モノマー；エチレン、プロピレン、イソプレン、ブタジエンなどのオレフィン系モノマー；ビニルエーテルなどのビニルエーテル系モノマー；などが挙げられる。 Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Isobutyl, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) ) 2-Ethylhexyl acrylate, Isooctyl (meth) acrylate, Nonyl (meth) acrylate, Isononyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate and other (meth) acrylic acid alkyl esters Acrylic monomer containing epoxy groups such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; vinyl ester-based monomers such as vinyl acetate and vinyl propionate; hydroxyethyl (meth) acrylate, (meth) acrylic acid Hydroxyl group-containing monomers such as hydroxypropyl and hydroxybutyl (meth) acrylate; (meth) alkoxyalkyl acrylate monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ethylene, propylene, isoprene, Olefin-based monomers such as butadiene; vinyl ether-based monomers such as vinyl ether; and the like can be mentioned.
　他のモノマーとしては、また、ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ジビニルベンゼン、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレートなどの多官能モノマーも挙げられる。 Other monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di. (Meta) Acrylate, Glycerindi (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Epoxy Acrylate, Polyester Acrylate, Urethane Acrylate, Divinylbenzene, Polyfunctional monomers such as butyl di (meth) acrylate and hexyl di (meth) acrylate can also be mentioned.
　他のモノマーとしては、また、窒素原子含有モノマー（例えば、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチルなどの（メタ）アクリル酸アミノアルキル系モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヒドロキシ（メタ）アクリルアミドなどの（Ｎ－置換）アミド系モノマー；アクリロニトリル、メタクリロニトリルなどのシアノアクリレート系モノマー；２－メタクリロイルオキシエチルイソシアネート等のイソシアネート基含有モノマーなど）も挙げられる。 Other monomers also include (meth) nitrogen atom-containing monomers (eg, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like. ) Aminoalkyl acrylate monomers; (N-substituted) amide monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxy (meth) acrylamide; acrylonitrile , Cyanoacrylate-based monomers such as methacrylonitrile; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate).
　粘着剤組成物ａ２は、オリゴマー（Ｘ）以外のオリゴマー（Ｙ）を含んでいてもよい。しかし、本発明の効果をより発現させ得る点で、オリゴマー（Ｙ）の含有量は少ないほうが好ましい。 The pressure-sensitive adhesive composition a2 may contain an oligomer (Y) other than the oligomer (X). However, it is preferable that the content of the oligomer (Y) is small in that the effects of the present invention can be more exhibited.
　本発明の効果をより発現させ得る点で、粘着剤組成物ａ２中のオリゴマー（Ｙ）の含有割合は、粘着剤組成物ａ２に含まれるアクリル系ポリマー１００重量部に対して、好ましくは５０重量部以下であり、より好ましくは４０重量部以下であり、さらに好ましくは３０重量部以下であり、特に好ましくは２５重量部以下である。 The content ratio of the oligomer (Y) in the pressure-sensitive adhesive composition a2 is preferably 50% by weight with respect to 100 parts by weight of the acrylic polymer contained in the pressure-sensitive adhesive composition a2 in that the effects of the present invention can be more exhibited. It is less than or equal to parts, more preferably 40 parts by weight or less, further preferably 30 parts by weight or less, and particularly preferably 25 parts by weight or less.
　オリゴマー（Ｙ）は、好ましくは、二環以下の環式構造を有するアクリル系モノマーを主成分とし、かつ、カルボキシル基含有モノマーをモノマー成分全量１００重量部に対して１重量部～１０重量部含んでいるモノマー組成物から得られるオリゴマーである。 The oligomer (Y) preferably contains an acrylic monomer having a cyclic structure of two rings or less as a main component, and contains 1 part by weight to 10 parts by weight of a carboxyl group-containing monomer with respect to 100 parts by weight of the total amount of the monomer components. It is an oligomer obtained from the monomer composition.
　二環以下の環式構造としては、芳香族性環、非芳香族性環のいずれであってもよいが、非芳香族性環が好ましい。芳香族性環としては、例えば、芳香族炭化水素環（例えば、ベンゼン環や、ナフタレン等における縮合炭素環など）や各種芳香族性複素環などが挙げられる。非芳香族性環としては、非芳香族性脂環式環（シクロペンタン環、シクロヘキサン環、シクロヘプタン環、シクロオクタン環などのシクロアルカン環；シクロヘキセン環などのシクロアルケン環など）、非芳香族性橋かけ環（例えば、ピナン、ピネン、ボルナン、ノルボルナン、ノルボルネンなどにおける二環式炭化水素環）などが挙げられる。 The cyclic structure having two or less rings may be either an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferable. Examples of the aromatic ring include an aromatic hydrocarbon ring (for example, a benzene ring, a condensed carbon ring in naphthalene and the like), and various aromatic heterocycles. Examples of the non-aromatic ring include a non-aromatic alicyclic ring (cycloalkane ring such as cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring; cycloalkene ring such as cyclohexene ring) and non-aromatic ring. Sexual bridging rings (eg, bicyclic hydrocarbon rings in pinan, pinen, bornan, norbornene, norbornene, etc.) and the like can be mentioned.
　二環以下の環式構造を有するアクリル系モノマーとしては、例えば、（メタ）アクリル酸シクロヘキシル等の（メタ）アクリル酸シクロアルキルエステル、（メタ）アクリル酸フェニル等の（メタ）アクリル酸アリールエステル、（メタ）アクリル酸フェノキシエチル等の（メタ）アクリル酸アリールオキシアルキルエステル、（メタ）アクリル酸ベンジル等の（メタ）アクリル酸アリールアルキルエステル、スチレンやα－メチルスチレン等のスチレン系モノマーなどの分子内に環状構造を有するエチレン性不飽和単量体が挙げられる。 Examples of the acrylic monomer having a cyclic structure of two or less rings include (meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylic acid, and (meth) acrylic acid aryl esters such as phenyl (meth) acrylic acid. Molecules such as (meth) acrylic acid aryloxyalkyl ester such as (meth) phenoxyethyl acrylate, (meth) acrylic acid arylalkyl ester such as (meth) benzyl acrylate, and styrene-based monomers such as styrene and α-methylstyrene. Examples thereof include an ethylenically unsaturated monomer having a cyclic structure inside.
　二環以下の環式構造を有するアクリル系モノマーとしては、好ましくは、メタクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニルなどの非芳香族性環を有する（メタ）アクリル酸エステルが挙げられ、透明性の観点から、より好ましくは、メタクリル酸シクロヘキシルが挙げられる。 Examples of the acrylic monomer having a cyclic structure of two or less rings include a (meth) acrylic acid ester having a non-aromatic ring such as cyclohexyl methacrylate and isobornyl (meth) acrylate, which are transparent. From the viewpoint, cyclohexyl methacrylate is more preferable.
　二環以下の環式構造を有するアクリル系モノマーは、１種のみであってもよいし、２種以上であってもよい。 The acrylic monomer having a cyclic structure of two or less rings may be only one kind or two or more kinds.
　オリゴマー（Ｙ）を得るために用いられるモノマー組成物に含まれる全モノマー成分１００重量部に対する、二環以下の環式構造を有するアクリル系モノマーの含有割合は、好ましくは５０重量部～９９重量部であり、より好ましくは７０重量部～９９重量部であり、さらに好ましくは８０重量部～９８重量部であり、特に好ましくは９０重量部～９７重量部であり、最も好ましくは９２重量部～９６重量部である。 The content ratio of the acrylic monomer having a cyclic structure of two rings or less with respect to 100 parts by weight of all the monomer components contained in the monomer composition used for obtaining the oligomer (Y) is preferably 50 parts by weight to 99 parts by weight. It is more preferably 70 parts by weight to 99 parts by weight, further preferably 80 parts by weight to 98 parts by weight, particularly preferably 90 parts by weight to 97 parts by weight, and most preferably 92 parts by weight to 96 parts by weight. It is a part by weight.
　オリゴマー（Ｙ）は、モノマー成分としてカルボキシル基含有モノマーを含んでいてもよい。このようなカルボキシル基含有モノマーとしては、アクリル系ポリマーを構成し得るカルボキシル基含有モノマーと同様に、例えば、（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸などが挙げられる。また、これらのカルボキシル基含有モノマーの酸無水物（例えば、無水マレイン酸、無水イコタン酸などの酸無水物基含有モノマー）も、カルボキシル基含有モノマーとして挙げられる。 The oligomer (Y) may contain a carboxyl group-containing monomer as a monomer component. Examples of such a carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, as in the case of the carboxyl group-containing monomer that can form an acrylic polymer. Further, acid anhydrides of these carboxyl group-containing monomers (for example, acid anhydride group-containing monomers such as maleic anhydride and icotanic anhydride) can also be mentioned as carboxyl group-containing monomers.
　オリゴマー（Ｙ）を得るために用いられるモノマー組成物に含まれる全モノマー成分１００重量部に対する、カルボキシル基含有モノマーの含有割合は、好ましくは１重量部～１０重量部であり、好ましくは２重量部～９重量部であり、さらに好ましくは３重量部～８重量部であり、特に好ましくは４重量部～７重量部である。 The content ratio of the carboxyl group-containing monomer to 100 parts by weight of all the monomer components contained in the monomer composition used for obtaining the oligomer (Y) is preferably 1 part by weight to 10 parts by weight, preferably 2 parts by weight. It is ~ 9 parts by weight, more preferably 3 parts by weight to 8 parts by weight, and particularly preferably 4 parts by weight to 7 parts by weight.
　オリゴマー（Ｙ）を得るために用いられるモノマー組成物には、二環以下の環式構造を有するアクリル系モノマー以外に、他のモノマーが含まれていてもよい。このような他のモノマーは、１種のみであってもよいし、２種以上であってもよい。 The monomer composition used to obtain the oligomer (Y) may contain other monomers in addition to the acrylic monomer having a cyclic structure of two or less rings. Such other monomers may be only one kind or two or more kinds.
　他のモノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシルなどの（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジルなどのエポキシ基含有アクリル系モノマー；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル系モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチルなどのヒドロキシル基含有モノマー；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチルなどの（メタ）アクリル酸アルコキシアルキル系モノマー；エチレン、プロピレン、イソプレン、ブタジエンなどのオレフィン系モノマー；ビニルエーテルなどのビニルエーテル系モノマー；などが挙げられる。 Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Isobutyl, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) ) 2-Ethylhexyl acrylate, Isooctyl (meth) acrylate, Nonyl (meth) acrylate, Isononyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate and other (meth) acrylic acid alkyl esters Acrylic monomer containing epoxy groups such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; vinyl ester-based monomers such as vinyl acetate and vinyl propionate; hydroxyethyl (meth) acrylate, (meth) acrylic acid Hydroxyl group-containing monomers such as hydroxypropyl and hydroxybutyl (meth) acrylate; (meth) alkoxyalkyl acrylate monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ethylene, propylene, isoprene, Olefin-based monomers such as butadiene; vinyl ether-based monomers such as vinyl ether; and the like can be mentioned.
　他のモノマーとしては、例えば、ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ジビニルベンゼン、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレートなどの多官能モノマーも挙げられる。 Examples of other monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol di. (Meta) Acrylate, Glycerindi (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Epoxy Acrylate, Polyester Acrylate, Urethane Acrylate, Divinylbenzene, Polyfunctional monomers such as butyl di (meth) acrylate and hexyl di (meth) acrylate can also be mentioned.
　他のモノマーとしては、窒素原子含有モノマー（例えば、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチルなどの（メタ）アクリル酸アミノアルキル系モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヒドロキシ（メタ）アクリルアミドなどの（Ｎ－置換）アミド系モノマー；アクリロニトリル、メタクリロニトリルなどのシアノアクリレート系モノマー；２－メタクリロイルオキシエチルイソシアネート等のイソシアネート基含有モノマーなど）も挙げられる。しかしながら、このような窒素原子含有モノマーは加熱下における粘着剤黄変の原因となり得るため、用いなくてもよい場合は用いないことが好ましい。 Other monomers include nitrogen atom-containing monomers (eg, (meth) acrylics such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate. Aminoalkyl acid-based monomers; (N-substituted) amide-based monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-hydroxy (meth) acrylamide; acrylonitrile, methacryl Also included are cyanoacrylate-based monomers such as lonitrile; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate). However, since such a nitrogen atom-containing monomer can cause yellowing of the pressure-sensitive adhesive under heating, it is preferable not to use it when it is not necessary to use it.
　オリゴマー（Ｘ）やオリゴマー（Ｙ）は、本発明の効果を損なわない範囲で、任意の適切な重合方法により調製することができる。アクリル系ポリマーの重合方法としては、例えば、溶液重合方法、乳化重合方法、塊状重合方法、紫外線照射による重合方法などが挙げられ、透明性、耐水性、コストなどの点で、溶液重合方法が好ましい。 The oligomer (X) and the oligomer (Y) can be prepared by any suitable polymerization method as long as the effects of the present invention are not impaired. Examples of the polymerization method of the acrylic polymer include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method by irradiation with ultraviolet rays, and the like, and the solution polymerization method is preferable in terms of transparency, water resistance, cost, and the like. ..
　重合に際して用いられ得る重合開始剤、連鎖移動剤などは、本発明の効果を損なわない範囲で、任意の適切なものを採用し得る。 As the polymerization initiator, chain transfer agent, etc. that can be used in the polymerization, any appropriate one can be adopted as long as the effect of the present invention is not impaired.
　重合開始剤の使用量は、本発明の効果を損なわない範囲で、任意の適切な量を採用し得る。このような使用量としては、例えば、モノマー成分全量に対して０．１重量％～１５重量％が好ましい。 As the amount of the polymerization initiator used, any appropriate amount can be adopted as long as the effect of the present invention is not impaired. As such an amount to be used, for example, 0.1% by weight to 15% by weight is preferable with respect to the total amount of the monomer components.
　連鎖移動剤の使用量は、本発明の効果を損なわない範囲で、任意の適切な量を採用し得る。このような使用量としては、例えば、モノマー成分全量に対して０．０１重量％～１５重量％が好ましい。 The amount of the chain transfer agent used may be any appropriate amount as long as the effect of the present invention is not impaired. As such an amount to be used, for example, 0.01% by weight to 15% by weight is preferable with respect to the total amount of the monomer components.
　溶液重合方法においては、各種の一般的な溶剤を用いることができる。このような溶剤としては、例えば、酢酸エチル、酢酸ｎ－ブチル等のエステル類；トルエン、ベンゼン等の芳香族炭化水素類；ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類；メチルエチルケトン、メチルイソブチルケトン等のケトン類；などの有機溶剤が挙げられる。溶剤は、１種のみであってもよいし、２種以上であってもよい。 In the solution polymerization method, various general solvents can be used. Examples of such a solvent 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; cyclohexane and methyl. Examples thereof include organic solvents such as alicyclic hydrocarbons such as cyclohexane; and ketones such as methyl ethyl ketone and methyl isobutyl ketone; The solvent may be only one type or two or more types.
　オリゴマー（Ｘ）、（Ｙ）は、重量平均分子量が、好ましくは３０００～６０００であり、より好ましくは３３００～５５００であり、さらに好ましくは３５００～５０００である。 The oligomers (X) and (Y) have a weight average molecular weight of preferably 3000 to 6000, more preferably 3300 to 5500, and even more preferably 3500 to 5000.
　オリゴマー（Ｘ）、（Ｙ）の重量平均分子量は、重合開始剤や連鎖移動剤の種類やその使用量、重合の際の温度や時間の他、モノマー濃度、モノマー滴下速度などによりコントロールすることができる。 The weight average molecular weight of the oligomers (X) and (Y) can be controlled by the type and amount of the polymerization initiator and chain transfer agent, the temperature and time during polymerization, the monomer concentration, the monomer dropping rate, and the like. it can.
　粘着剤組成物ａ２がアクリル系ポリマーとオリゴマーを含んでいる場合において、アクリル系ポリマーとオリゴマーとの割合としては、オリゴマーが、アクリル系ポリマー１００重量部に対して、好ましくは１０重量部～３５重量部であり、より好ましくは１５重量部～３０重量部である。粘着剤組成物ａ２がアクリル系ポリマーとオリゴマーを含んでいる場合において、アクリル系ポリマーとオリゴマーとの割合が上記範囲内にあれば、本発明の効果をより発現し得る。 When the pressure-sensitive adhesive composition a2 contains an acrylic polymer and an oligomer, the ratio of the acrylic polymer to the oligomer is such that the oligomer is preferably 10 parts by weight to 35 parts by weight with respect to 100 parts by weight of the acrylic polymer. It is a part, more preferably 15 parts by weight to 30 parts by weight. When the pressure-sensitive adhesive composition a2 contains an acrylic polymer and an oligomer, the effect of the present invention can be further exhibited if the ratio of the acrylic polymer and the oligomer is within the above range.
　粘着剤組成物ａ２には、必要に応じて、紫外線吸収剤、酸化防止剤、光安定剤、老化防止剤、粘着付与剤、可塑剤、軟化剤、充填剤、着色剤（顔料や染料など）、界面活性剤、帯電防止剤などの公知の添加剤が含まれていてもよい。 The pressure-sensitive adhesive composition a2 contains, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, an anti-aging agent, a tackifier, a plasticizer, a softener, a filler, a colorant (pigment, dye, etc.). , Known additives such as surfactants and antistatic agents may be included.
＜１－３．剥離シート＞
　粘着剤層Ａ２の表面には、保護のために、剥離シートが設けられていてもよい。剥離シートは、１層であってもよいし、２層以上であってもよい。 <1-3. Release sheet>
A release sheet may be provided on the surface of the pressure-sensitive adhesive layer A2 for protection. The release sheet may have one layer or two or more layers.
　剥離シートの厚みとしては、本発明の効果をより発現させ得る点で、好ましくは５μｍ～３００μｍであり、より好ましくは１０μｍ～２００μｍであり、さらに好ましくは１０μｍ～１５０μｍであり、特に好ましくは１０μｍ～１３０μｍであり、最も好ましくは２０μｍ～１２０μｍである。 The thickness of the release sheet is preferably 5 μm to 300 μm, more preferably 10 μm to 200 μm, still more preferably 10 μm to 150 μm, and particularly preferably 10 μm to 10 μm in that the effects of the present invention can be more exhibited. It is 130 μm, most preferably 20 μm to 120 μm.
　剥離シートは、樹脂基材フィルムを含む。 The release sheet contains a resin base film.
　樹脂基材フィルムとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル系樹脂から構成されるプラスチックフィルム；ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリメチルペンテン（ＰＭＰ）、エチレン－プロピレン共重合体、エチレン－酢酸ビニル共重合体（ＥＶＡ）等のα－オレフィンをモノマー成分とするオレフィン系樹脂から構成されるプラスチックフィルム；ポリ塩化ビニル（ＰＶＣ）から構成されるプラスチックフィルム；酢酸ビニル系樹脂から構成されるプラスチックフィルム；ポリカーボネート（ＰＣ）から構成されるプラスチックフィルム；ポリフェニレンスルフィド（ＰＰＳ）から構成されるプラスチックフィルム；ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）等のアミド系樹脂から構成されるプラスチックフィルム；ポリイミド系樹脂から構成されるプラスチックフィルム；ポリエーテルエーテルケトン（ＰＥＥＫ）から構成されるプラスチックフィルム；ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のオレフィン系樹脂から構成されるプラスチックフィルム；ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン－フッ化ビニリデン共重合体などのフッ素系樹脂などから構成されるプラスチックフィルム；などが挙げられる。 Examples of the resin base film include plastic films composed of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); polyethylene (PE), polypropylene (PP), and the like. A plastic film composed of an olefin resin containing α-olefin such as polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) as a monomer component; polyvinyl chloride (PVC). Plastic film composed of; plastic film composed of vinyl acetate resin; plastic film composed of polycarbonate (PC); plastic film composed of polyphenylene sulfide (PPS); polyamide (nylon), total aromatic polyamide Plastic film composed of amide resin such as (aramid); plastic film composed of polyimide resin; plastic film composed of polyether ether ketone (PEEK); polyethylene (PE), polypropylene (PP), etc. Plastic film composed of olefin resin; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer A plastic film composed of a fluororesin or the like;
　樹脂基材フィルムは、１層のみであってもよいし、２層以上であってもよい。樹脂基材フィルムは、延伸されたものであってもよい。 The resin base film may have only one layer or two or more layers. The resin base film may be a stretched one.
　樹脂基材フィルムは、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理などが挙げられる。 The resin base film may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
　樹脂基材フィルムには、本発明の効果を損なわない範囲で、任意の適切な添加剤が含まれていてもよい。 The resin base film may contain any suitable additive as long as the effects of the present invention are not impaired.
　剥離シートは、粘着剤層Ａ２からの剥離性を高めるため、離型層を有していてもよい。剥離シートが離型層を有する場合、離型層の側が、粘着剤層Ａ２に直接に積層されてなる。 The release sheet may have a release layer in order to improve the release property from the pressure-sensitive adhesive layer A2. When the release sheet has a release layer, the release layer side is directly laminated on the pressure-sensitive adhesive layer A2.
　離型層の形成材料は、本発明の効果を損なわない範囲で、任意の適切な形成材料を採用し得る。このような形成材料としては、例えば、シリコーン系離型剤、フッ素系離型剤、長鎖アルキル系離型剤、脂肪酸アミド系離型剤などが挙げられる。これらのなかでも、シリコーン系離型剤が好ましい。離型層は、塗布層として形成することができる。 As the material for forming the release layer, any suitable forming material can be adopted as long as the effect of the present invention is not impaired. Examples of such a forming material include a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, and a fatty acid amide-based release agent. Among these, a silicone-based release agent is preferable. The release layer can be formed as a coating layer.
　離型層の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは１０ｎｍ～２０００ｎｍであり、より好ましくは１０ｎｍ～１５００ｎｍであり、さらに好ましくは１０ｎｍ～１０００ｎｍであり、特に好ましくは１０ｎｍ～５００ｎｍである。 As the thickness of the release layer, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 10 nm to 2000 nm, more preferably 10 nm to 1500 nm, further preferably 10 nm to 1000 nm, and particularly preferably 10 nm to 500 nm.
　離型層は、１層のみであってもよいし、２層以上であってもよい。 The release layer may be only one layer or two or more layers.
　シリコーン系離型層としては、例えば、付加反応型シリコーン樹脂が挙げられる。付加反応型シリコーン樹脂としては、具体的には、例えば、信越化学工業製のＫＳ－７７４、ＫＳ－７７５、ＫＳ－７７８、ＫＳ－７７９Ｈ、ＫＳ－８４７Ｈ、ＫＳ－８４７Ｔ；東芝シリコーン製のＴＰＲ－６７００、ＴＰＲ－６７１０、ＴＰＲ－６７２１；東レ・ダウ・コーニング製のＳＤ７２２０、ＳＤ７２２６；などが挙げられる。シリコーン系離型層の塗布量（乾燥後）は、好ましくは０．０１ｇ／ｍ２～２ｇ／ｍ２であり、より好ましくは０．０１ｇ／ｍ２～１ｇ／ｍ２であり、さらに好ましくは０．０１ｇ／ｍ２～０．５ｇ／ｍ２である。 Examples of the silicone-based release layer include an addition reaction type silicone resin. Specific examples of the addition reaction type silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, and KS-847T manufactured by Shin-Etsu Chemical Co., Ltd .; TPR-made by Toshiba Silicone. 6700, TPR-6710, TPR-6721; SD7220, SD7226 manufactured by Toray Dow Corning; and the like. The coating amount (after drying) of the silicone-based release layer is preferably 0.01 g / m 2 to 2 g / m 2 , more preferably 0.01 g / m 2 to 1 g / m 2, and even more preferably 0.01 g / m 2 to 1 g / m 2. It is 0.01 g / m 2 to 0.5 g / m 2 .
　離型層の形成は、例えば、上記の形成材料を、任意の適切な層上に、リバースグラビアコート、バーコート、ダイコート等、従来公知の塗布方式により塗布した後に、通常、１２０～２００℃程度で熱処理を施すことにより硬化させることにより行うことができる。また、必要に応じて熱処理と紫外線照射等の活性エネルギー線照射とを併用してもよい。 The release layer is formed, for example, by applying the above-mentioned forming material on any suitable layer by a conventionally known coating method such as reverse gravure coat, bar coat, die coat, etc., and then usually about 120 to 200 ° C. It can be carried out by curing by applying heat treatment in. Further, if necessary, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination.
　剥離シートは、帯電防止層を有していてもよい。 The release sheet may have an antistatic layer.
　帯電防止層の厚みとしては、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは１ｎｍ～１０００ｎｍであり、より好ましくは５ｎｍ～９００ｎｍであり、さらに好ましくは７．５ｎｍ～８００ｎｍであり、特に好ましくは１０ｎｍ～７００ｎｍである。 As the thickness of the antistatic layer, any appropriate thickness can be adopted as long as the effect of the present invention is not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, further preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.
　帯電防止層は、１層のみであってもよいし、２層以上であってもよい。 The antistatic layer may be only one layer or two or more layers.
　帯電防止層としては、帯電防止効果を奏することができる層であれば、本発明の効果を損なわない範囲で、任意の適切な帯電防止層を採用し得る。このような帯電防止層としては、好ましくは、導電性ポリマーを含む導電コート液を任意の適切な基材層上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液を樹脂基材フィルム上にコーティングして形成される帯電防止層である。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。 As the antistatic layer, any appropriate antistatic layer can be adopted as long as it can exert an antistatic effect, as long as the effect of the present invention is not impaired. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on an arbitrary suitable base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a resin base film. Specific coating methods include a roll coating method, a bar coating method, and a gravure coating method.
　導電性ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な導電性ポリマーを採用し得る。このような導電性ポリマーとしては、例えば、π共役系導電性ポリマーにポリアニオンがドープされた導電性ポリマーなどが挙げられる。π共役系導電性ポリマーとしては、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレンなどの鎖状導電性ポリマーが挙げられる。ポリアニオンとしては、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリメタクリルカルボン酸などが挙げられる。導電性ポリマーは、１種のみであってもよいし、２種以上であってもよい。 As the conductive polymer, any suitable conductive polymer can be adopted as long as the effects of the present invention are not impaired. Examples of such a conductive polymer include a conductive polymer in which a π-conjugated conductive polymer is doped with a polyanion. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, ethyl acrylate sulfonic acid, polymethacrylcarboxylic acid and the like. The conductive polymer may be only one kind or two or more kinds.
＜１－４．機能層Ａ３＞ <1-4. Functional layer A3>
　補強用フィルムは、機能層Ａ３と基材層Ａ１と粘着剤層Ａ２をこの順に含んでいてもよい。すなわち、補強用フィルムの別の一つの実施形態は、図２に示すように、機能層Ａ３（３０）と基材層Ａ１（１０）と粘着剤層Ａ２（２０）とからなる。 The reinforcing film may include the functional layer A3, the base material layer A1, and the pressure-sensitive adhesive layer A2 in this order. That is, another embodiment of the reinforcing film comprises a functional layer A3 (30), a base material layer A1 (10), and an adhesive layer A2 (20), as shown in FIG.
　機能層Ａ３は、任意に備えられていてもよい層であり、補強用フィルムに各種機能を付与し得る層である。 The functional layer A3 is a layer that may be arbitrarily provided, and is a layer that can impart various functions to the reinforcing film.
　機能層Ａ３の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは１ｎｍ～１０００ｎｍであり、より好ましくは２ｎｍ～８００ｎｍであり、さらに好ましくは５ｎｍ～４００ｎｍであり、特に好ましくは１０ｎｍ～２００ｎｍである。 As the thickness of the functional layer A3, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 2 nm to 800 nm, further preferably 5 nm to 400 nm, and particularly preferably 10 nm to 200 nm.
　機能層Ａ３は、１層のみであってもよいし、２層以上であってもよい。 The functional layer A3 may be only one layer or two or more layers.
　機能層Ａ３としては、本発明の効果を損なわない範囲で、任意の適切な機能層を採用し得る。このような機能層としては、例えば、帯電防止層、反射防止層、アンチグレア層、ハードコート層などが挙げられ、本発明の効果をより発現させ得る点では、反射防止層が選択され得る。 As the functional layer A3, any appropriate functional layer can be adopted as long as the effect of the present invention is not impaired. Examples of such a functional layer include an antistatic layer, an antireflection layer, an antiglare layer, a hard coat layer, and the like, and an antireflection layer can be selected in that the effects of the present invention can be more exhibited.
　反射防止層としては、本発明の効果を損なわない範囲で、任意の適切な反射防止層を採用し得る。このような反射防止層としては、例えば、特開２０１９－１４４５７７号公報などに記載の反射防止層が挙げられる。 As the antireflection layer, any appropriate antireflection layer can be adopted as long as the effect of the present invention is not impaired. Examples of such an antireflection layer include the antireflection layer described in JP-A-2019-144557.
　機能層Ａ３としては、帯電防止効果を発現させるために、帯電防止層も好ましく選択され得る。 As the functional layer A3, an antistatic layer may also be preferably selected in order to exhibit an antistatic effect.
　機能層Ａ３として、反射防止層と帯電防止層の両方が選択される場合は、反射防止層の機能をより発現させ得る点で、基材層Ａ１側に帯電防止層を配置することが好ましい。 When both the antireflection layer and the antistatic layer are selected as the functional layer A3, it is preferable to arrange the antistatic layer on the base material layer A1 side in that the function of the antireflection layer can be more exhibited.
　帯電防止層としては、帯電防止効果を奏することができる層であれば、本発明の効果を損なわない範囲で、任意の適切な帯電防止層を採用し得る。このような帯電防止層としては、好ましくは、導電性ポリマーを含む導電コート液を任意の適切な基材層上にコーティングして形成される帯電防止層である。具体的には、例えば、導電性ポリマーを含む導電コート液を基材層Ａ１上にコーティングして形成される帯電防止層である。具体的なコーティングの方法としては、ロールコート法、バーコート法、グラビアコート法などが挙げられる。 As the antistatic layer, any appropriate antistatic layer can be adopted as long as it can exert an antistatic effect, as long as the effect of the present invention is not impaired. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on an arbitrary suitable base material layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a base material layer A1. Specific coating methods include a roll coating method, a bar coating method, and a gravure coating method.
　導電性ポリマーとしては、本発明の効果を損なわない範囲で、任意の適切な導電性ポリマーを採用し得る。このような導電性ポリマーとしては、例えば、π共役系導電性ポリマーにポリアニオンがドープされた導電性ポリマーなどが挙げられる。π共役系導電性ポリマーとしては、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレンなどの鎖状導電性ポリマーが挙げられる。ポリアニオンとしては、ポリスチレンスルホン酸、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリル酸エチルスルホン酸、ポリメタクリルカルボン酸などが挙げられる。 As the conductive polymer, any suitable conductive polymer can be adopted as long as the effects of the present invention are not impaired. Examples of such a conductive polymer include a conductive polymer in which a π-conjugated conductive polymer is doped with a polyanion. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, ethyl acrylate sulfonic acid, polymethacrylcarboxylic acid and the like.
＜１－５．補強用フィルムの用途、補強用フィルム付光学部材、補強用フィルム付電子部材＞
　本発明の補強用フィルムは、任意の適切な部材である被着体に貼り付けられる。代表的には、本発明の補強用フィルムは、光学部材または電子部材である被着体に貼り付けられる。この場合、本発明の補強用フィルムの粘着剤層Ａ２の露出面側が、光学部材または電子部材である被着体に貼り付けられる。このようにして、本発明の補強用フィルム付光学部材または補強用フィルム付電子部材が得られる。すなわち、本発明の補強用フィルム付光学部材または補強用フィルム付電子部材は、本発明の補強用フィルムを備える。 <1-5. Applications of reinforcing film, optical member with reinforcing film, electronic member with reinforcing film>
The reinforcing film of the present invention is attached to an adherend, which is an arbitrary suitable member. Typically, the reinforcing film of the present invention is attached to an adherend which is an optical member or an electronic member. In this case, the exposed surface side of the pressure-sensitive adhesive layer A2 of the reinforcing film of the present invention is attached to an adherend which is an optical member or an electronic member. In this way, the optical member with a reinforcing film or the electronic member with a reinforcing film of the present invention can be obtained. That is, the optical member with a reinforcing film or the electronic member with a reinforcing film of the present invention includes the reinforcing film of the present invention.
≪２．表面保護フィルム≫
　表面保護フィルムは、補強用フィルムの基材層Ａ１側に配置される。基材層Ａ１が機能層Ａ３を有する場合は、機能層Ａ３の側に表面保護フィルムが配置される。 ≪2. Surface protection film ≫
The surface protective film is arranged on the base material layer A1 side of the reinforcing film. When the base material layer A1 has the functional layer A3, the surface protective film is arranged on the side of the functional layer A3.
　表面保護フィルムの厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは４μｍ～５００μｍであり、より好ましくは１０μｍ～４００μｍであり、さらに好ましくは１５μｍ～３５０μｍであり、特に好ましくは２０μｍ～３００μｍである。 As the thickness of the surface protective film, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 4 μm to 500 μm, more preferably 10 μm to 400 μm, further preferably 15 μm to 350 μm, and particularly preferably 20 μm to 300 μm.
　表面保護フィルムは、基材層Ｂ１と粘着剤層Ｂ２を含む。表面保護フィルムは、基材層Ｂ１と粘着剤層Ｂ２を有していれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していてもよい。 The surface protective film includes a base material layer B1 and an adhesive layer B2. The surface protective film may have any other suitable layer as long as it has the base material layer B1 and the pressure-sensitive adhesive layer B2, as long as the effects of the present invention are not impaired.
　粘着剤層Ｂ２の表面には、保護のために、剥離シートが設けられていてもよい。 A release sheet may be provided on the surface of the adhesive layer B2 for protection.
　基材層Ｂ１の表面には、各種機能を付与するために、機能層Ｂ３が設けられていてもよい。 A functional layer B3 may be provided on the surface of the base material layer B1 in order to impart various functions.
　表面保護フィルムの厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは５μｍ～５００μｍであり、より好ましくは１０μｍ～４５０μｍであり、さらに好ましくは１５μｍ～４００μｍであり、特に好ましくは２０μｍ～３００μｍである。 As the thickness of the surface protective film, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 5 μm to 500 μm, more preferably 10 μm to 450 μm, further preferably 15 μm to 400 μm, and particularly preferably 20 μm to 300 μm.
　表面保護フィルムの一つの実施形態は、図３に示すように、基材層Ｂ１（４０）と粘着剤層Ｂ２（５０）と剥離シート（６０）とからなる。 As shown in FIG. 3, one embodiment of the surface protective film comprises a base material layer B1 (40), an adhesive layer B2 (50), and a release sheet (60).
　表面保護フィルムの一つの実施形態は、図４に示すように、機能層Ｂ３（７０）と基材層Ｂ１（４０）と粘着剤層Ｂ２（５０）と剥離シート（６０）とからなる。 As shown in FIG. 4, one embodiment of the surface protective film comprises a functional layer B3 (70), a base material layer B1 (40), an adhesive layer B2 (50), and a release sheet (60).
＜２－１．基材層Ｂ１＞
　基材層Ｂ１としては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な材料から形成される基材を採用し得る。このような材料としては、例えば、＜１－１．基材層Ａ１＞の項目で例示したものが挙げられる。 <2-1. Base material layer B1>
As the base material layer B1, a base material formed from any suitable material can be adopted depending on the intended purpose, as long as the effects of the present invention are not impaired. Examples of such a material include <1-1. Examples thereof include those exemplified in the item of base material layer A1>.
　基材層Ｂ１は、１層のみであってもよいし、２層以上であってもよい。 The base material layer B1 may be only one layer or two or more layers.
　基材層Ｂ１の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは４μｍ～３５０μｍであり、より好ましくは８μｍ～３２５μｍであり、さらに好ましくは１２μｍ～２９０μｍであり、特に好ましくは１５μｍ～２０５μｍである。 As the thickness of the base material layer B1, any appropriate thickness can be adopted according to the purpose as long as the effects of the present invention are not impaired. Such a thickness is preferably 4 μm to 350 μm, more preferably 8 μm to 325 μm, further preferably 12 μm to 290 μm, and particularly preferably 15 μm to 205 μm.
　基材層Ｂ１は、帯電防止剤を含んでいてもよい。帯電防止剤を含む基材層Ｂ１としては、例えば、帯電防止剤が練り込まれた樹脂シートが用いられ得る。このような樹脂シートは、樹脂と帯電防止剤とを含む基材層Ｂ１形成用組成物から形成され得る。 The base material layer B1 may contain an antistatic agent. As the base material layer B1 containing the antistatic agent, for example, a resin sheet in which the antistatic agent is kneaded can be used. Such a resin sheet can be formed from a composition for forming a base material layer B1 containing a resin and an antistatic agent.
　基材層Ｂ１そのものが帯電防止剤として作用してもよい。例えば、基材層Ｂ１の材料として金属箔を採用する場合は、基材層Ｂ１そのものが帯電防止剤として作用し得る。 The base material layer B1 itself may act as an antistatic agent. For example, when a metal foil is used as the material of the base material layer B1, the base material layer B1 itself can act as an antistatic agent.
　基材層Ｂ１は、表面処理が施されていてもよい。表面処理としては、例えば、コロナ処理、プラズマ処理、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理、下塗り剤によるコーティング処理などが挙げられる。 The base material layer B1 may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
　有機コーティング材料としては、例えば、＜１－１．基材層Ａ１＞の項目で例示したものが挙げられる。 As an organic coating material, for example, <1-1. Examples thereof include those exemplified in the item of base material layer A1>.
　基材層Ｂ１には、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な他の添加剤が含まれていてもよい。 The base material layer B1 may contain any other suitable additive, depending on the intended purpose, as long as the effects of the present invention are not impaired.
＜２－２．粘着剤層Ｂ２＞
　粘着剤層Ｂ２の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは１μｍ～１５０μｍであり、より好ましくは２μｍ～１２５μｍであり、さらに好ましくは３μｍ～１１０μｍであり、特に好ましくは５μｍ～９５μｍである。 <2-2. Adhesive layer B2>
As the thickness of the pressure-sensitive adhesive layer B2, any appropriate thickness can be adopted depending on the intended purpose as long as the effects of the present invention are not impaired. Such a thickness is preferably 1 μm to 150 μm, more preferably 2 μm to 125 μm, further preferably 3 μm to 110 μm, and particularly preferably 5 μm to 95 μm.
　粘着剤層Ｂ２としては、本発明の効果を損なわない範囲で、任意の適切な粘着剤から構成される粘着剤層を採用し得る。このような粘着剤としては、例えば、特開２０１９－１２７５２６号公報に記載の粘着剤層を構成する粘着剤が挙げられ、好ましくは、該公報に記載の、アクリル系粘着剤、ウレタン系粘着剤、シリコーン系粘着剤からなる群から選ばれる少なくとも１種が挙げられる。 As the pressure-sensitive adhesive layer B2, a pressure-sensitive adhesive layer composed of any suitable pressure-sensitive adhesive can be adopted as long as the effects of the present invention are not impaired. Examples of such a pressure-sensitive adhesive include the pressure-sensitive adhesives constituting the pressure-sensitive adhesive layer described in JP-A-2019-127526, preferably the acrylic pressure-sensitive adhesive and the urethane-based pressure-sensitive adhesive described in the publication. , At least one selected from the group consisting of silicone-based pressure-sensitive adhesives.
＜２－３．剥離シート＞
　粘着剤層Ｂ２の表面には、保護のために、剥離シートが設けられていてもよい。剥離シートは、１層であってもよいし、２層以上であってもよい。 <2-3. Release sheet>
A release sheet may be provided on the surface of the pressure-sensitive adhesive layer B2 for protection. The release sheet may have one layer or two or more layers.
　表面保護フィルムが有し得る剥離シートについては、＜１－３．剥離シート＞の項目での説明を援用し得る。 Regarding the release sheet that the surface protective film can have, <1-3. The explanation in the item of release sheet> can be used.
＜２－４．機能層Ｂ３＞ <2-4. Functional layer B3>
　表面保護フィルムは、機能層Ｂ３と基材層Ｂ１と粘着剤層Ｂ２をこの順に含んでいてもよい。 The surface protective film may include the functional layer B3, the base material layer B1 and the adhesive layer B2 in this order.
　機能層Ｂ３は、任意に備えられていてもよい層であり、補強用フィルムに各種機能を付与し得る層である。 The functional layer B3 is a layer that may be provided arbitrarily, and is a layer that can impart various functions to the reinforcing film.
　機能層Ｂ３の厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは１ｎｍ～１０００ｎｍであり、より好ましくは２ｎｍ～８００ｎｍであり、さらに好ましくは５ｎｍ～４００ｎｍであり、特に好ましくは１０ｎｍ～２００ｎｍである。 As the thickness of the functional layer B3, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 1 nm to 1000 nm, more preferably 2 nm to 800 nm, further preferably 5 nm to 400 nm, and particularly preferably 10 nm to 200 nm.
　機能層Ｂ３は、１層のみであってもよいし、２層以上であってもよい。 The functional layer B3 may be only one layer or two or more layers.
　機能層Ｂ３については、＜１－４．機能層Ａ３＞の項目での説明を援用し得る。 For functional layer B3, <1-4. The explanation in the item of functional layer A3> can be incorporated.
≪３．表面保護フィルム付補強用フィルム≫
　本発明の表面保護フィルム付補強用フィルムは、本発明の補強用フィルムの基材層Ａ１側に表面保護フィルムを備える。本発明の補強用フィルムが基材層Ａ１上にさらに機能層Ａ３を有する場合は、該機能層Ａ３の表面に、表面保護フィルムが備えられる。 ≪3. Reinforcing film with surface protection film ≫
The reinforcing film with a surface protective film of the present invention includes a surface protective film on the base material layer A1 side of the reinforcing film of the present invention. When the reinforcing film of the present invention further has a functional layer A3 on the base material layer A1, a surface protective film is provided on the surface of the functional layer A3.
　本発明の表面保護フィルム付補強用フィルムは、補強用フィルムと表面保護フィルムを有する。本発明の表面保護フィルム付補強用フィルムは、補強用フィルムと表面保護フィルムを有していれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していてもよい。 The reinforcing film with a surface protective film of the present invention has a reinforcing film and a surface protective film. The reinforcing film with a surface protective film of the present invention may have any suitable other layer as long as it has the reinforcing film and the surface protective film, as long as the effects of the present invention are not impaired. ..
　本発明の表面保護フィルム付補強用フィルムにおいては、補強用フィルムが基材層Ａ１と粘着剤層Ａ２を含み、表面保護フィルムが基材層Ｂ１と粘着剤層Ｂ２を含む。 In the reinforcing film with a surface protective film of the present invention, the reinforcing film includes a base material layer A1 and an adhesive layer A2, and the surface protective film includes a base material layer B1 and an adhesive layer B2.
　本発明の表面保護フィルム付補強用フィルムの厚みとしては、本発明の効果を損なわない範囲で、目的に応じて、任意の適切な厚みを採用し得る。このような厚みとしては、好ましくは９μｍ～１３００μｍであり、より好ましくは２０μｍ～１０５０μｍであり、さらに好ましくは３５μｍ～９００μｍであり、特に好ましくは４５μｍ～７５０μｍである。 As the thickness of the reinforcing film with the surface protective film of the present invention, any appropriate thickness can be adopted according to the purpose as long as the effect of the present invention is not impaired. Such a thickness is preferably 9 μm to 1300 μm, more preferably 20 μm to 1050 μm, further preferably 35 μm to 900 μm, and particularly preferably 45 μm to 750 μm.
　本発明の表面保護フィルム付補強用フィルムは、補強用フィルムと表面保護フィルムを、基材層Ａ１（基材層Ａ１上にさらに機能層Ａ３を有する場合は、該機能層Ａ３）と表面保護フィルムの粘着剤層Ｂ２（粘着剤層Ｂ２上に剥離シートが設けられている場合は、該剥離シートを剥離して露出させた粘着剤層Ｂ２）が直接に積層されてなるように張り合わせることにより得ることができる。 In the reinforcing film with a surface protective film of the present invention, the reinforcing film and the surface protective film are combined with the base material layer A1 (if the base material layer A1 further has the functional layer A3, the functional layer A3) and the surface protective film. (If a release sheet is provided on the pressure-sensitive adhesive layer B2, the pressure-sensitive adhesive layer B2 exposed by peeling off the release sheet) is directly laminated and laminated. Obtainable.
　本発明の表面保護フィルム付補強用フィルムの一つの実施形態は、図５に示すように、基材層Ａ１（１０）と粘着剤層Ａ２（２０）とからなる補強用フィルムと、基材層Ｂ１（４０）と粘着剤層Ｂ２（５０）からなる表面保護フィルムとが、基材層Ａ１（１０）と粘着剤層Ｂ２（５０）が直接に積層されてなるように張り合わせられた形態である。 As shown in FIG. 5, one embodiment of the reinforcing film with a surface protective film of the present invention includes a reinforcing film composed of a base material layer A1 (10) and an adhesive layer A2 (20), and a base material layer. The surface protective film composed of B1 (40) and the pressure-sensitive adhesive layer B2 (50) is laminated so that the base material layer A1 (10) and the pressure-sensitive adhesive layer B2 (50) are directly laminated. ..
　本発明の表面保護フィルム付補強用フィルムは、該表面保護フィルム付補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後に、表面保護フィルムを剥離した後の、補強用フィルムの５８０ｎｍでの光反射率変化率が、好ましくは５．０％以下であり、より好ましくは４．８％であり、さらに好ましくは４．５％であり、さらに好ましくは４．２％であり、さらに好ましくは４．０％であり、特に好ましくは３．７％であり、最も好ましくは３．５％である。上記光反射率変化率が上記範囲内にあれば、補強用フィルム越しに光学部材や電子部材の検査がされる際に、検査性が低下しない、補強用フィルムを提供することができる。 The reinforcing film with a surface protective film of the present invention is the reinforcing film after the surface protective film is peeled off after the reinforcing film with the surface protective film is stored in an environment of 60 ° C. and 90% RH for one week. The rate of change in light reflectance at 580 nm is preferably 5.0% or less, more preferably 4.8%, still more preferably 4.5%, still more preferably 4.2%. It is more preferably 4.0%, particularly preferably 3.7%, and most preferably 3.5%. When the light reflectance change rate is within the above range, it is possible to provide a reinforcing film that does not deteriorate inspectability when an optical member or an electronic member is inspected through the reinforcing film.
≪４．補強用フィルムの使用形態≫
　本発明の補強用フィルムは、代表的には、光学部材または電子部材である被着体に貼り付けられる。具体的には、本発明の補強用フィルムの粘着剤層Ａ２の露出面が、光学部材または電子部材である被着体に貼り付けられる。粘着剤層Ａ２の表面に剥離シートが設けられている場合は、該剥離シートを剥離して露出した粘着剤層Ａ２が、光学部材または電子部材である被着体に貼り付けられる。 ≪4. Usage form of reinforcing film ≫
The reinforcing film of the present invention is typically attached to an adherend which is an optical member or an electronic member. Specifically, the exposed surface of the pressure-sensitive adhesive layer A2 of the reinforcing film of the present invention is attached to an adherend which is an optical member or an electronic member. When a release sheet is provided on the surface of the pressure-sensitive adhesive layer A2, the pressure-sensitive adhesive layer A2 exposed by peeling the release sheet is attached to an adherend which is an optical member or an electronic member.
　上記光学部材または電子部材である被着体としては、例えば、例えば、ＬＥＤ、マイクロＬＥＤ、ミニＬＥＤ、ＯＬＥＤが挙げられる。このような被着体として、代表的には、ＯＬＥＤである。 Examples of the adherend which is the optical member or the electronic member include LEDs, micro LEDs, mini LEDs, and OLEDs. A typical such adherend is an OLED.
　本発明の補強用フィルムが発現する効果をより活用させ得る点で、上記ＯＬＥＤは、好ましくは、フォルダブル部材、フレキシブル部材、およびローラブル部材からなる群から選ばれる少なくとも１種である。 The OLED is preferably at least one selected from the group consisting of foldable members, flexible members, and rollable members, in that the effect of the reinforcing film of the present invention can be further utilized.
　フォルダブル部材は、可動屈曲部を有する（折りたたむことが可能な）部材であり、フレキシブル部材は、曲げることが可能な部材であり、ローラブル部材は、丸めることが可能な部材である。 The foldable member is a member having a movable bending portion (foldable), the flexible member is a bendable member, and the rollable member is a rollable member.
≪５．表面保護フィルム付補強用フィルムの使用方法≫
　本発明の表面保護フィルム付積層フィルムの使用方法は、本発明の表面保護フィルム付補強用フィルムが備える粘着剤層Ａ２を露出させて該粘着剤層Ａ２を被着体に貼り付け、次いで、表面保護フィルムを剥離する。本発明の表面保護フィルム付補強用フィルムにおいて、粘着剤層Ａ２の表面に剥離シートが設けられている場合は、まず、剥離シートを剥がして粘着剤層Ａ２の一方の粘着剤層表面を露出させ、該粘着剤層表面を、被着体に貼り付ける。次いで、表面保護フィルムを剥離する。 ≪5. How to use the reinforcing film with surface protection film ≫
In the method of using the laminated film with a surface protective film of the present invention, the pressure-sensitive adhesive layer A2 provided in the reinforcing film with a surface protection film of the present invention is exposed, the pressure-sensitive adhesive layer A2 is attached to an adherend, and then the surface is used. Peel off the protective film. In the reinforcing film with a surface protective film of the present invention, when a release sheet is provided on the surface of the pressure-sensitive adhesive layer A2, first, the release sheet is peeled off to expose the surface of one of the pressure-sensitive adhesive layers A2. , The surface of the pressure-sensitive adhesive layer is attached to the adherend. Then, the surface protective film is peeled off.
　このようにして、補強用フィルムが被着体に貼り付けられた部材が得られる。 In this way, a member to which the reinforcing film is attached to the adherend can be obtained.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。なお、実施例等における、試験および評価方法は以下のとおりである。なお、「部」と記載されている場合は、特記事項がない限り「重量部」を意味し、「％」と記載されている場合は、特記事項がない限り「重量％」を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods in the examples and the like are as follows. In addition, when it is described as "part", it means "part by weight" unless there is a special note, and when it is described as "%", it means "% by weight" unless there is a special note.
＜重量平均分子量の測定＞
　重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）法により測定した。具体的には、ＧＰＣ測定装置として、商品名「ＨＬＣ－８１２０ＧＰＣ」（東ソー株式会社製）を用いて、下記の条件にて測定し、標準ポリスチレン換算値により算出した。
（分子量測定条件）
・サンプル濃度：０．２重量％（テトラヒドロフラン溶液）
・サンプル注入量：１０μＬ
・カラム：商品名「ＴＳＫｇｕａｒｄｃｏｌｕｍｎ　ＳｕｐｅｒＨＺ－Ｈ（１本）＋ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ（２本）」（東ソー株式会社製）
・リファレンスカラム：商品名「ＴＳＫｇｅｌ　ＳｕｐｅｒＨ－ＲＣ（１本）」（東ソー株式会社製）
・溶離液：テトラヒドロフラン（ＴＨＦ）
・流量：０．６ｍＬ／ｍｉｎ
・検出器：示差屈折計（ＲＩ）
・カラム温度（測定温度）：４０℃ <Measurement of weight average molecular weight>
The weight average molecular weight was measured by gel permeation chromatography (GPC) method. Specifically, it was measured under the following conditions using the trade name "HLC-8120 GPC" (manufactured by Tosoh Corporation) as a GPC measuring device, and calculated by a standard polystyrene conversion value.
(Molecular weight measurement conditions)
-Sample concentration: 0.2% by weight (tetrahydrofuran solution)
-Sample injection volume: 10 μL
-Column: Product name "TSKguardcolum SuperHZ-H (1) + TSKgel SuperHZM-H (2)" (manufactured by Tosoh Corporation)
-Reference column: Product name "TSKgel SuperH-RC (1)" (manufactured by Tosoh Corporation)
-Eluent: tetrahydrofuran (THF)
・ Flow rate: 0.6 mL / min
・ Detector: Differential refractometer (RI)
-Column temperature (measurement temperature): 40 ° C
＜光反射率変化率（表面保護フィルムなし）＞
　実施例または比較例で得られた補強用フィルムから剥離シートを剥がして、補強用フィルムの粘着剤面を、厚み１ｍｍの黒アクリル板に貼り合わせた後、５８０ｎｍおける基材側からの光反射率を分光光度計（日立製作所社製、型式：Ｕ－４１００）で測定し、光反射率Ｒ１（％）を求めた。次いで、実施例または比較例で得られた補強用フィルムを、６０℃、９０％ＲＨの環境下で１週間保管した後、２３℃で３０分放置して室温に戻し、剥離シートを剥がした後、残った補強用フィルムについて同様に、補強用フィルムの粘着剤面を、厚み１ｍｍの黒アクリル板に貼り合わせた後、５８０ｎｍおける基材側からの光反射率を測定し、光反射率Ｒ２（％）を求めた。得られた光反射率の値を用いて、光反射率の変化率（光反射率変化率）ΔＲ（％）＝（Ｒ２－Ｒ１）／（Ｒ１）×１００を算出した。なお、上記の黒アクリル板は、黒色の樹脂板であれば測定値には影響がないので、他の黒色の樹脂板も採用し得る。 <Light reflectance change rate (without surface protective film)>
The release sheet is peeled off from the reinforcing film obtained in Examples or Comparative Examples, and the adhesive surface of the reinforcing film is attached to a black acrylic plate having a thickness of 1 mm, and then the light reflectance from the base material side at 580 nm. Was measured with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100), and the light reflectance R1 (%) was determined. Next, the reinforcing film obtained in Example or Comparative Example was stored for 1 week in an environment of 60 ° C. and 90% RH, left at 23 ° C. for 30 minutes to return to room temperature, and then the release sheet was peeled off. Similarly, for the remaining reinforcing film, the adhesive surface of the reinforcing film was attached to a black acrylic plate having a thickness of 1 mm, and then the light reflectance from the base material side at 580 nm was measured, and the light reflectance R2 ( %) Was asked. Using the obtained light reflectance value, the rate of change in light reflectance (rate of change in light reflectance) ΔR (%) = (R2-R1) / (R1) × 100 was calculated. If the black acrylic plate is a black resin plate, the measured value is not affected. Therefore, another black resin plate can be used.
＜光反射率変化率（表面保護フィルムあり）＞
　実施例または比較例で得られた補強用フィルムから剥離シートを剥がして、補強用フィルムの粘着剤面を、厚み１ｍｍの黒アクリル板に貼り合わせた後、５８０ｎｍおける基材側からの光反射率を分光光度計（日立製作所社製、型式：Ｕ－４１００）で測定し、光反射率Ｒ１（％）を求めた。次いで、対応する実施例または比較例で得られた補強用フィルムと表面保護フィルムとの積層体（表面保護フィルム付補強用フィルム）を、６０℃、９０％ＲＨの環境下で１週間保管した後、２３℃で３０分放置して室温に戻し、表面保護フィルムと剥離シートを剥がした後、残った補強用フィルムについて同様に、補強用フィルムの粘着剤面を、厚み１ｍｍの黒アクリル板に貼り合わせた後、５８０ｎｍおける基材側からの光反射率を測定し、光反射率Ｒ２（％）を求めた。得られた光反射率の値を用いて、光反射率の変化率（光反射率変化率）ΔＲ（％）＝（Ｒ２－Ｒ１）／（Ｒ１）×１００を算出した。なお、上記の黒アクリル板は、黒色の樹脂板であれば測定値には影響がないので、他の黒色の樹脂板も採用し得る。 <Light reflectance change rate (with surface protective film)>
The release sheet is peeled off from the reinforcing film obtained in Examples or Comparative Examples, and the adhesive surface of the reinforcing film is attached to a black acrylic plate having a thickness of 1 mm, and then the light reflectance from the base material side at 580 nm. Was measured with a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100), and the light reflectance R1 (%) was determined. Then, after storing the laminate (reinforcing film with surface protective film) of the reinforcing film and the surface protective film obtained in the corresponding Example or Comparative Example in an environment of 60 ° C. and 90% RH for one week. After leaving it at 23 ° C. for 30 minutes to return to room temperature and peeling off the surface protective film and the release sheet, the adhesive surface of the reinforcing film was similarly attached to a black acrylic plate having a thickness of 1 mm. After the combination, the light reflectance from the base material side at 580 nm was measured, and the light reflectance R2 (%) was determined. Using the obtained light reflectance value, the rate of change in light reflectance (rate of change in light reflectance) ΔR (%) = (R2-R1) / (R1) × 100 was calculated. If the black acrylic plate is a black resin plate, the measured value is not affected. Therefore, another black resin plate can be used.
＜ヘイズ変化率＞
　実施例または比較例で得られた補強用フィルムから剥離シートを剥がして、ヘイズをヘイズメータ（村上色彩社製、型式：ＨＭ－１５０）で測定し、ヘイズＨ１（％）を求めた。次いで、実施例または比較例で得られた補強用フィルムを、６０℃、９０％ＲＨの環境下で１週間保管した後、２３℃で３０分放置して室温に戻し、剥離シートを剥離した後、残った補強用フィルムについて同様にヘイズを測定し、ヘイズＨ２（％）を求めた。得られたヘイズの値を用いて、ヘイズ変化率ΔＨ（％）＝（Ｈ２－Ｈ１）／（Ｈ１）×１００を算出した。 <Haze change rate>
The release sheet was peeled off from the reinforcing film obtained in Examples or Comparative Examples, and haze was measured with a haze meter (manufactured by Murakami Color Co., Ltd., model: HM-150) to determine haze H1 (%). Next, the reinforcing film obtained in Example or Comparative Example was stored in an environment of 60 ° C. and 90% RH for 1 week, left at 23 ° C. for 30 minutes to return to room temperature, and then the release sheet was peeled off. The haze was measured in the same manner for the remaining reinforcing film, and the haze H2 (%) was determined. Using the obtained haze value, the haze change rate ΔH (%) = (H2-H1) / (H1) × 100 was calculated.
＜全光線透過率＞
　実施例または比較例で使用する基材層の、５８０ｎｍおける透過率を、分光光度計（日立製作所社製、型式：Ｕ－４１００）を用いて測定した。 <Total light transmittance>
The transmittance of the base material layer used in Examples or Comparative Examples at 580 nm was measured using a spectrophotometer (manufactured by Hitachi, Ltd., model: U-4100).
＜対ＰＥＴフィルム粘着力＞
　剥離シートを剥がした補強用フィルム（幅２５ｍｍ×長さ１４０ｍｍ）を、ガラスに裏打ちをしたＰＥＴフィルム「ルミラーＳ１０＃２５」（東レ株式会社製）へ２ｋｇハンドローラー１往復にて貼着した。その後、２３℃の環境温度下で３０分間放置した。
　上記のようにして得られた評価用試料を、引っ張り試験機にて測定した。引っ張り試験機としては、島津製作所社製の商品名「オートグラフＡＧ－Ｘｐｌｕｓ　ＨＳ　６０００ｍｍ／ｍｉｎ高速モデル（ＡＧ－５０ＮＸ　ｐｌｕｓ）」を用いた。引っ張り試験機に評価用試料をセットした後、引っ張り試験を開始した。引っ張り試験の条件は、剥離角度：１８０度、剥離速度（引っ張り速度）：３００ｍｍ／分とした。上記ＰＥＴフィルムから補強用フィルムを剥離した時の荷重を測定し、その際の平均荷重を補強用フィルムの対ＰＥＴフィルム粘着力とした。 <Adhesive strength against PET film>
A reinforcing film (width 25 mm x length 140 mm) from which the release sheet had been peeled off was attached to a PET film "Lumirror S10 # 25" (manufactured by Toray Industries, Inc.) lined with glass by one reciprocating 2 kg hand roller. Then, it was left for 30 minutes at an environmental temperature of 23 ° C.
The evaluation sample obtained as described above was measured with a tensile tester. As the tensile tester, a trade name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the tensile test was started. The conditions of the tensile test were a peeling angle: 180 degrees and a peeling speed (pulling speed): 300 mm / min. The load when the reinforcing film was peeled off from the PET film was measured, and the average load at that time was taken as the adhesive strength of the reinforcing film to the PET film.
＜対ＰＥＴフィルム粘着力(６０℃×６０分間加熱後)＞
　剥離シートを剥がした補強用フィルム（幅２５ｍｍ×長さ１４０ｍｍ）を、ガラスに裏打ちをしたＰＥＴフィルム「ルミラーＳ１０＃２５」（東レ株式会社製）へ２ｋｇハンドローラー１往復にて貼着した。その後、６０℃の環境温度下で６０分間放置した。
　上記のようにして得られた評価用試料を、引っ張り試験機にて測定した。引っ張り試験機としては、島津製作所社製の商品名「オートグラフＡＧ－Ｘｐｌｕｓ　ＨＳ　６０００ｍｍ／ｍｉｎ高速モデル（ＡＧ－５０ＮＸ　ｐｌｕｓ）」を用いた。引っ張り試験機に評価用試料をセットした後、引っ張り試験を開始した。引っ張り試験の条件は、剥離角度：１８０度、剥離速度（引っ張り速度）：３００ｍｍ／分とした。上記ＰＥＴフィルムから補強用フィルムを剥離した時の荷重を測定し、その際の平均荷重を補強用フィルムの対ＰＥＴフィルム粘着力とした。 <Adhesive strength against PET film (after heating at 60 ° C for 60 minutes)>
A reinforcing film (width 25 mm x length 140 mm) from which the release sheet had been peeled off was attached to a PET film "Lumirror S10 # 25" (manufactured by Toray Industries, Inc.) lined with glass by one reciprocating 2 kg hand roller. Then, it was left for 60 minutes at an environmental temperature of 60 ° C.
The evaluation sample obtained as described above was measured with a tensile tester. As the tensile tester, a trade name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the tensile test was started. The conditions of the tensile test were a peeling angle: 180 degrees and a peeling speed (pulling speed): 300 mm / min. The load when the reinforcing film was peeled off from the PET film was measured, and the average load at that time was taken as the adhesive strength of the reinforcing film to the PET film.
〔製造例１〕：（メタ）アクリル系重合体（１）の製造
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、２－エチルヘキシルアクリレート（日本触媒社製）：６５部、Ｎ－ビニルピロリドン（日本触媒社製）：１５部、ヒドロキシエチルアクリレート（東亜合成社製）：１３部、メチルメタクリレート（三菱瓦斯化学社製）：７部、重合開始剤として２，２’－アゾビスイソブチロニトリル（和光純薬工業社製）：０．２部、酢酸エチル：１５６重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６３℃付近に保って１０時間重合反応を行い、重量平均分子量７０万の（メタ）アクリル系重合体（１）の溶液（固形分濃度＝４０重量％）を調製した。 [Production Example 1]: Production of (meth) acrylic polymer (1) 2-Ethylhexyl acrylate (manufactured by Nippon Catalyst Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. : 65 parts, N-vinylpyrrolidone (manufactured by Nippon Catalyst Co., Ltd.): 15 parts, hydroxyethyl acrylate (manufactured by Toa Synthetic Co., Ltd.): 13 parts, methyl methacrylate (manufactured by Mitsubishi Gas Chemicals Co., Ltd.): 7 parts, 2, as a polymerization initiator 2'-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts, ethyl acetate: 156 parts by weight were charged, nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was 63. The polymerization reaction was carried out for 10 hours while maintaining the temperature at around ° C. to prepare a solution (solid content concentration = 40% by weight) of the (meth) acrylic polymer (1) having a weight average molecular weight of 700,000.
〔製造例２〕：（メタ）アクリル系重合体（２）の製造
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、ブチルアクリレート（日本触媒社製）：１００部、アクリル酸（東亜合成社製）：７．５部、重合開始剤として２，２’－アゾビスイソブチロニトリル（和光純薬工業社製）：０．２部、酢酸エチル：１５６重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６３℃付近に保って１０時間重合反応を行い、重量平均分子量７０万の（メタ）アクリル系重合体（２）の溶液（固形分濃度＝４０重量％）を調製した。 [Production Example 2]: Production of (meth) acrylic polymer (2) Butyl acrylate (manufactured by Nippon Catalyst Co., Ltd.): 100 in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. Parts, Acrylic acid (manufactured by Toa Synthetic Co., Ltd.): 7.5 parts, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts, ethyl acetate: 156 weight A (meth) acrylic polymer having a weight average molecular weight of 700,000 (2) was prepared, and nitrogen gas was introduced while gently stirring the flask, and the polymerization reaction was carried out for 10 hours while keeping the liquid temperature in the flask at around 63 ° C. Solution (solid content concentration = 40% by weight) was prepared.
〔製造例３〕：（メタ）アクリル系重合体（３）の製造
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、２－エチルヘキシルアクリレート（日本触媒社製）：９６部、ヒドロキシエチルアクリレート（東亜合成社製）：４部、重合開始剤として２，２’－アゾビスイソブチロニトリル（和光純薬工業社製）：０．２部、酢酸エチル：１５６重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６３℃付近に保って１０時間重合反応を行い、重量平均分子量５０万の（メタ）アクリル系重合体（３）の溶液（固形分濃度＝４０重量％）を調製した。 [Production Example 3]: Production of (meth) acrylic polymer (3) 2-Ethylhexyl acrylate (manufactured by Nippon Catalyst Co., Ltd.) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. : 96 parts, hydroxyethyl acrylate (manufactured by Toa Synthetic Co., Ltd.): 4 parts, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts, ethyl acetate: 156 parts A (meth) acrylic polymer having a weight average molecular weight of 500,000 (3) was charged with a weight portion, introduced with nitrogen gas while gently stirring, and the polymerization reaction was carried out for 10 hours while keeping the liquid temperature in the flask at around 63 ° C. ) (Solid content concentration = 40% by weight) was prepared.
〔製造例４〕：（メタ）アクリル系オリゴマー（４）の製造
　モノマー成分としてメタクリル酸シクロヘキシル［ホモポリマー（ポリメタクリル酸シクロヘキシル）のガラス転移温度：６６℃］：９５重量部、アクリル酸：５重量部、連鎖移動剤として２－メルカプトエタノール：３重量部、重合開始剤として２，２´－アゾビスイソブチロニトリル：０．２重量部、および重合溶媒としてトルエン：１０３．２重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら、１時間攪拌した。このようにして、重合系内の酸素を除去した後、７０℃に昇温し、３時間反応させ、さらに、７５℃で２時間反応させ、重量平均分子量４０００の（メタ）アクリル系オリゴマー（４）の溶液（固形分濃度＝５０重量％）を調製した。 [Production Example 4]: Production of (meth) acrylic oligomer (4) Cyclohexyl methacrylate as a monomer component [Glass transition temperature of homopolymer (polycyclohexyl methacrylate): 66 ° C.]: 95 parts by weight, acrylic acid: 5 weight by weight Parts, 2-mercaptoethanol: 3 parts by weight as a chain transfer agent, 2,2'-azobisisobutyronitrile: 0.2 parts by weight as a polymerization initiator, and toluene: 103.2 parts by weight as a polymerization solvent. The mixture was placed in a separable flask and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 70 ° C., reacted for 3 hours, and further reacted at 75 ° C. for 2 hours to obtain a (meth) acrylic oligomer having a weight average molecular weight of 4000 (4). ) (Solid content concentration = 50% by weight) was prepared.
〔製造例５〕：（メタ）アクリル系オリゴマー（５）の製造
　攪拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた４つ口フラスコに、トルエン１００重量部、ジシクロペンタニルメタクリレート（ＤＣＰＭＡ）（商品名：ＦＡ－５１３Ｍ、日立化成工業社製）：６０重量部、メチルメタクリレート（ＭＭＡ）：４０重量部、および連鎖移動剤としてチオグリコール酸メチル：３．５重量部を投入した。そして、７０℃にて窒素雰囲気下で１時間攪拌した後、重合開始剤として２，２’－アゾビスイソブチロニトリル：０．２重量部を投入し、７０℃で２時間反応させ、続いて８０℃で４時間反応させた後に、９０℃で１時間反応させ、重量平均分子量４０００の（メタ）アクリル系オリゴマー（５）の溶液（固形分濃度＝５１重量％）を調製した。 [Production Example 5]: Production of (meth) acrylic oligomer (5) 100 parts by weight of toluene and dicyclopenta in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel. Nyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Kasei Kogyo Co., Ltd.): 60 parts by weight, methyl methacrylate (MMA): 40 parts by weight, and methyl thioglycolate as a chain transfer agent: 3.5 parts by weight. I put it in. Then, after stirring at 70 ° C. under a nitrogen atmosphere for 1 hour, 0.2 parts by weight of 2,2'-azobisisobutyronitrile: 0.2 part by weight was added as a polymerization initiator, and the mixture was reacted at 70 ° C. for 2 hours, followed by After reacting at 80 ° C. for 4 hours, the reaction was carried out at 90 ° C. for 1 hour to prepare a solution (solid content concentration = 51% by weight) of the (meth) acrylic oligomer (5) having a weight average molecular weight of 4000.
〔製造例６〕：（メタ）アクリル系オリゴマー（６）の製造
　攪拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた４つ口フラスコに、トルエン１００重量部、メチルメタクリレート（ＭＭＡ）４０重量部、ブチルメタクリレート（ＢＭＡ）２０重量部、２－エチルヘキシルメタクリレート（２－ＥＨＭＡ）２０重量部、官能基当量が９００ｇ／ｍｏｌのポリオルガノシロキサン骨格含有メタクリレートモノマー（商品名：Ｘ－２２－１７４ＡＳＸ、信越化学工業株式会社製）１７重量部、官能基当量が４６００ｇ／ｍｏｌのポリオルガノシロキサン骨格含有メタクリレートモノマー（商品名：Ｘ－２２－１７４ＤＸ、信越化学工業株式会社製）３重量部、および連鎖移動剤としてチオグリコール酸メチル０．５１重量部を、投入した。そして、７０℃にて窒素雰囲気下で１時間撹拌した後、熱重合開始剤としてアゾビスイソブチロニトリル０．２重量部を投入し、７０℃で２時間反応させた後に、熱重合開始剤としてアゾビスイソブチロニトリル０．１重量部を投入し、続いて８０℃で５時間反応させ、重量平均分子量２１３００の（メタ）アクリル系オリゴマー（６）の溶液（固形分濃度＝５０重量％）を調製した。 [Production Example 6]: Production of (meth) acrylic oligomer (6) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a cooler, and a dropping funnel, 100 parts by weight of toluene and methyl methacrylate ( 40 parts by weight of MMA), 20 parts by weight of butyl methacrylate (BMA), 20 parts by weight of 2-ethylhexyl methacrylate (2-EHMA), and a polyorganosiloxane skeleton-containing methacrylate monomer having a functional group equivalent of 900 g / mol (trade name: X-22). -174ASX, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 17 parts by weight, 3 parts by weight of polyorganosiloxane skeleton-containing methacrylate monomer (trade name: X-22-174DX, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) with a functional group equivalent of 4600 g / mol, And 0.51 part by weight of methyl thioglycolate was added as a chain transfer agent. Then, after stirring at 70 ° C. in a nitrogen atmosphere for 1 hour, 0.2 parts by weight of azobisisobutyronitrile was added as a thermal polymerization initiator, and the mixture was reacted at 70 ° C. for 2 hours, and then the thermal polymerization initiator was added. 0.1 part by weight of azobisisobutyronitrile was added thereto, and the mixture was subsequently reacted at 80 ° C. for 5 hours to obtain a solution of the (meth) acrylic oligomer (6) having a weight average molecular weight of 21300 (solid content concentration = 50% by weight). ) Was prepared.
〔製造例７〕：（メタ）アクリル系粘着剤組成物（１）の製造
　製造例１で得られた（メタ）アクリル系重合体（１）の溶液に、（メタ）アクリル系重合体（１）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で１．０重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（１）を調製した。 [Production Example 7]: Production of (meth) acrylic pressure-sensitive adhesive composition (1) The (meth) acrylic polymer (1) was added to the solution of the (meth) acrylic polymer (1) obtained in Production Example 1. ), 1.0 part by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent was added to 100 parts by weight of the solid content of the solution to make the total solid content 25% by weight. The (meth) acrylic pressure-sensitive adhesive composition (1) was prepared by diluting with ethyl acetate and stirring with a disper.
〔製造例８〕：（メタ）アクリル系粘着剤組成物（２）の製造
　製造例２で得られた（メタ）アクリル系重合体（２）の溶液に、（メタ）アクリル系重合体（２）の溶液の固形分１００重量部に対して、架橋剤としてＴＥＴＲＡＤ－Ｃ（三菱瓦斯化学社製）を固形分換算で０．０７５重量部、製造例４で得られた（メタ）アクリル系オリゴマー（４）の溶液を固形分換算で２０重量部を加えて、溶液全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（２）を調製した。 [Production Example 8]: Production of (meth) acrylic pressure-sensitive adhesive composition (2) In the solution of the (meth) acrylic polymer (2) obtained in Production Example 2, the (meth) acrylic polymer (2) ), 0.075 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemicals, Inc.) as a cross-linking agent with respect to 100 parts by weight of the solid content of the solution of), the (meth) acrylic oligomer obtained in Production Example 4. Add 20 parts by weight of the solution of (4) in terms of solid content, dilute with ethyl acetate so that the solid content of the whole solution becomes 25% by weight, stir with a disper, and (meth) acrylic pressure-sensitive adhesive composition. (2) was prepared.
〔製造例９〕：（メタ）アクリル系粘着剤組成物（３）の製造
　製造例３で得られた（メタ）アクリル系重合体（３）の溶液に、（メタ）アクリル系重合体（３）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で０．１重量部を、製造例５で得られた（メタ）アクリル系オリゴマー（５）の溶液を固形分換算で５重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（３）を調製した。 [Production Example 9]: Production of (meth) acrylic pressure-sensitive adhesive composition (3) In the solution of the (meth) acrylic polymer (3) obtained in Production Example 3, the (meth) acrylic polymer (3) ), 0.1 part by weight of coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent in terms of solid content was obtained with respect to 100 parts by weight of the solid content of the solution (meth) acrylic oligomer (meth) obtained in Production Example 5. Add 5 parts by weight of the solution of 5) in terms of solid content, dilute with ethyl acetate so that the total solid content becomes 25% by weight, stir with a disper, and (meth) acrylic pressure-sensitive adhesive composition (3). ) Was prepared.
〔製造例１０〕：（メタ）アクリル系粘着剤組成物（４）の製造
　製造例３で得られた（メタ）アクリル系重合体（３）の溶液に、（メタ）アクリル系重合体（３）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で０．１重量部を、製造例５で得られた（メタ）アクリル系オリゴマー（５）の溶液を固形分換算で７．５重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（４）を調製した。 [Production Example 10]: Production of (meth) acrylic pressure-sensitive adhesive composition (4) In the solution of the (meth) acrylic polymer (3) obtained in Production Example 3, the (meth) acrylic polymer (3) ), 0.1 part by weight of coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent in terms of solid content was obtained with respect to 100 parts by weight of the solid content of the solution (meth) acrylic oligomer (meth) obtained in Production Example 5. Add 7.5 parts by weight of the solution of 5) in terms of solid content, dilute with ethyl acetate so that the total solid content becomes 25% by weight, stir with a disper, and (meth) acrylic pressure-sensitive adhesive composition. (4) was prepared.
〔製造例１１〕：（メタ）アクリル系粘着剤組成物（５）の製造
　製造例３で得られた（メタ）アクリル系重合体（３）の溶液に、（メタ）アクリル系重合体（３）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で０．１重量部を、製造例５で得られた（メタ）アクリル系オリゴマー（５）の溶液を固形分換算で１０重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（５）を調製した。 [Production Example 11]: Production of (meth) acrylic pressure-sensitive adhesive composition (5) In the solution of the (meth) acrylic polymer (3) obtained in Production Example 3, the (meth) acrylic polymer (3) ), 0.1 part by weight of coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent in terms of solid content was obtained with respect to 100 parts by weight of the solid content of the solution (meth) acrylic oligomer (meth) obtained in Production Example 5. Add 10 parts by weight of the solution of 5) in terms of solid content, dilute with ethyl acetate so that the total solid content becomes 25% by weight, stir with a disper, and (meth) acrylic pressure-sensitive adhesive composition (5). ) Was prepared.
〔製造例１２〕：（メタ）アクリル系粘着剤組成物（６）の製造
　製造例３で得られた（メタ）アクリル系重合体（３）の溶液に、（メタ）アクリル系重合体（３）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で４．０重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（６）を調製した。 [Production Example 12]: Production of (meth) acrylic pressure-sensitive adhesive composition (6) In the solution of the (meth) acrylic polymer (3) obtained in Production Example 3, the (meth) acrylic polymer (3) ), 4.0 parts by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent was added to 100 parts by weight of the solid content of the solution to make the total solid content 25% by weight. The (meth) acrylic pressure-sensitive adhesive composition (6) was prepared by diluting with ethyl acetate and stirring with a disper.
〔製造例１３〕：（メタ）アクリル系粘着剤組成物（７）の製造
　製造例１で得られた（メタ）アクリル系重合体（１）の溶液に、（メタ）アクリル系重合体（１）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で１．０重量部を、製造例６で得られた（メタ）アクリル系オリゴマー（６）の溶液を固形分換算で２．０重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（７）を調製した。 [Production Example 13]: Production of (meth) acrylic pressure-sensitive adhesive composition (7) In the solution of the (meth) acrylic polymer (1) obtained in Production Example 1, the (meth) acrylic polymer (1) ), 1.0 part by weight of coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent in terms of solid content was obtained with respect to 100 parts by weight of the solid content of the solution (meth) acrylic oligomer (meth) obtained in Production Example 6. Add 2.0 parts by weight of the solution of 6) in terms of solid content, dilute with ethyl acetate so that the total solid content becomes 25% by weight, stir with a disper, and (meth) acrylic pressure-sensitive adhesive composition. (7) was prepared.
〔製造例１４〕：（メタ）アクリル系粘着剤組成物（８）の製造
　製造例１で得られた（メタ）アクリル系重合体（１）の溶液に、（メタ）アクリル系重合体（１）の溶液の固形分１００重量部に対して、架橋剤としてコロネートＨＬ（日本ポリウレタン社製）を固形分換算で２．５重量部を、製造例６で得られた（メタ）アクリル系オリゴマー（６）の溶液を固形分換算で２．５重量部を加えて、全体の固形分が２５重量％となるように酢酸エチルで希釈し、ディスパーで攪拌し、（メタ）アクリル系粘着剤組成物（８）を調製した。 [Production Example 14]: Production of (meth) acrylic pressure-sensitive adhesive composition (8) In the solution of the (meth) acrylic polymer (1) obtained in Production Example 1, the (meth) acrylic polymer (1) ), 2.5 parts by weight of coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent in terms of solid content was obtained with respect to 100 parts by weight of the solid content of the solution (meth) acrylic oligomer (meth) obtained in Production Example 6. Add 2.5 parts by weight of the solution of 6) in terms of solid content, dilute with ethyl acetate so that the total solid content becomes 25% by weight, stir with a disper, and (meth) acrylic pressure-sensitive adhesive composition. (8) was prepared.
〔製造例１５〕：反射防止層形成用塗料組成物の製造
　２００ｍＬのガラス製容器に、エタノール：６０ｇ、ＺｎＯ微粒子の水分散ゾル（平均一次粒子径：２０ｎｍ、平均凝集粒子径：４０ｎｍ、固形分換算濃度：２０重量％）：３０ｇ、テトラエトキシシラン（ＳｉＯ２固形分濃度：２９重量％）：１０ｇを入れ、アンモニア水溶液を添加してｐＨを１０とし、２０℃で６時間撹拌して、コア－シェル粒子の分散液（固形分濃度：６重量％）：１００ｇを得た。得られたコア－シェル粒子の分散液：１００ｇに、強酸性カチオン交換樹脂（総交換容量：２．０ｍｅｑ／ｍＬ以上）を１００ｇ加え、１時間撹拌してｐＨが４となった後、ろ過により強酸性カチオン交換樹脂を除去し、ＳｉＯ２からなる球状中空微粒子の分散液を得た。得られた分散液を限外ろ過により固形分濃度２０重量％まで濃縮した。球状中空微粒子は二次凝集していた。球状中空微粒子の外殻の厚さは５ｎｍであり、平均一次粒子径の１／６であった。球状中空微粒子の平均凝集粒子径は４０ｎｍ、アスペクト比は１．０であった。
　２００ｍＬのガラス製容器に、得られた球状中空微粒子の分散液（固形分濃度：２０重量％）：２ｇ、繊維状中実微粒子の分散液（日産化学工業社製、ＩＰＡ－ＳＴ－ＵＰ、平均凝集粒子径（平均一次粒子径）：９０ｎｍ、アスペクト比：７．０、固形分濃度：１５重量％）：２ｇ、エタノール：９０ｇ、ケイ酸オリゴマー溶液（固形分濃度：５重量％）：６ｇを入れ、１０分間撹拌して、反射防止層形成用塗料組成物を得た。 [Production Example 15]: Production of coating composition for forming an antireflection layer In a 200 mL glass container, an aqueous dispersion sol of ethanol: 60 g and ZnO fine particles (average primary particle diameter: 20 nm, average aggregated particle diameter: 40 nm, solid content). Conversion concentration: 20% by weight): 30 g, tetraethoxysilane (SiO 2 solid content concentration: 29% by weight): 10 g was added, an aqueous ammonia solution was added to adjust the pH to 10, and the core was stirred at 20 ° C. for 6 hours. -A dispersion of shell particles (solid content concentration: 6% by weight): 100 g was obtained. To 100 g of the obtained dispersion of core-shell particles, 100 g of a strong acid cation exchange resin (total exchange capacity: 2.0 meq / mL or more) was added, and the mixture was stirred for 1 hour to a pH of 4, and then filtered. The strong acid cation exchange resin was removed to obtain a dispersion of spherical hollow fine particles made of SiO 2. The obtained dispersion was concentrated to a solid content concentration of 20% by weight by ultrafiltration. The spherical hollow fine particles were secondary aggregated. The thickness of the outer shell of the spherical hollow fine particles was 5 nm, which was 1/6 of the average primary particle diameter. The average agglomerated particle size of the spherical hollow fine particles was 40 nm, and the aspect ratio was 1.0.
In a 200 mL glass container, the obtained dispersion of spherical hollow fine particles (solid content concentration: 20% by weight): 2 g, dispersion of fibrous solid fine particles (manufactured by Nissan Chemical Industries, Ltd., IPA-ST-UP, average) Aggregated particle size (average primary particle size): 90 nm, aspect ratio: 7.0, solid content concentration: 15% by weight): 2 g, ethanol: 90 g, silicic acid oligomer solution (solid content concentration: 5% by weight): 6 g. The mixture was added and stirred for 10 minutes to obtain a coating composition for forming an antireflection layer.
〔製造例１６〕：反射防止層を有するＴＡＣフィルム基材（Ａ）の製造
　製造例１５で得られた反射防止層形成用塗料組成物を、セルローストリアセテート（以下、「ＴＡＣ」と称することがある）フィルム（ＴＧ６０ＵＬ、富士フイルム社製）の片面に塗布し、回転数２００ｒｐｍで６０秒間スピンコートして均一化した後、２００℃で３０分間乾燥し、膜厚１００ｎｍの反射防止層を形成した。このようにして、反射防止層を有するセルローストリアセテートフィルム基材を得た。 [Production Example 16]: Production of TAC film base material (A) having an antireflection layer The coating composition for forming an antireflection layer obtained in Production Example 15 may be referred to as cellulose triacetate (hereinafter, "TAC"). ) The film (TG60UL, manufactured by FUJIFILM Corporation) was applied to one side, spin-coated at a rotation speed of 200 rpm for 60 seconds to homogenize, and then dried at 200 ° C. for 30 minutes to form an antireflection layer having a film thickness of 100 nm. In this way, a cellulose triacetate film base material having an antireflection layer was obtained.
〔製造例１７〕：反射防止層を有するＰＥＴフィルム基材（Ｂ）の製造
　製造例１５で得られた反射防止層形成用塗料組成物を、ポリエチレンテレフタレート（以下、「ＰＥＴ」と称することがある）フィルム（ルミラーＵ４８、東レ社製）の片面に塗布し、回転数２００ｒｐｍで６０秒間スピンコートして均一化した後、２００℃で３０分間乾燥し、膜厚１００ｎｍの反射防止層を形成した。このようにして、反射防止層を有するポリエチレンテレフタレートフィルム基材を得た。 [Production Example 17]: Production of PET film base material (B) having an antireflection layer The coating composition for forming an antireflection layer obtained in Production Example 15 may be referred to as polyethylene terephthalate (hereinafter, “PET”). ) A film (Lumirror U48, manufactured by Toray Co., Ltd.) was applied to one side, spin-coated at a rotation speed of 200 rpm for 60 seconds to homogenize, and then dried at 200 ° C. for 30 minutes to form an antireflection layer having a film thickness of 100 nm. In this way, a polyethylene terephthalate film base material having an antireflection layer was obtained.
〔製造例１８〕：表面保護フィルム（Ｃ）の製造
　製造例１３で得られた（メタ）アクリル系粘着剤組成物（７）を、ポリエステル樹脂からなる基材（商品名：「ルミラーＳ１０」、厚み３８μｍ、東レ社製）にファウンテンロールで乾燥後の厚みが２１μｍとなるように塗布し、乾燥温度１３０℃、乾燥時間３０秒の条件でキュアーして乾燥した。このようにして、基材上に粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ）を得た。得られた表面保護フィルム（Ｃ）は、常温で７日間エージングを行った。 [Production Example 18]: Production of Surface Protective Film (C) The (meth) acrylic pressure-sensitive adhesive composition (7) obtained in Production Example 13 is used as a base material made of a polyester resin (trade name: "Lumirer S10"). It was applied to a thickness of 38 μm (manufactured by Toray Industries, Inc.) with a fountain roll so that the thickness after drying was 21 μm, cured under the conditions of a drying temperature of 130 ° C. and a drying time of 30 seconds, and dried. In this way, an adhesive layer was produced on the substrate. Next, the surface of the obtained pressure-sensitive adhesive layer was treated with silicone on one surface of a release sheet made of a polyester resin having a thickness of 25 μm (trade name “MRF25”, thickness 25 μm, manufactured by Mitsubishi Chemical Corporation). The surfaces were bonded together to obtain a surface protective film (C). The obtained surface protective film (C) was aged at room temperature for 7 days.
〔実施例１〕
　（メタ）アクリル系粘着剤組成物（１）を、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面に、乾燥後の厚みが２５μｍとなるように塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥した。このようにして、シリコーン処理面に（メタ）アクリル系粘着剤組成物（１）から形成された粘着剤層を設けた。次いで、得られた粘着剤層の表面に、反射防止層を有するＴＡＣフィルム基材（Ａ）の反射防止層が施されていない面を貼合せて、補強用フィルム（１）を得た。得られた補強用フィルム（１）は、常温で７日間エージングを行った。結果を表１に示した。 [Example 1]
A release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) made of a polyester resin having a thickness of 25 μm in which one surface of the (meth) acrylic pressure-sensitive adhesive composition (1) is treated with silicone. It was applied to the silicone-treated surface so that the thickness after drying was 25 μm, cured under the conditions of a drying temperature of 130 ° C. and a drying time of 3 minutes, and dried. In this way, the pressure-sensitive adhesive layer formed from the (meth) acrylic pressure-sensitive adhesive composition (1) was provided on the silicone-treated surface. Next, a surface of the TAC film base material (A) having an antireflection layer and not provided with the antireflection layer was attached to the surface of the obtained pressure-sensitive adhesive layer to obtain a reinforcing film (1). The obtained reinforcing film (1) was aged at room temperature for 7 days. The results are shown in Table 1.
〔実施例２〕
　表１に示すように、基材を、反射防止層を有するＰＥＴフィルム基材（Ｂ）に変更した以外は、実施例１と同様に行い、補強用フィルム（２）を得た。結果を表１に示した。 [Example 2]
As shown in Table 1, a reinforcing film (2) was obtained in the same manner as in Example 1 except that the base material was changed to a PET film base material (B) having an antireflection layer. The results are shown in Table 1.
〔実施例３〕
　表１に示すように、基材を、ＴＡＣフィルム（ＴＧ６０ＵＬ、富士フイルム社製）に変更した以外は、実施例１と同様に行い、補強用フィルム（３）を得た。結果を表１に示した。 [Example 3]
As shown in Table 1, a reinforcing film (3) was obtained in the same manner as in Example 1 except that the base material was changed to a TAC film (TG60UL, manufactured by FUJIFILM Corporation). The results are shown in Table 1.
〔実施例４〕
　表１に示すように、基材を、ＰＥＴフィルム（ルミラーＵ４８、東レ社製）に変更した以外は、実施例１と同様に行い、補強用フィルム（４）を得た。結果を表１に示した。 [Example 4]
As shown in Table 1, a reinforcing film (4) was obtained in the same manner as in Example 1 except that the base material was changed to a PET film (Lumilar U48, manufactured by Toray Industries, Inc.). The results are shown in Table 1.
〔実施例５〕
　表１に示すように、基材を、ポリイミド（以下、「ＰＩ」と称することがある）フィルム（ネオプリムＳ－１００、三菱瓦斯化学社製）に変更した以外は、実施例１と同様に行い、補強用フィルム（５）を得た。結果を表１に示した。 [Example 5]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the base material was changed to a polyimide (hereinafter sometimes referred to as “PI”) film (Neoprim S-100, manufactured by Mitsubishi Gas Chemical Company, Inc.). , A reinforcing film (5) was obtained. The results are shown in Table 1.
〔実施例６〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（２）に変更した以外は、実施例１と同様に行い、補強用フィルム（６）を得た。結果を表１に示した。 [Example 6]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (6) was obtained. The results are shown in Table 1.
〔実施例７〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（２）に変更した以外は、実施例２と同様に行い、補強用フィルム（７）を得た。結果を表１に示した。 [Example 7]
As shown in Table 1, the same procedure as in Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (7) was obtained. The results are shown in Table 1.
〔実施例８〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（２）に変更した以外は、実施例３と同様に行い、補強用フィルム（８）を得た。結果を表１に示した。 [Example 8]
As shown in Table 1, the same procedure as in Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (8) was obtained. The results are shown in Table 1.
〔実施例９〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（２）に変更した以外は、実施例４と同様に行い、補強用フィルム（９）を得た。結果を表１に示した。 [Example 9]
As shown in Table 1, the same procedure as in Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2), and the reinforcing film was formed. (9) was obtained. The results are shown in Table 1.
〔実施例１０〕
　実施例１で得られた補強用フィルム（１）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１０）を得た。結果を表１に示した。 [Example 10]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (1) obtained in Example 1 to obtain a reinforcing film (10) with a surface protective film. .. The results are shown in Table 1.
〔実施例１１〕
　実施例２で得られた補強用フィルム（２）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１１）を得た。結果を表１に示した。 [Example 11]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (2) obtained in Example 2 to obtain a reinforcing film (11) with a surface protective film. .. The results are shown in Table 1.
〔実施例１２〕
　実施例３で得られた補強用フィルム（３）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１２）を得た。結果を表１に示した。 [Example 12]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (3) obtained in Example 3 to obtain a reinforcing film (12) with a surface protective film. .. The results are shown in Table 1.
〔実施例１３〕
　実施例４で得られた補強用フィルム（４）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１３）を得た。結果を表１に示した。 [Example 13]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (4) obtained in Example 4 to obtain a reinforcing film (13) with a surface protective film. .. The results are shown in Table 1.
〔実施例１４〕
　実施例５で得られた補強用フィルム（５）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１４）を得た。結果を表１に示した。 [Example 14]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (5) obtained in Example 5 to obtain a reinforcing film (14) with a surface protective film. .. The results are shown in Table 1.
〔実施例１５〕
　実施例６で得られた補強用フィルム（６）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１５）を得た。結果を表１に示した。 [Example 15]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (6) obtained in Example 6 to obtain a reinforcing film (15) with a surface protective film. .. The results are shown in Table 1.
〔実施例１６〕
　実施例７で得られた補強用フィルム（７）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１６）を得た。結果を表１に示した。 [Example 16]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (7) obtained in Example 7 to obtain a reinforcing film (16) with a surface protective film. .. The results are shown in Table 1.
〔実施例１７〕
　実施例８で得られた補強用フィルム（８）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１７）を得た。結果を表１に示した。 [Example 17]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (8) obtained in Example 8 to obtain a reinforcing film (17) with a surface protective film. .. The results are shown in Table 1.
〔実施例１８〕
　実施例９で得られた補強用フィルム（９）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（１８）を得た。結果を表１に示した。 [Example 18]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (9) obtained in Example 9 to obtain a reinforcing film (18) with a surface protective film. .. The results are shown in Table 1.
〔実施例１９〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（７）に変更した以外は、実施例１と同様に行い、補強用フィルム（１９）を得た。結果を表１に示した。 [Example 19]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (19) was obtained. The results are shown in Table 1.
〔実施例２０〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（７）に変更した以外は、実施例２と同様に行い、補強用フィルム（２０）を得た。結果を表１に示した。 [Example 20]
As shown in Table 1, the same procedure as in Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (20) was obtained. The results are shown in Table 1.
〔実施例２１〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（７）に変更した以外は、実施例３と同様に行い、補強用フィルム（２１）を得た。結果を表１に示した。 [Example 21]
As shown in Table 1, the same procedure as in Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (21) was obtained. The results are shown in Table 1.
〔実施例２２〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（７）に変更した以外は、実施例４と同様に行い、補強用フィルム（２２）を得た。結果を表１に示した。 [Example 22]
As shown in Table 1, the same procedure as in Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (22) was obtained. The results are shown in Table 1.
〔実施例２３〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（７）に変更した以外は、実施例５と同様に行い、補強用フィルム（２３）を得た。結果を表１に示した。 [Example 23]
As shown in Table 1, the same procedure as in Example 5 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (7), and the reinforcing film was formed. (23) was obtained. The results are shown in Table 1.
〔実施例２４〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（８）に変更した以外は、実施例１と同様に行い、補強用フィルム（２４）を得た。結果を表１に示した。 [Example 24]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (24) was obtained. The results are shown in Table 1.
〔実施例２５〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（８）に変更した以外は、実施例２と同様に行い、補強用フィルム（２５）を得た。結果を表１に示した。 [Example 25]
As shown in Table 1, the same procedure as in Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (25) was obtained. The results are shown in Table 1.
〔実施例２６〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（８）に変更した以外は、実施例３と同様に行い、補強用フィルム（２６）を得た。結果を表１に示した。 [Example 26]
As shown in Table 1, the same procedure as in Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (26) was obtained. The results are shown in Table 1.
〔実施例２７〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（８）に変更した以外は、実施例４と同様に行い、補強用フィルム（２７）を得た。結果を表１に示した。 [Example 27]
As shown in Table 1, the same procedure as in Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (27) was obtained. The results are shown in Table 1.
〔実施例２８〕
　表１に示すように、（メタ）アクリル系粘着剤組成物（１）を、（メタ）アクリル系粘着剤組成物（８）に変更した以外は、実施例５と同様に行い、補強用フィルム（２８）を得た。結果を表１に示した。 [Example 28]
As shown in Table 1, the same procedure as in Example 5 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (8), and the reinforcing film was formed. (28) was obtained. The results are shown in Table 1.
〔実施例２９〕
　実施例１９で得られた補強用フィルム（１９）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（２９）を得た。結果を表１に示した。 [Example 29]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (19) obtained in Example 19 to obtain a reinforcing film (29) with a surface protective film. .. The results are shown in Table 1.
〔実施例３０〕
　実施例２０で得られた補強用フィルム（２０）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３０）を得た。結果を表１に示した。 [Example 30]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (20) obtained in Example 20 to obtain a reinforcing film (30) with a surface protective film. .. The results are shown in Table 1.
〔実施例３１〕
　実施例２１で得られた補強用フィルム（２１）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３１）を得た。結果を表１に示した。 [Example 31]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (21) obtained in Example 21 to obtain a reinforcing film (31) with a surface protective film. .. The results are shown in Table 1.
〔実施例３２〕
　実施例２２で得られた補強用フィルム（２２）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３２）を得た。結果を表１に示した。 [Example 32]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (22) obtained in Example 22 to obtain a reinforcing film (32) with a surface protective film. .. The results are shown in Table 1.
〔実施例３３〕
　実施例２３で得られた補強用フィルム（２３）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３３）を得た。結果を表１に示した。 [Example 33]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (23) obtained in Example 23 to obtain a reinforcing film (33) with a surface protective film. .. The results are shown in Table 1.
〔実施例３４〕
　実施例２４で得られた補強用フィルム（２４）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３４）を得た。結果を表１に示した。 [Example 34]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (24) obtained in Example 24 to obtain a reinforcing film (34) with a surface protective film. .. The results are shown in Table 1.
〔実施例３５〕
　実施例２５で得られた補強用フィルム（２５）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３５）を得た。結果を表１に示した。 [Example 35]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (25) obtained in Example 25 to obtain a reinforcing film (35) with a surface protective film. .. The results are shown in Table 1.
〔実施例３６〕
　実施例２６で得られた補強用フィルム（２６）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３６）を得た。結果を表１に示した。 [Example 36]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (26) obtained in Example 26 to obtain a reinforcing film (36) with a surface protective film. .. The results are shown in Table 1.
〔実施例３７〕
　実施例２７で得られた補強用フィルム（２７）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３７）を得た。結果を表１に示した。 [Example 37]
The surface protective film (C) obtained in Production Example 18 was bonded onto the base material of the reinforcing film (27) obtained in Example 27 to obtain a reinforcing film (37) with a surface protective film. .. The results are shown in Table 1.
〔実施例３８〕
　実施例２８で得られた補強用フィルム（２８）の基材上に、製造例１８で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（３８）を得た。結果を表１に示した。 [Example 38]
The surface protective film (C) obtained in Production Example 18 was laminated on the base material of the reinforcing film (28) obtained in Example 28 to obtain a reinforcing film (38) with a surface protective film. .. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
〔比較例１〕
　（メタ）アクリル系粘着剤組成物（３）を、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面に、乾燥後の厚みが２５μｍとなるように塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥した。このようにして、シリコーン処理面に（メタ）アクリル系粘着剤組成物（３）から形成された粘着剤層を設けた。次いで、得られた粘着剤層の表面に、反射防止層を有するＴＡＣフィルム基材（Ａ）の反射防止層が施されていない面を貼合せて、補強用フィルム（Ｃ１）を得た。得られた補強用フィルム（Ｃ１）は、常温で７日間エージングを行った。結果を表２に示した。 [Comparative Example 1]
A release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) made of a polyester resin having a thickness of 25 μm in which one surface of the (meth) acrylic pressure-sensitive adhesive composition (3) is treated with silicone. It was applied to the silicone-treated surface so that the thickness after drying was 25 μm, cured under the conditions of a drying temperature of 130 ° C. and a drying time of 3 minutes, and dried. In this way, the pressure-sensitive adhesive layer formed from the (meth) acrylic pressure-sensitive adhesive composition (3) was provided on the silicone-treated surface. Next, a surface of the TAC film base material (A) having an antireflection layer and not provided with the antireflection layer was attached to the surface of the obtained pressure-sensitive adhesive layer to obtain a reinforcing film (C1). The obtained reinforcing film (C1) was aged at room temperature for 7 days. The results are shown in Table 2.
〔比較例２〕
　表２に示すように、基材を、反射防止層を有するＰＥＴフィルム基材（Ｂ）に変更した以外は、比較例１と同様に行い、補強用フィルム（Ｃ２）を得た。結果を表２に示した。 [Comparative Example 2]
As shown in Table 2, a reinforcing film (C2) was obtained in the same manner as in Comparative Example 1 except that the base material was changed to a PET film base material (B) having an antireflection layer. The results are shown in Table 2.
〔比較例３〕
　表２に示すように、基材を、ＴＡＣフィルム（ＴＧ６０ＵＬ、富士フイルム社製）に変更した以外は、比較例１と同様に行い、補強用フィルム（Ｃ３）を得た。結果を表２に示した。 [Comparative Example 3]
As shown in Table 2, a reinforcing film (C3) was obtained in the same manner as in Comparative Example 1 except that the base material was changed to a TAC film (TG60UL, manufactured by FUJIFILM Corporation). The results are shown in Table 2.
〔比較例４〕
　表２に示すように、基材を、ＰＥＴフィルム（ルミラーＵ４８、東レ社製）に変更した以外は、比較例１と同様に行い、補強用フィルム（Ｃ４）を得た。結果を表２に示した。 [Comparative Example 4]
As shown in Table 2, a reinforcing film (C4) was obtained in the same manner as in Comparative Example 1 except that the base material was changed to a PET film (Lumilar U48, manufactured by Toray Industries, Inc.). The results are shown in Table 2.
〔比較例５〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（４）に変更した以外は、比較例１と同様に行い、補強用フィルム（Ｃ５）を得た。結果を表２に示した。 [Comparative Example 5]
As shown in Table 2, the same procedure as in Comparative Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C5) was obtained. The results are shown in Table 2.
〔比較例６〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（４）に変更した以外は、比較例２と同様に行い、補強用フィルム（Ｃ６）を得た。結果を表２に示した。 [Comparative Example 6]
As shown in Table 2, the same procedure as in Comparative Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C6) was obtained. The results are shown in Table 2.
〔比較例７〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（４）に変更した以外は、比較例３と同様に行い、補強用フィルム（Ｃ７）を得た。結果を表２に示した。 [Comparative Example 7]
As shown in Table 2, the same procedure as in Comparative Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C7) was obtained. The results are shown in Table 2.
〔比較例８〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（４）に変更した以外は、比較例４と同様に行い、補強用フィルム（Ｃ８）を得た。結果を表２に示した。 [Comparative Example 8]
As shown in Table 2, the same procedure as in Comparative Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4), and the reinforcing film was used. (C8) was obtained. The results are shown in Table 2.
〔比較例９〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（５）に変更した以外は、比較例１と同様に行い、補強用フィルム（Ｃ９）を得た。結果を表２に示した。 [Comparative Example 9]
As shown in Table 2, the same procedure as in Comparative Example 1 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C9) was obtained. The results are shown in Table 2.
〔比較例１０〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（５）に変更した以外は、比較例２と同様に行い、補強用フィルム（Ｃ１０）を得た。結果を表２に示した。 [Comparative Example 10]
As shown in Table 2, the same procedure as in Comparative Example 2 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C10) was obtained. The results are shown in Table 2.
〔比較例１１〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（５）に変更した以外は、比較例３と同様に行い、補強用フィルム（Ｃ１１）を得た。結果を表２に示した。 [Comparative Example 11]
As shown in Table 2, the same procedure as in Comparative Example 3 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C11) was obtained. The results are shown in Table 2.
〔比較例１２〕
　表２に示すように、（メタ）アクリル系粘着剤組成物（３）を、（メタ）アクリル系粘着剤組成物（５）に変更した以外は、比較例４と同様に行い、補強用フィルム（Ｃ１２）を得た。結果を表２に示した。 [Comparative Example 12]
As shown in Table 2, the same procedure as in Comparative Example 4 was carried out except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5), and the reinforcing film was used. (C12) was obtained. The results are shown in Table 2.
〔比較例１３〕
　比較例１で得られた補強用フィルム（Ｃ１）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１３）を得た。結果を表２に示した。 [Comparative Example 13]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C1) obtained in Comparative Example 1 to obtain a reinforcing film (C13) with a surface protective film. .. The results are shown in Table 2.
〔比較例１４〕
　比較例２で得られた補強用フィルム（Ｃ２）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１４）を得た。結果を表２に示した。 [Comparative Example 14]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C2) obtained in Comparative Example 2 to obtain a reinforcing film (C14) with a surface protective film. .. The results are shown in Table 2.
〔比較例１５〕
　比較例３で得られた補強用フィルム（Ｃ３）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１５）を得た。結果を表２に示した。 [Comparative Example 15]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C3) obtained in Comparative Example 3 to obtain a reinforcing film (C15) with a surface protective film. .. The results are shown in Table 2.
〔比較例１６〕
　比較例４で得られた補強用フィルム（Ｃ４）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１６）を得た。結果を表２に示した。 [Comparative Example 16]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C4) obtained in Comparative Example 4 to obtain a reinforcing film (C16) with a surface protective film. .. The results are shown in Table 2.
〔比較例１７〕
　比較例５で得られた補強用フィルム（Ｃ５）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１７）を得た。結果を表２に示した。 [Comparative Example 17]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C5) obtained in Comparative Example 5 to obtain a reinforcing film (C17) with a surface protective film. .. The results are shown in Table 2.
〔比較例１８〕
　比較例６で得られた補強用フィルム（Ｃ６）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１８）を得た。結果を表２に示した。 [Comparative Example 18]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C6) obtained in Comparative Example 6 to obtain a reinforcing film (C18) with a surface protective film. .. The results are shown in Table 2.
〔比較例１９〕
　比較例７で得られた補強用フィルム（Ｃ７）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ１９）を得た。結果を表２に示した。 [Comparative Example 19]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C7) obtained in Comparative Example 7 to obtain a reinforcing film (C19) with a surface protective film. .. The results are shown in Table 2.
〔比較例２０〕
　比較例８で得られた補強用フィルム（Ｃ８）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ２０）を得た。結果を表２に示した。 [Comparative Example 20]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C8) obtained in Comparative Example 8 to obtain a reinforcing film (C20) with a surface protective film. .. The results are shown in Table 2.
〔比較例２１〕
　比較例９で得られた補強用フィルム（Ｃ９）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ２１）を得た。結果を表２に示した。 [Comparative Example 21]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C9) obtained in Comparative Example 9 to obtain a reinforcing film (C21) with a surface protective film. .. The results are shown in Table 2.
〔比較例２２〕
　比較例１０で得られた補強用フィルム（Ｃ１０）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ２２）を得た。結果を表２に示した。 [Comparative Example 22]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C10) obtained in Comparative Example 10 to obtain a reinforcing film (C22) with a surface protective film. .. The results are shown in Table 2.
〔比較例２３〕
　比較例１１で得られた補強用フィルム（Ｃ１１）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ２３）を得た。結果を表２に示した。 [Comparative Example 23]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C11) obtained in Comparative Example 11 to obtain a reinforcing film (C23) with a surface protective film. .. The results are shown in Table 2.
〔比較例２４〕
　比較例１２で得られた補強用フィルム（Ｃ１２）の基材上に、製造例１５で得られた表面保護フィルム（Ｃ）を貼り合わせて、表面保護フィルム付補強用フィルム（Ｃ２４）を得た。結果を表２に示した。 [Comparative Example 24]
The surface protective film (C) obtained in Production Example 15 was laminated on the base material of the reinforcing film (C12) obtained in Comparative Example 12 to obtain a reinforcing film (C24) with a surface protective film. .. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の補強用フィルム、表面保護フィルム付補強用フィルムは、代表的には、光学部材や電子部材の分野で利用可能である。 The reinforcing film of the present invention and the reinforcing film with a surface protective film can be typically used in the fields of optical members and electronic members.
１０００　表面保護フィルム付補強用フィルム
１００　　補強用フィルム
２００　　表面保護フィルム
１０　　　基材層Ａ１
２０　　　粘着剤層Ａ２
３０　　　機能層Ａ３
４０　　　基材層Ｂ１
５０　　　粘着剤層Ｂ２
６０　　　剥離シート
７０　　　機能層Ｂ３ 1000 Reinforcing film with surface protective film 100 Reinforcing film 200 Surface protective film 10 Base material layer A1
20 Adhesive layer A2
30 Functional layer A3
40 Base material layer B1
50 Adhesive layer B2
60 Release sheet 70 Functional layer B3

Claims (9)

  1. 　基材層Ａ１と粘着剤層Ａ２を含む補強用フィルムであって、
    　該補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後の５８０ｎｍでの光反射率変化率が２．０％以下である、
    　補強用フィルム。     A reinforcing film containing a base material layer A1 and an adhesive layer A2.
    The rate of change in light reflectance at 580 nm after storing the reinforcing film in an environment of 60 ° C. and 90% RH for 1 week is 2.0% or less.
    Reinforcing film.
  2. 　前記補強用フィルムを６０℃、９０％ＲＨの環境下で１週間保管した後のヘイズ変化率が１０．０％以下である、請求項１に記載の補強用フィルム。 The reinforcing film according to claim 1, wherein the haze change rate after storing the reinforcing film in an environment of 60 ° C. and 90% RH for one week is 10.0% or less.
  3. 　前記基材層Ａ１の全光線透過率が９０％以上である、請求項１または２に記載の補強用フィルム。 The reinforcing film according to claim 1 or 2, wherein the total light transmittance of the base material layer A1 is 90% or more.
  4. 　前記粘着剤層Ａ２をＰＥＴフィルムに貼り付けて２３℃で３０分間放置した後の、剥離角度１８０度、剥離速度３００ｍｍ／ｍｉｎにおける対ＰＥＴフィルム粘着力が０．３０Ｎ／２５ｍｍ以上である、請求項１から３までのいずれかに記載の補強用フィルム。 The claim that the adhesive force against PET film at a peeling angle of 180 degrees and a peeling speed of 300 mm / min after the pressure-sensitive adhesive layer A2 is attached to a PET film and left at 23 ° C. for 30 minutes is 0.30 N / 25 mm or more. The reinforcing film according to any one of 1 to 3.
  5. 　光学部材または電子部材である被着体に貼り付けられる、請求項１から４までのいずれかに記載の補強用フィルム。 The reinforcing film according to any one of claims 1 to 4, which is attached to an adherend which is an optical member or an electronic member.
  6. 　請求項１から４までのいずれかに記載の補強用フィルムを備える、補強用フィルム付光学部材または補強用フィルム付電子部材。 An optical member with a reinforcing film or an electronic member with a reinforcing film, comprising the reinforcing film according to any one of claims 1 to 4.
  7. 　請求項１から４までのいずれかに記載の補強用フィルムの前記基材層Ａ１側に表面保護フィルムを備える、表面保護フィルム付補強用フィルム。 A reinforcing film with a surface protective film provided with a surface protective film on the base material layer A1 side of the reinforcing film according to any one of claims 1 to 4.
  8. 　前記表面保護フィルム付補強用フィルムを、６０℃、９０％ＲＨの環境下で１週間保管した後に、前記表面保護フィルムを剥離した後の、前記補強フィルムの５８０ｎｍでの光反射率変化率が５．０％以下である、請求項７に記載の表面保護フィルム付補強用フィルム。 After storing the reinforcing film with a surface protective film in an environment of 60 ° C. and 90% RH for one week, the rate of change in light reflectance of the reinforcing film at 580 nm after peeling off the surface protective film is 5. The reinforcing film with a surface protective film according to claim 7, which is 0.0% or less.
  9. 　請求項７または８に記載の表面保護フィルム付補強用フィルムが備える粘着剤層Ａ２を露出させて該粘着剤層Ａ２を被着体に貼り付け、次いで、前記表面保護フィルムを剥離する、表面保護フィルム付補強用フィルムの使用方法。 Surface protection in which the pressure-sensitive adhesive layer A2 included in the reinforcing film with a surface protection film according to claim 7 or 8 is exposed, the pressure-sensitive adhesive layer A2 is attached to an adherend, and then the surface protection film is peeled off. How to use the reinforcing film with film.
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